JP2008214449A - Thermal or active energy ray curable adhesive - Google Patents

Abstract

（式中、Ｒ¹〜Ｒ¹⁸は、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を有していてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基）で表わされ、該化合物の異性体の含有量が、該化合物とその異性体の総和に対して、ガスクロマトグラフィーによるピーク面積の割合として２０％以下である脂環式ジエポキシ化合物（Ａ１）、又は、前記脂環式ジエポキシ化合物（Ａ１）とそれ以外のエポキシ化合物（Ａ２）からなるエポキシ樹脂（Ａ）を含有する熱又は活性エネルギー線硬化型接着剤。
【選択図】なしA thermal or active energy ray curable adhesive having excellent adhesion between different materials is provided.
The following formula (1)

(Wherein R ^{1 to} R ¹⁸ are each a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may have a halogen atom, or an alkoxy group that may have a substituent). The cycloaliphatic diepoxy compound (A1), in which the content of isomers of the compound is 20% or less as a ratio of the peak area by gas chromatography with respect to the sum of the isomers and the compound, A thermal or active energy ray-curable adhesive containing an epoxy resin (A) comprising a cyclic diepoxy compound (A1) and another epoxy compound (A2).
[Selection figure] None

Description

  The present invention uses a thermal or active energy ray-curable adhesive that can be cured by irradiation with heat or an active energy ray to form a cured product having excellent adhesion, sealing properties, and adhesive strength, and the adhesive. The present invention relates to a bonded body (for example, an electronic device) and a bonding method. The present invention also relates to an anisotropic conductive adhesive in which conductive particles are dispersed in the adhesive, and an electronic device joined with the anisotropic conductive adhesive. More specifically, the present invention relates to electrical connection between fine circuits, more particularly connection between an LCD (Liquid Crystal Display) and a flexible circuit board (hereinafter FPC), COF (Chip On Fpc) and TCP (Tape Carrier Package). Thermally or active energy ray-curable adhesive that can be used for connection of semiconductor ICs and micro-bonding of IC mounting substrates, etc., particularly anisotropic conductive adhesives that can be connected and have excellent adhesion and connection reliability, and the like The present invention relates to an electronic device formed by bonding electronic components with an adhesive.

  In recent years, display devices using liquid crystal or organic EL have been mounted on various portable devices, and miniaturization, thinning, and weight reduction of portable devices have been promoted. A substrate or a display portion of a display device using liquid crystal or organic EL uses glass, a metal such as aluminum, a synthetic resin such as PET, or a semi-synthetic resin such as acetylcellulose. Among these materials, a thin film film made of a resin and an adhesive that easily and strongly bonds different types of materials in a short time are desired.

  Conventionally, an active energy ray curable adhesive such as ultraviolet rays has been used to cure and bond easily in a short time. The active energy ray-curable adhesive has a cationic polymerizable compound containing a cationic polymerizable compound having an epoxy group or a vinyl group and a cationic polymerization initiator that generates a cation by irradiation with active energy rays, and a radical polymerizable unsaturated group. Those containing a radical polymerizable compound and a radical polymerization initiator that generates radicals upon irradiation with active energy rays are known. However, radical polymerization type adhesives are characterized by a relatively fast curing speed, but they are inferior in surface curability due to insufficient adhesion to materials and processability, and inhibition of curing by oxygen. However, there is a problem that facilities such as nitrogen sealing are necessary. On the other hand, cationic polymerization type adhesives have advantages such as better adhesion to materials and workability compared to radical polymerization type adhesives, and do not require equipment such as nitrogen encapsulation. There was a problem that the speed was slow. A technique that solves this problem by using an alicyclic compound containing an oxetanyl group is disclosed (for example, see Patent Document 1), but a cured product having good adhesive strength is desired. In particular, an adhesive having good adhesion by bonding a thin film such as a film is desired.

  In recent years, the need for various fine circuit connections such as connection between LCD and TCP, or connection between TCP and PCB (printed wiring board) has increased dramatically. As the connection method, conductive particles are used in the adhesive resin. Dispersed anisotropically conductive adhesives have been used. In this method, an anisotropic conductive adhesive is sandwiched between members to be connected and heated and pressed to maintain electrical insulation between adjacent terminals in the surface direction, while electrically conducting between upper and lower terminals. . For this anisotropic conductive adhesive, an adhesive made of thermosetting resin is used to obtain high connection reliability, and among them, an epoxy resin system that can realize adhesion to the adherend and moisture resistance reliability is used. (See, for example, Patent Documents 2 and 3).

  Recently, LCD modules have become larger, more accurate, and have a narrower frame. Along with this, connection pitches and connection widths are rapidly increasing. Therefore, for example, in the connection between the LCD and the TCP, the connection portion is displaced due to the elongation of the TCP due to the heating at the time of connection, or because the connection portion is thin, the members inside the LCD are thermally at the temperature at the time of connection. In connection between TCP and PCB, there is a problem that the length of the PCB is long and the PCB and LCD are warped by heating at the time of connection and the TCP wiring is disconnected. In order to solve these problems, there has been a demand for an anisotropic conductive adhesive that can be connected at a low temperature in a short time while maintaining sufficient connection reliability.

  In response to such market demands, an epoxy resin thermosetting anisotropic conductive adhesive has been proposed. Among anisotropic conductive adhesives, anisotropic conductive adhesives that can be cured at low temperature in a short time include resin compositions containing radical polymerizable resins, organic peroxides, and thermoplastic elastomers. A material in which conductive particles are dispersed has also been proposed (see, for example, Patent Document 4). However, with this resin system, connection at a low temperature and in a short time is possible, but there are large curing shrinkages and poor adhesion after connection to various adherends, which is sufficient in terms of connection reliability. It wasn't.

  On the other hand, it is known that an epoxy compound having two alicyclic skeletons in a molecule is useful as an ultraviolet curable adhesive or the like. For example, Japanese Patent Application Laid-Open No. 2004-99467 (Patent Document 5) discloses that a bicyclohexyl-3,3′-diene compound is epoxidized with an organic percarboxylic acid to produce 3,4,3 ′, 4′-diepoxybiphenyl. A method for obtaining a cyclohexyl compound is disclosed. In addition, in Russian literature (Neftekhimiya, 1972, 12, 353) (Non-patent literature 1), a bicyclohexyl-3,3'-diene compound is used with t-butyl hydroperoxide and a catalytic amount of molybdenum chloride (V). And epoxidation to obtain 3,4,3 ', 4'-diepoxybicyclohexyl compounds. JP-A-2004-204228 (Patent Document 6) discloses a curable epoxy resin composition containing a 3,4,3 ′, 4′-diepoxybicyclohexyl compound obtained by the above production method and its A cured product is disclosed. JP-A-2005-146038 (Patent Document 7) discloses an ultraviolet curable adhesive containing a 3,4,3 ′, 4′-diepoxybicyclohexyl compound. However, the epoxy resin composition containing the 3,4,3 ′, 4′-diepoxybicyclohexyl compound obtained by the above production method is not sufficiently reactive during curing, and the cured product is also heat resistant. In view of the above, it did not always have satisfactory physical properties. Further, when the epoxy resin composition is used as an adhesive, there is a problem that sufficient adhesive strength cannot be obtained, and the adhesive strength is not constant and is inferior in reliability.

JP 2003-213243 A Japanese Patent Laid-Open No. 5-21094 JP 2002-327162 A JP 2000-44905 A JP 2004-99467 A Neftekhimiya, 1972, 12, 353 JP 2004-204228 A JP 2005-146038 A

The object of the present invention is to cure quickly by irradiation with active energy rays such as heat or ultraviolet rays that do not require equipment such as nitrogen sealing, heat resistance and adhesion, especially adhesion of thin films such as films, Another object of the present invention is to provide a heat or active energy ray-curable adhesive having excellent adhesion between different materials.
Another object of the present invention is to provide a heat or active energy ray-curable adhesive that provides a sufficient adhesive strength and has a constant adhesive strength and high adhesive reliability.
Still another object of the present invention is to enable connection at a low temperature and in a short time in electrical connection between fine circuits such as connection between LCD and TCP and connection between TCP and PCB, and high adhesion and connection. An object of the present invention is to provide a heat or active energy ray curable adhesive, particularly an anisotropic conductive adhesive, which can provide reliability.
Another object of the present invention is to provide an adhesive body such as an electronic device having high adhesion or connection reliability, and a method for bonding an adherend.

  As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge. That is, when the 3,4,3 ′, 4′-diepoxybicyclohexyl compound obtained by the conventional method is analyzed in detail, in addition to the target 3,4,3 ′, 4′-diepoxybicyclohexyl compound, It was found that isomers having different positions of epoxy groups on the cyclohexane ring were contained in a small amount. Until now, it has not been known that such isomers are contained in a large amount in 3,4,3 ′, 4′-diepoxybicyclohexyl compounds obtained by conventional methods. Since this isomer is close in physical properties such as boiling point to the 3,4,3 ′, 4′-diepoxybicyclohexyl compound, it is difficult to separate it once it is formed. Therefore, as a result of investigating the cause of such isomer contamination, the bicyclohexyl-3,3'-diene compound used as a raw material for epoxidation contains many isomers having different double bond positions. I understood. For example, when a bicyclohexyl-3,3′-diene compound is synthesized by a dehydration reaction of a 4,4′-dihydroxybicyclohexyl compound, this positional isomer is added with water or dehydrated due to the presence of by-product water. It is considered that the separation is repeated and the position of the double bond is generated by moving. Since this isomer is also similar in physical properties such as boiling point to the bicyclohexyl-3,3'-diene compound, it is difficult to separate once produced. As a method for producing a bicyclohexyl-3,3'-diene compound, a method in which hydrogenated biphenol (4,4'-dihydroxybicyclohexyl) is intramolecularly dehydrated in a solvent in the presence of potassium hydrogen sulfate or the like is known. However, in this method, since the solid hydrogenated biphenol is melted and reacted, the by-product water is difficult to escape from the system, and the by-product water stays for a long time. It was found that the amount of isomers and other by-products produced was extremely high. On the other hand, in JP-A-2005-97274, hydrogenated biphenol is subjected to intramolecular dehydration without solvent in the presence of an alkali metal hydrogensulfate such as potassium hydrogensulfate to produce water and bicyclohexyl-3,3'-diene. Is rapidly distilled off from the reactor to obtain bicyclohexyl-3,3'-diene. According to this method, side reaction can be suppressed and bicyclohexyl-3,3'-diene having higher purity can be obtained. However, when the reaction product is analyzed in detail by gas chromatography using a capillary column, Also in the production method, the ratio of bicyclohexyl-3,3'-diene and its isomer was at most 80:20, and it was found that the isomer was considerably contained. Accordingly, various studies were made on the production of bicyclohexyl-3,3'-diene compounds with a low isomer content. When hydrogenated biphenol was subjected to an intramolecular dehydration reaction under specific reaction conditions, the isomer content ratio was reduced. It has been found that very little bicyclohexyl-3,3'-diene can be obtained in a simple and high yield. When bicyclohexyl-3,3′-diene having a very low isomer content ratio is used as a raw material, 3,4,3 ′, 4 ′ having a very low isomer content ratio is obtained. -Diepoxy bicyclohexyl is obtained, and when a curable epoxy resin composition containing such 3,4,3 ', 4'-diepoxy bicyclohexyl is cured, the curing reaction is only extremely fast. However, it was found that the glass transition temperature of the cured product was increased and the physical properties such as heat resistance were greatly improved. Further, it has been found that when such an epoxy resin composition containing 3,4,3 ′, 4′-diepoxybicyclohexyl is used as an adhesive, a high and constant adhesive strength can be obtained. The present invention has been completed based on these findings and further research.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を有していてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す）
で表される３，４，３′，４′−ジエポキシビシクロヘキシル化合物であって、該３，４，３′，４′−ジエポキシビシクロヘキシル化合物の異性体の含有量が、３，４，３′，４′−ジエポキシビシクロヘキシル化合物とその異性体の総和に対して、ガスクロマトグラフィーによるピーク面積の割合として２０％以下である脂環式ジエポキシ化合物（Ａ１）、若しくは下記式（２）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を有していてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す）
で表されるビシクロヘキシル−３，３′−ジエン化合物であって、該ビシクロヘキシル−３，３′−ジエン化合物の異性体の含有量が、ビシクロヘキシル−３，３′−ジエン化合物とその異性体の総和に対して、ガスクロマトグラフィーによるピーク面積の割合として２０％未満である脂環式ジエン化合物をエポキシ化することにより得られる脂環式ジエポキシ化合物（Ａ１′）、又は、前記脂環式ジエポキシ化合物（Ａ１）若しくは脂環式ジエポキシ化合物（Ａ１′）とそれ以外のエポキシ化合物（Ａ２）からなるエポキシ樹脂（Ａ）を含有する熱又は活性エネルギー線硬化型接着剤を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
Wherein the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound is 3,4,3 ′, 4′-diepoxybicyclohexyl compound. , 3 ′, 4′-diepoxy bicyclohexyl compound and its isomers, the alicyclic diepoxy compound (A1) having a peak area ratio of 20% or less by gas chromatography or the following formula (2) )

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
A bicyclohexyl-3,3′-diene compound represented by the formula: wherein the isomer content of the bicyclohexyl-3,3′-diene compound is such that the bicyclohexyl-3,3′-diene compound and its isomer The alicyclic diepoxy compound (A1 ′) obtained by epoxidizing an alicyclic diene compound having a peak area ratio of less than 20% by gas chromatography with respect to the total body, or the alicyclic Provided is a thermal or active energy ray-curable adhesive containing an epoxy resin (A) comprising a diepoxy compound (A1) or an alicyclic diepoxy compound (A1 ′) and another epoxy compound (A2).

In the adhesive, R ^{1 to} R ¹⁸ in formula (1) or formula (2) may all be hydrogen atoms.

  The epoxy resin (A) is composed of 99 to 10% by weight of the alicyclic diepoxy compound (A1) or (A1 ′) and 1 to 90% by weight of the epoxy compound (A2) [of (A1) or (A1 ′) and (A2)]. Total may be 100 wt%]. The epoxy resin (A) is composed of 80 to 10% by weight of the alicyclic diepoxy compound (A1) or (A1 ′) and 20 to 90% by weight of the epoxy compound (A2) [(A1) or (A1 ′) and (A2 ) May be comprised of 100% by weight.

  The adhesive may be a thermosetting adhesive containing a curing agent (B) together with the epoxy resin (A). The thermosetting adhesive may be an adhesive in which the curing agent (B) is a phenol resin (B1) and further contains a curing accelerator (C). Further, the curing agent (B) may be a curing agent (B2) that acts as an initiator that releases a substance that initiates cationic polymerization by heating. The compounding quantity of a hardening | curing agent (B2) is 0.05-20 weight part with respect to 100 weight part of epoxy resins (A), for example.

  The adhesive may be an active energy ray curable adhesive containing a photopolymerization initiator (D) together with the epoxy resin (A). This active energy ray-curable adhesive further contains an epoxy group or an acrylic resin (E) having an epoxy group and a hydroxyl group, and / or a caprolactone-modified polyol compound (F) having 2 to 4 hydroxyl groups in the molecule. It may be. The compounding quantity of an acrylic resin (E) is about 1-85 weight part with respect to 100 weight part of epoxy-type resin (A), for example. Moreover, the compounding quantity of the caprolactone modified polyol compound (F) which has 2-4 hydroxyl groups in a molecule | numerator is about 1-50 weight part with respect to 100 weight part of epoxy group resins (A), for example. The blending amount of the photopolymerization initiator (D) is, for example, 100 parts by weight of the epoxy resin (A), but includes an acrylic resin (E) and / or a caprolactone-modified polyol compound (F). It is about 0.01-20 weight part with respect to 100 weight part of total amounts of (A), acrylic resin (E), and a caprolactone modified polyol compound (F).

  The adhesive may further contain an elastomer (G). Moreover, the anisotropic conductive adhesive which disperse | distributed electroconductive particle (H) in the adhesive agent may be sufficient.

  The present invention also provides an adhesive body formed using the adhesive. The adhesive body includes an electronic device formed by joining electronic components with the adhesive. Examples of the electronic component include a semiconductor element, a semiconductor device, a printed circuit board, a liquid crystal display (LCD) panel, a plasma display (PDP) panel, an electroluminescence (EL) panel, and a field emission display (FED) panel.

  The present invention further provides an adhesion method characterized in that an adherend is adhered by the adhesive. The adherend includes an electronic component.

  The adhesive of the present invention is cured quickly by irradiation with active energy rays such as heat or ultraviolet rays without requiring facilities such as nitrogen sealing, and heat resistance and adhesion, particularly adhesion of thin films such as films, And excellent adhesion between different materials. In addition, according to the adhesive of the present invention, not only a sufficient adhesive strength can be obtained, but also the adhesive strength is constant and high adhesion reliability can be obtained. Furthermore, in the electrical connection between the fine circuits such as the connection between the LCD and the TCP and the connection between the TCP and the PCB, the connection can be made at a low temperature and in a short time, and high adhesion and connection reliability can be obtained. . The adhesive body of the present invention has excellent adhesion reliability and connection reliability. In addition, according to the adherend connection method of the present invention, high adhesion reliability and connection reliability can be obtained.

  The heat or active energy ray-curable adhesive of the present invention comprises the alicyclic diepoxy compound (A1) or the alicyclic diepoxy compound (A1 ′), or the alicyclic diepoxy compound (A1) or The epoxy resin (A) which consists of an alicyclic diepoxy compound (A1 ') and the other epoxy compound (A2) is contained.

[Alicyclic diepoxy compounds (A1) and (A1 ′)]
The alicyclic diepoxy compound (A1) in the present invention is a 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1), which is contained as an impurity. The content of isomers of 4,3 ', 4'-diepoxybicyclohexyl compound is determined by gas chromatography with respect to the sum of 3,4,3', 4'-diepoxybicyclohexyl compound and its isomer. The ratio of the peak area is 20% or less.

In formula (1), the halogen atoms in R ^{1 to} R ¹⁸ include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group in the “hydrocarbon group optionally having an oxygen atom or halogen atom” include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Is mentioned. Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl and decyl groups (for example, carbon number An alkyl group having 1 to 10 carbon atoms, preferably about 1 to 5 carbon atoms; an alkenyl group such as vinyl or an allyl group (for example, an alkenyl group having 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms); Alkynyl groups (for example, alkynyl groups having 2 to 10 carbon atoms, preferably about 2 to 5 carbon atoms). Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups; bridged cyclic groups and the like. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. Examples of the hydrocarbon group having an oxygen atom include a group in which an oxygen atom is interposed in the carbon chain of the hydrocarbon group (for example, an alkoxyalkyl group such as a methoxymethyl group or an ethoxymethyl group). . As the hydrocarbon group having a halogen atom, for example, one or more hydrogen atoms of the hydrocarbon group such as chloromethyl group, trifluoromethyl group, chlorophenyl group are halogen atoms (fluorine, chlorine, bromine or iodine atoms). ). The alkoxy group in the “optionally substituted alkoxy group” is an alkoxy group having about 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy group or the like. Groups and the like. As a substituent of an alkoxy group, the said halogen atom etc. are mentioned, for example.

Among the 3,4,3 ′, 4′-diepoxybicyclohexyl compounds represented by the formula (1), 3,4,3 ′, 4′-diepoxy in which R ^{1 to} R ¹⁸ are all hydrogen atoms Bicyclohexyl is particularly preferred.

Since 3,4,3 ′, 4′-diepoxybicyclohexyl compounds and their isomers have similar physical properties such as boiling point, they cannot often be separated by a general gas chromatography apparatus. Therefore, it is desirable to perform quantitative analysis of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomers by gas chromatography using a capillary column having higher resolution. Quantitative analysis of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomer by gas chromatography can be performed under the following measurement conditions. The structure of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound and its isomer can be confirmed by, for example, NMR, GC-MS, GC-IR and the like.
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 30 m, film thickness 0.25 μm, inner diameter 0.32 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 1.0 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Temperature rise pattern (column): Hold at 100 ° C. for 2 minutes, heat up to 300 ° C. at 5 ° C./minute, hold at 300 ° C. for 10 minutes Split ratio: 100
Sample: 1 μl (epoxy compound: acetone = 1: 40)

  In the alicyclic diepoxy compound (A1), the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound contained as an impurity is 3,4,3 ′, 4′-diene. The ratio of the peak area by gas chromatography is 20% or less (preferably 18% or less, more preferably 16% or less) with respect to the sum of the epoxybicyclohexyl compound (main compound) and its isomers. Such an alicyclic diepoxy compound has a markedly faster curing reaction rate than that having a content of the isomer exceeding 20%, and the glass transition temperature of the cured product after curing is significantly increased. Physical properties such as heat resistance are remarkably improved. Further, when used as an adhesive, the adhesive strength is remarkably improved, and the adhesive strength is constant and high adhesive reliability is obtained.

Such an alicyclic diepoxy compound (A1) is, for example, a bicyclohexyl-3,3′-diene compound represented by the above formula (2), and the bicyclohexyl-3,3′-diene compound. The content of isomers (isomers with different double bond positions) is less than 20% as a proportion of peak area by gas chromatography with respect to the sum of the bicyclohexyl-3,3'-diene compound and its isomers. It can be produced by epoxidizing an alicyclic diene compound (for example, 19.5% or less, preferably 15% or less). The alicyclic diepoxy compound obtained by this production method is referred to as “alicyclic diepoxy compound (A1 ′)”. In formula (2), R ^{1 to} R ¹⁸ are the same as described above.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は前記に同じ）
で表される４，４′−ジヒドロキシビシクロヘキシル化合物を、有機溶媒中、脱水触媒の存在下、副生する水を留去しながら脱水反応を行うことにより得られる。 Here, the bicyclohexyl-3,3′-diene compound represented by the formula (2) having a small isomer content used as a raw material is, for example, the following formula (3):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same as above)
Is obtained by performing a dehydration reaction in an organic solvent while distilling off by-product water in the presence of a dehydration catalyst.

  More specifically, for example, in the presence of a dehydration catalyst that dissolves the 4,4′-dihydroxybicyclohexyl compound represented by the formula (3) in a liquid or reaction solution under the reaction conditions in an organic solvent (i). Heating to a temperature of 130 to 200 ° C. under a pressure exceeding 20 Torr (2.67 kPa), and performing a dehydration reaction while distilling off by-product water, and (ii) following the step (i), The reaction mixture is heated to a temperature of 100 to 220 ° C. under a pressure of 200 Torr (26.7 kPa) or less to distill the produced bicyclohexyl-3,3′-diene compound represented by the formula (2). It can manufacture by passing through a process. This method will be described below.

  A typical example of the compound represented by the formula (3) is 4,4′-dihydroxybicyclohexyl (hydrogenated biphenol).

  The organic solvent used in the step (i) is not particularly limited as long as it is an inert solvent under the reaction conditions, but is preferably a liquid at 25 ° C. and having a boiling point of about 120 to 200 ° C. Typical examples of preferable organic solvents include aromatic hydrocarbons such as xylene, cumene, and pseudocumene; and aliphatic hydrocarbons such as dodecane and undecane. As an organic solvent, in order to easily separate and remove by-product water, an organic solvent that is azeotropic with water and can be separated from water may be used. A solvent that reacts in the presence of an acid such as a ketone or ester is not preferable even if the boiling point is in the above range. Alcohol is not preferred because it may cause a dehydration reaction.

  The amount of the organic solvent used can be appropriately selected in consideration of operability, reaction rate and the like, but is usually about 50 to 1000 parts by weight with respect to 100 parts by weight of the substrate 4,4′-dihydroxybicyclohexyl compound. Yes, preferably about 80 to 800 parts by weight, more preferably about 100 to 500 parts by weight.

  The dehydration catalyst used in the step (i) is not particularly limited as long as it has a dehydration activity and is liquid under the reaction conditions or can be dissolved in the reaction liquid (completely dissolved in the use amount described later). Those having no activity or as low as possible with respect to the reaction solvent are preferable. The dehydration catalyst that is liquid under the reaction conditions is preferably one that is finely dispersed in the reaction solution. As the dehydration catalyst, usually, inorganic acids such as phosphoric acid and sulfuric acid, acids such as sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid, or salts thereof, in particular, complete with an organic base of the acid. Neutralized or partially neutralized salts are used. A dehydration catalyst can be used individually or in combination of 2 or more types.

  When using a neutralized salt of an acid with an organic base, a neutralized salt (fully or partially neutralized salt) may be isolated and purified from a reaction mixture obtained by reacting an acid with an organic base. However, a reaction mixture obtained by reacting an acid with an organic base (containing a completely neutralized salt and / or a partially neutralized salt) can be used as it is. In the latter case, the reaction mixture may contain free acid. In the latter case, the mixing ratio of the acid and the organic base is, for example, about 0.01 to 1 equivalent, preferably about 0.05 to 0.5 equivalent, more preferably about 1 to 1 equivalent of the acid. Is about 0.1 to 0.47 equivalent. In particular, when a reaction mixture of sulfuric acid and organic base is used, the mixing ratio of sulfuric acid and organic base is preferably 0.02 to 2 mol, more preferably 0.1 to 1 mol of sulfuric acid. The amount is about 1.0 to 1.0 mol, particularly preferably about 0.2 to 0.95 mol. Moreover, when using the neutralized salt by the organic base of an acid, an acid and an organic base may be added separately and the neutralized salt may be formed in a system.

  The organic base may be any organic compound that exhibits basicity. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene. -5 (DBN), 1,4-diazabicyclo [2.2.2] octane, piperidine, N-methylpiperidine, pyrrolidine, N-methylpyrrolidine, triethylamine, tributylamine, trioctylamine, benzyldimethylamine, 4-dimethyl Examples include amines such as aminopyridine and N, N-dimethylaniline (particularly tertiary amines); nitrogen-containing aromatic heterocyclic compounds such as pyridine, collidine, quinoline and imidazole; guanidines; hydrazines and the like. Among these, third compounds such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), triethylenediamine, triethylamine and the like. Secondary amines (particularly cyclic amines), guanidines and hydrazines are preferred, and DBU, DBN, triethylenediamine and triethylamine are particularly preferred. Moreover, as an organic base, the thing of pKa11 or more is preferable and the thing whose boiling point is 150 degreeC or more is preferable.

  When an alkali metal salt of sulfuric acid such as potassium hydrogen sulfate is used as a dehydration catalyst, the content of the isomer of the bicyclohexyl-3,3'-diene compound is reduced to that of the bicyclohexyl-3,3'-diene compound and its isomer. An area ratio by gas chromatography of less than 20% is not obtained with respect to the sum. When ammonium bisulfate is used as the dehydration catalyst, the content of isomers of the bicyclohexyl-3,3'-diene compound is the sum of the bicyclohexyl-3,3'-diene compound and its isomer. On the other hand, a peak area ratio by gas chromatography of about 19% is obtained.

  Therefore, as a dehydration catalyst, completely neutralized salts or partially neutralized salts of organic acids such as sulfonic acids (p-toluenesulfonic acid, etc.), phosphoric acid, sulfuric acid, sulfonic acids (p-toluenesulfonic acid, etc.), phosphoric acid A completely neutralized salt or a partially neutralized salt with an organic base, and a completely neutralized salt or a partially neutralized salt with an organic base of sulfuric acid are preferred. Of these, sulfonic acids (particularly p-toluenesulfonic acid), completely neutralized salts or partially neutralized salts of organic acids with sulfonic acids, and completely neutralized salts or partially neutralized salts of sulfuric acid with organic bases are particularly preferable. A completely neutralized salt or a partially neutralized salt (particularly a partially neutralized salt) of sulfuric acid with an organic base is preferred.

  The amount of the dehydration catalyst used is, for example, 0.001 to 0.5 mol, preferably 0.001 to 0, per 1 mol of the 4,4′-dihydroxybicyclohexyl compound represented by the formula (3) as the raw material. 0.3 mol, more preferably 0.005 to 0.2 mol.

  The pressure is different between the step (i) and the step (ii). In the reaction solution of step (i), only one of the unreacted 4,4′-dihydroxybicyclohexyl compound and the two cyclohexane rings to which the hydroxyl group in the 4,4′-dihydroxybicyclohexyl compound is bonded. A reaction intermediate converted into a cyclohexene ring by intramolecular dehydration, the target bicyclohexyl-3,3′-diene compound, by-product water, a dehydration catalyst, and a reaction solvent coexist. In this step (i), by-product water is distilled, but at this time, it is not desirable to distill the reaction intermediate from the following points. That is, (1) the reaction intermediate can be converted into the target compound by further intramolecular dehydration, and thus distilling it causes a decrease in the yield of the target compound. (2) The reaction intermediate is generally Since it is a sublimable solid, when using a distillation column, the solid precipitates in the distillation path of by-product water, so that the distillation path is blocked and the pressure inside the reactor is increased, and the reaction vessel Cause troubles such as rupture, breakage, and scattering of the reaction solution. Therefore, in the step (i), the dehydration reaction is performed while distilling off by-product water under a pressure exceeding 20 Torr (2.67 kPa) so that the reaction intermediate is not distilled. The pressure is preferably higher than 20 Torr and lower than normal pressure (higher than 2.67 kPa and lower than 0.1 MPa), more preferably higher than 100 Torr and lower than normal pressure (higher than 13.3 kPa and lower than 0.1 MPa), more preferably higher than 200 Torr. Normal pressure or lower (higher than 26.7 kPa and 0.1 MPa or lower), and normal pressure is particularly preferable from the viewpoint of operability. The temperature (reaction temperature) in the step (i) is 130 to 200 ° C, preferably 140 to 195 ° C, more preferably 150 to 195 ° C. If the temperature is too high, side reactions occur and the yield decreases. If the temperature is too low, the reaction rate becomes slow. The reaction time is, for example, about 1 to 10 hours, preferably about 2 to 6 hours for a synthetic scale of about 3 L.

  On the other hand, in step (ii), the target bicyclohexyl-3,3'-diene compound is distilled from the reaction mixture after distilling by-product water. The reaction mixture obtained in step (i) may be directly used in step (ii), but if necessary, the reaction mixture may be appropriately extracted, washed, adjusted in liquidity, etc. You may use for process (ii) after giving a process. When the boiling point of the organic solvent used in the reaction is lower than the boiling point of the target bicyclohexyl-3,3′-diene compound, the organic solvent is usually distilled off and then bicyclohexyl-3,3′-diene. The compound is distilled off.

  In this step (ii), since the reaction intermediate is hardly present, problems such as clogging of the distillation path do not occur even when the pressure is lowered, and when the pressure is high, it takes time to distill the target compound. Operate at a pressure of 200 Torr (26.7 kPa) or less. The pressure in step (ii) is preferably lower than the pressure in step (i). For example, the difference between the pressure in step (i) and the pressure in step (ii) (the former-the latter) is, for example, 100 Torr or more (13.3 kPa or more), preferably 200 Torr or more (26.7 kPa or more), more preferably 500 Torr or more. (66.7 kPa or more). The pressure in step (ii) is preferably 3 to 200 Torr (0.40 to 26.7 kPa), more preferably 3 to 100 Torr (0.40 to 13.3 kPa), and still more preferably 3 to 20 Torr (0.40 to 0.40). 2.67 kPa). The temperature of process (ii) is 100-220 degreeC, Preferably it is 120-180 degreeC, More preferably, it is about 130-150 degreeC grade. If the temperature is too high, side reactions are liable to occur and the recovery rate of the bicyclohexyl-3,3′-diene compound decreases. On the other hand, if the temperature is too low, the distilling rate becomes slow.

  In order to distill a bicyclohexyl-3,3'-diene compound, etc., for example, when a distillation apparatus is attached to a reactor, etc., a distillation column, an Oldershaw type distillation apparatus, etc. are generally used as the distillation apparatus. Any distillation apparatus having a reflux ratio can be used without particular limitation.

  The bicyclohexyl-3,3′-diene compound distilled in step (ii) can be further purified as necessary. As a purification method, when a very small amount of water is contained, separation using a difference in specific gravity is possible, but purification by distillation is generally preferable.

  According to such a method, by-product water is produced under specific reaction conditions in the presence of a dehydration catalyst that dissolves the raw 4,4'-dihydroxybicyclohexyl compound in an organic solvent in a liquid state or reaction solution under the reaction conditions. After the reaction while distilling off, the produced bicyclohexyl-3,3'-diene compound is distilled off under specific conditions, so that the reaction can be carried out at a relatively low temperature and in a relatively short time. Can prevent side reactions such as conversion, and can prevent loss due to distillation of reaction intermediates and blockage due to sublimation, etc., so that high purity bicyclohexyl-3,3'-diene compound with low impurity content can be easily and high It can be efficiently obtained in a yield. That is, the content of the isomer of the bicyclohexyl-3,3′-diene compound represented by the formula (2) is determined by gas chromatography with respect to the sum of the bicyclohexyl-3,3′-diene compound and its isomer. An alicyclic diene compound having a peak area ratio of less than 20% (for example, 19.5% or less, preferably 15% or less) can be obtained.

  In addition, in the conventional method, for example, the method described in JP-A No. 2000-169399, a long reaction time is required. Therefore, a large amount of undesirable by-products are generated due to side reactions such as isomerization. By-product isomers have physical properties such as boiling point and solvent solubility that are close to those of the target compound, so that once produced, separation becomes extremely difficult. When such a cyclic olefin compound containing a large amount of by-products is epoxidized and used as a curable resin, a cured product having low physical properties such as heat resistance cannot be obtained during curing. Bicyclohexyl-3,3'-diene compounds and their isomers are very similar in physical properties such as boiling point, and therefore cannot be separated by a general gas chromatography apparatus. The yield and purity of the cyclohexyl-3,3'-diene compound are described in a higher manner. The analysis of the bicyclohexyl-3,3'-diene compound and its isomer is preferably carried out by gas chromatography using a capillary column having a high resolution.

The quantitative analysis of the bicyclohexyl-3,3′-diene compound and its isomer by gas chromatography can be carried out under the following measurement conditions. The structure of the bicyclohexyl-3,3′-diene compound and its isomer can be confirmed by, for example, NMR, GC-MS, GC-IR and the like.
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 60m, inner diameter 0.32mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 2.6 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Temperature rise pattern (column): Hold at 60 ° C. for 5 minutes, temperature rise to 300 ° C. at 10 ° C./minute Split ratio: 100
Sample: 1 μl

  The epoxidation method of the bicyclohexyl-3,3′-diene compound is not particularly limited. For example, a method using an organic percarboxylic acid as an oxidizing agent (epoxidizing agent), a hydroperoxide such as t-butyl hydroperoxide, and the like. Although any method using a metal compound such as a molybdenum compound may be used, a method using an organic percarboxylic acid is preferable from the viewpoint of safety, economy, yield, and the like. Hereinafter, this method will be described.

  As the organic percarboxylic acid, for example, performic acid, peracetic acid, perbenzoic acid, perisobutyric acid, trifluoroperacetic acid and the like can be used. Among organic percarboxylic acids, peracetic acid is a preferred epoxidizing agent because of its high reactivity and high stability. Among them, the use of an organic percarboxylic acid substantially free of water, specifically, having a water content of 0.8% by weight or less, preferably 0.6% by weight or less has a high epoxidation rate. This is preferable in that a compound is obtained. The organic percarboxylic acid substantially free of water is produced by air oxidation of aldehydes, for example, acetaldehyde. For example, peracetic acid is disclosed in German Patent Publication No. 1418465 and JP-A 54-30006. Manufactured by the described method. According to this method, it is possible to synthesize organic percarboxylic acid in a large amount continuously, compared with the case where organic percarboxylic acid is synthesized from hydrogen peroxide and extracted with a solvent to produce organic percarboxylic acid. Therefore, it can be obtained substantially inexpensively.

  The amount of the epoxidizing agent is not strictly limited, and the optimum amount in each case depends on the individual epoxidizing agent used, the reactivity of the bicyclohexyl-3,3'-diene compound, and the like. The amount of the epoxidizing agent is, for example, about 1.0 to 3.0 mol, preferably about 1.05 to 1.5 mol with respect to 1 mol of the unsaturated group. From the viewpoint of economy and side reaction, it is usually disadvantageous to exceed 3.0 times mol.

  The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw material. As the solvent, it can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and in the case of peracetic acid, esters, aromatic compounds, ethers and the like can be used. Particularly preferred solvents are ethyl acetate, hexane, cyclohexane, toluene, benzene and the like, and ethyl acetate is particularly preferred. The reaction temperature is determined by the reactivity of the epoxidizing agent used and the bicyclohexyl-3,3'-diene compound. For example, the reaction temperature when peracetic acid is used is preferably 20 to 70 ° C. If it is less than 20 ° C., the reaction is slow, and if it exceeds 70 ° C., peracetic acid decomposes with heat generation, which is not preferable.

  No special operation is required for the crude liquid obtained by the reaction. For example, the crude liquid may be aged by stirring for 1 to 5 hours. Isolation of the epoxy compound from the obtained crude liquid is an appropriate method, such as a method of precipitating with a poor solvent, a method of pouring the epoxy compound into hot water with stirring and distilling off the solvent, a method of directly removing the solvent, It can be carried out by a method such as isolation by distillation purification.

  Thus, the isomer content (isomer ratio) of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound represented by the formula (1) is represented by the formula (1) 3. , 4,3 ', 4'-diepoxybicyclohexyl compound and its isomers, the peak area ratio by gas chromatography is 20% or less (preferably 18% or less, more preferably 16% or less) An alicyclic diepoxy compound can be obtained.

[Epoxy compound (A2)]
In the present invention, together with the alicyclic diepoxy compound (A1) or (A1 ′), the other epoxy compound (A2) [may be simply referred to as “epoxy compound (A2)”] can be used. By combining the alicyclic diepoxy compound (A1) or (A1 ′) and the epoxy compound (A2), it is possible to improve moisture resistance, hardness of the resulting bonded body (hardness of the adhesive film), and adhesion. .

  As the epoxy compound (A2), an epoxy compound having one or more, preferably two or more epoxy groups in the molecule can be used. This epoxy group may be an alicyclic epoxy group (an epoxy group formed by including two carbon atoms constituting the cycloaliphatic skeleton) or an epoxy group other than the alicyclic epoxy group. Specific examples of the compound having an alicyclic epoxy group in the molecule include an epoxy compound represented by the following formula (4), limonene dioxide, di (3,4-epoxycyclohexyl) adipate, (3,4-epoxycyclohexyl). ) Methyl-3,4-epoxycyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-di (3,4 -Epoxy cyclohexane carboxylic acid) ester etc. are mentioned. On the other hand, as a compound having an epoxy group other than an alicyclic epoxy group in the molecule, various bisphenol-type diglycidyl ethers represented by bisphenol A type, F type, S type and brominated bisphenol A type (commercially available products include: , Epicoat 828, 806 (manufactured by Japan Epoxy Resin Co., Ltd.), YD-128 (manufactured by Toto Kasei Co., Ltd.), etc. -4000 (manufactured by Japan Epoxy Resin Co., Ltd.)). In addition, glycidyl ether having a cycloaliphatic skeleton such as diglycidyl ether of cyclohexanedimethanol (commercially available products such as DME-100 (manufactured by Nippon Nippon Chemical Co., Ltd.)), glycidyl ether of novolac type phenol resin, DCPD, etc. Polycyclic aromatic glycidyl ethers such as glycidyl ether and naphthalene of copolymerized novolak type phenol resins, and epoxy resins having terminal epoxies in the alicyclic skeleton (commercially available products include EHPE-3150, EHPE-3150CE (Daicel Chemical Industries, Ltd.) Etc.), silicone resins having epoxy groups (commercially available products include A-186 (manufactured by Nihon Unicar), KBM303, KBM403, KBM42 (manufactured by Shin-Etsu Chemical Co., Ltd.)), dimer acid diglycidyl ester, diphthalate Glycidyl ester, etc. And the like. An epoxy compound (A2) can be used individually or in combination of 2 or more types. In addition, the compound represented by following formula (4) can be manufactured by the method shown by Unexamined-Japanese-Patent No. 2006-52187.

  In the thermosetting adhesive, as the epoxy compound (A2), in particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated bisphenol A glycidyl ether type epoxy resin such as A, polycyclic aromatic glycidyl ether such as naphthalene, dimer acid diglycidyl ester, epoxy compound having a glycidyl group such as phthalic acid diglycidyl ester, or epoxy compound and fat having the glycidyl group A combination with an epoxy compound having a cyclic epoxy group is preferred. In the active energy ray-curable adhesive, as the epoxy compound (A2), in particular, an epoxy compound having an alicyclic epoxy group, for example, a compound represented by the above formula (4), (3,4-epoxycyclohexyl) ) Methyl-3,4-epoxycyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, and the like are preferable.

  In the heat or active energy ray-curable adhesive of the present invention, an alicyclic diepoxy compound (A1) or an alicyclic diepoxy compound (A1 ′) from the viewpoints of curability, adhesion, moisture resistance, film hardness, economy, and the like. ) And other epoxy compounds (A2) are preferably used in combination. The component (A1) [or (A1 ′)] is a component that strengthens the bond between the surface of the adherend and the adhesive. On the other hand, the component (A2) is used in combination with the component (A1) to adjust various properties of the adhesive. When the alicyclic diepoxy compound (A1) or the alicyclic diepoxy compound (A1 ′) and the other epoxy compound (A2) are mixed and used, the alicyclic epoxy compound (A1) [or (A1 ′)] Is preferably 99 to 10% by weight, more preferably 80 to 10% by weight, still more preferably 70 to 20% by weight based on the total amount of (A1) [or (A1 ′)] and (A2). %, Particularly preferably 60 to 30% by weight. The compounding ratio of the epoxy compound (A2) is preferably 1 to 90% by weight, more preferably 20 to 90% by weight, still more preferably with respect to the total amount of (A1) [or (A1 ′)] and (A2). Is 30 to 80% by weight, particularly preferably 40 to 70% by weight. By blending at the above ratio, both excellent curability and good adhesiveness due to the three-dimensional crosslinking effect can be achieved. If it is out of the above range, for example, when the irradiation amount of the active energy ray is low, the curability of the adhesive may be lowered, or the hardness and adhesion of the obtained adhesive may be inferior. In the case of a thermosetting adhesive, if the amount of the epoxy compound (A2) in the epoxy resin (A) exceeds 90% by weight, for example, when used as an anisotropic conductive adhesive, Curability tends to be poor, and if it is less than 20% by weight, moisture resistance tends to be inferior. Therefore, when used as an anisotropic conductive adhesive, sufficient connection reliability may not be obtained.

[Thermosetting adhesive]
The adhesive of the present invention contains a curing agent (B) when used as a thermosetting adhesive. As the curing agent (B), a phenol resin (B1), a curing agent (B2) that acts as an initiator for releasing a substance that initiates cationic polymerization by heating (sometimes simply referred to as “curing agent (B2)”). Acid anhydride (B3) or the like is used. In addition, when a radically polymerizable compound is included in the adhesive, a radical polymerization initiator may be used.

  Examples of the phenol resin (B1) include a resin obtained by polymerizing phenol or cresol using formaldehyde. The phenol resin may be a resin obtained by copolymerizing a compound having an alicyclic or aromatic cyclic structure such as dicyclopentadiene, naphthalene, or biphenyl. In this case, the copolymerization ratio is not particularly limited, but it is desirable that two or more phenolic hydroxyl groups per molecule be used as a curing agent. The molecular weight is preferably a number average molecular weight of 250 to 5,000, more preferably about 280 to 4,000. If the molecular weight exceeds the above upper limit, blending in the case of forming a resin composition tends to be difficult, and the viscosity of the resin composition may become too high and workability may be reduced. Since the number of functional groups is insufficient, the cross-linking is sweetened (the cross-linking density is lowered), and the adhesiveness may be lowered.

  Examples of the phenol resin (B1) include PSM-4324 (softening point: 98 to 102 ° C.), PSM-4326 (softening point: 118 to 122 ° C.), and PSM-4327 mainly composed of phenol novolak or cresol novolak. (Softening point: 93 to 97 ° C.), PSM-4261 (softening point: 80 to 84 ° C.), PSM-6842 (softening point: 93 to 97 ° C.), PSM-6856 (softening point: 105 to 115 ° C.) , Manufactured by Gunei Chemical Industry Co., Ltd.], MMC-200, EM-60, PM-8375, PM-9245, PM-9610, PM-9615, PM-9630K, PM-9640, PM-9985L, PM-9820 , PM-9830, PM-9850, AM-100, AM-113, TM-4120, TM-EP230 [above, Sumitomo Bakery Manufactured by Co., Ltd.], BRM-470 (softening point: 66-76 ° C.), BRG-557 (softening point: 82-88 ° C.), BRG-558 (softening point: 93-98 ° C.), CRG-951 (softening) Point: 93 to 99 ° C.), BRP-2444 (softening point: 76 to 86 ° C.), CRM-973 (softening point: 80 to 95 ° C.) [above, Showa Polymer Co., Ltd.] and the like are used as commercial products. Is possible.

  The amount of the phenol resin (B1) added is preferably 20 to 200 parts by weight, more preferably 30 to 180 parts by weight, still more preferably 40 to 170 parts by weight (or epoxy) based on 100 parts by weight of the epoxy resin (A). The phenolic hydroxyl group is preferably from 0.3 to 1.8 mol, more preferably from 0.4 to 1.7 mol, still more preferably from 0.45 to 1.6 mol, based on 1 mol of the epoxy group of the resin (A). ). If the amount is less than 20 parts by weight (or 0.3 mol with respect to 1 mol of the epoxy group of the epoxy resin (A)), the crosslinking density may be insufficient, the adhesive strength may be reduced, and the reliability may be reduced. If the amount exceeds 1.8 parts (or 1.8 mol with respect to 1 mol of the epoxy group of the epoxy resin (A)), the crosslinking density may be insufficient and the reliability may be lowered.

  The curing agent (B2) used in the present invention is a curing agent (thermal cationic polymerization initiator) that acts as an initiator that releases a substance that initiates cationic polymerization by heating. Specifically, the curing formula (5) The compound shown by-(8) is illustrated.

In formula (5), R ¹⁹ represents a hydrogen atom, an acetyl group or a methoxycarbonyl group. R ²⁰ and R ²¹ are each a hydrogen atom, an alkyl group having a halogen atom or C ₁ -C _4. R ²² represents a hydrogen atom, a methyl group, a methoxy group or a halogen atom. R ²³ represents a C _{1 to} C ₄ alkyl group. X ⁻ represents SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or BF ₄ ⁻ .

In the formula (6), R ²⁴ represents a hydrogen atom, acetyl group, methoxycarbonyl group, methyl group, ethoxycarbonyl group, t-butoxycarbonyl group, benzoyl group, phenoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethoxy. A carbonyl group or a p-methoxybenzylcarbonyl group is shown. R ²⁵ and R ²⁶ each represent a hydrogen atom, a halogen atom or a C ₁ -C ₄ alkyl group. R ²⁷ and R ²⁸ each represent a hydrogen atom, a methyl group, a methoxy group or a halogen atom. X ^- has the same meaning as above.

In the formula (7), R ²⁹ represents an ethoxy group, a phenyl group, a phenoxy group, a benzyloxy group, a chloromethyl group, a dichloromethyl group, a trifluoromethyl group or a trifluoromethyl group. R ³⁰ and R ³¹ each represent a hydrogen atom, a halogen atom or a C ₁ -C ₄ alkyl group. R ³² represents a hydrogen atom, a methyl group, a methoxy group or a halogen atom. R ³³ represents an alkyl group of C ₁ -C _4. X ^- has the same meaning as above.

In the formula (8), R ³⁴ is a hydrogen atom, acetyl group, methoxycarbonyl group, methyl group, ethoxycarbonyl group, t-butoxycarbonyl group, benzoyl group, phenoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethoxy. A carbonyl group or a p-methoxybenzylcarbonyl group is shown. R ³⁵ and R ³⁶ are each a hydrogen atom, an alkyl group having a halogen atom or C ₁ -C _4. R ³⁷ and R ³⁸ each represent a methyl group or an ethyl group. X ^- has the same meaning as above.

  Examples of the curing agent (B2) include aryldiazonium salts [for example, PP-33 (manufactured by Asahi Denka Kogyo Co., Ltd.)], aryliodonium salts, arylsulfonium salts [for example, FC-509, FC-540 (3M ), UVE1014 (GE), UVI-6974, UVI-6970, UVI-6990, UVI-6950 (Union Carbide), SP-170, SP-150, CP-66, CP -77 etc. (manufactured by Asahi Denka Kogyo Co., Ltd.)], SI-60L, SI-80L, SI-100L, SI-110L (manufactured by Sanshin Chemical Industry Co., Ltd.), allene-ion complexes [for example, CG -24-61 (Ciba Geigy)].

  Further, as the curing agent (B2), a system of a chelate compound of a metal such as aluminum or titanium and an acetoacetate ester or a diketone and a silanol or a phenol can be used. Examples of the chelate compound include aluminum acetylacetonate. Examples of silanols or phenols include triphenylsilanol and bisphenol S.

  The compounding quantity of a hardening | curing agent (B2) is 0.01-20 weight part with respect to 100 weight part of epoxy resins (A), 0.05-20 weight part is preferable, More preferably, it is 0.1-20 weight part. It is 5 parts by weight, more preferably in the range of 0.1 to 3 parts by weight. By mix | blending in this range, favorable hardened | cured materials, such as heat resistance, transparency, a weather resistance, can be obtained. When there is too little quantity of a hardening | curing agent (B2), sclerosis | hardenability will become inadequate, and when too large, the physical property of hardened | cured material may be reduced.

Examples of the acid anhydride (B3) include polybasic acid anhydrides. Specifically, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, Δ ⁴ -tetrahydrophthalic anhydride 4-methyl-Δ ⁴ -tetrahydrophthalic anhydride, 3-methyl-Δ ⁴ -tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4- (4-methyl-3 -Pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, maleic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, vinyl ether-anhydride Maleic acid copolymer, alkyl styrene-maleic anhydride copolymer and the like.

  The compounding amount of the acid anhydride (B3) is preferably 60 to 160 parts by weight with respect to 100 parts by weight of the epoxy resin (A), and stoichiometrically with respect to 1 equivalent of the epoxy group of the epoxy resin (A). 0.7 to 1.3 equivalents, more preferably 0.8 to 1.2 equivalents, and still more preferably 0.9 to 1.1 equivalents. When the blending amount of the acid anhydride (B3) is out of the above range, the curability is deteriorated, and the performance of the anisotropic conductive adhesive or the electronic device joined using the same may be deteriorated.

  When using a phenol resin (B1) or an acid anhydride (B3) as the curing agent (B) of the present invention, it is preferable to use a curing accelerator (C) together. The curing accelerator (C) is a compound having a function of accelerating the curing reaction when the epoxy resin (A) is cured by the phenol resin (B1) or the acid anhydride (B3), and the following (i) to (iv) ), And can be used alone or in admixture of two or more. In addition, when using a hardening | curing agent (B2) as a hardening | curing agent (B), it is usually unnecessary to use a hardening accelerator (C).

  (I) Tertiary amines or imidazoles and / or their organic carboxylates, specifically 2,4,6-tris (diaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1, Examples thereof include 8-diazabiscyclo (5,4,0) undecene-7 (hereinafter abbreviated as “DBU”) alone or an octylate thereof.

  (Ii) Phosphines and / or quaternary salts thereof, specifically, triphenylphosphine, tributylphosphine, benzyltriphenylphosphonium bromine salt, benzyltributylphosphonium bromine salt and the like.

  (Iii) Organic carboxylic acid metal salts, specifically, zinc octylate, zinc laurate, zinc stearate, tin octylate and the like that do not have a carbon double bond inferior in light resistance. The organic carboxylic acid metal salt is in proportion to the increase in the carbon number of the organic carboxylic acid component, and the solubility in the epoxy resin decreases.

  (Iv) Metal-organic chelate compounds, specifically, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc chelate, ethyl zinc acetoacetate chelate composed of zinc and β-diketone that do not affect translucency Can be mentioned.

  The compounding quantity of a hardening accelerator (C) is as follows. For example, when the phenol resin (B1) is used as the curing agent (B), 50 to 150 parts by weight of the phenol resin (B1) and 100% by weight of the curing accelerator (C) with respect to 100 parts by weight of the epoxy resin (A). It is preferable to mix in a ratio of 0.05 to 10 parts by weight. Moreover, when using an acid anhydride (B3) as a hardening | curing agent (B), 60-160 weight part of acid anhydride (B3) with respect to 100 weight part of epoxy resins (A), hardening accelerator (C ) 0.05 parts by weight (preferably 3 parts by weight) to 7 parts by weight (preferably 5 parts by weight). If the blending amount of the curing accelerator (C) is less than the above lower limit values, curing may be insufficient or a long time may be required for curing. Since (for example, adhesiveness and heat resistance) may deteriorate, neither is preferable.

  It is preferable to further use an elastomer (G) for the thermosetting adhesive of the present invention. The elastomer used in the present invention is more preferably a reactive elastomer. The elastomer used in the present invention is not particularly limited, but has an ability to form a film, such as phenoxy resin, polyester resin, polyurethane resin, polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene. Polymer, polyacetal resin, polyvinyl butyral resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl acetate resin, nylon , A styrene-isoprene copolymer, a styrene-butylene-styrene block copolymer, and the like may be used alone or in admixture of two or more.

  Although the compounding quantity of an elastomer (G) is not specifically limited, It is preferable that it is 10-300 weight part with respect to 100 weight part of epoxy resins (A). If the blending amount exceeds 300 parts by weight, the fluidity when an anisotropic conductive adhesive is used will be insufficient, and sufficient connection reliability will not be obtained, or wettability with various adherends will be reduced and sufficient adhesion Sexuality may not be obtained. Further, if it is less than 10 parts by weight, the problem of poor film-forming properties when used as an anisotropic conductive adhesive, the problem of poor adhesion to various adherends due to the high modulus of the cured product, and thermal shock Problems such as poor connection reliability after testing may occur.

  An appropriate amount of a coupling agent may be added to the thermosetting adhesive of the present invention as necessary. The purpose of adding the coupling agent is to improve the adhesion property of the adhesion interface of the anisotropic conductive adhesive, and to improve the heat resistance and moisture resistance. Although it does not specifically limit as a coupling agent, A silane coupling agent can be used conveniently, for example, (gamma) -glycidoxypropyl triethoxysilane, (beta)-(3,4 epoxy cyclohexyl) ethyltrimethoxy. Examples include silane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and γ-ureidopropyltriethoxysilane. These coupling agents can be used alone or in combination of two or more.

  Furthermore, the thermosetting adhesive of the present invention has various additives such as non-reactive diluents such as solvents, reactive diluents, etc., for improving various properties such as resin compatibility, stability, and workability. , Thixotropic agents, thickeners, inorganic fillers and the like may be added as appropriate. In addition, silicone-based and fluorine-based antifoaming agents, flame retardants, antioxidants, ultraviolet absorbers, ion adsorbents, colorants, pigments, stress reducing agents, flexibility imparting agents, waxes, halogen trapping agents, Various additives conventionally used in epoxy resin compositions such as leveling agents and wetting improvers can also be blended. Furthermore, it may contain a thermoplastic resin, a thermosetting resin, organic or inorganic nanoparticles, if necessary.

  Conductive particles (H) can be dispersed in the thermosetting adhesive of the present invention and used as an anisotropic conductive adhesive. The composition of the conductive particles used in the present invention is not particularly limited. For example, as the metal particles, gold, silver, zinc, tin, solder, indium, palladium, or the like may be used alone or in combination of two or more. In addition, as the particles obtained by metal coating the polymer core material, the epoxy resin, urethane resin, melamine resin, phenol resin, acrylic resin, polyester resin, polystyrene resin, styrene-butadiene copolymer, etc. One or a combination of two or more polymers, or a combination of one or more of gold, nickel, silver, copper, zinc, tin, indium, palladium, aluminum, etc. Is preferably used. Also, the thickness of the metal thin film is not particularly limited, but if it is too thin, the connection becomes unstable when an anisotropic conductive adhesive is used, and if it is too thick, aggregation occurs. In this case, since there is a possibility of causing insulation failure, 0.01 to 10 μm is preferable. Further, since the connection becomes unstable if the metal thin film is uneven or chipped, it is preferable that the metal thin film is uniformly coated. The particle size, material, and blending amount of the conductive particles can be appropriately selected depending on the pitch and pattern of the circuit to be connected, the thickness and material of the circuit terminal, and the like.

  It is preferable that the compounding quantity of electroconductive particle (H) is 0.1-10 volume% with respect to the epoxy resin composition before electroconductive particle mixing | blending. If the blending amount exceeds 10% by volume, the absolute amount of conductive particles in the anisotropic conductive adhesive increases, so that the insulation between the adherend connection terminals may be extremely lowered. Further, if the amount is less than 0.1% by volume, the absolute amount of conductive particles in the anisotropic conductive adhesive decreases, so that the conductive particles on the adherend connection terminal are insufficient, and the connection resistance value is extremely low. May be higher.

  The resin composition (substantial adhesive composition) which is the main component of the thermosetting adhesive of the present invention is prepared by stirring and mixing the above-described components with a mixer such as a blender. . Although the temperature at the time of stirring and mixing changes also with the kind of hardening | curing agent to mix | blend, the kind of hardening catalyst, etc., it is usually preferable to set to about 10-60 degreeC. If the set temperature at the time of preparation is less than 10 ° C., the viscosity may be too high and uniform stirring and mixing operations may be difficult. Conversely, if the temperature at the time of preparation is too high, a curing reaction will occur and normal epoxy will be used. Since a resin composition may not be obtained, it is not preferable. When stirring and mixing, a general-purpose device such as a uniaxial or multi-axial extruder, kneader, or dissolver equipped with a decompression device may be used, for example, by stirring and mixing for about 10 minutes. .

  The thermosetting adhesive of the present invention is applied to the surface of an adherend such as an electronic component such as a substrate or a wiring board, and the adherends are overlapped and cured by heat to adhere the adherend. be able to. The electronic component attached to the adhesive is not particularly limited. For example, a semiconductor element, a semiconductor device, a printed circuit board, a liquid crystal display (LCD) panel, a plasma display (PDP) panel, an electroluminescence (EL) panel, a field emission display. (FED) panel etc. are mentioned.

  The temperature at the time of hardening is 30-240 degreeC, for example, Preferably it is 35-200 degreeC. Curing may be performed in two stages. For example, when thermosetting using a thermal cationic polymerization initiator, after first curing at a temperature of 30 to 100 ° C (preferably 30 to 80 ° C), 110 to 240 ° C (preferably 120 to 200 ° C). A cured product having good physical properties such as transparency and heat resistance can be obtained by secondarily curing at a temperature of 2 ° C. Moreover, especially when joining and adhesion | attachment of an electronic component, 70-200 degreeC is preferable, More preferably, it is 75-190 degreeC, More preferably, it is 80-180 degreeC. The curing time is preferably 5 to 1200 seconds, more preferably 10 to 900 seconds, and still more preferably 15 to 600 seconds in order to avoid the influence of heating of the electronic components to be joined. In this way, an adhesive body such as an electronic device having excellent reliability is provided.

[Active energy ray-curable adhesive]
The adhesive of the present invention contains a photopolymerization initiator (D) when used as an active energy ray-curable adhesive. The photopolymerization initiator (D) in the present invention is a compound (photocation polymerization initiator) that generates a cationic species by irradiation with active energy rays such as ultraviolet rays to initiate polymerization, and includes, for example, the following formulas (I) to (I): Mention may be made of hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts and other cationic polymerization initiators represented by XV).

(In the above formula, Ar represents an aryl group such as a phenyl group, and X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ ).

(In the above formula, R ³⁹ represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and r represents an integer of 0 to 3. X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF. ₆ ^- represents a)

(In the above formula, Y ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ or SbF ₅ (OH) ⁻ ).

(In the formula, X ^- is PF ₆ ^-, SbF ₆ ^- or AsF ₆ ^- represents a)

(In the formula, X ^- is PF ₆ ^-, SbF ₆ ^- or AsF ₆ ^- represents a)

（上記式中、Ｘ^-はＰＦ₆ ^-、ＳｂＦ₆ ^- 又はＡｓＦ₆ ^-を表す）

(In the formula, X ^- is PF ₆ ^-, SbF ₆ ^- or AsF ₆ ^- represents a)

(In the above formula, R ⁴⁰ represents an aralkyl group having 7 to 15 carbon atoms or an alkenyl group having 3 to 9 carbon atoms, R ⁴¹ represents a hydrocarbon group or hydroxyphenyl group having 1 to 7 carbon atoms, R ⁴² represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom,
X ^- is PF ₆ ^- represents a) ^-, SbF ₆ ^- or AsF ₆

(In the above formula, R ⁴³ and R ⁴⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms)

(In the above formula, R ⁴⁵ and R ⁴⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms)

  A commercial item can also be used as a photoinitiator (D). Commercially available products include, for example, UVACURE1591 (manufactured by Daicel Cytec Co., Ltd.), Irgacure 264 (manufactured by Ciba Geigy Co., Ltd.), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), Syracure UVI-6970, UVI-6974, UVI-6990 (all manufactured by Union Carbide, USA), SI-60L, SI-100L (all manufactured by Sanshin Chemical Industry), Optomer SP-150, SP-170, SP-152, SP-172, R-gen-BF1172 (manufactured by Double Bond Chemical), Irgacure 250 (manufactured by Ciba Specialty Chemical), UV1240, UV1241, UV2257 (manufactured by Doitron) and the like can be mentioned.

  The blending amount of the photopolymerization initiator (D) is 100 parts by weight of the epoxy resin (A) (provided that the acrylic resin (E) and / or the caprolactone-modified polyol compound (F) is contained) ), Acrylic resin (E) and caprolactone-modified polyol compound (F) in a total amount of 100 parts by weight), preferably 0.01 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 1 -10 parts by weight. That is, for example, when only (A) is used among the components (A), (E), and (F) in the active energy ray-curable adhesive of the present invention, the amount of the component (A) is 100 parts by weight. In the case where the component (E) and / or the component (F) is used together with the component (A), the total amount of (A), (E) and (F) is preferable. It is preferable to make it the said compounding quantity range with respect to 100 weight part.

  The acrylic resin (E) in the present invention is an acrylic resin having an epoxy group or an acrylic resin having an epoxy group and a hydroxyl group. The acrylic resin (E) can be obtained by polymerizing a monomer containing an epoxy group or copolymerizing a monomer containing an epoxy group and a monomer containing a hydroxyl group. Examples of the monomer containing an epoxy group include glycidyl ether, a compound having a similar terminal epoxy, a (meth) acrylic acid ester having an alicyclic epoxy group, and the like. Specific examples include glycidyl methacrylate, 2-methyl-glycidyl methacrylate, epoxidized isoprenyl methacrylate, “CYM M-100” and “CYM A-400” [manufactured by Daicel Chemical Industries, Ltd.]. On the other hand, examples of the monomer containing a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and monomers obtained by modifying these hydroxyl group-containing acrylates with caprolactone [trade names “FM-1”, “FM-3”, “ FM-10 "," FA-1 "," FA-3 "; manufactured by Daicel Chemical Industries, Ltd.].

  In the acrylic resin (E), as a monomer, in addition to a monomer containing an epoxy group and a monomer containing a hydroxyl group, other copolymerizable monomers can be used for copolymerization. Other copolymerizable monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-, i- or t-butyl acrylate, n-, i- or t-butyl methacrylate, hexyl acrylate, hexyl methacrylate Alkyl or cycloalkyl esters of 1 to 24 carbon atoms of acrylic acid or methacrylic acid such as, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc .; 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate A hydroxyalkyl ester of 1 to 8 carbon atoms of acrylic acid or methacrylic acid such as relate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate; α, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid β-ethylenically unsaturated carboxylic acid; acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-butoxymethyl Acrylamide or methacrylamide such as acrylamide or derivatives thereof; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene; vinyl propionate, vinyl acetate, Acrylonitrile, methacrylonitrile, vinyl pivalate, veova monomer (manufactured by Shell Chemical Co., Ltd., vinyl ester of branched fatty acid), silaplane FM0711, FM0721, FM0725 (all of which are manufactured by Chisso, polydimethylsiloxane having a methacryloyl group at the terminal) Macromonomer) and other vinyl monomers. As the other copolymerizable monomer, among these, acrylic acid or methacrylic acid alkyl having 1 to 24 carbon atoms (particularly having 1 to 12 carbon atoms) is preferred.

  The acrylic resin (E) is a monomer component composed of the above-mentioned epoxy group-containing monomer, or an epoxy group-containing monomer and a hydroxyl group-containing monomer, and other monomers that can be copolymerized as necessary, for example, in the presence of a radical polymerization initiator or In the absence, it can be obtained by polymerization by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like. When synthesizing the acrylic resin (E) by solution polymerization, the epoxy resin (A) is preferably used as a solvent. The monomer may be dissolved in an organic solvent such as toluene and added to the polymerization system. When an epoxy resin (A) is used as a solvent, a mixture of an acrylic resin (E) obtained by polymerization and the epoxy resin (A) (when an organic solvent such as toluene is used, the organic solvent is distilled off. The concentrate obtained as described above can be used as it is for the preparation of the adhesive of the present invention. In this case, the ratio (weight ratio) between the acrylic resin (E) and the epoxy resin (A) is not particularly limited, but is preferably about 10/90 to 50/50, for example. When the ratio is too small, the effect of improving the strength due to the blending of the acrylic resin (E) tends to be low, and conversely, when the ratio is too large, the viscosity of the composition increases and the workability tends to deteriorate.

  Examples of the polymerization initiator include potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, Lauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, AIBN (2,2′- Azobisisobutyronitrile), ABN-E (2,2′-azobis (2-methylbutyronitrile)), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile)), perbutyl O (t-butylperoxy 2-ethylhexanoate) It can be used.

  The amount of the polymerization initiator used is preferably 1 to 10 parts by weight, more preferably 3 to 6 parts by weight with respect to 100 parts by weight of the monomer. A part of the polymerization initiator may be charged in the reactor in advance, or may be added to the monomer or dropped separately without being added. Further, after the monomer is charged, a polymerization initiator may be additionally charged.

  The polymerization temperature is preferably 90 to 130 ° C, more preferably 100 to 120 ° C. When the temperature is 130 ° C. or higher, polymerization may become unstable and a large amount of high molecular weight compounds may be produced, which may be undesirable. On the other hand, at 90 ° C. or lower, the polymerization time may be long.

The blending ratio of each monomer component in the polymerization of the acrylic resin (E) is preferably in the following range with respect to 100 parts by weight of the total amount of monomer components.
Epoxy group-containing monomer: 3 to 45 parts by weight (preferably 5 to 40 parts by weight)
Hydroxyl group-containing monomer: 3 to 45 parts by weight (preferably 5 to 40 parts by weight)
Other monomer: 94 to 10 parts by weight (preferably 90 to 20 parts by weight)

  The number average molecular weight of the acrylic resin (E) is, for example, 1,000 to 100,000, preferably 1500 to 30,000.

  The amount of the epoxy group in the acrylic resin (E) is preferably 6 to 11% when the oxirane oxygen concentration is the sum of the epoxy compound having cationic polymerizability and the acrylic resin having a functional group that reacts with the cationic species, More preferably, it is 7.5 to 9.5%. Moreover, the amount of the hydroxyl group in the acrylic resin having a hydroxyl group in addition to the epoxy group is preferably 1 to 300 mg-KOH / g, more preferably 1.5 to 250 mg-KOH / g as a hydroxyl value.

  1-85 weight part is preferable with respect to 100 weight part of epoxy resins (A), as for the compounding quantity of an acrylic resin (E), More preferably, it is 3-70 weight part, More preferably, it is 5-60 weight part. When the blending amount is less than 1 part by weight, the blending effect (strength improving effect) of the acrylic resin (E) may not be obtained. When the blending amount exceeds 85 parts by weight, the adhesive strength of the resulting cured product decreases. There is.

  The polyol compound (F) in the present invention is a caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule. Specifically, the following are exemplified. As those having two hydroxyl groups, "PCL-205", "PCL-212", "PCL-240", "PCL-L208AL", "PCL-L220AL", "PCL-220EC", "PCL-CD220PL" , “PCL-CD210HL” [manufactured by Daicel Chemical Industries, Ltd.]. As those having 3 hydroxyl groups, “PCL-303”, “PCL-308”, “PCL-L320AL” [manufactured by Daicel Chemical Industries, Ltd.], and those having 4 hydroxyl groups as “PCL- 410 ”,“ PCL-420D ”[manufactured by Daicel Chemical Industries, Ltd.].

  1-50 weight part is preferable with respect to 100 weight part of epoxy resins (A), as for the compounding quantity of a polyol compound (F), More preferably, it is 3-45 weight part, More preferably, it is 5-40 weight part. When the blending amount is less than 1 part by weight, the blending effect (strength improving effect) of the polyol compound (F) may not be obtained. When the blending amount exceeds 50 parts by weight, the adhesive strength of the resulting cured product decreases. There is.

  In addition to the above (A), (D), (E), and (F), the energy ray curable adhesive of the present invention includes, if necessary, a sensitizer; an amount of coloring pigment that does not significantly inhibit curing Pigments such as extender pigments and dyes; polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, modified resins such as epoxidized polybutadiene resins; organic resin fine particles; solvents and the like can be blended.

  The sensitizer is blended for the purpose of further improving the curability by active energy rays, and examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. The blending amount of the sensitizer is usually preferably 10 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the epoxy resin (A).

When the modified resin is blended, the modified resin is usually preferably 0.1 to 50 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
It is preferable.

  Various surfactants can be added to prevent leveling and improve coating performance. As the surfactant, silicon compounds and fluorine compounds can be used.

  It is also possible to use organic resin fine particles. The organic resin fine particles are preferably organic resin fine particles having a particle diameter in the range of 50 to 500 nm, and examples thereof include acrylic resin fine particles whose inside is three-dimensionally cross-linked. Organic resin fine particles are obtained by pulverizing an organic polymer into fine particles; polymer fine particles obtained by emulsion polymerization in water in the presence of an emulsifier; dried and pulverized; organic in the presence of a polymer stabilizer. Examples thereof include those obtained by drying and pulverizing polymer fine particles obtained by dispersion polymerization in a solvent. By blending organic resin fine particles with the adhesive of the present invention, the adhesion and workability of the coating film can be improved. When the organic resin fine particles are blended, the blending amount of the organic resin fine particles is usually preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A). It is.

  In the active energy ray-curable adhesive, the elastomer (G) can be blended as in the case of the thermosetting adhesive. The compounding amount of the elastomer (G) is the same as described above. In addition, various additives described in the section of the thermosetting adhesive can also be added. Furthermore, like the thermosetting adhesive, the conductive particles (H) can be dispersed in the energy ray curable adhesive and used as an anisotropic conductive adhesive. The compounding quantity of electroconductive particle (H) is the same as that of the above.

  The active energy ray-curable adhesive of the present invention can be prepared by mixing the components described above and stirring the mixture so as to form a uniform adhesive. For example, it can be prepared by mixing each component, heating as necessary, for example, at about 50 ° C., and stirring for about 10 minutes until uniform with a stirrer such as a dissolver. it can.

  The active energy ray-curable adhesive of the present invention is applied to the surface of an adherend by a method such as roll coating, spray coating, brush coating, bar coating, roller coating, silk screen printing, and the like. Can be bonded to each other by irradiating active energy rays and curing the adhesive. When the adhesive contains a solvent, after the application, the solvent is removed by heating or the like, and then cured by irradiation with active energy rays. Irradiation conditions can be changed as appropriate according to the type and thickness of the applied adhesive. As the active energy ray to be irradiated, ultraviolet rays are preferable, and the wavelength is usually within the range of 200 to 600 nm, and an irradiation source having a sensitive wavelength is appropriately selected according to the type of the cationic polymerization initiator. You can select and use.

When ultraviolet rays are used as the active energy ray, examples of the irradiation source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. Irradiation condition to the coating film, usually, a dose of preferably 10~1000mJ / cm ^2, more preferably 50 to 500 mJ / cm ^2.

  Moreover, you may heat an adhesive agent as needed after active energy ray irradiation. By heating, unreacted substances in the adhesive can be reduced, and the curability of the coating film by irradiation with active energy rays and the distortion generated by the molding process can be reduced. In some cases, the heating can improve the hardness and adhesion of the adhesive. The said heating can be normally performed on the conditions for 1 to 30 minutes at the atmospheric temperature of 150-200 degreeC.

  The active energy ray-curable adhesive of the present invention can be used for metals such as glass and aluminum, synthetic resins such as PET, semi-synthetic resins such as acetylcellulose, and the like. Among these, it is preferably used for a thin film material such as a film. In addition, it exhibits excellent adhesion between inorganic materials such as glass and different materials such as resins such as PET and acetylcellulose.

  By bonding the two or more adherends using the active energy ray-curable adhesive of the present invention, an adhesive having excellent adhesion reliability can be obtained. Although it does not specifically limit as a use of the adhesive body of this invention, The display apparatus of portable apparatuses, such as a liquid crystal panel of a mobile telephone, etc. are mentioned.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Analysis method]
(1) Gas chromatography (GC analysis) of bicyclohexyl-3,3'-diene and its isomers
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 60m, inner diameter 0.32mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 2.6 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 250 ° C
Temperature rise pattern (column): Hold at 60 ° C. for 5 minutes, temperature rise to 300 ° C. at 10 ° C./minute Split ratio: 100
Sample: 1 μl
The ratio of bicyclohexyl-3,3'-diene and its isomer was determined as follows. That is, the GC analysis was performed under the above conditions, and the area of the maximum peak (bicyclohexyl-3,3′-diene) appearing around a retention time of 20.97 minutes and the peak around 20.91 minutes (isomers) appearing just before that ), The content ratio of the isomer to the bicyclohexyl-3,3′-diene was determined. That is, the isomer ratio (%) is calculated as isomer area ÷ (isomer area + bicyclohexyl-3,3′-diene area) × 100.

(2) Gas chromatography (GC analysis) of 3,4,3 ', 4'-diepoxybicyclohexyl and its isomers
Measuring device: HP6890 (manufactured by Hewlett-Packard Company)
Column: HP-5, length 30 m, film thickness 0.25 μm, inner diameter 0.32 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Carrier gas: Nitrogen Carrier gas flow rate: 1.0 ml / min Detector: FID
Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Temperature rise pattern (column): Hold at 100 ° C. for 2 minutes, heat up to 300 ° C. at 5 ° C./minute, hold at 300 ° C. for 10 minutes Split ratio: 100
Sample: 1 μl (epoxy compound: acetone = 1: 40)
The ratio of 3,4,3 ', 4'-diepoxybicyclohexyl and its isomer was determined as follows. That is, the GC analysis was performed under the above conditions, and two maximum peaks appearing around a retention time of 19.8 minutes to 20.0 minutes (two (main) peaks having the longest retention time among the peaks of the compound having the same molecular weight) [3 , 4,3 ', 4'-diepoxybicyclohexyl (the two peaks are due to the presence of isomers based on the steric positional relationship between the oxirane oxygen bonded to the cyclohexane ring and the other cyclohexane ring) )] And three peaks near 19.1 to 19.5 minutes appearing immediately before that (peaks other than the two (main) peaks having the longest retention time among the peaks of the compound having the same molecular weight) ( The content ratio of the isomer to the 3,4,3 ′, 4′-diepoxybicyclohexyl was determined based on the total area of the isomer). That is, the isomer ratio (%) is calculated by (total isomer area) / (total isomer area + 3,4,3 ′, 4′-diepoxybicyclohexyl total area) × 100.

(3) GC-MS analysis of 3,4,3 ′, 4′-diepoxybicyclohexyl and its isomers Measuring apparatus: HP 6890 (GC part), 5973 (MS part) manufactured by Hewlett-Packard Company
Column: HP-5MS, length 30 m, film thickness 0.25 μm, inner diameter 0.25 mm
Liquid phase 5% -diphenyl-95% -dimethylpolysiloxane Temperature rising pattern (column): held at 100 ° C. for 2 minutes, heated to 300 ° C. at 5 ° C./minute, held at 300 ° C. for 18 minutes Inlet temperature: 250 ℃
MSD transfer line temperature: 280 ° C
Carrier gas: helium Carrier gas flow rate: 0.7 ml / min (constant flow)
Split ratio: Splitless Sample injection volume: 1.0 μl
Measurement mode: EI
Ion source temperature: 230 ° C
Quadrupole temperature: 106 ° C
MS range: m / z = 25-400
Sample preparation: 0.1 g of sample was dissolved in 3.0 g of acetone. The alicyclic diepoxy compound obtained in Synthesis Example 1 was subjected to GC-MS analysis. The results (gas chromatogram and MS spectrum of each component) are shown in FIGS. Retention times of 17.73 minutes, 17.91 minutes, and 18.13 minutes are the isomer peaks of 3,4,3 ', 4'-diepoxybicyclohexyl, 18.48 minutes, and 18.69 minutes. Are peaks of 3,4,3 ′, 4′-diepoxybicyclohexyl. Since the analysis conditions are slightly different from those in the case of the GC analysis, the retention time of each peak is different, but the appearance order is the same. FIG. 6 is an MS spectrum of a gas chromatogram and a peak at a retention time of 17.73 minutes, and FIG. 7 is an enlarged view thereof. FIG. 8 is an MS spectrum of a gas chromatogram and a peak at a retention time of 17.91 minutes, and FIG. 9 is an enlarged view thereof. FIG. 10 is an MS spectrum of a gas chromatogram and a peak at a retention time of 18.13 minutes, and FIG. 11 is an enlarged view thereof. FIG. 12 is a gas chromatogram and an MS spectrum of a peak having a retention time of 18.48 minutes, and FIG. 13 is an enlarged view thereof. FIG. 14 is a gas chromatogram and an MS spectrum of a peak having a retention time of 18.69 minutes, and FIG. 15 is an enlarged view thereof. According to the MS spectrum, any of the above components has a molecular ion peak of m / z = 194.

で表される水添ビフェノール（＝４，４′−ジヒドロキシビシクロヘキシル）１０００ｇ（５．０５モル）、上記で調製した脱水触媒１２５ｇ（硫酸として０．６８モル）、プソイドクメン１５００ｇを入れ、フラスコを加熱した。内温が１１５℃を超えたあたりから水の生成が確認された。さらに昇温を続けてプソイドクメンの沸点まで温度を上げ（内温１６２〜１７０℃）、常圧で脱水反応を行った。副生した水は留出させ、脱水管により系外に排出した。なお、脱水触媒は反応条件下において液体であり反応液中に微分散していた。３時間経過後、ほぼ理論量の水（１８０ｇ）が留出したため反応終了とした。反応終了液を１０段のオールダーショウ型の蒸留塔を用い、プソイドクメンを留去した後、内部圧力１０Ｔｏｒｒ（１．３３ｋＰａ）、内温１３７〜１４０℃にて蒸留し、７３１ｇのビシクロヘキシル−３，３′−ジエンを得た。ＧＣ分析の結果、得られたビシクロヘキシル−３，３′−ジエン中にはその異性体が含まれており（ＧＣ−ＭＳ分析により確認）、下記式（２ａ）

で表されるビシクロヘキシル−３，３′−ジエンとその異性体の含有比は９１：９であった（図５参照）。
得られたビシクロヘキシル−３，３′−ジエン（異性体を含む）２４３ｇ、酢酸エチル７３０ｇを反応器に仕込み、窒素を気相部に吹き込みながら、かつ、反応系内の温度を３７．５℃になるようにコントロールしながら約３時間かけて３０重量％過酢酸の酢酸エチル溶液（水分率０．４１重量％）２７４ｇを滴下した。過酢酸溶液滴下終了後、４０℃で１時間熟成し反応を終了した。さらに３０℃で反応終了時の粗液を水洗し、７０℃／２０ｍｍＨｇで低沸点化合物の除去を行い、脂環式エポキシ化合物２７０ｇを得た。このときの収率は９３％であった。粘度（２５℃）を測定したところ、８４ｍＰａ・ｓであった。得られた脂環式エポキシ化合物のオキシラン酸素濃度は１５．０重量％であった。また¹Ｈ−ＮＭＲの測定では、δ４．５〜５ｐｐｍ付近の内部二重結合に由来するピークが消失し、δ３．１ｐｐｍ付近にエポキシ基に由来するプロトンのピークの生成が確認され、下記式（１ａ）

で表される３，４，３′，４′−ジエポキシビシクロヘキシルであることが確認された。ＧＣ分析の結果、得られた脂環式エポキシ化合物中には３，４，３′，４′−ジエポキシビシクロヘキシルとその異性体が含まれており、異性体比率は９％であった（図１参照）。なお、異性体比率は次式により算出した。
異性体比率＝（２２６２＋１７１５＋５７０２）÷（２２６２＋１７１５＋５７０２ ＋２８５１４＋７４５８７）×１００＝９％ Synthesis Example 1 (Synthesis of alicyclic diepoxy compound; isomer ratio 9%)
A dehydration catalyst was prepared by stirring and mixing 70 g (0.68 mol) of 95 wt% sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
The following formula (3a) was added to a 3 liter flask equipped with a stirrer, a thermometer, and a dehydration pipe and a heated distillation pipe.

1000 g (5.05 mol) of hydrogenated biphenol (= 4,4′-dihydroxybicyclohexyl) represented by the above, 125 g of the dehydration catalyst prepared above (0.68 mol as sulfuric acid), and 1500 g of pseudocumene were added, and the flask was heated. did. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the temperature to the boiling point of pseudocumene (internal temperature 162 to 170 ° C.), and dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After about 3 hours, almost theoretical amount of water (180 g) was distilled, and the reaction was terminated. Pseudocumene was distilled off using a 10-stage Oldershaw type distillation column, and the reaction-terminated liquid was distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 137 to 140 ° C. to obtain 731 g of bicyclohexyl-3. , 3'-diene was obtained. As a result of GC analysis, the obtained bicyclohexyl-3,3′-diene contained the isomer (confirmed by GC-MS analysis), and the following formula (2a)

The content ratio of bicyclohexyl-3,3′-diene represented by the formula (1) and its isomer was 91: 9 (see FIG. 5).
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of an alicyclic epoxy compound. The yield at this time was 93%. It was 84 mPa * s when the viscosity (25 degreeC) was measured. The oxirane oxygen concentration of the obtained alicyclic epoxy compound was 15.0% by weight. Further, in the measurement of ¹ H-NMR, the peak derived from the internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and the generation of a proton peak derived from the epoxy group was confirmed in the vicinity of δ3.1 ppm. 1a)

It was confirmed that it was 3,4,3 ′, 4′-diepoxybicyclohexyl represented by the following formula. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ′, 4′-diepoxybicyclohexyl and its isomer, and the isomer ratio was 9% ( (See FIG. 1). The isomer ratio was calculated by the following formula.
Isomeric ratio = (2262 + 1715 + 5702) ÷ (2262 + 1715 + 5702 + 28514 + 74587) x 100 = 9%

Synthesis Example 2 (Synthesis of alicyclic diepoxy compound; isomer ratio 14%)
Into a 3 liter flask equipped with a stirrer, a thermometer, a dehydration tube and a heated distillation pipe, hydrogenated biphenol 840 g (4.24 mol), phosphoric acid 170 g (1.73 mol), undecane 2350 g And the flask was heated. The generation of water was confirmed when the internal temperature exceeded 110 ° C. The temperature was further raised to raise the temperature to the boiling point of undecane (internal temperature 189 to 194 ° C.), and a dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. In addition, p-toluenesulfonic acid was completely dissolved in the reaction solution under the reaction conditions. After about 5 and a half hours, the reaction was terminated because almost the theoretical amount of water (150 g) was distilled. After the reaction was completed, the undecane was distilled off using a 10-stage Oldershaw type distillation column, and then distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 138 to 141 ° C. to obtain 474.2 g of bicyclohexyl. -3,3'-diene was obtained. As a result of GC analysis, the resulting bicyclohexyl-3,3'-diene contained isomers, and the content ratio of bicyclohexyl-3,3'-diene and isomers was 87:13. .
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 261 g of an alicyclic epoxy compound. The yield at this time was 90%. It was 75 mPa * s when the viscosity (25 degreeC) was measured. The oxirane oxygen concentration of the obtained alicyclic epoxy compound was 15.0% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. , 3 ′, 4′-diepoxybicyclohexyl was confirmed. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ′, 4′-diepoxybicyclohexyl and its isomer, and the isomer ratio was 14% ( (See FIG. 2). The isomer ratio was calculated by the following formula.
Isomeric ratio = (2821 + 2108 + 6988) ÷ (2821 + 2108 + 6988 + 20792 + 54602) × 100 = 14%

Synthesis Example 3 (Synthesis of alicyclic diepoxy compound; isomer 17%)
In a 5 liter flask equipped with a stirrer, 20-stage Oldershaw type distillation column, thermometer, hydrogenated biphenol 1000 g (5.05 mol), ammonium hydrogen sulfate 40 g (0.265 mol), cumene 2800 g. And the flask was heated. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised, the reaction was continued while distilling by-product water from the top of the distillation column, the temperature was raised to the boiling point of cumene (internal temperature: 165 to 170 ° C.), and dehydration reaction was carried out at normal pressure. Ammonium hydrogen sulfate was a solid under the reaction conditions, and most of it was not dissolved in the reaction solution. After 6 and a half hours, 94% of the theoretical amount of water (170.9 g) was distilled, and the reaction was terminated. After completion of the reaction, the inside of the system was depressurized to distill off cumene, and then the pressure was reduced to 10 Torr (1.33 kPa) and distilled at an internal temperature of 137 to 141 ° C. to obtain 590 g of bicyclohexyl-3,3′-diene. Obtained. As a result of GC analysis, the obtained bicyclohexyl-3,3'-diene contained isomers, and the content ratio of bicyclohexyl-3,3'-diene and isomers was 81:19. .
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 269 g of an alicyclic epoxy compound. The yield at this time was 92%. It was 69 mPa * s when the viscosity (25 degreeC) was measured. The obtained alicyclic epoxy compound had an oxirane oxygen concentration of 14.9% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. , 3 ′, 4′-diepoxybicyclohexyl was confirmed. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ', 4'-diepoxybicyclohexyl and its isomer, and the isomer ratio was 17% (Fig. 3). The isomer ratio was calculated by the following formula.
Isomeric ratio = (3668 + 2724 + 9033) ÷ (3668 + 2724 + 9033 + 20413 + 53424) × 100 = 17%

Comparative Synthesis Example 1
6 kg of hydrogenated biphenol and 620 g of potassium hydrogen sulfate were added to a 10-liter four-necked flask equipped with a stirrer, a 20-stage distillation column, and a thermometer. Subsequently, the flask was heated to 180 ° C., and after stirring the hydrogenated biphenol, stirring was started. The reaction was continued while distilling by-product water from the top of the distillation column, and after 3 hours, the pressure in the reaction system was reduced to 10 Torr (1.33 kPa), and water and bicyclohexyl-3,3'-diene were distilled. Distilled out of the system continuously from the top of the tower. The water and bicyclohexyl-3,3'-diene distilled off outside the system were separated into two layers with a decanter, and only the upper layer liquid was taken out. Thereafter, the reaction temperature was raised to 220 ° C. over 4 hours, and the reaction was terminated when the distillation of water and bicyclohexyl-3,3′-diene ceased. The yield of the distillate crude liquid of bicyclohexyl-3,3'-diene was 4507 g. 4500 g of the above dicyclohexyl-3,3′-diene distillate was put into a 5 liter four-necked flask equipped with a stirrer, 20-stage distillation column and thermometer, and heated to 180 ° C. with an oil bath. did. Thereafter, the pressure in the reaction system is reduced to 10 Torr (1.33 kPa), and water is distilled off, and then the temperature of the uppermost stage of the distillation column is maintained at 145 ° C., and bicyclohexyl-3, 3'-Diene was purified by distillation to obtain a colorless and transparent liquid. Yield was 4353 g. As a result of performing GC analysis on the liquid, the resulting bicyclohexyl-3,3'-diene contained isomers, and the content ratio of bicyclohexyl-3,3'-diene and isomers was 80. : 20.
243 g of the obtained bicyclohexyl-3,3′-diene (including isomer) and 730 g of ethyl acetate were charged into the reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was 37.5 ° C. 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over a period of about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 267 g of an alicyclic epoxy compound. The yield at this time was 92%. It was 63 mPa * s when the viscosity (25 degreeC) was measured. The obtained alicyclic epoxy compound had an oxirane oxygen concentration of 14.9% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. , 3 ′, 4′-diepoxybicyclohexyl was confirmed. As a result of GC analysis, the obtained alicyclic epoxy compound contained 3,4,3 ', 4'-diepoxybicyclohexyl and its isomer, and the isomer ratio was 21% (Fig. 4). The isomer ratio was calculated by the following formula.
Isomeric ratio = (5404 + 3923 + 13067) ÷ (5404 + 3923 + 130 67 + 23563 + 60859) × 100 = 21%

Synthesis Example 4 [Synthesis of acrylic resin (E-1)]
In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name “CEL-2021P” manufactured by Daicel Chemical Industries, Ltd.) 233g was charged. Then, the temperature was raised to 105-110 ° C. while blowing air, 55 g of methyl methacrylate, 15 g of n-butyl methacrylate, 20 g of hydroxyethyl methacrylate, 10 g of “CYM M-100” (manufactured by Daicel Chemical Industries), azobisisobuty 3 g of ronitrile and 0.3 g of paramethoxyphenol were added dropwise over 3 hours. After completion of dropping, the reaction was terminated by stirring for 1 hour to obtain an acrylic resin (E-1) having an epoxy group and a hydroxyl group. The acrylic resin (E-1) had a hydroxyl value of 23.6 KOHmg / g and an oxirane oxygen concentration of 8.0% by weight.

Synthesis Example 5 [Synthesis of acrylic resin (E-2)]
Monomers added to CEL-2021P (233 g) were changed to 65 g of methyl methacrylate, 10 g of n-butyl methacrylate, 15 g of hydroxyethyl methacrylate, 10 g of glycidyl methacrylate, 3 g of azobisisobutyronitrile, and 0.3 g of paramethoxyphenol. Acrylic resin (E-2) was obtained in the same manner as in Synthesis Example 4 except for the above. The hydroxyl value of the acrylic resin (E-2) was 18.3 KOHmg / g, and the oxirane oxygen concentration was 8.5% by weight.

Synthesis Example 6 [Synthesis of Alicyclic Epoxy Compound Represented by Formula (4) above]
In a 10 liter reactor equipped with a 10-stage distillation column, 6110 g of 3-cyclohexenylmethyl-3-cyclohexenecarboxylate as a starting material and 400 g of 1,4-cyclohexanedimethanol were charged and dissolved at 90 ° C. After confirmation of dissolution, tetrabutoxy titanate was charged in an amount corresponding to 30 ppm by weight with respect to the starting material, and the pressure was reduced to 170 ° C. and 8 torr (1.06 kPa). The reaction was carried out while distilling by-produced 3-cyclohexenylmethanol, and when the distillation of 3-cyclohexenylmethanol almost stopped, the heating was stopped and the transesterification reaction was terminated. Then, it washed with water for 1 hour at 60 degreeC using the ion exchange water 1.0 weight times of the reaction crude liquid, and left still for 30 minutes. After separation of the aqueous layer, 3-cyclohexenylmethyl-3-cyclohexenecarboxylate and 3-cyclohexenylmethanol remaining in the washing solution at a jacket temperature of 177 ° C. and a pressure of 4.5 torr (0.60 kPa) in a thin film evaporator. By distilling off, 838 g of an alicyclic diolefin polyvalent ester compound was obtained. The hue (APHA) of this compound was 60.
Next, 100 g of the obtained alicyclic diolefin polyvalent ester compound and 300 g of ethyl acetate were charged into a 1-liter jacketed flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, and nitrogen was vapor-phased. 186 g of a substantially anhydrous ethyl acetate solution of peracetic acid (peracetic acid concentration 29.1%, water content 0.41%) over about 2 hours while maintaining the temperature in the reaction system at 40 ° C. Was dripped. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 4 hours. The reaction crude liquid was washed with water at 30 ° C. and deboiling was performed at 70 ° C. and 30 torr (3.99 kPa) to obtain 207.0 g of an alicyclic epoxy compound represented by the formula (4). The obtained alicyclic epoxy compound had an oxirane oxygen concentration of 7.90%. ^{From 1} H-NMR analysis, it was confirmed that a peak derived from a double bond around δ 5.0 to 5.8 almost disappeared, and a proton peak derived from an epoxy group was found around δ 2.9 to 3.3. It was.

Examples 1-5, Comparative Examples 1-2
A thermosetting adhesive was prepared at a blending ratio described in Table 1, and each physical property was measured as follows. The blending of each component was carried out by mixing with stirring for 20 minutes at room temperature using “Foam Extracting Taro” manufactured by Shinky Corporation. The results are shown in Table 1.

The abbreviations in the table are as follows.
Synthetic Example 1: Cycloaliphatic diepoxy compound obtained in Synthetic Example 1 Synthetic Example 2: Cycloaliphatic diepoxy compound obtained in Synthetic Example 2 Comparative Synthetic Example 1: Cycloaliphatic diepoxy compound obtained in Comparative Synthetic Example 1 YD-128: “YD-128” (liquid bisphenol A type epoxy resin) manufactured by Tohto Kasei Kogyo Co., Ltd.
Epicoat 806: “Epicoat 806” (liquid bisphenol F type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.
EXA-4700: “EXA-4700” (naphthalene-based tetrafunctional epoxy resin) manufactured by Dainippon Ink & Chemicals, Inc.
Phenol resin: “PSM-4327” manufactured by Gunei Chemical Industry Co., Ltd. (softening point: 93 to 97 ° C.)
TPP: Triphenylphosphine SI-100L: “SI-100L” (thermal cationic polymerization initiator) manufactured by Sanshin Chemical Industry Co., Ltd.

(Heat resistance test 1)
The adhesives of Examples 1 to 4 and Comparative Example 2 prepared according to Table 1 were subjected to primary curing at 100 ° C. for 3 hours, and then subjected to secondary curing at 150 ° C. for 3 hours to prepare samples. The glass transition point Tg (° C.) of this cured product was measured by TMA (thermomechanical analysis) under the condition of a temperature rising rate of 5 ° C./min. As a measuring device, “TMA / SS6000” (manufactured by Seiko Instruments Inc.) was used. As the linear expansion coefficient (linear expansion coefficient: ppm / ° C.), an average value of dimensional change from 50 ° C. to 200 ° C. of TMA (thermomechanical analysis) measured at a heating rate of 5 ° C./min was taken.

(Heat resistance test 2)
The adhesives of Example 5 and Comparative Example 1 prepared according to Table 1 were subjected to primary curing at 45 ° C. for 2 hours, and then subjected to secondary curing at 150 ° C. for 1 hour to prepare samples. The glass transition point Tg (° C.) of this cured product was measured by TMA (thermomechanical analysis) under the condition of a temperature rising rate of 5 ° C./min. As a measuring device, “TMA / SS6000” (manufactured by Seiko Instruments Inc.) was used. As the linear expansion coefficient (linear expansion coefficient: ppm / ° C.), an average value of dimensional change from 50 ° C. to 200 ° C. of TMA (thermomechanical analysis) measured at a heating rate of 5 ° C./min was taken.

(Measurement of adhesive strength)
As the adherend, an FPC (pitch: 150 μm, number of terminals: 400) and a glass substrate (manufactured by Matsushita Electric Works Co., Ltd.) obtained by applying Ni / Au plating to copper foil / polyimide = 8 μm / 38 μm were used. On the adherend, the thermosetting adhesives obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were transferred by a transfer method, pressure-bonded under conditions of 160 ° C., 3 MPa, and 10 seconds, and a 90 ° peel test. The adhesive strength (kPa) was measured by (according to JIS 6854-1).

  As shown in Table 1, the cured products obtained by curing the thermosetting adhesives of the examples are more resistant to heat and the cured products obtained by curing the thermosetting adhesives of the comparative examples. Excellent adhesion.

Examples 6-7, Comparative Examples 3-4
Thermosetting adhesives were prepared at the compounding ratios listed in Table 2. In the preparation, 30 parts by weight of toluene was used as a solvent with respect to 100 parts by weight of the resin composition. After this adhesive resin is mixed and uniformly dispersed, it is cast and dried on a polyethylene terephthalate film subjected to a release treatment so that the thickness after drying is 15 μm, and then cut to a width of 1.5 mm. An anisotropic conductive adhesive was obtained. The following physical properties of this adhesive were measured. The results are shown in Table 2.

The abbreviations in the table are as follows.
Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane conductive particles: manufactured by Nippon Chemical Industry Co., Ltd., gold-nickel plating resin powder “GRN-MX” (particle diameter 20 μm)
Other abbreviations are the same as described above.

(Measurement of adhesive strength)
As the adherend, an FPC (pitch: 150 μm, number of terminals: 400) and a glass substrate (manufactured by Matsushita Electric Works Co., Ltd.) obtained by applying Ni / Au plating to copper foil / polyimide = 8 μm / 38 μm were used. The thermosetting adhesives obtained in Examples 6 to 7 and Comparative Examples 3 to 4 were transferred onto the adherend by a transfer method, and pressure-bonded under conditions of 160 ° C., 3 MPa, and 10 seconds, and a 90 ° peel test. The adhesive strength (kPa) was measured by (according to JIS 6854-1).

(Measurement of connection reliability)
As the adherend, an FPC (pitch: 150 μm, number of terminals: 400) and a glass substrate (manufactured by Matsushita Electric Works Co., Ltd.) obtained by applying Ni / Au plating to copper foil / polyimide = 8 μm / 38 μm were used. On the adherend, the thermosetting adhesives obtained in Examples 6 to 7 and Comparative Examples 3 to 4 were transferred by a transfer method and pressure-bonded under conditions of 160 ° C., 3 MPa, and 10 seconds to produce a sample. did. The connection resistance was measured by the two-terminal method immediately after sample preparation and after leaving at a temperature of 85 ° C., a humidity of 85% and 800 hours. Those that could not be measured were defined as OPEN (conducting failure). In the table, ◯ indicates conduction and x indicates conduction failure.

  As shown in Table 2, the thermosetting adhesives of the examples had excellent adhesiveness and connection reliability. On the other hand, the thermosetting adhesive of the comparative example was inferior in adhesiveness and connection reliability.

Examples 8-11 and Comparative Examples 5-8
Each component shown in Table 3 was added to a 500 ml flask equipped with a stirrer and a thermometer, and stirred at 30 ° C. for 20 minutes to obtain an active energy ray-curable adhesive. The adhesive strength of each adhesive was measured by the following method to evaluate the adhesive strength. The results are shown in Tables 4-8.

The abbreviations in the table are as follows.
Synthesis Example 3: Alicyclic diepoxy compound obtained in Synthesis Example 3 Comparative Synthesis Example 1: Alicyclic diepoxy compound obtained in Comparative Synthesis Example 1 Synthesis Example 4: Acrylic resin obtained in Synthesis Example 4 [Acrylic resin (E-1) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate mixture]
Synthesis Example 5: Acrylic resin obtained in Synthesis Example 5 [A mixture of acrylic resin (E-2) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate]
Synthesis Example 6: Alicyclic epoxy compound obtained in Synthesis Example 6 [alicyclic epoxy compound represented by the above formula (4)]
PCL308: “Placcel 308” manufactured by Daicel Chemical Industries, Ltd. (trifunctional polyester polyol; caprolactone-modified polyol compound)
PCL220EC: “Placcel 220EC” manufactured by Daicel Chemical Industries, Ltd. (bifunctional polyester polyol; caprolactone-modified polyol compound)
A-186: “NAC Silicon A-186” manufactured by Nippon Unicar Co., Ltd. [β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane]
L-7604: Nippon Unicar Co., Ltd. “L-7604” (surfactant)
UVACURE 1591: “UVACURE 1591” (photocation polymerization initiator) manufactured by Daicel-Cytec Co., Ltd.

(Measurement of adhesive strength)
In the case of glass, 1 mm thickness, Al plate (aluminum plate) 0.5 mm thickness, PET (polyester film) 200 μm thickness, Ac cell (acetylcellulose film) 200 μm thickness, and prepare 15 mm wide test pieces, The overlap length is 5 mm, the adhesive is applied to the overlap portion to a thickness of 20 μm, bonded and fixed while removing bubbles, and irradiated with a high-pressure mercury lamp 120 w × 10 m × 4 passes (irradiation amount 1200 mJ / cm ² ) The adhesive strength (kg / 15 mm) was measured with a tensile tester. All tests were performed at 23 ° C.
Measurements were made on combinations (5 items) of PET / PET, glass / glass, glass / PET, Al plate / PET, and glass / Ac cell, and the following cases were considered to have good adhesion in each item.
PET / PET: Adhesive strength of 14 kg / 15 mm or more, standard deviation of 5 times of measurement is less than 0.3 Glass / glass: Glass breaking Glass / PET: Adhesion strength of 13 kg / 15 mm or more, 5 times of measurement Standard deviation is less than 0.3 Al plate / PET: Adhesive strength of 16 kg / 15 mm or more, standard deviation at 5 times of measurement is less than 0.3 Glass / Ac cell: Film break

(Evaluation)
In each item, those satisfying the criteria were evaluated as satisfactory adhesiveness (◯), and those not satisfying the criteria were evaluated as an insufficient level (×) as an adhesive.

(Comprehensive evaluation)
Furthermore, among the above five items, all (5 items) are good when the adhesion is good (、 ４), when 4 items are good, the adhesion is good (◯), and when 3 items are not, the adhesion is not good. Sufficient (Δ), 2 or less cases were judged as poor adhesion (x). Note that Δ and × are insufficient levels for use as an adhesive.

  As shown in Tables 3 to 8, the active energy ray-curable adhesives of Examples 8 to 11 exhibited excellent adhesiveness. On the other hand, the active energy ray-curable adhesives of Comparative Examples 5 to 8 were inferior in performance due to insufficient adhesive force.

2 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 1. FIG. 3 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 2. FIG. 4 is a GC analysis chart of the alicyclic diepoxy compound obtained in Synthesis Example 3. 2 is a GC analysis chart of an alicyclic diepoxy compound obtained in Comparative Synthesis Example 1. FIG. 2 is a GC analysis chart of bicyclohexyl-3,3′-diene obtained in Synthesis Example 1. FIG. It is a gas chromatogram (upper figure) in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 17.73 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 17.73 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 17.91 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 17.91 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.13 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.13 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.48 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.48 minutes. It is a gas chromatogram (upper figure) in GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and MS spectrum (lower figure) of the peak of retention time 18.69 minutes. It is the enlarged view (upper figure) of the gas chromatogram in the GC-MS analysis of the alicyclic diepoxy compound obtained by the synthesis example 1, and the enlarged view (lower figure) of the MS spectrum of the peak of retention time 18.69 minutes.

Claims (20)

Following formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
Wherein the isomer content of the 3,4,3 ′, 4′-diepoxybicyclohexyl compound is 3,4,3 ′, 4′-diepoxybicyclohexyl compound. , 3 ′, 4′-diepoxy bicyclohexyl compound and its isomers, the alicyclic diepoxy compound (A1) having a peak area ratio of 20% or less by gas chromatography or the following formula (2) )

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group optionally having a halogen atom, or an alkoxy group optionally having a substituent. )
A bicyclohexyl-3,3′-diene compound represented by the formula: wherein the isomer content of the bicyclohexyl-3,3′-diene compound is such that the bicyclohexyl-3,3′-diene compound and its isomer The alicyclic diepoxy compound (A1 ′) obtained by epoxidizing an alicyclic diene compound having a peak area ratio of less than 20% by gas chromatography with respect to the total body, or the alicyclic A thermal or active energy ray-curable adhesive containing an epoxy resin (A) comprising a diepoxy compound (A1) or an alicyclic diepoxy compound (A1 ′) and another epoxy compound (A2). The adhesive according to claim 1, wherein all of R ^{1 to} R ^{18 in} formula (1) or formula (2) are hydrogen atoms.   The epoxy resin (A) is an alicyclic diepoxy compound (A1) or (A1 ′) 99 to 10% by weight and an epoxy compound (A2) 1 to 90% by weight [(A1) or (A1 ′) and (A2)] The adhesive according to claim 1 or 2, wherein the total is 100 wt%.   The epoxy resin (A) is an alicyclic diepoxy compound (A1) or (A1 ′) 80 to 10% by weight and an epoxy compound (A2) 20 to 90% by weight [(A1) or (A1 ′) and (A2)]. The adhesive according to claim 1 or 2, wherein the total is 100 wt%.   The adhesive according to any one of claims 1 to 4, which is a thermosetting adhesive containing a curing agent (B) together with the epoxy resin (A).   The adhesive according to claim 5, wherein the curing agent (B) is a phenol resin (B1) and further contains a curing accelerator (C).   The adhesive according to claim 5, wherein the curing agent (B) is a curing agent (B2) that acts as an initiator for releasing a substance that initiates cationic polymerization by heating.   The adhesive according to claim 7, wherein 0.05 to 20 parts by weight of the curing agent (B2) is blended with respect to 100 parts by weight of the epoxy resin (A).   The adhesive according to any one of claims 1 to 4, which is an active energy ray-curable adhesive containing an epoxy resin (A) and a photopolymerization initiator (D).   Furthermore, the adhesive agent of Claim 9 containing the acrylic resin (E) which has an epoxy group or an epoxy group, and a hydroxyl group, and / or the caprolactone modified polyol compound (F) which has 2-4 hydroxyl groups in a molecule | numerator.   The adhesive according to claim 10, wherein 1 to 85 parts by weight of the acrylic resin (E) is blended with 100 parts by weight of the epoxy group resin (A).   The adhesive according to claim 10, wherein 1 to 50 parts by weight of a caprolactone-modified polyol compound (F) having 2 to 4 hydroxyl groups in the molecule is blended with 100 parts by weight of the epoxy group resin (A).   When 100 parts by weight of the epoxy resin (A) includes an acrylic resin (E) and / or a caprolactone-modified polyol compound (F), the epoxy resin (A), the acrylic resin (E), and a caprolactone-modified polyol compound ( The adhesive according to any one of claims 9 to 12, wherein 0.01 to 20 parts by weight of the photopolymerization initiator (D) is blended with respect to 100 parts by weight of the total amount of F).   Furthermore, the adhesive agent in any one of Claims 1-13 containing an elastomer (G).   The adhesive according to any one of claims 1 to 14, which is an anisotropic conductive adhesive in which conductive particles (H) are dispersed in an adhesive.   The adhesive body formed using the adhesive agent in any one of Claims 1-15.   The adhesive body according to claim 16, which is an electronic device formed by joining electronic components with the adhesive according to claim 1.   The electronic component is any one of a semiconductor element, a semiconductor device, a printed circuit board, a liquid crystal display (LCD) panel, a plasma display (PDP) panel, an electroluminescence (EL) panel, or a field emission display (FED) panel. The adhesive body described.   A bonding method comprising bonding an adherend with the adhesive according to any one of claims 1 to 15.   The bonding method according to claim 19, wherein the adherend is an electronic component.

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