JP2016008303A - Epoxy resin composition, adhesive, cured product and electronic member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition capable of retaining adhesive strength independently of the type of a filler and retaining adhesive strength even after the exposure to an elevated temperature.SOLUTION: The epoxy resin composition according to the invention comprises (A) an epoxy resin that has a backbone as described by the predetermined general formula (1) and that does not contain bromine; (B) an epoxy resin that is liquid at 25°C; and (C) a curing agent. An adhesive according to the invention comprises the above-mentioned epoxy resin composition. Moreover, a cured product according to the invention is obtained by curing the above-mentioned epoxy resin composition. Furthermore, an electronic member according to the invention comprises the above-mentioned cured product.

Description

  The present invention relates to an epoxy resin composition, an adhesive, a cured product, and an electronic member.

  In the field of bonding electronic components, bonding with a thermosetting resin such as an epoxy resin has been used. In recent years, along with miniaturization and high functionality, dimensional stability and high adhesion are required. Therefore, it is required to improve the adhesive force while blending the filler. In addition, since it may be placed under high temperature due to changes in its use environment, the adhesion retention when exposed to high temperature is also important.

  As a highly adhesive resin, Patent Document 1 describes an epoxy resin containing an oxazolidone ring. Further, Patent Document 2 describes a resin composition in which two specific types of fillers are blended to reduce the linear expansion coefficient and maintain the adhesive force to improve the plating penetration.

Japanese Patent No. 3322909 Japanese Patent No. 5192259

  However, the techniques described in Patent Documents 1 and 2 have not been studied from the viewpoint of a cured epoxy resin. Therefore, when a general-purpose inorganic filler is used, the adhesive force is significantly reduced. Furthermore, even after being exposed to high temperatures, the adhesive force cannot be maintained, and there is a tendency for it to drop significantly.

  The present invention has been made in view of the above-described problems of the prior art, and the object of the present invention is to maintain the adhesive force regardless of the type of filler and to maintain the adhesive force even after being exposed to high temperatures. It is providing the epoxy resin composition which can be hold | maintained.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by including at least two types of epoxy resins with a specific composition.

（式（１）中、Ｒ₁は２価の芳香族基を表し、Ｒ₂は、置換基を有していてもよい２価の官能基を表す。）
［２］
平均粒径０．０５μｍ〜１００μｍの（Ｄ）充填剤をさらに含む、［１］に記載のエポキシ樹脂組成物。
［３］
（Ａ）エポキシ樹脂と（Ｂ）液状エポキシ樹脂との質量比（（Ａ）エポキシ樹脂の質量／（Ｂ）液状エポキシ樹脂の質量）が、０．５／９９．５〜８０／２０である、［１］又は［２］に記載のエポキシ樹脂組成物。
［４］
前記一般式（１）中のＲ₂が、イソホロン、ベンゼン、トルエン、ジフェニルメタン及びナフタレンのいずれか１つに由来する２価の官能基、ヘキサメチレン基並びに−（ＣＨ₂−Ｃ₆Ｈ₄）_n−からなる群より選択される、［１］〜［３］のいずれか１項に記載のエポキシ樹脂組成物。
［５］
前記（Ｂ）エポキシ樹脂が、下記一般式（２）で表される樹脂を含む、［１］〜［４］のいずれか１項に記載のエポキシ樹脂組成物：
Ｇ₁−（ＯＲ₃）_m−Ｏ−Ｒ₄−Ｏ−（Ｒ₃Ｏ）_n−Ｇ₂ （２）
（式（２）中、ｍ及びｎは、それぞれ独立に、１〜１１の整数であり、かつ、３≦（ｍ＋ｎ）≦１２を満たし、（ｍ＋ｎ）個のＲ₃は、それぞれ独立に、炭素原子数１〜１０のアルキレン基を表し、Ｒ₄は、炭素原子数６〜３０の２価の芳香族基を表し、Ｇ₁は、グリシジル基を表し、Ｇ₂は、水素原子又はグリシジル基を表す。）。
［６］
前記（Ｄ）充填剤が、平均粒径が０．１μｍ〜３０μｍの無機充填剤を含む、［２］〜［５］のいずれか１項に記載のエポキシ樹脂組成物。
［７］
［１］〜［６］のいずれか１項に記載のエポキシ樹脂組成物を含む、接着剤。
［８］
［１］〜［６］のいずれか１項に記載のエポキシ樹脂組成物を硬化させて得られる、硬化物。
［９］
［８］に記載の硬化物を含む、電子部材。 That is, the gist of the present invention is as follows.
[1]
(A) an epoxy resin having a skeleton of the following general formula (1) and not containing bromine;
(B) an epoxy resin that is liquid at 25 ° C .;
(C) a curing agent;
An epoxy resin composition comprising:

(In formula (1), R ₁ represents a divalent aromatic group, and R ₂ represents a divalent functional group which may have a substituent.)
[2]
The epoxy resin composition according to [1], further comprising (D) a filler having an average particle size of 0.05 μm to 100 μm.
[3]
The mass ratio of (A) epoxy resin to (B) liquid epoxy resin ((A) mass of epoxy resin / (B) mass of liquid epoxy resin) is 0.5 / 99.5 to 80/20, The epoxy resin composition according to [1] or [2].
[4]
R ₂ in the general formula (1) is a divalent functional group derived from any one of isophorone, benzene, toluene, diphenylmethane and naphthalene, a hexamethylene group, and — (CH ₂ —C ₆ H ₄ ) _n. The epoxy resin composition according to any one of [1] to [3], selected from the group consisting of:
[5]
The epoxy resin composition according to any one of [1] to [4], wherein the (B) epoxy resin includes a resin represented by the following general formula (2):
G ₁ — (OR ₃ ) _m —O—R ₄ —O— (R ₃ O) _n —G ₂ (2)
(In the formula (2), m and n are each independently an integer of 1 to 11, and satisfy 3 ≦ (m + n) ≦ 12, and (m + n) R ₃ are each independently carbon. Represents an alkylene group having 1 to 10 atoms, R ₄ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. Represents.)
[6]
The epoxy resin composition according to any one of [2] to [5], wherein the (D) filler includes an inorganic filler having an average particle diameter of 0.1 μm to 30 μm.
[7]
An adhesive comprising the epoxy resin composition according to any one of [1] to [6].
[8]
A cured product obtained by curing the epoxy resin composition according to any one of [1] to [6].
[9]
The electronic member containing the hardened | cured material as described in [8].

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which can hold | maintain adhesive force irrespective of the kind of filler, and can hold | maintain adhesive force even after exposed to high temperature can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The epoxy resin composition of the present embodiment has a skeleton represented by the following general formula (1) and does not contain bromine (A) an epoxy resin, and (B) an epoxy resin that is liquid at 25 ° C. (C) a curing agent.

（式（１）中、Ｒ₁は２価の芳香族基を表し、Ｒ₂は、置換基を有していてもよい２価の官能基を表す。）

(In formula (1), R ₁ represents a divalent aromatic group, and R ₂ represents a divalent functional group which may have a substituent.)

  Since the epoxy resin composition of the present embodiment is configured as described above, it can maintain an adhesive force regardless of the type of filler, and can maintain an adhesive force even after being exposed to a high temperature.

[(A) Epoxy resin]
(A) The epoxy resin is an epoxy resin having a skeleton represented by the following general formula (1), and the structure does not contain a bromine atom. In addition, it can confirm that the (A) epoxy resin does not contain a bromine by the point (fluorescence X-ray measurement) as described in the below-mentioned Example.

  By having the structure of the general formula (1), an improvement in adhesive strength with an organic base material or metal is seen, and in particular, a reduction in adhesive strength when exposed to high temperatures is improved. By adopting a structure that does not contain a bromine atom, it is possible to prevent a decrease in adhesive force due to dissociation of a bromine bond.

R ₁ in the general formula (1) is not limited to the following, but is a group consisting of biphenyls, bisphenol A, bisphenol Fs, bisphenol AFs, bisphenol ACs, bisphenol Ss, phenol novolacs and cresol novolacs. One or more selected skeletons may be included, and these skeletons may have a substituent.

R ₂ in the general formula (1) is not limited to the following as a divalent functional group, and examples thereof include a single bond, an optionally substituted alkylene group, and an optionally substituted arylene group. It is done. “Alkylene group” means a divalent group derived by further removing one hydrogen atom at any position from an “alkyl group”, and is not limited to the following, but includes, for example, a methylene group, an ethylene group, a methyl group Examples include ethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, trimethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, and the like. , Methylene group, ethylene group, methylethylene group, 1,1-dimethylethylene group, trimethylene group and the like. The “arylene group” of the optionally substituted arylene group represented by R ₂ means a divalent group derived from the “aryl group” by further removing one hydrogen atom at an arbitrary position. Examples of the optionally substituted alkylene group and arylene group represented by R ₂ include those substituted with one or more substituents at substitutable positions. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl). Group, tert-butyl group, pentyl group, hexyl group), aryl group (for example, phenyl group, naphthyl group), aralkyl group (for example, benzyl group, phenethyl group), alkoxy group (for example, methoxy group, ethoxy group), etc. Is mentioned. In the present embodiment, R ₂ is a divalent functional group derived from any one of isophorone, benzene, toluene, diphenylmethane, and naphthalene, a hexamethylene group, and — (CH ₂ —C ₆ H ₄ ) _n — ( It is preferably selected from the group consisting of a group having a polymethylene polyphenylene polyphenyl skeleton). By having these groups, the stability to heat tends to be further improved.

  (A) As an epoxy equivalent of an epoxy resin, it is preferable that it is 180-2400, 190-1700 are more preferable, and 200-1000 are still more preferable. When the epoxy equivalent is in the above range, the hand link property tends to be improved, and as a result, the internal stress at the time of curing tends to be small and the adhesive force tends to be further improved.

  (A) The number average molecular weight of the epoxy resin is preferably 360 to 4800, more preferably 420 to 3900, and still more preferably 480 to 3000. When the said number average molecular weight exists in the said range, it is preferable from a viewpoint of improvement of solvent solubility improvement or compatibility with another epoxy resin.

[(B) Epoxy resin]
(B) The epoxy resin is not particularly limited as long as it is liquid at 25 ° C., and various known resins can be appropriately selected and used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered-in type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol Examples include novolak type epoxy resins, naphthol novolak type epoxy resins, bis A novolak type epoxy resins, dicyclopentadiene / phenol epoxy resins, alicyclic amine epoxy resins, and aliphatic amine epoxy resins. These can be used alone or in combination of two or more.

  (B) “Liquid at 25 ° C.” in the epoxy resin means that when heated at 120 ° C. or more for 2 hours, cooled to 25 ° C., and measured with an E-type viscometer within 2 hours after becoming 25 ° C. It indicates that the viscosity (viscosity at 25 ° C.) is 300000 mPa · s or less.

(B) It is preferable that an epoxy resin contains resin represented by following formula (2) from a viewpoint of initial adhesive force.
G ₁ — (OR ₃ ) _m —O—R ₄ —O— (R ₃ O) _n —G ₂ (2)
(In the formula (2), m and n are each independently an integer of 1 to 11, and satisfy 3 ≦ (m + n) ≦ 12, and (m + n) R ₃ are each independently carbon. Represents an alkylene group having 1 to 10 atoms, R ₄ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. Represents.)

In formula (2), R ₃ is not particularly limited as long as it is an alkylene group having 1 to 10 carbon atoms. That is, R ₃ may be linear or branched. Furthermore, R ₃ may contain an unsaturated bond group. The carbon number of R ₃ is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 3 from the viewpoint of ease of manufacture. Preferable specific examples of R ₃ include, but are not limited to, for example, —C ₂ H ₄ —, —C ₃ H ₆ — and the like.

In formula (2), R ₄ is not particularly limited as long as it is a divalent aromatic group having 6 to 30 carbon atoms. R ₄ is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and is a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of ease of production. More preferred.

Specific examples of R ₄ include, but are not limited to, phenylene group, naphthylene group, biphenylene group; bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetramethylbiphenyl, tetrabromobiphenyl, diphenyl ether, benzophenone , A divalent fragrance derived from one selected from the group consisting of phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin and catechol Family groups and the like.

R ₄ is at least one selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3) from the viewpoint of heat resistance. More preferred.

（Ｒ₅及びＲ₆は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、炭素数１〜１２のアルコキシ基、カルボキシル基又は炭素数１〜１２のアルキル基を表し、Ｘは、炭素数１〜１０のアルキレン基、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−又は−Ｓ−Ｓ−を表す。）

(R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, or an alkyl group having 1 to 12 carbon atoms, and X is a carbon number of 1 10 alkylene group, -O -, - CO -, - COO -, - S -, - SO -, - SO 2 - or an -S-S-).

R ₅ and R ₆ may be a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, or an alkyl group having 1 to 12 carbon atoms, among them, a stable raw material From the viewpoint of supply, a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a methyl group, an ethyl group, or a tert-butyl group is preferable.

  Examples of the divalent aromatic group having the structure represented by the formula (3) include bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, diphenyl ether, benzophenone, phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, and diphenyl. Examples thereof include a divalent aromatic group derived from one selected from the group consisting of sulfone and diphenyl disulfide.

  M and n in the formula (2) are each independently an integer of 1 to 11, and satisfy the relationship of 3 ≦ (m + n) ≦ 12. In the formula (2), (m + n) is set to 3 or more from the viewpoint of ensuring sufficient flexibility, and (m + n) is set to 12 or less from the viewpoint of effectively preventing a decrease in handling property due to an increase in viscosity. .

  In the epoxy resin, the proportion of the component satisfying 3 ≦ (m + n) ≦ 12 of the formula (2) (hereinafter sometimes referred to as “component a”) is preferably 30 mol% or more and 70 mol% or less. More preferably, it is 40 mol% or more and 60 mol% or less. If the ratio of component a is 30 mol% or more, sufficient flexibility tends to be obtained. Moreover, if the ratio of a component is 70 mol% or less, it will become low viscosity and it exists in the tendency for handling property to improve.

By having the structure represented by (R ₃ O) _n in the formula (2), the cured product of the (B) epoxy resin tends to further improve the adhesiveness to the metal.

  The use of a combination of (A) an epoxy resin and (B) an epoxy resin is a feature of the epoxy resin composition according to this embodiment. By using together the epoxy resin of (A) and (B), the adhesive force between organic base materials or between metals, and between an organic base material and a metal improves.

  The mass ratio of (A) epoxy resin to (B) epoxy resin is 0.5 / 99.5 to 80/20 (wt ratio) in terms of (A) mass of epoxy resin / (B) mass of epoxy resin. Is preferred. The mass ratio is more preferably 5.0 / 95.0 to 70/30, still more preferably 10/90 to 60/40. (A) When the epoxy resin is 0.5 wt% or more, there is a tendency to more effectively prevent a decrease in adhesive strength when a filler is added, and when it is 80 wt% or less, the initial adhesive strength is kept higher. It tends to be possible.

[(C) Curing agent]
(C) If a hardening | curing agent can be used for the epoxy resin composition of this embodiment, ie, can harden | cure an epoxy resin, a structure etc. will not be specifically limited. Specific examples of the (C) curing agent include, but are not limited to, amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and latent curing agents.

  Examples of the amine curing agent include, but are not limited to, aliphatic amines and aromatic amines. Examples of the aliphatic amine include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1, Examples include 3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane. Examples of aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-amino. Examples include benzoate.

  Examples of the phenolic curing agent include, but are not limited to, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified Examples thereof include phenol resins, aminotriazine-modified phenol resins, naphthol novolak resins, naphthol-phenol co-condensation novolak resins, naphthol-cresol co-condensation novolak resins, and allyl acrylic phenol resins.

  Examples of the acid anhydride curing agent include, but are not limited to, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

  Examples of the latent curing agent include, but are not limited to, imidazole-based latent curing agents and those encapsulating amine adducts. Commercially available products can also be used. For example, “PN23”, “PN40”, “PN-H” such as Amicure series (manufactured by Ajinomoto Fine Techno Co.), “HX-3088”, “HX-3941”, “ Novacure series (manufactured by Asahi Kasei E-Materials Co., Ltd.) such as “HX-3742”.

  The above-mentioned (C) curing agent may be used alone or in combination of two or more. When using 2 or more types together, a part may be called "curing agent" and the remainder may be called "curing accelerator". The curing agent here means one having a function of reacting with an epoxy resin by heat or light and crosslinking, and the curing accelerator mainly does not react with the epoxy resin itself, but is an epoxy. It has a function that facilitates the reaction between the resin and the curing agent.

  Although content of (C) hardening | curing agent in the epoxy resin composition of this embodiment is not specifically limited, Preferably it is 2-40 mass%, More preferably, it is 3-30 mass%, More preferably, it is 4 ˜20 mass%. (C) When content of a hardening | curing agent is made into the said range, it exists in the tendency which the reactivity of a epoxy resin composition, a mechanical characteristic, heat resistance, etc. improve more.

  The epoxy resin composition of the present embodiment may include (D) a filler, (E) other epoxy resin components, additives, and the like in addition to the above-described constituent requirements.

  (D) Although it does not specifically limit as a filler, It is preferable that an average particle diameter is 0.05 micrometer-100 micrometers. When the average particle diameter is 0.05 μm or more, the (D) filler tends to be blended in an appropriate amount in the composition, and better heat resistance tends to be obtained. Moreover, when an average particle diameter is 100 micrometers or less, it exists in the tendency for the continuous cured crosslinked material to be easy to be obtained, and for the better adhesive force to be obtained. Furthermore, when the average particle diameter is 30 μm or less, it is preferable from the viewpoint of application to a narrow gap. From the viewpoint described above, the average particle size is more preferably 0.1 μm to 30 μm, still more preferably 0.1 μm to 20 μm, and still more preferably 0.1 μm to 10 μm. In addition, when the average particle diameter of the (D) filler is within the above range, the internal stress at the time of curing of the epoxy resin composition for liquid sealing is obtained by using the (A) epoxy resin and the (D) filler together. It can be suppressed, and it is considered that the adhesion to the metal part to be sealed is further improved. (D) The average particle diameter of the filler is a value of an average particle diameter d50 measured by a dry particle size distribution meter.

  (D) The filler is preferably an inorganic filler. Examples of inorganic fillers include, but are not limited to, for example, silicates such as talc, calcined clay, unfired clay, mica, glass; titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), synthesis Oxides such as silica powder such as silica and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; barium sulfate, calcium sulfate and the like Sulfates such as calcium sulfite; Borate salts such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, etc. It is done. Among these, fused silica, crystalline silica, and synthetic silica powder are preferable from the viewpoint of improving the heat resistance, moisture resistance, strength, and the like of the epoxy resin composition. By using these, the thermal linear expansion coefficient can be more effectively suppressed, so that improvement of the cooling cycle test result is expected. These (D) fillers may be used individually by 1 type, and may use 2 or more types together.

  Although content of (D) inorganic filler in the epoxy resin composition of this embodiment is not specifically limited, Preferably it is 40-90 mass%, More preferably, it is 60-85 mass%. (D) When content of an inorganic filler shall be 40 mass% or more, it exists in the tendency which can implement | achieve the more excellent low linear expansion. (D) When content of an inorganic filler shall be 90 mass% or less, it exists in the tendency which can suppress the raise of an elasticity modulus more effectively.

  (D) It is preferable that the inorganic filler is surface-treated with a silane coupling agent. Although the performance is exhibited by adding a silane coupling agent to the epoxy resin composition, the epoxy resin composition can be obtained by performing a surface treatment of the inorganic filler (D) with a silane coupling agent as a pretreatment. It tends to be possible to realize further lower viscosity.

  Examples of the silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloro Propylmethyldi Tokishishiran, silane coupling agents such as 3-chloropropyl trimethoxysilane. Among these, from the viewpoint of adhesive strength, a silane coupling agent having a polymerizable functional group is preferable.

  (E) Other epoxy resin components are distinguished from (A) epoxy resin and (B) epoxy resin in the present embodiment. That is, (E) other epoxy resin components have a viscosity measured by an E-type viscometer at 25 ° C. higher than 300,000 mPa · s. Specific examples include, but are not limited to, skeletons of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered-in type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, triphenyl. Methane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bis A novolac type epoxy resin, dicyclopentadiene / phenol epoxy resin, alicyclic amine epoxy resin, aliphatic amine epoxy resin These properties are changed from semi-solid to solid. These can be used alone or in combination of two or more.

  The epoxy resin composition of the present embodiment may further contain other additives such as a flame retardant, a liquid stress agent, a silane coupling agent, a diluent, a leveling agent, and a pigment as necessary. Any suitable one can be selected as long as the effects of the present embodiment can be obtained.

  Examples of the flame retardant include, but are not limited to, bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and inorganic flame retardants. Examples of the brominated flame retardant include, but are not limited to, tetrabromophenol and the like. Examples of the phosphorus-based flame retardant include, but are not limited to, for example, 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and epoxy derivatives thereof, triphenylphosphine and derivatives thereof, phosphate esters, Examples thereof include condensed phosphate esters and phosphazene compounds. Examples of the nitrogen-based flame retardant include, but are not limited to, guanidine-based flame retardant, triazine structure-containing phenol, melamine polyphosphate, and isocyanuric acid. Examples of the inorganic flame retardant compound include, but are not limited to, magnesium hydroxide and aluminum hydroxide. Magnesium hydroxide is preferable from the viewpoint of heat resistance.

  Although content of a flame retardant is not specifically limited, It is preferable that it is 5-200 mass% with respect to the total amount of an epoxy resin composition, and it is more preferable that it is 10-100 mass%.

  Examples of the liquid low stress agent include, but are not limited to, polyalkylene glycols and amine modified products thereof, organic rubbers such as polybutadiene and acrylonitrile, silicone rubbers such as dimethylsiloxane, and silicone oils. These may be used individually by 1 type and may use 2 or more types together. Although content of a liquid low stress agent is not specifically limited, It is preferable that it is 5-40 mass% with respect to an epoxy resin, and it is more preferable that it is 10-20 mass%.

  Examples of the silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloro Propylmethyldi Tokishishiran, silane coupling agents such as 3-chloropropyl trimethoxysilane. Among these, from the viewpoint of adhesive strength, a silane coupling agent having a polymerizable functional group is preferable.

  Examples of the diluent include, but are not limited to, a polyfunctional acrylate compound containing an acrylic group and a glycidyl type reactive diluent containing a monofunctional glycidyl group. These may be used individually by 1 type and may use 2 or more types together. Although content of a diluent is not specifically limited, It is preferable that it is 1-40 mass% with respect to an epoxy resin, and it is more preferable that it is 5-30 mass%.

  Examples of the leveling agent include, but are not limited to, a silicon leveling agent and an acrylic leveling agent.

  The cured product of the present embodiment is obtained by curing the epoxy resin composition of the present embodiment. That is, the cured product of this embodiment can be obtained by thermally curing the epoxy resin composition by a conventionally known method or the like. More specifically, for example, an epoxy resin or an epoxy resin composition in the present embodiment, a curing agent, further a curing accelerator, an inorganic filler, a compounding agent, etc., if necessary, using an extruder, kneader, roll, etc. It is possible to obtain an epoxy resin composition as a precursor by sufficiently mixing until uniform. Thereafter, the obtained epoxy resin composition is molded by casting or using a transfer molding machine, an injection molding machine, and the like, and further heated at about 80 to 200 ° C. for about 2 to 10 hours. Can be obtained.

  Further, the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg can be obtained by impregnating the composition with heat and drying. A cured product can also be obtained by subjecting the obtained prepreg to hot press molding or the like. The epoxy resin composition and cured product of the present embodiment can be used for various applications in which an epoxy resin is conventionally used as a material. For example, it is particularly useful as an application of an electronic member (for example, a sealing material, an adhesive, a printed board material, a paint, a composite material, etc.). Among them, it is preferably used for conductive adhesives such as underfill, adhesives, bonding pastes, bonding films (for example, interlayer insulating materials), anisotropic conductive films (ACF), and the like. By using them, the features of the present embodiment such as the adhesive strength and the adhesive strength retention after the thermal history can be utilized. In addition to the above, the epoxy resin composition and the cured product of the present embodiment are also suitably used as a coating material, a prepreg, a heat conductive material, a fuel cell sealing material, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited at all by these Examples. In the following, “part” is based on mass unless otherwise specified.

  For the following reagents, commercially available products were used without any particular purification. The average particle size was determined by measuring with a laser diffraction particle size distribution measuring device “HELOS & RODOS” (manufactured by Sympatec) at a dispersion pressure of 2.0 bar.

(A) Component General formula (1) Epoxy resin containing skeleton and free of bromine (AER4152 manufactured by Asahi Kasei E-Materials Co., Ltd.)

(B) Component Liquid epoxy resin A (Asa 260, manufactured by Asahi Kasei E-Materials Co., Ltd.)
Liquid epoxy resin B (made by ADEKA, "EP-4088")

(C) Component Hardener A (Diaminodiphenylmethane, Wako Pure Chemicals Reagent)
Curing agent B (4-methylhexahydrophthalic anhydride (acid anhydride), “Licacid MHT”)
Curing agent C (Allyl group-containing phenol (liquid phenol resin), “MEH8000H”)

Component (D) Silica A (manufactured by Tatsumori, “AC-5V”, average particle size 5 μm)
Silica B (manufactured by Tatsumori, “MSS-6”, average particle size 24 μm)
Alumina (Nippon Light Metal Co., Ltd. “BF013”, average particle size 1.2 μm)
Boron nitride (manufactured by Denki Kagaku Kogyo Co., Ltd., “Denkaphoron GP”, average particle size 8.0 μm)

Component (E) Other epoxy resin E (epoxy cresol novolac resin, manufactured by Asahi Kasei E-Materials, “AERECN1299”)

Other components General formula (1) Epoxy resin containing a skeleton and containing bromine (AER4100, manufactured by Asahi Kasei E-Materials Co., Ltd.)
Curing accelerator (2-methylimidazole, “2MZ”)

  Next, each measurement method, evaluation method, and test method will be described.

(1) Shear adhesiveness A 100 μm-thick fluororesin heat-resistant tape was applied to the surface of a standard test piece C1100P (manufactured by Nippon Test Panel Co., Ltd.) and masked so that a 25 mm × 5 mm gap was formed on the surface of the standard test piece. The epoxy resin composition was applied to the gap (25 mm × 5 mm) and sandwiched by another standard test piece C1100P. By heating it at 180 ° C. for 2 hours, the epoxy resin composition was thermally cured to obtain a sample. The obtained sample was subjected to tensile shear measurement using a tensile tester AGS-X 5 kN in a constant temperature and humidity chamber at 23 ° C. and 50% RH.

(2) Infrared absorption spectrum (IR)
Measurement was performed in the range of 600 to 4000 cm ⁻¹ using JASCO Corporation FT / IR-6100.

(3) Fluorescent X-ray SPECTRO PHOENIX was used to measure whether a peak appeared at the bromine element position.

[Production Example 1]
In the reactor, 100 parts by mass of bisphenol A type epoxy resin (trade name: AER260, manufactured by Asahi Kasei E-Materials, epoxy equivalent 188 g / eq), and tetrabutylammonium bromide (trade name: tetra-n bromide) -Butylammonium, Wako Pure Chemical Industries, Ltd. (0.04 parts by mass) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 20.0 parts by mass of tolylene diisocyanate (trade name: Coronate T80 (trademark), manufactured by Nippon Polyurethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain a modified epoxy resin I. When the obtained resin was subjected to IR measurement, peaks were observed at 1750 cm ⁻¹ and 910 cm ⁻¹ , and it was confirmed that the resin contained an oxazolidone ring and an epoxy group. Further, when X-ray fluorescence was measured, there was no peak for elemental bromine.

[Production Example 2]
In the reactor, 100 parts by mass of bisphenol A type epoxy resin (trade name: AER260, manufactured by Asahi Kasei E-Materials, epoxy equivalent 188 g / eq), and tetrabutylammonium bromide (trade name: tetra-n bromide) -Butylammonium, Wako Pure Chemical Industries, Ltd. (0.04 parts by mass) was added, and the mixture was stirred and heated to adjust the internal temperature to 175 ° C. Furthermore, 12.6 parts by mass of tolylene diisocyanate (trade name: Coronate T100 (trademark), manufactured by Nippon Polyurethane Co., Ltd.) as a raw material isocyanate compound was charged into the reactor over 90 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 8 hours to obtain a modified epoxy resin II. When the obtained resin was subjected to IR measurement, peaks were observed at 1750 cm ⁻¹ and 910 cm ⁻¹ , and it was confirmed that the resin contained an oxazolidone ring and an epoxy group. Further, when X-ray fluorescence was measured, there was no peak for elemental bromine.

[Production Example 3]
270 g of dialcohol obtained by addition reaction of 5 mol of propylene oxide to 1 mol of bisphenol A in a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, and epichlorohydride Phosphorus (463 g, 5.00 mol) and a 50 mass% tetramethylammonium chloride aqueous solution (10 g) were mixed, heated under reduced pressure, and refluxed at 60 to 65 ° C. And 400 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours. During the addition, water was continuously removed as an azeotrope with epichlorohydrin and only the condensed epichlorohydrin layer was continuously returned to the reactor. Thereafter, the mixture was further reacted for 2 hours, and then the mixture was cooled and washed repeatedly with water to remove by-produced sodium chloride. Excess epichlorohydrin was removed by distillation under reduced pressure to obtain a crude resin. 100 g of the obtained crude resin was dissolved in 200 g of methyl isobutyl ketone, 0.22 g of 50% by mass aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. The methyl isobutyl ketone was distilled off by washing with water, and the formula ( 2) was obtained (R ₃ = —CH ₂ —CH (CH ₃ ) —O—, R ₄ = bisphenol A, G ₂ = glycidyl group). The obtained epoxy resin A had an epoxy equivalent of 371 g / eq and a viscosity at 25 ° C. of 952 m · Pas. (M + n) in the formula (2) was 5.

[Example 1]
It compounded according to the mixing | blending in a table | surface, measured the following four types of shear adhesive force, and gave each change rate.
Adhesive strength 1: An epoxy resin composition excluding the component (D) in the table was uniformly heated and mixed at 80 ° C., and the shear adhesive strength was measured.
Adhesive strength 2: All components including the component (D) in the table were heated and mixed at 80 ° C., and the shear adhesive strength was measured.
Adhesive strength 3: All components including the component (D) in the table are heated and mixed at 80 ° C., a test piece is prepared, and the test piece is heated at 150 ° C. for 5 minutes in a heating furnace TCE-N300. Shear adhesion was measured after the piece reached 150 ° C.
Adhesive strength 4: All components including the component (D) in the table were heated and mixed, a test piece was prepared, and the test piece was put into a furnace at 260 ° C. for 2 minutes. Shear adhesive strength was measured on the sample after the addition.
Rate of change A = (Adhesive strength 1−Adhesive strength 2) / Adhesive strength 1 × 100 (%)
Rate of change B = (Adhesive strength 2−Adhesive strength 3) / Adhesive strength 2 × 100 (%)
Rate of change C = (Adhesive strength 2−Adhesive strength 4) / Adhesive strength 2 × 100 (%)

[Examples 2-7, Comparative Examples 1-4]
Various evaluations were performed in the same manner as in Example 1 with the formulation shown in Table 1. The results are shown in Table 1.

  As is clear from Table 1, the epoxy resin compositions of Examples 1 to 7 can retain the adhesive force regardless of the type of filler, and can retain the adhesive force even after being exposed to high temperatures. .

Claims (9)

(A) an epoxy resin having a skeleton of the following general formula (1) and not containing bromine;
(B) an epoxy resin that is liquid at 25 ° C .;
(C) a curing agent;
An epoxy resin composition comprising:

(In formula (1), R ₁ represents a divalent aromatic group, and R ₂ represents a divalent functional group which may have a substituent.)   The epoxy resin composition according to claim 1, further comprising (D) a filler having an average particle diameter of 0.05 μm to 100 μm.   The mass ratio of (A) epoxy resin to (B) liquid epoxy resin ((A) mass of epoxy resin / (B) mass of liquid epoxy resin) is 0.5 / 99.5 to 80/20, The epoxy resin composition according to claim 1 or 2. R ₂ in the general formula (1) is a divalent functional group derived from any one of isophorone, benzene, toluene, diphenylmethane and naphthalene, a hexamethylene group, and — (CH ₂ —C ₆ H ₄ ) _n. The epoxy resin composition according to any one of claims 1 to 3, which is selected from the group consisting of-. The epoxy resin composition according to any one of claims 1 to 4, wherein the (B) epoxy resin includes a resin represented by the following general formula (2):
G ₁ — (OR ₃ ) _m —O—R ₄ —O— (R ₃ O) _n —G ₂ (2)
(In the formula (2), m and n are each independently an integer of 1 to 11, and satisfy 3 ≦ (m + n) ≦ 12, and (m + n) R ₃ are each independently carbon. Represents an alkylene group having 1 to 10 atoms, R ₄ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. Represents.)   The epoxy resin composition according to any one of claims 2 to 5, wherein the (D) filler includes an inorganic filler having an average particle diameter of 0.1 to 30 µm.   The adhesive agent containing the epoxy resin composition of any one of Claims 1-6.   Hardened | cured material obtained by hardening the epoxy resin composition of any one of Claims 1-6.   The electronic member containing the hardened | cured material of Claim 8.