JPWO2018020941A1 - Epoxy composition, curing method thereof and storage method thereof - Google Patents

Abstract

The epoxy composition of the present invention is an epoxy composition containing an epoxy compound and an onium salt, wherein the epoxy compound is composed of a single component or two or more components, and the onium salt has a reaction initiation temperature of It is 45 ° C. or higher, and the compounding ratio (Y mass%) of the epoxy equivalent (X) of the epoxy compound and the onium salt when the mass of the epoxy compound is 100 mass% is within a predetermined range. The curing method of the present invention is characterized in that the epoxy composition is heat-treated at a temperature of 60 ° C. or higher. The storage method of the present invention is characterized in that the epoxy composition is stored at a temperature of 0 ° C. or more and a temperature at which the onium salt starts to react.

Description

  The present invention relates to an epoxy composition, a method of curing the same, and a method of storing the same.

  Since General Electric Company (abbr .: GE) of the United States succeeded in the ring-opening polymerization of the epoxy group using an onium salt in 1975, light and thermal onium salts were epoxy compositions (epoxy resins). Renewed as a new latent curing catalyst, various onium salts have been researched and developed at home and abroad.

  The onium salt one-component epoxy composition is (a) capable of curing and curing in a short time, (b) easy to blend, (c) less odor and vapor at the time of heat curing, and friendly to the human body and the environment (d) (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 (tenacity, high strength, electrical properties, It has excellent characteristics such as developing as it is without loss of solvent resistance etc.). These features are described below.

(A) Short-time curing prescription The reaction mechanism of the onium salt and the epoxy compound is that the onium ion excited by energy such as light and heat opens the epoxy group and forms a self condensation network at once by chain reaction and It has become. On the other hand, the curing reaction proceeds by condensation reaction of an ordinary epoxy compound with an equivalent amount of amines and the like.

(B) Ease of formulation Thermally active latent onium salts have little influence on physical property values even by rough measurement. For this reason, the combination of the thermally active latent onium salt and the epoxy compound is extremely simple, and effects can be exhibited even with a small amount of addition. Therefore, no skill is required for handling. In contrast, curing agents such as common amines need to accurately measure the equivalent weight to the epoxy compound.

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

(D) Long working life Epoxy compositions containing a common latent latent hardener based on amine have been bothersome in terms of management in that they must all be stored frozen. On the other hand, many epoxy compositions containing a thermally active onium salt, in which the reaction initiation temperature is clearly higher than room temperature, are stable at room temperature, and there is no need for frozen storage. This is also advantageous for work efficiency and energy saving. In particular, the frozen and stored epoxy composition needs to be returned from freezing temperature to normal temperature before use. At this time, the water contained in the surrounding air is condensed and contained, and the time required to return to normal temperature is long. Furthermore, there is a problem that the excess epoxy composition needs to be returned to a frozen state.

(E) Transparency A common amine-based curing agent often has a colored amine itself due to its structure. Even when a transparent amine is used, the amine is sensitive to heat and tends to be colored during heat curing. For this reason, it was difficult to obtain a colorless and transparent cured product without some manipulation. On the other hand, in the case of the onium salt, since the onium salt itself is transparent, a colorless and transparent cured product can be easily obtained by using an epoxy composition that becomes a colorless and transparent epoxy resin.

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

  The onium salt-containing one-part epoxy composition is a composition having the characteristics as described above. However, the activity of the onium salt was often uneven. For this reason, it has been difficult to select a well-balanced onium salt capable of achieving both low temperature activity and potential from a wide variety of onium salts.

  In film applications for electric materials using an epoxy composition as an adhesive, polyimide films having a high glass transition temperature and high dimensional stability up to a high temperature region are widely used. Polyimide films are very expensive compared to films of other materials. For this reason, although heat resistance and dimensional stability are inferior, it can respond also to various processing and the use of various films called cheaper PET and an engineering plastic is increasing. These inexpensive films are also used in large amounts in applications such as electrical materials.

  For example, PET film is certified to have a continuous use temperature of 106 ° C. according to UL standard (UL 746). However, when the epoxy composition is cured at a high temperature, distortion occurs between the epoxy resin and the substrate film upon curing. This distortion could be a fatal defect in precision electronic materials.

  Also, as a feature of the epoxy composition, there is a problem that although the adhesion is excellent, the epoxy resin is generally hard. The hardness of the epoxy resin was not suitable for the application of the film, even if it was given flexibility. From this, it has been desired to develop an epoxy resin to which flexibility has been imparted so as to be deformed following the film, and a one-component epoxy composition which can be strongly cured at a low temperature.

  In addition, epoxy compositions are used in large amounts other than film applications. Many electrical and electronic parts in general are sensitive to heat, and the appearance of a one-part epoxy composition which can be cured at a low temperature and for a short time with little thermal shock has been desired.

  In industrial line production, the biggest advantage of low temperature and short time curing is cost reduction by productivity improvement and energy saving. However, the problem of the room temperature stability of the one-pack type epoxy composition has arisen in the development thereof, and a low temperature, short curing formulation has been a dream for many years.

  In particular, ultra-soft cured physical properties such as high hardness, high strength one-component epoxy compositions that can be cured at low temperatures of 60 to 80 ° C., and films with opposite properties, which have been desired for electronic materials applications A one-part epoxy composition has not yet been found.

  For example, in the case of a combination of an onium salt having a reaction start temperature close to room temperature and a conventional epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: JER 828), the shelf life is short, and when mixed with the epoxy composition, the reaction starts immediately Many are considered to be incapable of becoming a one-pack latent curing composition. On the other hand, in the case of a combination of an onium salt having a high reaction initiation temperature and an epoxy resin (trade name: JER 828), the shelf life is long and stable, but at a low temperature of less than 100 ° C, particularly 60 ° C to 80 ° C. There was no known cure.

  Moreover, the usage-amount of the onium salt with respect to 100 weight part of epoxy resins in onium salt mixing | blending one-component epoxy resin is described, for example in patent documents 1-2. 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 the aromatic hydrogenated epoxy compound, the amount used and the curing characteristics of the epoxy resin However, no report has been made to clarify and study in detail the properties of the cured product, in particular the compounding amounts of the epoxy equivalent and the onium salt.

  Moreover, although these patent documents describe the onium salt 0.17 parts by weight with respect to 100 parts by weight of the epoxy resin in both examples, curing conditions of various epoxy resins from the relationship between the epoxy equivalent and the onium salt content, In particular, no report has been made to examine in detail the properties of the cured product at a curing temperature of less than 100 ° C.

  The present invention has been made against the background of the problems of the prior art, and becomes a cured product of high strength and high hardness, which is a field where epoxy resins curable in a low temperature and short time are excellent, and epoxy resins are not good. It is an object of the present invention to provide an epoxy composition which becomes a cured product having both super flexibility and bending resistance to follow a flexible film which is a field to be cured, a curing method thereof and a storage method thereof.

  The epoxy composition of the present invention for solving the above problems is an epoxy composition containing an epoxy compound and an onium salt, wherein the epoxy compound is composed of a single component or a plurality of two or more components, and the onium salt is The reaction initiation temperature when heated together with the bisphenol A liquid epoxy resin is 45 ° C. or higher, and the blending ratio of the onium salt when the epoxy equivalent (X) of the epoxy compound and the mass of the epoxy compound are 100 mass% (Ymass %), When the epoxy equivalent of the epoxy compound is less than 1000, 0.5 × exp (−0.003 ×) ≦ Y ≦ 250 × exp (−0.003 ×), and the epoxy equivalent of the epoxy compound Is 1,000 or more, it is characterized by being in the range of 0.02 ≦ Y ≦ 40.

  The curing method of the epoxy composition of the present invention is characterized in that the epoxy composition according to any one of claims 1 to 10 is heat-treated at a temperature of 60 ° C or more. That is, the epoxy composition of the present invention is heat-treated at a temperature of 60 ° C. or more.

  The epoxy composition of the present invention is an epoxy composition that can be cured at a low temperature, which is difficult with conventional one-part epoxy compositions. And, the epoxy composition of the present invention obtains both a high-hardness and high-strength epoxy resin that the conventional epoxy composition is good at, and a flexible super-soft epoxy resin like a film that the epoxy composition is not good at be able to. For this reason, the epoxy composition of this invention can be used also for uses, such as various electricity sensitive to heat, electronic material, and various films. As a result, the epoxy composition of the present invention exhibits the effects of improving productivity by curing at a low temperature and in a short time, reducing costs by energy saving and improving workability in industrial line production.

In the method of curing the epoxy composition of the present invention, a cured resin of a tough epoxy composition can be obtained by heat treating the epoxy composition at a temperature of 60 ° C. or higher. The curing method of the epoxy composition of the present invention is a curing method of the epoxy composition of the present invention.
The method of curing the epoxy composition of the present invention is preferably heat-treated at a temperature of 80 ° C. or less. In the epoxy composition, it is possible to control the curing temperature by selecting the optimum blending ratio of the epoxy equivalent and the onium salt. The temperature of the heat treatment in the present invention enables storage at room temperature, which was difficult in the conventional medium / low temperature one-component latent curing agent epoxy composition. In addition, the reaction initiation temperature can be significantly reduced compared to the medium-high temperature type one-component latent curing agent epoxy composition, and curing starts easily at a low heating temperature.

  The method for storing the epoxy composition of the present invention is characterized in that the epoxy composition according to any one of claims 1 to 10 is stored at a temperature of 0 ° C. or more and a reaction initiation temperature of the onium salt. . That is, it is characterized in that the epoxy composition of the present invention is stored at a temperature of 0 ° C. or more and a reaction initiation temperature of the onium salt or less.

The epoxy composition according to the storage method of the present invention is an epoxy composition that can be stored at temperatures around room temperature. In the epoxy composition, it is possible to control the curing temperature by selecting the optimum blending ratio of the epoxy equivalent and the onium salt. And the epoxy composition of this invention can be preserve | saved in conventional epoxy composition, without using storage (freezing preservation) in low temperature. As a result, the epoxy composition of the present invention exhibits the effects of improvement of productivity, cost reduction by energy saving and improvement of workability by not performing freezing storage in storage and storage.
The epoxy composition of the present invention can, of course, be stored at a temperature of 0 ° C. or less. That is, frozen storage is possible.

FIG. 1 is a graph showing the relationship between the epoxy equivalent and the blending ratio of the onium salt. FIG. 2 is a graph showing the relationship between epoxy equivalent and volume resistivity. FIG. 3 is a graph showing the relationship between the compounding ratio of epoxy equivalent and onium salt, and tensile shear force.

Embodiment

Hereinafter, the present invention will be specifically described using embodiments.
(Epoxy composition)
The epoxy composition of the present embodiment is an epoxy composition containing an epoxy compound and an onium salt. An epoxy compound consists of a single component, or two or more types of components. The onium salt has a reaction initiation temperature of 45 ° C. or more and 75 ° C. or less when heated with the bisphenol A liquid epoxy resin. The compounding ratio (Y parts by mass) of the epoxy equivalent (X) of the epoxy compound and the onium salt relative to 100 parts by mass of the epoxy compound is 0.5 × exp (-0.003 ×) when the epoxy equivalent of the epoxy compound is less than 1000. In the case where the epoxy equivalent of the epoxy compound is 1000 or more, it is in the range of 0.02 ≦ Y ≦ 40.

  The epoxy composition of the present embodiment is an epoxy composition containing an epoxy compound and an onium salt. The epoxy composition of the present embodiment is a one-pack type epoxy composition because it contains an epoxy compound and an onium salt.

The onium salt initiates ring-opening polymerization of the epoxy group of the epoxy compound.
The onium salt has a reaction initiation temperature of 45 ° C. or higher when heated with a bisphenol A liquid epoxy resin. That is, the reaction initiation temperature when heated with the epoxy compound is 45 ° C. or higher. When the reaction initiation temperature is in this temperature range, the epoxy composition of this embodiment starts to cure at a relatively low temperature and does not cure at room temperature.
The upper limit of the reaction initiation 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 less, preferably 75 ° C. or less. The reaction initiation temperature of the onium salt is more preferably 50 ° C. or more and 65 ° C. or less.
As the reaction initiation temperature of the onium salt with the bisphenol A liquid epoxy resin, the measurement result by differential scanning calorimetry (DSC) described later can be used.

Although an onium salt can express an effect by using one type of compound, you may use two or more types of multiple types as needed.
The specific compound is not limited as long as it has the above-mentioned properties as the onium salt. For example, N- (α-phenylbenzyl) -4-cyanopyridinium hexafluoroantimonate, N- (1-naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, N-cinnamylyl as a pyridinium salt excellent in low-temperature curing properties Examples thereof include -2-cyanopyridinium hexafluoroantimonate, N-cinnamyl-4-cyanopyridinium hexafluoroantimonate, N-cinnamyl-2-chloronium hexafluoroantimonate and the like.

  1-Naphthylmethyldimethylsulfonium hexafluoroantimonate, 1-naphthylmethyltetramethylenesulfonium hexafluoroantimonate, cinnamyl dimethylsulfonium hexafluoroantimonate, cinnamyl tetramethylene sulfonium hexanone as an aliphatic sulfonium salt excellent in low temperature curing property Fluoroantimonate, 9-fluorenyldimethylsulfonium hexafluoroantimonate, 9-fluorene tetramethylene sulfonium hexafluoroantimonate and the like can be mentioned.

  N-methyl-4-cyanopyridinium hexafluoroantimonate, N-methyl-2-chloropyridinium hexafluoroantimonate, N-methyl-2-methoxypyridinium hexafluoroantimonate as an N-methyl ammonium salt which is heat and photo activity , N-methyl-2,6-dimethylpyridinium hexafluoroantimonate, N-methyl-2-chloro-6-methoxypyridinium hexafluoroantimonate, N-methyl-3-bromoquinolium hexafluoroantimonate, N -Benzyl-2-cyano pyridinium hexafluoroantimonate etc. can be mentioned.

  N-benzyl-3-bromoquinolium hexafluoroantimonate, N- (α-phenylbenzyl) -3-bromoquinolium hexafluoroantimonate, N- (1-naphthyl) as a quinolium salt having heat and light activity Examples include methyl) -3-bromoquinolium hexafluoroantimonate, N-cinnamyl-3-bromoquinolium hexafluoroantimonate and the like.

  N-benzylpyrazinium hexafluoroantimonate, N- (4-nitrobenzyl) pyrazinium hexafluoroantimonate, N- (4-methoxybenzyl) pyrazinium hexafluoro as ammonium salts which are heat and light activity Antimonate, N- (α-phenylbenzyl) pyrazinium hexafluoroantimonate, N-cinnamyl pyrazinium hexafluoroantimonate, N- (1-naphthylmethyl) pyrazinium hexafluoroantimonate, N- Examples thereof include benzyl-4-bromo-N, N-dimethylanilinium hexafluoroantimonate, N- (1-naphthylmethyl) -4-bromo-N, N-dimethylanilinium hexafluoroantimonate and the like.

  As an ammonium salt having high heat and light activity, N-methyl-2-methyl-, N-methyl-2- (4-methyl-) benzothiazolium hexafluoroantimonate, N-methyl-2- (1 And -methyl-) benzothiazolium hexafluoroantimonate, N-methyl-2-benzylthiopyridinium hexafluoroantimonate and the like can be mentioned.

  As an aromatic sulfonium salt excellent in thermal activity and photoactivity, 2-indanylphenylmethylsulfonium hexafluorophosphonate, 1-ethoxycarbonylethylphenylmethylsulfonium hexafluorophosphonate, phenylmethyl-2-methyl-2-phenylpropylsulfonium hexame Fluorophosphonate, 2-phenylethylphenylmethylsulfonium hexafluorophosphonate, 2-phenylpropylphenylmethylsulfonium hexafluorophosphonate, 2- (4-methoxyphenyl) ethylphenylmethylsulfonium hexafluorophosphonate, 3- (4-methoxyphenyl)- 2-Propylphenylmethylsulfonium hexafluorophosphonate, 4-hydroxyphenylbenzylmethylsulfonium Hexafluorobutene phosphonate can compounds such as benzyl dimethyl sulfonium hexafluorophosphonate be used in the present invention as long as it exhibits the above characteristics.

  The sulfonium baud rate complex (Sony Chemical Co., Ltd., Dexceria Riz Co., Ltd.), 2-butene-1-thionia cyclopentahexafluoroantimonate (Asahi Denka Kogyo Co., Ltd., trade name) are commercially available. : CP 66), 3-Methyl 2-butene-1-thionia cyclopentahexafluoroantimonate (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: CP77), dibutylphenyliodonium hexafluorophosphonate (manufactured by Midori Kagaku Co., Ltd.), benzyl Methyl-p-methoxycarbonyloxyphenyl sulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-45), 1-naphthylmethylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (Three Shin Chemical Industry Co., Ltd.) Stock company (Trade name: SI-60), 2-methylbenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-80), 2-methylbenzyl methyl p-methoxy Carbonyloxy phenyl sulfonium tetrakis (pentafluorophenyl) borate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-B2A), benzylmethyl p-methoxycarbonyloxyphenyl sulfonium tetrakis (pentafluorophenyl) borate (Shinshin Chemical Industry Co., Ltd. Company-made, trade name: SI-B3A), triphenylsulfonium hexafluorophosphonate (made by Midori-Chemical Co., Ltd.), triphenylsulfonium hexafluoroantimonate (made by Midori-Chemical Co., Ltd.), triarylsulfonium hexanoate Le Oro phosphonate (Dow Chemical Japan Co., Ltd., trade name: UVI-6990) can be used to show the above characteristics from compound such.

In the present embodiment, the onium salt may be mixed with an auxiliary. As the auxiliaries, there can be mentioned an activity regulator which regulates the activity of polymerization, and an assistant which improves the storage stability having a reaction suppressing effect. Although the addition amount of the auxiliary agent is not limited, when the total mass of the onium salt and the auxiliary agent is 100 mass%, it is preferable to add so as to be 10 mass% or less. The onium salt may not be mixed with the auxiliary agent. That is, 0 mass% may be sufficient.
In the present embodiment, examples of the auxiliary added to the onium salt include San-aid Chemical Industry Co., Ltd., trade name: San Aid SI auxiliary.
An epoxy compound consists of a compound which has an epoxy group. The epoxy group of the epoxy compound is ring-opened by the onium salt and cured by the polymerization reaction.

  An epoxy compound consists of a single component, or two or more types of components. Although an epoxy compound may be used by what consists of one type (single component), you may be what combined the several epoxy compound (two or more types of multiple components). The epoxy equivalent can be adjusted by combining a plurality of epoxy compounds (two or more kinds of components).

  The epoxy compound has an epoxy equivalent (X) and a compounding ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass%, and when the epoxy equivalent of the epoxy compound is less than 1000, 0. 0. In the range of 5 × exp (−0.003 ×) ≦ Y ≦ 250 × exp (−0.003 ×) and the epoxy equivalent of the epoxy compound is 1000 or more, it is in the range of 0.02 ≦ Y ≦ 40. is there.

  When the compounding ratio (Y) of the epoxy equivalent (X) and the onium salt satisfies this relationship, the curing reaction at relatively low temperature conditions can be sufficiently advanced. In addition, an epoxy equivalent is an epoxy equivalent measured in the state in which the epoxy compound contained all the epoxy components. The specific measurement method will be described later.

  Here, when Y is smaller than this range, the curing reaction under relatively low temperature conditions can not be sufficiently advanced. When Y is larger than this range, although curing reaction proceeds, it becomes difficult to sufficiently express physical properties after curing.

  The range of this compounding ratio is in the range of 3 × exp (−0.003 ×) ≦ Y ≦ 200 × exp (−0.003 ×) when the epoxy equivalent of the epoxy compound is less than 1000, and the epoxy equivalent of the epoxy compound is Is preferably in the relationship of 0.3 ≦ Y ≦ 20. When the epoxy equivalent of the epoxy compound is less than 1000, it is in the range of 5 × exp (−0.003 ×) ≦ Y ≦ 150 × exp (−0.003 ×), and 0 when the epoxy equivalent of the epoxy compound is 1000 or more It is further preferable that the relationship of 6 ≦ Y ≦ 10 is satisfied.

  The specific compound is not limited as long as the epoxy compound of this embodiment has the above-mentioned properties. For example, bisphenol A epoxy resin (made by Mitsubishi Chemical Corporation, trade name: JER 828 or JER 834), bisphenol F epoxy resin (made by ADEKA, trade name: EP-4901), bisphenol E epoxy resin (purine Co., Ltd.) Made by Tech, trade name: R710, hydrogenated bisphenol A epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: YX8000 and YX8034), bisphenol A type polymer epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: JER1256) Phenolic novolac epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: JER152), Cresol novolac epoxy resin (DIC Co., Ltd., trade name: N660), biphenyl epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: YX4000), Naf Ren-type epoxy resin (manufactured by DIC Corporation, trade name: HP-4032D), cyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name: HP-7200), and the like.

  Also in the epoxy compound, an auxiliary may be mixed. 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 polymerization activity. The addition amount of the auxiliary is not limited. It can be added in a preferred amount for each auxiliary.

  Examples of auxiliary agents (viscosity modifiers, viscosity stabilizers) to be added to the epoxy compound include, for example, alkyl glycidyl ether type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YED216D), compound having a monovalent epoxy group (Mitsubishi Chemical Co., Ltd. make, brand name: YED188 and YED122) can be mentioned.

  The epoxy composition of this embodiment may be formed only from the epoxy compound and the onium salt, or may contain other components. In addition, another component shows the component (The component which does not accelerate | stimulate or inhibit the ring-opening polymerization reaction of an epoxy group) which does not affect reaction with an onium salt and an epoxy compound.

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

  The epoxy composition of this form can be used as an adhesive. The epoxy composition of this embodiment is an epoxy composition which can be cured at a low temperature, which was difficult with the conventional one-pack type epoxy composition, so that the high hardness and high strength that the conventional epoxy composition excels at Both of the epoxy resin of the present invention and a flexible super flexible epoxy resin like a film which the conventional epoxy composition is not good at. Therefore, the epoxy composition of the present embodiment exhibits the effects of improvement of productivity by curing at low temperature and short time, cost reduction by energy saving and improvement of workability in industrial line production.

The epoxy composition of the present embodiment may contain a filler. Fillers can include those used in conventional epoxy compositions. By containing the filler, (the cured product of) the epoxy composition can be provided with desired properties.
As a filler, metal particle powder, inorganic particle powder, carbon powder, organic particle powder etc. can be mentioned. The filler is more preferably an amorphous silica powder.
When the epoxy composition of this form contains a filler, the compounding ratio is not limited. For example, when the epoxy composition of this form contains a silica powder as a filler, it is preferable that it is 20 mass% or less, when the mass of the whole epoxy composition is 100 mass%. The blending ratio of the filler is more preferably 10 mass% or less, and still more preferably 5 mass% or less.
That is, when the mass of the whole epoxy composition is 100 mass%, it is preferable to contain the filler which consists of amorphous silica by 20 mass% or less.

The epoxy composition of the present embodiment can also be suitably used as a conductive adhesive. The conductive adhesive can be formed by adding a conductive material to the epoxy composition of this embodiment. The material of the conductivity imparting 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 polymer or filler, carbon black, carbon fiber, graphite, nano silver, nano copper, nano aluminum, nano gold, nano nickel, carbon nanotube Etc. can be mentioned. The particle shape of the conductive powder is also not limited, and may be spherical, needle-like, flake-like or the like, and more preferably flake-like. The conductive powder may be of one type, but may be a combination of a plurality of conductive powders different in particle shape, particle diameter, surface cleanliness and the like.
Among them, it is more preferable to use flake-like silver powder as the conductivity imparting agent. The silver powder may be of one type, but may be a combination of a plurality of silver powders different in particle shape, particle diameter, surface cleanliness and the like.
In addition, the silver powder can exhibit the same effect whether it is washed or unwashed.

  When using silver powder, it is preferable that the usage-amount is 75-95 mass%, when mass of the whole epoxy composition (or electroconductive adhesive agent) is 100 mass%. If it is less than 75 mass%, sufficient conductivity can not be obtained. If the content is more than 95 mass%, the proportion of the epoxy composition decreases, the brittleness after curing increases, and the function as an adhesive does not sufficiently appear. When using silver powder, it is more preferable that it is 80-92 mass% when it is 100 mass% of the whole epoxy composition, and it is still more preferable that it is 85-90 mass%.

  When using silver powder, it is preferable that it is a powder of flaky particle. The flake shape is also referred to as a flake 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. Flaky particles are more likely to be in contact with other adjacent particles as compared to spherical particles. That is, it is easy to form a conductive path.

  When using silver powder, it is preferable that the viscosity in 25 degreeC of the viscosity of a conductive adhesive is 1-90 Pa.s. The viscosity of the conductive adhesive can be measured by the measurement method described later. When the viscosity at 25 ° C is in this range, it can be handled as a conductive adhesive. When the viscosity is less than 1 Pa · s, it becomes difficult to prevent the sedimentation of the silver powder. When the viscosity increases beyond 90 Pa · s, the viscosity of the conductive adhesive becomes high, making it difficult to handle when used. 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 this form contains silver powder by 75-95 mass%, when the whole is 100 mass%, and the viscosity in 25 degreeC is 1-90 Pa.s. The silver powder is more preferably in the form of flakes.

In the epoxy composition of the present embodiment, it is preferable that the epoxy equivalent of the epoxy compound is 1000 or more, and the volume resistivity is 2 × 10 ⁻⁴ Ωcm or less. The epoxy composition of this embodiment has excellent conductivity (low volume resistivity) of 2 × 10 ⁻⁴ Ωcm or less, while the epoxy equivalent of the epoxy compound is as large as 1000 or more.

In the epoxy composition of this form, the relationship between the mass part of the onium salt in the epoxy compound from which an epoxy equivalent differs, and a volume resistivity is shown in FIG. The relationship between the epoxy equivalent and the volume resistivity in the case of containing the onium salt in 2 parts by mass with respect to the epoxy compound is shown in FIG. In addition, the epoxy compound used the epoxy compound whose epoxy equivalent is 165, 186, 194, 250, 263, 470, 1004, 2605, 7318. The epoxy compound and the onium salt are the compounds used in the following examples and the corresponding onium salts.
In these samples, the volume resistivity was measured under the curing conditions of 80 ° C. × 60 minutes, as in Example 33 described later.

As shown in FIGS. 1 and 2, the epoxy compound having an epoxy equivalent of 1000 or more is excellent in conductivity of 2 × 10 ⁻⁴ Ωcm or less, and further, 1 × 10 ⁻⁴ Ωcm or less, that is, 10 ⁻⁵ Ωcm. Demonstrate the nature. Volume resistivity on the order of 10 ^<-5 > ohm cm is a level of conductivity that is difficult to achieve with conventional epoxy compositions.
As described above, when conductive powder (silver powder) is blended into the epoxy composition of the present embodiment, the relationship between the epoxy equivalent and the onium salt content is intensively examined. The relationship was clarified, and it was clearly found that there was an optimal blending area.

Furthermore, in the epoxy composition of this embodiment, the relationship between the tensile shear force and the mass part of the onium salt in the epoxy compounds having different epoxy equivalents is shown in FIG. In addition, the epoxy compound used the epoxy compound whose epoxy equivalent is 165, 186, 194, 250, 263, 470, 1004, 2605, 7318. The epoxy compound and the onium salt are the compounds used in the following examples and the corresponding onium salts.
In these samples, the tensile shear force (die shear strength) was measured under the curing conditions of 80 ° C. × 60 minutes, as in Example 33 described later.

  As shown in FIG. 3, in a plurality of epoxy compounds having different epoxy equivalents, the tensile shear force (adhesion to the adherend) exerts a high stress (adhesion) of 5 MPa in any epoxy compound. I know what I can do. 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 adhesion.

The conductive adhesive preferably contains silica in an amount of 0.01 to 20 mass%, based on 100 mass% of the total. Silica improves the dispersibility of silver powder in the epoxy composition and prevents sedimentation in the conductive adhesive. If the content of silica is less than 0.01 mass%, the effect of the addition is not sufficiently exhibited. When the content is more than 20 mass%, the adhesion and conductivity tend to be reduced. As for content of a silica, 5 mass% or less is more preferable, and 2 mass% or less is still more preferable.
As the silica, silica used as a filler of a conventional conductive adhesive can be used, nano-silica having a particle diameter of nm unit is more preferable, and hydrophobic nano-silica is still more preferable. The silica can use the commercially available nano silica which consists of amorphous.

The epoxy composition of the present embodiment is characterized in that when used as an adhesive, it exhibits strong adhesive strength at relatively low temperature and in a short time processing. Adhesive strength can be defined by die shear tensile shear strength. The die shear tensile shear strength can be determined 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 an epoxy composition is more preferable because it leads to an improvement in productivity especially in an industrial production line. It is further preferable that the material exhibits a tensile shear strength of 10 MPa or more after heat treatment at 70 to 80 ° C. for 60 minutes.
The epoxy composition of the present embodiment is preferably used as an adhesive, and is preferably used as a conductive adhesive when a conductive material is added.

The epoxy composition of the present embodiment preferably contains a reinforcing material. By containing the reinforcing material, the epoxy composition of the present embodiment can obtain a cured product containing the reinforcing material. The 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. The reinforcing material may be a dense or porous structure or a fibrous material. Further, the material is not limited, and carbon, metal, inorganic material, organic material and the like can be mentioned. Furthermore, the reinforcing material is preferably a structural material formed by arranging these fibers.
That is, the reinforcing material is a dense or porous structure made of an aggregate of one or more fibers selected from carbon fibers, metal fibers, inorganic fibers, organic fibers, and / or organic or inorganic materials. Is preferred. The fiber aggregate refers to a state in which fibers are aligned in a predetermined direction (arbitrary angle) or a state in which at least adjacent short fibers are intertwined. The reinforcing material is more preferably a band-like body in which fibers are aligned in a predetermined direction, a woven fabric of each of the fibers, and a non-woven fabric of each 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. Preferably, it is 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, in the epoxy composition of the present embodiment, the reaction between the epoxy compound and the onium salt is initiated, and the epoxy composition of the present embodiment is cured. Also, heating at this temperature allows curing to be completed quickly.
The heat treatment temperature is not limited and is a temperature higher than the reaction initiation temperature of the onium salt contained in the epoxy composition. Preferably, the temperature is about the reaction initiation temperature of the onium salt to the reaction initiation temperature + 30 ° C. More preferably, the temperature is about the reaction initiation temperature of the onium salt to about the reaction initiation temperature + 10 ° C.

The upper limit of the heat treatment temperature is not limited either, and may be higher than the reaction initiation temperature of the onium salt contained in the epoxy composition. Preferably, the temperature is about the reaction initiation temperature of the onium salt to the reaction initiation temperature + 30 ° C. In particular, in the application to film (film-like member) and heat sensitive electronic component applications, a temperature of about reaction initiation temperature of onium salt to reaction initiation temperature + 10 ° C. is preferable.
It is preferable to heat-process at the temperature of 80 degrees C or less. In the case of an epoxy composition using an onium salt having a reaction initiation temperature of 45 to 75 ° C., the curing reaction can proceed at a low temperature of 60 to 80 ° C.
In the epoxy composition, it is possible to control the curing temperature by selecting the optimum blending ratio of the epoxy equivalent and the onium salt. The curing temperature is a temperature within a range of a temperature at which a curing reaction starts to a temperature at which a curing reaction is completed (a temperature at which a curing reaction proceeds). That is, when the temperature in the heat treatment changes (rise in temperature), the curing temperature is either the temperature at which the curing reaction starts, the temperature at which the curing reaction is completed, or the temperature at which the curing reaction is in progress. It may be a temperature, preferably the temperature at which the curing reaction starts. As a result, a curing reaction can be performed under conditions which can not be considered as curing conditions for ordinary epoxy resins. 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, second speed curing).
The curing temperature of the epoxy composition of this embodiment is not limited. In order to shorten the curing time, it is preferable to set the curing temperature high.

In the heat treatment, the heating time is preferably 5 seconds or more and 5 minutes or less. When the heating time falls 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. The epoxy composition of this embodiment can complete curing of the epoxy composition with heating of 5 minutes or less because the curing reaction proceeds rapidly. 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 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 The heating time may be 15 minutes or more, 20 minutes or more, 30 minutes or more, 60 minutes or more, or 120 minutes or more.
The epoxy composition cures sufficiently when the heating time falls 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 heat treatment is not limited to the atmosphere. The atmosphere can be appropriately selected from an atmosphere such as an air atmosphere, an oxidizing atmosphere containing oxygen, and an inert gas atmosphere such as argon gas. An atmospheric atmosphere is preferred. The pressure of the heat treatment atmosphere is not limited either. It can select suitably from conditions, such as atmospheric pressure, pressure reduction conditions, pressurization conditions. Atmospheric pressure is preferred.

As for the heat treatment, it is preferable to appropriately determine the heat treatment temperature and the heating time. When the heat treatment temperature becomes high, the heating time can be shortened. Conversely, when the heat treatment temperature is lowered, the epoxy composition can be cured by prolonging the heating time.
For example, in the configuration of sample 5 described later, cured products obtained under the conditions of 70 ° C. × 1 hr, 80 ° C. × 1 hr, 100 ° C. × 1 hr, 150 ° C. × 1 hr, 200 ° C. × 1 hr have high adhesion strength of 13 MPa to 28 MPa. Indicates That is, a cured product exhibiting high adhesive strength can be obtained.
Similarly, as shown in Table 8 below, high adhesion of about 20 to 30 MPa under heat treatment conditions of 155 ° C. × 60 seconds, 175 ° C. × 60 seconds, and 200 ° C. × 60 seconds, which also relates to the amount of onium salt Indicates Curing in seconds is possible, improving work efficiency. Furthermore, even when an onium salt having a reaction initiation temperature of 136 ° C. is used, high adhesion of 15 to 45 MPa is exhibited at 275 ° C. × 30 seconds and 275 ° C. × 45 seconds.
As shown in samples 241 to 245 in Table 9 below, after storing the epoxy composition at 40 ° C. for 4 weeks, it is as high as 25 to 35 MPa at 150 ° C. × 1 hr, 250 ° C. × 90 seconds, 250 ° C. × 120 seconds Indicates adhesion.

(Preservation method)
The storage method of the epoxy composition of this form can store the epoxy composition of this form at the temperature of 0 degreeC or more and below the reaction start temperature of onium salt. That is, the epoxy composition of this embodiment can be stored at a temperature above the freezing temperature of the epoxy composition and below the reaction initiation temperature of the onium salt. The storage temperature is preferably a temperature lower than the reaction initiation temperature by about 10 to 20 ° C., more preferably normal temperature (0 to 40 ° C.), and still more preferably 5 to 30 ° C.
It is of course also possible to store the epoxy composition of this embodiment at a temperature lower than 0 ° C. (freeze storage). In the conventional one-pack type epoxy composition using an amine, the reaction proceeds without stopping (the reaction proceeds at a rate-limited even during frozen storage). However, in the epoxy composition of this embodiment, the reaction is stopped particularly in the semi-cured state. Therefore, long-term storage is possible at temperatures lower than 0 ° C.

Specifically, as described above, in the epoxy composition of the present embodiment, the curing reaction starts when the temperature exceeds the reaction initiation temperature. In other words, keeping the temperature lower than the reaction start temperature enables storage. That is, storage at low temperature is possible.
The state (reaction step) of the epoxy composition in the storage method of the present embodiment is not limited. Even in the uncured state in which the epoxy composition and the onium salt are mixed, or in the semi-cured state (generally referred to as B-stage), which is an intermediate stage of the reaction of the thermosetting resin, either May be.

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

The storage method of this embodiment can be applied to an epoxy composition obtained by blending an onium salt having a higher reaction initiation temperature in addition to the above-described epoxy composition. For example, it is applicable to the epoxy composition which mix | blended the onium salt whose reaction start temperature is 100 degreeC or more. As such an onium salt, for example, Sanshin Chemical Industry Co., Ltd., trade name: SI-100 (reaction start temperature: about 100 ° C.) or SI-150 (reaction start temperature: about 150 ° C.) it can.
In addition, the preservation | save method of the epoxy composition of this form is a preservation | save method applicable to preservation | save of the epoxy composition of this form. The epoxy composition of this embodiment may be stored at a temperature below the reaction initiation temperature of the onium salt and at a temperature below 0 ° C. That is, frozen storage is possible.
According to the storage method of this embodiment, even if it is an epoxy composition useful as a composite material, as shown in samples 251 to 256 of Table 10 described later, if an onium salt is selected, the epoxy resin as it is or reinforced Materials (eg, SiC, sintered aluminum and carbon fibers) are stored in the semi-cured state (usually referred to as a B-stage resin) and stored at room temperature for 1 year, then 20 to 30 MPa at 150 ° C. for 60 minutes It shows high adhesion.

Hereinafter, the present invention will be specifically described using examples.
In addition, the physical-property value etc. of an epoxy composition and its hardened | cured material were measured by the method as described in the following.

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

  A 10 mg sample containing the onium salt solution and a bisphenol A type liquid epoxy resin (Mitsubishi Chemical Co., Ltd., trade name: JER 828) at a mass ratio of 2: 100 is enclosed in a special aluminum pan.

  This sample is set in a DSC apparatus (manufactured by Seiko Instruments Inc., trade name: DSC6200), and measured at a temperature rising rate of 10 ° C./minute in a temperature range of 30 ° C. to 250 ° C. The reaction initiation temperature is a temperature at which the baseline of the DSC begins to shift to the exothermic side due to the reaction. Specifically, a base line from which noise is removed by processing is determined, and the intersection of the tangents is used as the heat generation start temperature.

(B) Epoxy equivalent It measures by the method based on JIS K 7236: 2001.
Specifically, in the case of a liquid epoxy resin, in the state as it is, in the case of a solid epoxy resin, the one dissolved in a solid content of 40 wt% is 6.0 × 10 ^{−4 to} 9.0 × 10 ^{−4 in} a 100 mL beaker A sample corresponding to mol of epoxy group is taken and precisely weighed (significant number: 0.1 mg digit).
10 mL of chloroform is added to the weighed epoxy solution and stirred and dissolved by a stirrer containing a stirring bar.

Next, add 20 mL of acetic acid and 10 mL of tetraethylammonium bromide solution.
Immerse the electrode and titrate with a 0.1 mol / L perchloric acid-acetic acid standard solution.
Perform a blank test in the same way and leave it blank.
For titration, an automatic titrator (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.) are used. The internal liquid of the reference electrode is measured using a saturated sodium perchlorate / acetic acid solution.

(C) Viscosity measurement of solution Using an E-type viscometer (trade name: RE-80U, manufactured by Toki Sangyo Co., Ltd.), a 2-minute value of 3 rpm cone 5 rpm at 25 ° C. is measured.

(D) Heat curing treatment of epoxy composition For heat curing, a hot air oven (made by Isuzu Co., Ltd., trade name: AT-S13) with a temperature accuracy of ± 3 ° C. is used. Insert a thermometer into the vicinity of the sample in the oven and inside the oven, and check the indicated temperature of the oven and the three temperatures added. The processing temperature (heat curing temperature) adopts the temperature near the sample. When the sample is placed in an oven, the temperature in the vicinity of the sample decreases after the temperature of the sample slightly decreases due to the effect of the heat capacity of the adherend (adherend) (the amount of heat increases when the heat capacity of the adherend is large). The curing treatment is started when the temperature returns to -2 ° C of the set temperature (usually, about 2 to 3 minutes), and the curing treatment is performed for a predetermined time (30 minutes, 60 minutes, 180 minutes) therefrom.
If the predetermined time is in seconds (10, 30, 60 seconds) (in the case of so-called second curing), the oven is replaced with a heating device such as a hot plate.

(E) Adhesive strength (die shear tensile shear strength)
An epoxy resin solution containing an onium salt is dropped on a regular slide glass (Matsunami Glass Industry Co., Ltd., trade name: S1112) as an adherend in a semispherical shape of about 2 mm, and one side is 2 mm square × thick on that. A silicon chip of 0.5 mm in diameter is placed and pressed with tweezers and subjected to the above-mentioned heat curing reaction.

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

  The judgment criteria were ((20 MPa or more), ((5 MPa or more and less than 20 MPa), Δ (2 MPa or more and less than 5 MPa), × (less than 2 MPa), and × (uncured). The adherends and jigs are all degreased with acetone.

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

With respect to the cured coating film, the electrode distance is set to 50 mm, and the electric resistance value is measured using a digital multimeter (manufactured by Takeda Riken Co., Ltd., trade name: TR6851).
(Calculation method of volume resistance) = electrical resistance value (Ω) × cross-sectional area (film thickness × film width) / measurement distance).
The film thickness measurement used the measuring apparatus (Ono Sokki Co., Ltd. make, brand name: ST-011). Judgment criteria are ◎ (9 × 10 ⁻⁵ Ωcm or less), ((10 ⁻⁴ Ωcm order), Δ (10 ⁻³ Ωcm order), × (10 ⁻² Ωcm order or more).

(G) Color tone determination Regular slide glass (made by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (made by Toray DuPont Co., Ltd., trade name: Kapton), or PET film with a thickness of 100 μm as an adherend On Toray Industries, Inc., trade name: Lumilar S10), an epoxy resin solution containing an onium salt is dropped in a hemispherical shape of about 5 mm, and subjected to the above-mentioned heat curing reaction.
Visually determine the cured coating. Evaluation criteria are す る (colorless and transparent),) (finely colored transparent), and x (yellowish brown).

(H) Bending resistance, bending resistance test Regular slide glass (made by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (made by Toray DuPont Co., trade name: Kapton), or thickness as an adherend 100 [mu] m PET film (manufactured by Toray Industries, Inc., trade name: Lumirror S10) of cutting the strip-shaped about 30 × 100 mm, a length epoxy resin composition of about 50mm uniformly a width of about 10mm in prospect of 50μm thickness Apply to make a sample.

The curing reaction is carried out by the above method, and in the bending test, the position is shifted between the surface and the back surface of the coated film and bent 180 ° to visually judge any cracks or cracks in the coating film. The criteria for the bending resistance test are 〇 (no cracking), ((fine cracking or one cracking), and x (both cracking or peeling).
Also in this evaluation, all adherends, jigs and the like are degreased with acetone.

(I) Cross-cut test Regular slide glass (made by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (made by Toray DuPont Co., trade name: Kapton), or a strip of about 30 × 100 mm as an adherend form a PET film having a thickness of 100μm was cut (manufactured by Toray Industries, Inc., trade name: Lumirror S10) or a polyimide film (manufactured by Du Pont-Toray Co., Ltd., trade name: Kapton), the approximately 13mm in prospect thickness 50μm width The epoxy resin composition of about 50 mm in length is uniformly applied to prepare a sample, which is cured by the above method. In addition, since PET film is 1 type of adhesivity, it corona-treated as it or as surface treatment, and used for comparison.

  The cured coating was no. After inserting 11 cuts at a distance of 1 mm with a cutter according to JIS K5400 using 315 Super Cutter Guide (made by Taiyo Kikai Co., Ltd.), change the direction of 90 ° and pull 11 more similarly, 100 eyes It is cut into a checkered coating film. The cellophane adhesive tape is strongly pressed so as to cover the grids, and pulled at a stretch at an angle of 45 ° to determine the number of remaining coating films. Judgment criteria are 〇 (more than 80 eyes), Δ (less than 80 eyes and more than 50 eyes), and x (less than 50 eyes).

(J) Rubbing test Regular slide glass (made by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (made by Toray DuPont Co., trade name: Kapton), or a strip of about 30 × 100 mm as an adherend The epoxy resin composition is applied to a film thickness of about 50 μm on a 100 μm thick PET film (Toray Industries, Inc., trade name: Lumirror S10), which is cut by the above method.

  The cured coated film is dipped in toluene and then rolled hard, and a load of 500 g is applied for 10 reciprocal frictions to visually judge the coating film change. Judgment criteria are 〇 (insoluble or no change), ((partially dissolved), x (50% or more dissolved).

(K) Storage stability test The prepared epoxy composition is put 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 predetermined period of time, it is subjected to an (E) adhesive strength (die shear tensile shear strength) test to measure the adhesive strength. In addition, as predetermined temperature, freezing temperature (-10 degreeC), refrigeration temperature (5 degreeC), room temperature (25 degreeC), the temperature for acceleration tests (40 degreeC) can be mentioned, for example.

Example 1 and Comparative Example 1
The epoxy composition of each sample of this example was prepared by the following method.
10 g of an epoxy compound having an epoxy equivalent of 186 (liquid, manufactured by Mitsubishi Chemical Corporation, trade name: JER 828) is weighed in a 20 mL screw cap bottle (manufactured by Nitden Chemical Glass Co., Ltd., trade name: SV-20).

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

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

  As shown in Table 1, in the epoxy composition of this example, the reaction initiation temperature of the onium salt was 28 ° C. (Sample 1, trade name: SI-25), 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, sample 6) Trade name: SI-80, 78 ° C (samples 7 to 8, PBPH), 83 ° C (sample 9, trade name: SI-B3A), 90 ° C (sample 10, PBBQ), 108 ° C (sample 11, trade name) Ones of SI-100 and 136 ° C. (Sample 12, trade name: SI-150) (commercially available products manufactured by Sanshin Chemical Industry Co., Ltd.) were used. The PBPH in Samples 7 to 8 is N- (α-phenylbenzyl) -3-bromoquinolium hexafluoroantimonate. The PBBQ of sample 10 is N- (α-phenylbenzyl) pyrazinium hexafluoroantimonate. These used what was prepared by the well-known method.

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

  Here, the value of exp (−0.003 ×) (= Z) determined from the epoxy equivalent weight 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 micro spatula was inserted into the mixed solution, and stirred for 3 to 5 minutes on a touch mixer (manufactured by Yamato Scientific Co., Ltd., trade name: MT-31) to obtain a uniform solution.
Thus, the epoxy composition of this example was prepared.

  The epoxy composition of this example was subjected to the measurement of the viscosity shown in the above (C) and the measurement of the die shear tensile shear strength shown in (E), and thereafter the curing treatment shown in (D) under the predetermined conditions shown in Table 1. Then, the color tone judgment 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 initiation temperature of the onium salt is within a predetermined range have 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 initiation temperature of the onium salt was smaller than the predetermined range (45 ° C.), it did not hold as a one-pack type epoxy composition. Specifically, the reaction time of the curing reaction was too short, or the storage stability deteriorated, and it was not established as a one-pack type epoxy composition. Moreover, the epoxy composition of samples 7 to 12 in which the reaction initiation temperature is higher than the range (excessively high temperature) is insufficiently cured at 70 to 80 ° C., and the die shear tensile shear strength is practically used as an adhesive. In particular it is too small.
Thus, it can be confirmed that the epoxy compositions of Samples 3 to 6 become cured products of 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 Example 1 and Comparative Example 1 except that the mixing ratio of the onium salt was changed. The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 2. In addition, evaluation was measured after hardening treatment as hardening conditions shown by (D) as conditions shown in Table 2.

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

  In the epoxy composition of this example, as shown in Table 2, when the mass of the onium salt is 100 mass% of the epoxy resin, 0.1 mass% (sample 21), 0.2 mass% (sample 22), 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), 15 mass% (sample 29), 60 mass% (sample 30), 100 mass% (sample 31), 140 mass% (sample 32), 160 mass% (sample 33), and 180 mass% (sample 34).

Here, the value of exp (−0.003 ×) (= Z) determined from the epoxy equivalent weight 186 is 0.572. The compounding ratio (Ymass%) of the onium salt of sample 23 to sample 32 satisfies the relationship of 0.286 (= 0.5 × Z) ≦ Y ≦ 143.088 (= 250 × Z).
Moreover, the compounding ratio (Ymass%) of the onium salt of samples 21-22 is less than 0.286. The compounding ratio (Ymass%) of the onium salt of samples 33 to 34 is greater than 143.088.

  As shown in Table 2, the epoxy compositions of Samples 23 to 32 in which the mixing ratio of the onium salt is within the predetermined range have 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, the epoxy compositions of Samples 21-22 and Large Samples 33-34 in which the compounding ratio of the onium salt is smaller than the predetermined range, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Furthermore, it can be confirmed that the epoxy compositions of Samples 23 to 32 become cured products of high strength by heating at 70 to 80 ° C.

[Example 3 and Comparative Example 3]
Weigh 10 g of solid epoxy resin with an epoxy equivalent of 2605 (Mitsubishi Chemical Co., Ltd., trade name: JER 1009) and 15 g of methyl ethyl ketone (MEK) in a 50 mL screw-cap bottle (made by Nidec Chemical Glass Co., Ltd., trade name: SV-50) The epoxy resin was dissolved to prepare an epoxy solution containing 40 mass% of epoxy compound. In addition, when a part of solvent evaporates at the time of melt | dissolution, the same amount of methyl ethyl ketone as the evaporation amount is added.

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

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

A stainless steel micro spatula was inserted and stirred for 3 to 5 minutes on a touch mixer (manufactured by Yamato Scientific Co., Ltd., trade name: MT-31) to obtain a uniform solution. Even when stirring, if part of the solvent is evaporated, methyl ethyl ketone of the same amount as the evaporation amount is added.
Thus, the epoxy composition of this example was prepared. The epoxy composition of this example corresponds to sample 46 in Table 3.

In the epoxy composition of this example, as shown in Table 3, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 41), 0.02 mass% (sample 42), 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 is 0.01 and less than 0.02 when the mass of the epoxy resin is 100 mass%, and the samples 42 to 49 have 0.02 ≦ 1. Since it is in the range of (= Y) ≦ 40, it is 60 for the sample 50, and 100 for the sample 51, both are excessively larger than 40.
The evaluation of this example was performed 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 Samples 42 to 49 in which the mixing ratio of the onium salt is within the predetermined range have 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, the epoxy compositions of the sample 41 and the large samples 50 to 51 in which the compounding ratio of the onium salt is smaller than the predetermined range, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Furthermore, it can be confirmed that the epoxy composition of Samples 42 to 49 becomes a cured product of 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 mixing ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 4. In addition, evaluation measured after hardening-processing on conditions shown in Table 4 the hardening conditions shown by (D).
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 806) was used as the epoxy compound. As the onium salt, one having a reaction start temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used in the same manner as Sample 5 of Example 1.

The mixing ratio of the onium salt is 0.2 mass% (sample 61), 0.3 mass% (sample 62), 2 mass% (sample 61) when the mass of the epoxy compound is 100 mass% as shown in Table 4. Samples 63), 20 mass% (sample 64), 50 mass% (sample 65), 150 mass% (sample 66), 160 mass% (sample 67) are contained.
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%, the sample 61 is less than 0.304 (= 0.5 × Z), 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 mixing ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 4. The measurement results measured in the same manner as in Example 4 are shown in Table 4.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. As the onium salt, one having a reaction initiation temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used in the same manner as in Example 4.

The mixing ratio of the onium salt is 0.2 mass% (sample 71), 0.3 mass% (sample 72), 2 mass% (sample 71) when the mass of the epoxy compound is 100 mass% as shown in Table 4. Samples 73), 10 mass% (sample 74), 50 mass% (sample 75), 140 mass% (sample 76), 150 mass% (sample 77) are contained.
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%, the sample 71 is less than 0.286 (= 0.5 × Z), and the sample 72 76 satisfies the relation 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 blending ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 4. The measurement results measured in the same manner as in Example 4 are shown in Table 4.
In this example, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Industry Co., Ltd., trade name: YX8000) was used as the epoxy compound. As the onium salt, one having a reaction initiation temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used in the same manner as in Example 4.

The mixing ratio of the onium salt is 0.2 mass% (sample 81), 0.3 mass% (sample 82), 2 mass% (sample 81), assuming that the mass of the epoxy compound is 100 mass% as shown in Table 4. Samples 83), 6 mass% (sample 84), 50 mass% (sample 85), 140 mass% (sample 86), 150 mass% (sample 87) are contained.
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%, the sample 81 is less than 0.279 (= 0.5 × Z), and the sample 82 .About.86 satisfies the relationship of 0.279 (= 0.5.times.Z) .ltoreq.Y.ltoreq.139.695 (= 250.times.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 blending ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 4. The measurement results measured in the same manner as in Example 4 are shown in Table 4.
In this example, an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. As the onium salt, one having a reaction initiation temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used in the same manner as in Example 4.

The mixing ratio of the onium salt is 0.2 mass% (sample 91), 0.3 mass% (sample 92), 2 mass% (sample 91) when the mass of the epoxy compound is 100 mass% as shown in Table 4. Samples 93), 5 mass% (sample 94), 50 mass% (sample 95), 110 mass% (sample 96), 120 mass% (sample 97) are contained.
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%, the sample 91 is less than 0.227 (= 0.5 × Z), and the sample 92 .About.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 compounding ratio of the epoxy equivalent and the onium salt is within the 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, the epoxy composition of the sample and the large sample in which the compounding ratio of the onium salt is smaller than the predetermined range, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.

  Furthermore, it can be confirmed that the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the predetermined range becomes a cured product of 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 sample 46 of Example 3 except that different epoxy compounds were used, and the mixing ratio of the onium salt to the epoxy resin was changed. The evaluation of this example was performed in the same manner as in Example 3. The measurement results measured in the same manner as in Example 3 are shown in Table 5. The evaluation was carried out after curing was performed under the conditions shown in Table 5 for the curing conditions shown in (D).
In this example, each sample was prepared at a ratio indicated in Table 5 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 470 (trade name: JER1001 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 50 mass%.

In the epoxy composition of this example, as shown in Table 5, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.1 mass% (sample 101), 0.2 mass% (sample 102), 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%, the sample 101 is less than 0.122 (= 0.5 × Z), and the sample 102 .About.106 satisfies the relationship of 0.122 (= 0.5.times.Z) .ltoreq.Y.ltoreq.61.036 (= 250.times.Z), and the sample 107 is larger than 61.036.

[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 blending ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 8. The measurement results measured in the same manner as in Example 8 are shown in Table 5.
In this example, each sample was prepared at a ratio indicated in Table 5 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 1004 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 1004AF) was used as the epoxy compound. This epoxy compound was prepared as an epoxy solution having a content ratio of 45 mass%.

In the epoxy composition of this example, as shown in Table 5, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 111), 0.02 mass% (sample 112), 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%, the sample 111 is less than 0.02, and the samples 112 to 116 have 0.02 ≦ Y. 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 blending ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 8. The measurement results measured in the same manner as in Example 8 are shown in Table 5.
In this example, each sample was prepared at a ratio indicated in Table 5 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 2605 (trade name: JER 1009, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 40 mass%.

In the epoxy composition of this example, as shown in Table 5, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 121), 0.02 mass% (sample 122), 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%, the sample 121 is smaller than 0.02, and the samples 122 to 126 have 0.02 ≦ Y ≦ The relationship of 40 is satisfied, and the sample 127 is larger 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 blending ratio of the onium salt to the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 8. The measurement results measured in the same manner as in Example 8 are shown in Table 5.
In this example, each sample was prepared at a ratio indicated in Table 5 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 7926 (trade name: JER1256 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 40 mass%.

In the epoxy composition of this example, as shown in Table 5, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 131), 0.02 mass% (sample 132), 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%, the sample 131 is less than 0.02, and the samples 132 to 136 have 0.02 ≦ Y. 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 compounding ratio of the epoxy equivalent and the onium salt is within the 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, the epoxy composition of the sample and the large sample in which the compounding ratio of the onium salt is smaller than the predetermined range, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Furthermore, it can be confirmed that the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the predetermined range becomes a cured product of high strength by heating at 80 ° C.

[Example 12]
The epoxy composition of this example was prepared in the same manner as Example 1 except that different epoxy compounds were used, and the ratio of the auxiliary to the onium salt was changed. The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 6. In addition, evaluation measured after hardening-processing on conditions shown in Table 6 the hardening conditions shown by (D).
In this example, each sample was prepared at a ratio indicated in Table 6 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  In the epoxy composition of this example, as shown in Table 6, the onium salt was an onium salt (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd.) , Trade name: SI aid) in a mass ratio of 100: 0 (sample 141), 99: 1 (sample 142), 97: 3 (sample 143), 95: 5 (sample 144), 93: 7 (sample) It prepared using what mixed in the ratio of sample 145-146), 90:10 (sample 147-148). Thus, the reaction initiation 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 the epoxy composition of this example, the mass ratio of the onium salt (component containing no auxiliary agent) is 0.286 (= 0.5 ×) when the mass of the epoxy compound is 100 mass% in each of the samples. Z) or more and 143.088 (= 250 × Z) or less.

  As shown in Table 6, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 if the onium salt is mixed with the auxiliaries.

  Furthermore, it can be confirmed that the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the predetermined range becomes a cured product of 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 ratio of the onium salt to the epoxy compound was changed, and the treatment conditions were further changed. The evaluation of this example was performed in the same manner as in Example 12. The measurement results measured in the same manner as in Example 12 are shown in Table 6.
In this example, each sample (samples 151 to 157) was prepared at a ratio indicated in Table 6 in accordance with the mixing ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 806) was used as the epoxy compound.
As shown in Table 6, the epoxy composition of this example was evaluated at a treatment temperature of 80 to 65 ° C. and a treatment time of 15 to 120 minutes.

  In the epoxy composition of this example, the mass ratio of the onium salt is 0.305 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all samples. 152. 393 (= 250 × Z) or less.

  As shown in Table 6, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

  On the other hand, the die shear tensile shear strength decreases as the processing conditions become lower temperature and shorter time. And it can confirm that it becomes a hardened | cured material of high intensity | strength by heating at 70-80 degreeC.

Example 14
The epoxy composition of this example was prepared as in Example 13 but using different epoxy compounds, using different onium salts, and further changing the processing conditions. The evaluation of this example was performed in the same manner as in Example 13. The measurement results measured in the same manner as in Example 13 are shown in Table 6.
In this example, each sample (samples 161 to 167) was prepared at a ratio indicated in Table 6 in accordance with the mixing ratio of the onium salt.

In this example, an onium salt having a reaction start temperature of 54 ° C. (trade name: SI-B2A, manufactured by Sanshin Chemical Industry Co., Ltd.) was used as the onium salt. An epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.
As shown in Table 6, the epoxy composition of this example was evaluated at a treatment temperature of 80 to 65 ° C. and a treatment time of 15 to 120 minutes.

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

  As shown in Table 6, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 if the onium salt is mixed with the auxiliaries.

  On the other hand, the die shear tensile shear strength decreases as the processing conditions become lower temperature and shorter time. And it can confirm that it becomes a hardened | cured material of high intensity | strength by heating at 70-80 degreeC.

[Example 15]
The epoxy composition of this example was prepared in the same manner as Example 10 except that different onium salts were used, and the mixing ratio of the onium salt and the processing conditions were changed. The evaluation of this example was performed in the same manner as in Example 14. The measurement results measured in the same manner as in Example 14 are shown in Table 6.
In this example, each sample (samples 171 to 175) was prepared at a ratio indicated in Table 6 in accordance with the mixing ratio of the onium salt.

In this example, an onium salt having a reaction start temperature of 52 ° C. (trade name: SI-45, manufactured by Sanshin Chemical Industry Co., Ltd.) was used as the onium salt. As an epoxy compound, an epoxy compound having an epoxy equivalent of 2605 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 1009) was used.
As shown in Table 6, the epoxy composition of this example was evaluated at a treatment temperature of 80 to 65 ° C. and a treatment time of 30 to 120 minutes.

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

  As shown in Table 6, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 if the onium salt is mixed with the auxiliaries.

  On the other hand, the die shear tensile shear strength decreases as the processing conditions become lower temperature and shorter time. And it can confirm that it becomes a hardened | cured material of high intensity | strength by heating at 70-80 degreeC.

[Example 16]
The epoxy composition of this example was prepared as in Example 12 but using different onium salts and further changing the processing conditions. The evaluation of this example was performed in the same manner as in Example 12. The measurement results measured in the same manner as in Example 12 are shown in Table 6.
In this example, each sample (samples 181 to 182) was prepared at a ratio indicated in Table 6 in accordance with the mixing ratio of the onium salt.

  In this example, an onium salt having a reaction start temperature of 71 ° C. (trade name: SI-80, manufactured by Sanshin Chemical Industry Co., Ltd.) was used as the onium salt. An epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

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

  As shown in Table 6, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 if the onium salt is mixed with the auxiliaries.

  On the other hand, the die shear tensile shear strength decreases as the processing conditions become lower temperature and shorter time. And it can confirm that it becomes a hardened | cured material of high intensity | strength by heating at 80 degreeC.

[Example 17]
The epoxy composition of this example was prepared as in Example 11 except that different epoxy compounds were used in combination. The evaluation of this example was performed in the same manner as in Example 11. The measurement results measured in the same manner as in Example 11 are shown in Table 7. The evaluation was carried out after curing was performed under the conditions shown in Table 7 for the curing conditions shown in (D).
In this example, the samples (Samples 191 to 192, Samples 193 to 194) were prepared at the ratio shown in Table 7 in accordance with the mixing ratio of the onium salt.

In this example, as the epoxy compound, a mixture of an epoxy compound having an epoxy equivalent of 7926 (trade name: JER1256) and an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828) in equal weights (both of them were used , Mitsubishi Chemical Industries, Ltd.). The epoxy equivalent of the mixture of epoxy compounds of this example is 4095. The epoxy compound was prepared as an epoxy solution having a content of 70 mass%.
In the present example, samples 191 to 192 and samples 193 to 194 were similarly prepared except that the mixing ratio of the onium salt was changed.

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

[Example 18]
The epoxy composition of this example was prepared in the same manner as Example 17 except that different epoxy compounds and an onium salt having a reaction initiation temperature of 61 ° C. were used. In this example, the onium salt and the activity modifier are prepared at a mass ratio of 97: 3, so that the reaction initiation temperature in the mixed state of the onium salt is 65 ° C. The evaluation of this example was performed in the same manner as in Example 17. The measurement results measured in the same manner as in Example 17 are shown in Table 7. Note that this example is an example in which processing conditions in evaluation are different.
In this example, only an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% when the mass of the epoxy compound is 100 mass% in each of the samples (samples 195 to 196). 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 as in Example 7. The evaluation of this example was performed 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 in the ratio shown according to Table 7 in accordance with the mixing ratio of the onium salt.

  In this example, as an 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 regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI) As the auxiliary agent, an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  In the epoxy composition of this example, the mass ratio of the onium salt is 0.227 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all the samples, and 113. 575 (= 250 x 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 further different onium salts were used. The evaluation of this example was performed in the same manner as in Example 19. The measurement results measured in the same manner as in Example 19 are shown in Table 7.
In this example, the respective samples (samples 202 to 203) were prepared at the ratio shown in accordance with Table 7 in which the mixing ratio of the onium salt is shown.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -80) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.

  In this example, a mixture of an epoxy compound having an epoxy equivalent of 194 (trade name: YX 8000) and an epoxy compound having an epoxy equivalent of 263 (trade name: YX 8034) in equal weights was used as the epoxy compound. The epoxy equivalent of the epoxy compound of this example (all are manufactured by Mitsubishi Chemical Industries, Ltd.) is 229.

  In the epoxy composition of this example, the mass ratio of the onium salt is 0.252 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all samples. 771 (= 250 × Z) or less.

[Example 21]
The epoxy composition of this example was prepared as in Example 20 except that different onium salts were used. The evaluation of this example was performed in the same manner as in Example 20. The measurement results measured in the same manner as in Example 20 are shown in Table 7.
In this example, each sample (samples 204 to 205) was prepared at the ratio shown in accordance with Table 7 in which the mixing ratio of the onium salt is shown.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and 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 regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.

  In this example, a mixture of an epoxy compound having an epoxy equivalent of 194 (trade name: YX 8000) and an epoxy compound having an epoxy equivalent of 263 (trade name: YX 8034) in equal weights was used as the epoxy compound. The epoxy equivalent of the epoxy compound of this example (all are manufactured by Mitsubishi Chemical Industries, Ltd.) is 229.

  In the epoxy composition of this example, the mass ratio of the onium salt is 0.252 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all samples. 771 (= 250 × Z) or less.

Example 22
The epoxy composition of this example was prepared in the same manner as Example 20 except that only one epoxy compound was used. The evaluation of this example was performed in the same manner as in Example 20. The measurement results measured in the same manner as in Example 20 are shown in Table 7.
In this example, each sample (samples 206 to 207) was prepared at the ratio shown in accordance with Table 7 in which the blending ratio of the onium salt is shown.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -80) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  In the epoxy composition of this example, the mass ratio of the onium salt is 0.227 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all the samples, and 113. 575 (= 250 x Z) or less.

[Example 23]
The epoxy composition of this example was prepared in the same manner as Example 1 except that the onium salt and the compounding ratio were different. The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 7.
In this example, the sample 208 was prepared at the ratio indicated in Table 7 in accordance with the mixing ratio of the onium salt.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -80) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  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, 143.088 (= 250 × Z) It is below.

Comparative Example 12
The epoxy composition of this example was prepared in the same manner as Example 23 except that the mixing ratio of the onium salt was different. The evaluation of this example was performed in the same manner as in Example 23. The measurement results measured in the same manner as in Example 23 are shown in Table 7.

In this example, as shown in Table 7 in accordance with Table 7, 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 an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 71 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -80) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  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 Example 1 except that the epoxy compound, the onium salt and the compounding ratio were different. The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 7.
In this example, each sample (samples 212 to 213) was prepared at a ratio indicated in Table 7 in accordance with the mixing ratio of the onium salt.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -100) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 172 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: YL983U) was used as the epoxy compound.

In the epoxy composition of this example, the mass ratio of the onium salt is 0.298 (= 0.5 × Z) or more when the mass of the epoxy compound is 100 mass% in all the samples.
Comparative Example 14

The epoxy composition of this example was prepared as in Example 23, except the onium salt was different. The evaluation of this example was performed in the same manner as in Example 23. The measurement results measured in the same manner as in Example 23 are shown in Table 7.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -100) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

  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). It is above and 143.088 (= 250xZ) or less.

Comparative Example 15
The epoxy composition of this example was prepared in the same manner as Example 22 except that the epoxy compound, the onium salt and the compounding ratio were different. The evaluation of this example was performed in the same manner as in Example 22. The measurement results measured in the same manner as in Example 22 are shown in Table 7.
In this example, each sample (samples 216 to 217) was prepared at a ratio indicated in Table 7 in accordance with the mixing ratio of the onium salt.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -100) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.
In this example, an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

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

Comparative Example 16
The epoxy composition of this example was prepared in the same manner as Example 23, except that the epoxy compound and the onium salt were different. The evaluation of this example was performed in the same manner as in Example 23. The measurement results measured in the same manner as in Example 23 are shown in Table 7.
In this example, each sample (samples 218 to 219) was prepared at a ratio indicated in Table 7 in accordance with the mixing ratio of the onium salt.
In this example, as an onium salt, an onium salt and an activity regulator were prepared to have a mass ratio of 97: 3, and an onium salt having a reaction start temperature of 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -150) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI adjuvant) were used.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

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

  As shown in Table 7, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

  Furthermore, the epoxy composition of each sample containing the onium salt having a reaction initiation temperature of 45 ° C. to 75 ° C., as shown in Tables 1 to 7, wherein the compounding ratio of epoxy equivalent and onium salt is within a predetermined range It can be confirmed that heating at 80 ° C. results in a cured product of high strength.

[Other evaluation]
The storage stability test shown in the above (K) was carried out on the above sample 26 and the epoxy composition prepared in the same manner as the sample 26 except that the onium salt was changed.
In this evaluation, the reaction initiation temperature as an 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: The storage stability of each sample prepared by appropriately blending the activity modifier was evaluated using SI-150). The predetermined time was one year.
In any of the samples, a cured product obtained by heating to a predetermined temperature (a temperature higher than the reaction initiation temperature of the onium salt) obtained a high adhesive strength of 5 MPa or more.
As mentioned above, it can be confirmed that the epoxy composition of each sample to be subjected to the present evaluation is an epoxy composition capable of long-term storage at 5 to 30 ° C. That is, it can be confirmed that the epoxy composition of each example is an epoxy composition capable of long-term storage at normal temperature.

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

  In the epoxy composition of this example, as shown in Table 8, when the mass of the onium salt is 100 mass% of the epoxy resin, 0.1 mass% (samples 221, 222, 223), 1 mass% (sample 224) , 225, 226), 20 mass% (samples 227, 228, 229), and 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 samples 221 to 223 and 0.286 for 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 and 230, and for samples 222, 225 and 228. The curing process of 175 ° C. × 60 seconds was performed, and the curing process of 200 ° C. × 60 seconds was applied to the samples 223, 226, 229, and 231, respectively.

  As shown in Table 8, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt is within the 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 is understood 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 Example 24 except using different epoxy compounds and onium salts, changing the compounding ratio of the onium salt to the epoxy compound, and further changing the treatment conditions. The evaluation of this example was performed in the same manner as in Example 24. The measurement results measured in the same manner as in Example 24 are shown in Table 8.
In this example, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Industry Co., Ltd., trade name: YX8000) was used as the epoxy compound.
In this example, the onium salt was prepared so that the mass ratio of the onium salt to the activity modifier was 99: 1, and the onium salt having a reaction start temperature of 108 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -100) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI aid) were used.

  In the epoxy composition of this example, as shown in Table 8, when the onium salt makes the mass of the epoxy resin 100 mass%, 0.5 mass% (samples 232, 233, 234), 1 mass% (sample 235) , 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.

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

  As shown in Table 8, the epoxy composition of sample 232 exhibits a die shear tensile shear strength of 3.2 MPa, and the epoxy composition of each sample 233 to 237 has 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 150 ° C. and moderate temperature.

[Example 26]
The epoxy composition of this example was prepared in the same manner as Example 24 except using different onium salts, changing the blending ratio of the onium salt to the epoxy compound, and further changing the processing conditions. The evaluation of this example was performed in the same manner as in Example 24. The measurement results measured in the same manner as in Example 24 are shown in Table 8.
In this example, the onium salt was prepared so that the mass ratio of the onium salt to the activity regulator was 99: 1, and the onium salt having a reaction start temperature of 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -150) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI adjuvant) were used.

  As shown in Table 8, in the epoxy composition of this example, the onium salt contains 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.

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

  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 even by heating at a medium and high temperature of 275 ° C.

[Example 27]
The epoxy composition of this example was prepared in the same manner as Example 2 except that different onium salts were used and the blending ratio of the onium salt to the epoxy compound was changed. As 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 to the activity regulator was 97: 3, and the onium salt having a reaction start temperature of 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI -150) and an activity regulator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI adjuvant) were used.

  In the epoxy composition of each sample of this example, as shown in Table 9, when the mass of the onium salt is 100 mass% of the epoxy resin, 1 mass% (samples 241 to 244) and 1.5 mass% (samples 241 to 244) Each of the samples 245) contains.

  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 measured the viscosity after one week, two weeks, three weeks and four weeks at 40 ° C. for each sample. Furthermore, the adhesion 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 upon storage at 40 ° C. That is, it can be confirmed that the epoxy composition of this example hardly cures even when stored for 4 weeks at 40 ° C., which is near room temperature.
Furthermore, there is technical common sense that when the viscosity after storage for 1 month at 40 ° C. is doubled, storage for 1 year at room temperature is possible. In view of this technical common sense, it can be seen that the epoxy composition of this example can be stored at ordinary temperature on an annual basis, since the change in viscosity is hardly observed.
Furthermore, according to samples 241 and 245, it is understood that curing at an intermediate temperature of 150 ° C. is possible. Moreover, according to the samples 242-244, it can confirm that quick curing is possible.
That is, the epoxy composition of this example can exhibit the above-described excellent effects even after long-term storage on an annual basis.

[Example 28]
The epoxy composition of this example was prepared in the same manner as Example 27 except using different epoxy compounds, changing the blending ratio of the onium salt to the epoxy compound, and further changing the processing conditions. The evaluation of this example was performed in the same manner as in Example 27. The measurement results measured in the same manner as in Example 27 are shown in Table 9.
In this example, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Industry Co., Ltd., trade name: YX8000) was used as the epoxy compound.

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

  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 in 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, the cured product of which is 5 MPa or more. That is, even when the epoxy composition of this example is stored at normal temperature, it can be confirmed that the cured product has high strength.

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

As shown in Table 9, the epoxy composition of each sample of this example contains the onium salt at 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 in each sample.

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

[Example 30]
The epoxy composition of this example was prepared in the same manner as Example 27 except that the compounding ratio of the onium salt to the epoxy compound was changed.
As evaluation of this example, it processed on the conditions shown in Table 10, was made into the semi-hardened state, and the storage stability test was done. The measurement results are shown in Table 10.

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

  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 even after storage for 1 year at room temperature for each sample. That is, even when the epoxy composition of this example is stored at room temperature as a semi-cured state, it can be confirmed that the cured product has high strength.
That is, the epoxy composition of this example can exhibit the above-described excellent effects even after long-term storage in the semi-cured state.

[Example 31]
The epoxy composition of this example was prepared the same as Example 30, except that it further contained a reinforcing material. As evaluation of this example, it processed on the conditions shown in Table 10, was made into the semi-hardened state, and the storage stability test was done. The measurement results are shown together 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. did. The reinforcing material is contained such that 89 mass% (sample 254), 70 mass% (sample 255), and 75 mass% (sample 256) when the mass of the epoxy composition (state including the reinforcing material) is 100 mass%. Do.
As SiC, SiC powder with an average particle size of 9.5 ± 8 μm (manufactured by Shinano Electric Smelting Co., Ltd., trade name: GP # 1200) was used.
As sintered Al, an aluminum short fiber with a fiber diameter of 100 μm (manufactured by Akao Aluminum Co., Ltd., a prototype) was used.
As 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 even after storage for 1 year at room temperature for each sample. That is, even when the epoxy composition of this example is stored at room temperature as a semi-cured state, it can be confirmed that the cured product has high strength.
That is, the epoxy composition of this example can exhibit the above-described excellent effects even after long-term storage in the semi-cured state.

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

  In the epoxy composition of this example, as shown in Table 10, the reaction initiation temperature of the onium salt is 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.

  In the epoxy composition of each sample of this example, as shown in Table 10, when the mass of the onium salt is 100 mass% of the epoxy resin, 0.5 mass% (samples 257 to 258, 260), 0. 0. Each is contained in 3 mass% (sample 259).

  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 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 for each sample even after storage for 1 year in a room temperature to refrigerated to frozen state. I understand that Specifically, for samples 251 to 258 and 260 at room temperature, for sample 259 using an onium salt having a reaction start temperature of 63 ° C., a high die shear of 5 MPa or more even after storage for 1 year in refrigeration or freezing It can be seen that it has a tensile shear strength. That is, even if it preserve | saves by room temperature-refrigeration-freezing as a semi-hardened state, the epoxy composition of this example can confirm that the hardened | cured material has high intensity | strength. Of course, there is no problem at all even if it is stored frozen as a conventional one-pack epoxy composition.
That is, the epoxy composition of this example can exhibit the above-described excellent effects even after long-term storage in the semi-cured state. That is, it is possible to stop the curing reaction by setting the epoxy composition of this example to a temperature lower than the reaction initiation temperature even in the semi-cured state. This is an excellent point of the epoxy composition of the present example, which is completely different from the conventional latent amine-curable one-part epoxy resin. The conventional latent amine-curable one-component epoxy resin can not stop the curing reaction even when the temperature is returned to room temperature in the semi-cured state once the curing reaction starts. For this reason, the storage in the semi-cured state of the latent amine curing type one-component epoxy resin used for a prepreg or the like has been forced to adopt a storage method which slows down the reaction rate under freezing at -30 ° C or lower. In the epoxy composition of this example, the curing reaction can be stopped by keeping the temperature below the reaction initiation temperature even in the semi-cured state, and such freezing is not necessary.

[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 the sample 267 of this example. Other samples are manufactured using this method as appropriate.
A 50 mL screw cap bottle (manufactured by Nichiden Chemical Glass Co., Ltd., trade name: SV-50), an onium salt having a reaction start temperature of 63 ° C. (trade name: SI-60), and an activity modifier (trade name: SI aid) ) (Both Sanshin Chemical Industry Co., Ltd.) were mixed and weighed in a proportion of 99: 1 by mass ratio, γ-butyl lactone was added as a solvent, the concentration of the onium salt was 33 mass%, and the activity regulator was 0. An onium salt solution containing 33 mass% was prepared. Weigh 3.6 g of the prepared onium salt solution.

  Then, 7.5 g of an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) 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 powder (trade name: AgC2351, AgC234) (both manufactured by Fukuda Metal Foil Industry Co., Ltd.) having different particle shapes are mixed at a mass ratio of 1: 1. 500 g of an Ag mixture was placed in a 1 L polybin (1 L polyethylene bottle), 250 ml of acetone was further added, shaken for 3 to 5 minutes, and Nutche / suction bottle filtration was repeated 3 times using filter paper 5A to clean naturally.
Add 52.5 g of the cleaned Ag mixed powder to the mixed solution.

A stainless steel micro spatula is inserted into a screw cap bottle measuring these three types, stirred for about 10 minutes on a touch mixer (manufactured by Yamato Scientific Co., Ltd., trade name: MT-31), and one liquid type conductivity of uniform solution It was an epoxy composition.
Thus, 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.
In the epoxy composition of this example, as shown in Table 11, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.1 mass% (sample 261), 0.3 mass% (sample 262), 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%, the sample 261 is less than 0.227 (= 0.5 × Z), and the samples 262 to 272 are 0. .227 (= 0.5 × Z) or more and 113.575 (= 250 × Z) or less, and the sample 273 is larger than 113.575 (= 250 × Z).
In the epoxy composition of this example, an Ag powder is blended at 87.5 mass% when the mass excluding the thermally decomposed onium salt and the solvent as a viscosity modifier from the entire epoxy composition is 100 mass%.
The evaluation of this example was performed in the same manner as in Example 1. The measurement results measured in the same manner as in Example 1 are shown in Table 8.

  The measurement of the viscosity shown in the above (C), the die shear tensile shear strength shown in (E), and the volume resistivity shown in (F) of the epoxy composition (conductive epoxy composition) of this example are performed, and then After the curing treatment shown in (D) under the predetermined conditions shown in Table 11, the color tone judgment 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.

  And as shown in Table 11, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent of this agent and onium salt exists in a predetermined | prescribed range has large die shear tensile shear strength with 5 Mpa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

[Example 34 and Comparative Example 19]
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 33. The measurement results measured in the same manner as in Example 33 are shown in Table 13. Furthermore, for the epoxy composition (conductive epoxy composition) of this example, the cross cut test shown in the above (I), the bending resistance shown in (H), the bending resistance test, the rubbing test shown in (J) Did.
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 806) was used as the epoxy compound.
In this example, the respective samples (samples 281 to 289) were prepared at the ratio shown in accordance with Table 12 in which the mixing ratio of the onium salt.

In the epoxy composition of this example, as shown in Table 12, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.1 mass% (sample 281), 0.5 mass% (sample 282), 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%, sample 281 is less than 0.305 (= 0.5 × Z), and samples 282 to 288 are 0. .305 (= 0.5 × Z) or more and 152.393 (= 250 × Z) or less, and the sample 289 is larger than 152.393 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

Example 35 and Comparative Example 20
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 34. The measurement results measured in the same manner as in Example 34 are shown in Table 15.
In this example, an epoxy compound having an epoxy equivalent of 186 (trade name: JER 828, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.

In this example, the respective samples (samples 291 to 299) were prepared at the ratio indicated in Table 14 in accordance with the mixing ratio of the onium salt.
In the epoxy composition of this example, as shown in Table 14, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.2 mass% (sample 291), 0.5 mass% (sample 292), 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%, the sample 291 is less than 0.286 (= 0.5 × Z), and the samples 292 to 298 are 0. 286 (= 0.5 × Z) or more and 143.088 (= 250 × Z) or less, and the sample 299 is larger than 143.088 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

As shown in Table 14, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt of this example is within the predetermined range, the solution viscosity at 25 ° C. is within the predetermined range of 7 to 40 Pa · s. It has become.
And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

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

In this example, each sample (samples 301 to 309) was prepared at a ratio indicated in Table 16 in accordance with the mixing ratio of the onium salt.
In the epoxy composition of this example, as shown in Table 16, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.2 mass% (sample 301), 0.3 mass% (sample 302), 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) Contain 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%, sample 301 is less than 0.279 (= 0.5 × Z), and samples 302 to 308 are 0. .279 (= 0.5 × Z) or more and 139.695 (= 250 × Z) or less, and the sample 309 is larger than 139.695 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

As shown in Table 16, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt of this example is within the predetermined range, the solution viscosity at 25 ° C. is within the predetermined range of 16 to 30 Pa · s. It has become.
And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

[Example 37 and Comparative Example 22]
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 34. The measurement results measured in the same manner as in Example 34 are shown in Table 19.
In this example, an epoxy compound having an epoxy equivalent of 250 (trade name: JER 834, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 60 mass%.
In this example, the respective samples (samples 311 to 319) were prepared at the ratio shown in accordance with Table 18 in which the mixing ratio of the onium salt is shown.

In the epoxy composition of this example, as shown in Table 18, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.2 mass% (sample 311), 0.5 mass% (sample 312), 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%, sample 311 is less than 0.236 (= 0.5 × Z), and samples 312 to 317 are 0. .236 (= 0.5 × Z) or more and 118.091 (= 250 × Z) or less, and samples 318 to 319 are larger than 118.091 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

[Example 38 and Comparative Example 23]
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 33. The measurement results measured in the same manner as in Example 33 are shown in Table 20.
In this example, an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034 manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound.
In this example, each sample (samples 321 to 333) was prepared at a ratio shown in accordance with Table 20 in which the mixing ratio of the onium salt is shown.

In the epoxy composition of this example, as shown in Table 20, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.1 mass% (sample 321), 0.3 mass% (sample 322), 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), and 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%, the sample 321 is less than 0.227 (= 0.5 × Z), and the samples 322 to 332 are 0. .227 (= 0.5 × Z) or more and 113.575 (= 250 × Z) or less, and the sample 333 is larger than 113.575 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

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

In the epoxy composition of this example, as shown in Table 21, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.1 mass% (sample 341), 0.2 mass% (sample 342), 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%, the sample 341 is less than 0.122 (= 0.5 × Z), and the samples 342 to 350 are 0. .122 (= 0.5 × Z) or more and 61.036 (= 250 × Z) or less, and the sample 351 is larger than 61.036 (= 250 × Z).
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

[Example 40 and Comparative Example 25]
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 33. The measurement results measured in the same manner as in Example 33 are shown in Table 22.
In this example, an epoxy compound having an epoxy equivalent of 1004 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: JER 1004AF) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 50 mass%.
In this example, the respective samples (samples 361 to 371) were prepared at the ratio shown in accordance with Table 22 in which the mixing ratio of the onium salt is shown.

In the epoxy composition of this example, as shown in Table 22, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 361), 0.03 mass% (sample 362), 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%, the sample 361 is less than 0.02, and the samples 362 to 370 are 0.02 or more and 40 or less, The sample 371 is larger than 40.
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

Example 41 and Comparative Example 26
The epoxy composition of this example was prepared as in Example 33 except that the epoxy compound was changed. The evaluation of this example was performed in the same manner as in Example 33. The measurement results measured in the same manner as in Example 33 are shown in Table 23.
In this example, an epoxy compound having an epoxy equivalent of 2605 (trade name: JER 1009, manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the epoxy compound. The epoxy compound was prepared as an epoxy solution having a content of 50 mass%.
In this example, the respective samples (samples 381 to 392) were prepared at the ratio shown in accordance with Table 23 in which the mixing ratio of the onium salt is shown.

In the epoxy composition of this example, as shown in Table 23, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 381), 0.03 mass% (sample 382), 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), and 60 mass% (sample 392).
In the epoxy composition of this example, when the mass of the epoxy compound is 100 mass%, the mass ratio of the onium salt 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.
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

As shown in Table 23, the epoxy composition of each sample in which the compounding ratio of the epoxy equivalent and the onium salt of this example is within the predetermined range, the solution viscosity at 25 ° C. is within the predetermined range of 12 to 22 Pa · s. It has become.
And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

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

In the epoxy composition of this example, as shown in Table 24, when the mass of the onium salt is 100 mass% of the epoxy compound, 0.01 mass% (sample 401), 0.03 mass% (sample 402), 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%, the sample 401 is less than 0.02, and the samples 402 to 411 are 0.02 or more and 40 or less, The sample 412 is larger than 40.
The epoxy composition of this example mixes Ag powder by 87.5 mass%, when the mass which remove | excludes the onium salt which thermally decomposes from the whole epoxy composition and a solvent is 100 mass%.

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

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength by heating at 80 ° C. and / or 150 ° C.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

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

In the epoxy composition of this example, the mass ratio of the onium salt is greater than 0.02 and less than 40 when the mass of the epoxy compound is 100 mass% in all the samples 421 to 422.
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 samples 421 and 422 are heat treatments which are 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 heating at 100 ° C. in Table 26 is held at 100 ° C. for 30 minutes. The heating at 125 ° C. is a heat treatment that is held at 100 ° C. for 30 minutes and held at 125 ° C. for 30 minutes. The heating at 150 ° C. is a heat treatment that is held at 150 ° C. for 30 minutes after the heating at 125 ° C. The heating at 175 ° C. is a heat treatment that is maintained at 175 ° C. for 30 minutes after the heating at 150 ° C. The heating at 200 ° C. is a heat treatment of holding 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 compounding ratio of the epoxy equivalent and the onium salt of this example is within the predetermined range, the solution viscosity at 25 ° C. is within the predetermined range of 25 Pa · s. ing.

  And 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 large die shear tensile shear strength can be obtained even if the onium salt is mixed with the activity modifier.

Furthermore, it can be confirmed that the epoxy composition of each sample becomes a cured product of high strength even when heated at 100 ° C. or higher.
In addition, 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 mentioned above, the epoxy composition of each sample of this example has the characteristic outstanding as a conductive epoxy composition (conductive adhesive).

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

Then, 5.40 g of an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Corporation, trade name: YX 8000) 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%.

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

A stainless steel micro spatula is inserted into a screw cap bottle into which these five types of substances are added, and stirred for 3 to 5 minutes on a touch mixer (manufactured by Yamato Scientific Co., Ltd., trade name: MT-31) Type conductive epoxy composition.
Thus, the conductive epoxy composition of sample 432 of this example was prepared.
Similarly, each sample of this example was prepared by changing the compounding ratio so as to obtain the composition described in Table 27.

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

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, in the tensile shear strength of this example, samples 431 to 436 had high tensile shear strength of 5 MPa or more. In addition, the tendency for tensile shear strength to fall is seen as the content ratio of silica increases. This is due to the relative decrease in the compounding ratio of the epoxy component.

Moreover, the volume resistance value of this example is a small resistance value of 10 ^<-4 > [ ^Omega] cm level in any of the samples. That is, the cured product of the epoxy composition of the present example exhibits excellent conductivity.
Furthermore, also in the test results of the cross cut test, 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 particle silica and a viscosity modifier.

[Other comparison]
Similarly, an epoxy composition having an epoxy equivalent of 186 (Mitsubishi Chemical Co., Ltd., trade name: JER 828) is prepared by blending fine particle silica (trade name: R972, manufactured by Nippon Aerosil Co., Ltd., trade name: R972) less than 20 mass% Physical properties (measurement of tensile shear strength). The tensile shear strength was as high as 20 MPa to 22 MPa.

The epoxy composition of epoxy equivalent 2605 (Mitsubishi Chemical Co., Ltd., trade name: JER 1009) is mixed and prepared with fine particle silica (trade name: R972, trade name: Nippon Aerosil Co., Ltd., trade name: R972) less than 20 mass%. It was subjected to (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 when it contains fine particulate silica, and is exerted regardless of the epoxy compound.

  From the above evaluation results, it is confirmed that the epoxy composition of each sample included in each example is an epoxy composition which can be cured at a low temperature, which was difficult in the conventional one-pack type epoxy composition. it can. And, the epoxy composition of each example has both the characteristics of a high hardness and high strength epoxy resin that the conventional epoxy composition is good at, and a flexible super flexible epoxy resin 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 also for applications such as various heat-sensitive electric and electronic materials and various films, and the productivity is improved by curing at low temperature and short time in industrial line production. Demonstrate the effect of cost reduction and energy saving and improvement of workability.

  Moreover, the epoxy composition (conductive epoxy resin) containing electroconductive particle becomes an electroconductive adhesive provided with high electroconductivity by containing electroconductive particle.

  Moreover, the epoxy composition of each Example is low temperature (60 degreeC or more and 80 degrees C or less) which was difficult with the conventional one-component epoxy composition by selecting the optimal compounding ratio of an epoxy equivalent and an onium salt. It becomes possible to carry out heat treatment, and a cured resin of a tough epoxy composition can be obtained. Furthermore, by selecting the optimum blending ratio of the epoxy equivalent and the onium salt, selecting the blending ratio of the onium salt and the activity modifier, and selecting the onium salt having different reaction initiation temperature, one conventional low temperature type liquid Epoxy compositions of the mold latent hardener allow storage at room temperature, which was difficult. In addition, the reaction initiation temperature can be much lower than that of the medium / high temperature type one-component latent curing agent epoxy composition, and curing starts easily at a low heating temperature.

Furthermore, in the relation between the onium salt and the epoxy equivalent, the epoxy composition having a large epoxy equivalent is also excellent in the test results of the bending resistance test. In particular, it is possible to bend (curve, deform) without breaking the cured product. That is, the epoxy composition of each Example can obtain a cured product having excellent flexibility.
In addition, the epoxy composition of Example 33 or later containing silver powder is a conductive composition (conductive adhesive) having excellent conductivity (low volume resistivity). In particular, excellent conductivity (low volume resistivity which can not be considered conventionally) of the order of 10 ^-5 Ωcm which can not be realized by the 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. Furthermore, according to the pattern printing of the electric circuit, it is possible to further reduce the generation of heat, so that thermal runaway due to heat storage and the like can be prevented.
In particular, according to the epoxy composition of Example 33 or later containing silver powder, it was found that a more excellent effect can be exhibited by setting the specific relationship between the epoxy equivalent and the blending amount of the onium salt in the optimum blending region.

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

[0005]
It becomes a cured product of high strength and high hardness, which is a field where epoxy resin that can be cured is good, and super flexibility and bending resistance that follow flexible films, which is a field where epoxy resin is not good It is an object of the present invention to provide an epoxy composition which is a cured product having the combination, a curing method thereof and a storage method thereof.
Means for Solving the Problem [0021]
An epoxy composition according to a first aspect of the present invention for solving the above problems is an epoxy composition containing an epoxy compound and an onium salt, and not containing a film forming resin and conductive particles, wherein the epoxy compound is The onium salt has a reaction initiation temperature of 45 ° C. or higher when heated with a bisphenol A liquid epoxy resin, and comprises an epoxy equivalent (X) of an epoxy compound, and an epoxy compound If the compounding ratio (Ymass%) of the onium salt when the mass of the onium salt is 100 mass%, and the epoxy equivalent of the epoxy compound is less than 1000, 0.5 × exp (−0.003 ×) ≦ Y ≦ 250 × exp In the range of (−0.003 ×), and in the case where the epoxy equivalent of the epoxy compound is 1000 or more, it is in the range of 0.02 ≦ Y ≦ 40. It is characterized by
An epoxy composition according to a second aspect of the present invention, which solves the above problems, is an epoxy composition containing an epoxy compound, an onium salt, and a silver powder, and containing no film forming resin, wherein the epoxy compound is Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A type polymer epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin And a single component selected from naphthalene type epoxy resins and cyclopentadiene type epoxy resins, or two or more types of components, and the onium salt has a reaction start temperature of 45 ° C. or higher when heated with a bisphenol A liquid epoxy resin And epoxy When the compounding ratio (Ymass%) of the onium salt when the epoxy equivalent (X) of the compound and the mass of the epoxy compound are 100 mass%, the epoxy equivalent of the epoxy compound is less than 1000, 0.5 × exp In the range of (−0.003 ×) ≦ Y ≦ 250 × exp (−0.003 ×), and in the case where the epoxy equivalent of the epoxy compound is 1000 or more, it is characterized by being in the range of 0.02 ≦ Y ≦ 40. And epoxy composition.
[0022]
The method for curing the epoxy composition of the present invention is characterized in that the epoxy composition according to any one of claims 1 to 35 is heat-treated at a temperature of 60 ° C or higher. That is, the epoxy composition of the first invention is heat-treated at a temperature of 60 ° C. or higher. The epoxy composition of the second invention is heat-treated at a temperature of 60 ° C. or higher.
[0023]
The epoxy composition of the present invention is an epoxy composition that can be cured at a low temperature, which is difficult with conventional one-part epoxy compositions. And, the epoxy composition of the present invention obtains both a high-hardness and high-strength epoxy resin that the conventional epoxy composition is good at, and a flexible super-soft epoxy resin like a film that the epoxy composition is not good at be able to. For this reason, the epoxy composition of this invention can be used also for uses, such as various electricity sensitive to heat, electronic material, and various films. As a result, the epoxy composition of the present invention exhibits the effects of improving productivity by curing at a low temperature and in a short time, reducing costs by energy saving and improving workability in industrial line production.

[0006]
[0024]
In the method of curing the epoxy composition of the present invention, a cured resin of a tough epoxy composition can be obtained by heat treating the epoxy composition at a temperature of 60 ° C. or higher. The curing method of the epoxy composition of the present invention is a curing method of the epoxy composition of the present invention.
The method of curing the epoxy composition of the present invention is preferably heat-treated at a temperature of 80 ° C. or less. In the epoxy composition, it is possible to control the curing temperature by selecting the optimum blending ratio of the epoxy equivalent and the onium salt. The temperature of the heat treatment in the present invention enables storage at room temperature, which was difficult in the conventional medium / low temperature one-component latent curing agent epoxy composition. In addition, the reaction initiation temperature can be significantly reduced compared to the medium-high temperature type one-component latent curing agent epoxy composition, and curing starts easily at a low heating temperature.
[0025]
The method for storing the epoxy composition of the present invention comprises storing the epoxy composition according to any one of claims 1 to 35 at a temperature higher than the freezing temperature of the epoxy composition and lower than the reaction initiation temperature of the onium salt. It is characterized by That is, the present invention is characterized in that the epoxy composition of the first invention is stored at a temperature above the freezing temperature of the epoxy composition and below the reaction initiation temperature of the onium salt. The epoxy composition of the second invention is stored at a temperature above the freezing temperature of the epoxy composition and below the reaction initiation temperature of the onium salt.
[0026]
The epoxy composition according to the storage method of the present invention is an epoxy composition that can be stored at temperatures around room temperature. In the epoxy composition, it is possible to control the curing temperature by selecting the optimum blending ratio of the epoxy equivalent and the onium salt. And the epoxy composition of this invention can be preserve | saved in conventional epoxy composition, without using storage (freezing preservation) in low temperature. As a result, the epoxy composition of the present invention exhibits the effects of improvement of productivity, cost reduction by energy saving and improvement of workability by not performing freezing storage in storage and storage.
The epoxy composition of the present invention can, of course, be stored at a temperature of 0 ° C. or less. That is, frozen storage is possible.
Brief Description of the Drawings [0027]
FIG. 1 is a graph showing the relationship between the epoxy equivalent and the blending ratio of the onium salt.
[FIG. 2] FIG. 2 is a graph showing the relationship between epoxy equivalent and volume resistivity.

Claims (10)

An epoxy composition comprising an epoxy compound and an onium salt,
The epoxy compound is composed of a single component, or two or more types of components,
The onium salt has a reaction initiation temperature of 45 ° C. or higher when heated with a bisphenol A liquid epoxy resin,
The compounding ratio (Y mass%) of the onium salt when the epoxy equivalent (X) of the epoxy compound and the mass of the epoxy compound are 100 mass%,
When the epoxy equivalent of the epoxy compound is less than 1000, it is in the range of 0.5 × exp (−0.003 ×) ≦ Y ≦ 250 × exp (−0.003 ×).
An epoxy composition characterized in that, when the epoxy equivalent of the epoxy compound is 1000 or more, 0.02 ≦ Y ≦ 40. Silver powder is contained at 75 to 95 mass%, when the whole is 100 mass%,
The epoxy composition according to claim 1, having a viscosity of 1 to 90 Pa · s at 25 ° C. The epoxy equivalent of the said epoxy compound is 1000 or more,
And the volume resistivity is 2x10 < ^-4 > ohm-cm or less, The epoxy composition of any one of Claims 1-2.   The epoxy composition according to any one of claims 1 to 3, wherein a tensile shear strength after heat treatment at 80 ° C for 60 minutes is 5 MPa or more.   The epoxy composition according to any one of claims 1 to 4, wherein the epoxy composition contains a reinforcing material.   A method of curing an epoxy composition, comprising heat-treating the epoxy composition according to any one of claims 1 to 5 at a temperature of 60 ° C or higher.   The method of curing an epoxy composition according to claim 6, wherein the heat treatment is performed at a temperature of 60 to 80C.   The method for curing an epoxy composition according to any one of claims 6 to 7, wherein the heat treatment has a heating time of 5 seconds to 5 minutes.   The preservation | save method of the epoxy composition characterized by preserve | saving the said epoxy composition of any one of Claims 1-5 at the temperature below 0 degreeC or more and reaction start temperature of the said onium salt.   The method for storing an epoxy composition according to claim 9, wherein the epoxy composition is in an uncured state or a semi-cured state.

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