TW201833214A - Epoxy resin composition - Google Patents

Abstract

Provided is an epoxy resin composition having not only rapid curing properties but also excellent electrical characteristics and water resistance after curing. Specifically, an epoxy resin composition is provided that contains a thermal cationic polymerization initiator and an epoxy resin having a specific structure.

Description

Epoxy resin composition

The present invention relates to an epoxy resin composition, a method for producing the same, use of the composition, and the like.

BACKGROUND OF THE INVENTION Epoxy resins are widely used in a variety of applications such as adhesives, electronic materials, or composite materials. However, epoxy resin materials often require higher performance, for example, as the manufacturing process is energy-saving, a quick-curing epoxy resin material is necessary. Moreover, in the field of electronic materials, it is expected that the performance of electric power will be further improved.

For example, Patent Document 1 describes an epoxy resin composition having excellent fast-curing properties by combining an epoxy resin and a cationic polymerization initiator. In the epoxy resin composition described in Patent Document 1, a barium borate salt is used as a cationic polymerization initiator to improve the curability. However, electrical properties and water resistance are not sufficient.

PRIOR ART DOCUMENT Patent Document Patent Document 1: International Publication No. 2012/042796 Patent Document 2: British Patent No. 1123960

Disclosure of the Invention Problems to be Solved by the Invention Accordingly, an object of the present invention is to provide an epoxy resin composition which has not only rapid curing properties but also excellent electrical properties and water resistance after curing, and a method for producing the same.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy resin composition containing a specific epoxy resin containing a ruthenium atom and a thermal cationic polymerization initiator can have excellent rapid hardenability. And an epoxy resin composition having low dielectric properties and water resistance after hardening. Based on this finding, the research is further repeated and the present invention is completed.

The present invention encompasses the subject matter recited below. Item 1. An epoxy resin composition comprising an epoxy resin represented by the following formula (1) and a thermal cationic polymerization initiator:

[Chemical Formula 1]

(wherein the X ring is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or having 2 saturated hydrocarbon rings and/or Or a ring of a structure of an unsaturated hydrocarbon ring; wherein R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same or different, and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom or the following Group represented by formula (3):

[Chemical Formula 2]

(wherein R ^{1 is the} same or different from each other, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part of carbon atoms It is selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ² represents an alkylene group having a carbon number of 1 to 18, and the group is bonded to a carbon atom directly bonded to a ruthenium atom. A part of the carbon atoms may be selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{3 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms and a carbon number of 2 to 9 An alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part of carbon atoms substituted by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; m represents 0 to 6 An integer of n; an integer of 0 to 3; wherein, at least one of R ^Xa , R ^Xb , R ^Xc and R ^Xd is a group represented by the formula (3), and constitutes a hydrocarbon ring for forming an X ring; ^Further , the hydrogen atom to which the carbon atoms of R ^Xa , R ^Xb , R ^Xc and R ^Xd are bonded may be substituted by a lower alkyl group, a lower alkoxy group, a lower alkenyl group or a halogen atom). Item 2. The epoxy resin composition according to Item 1, wherein the ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded is a ring represented by the following formula (2):

[Chemical Formula 3]

(wherein the X ¹ ring and the X ² ring are the same or different from each other, and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y represents a bond bond, and may also be substituted with a carbon number of 1 to 4 carbon atoms 1 to 6 An alkyl group, an oxygen atom (-O-), a sulfur atom (-S-), -SO- or -SO ₂ -). Item 3. The epoxy resin composition according to Item 1 or 2, wherein the saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms, and the unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms. Item 4. The epoxy resin composition according to Item 1, which comprises at least one epoxy resin selected from the group consisting of the following epoxy resins, and a thermal cationic polymerization initiator polymerization initiator; -iia) shown epoxy:

[Chemical Formula 4]

(wherein, X ⁱⁱ represents a divalent group obtained by removing a hydrogen atom from a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or a ring having a structure in which a ring of 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring is condensed. The divalent group shown by the formula (2 ^g -iia):

[Chemical Formula 5]

(wherein Y represents a bond bond, an alkyl group having 1 to 6 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), - SO- or -SO ₂ -); R ^{1 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the groups A part of the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{2 is the} same or different from each other, and represents an alkylene group having 1 to 18 carbon atoms, and the base is excluded. A part of the carbon atoms outside the carbon atom directly bonded to the ruthenium atom may be selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{3 is the} same or different from each other, and represents a carbon number of 1 to 18 An alkyl group, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have at least a part of carbon atoms selected from the group consisting of an oxygen atom and a nitrogen atom. 1 atomic substitution; m means an integer from 0 to 6; n represents an integer from 0 to 3; and an epoxy resin of the formula (1-iiia):

[Chemical Formula 6]

(wherein, X ⁱⁱⁱ represents a trivalent group obtained by removing three hydrogen atoms from a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or a ring having a structure in which a ring of 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring is condensed or the following a trivalent group represented by the formula (2 ^{g -} iiia):

[Chemical Formula 7]

(wherein Y is the same as the above); and R ¹ , R ² , R ³ , m and n are the same as defined above. The epoxy resin composition according to any one of items 1 to 4, wherein the thermal cationic polymerization initiator is selected from the group consisting of a phosphonium salt, a boron compound, and a mixture of a boron compound and a Lewis base. At least one. The epoxy resin composition according to any one of items 1 to 5, which contains 0.01 to 50 parts by mass of a thermal cationic polymerization initiator based on 100 parts by mass of the epoxy resin. Item 7. A cured product, which is a cured product of the epoxy resin composition according to any one of Items 1 to 6. Item 8. A semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover film, an electromagnetic wave shielding film, a printed substrate material or a composite material, which is used in any one of items 1 to 6 The epoxy resin composition according to the item or the cured product according to item 7. Item 9. The epoxy resin composition according to any one of items 1 to 6 or the cured product according to Item 7, which is used in a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, and an interlayer insulating film. The use of an adhesive layer, a cover film, an electromagnetic wave shielding film, a printed substrate material or a composite material. Item 10. The use of the epoxy resin composition according to any one of items 1 to 6 or the cured product according to item 7 for producing a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, An interlayer insulating film, an adhesive layer, a cover film, an electromagnetic wave shielding film, a printed substrate material, or a composite material.

Advantageous Effects of Invention The epoxy resin composition of the present invention contains a specific epoxy resin and a thermal cationic polymerization initiator, and therefore has excellent rapid curing properties, and the cured product has electrical properties (low dielectric properties) and heat resistance. Also, the water resistance is also good. Therefore, the epoxy resin composition of the present invention can be suitably used in, for example, a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover film, an electromagnetic wave shielding film, a printed substrate material, a composite material. And so on a wide range of uses.

Embodiments for Carrying Out the Invention Hereinafter, each embodiment of the present invention will be described in further detail.

The epoxy resin composition encompassed by the present invention contains the following formula (1):

[Chemical Formula 8]

The epoxy resin and the thermal cationic polymerization initiator are shown.

In the formula (1), R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom or a formula (3): Group:

[Chemical Formula 9]

(The following is sometimes referred to as "formula (3) group"). Further, the following lower alkyl group, lower alkoxy group and lower alkenyl group may be collectively referred to as "lower carbon substituent". In the present invention, a lower alkyl group or a lower alkoxy group is preferred among the lower carbon substituents.

However, at least one of R ^Xa , R ^Xb , R ^Xc and R ^Xd is a group of the formula (3). In other words, three of R ^Xa , R ^Xb , R ^Xc and R ^Xd are a hydrogen atom, a halogen atom or a lower carbon substituent and one is a group of the formula (3), or two are a hydrogen atom, a halogen atom or a lower carbon. The substituent is two and is a group of the formula (3), or one is a hydrogen atom, a halogen atom or a lower carbon substituent, and three are a group of the formula (3), or all of the group of the formula (3). More specifically, for example, R ^Xa , R ^Xb , R ^Xc and R ^Xd may be: (i) R ^Xa , R ^Xb and R ^Xc are a hydrogen atom, a halogen atom or a lower carbon substituent and R ^Xd is a formula (3) a group; (ii) R ^Xa and R ^Xb are a hydrogen atom, a halogen atom or a lower carbon substituent and R ^Xc and R ^Xd are a group of the formula (3); (iii) R ^Xa is a hydrogen atom, a halogen atom or a lower order a carbon substituent and R ^Xb , R ^Xc and R ^Xd are a group of the formula (3); or (iv) R ^Xa , R ^Xb , R ^Xc and R ^{Xd are} all a group of the formula (3). Further, among the R ^Xa , R ^Xb , R ^Xc and R ^Xd groups, a group other than the formula (3) is preferably a hydrogen atom or a lower carbon substituent.

In the formula (1), R ^Xa , R ^Xb , R ^Xc and R ^Xd may be the same or different from each other, and therefore, (i) when R ^Xa , R ^Xb and R ^Xc are a hydrogen atom, a halogen atom or a lower carbon substituent and R ^{When Xd} is a group of the formula (3), R ^Xa , R ^Xb and R ^Xc may be the same or different from each other; (ii) when R ^Xa and R ^Xb are a hydrogen atom, a halogen atom or a lower carbon substituent and R ^Xc and R ^Xd When it is a group of the formula (3), R ^Xa and R ^Xb may be the same or different from each other, and R ^Xc and R ^Xd may be the same or different from each other; (iii) when R ^Xa is a hydrogen atom, a halogen atom or a lower carbon substituent and When R ^Xb , R ^Xc and R ^Xd are a group of the formula (3), R ^Xb , R ^Xc and R ^Xd may be the same or different from each other; (iv) when R ^Xa , R ^Xb , R ^Xc and R ^{Xd are} all of the formula ( 3) In the case of a group, R ^Xa , R ^Xb , R ^Xc and R ^Xd may be the same or different. In addition, any of these cases is preferably the same as the group of the formula (3).

Further, when two or three of R ^Xa , R ^Xb , R ^Xc and R ^Xd are a halogen atom or a lower carbon substituent, the halogen atoms or lower carbon substituents may be the same or different. At this time, it is more preferable that 2 or 3 of R ^Xa , R ^Xb , R ^Xc and R ^Xd are the same lower carbon substituent.

In the present specification, the lower carbon substituent means a lower alkyl group, a lower alkoxy group or a lower alkenyl group. Here, the lower level means the carbon number 1 to 6 (1, 2, 3, 4, 5 or 6). The lower carbon substituent is desirably a lower alkyl group or a lower alkoxy group. Specifically, the lower alkyl group is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. The lower alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group.

Further, in the present specification, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom or a bromine atom.

In the formula (1), the X ring represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or has 2 saturated hydrocarbon rings bonded thereto. And/or a ring of the structure of the unsaturated hydrocarbon ring. In the present specification, a saturated hydrocarbon ring is preferably a saturated hydrocarbon ring having a carbon number of 4 to 8, (4, 5, 6, 7, or 8), and a cyclopentane ring, a cyclohexane ring or the like is particularly preferable. Further, in the present specification, the unsaturated hydrocarbon ring is preferably an unsaturated hydrocarbon ring having 4 to 8 (4, 5, 6, 7, or 8 carbon atoms), and a benzene ring or the like is particularly preferable. Further, in the present specification, a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed is a ring in which 2, 3 or 4 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed. Preferably, it is preferred to condense a ring having 2 or 3 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings. More specifically, a decahydronaphthalene ring, an adamantane ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a linked triphenyl ring, a tetrahydronaphthalene ring, 1, 2, 3, 4, 5, 6, 7,8-octahydronaphthalene ring, norbornene ring, and the like.

Further, in the present specification, a saturated hydrocarbon ring or an unsaturated hydrocarbon ring or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed is sometimes collectively referred to as a "hydrocarbon ring".

A ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded is represented by the following formula (2):

[Chemical Formula 10]

The ring shown is suitable.

In the formula (2), the X ¹ ring and the X ² ring are the same or different from each other, and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, both the X ¹ ring and the X ² ring may be a saturated hydrocarbon ring or both of them are unsaturated hydrocarbon rings, or one of them is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. Preferably, the X ¹ ring and the X ² ring are both saturated hydrocarbon rings or both are unsaturated hydrocarbon rings. For example, both the X ¹ ring and the X ² ring are benzene rings, both of which are cyclohexane rings or one of them is a benzene ring and the other is a cyclohexane ring, and both are benzene rings. good.

Further, Y represents a bond bond, an alkyl group having 1 to 6 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), -SO- Or -SO ₂ -. Here, the alkylene group having 1 to 6 carbon atoms may, for example, be a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group or a hexamethylene group. Further, the alkyl group having 1 to 4 carbon atoms which is a substituent may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. The alkylene group having 1 to 6 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms is preferably -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH ₂ CH(CH ₃ ). CH ₂ -, -CH ₂ C(CH ₃ ) ₂ CH ₂ -, and the like. Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, -S-, or -SO ₂ -, preferably a bond, a dimethylmethylene group, an oxygen atom, -SO ₂ -.

The ring represented by the formula (2) has been substituted by R ^Xa , R ^Xb , R ^Xc and R ^Xd . When the X ring in the formula (1) is a ring represented by the formula (2) and three of R ^Xa to R ^Xd are a hydrogen atom, a halogen atom or a lower carbon substituent and one is a group of the formula (3), X Any of the ^1- ring and X ² rings may also be substituted with a group of the formula (3). Further, when the ring represented by the formula (2) is substituted by 0, 1, 2 or 3 halogen atoms or a lower carbon substituent, a halogen atom or a lower carbon substituent (X ¹ ring substitution number: X ² ring) The number of substitutions may be (1:0), (0:1), (2:0), (1:1), (0:2), (3:0), (2:1), (1) :2) or (0:3). When two of R ^Xa to R ^Xd are a hydrogen atom, a halogen atom or a lower carbon substituent, and two of the groups are a group of the formula (3), either one of the X ¹ ring and the X ² ring may be a two formula ( 3) The group is substituted, or the X ¹ ring and the X ² ring may each be substituted by one group of the formula (3), and the X ¹ ring and the X ² ring are each substituted by one group of the formula (3). . In this case, when the ring represented by the formula (2) is substituted by 0, 1 or 2 halogen atoms or a lower carbon substituent, a halogen atom or a lower carbon substituent (the number of substitution of the X ¹ ring: the number of substitution of the X ² ring) ) may be (1:0), (0:1), (2:0), (1:1), or (0:2). When one of R ^Xa to R ^Xd is a hydrogen atom, a halogen atom or a lower carbon substituent and three are a group of the formula (3), three of the X ¹ ring and the X ² ring may be used ( 3) group, the (3) group and X ² ring is substituted with X ¹ ring is 2 formula 1 formula (3) group, or may be a X ¹ ring is one of formula (3) a group And the X ² ring is substituted by two groups of the formula (3), and the X ¹ ring is substituted by two groups of the formula (3) and the X ² ring is substituted by one group of the formula (3) or the ring of the X ¹ ring is one. The group of the formula (3) and the X ² ring are preferably substituted by two groups of the formula (3). In this case, when the ring represented by the formula (2) is substituted by 0 or 1 halogen atom or a lower carbon substituent, the halogen atom or the lower carbon substituent (the number of substitution of the X ¹ ring: the number of substitution of the X ² ring) may Is (1:0) or (0:1). When all of R ^Xa to R ^Xd are a group of the formula (3), either one of the X ¹ ring and the X ² ring may be substituted by four groups of the formula (3), and the X ¹ ring may be substituted by three formulas (3). a group and the X ² ring is substituted by one group of the formula (3), the X ¹ ring may be substituted by one group of the formula (3) and the X ² ring may be substituted with three groups of the formula (3), which may be X ¹ ring is substituted by 2 groups of formula (3) and X ² ring is substituted by 2 groups of formula (3), and ² groups of formula (3) are substituted by X ¹ ring and 2 formulas are represented by X ² ring (3) Substituting a group is preferred.

The tetravalent group represented by the formula (1') which is a part of the formula (1):

[Chemical Formula 11]

(In the formula (1'), the X ring is the same as the above), and a group represented by the following formula is particularly preferably mentioned. that is,

[Chemical Formula 12]

or

[Chemical Formula 13]

or

[Chemical Formula 14]

(The formula in the formula (2 ^g ) wherein Y is the same as the above).

In the formula (3), R ^{1 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part The carbon atom is substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The carbon atom is preferably a carbon atom which is not directly bonded to a ruthenium atom. Further, the carbon atom which may be substituted may be one or a plurality of (e.g., 2, 3, 4, 5 or 6) carbon atoms, and is preferably one carbon atom. Further, from the viewpoint of the simplicity of synthesis and the like, R ^{1 which is} bonded to the same ruthenium atom is preferably the same. Further, all of R ¹ present in the formula (1) are preferably the same.

The alkyl group having 1 to 18 carbon atoms represented by R ¹ is a linear or branched alkyl group, and may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tertiary butyl group. Base, n-pentyl, neopentyl, tertiary pentyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, n-decyl, Zheng 12 base and so on. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

The alkenyl group having 2 to 9 carbon atoms represented by R ¹ is a linear or branched alkenyl group, and may, for example, be a vinyl group, an allyl group, a 2-propenyl group, a butenyl group, a pentenyl group, a hexenyl group or a hexylene group. Alkenyl, octenyl, decenyl and the like. It is preferably an alkenyl group having 2 to 4 carbon atoms.

The cycloalkyl group represented by R ¹ may, for example, be a cycloalkyl group having 3 to 8 membered rings, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group and the like.

The aryl group represented by R ¹ may, for example, be a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a fluorenyl group, an ethylphenyl group, a naphthyl group and the like. Phenyl is preferred.

The aralkyl group represented by R ¹ may, for example, be an alkyl group substituted with an aryl group (especially a phenyl group) having 1 to 4 carbon atoms, and examples thereof include a benzyl group, an α-phenethyl group, a β-phenethyl group, and a β-methyl group. Phenylethyl and the like.

R ^{1 is} preferably an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.

In the formula (3), R ² represents an alkylene group having 1 to 18 carbon atoms. The alkylene group is a linear or branched alkylene group, and a linear alkyl group is preferred. Examples thereof include methylene, methylmethylene, ethylmethylene, dimethylmethylene, diethylmethylene, dimethylene (-CH ₂ CH ₂ -), and trimethylene ( -CH ₂ CH ₂ CH ₂ -), tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, hexamethylene, decamethylene, undecamethylene , dodecamethylene, thirteen methylene and the like. For example, the alkylene group having a carbon number of 2 to 18 is preferably an alkylene group having a carbon number of 2 to 10, more preferably an alkylene group having a carbon number of 2 to 8, more preferably an alkylene group having a carbon number of 2 to 6, particularly It is preferably an alkylene group having a carbon number of 2 to 5.

The carbon atom of the alkylene group having 1 to 18 carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The carbon atom is preferably a carbon atom which is not directly bonded to any of the ruthenium atom and the 3 to 8 member ring or the epoxy ring. Further, the carbon atom which may be substituted may be one or a plurality of (e.g., 2, 3, 4, 5 or 6) carbon atoms, and is preferably one carbon atom.

When the group is bonded to the ruthenium atom of R ² and is (*), it may be, for example, (*)-alkylene group having 2 to 9 carbon atoms and O-alkyl group having 1 to 8 carbon atoms. It is (*)-alkylene group having 2 to 4 carbon atoms and O-alkyl group having 1 to 3 carbon atoms, preferably (*)-carbon number 2 to 4 alkyl group-O-carbon number 1 The alkylene group of ~2 is particularly preferably (*)-alkyl 3 -alkyl-O-methylene-.

Specifically, (*)-(CH ₂ ) ₂ -O-CH ₂ -, (*)-(CH ₂ ) ₃ -O-CH ₂ -, (*)-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -, (*)-(CH ₂ ) ₅ -O-(CH ₂ ) ₄ -, etc., wherein (*)-(CH ₂ ) ₃ -O-CH ₂ - is preferred.

In the formula (3), m represents an integer of 0 to 6 (i.e., 0, 1, 2, 3, 4, 5 or 6). Also, n represents an integer from 0 to 3 (ie, 0, 1, 2, or 3). Here, the R ² -bonded group of the formula (3) (the side not bonded to the ruthenium atom) is represented by the formula (4) (hereinafter sometimes referred to as "the group of the formula (4)"), that is, As follows.

[Chemical Formula 15]

For the group of the formula (4), the case where m is an integer of 1 to 6 is specifically described by a structural formula, and when m=1, it is expressed as:

[Chemical Formula 16]

When m=2, it is expressed as:

[Chemical Formula 17]

When m=3, it is expressed as:

[Chemical Formula 18]

When m=4, it is expressed as:

[Chemical Formula 19]

When m=5, it is expressed as:

[Chemical Formula 20]

When m=6:

[Chemical Formula 21]

Then as shown in the previous paragraph.

When m is 0, the group of the formula (4) has only an epoxy ring and n is an integer of 0 to 3, and thus represents any of the following groups.

[Chemical Formula 22]

In the formula (3), R ² and R ^{3 are} bonded to a 3 to 8 member ring or an epoxy ring. In addition, n represents the number of R ³ bonded to the 3-8 member ring or the epoxy ring.

In the formula (3), R ^{3 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part The carbon atom is substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The carbon atom is preferably a carbon atom which is not directly bonded to a 3-8 member ring or an epoxy ring. Further, the carbon atom which may be substituted may be one or a plurality of (e.g., 2, 3, 4, 5 or 6) carbon atoms, and is preferably 1 carbon atom.

R ³ carbon atoms, an alkyl group having 1 to FIG 18, the carbon number of the alkenyl group having 2 to 9, cycloalkyl, aryl and aralkyl groups may be exemplified respectively as shown in the above-described substituents R ¹ corresponds to the same group of objects.

R ^{3 is} preferably an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group or an ethyl group.

Examples of the group of the ideal formula (3) include those in which R ¹ , R ² , R ³ , m and n are the same as those described above, and R ^{1 is} all the same, and R ³ (when plural is present). The group has 1, 2, 3 or 4 in the epoxy resin represented by the formula (1), and the groups may be the same or different from each other, and are preferably the same.

Further, as a particularly preferable specific example of the group of the formula (4), a group in which R ^{3 is the} same as the above, m represents 0, 1, 2, 3 or 4 and n represents 0, 1 or 2 is preferable. The following groups may be mentioned (wherein R ^{3 is the} same as the above).

[Chemical Formula 23]

The group of the formula (4) is present in the epoxy resin represented by the formula (1) in 1, 2, 3 or 4, and the groups may be the same or different from each other, and are preferably the same.

Further, the hydrogen atom constituting the hydrocarbon ring for forming the X ring and not bonded to the carbon atoms of R ^Xa , R ^Xb , R ^Xc and R ^Xd may be a lower carbon substituent or a halogen atom (preferably a lower carbon) Substituent) substitution. That is, when the X ring is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, the rings are formed and unbonded R ^Xa The hydrogen atom to which the carbon atoms of R ^Xb , R ^Xc and R ^Xd are bonded may also be substituted by a lower carbon substituent or a halogen atom (preferably a lower carbon substituent), and when the X ring is bonded to two saturated hydrocarbons a ring of a structure of a ring and/or an unsaturated hydrocarbon ring, which constitutes a carbon atom of the bonded saturated hydrocarbon ring and/or unsaturated hydrocarbon ring and which is not bonded to R ^Xa , R ^Xb , R ^Xc and R ^Xd The hydrogen atom of the junction may also be substituted by a lower carbon substituent or a halogen atom (preferably a lower carbon substituent). Further, in the case where the X ring is a ring represented by the formula (2), the carbon atoms constituting the X ¹ ring and the X ² ring and not bonded to R ^Xa , R ^Xb , R ^Xc and R ^Xd may be referred to. The bonded hydrogen atom may also be substituted by a lower carbon substituent or a halogen atom (preferably a lower carbon substituent).

In the present specification, a carbon atom constituting a hydrocarbon ring for forming an X ring and not bonded to R ^Xa , R ^Xb , R ^Xc and R ^Xd may be referred to as "a carbon atom not bonded to R ^Xa-d ".

The lower carbon substituent or the halogen atom of the hydrogen atom to which the carbon atom to which R ^Xa-d is bonded may be substituted, and it is preferred that only one carbon atom which is not bonded to R ^Xa-d is bonded to only one of the aforementioned lower carbon substitutions. Base or halogen atom. That is, when the bond is not bonded to the R ^Xa-d of the carbon atoms is substituted with a hydrogen atom, is not bonded to R ^Xa-d are bonded to carbon atoms of hydrogen atom to only one hydrogen atom is substituted by a carbon-lower Or a halogen atom substitution is preferred. Further, the number of substitutions (i.e., the total of the lower carbon substituent and the halogen atom) is preferably less than the number of carbon atoms which are not bonded to R ^Xa-d . More specifically, the number of substitutions is preferably 1 to 6 (1, 2, 3, 4, 5 or 6), and 1 to 4 is preferred, and 1 to 2 is more preferred. Further, especially when the X ring is a ring represented by the formula (2), the hydrogen atom which may be substituted is preferably a hydrogen atom to which a carbon atom which is not bonded to Y is bonded.

When at least one of R ^Xa , R ^Xb , R ^Xc and R ^Xd is a lower carbon substituent and when at least one lower carbon substituent is bonded to a carbon atom which is not bonded to R ^Xa-d , all of the lower carbon substituents are preferably the same. That is, when a lower carbon substituent is present in R ^Xa , R ^Xb , R ^Xc and R ^Xd and a lower carbon substituent bonded to a carbon atom not bonded to R ^Xa-d is present, all of the lower carbon substituents are preferably the same. . Further, although not particularly limited, when at least one of R ^Xa , R ^Xb , R ^Xc and R ^Xd is a halogen atom and at least one halogen atom is bonded to a carbon atom to which R ^Xa-d is not bonded, all of The halogen atom should be the same. That is, when a halogen atom is present in R ^Xa , R ^Xb , R ^Xc and R ^Xd and a halogen atom to which a carbon atom of R ^Xa-d is not bonded is present, all of the halogen atoms are preferably the same.

More specifically, if the tetravalent group represented by the above formula (1') is as follows:

[Chemical Formula 24]

The epoxy resin represented by the formula (1) can be preferably exemplified by the epoxy resin represented by the following formula (1-X1):

[Chemical Formula 25]

(In the formula (1-X1), R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as ^defined above, and R ^Xg1 and R ^{Xg2 are the} same or different from each other, and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a lower alkenyl group) . In the formula (1-X1), R ^Xa , R ^Xb , R ^Xc , R ^Xd , R ^Xg1 and R ^Xg2 are preferably bonded to different carbon atoms on the benzene ring. In the epoxy resin represented by the formula (1-X1), it is preferred that R ^Xg1 and R ^Xg2 are hydrogen atoms.

Among the epoxy resins represented by the formula (1-X1), a more preferable one is an epoxy resin represented by the formula (1-X1a):

[Chemical Formula 26]

(In the formula (1-X1a), R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as ^defined above, and R ^Xg1 and R ^{Xg2 are the} same as ^defined above); or an epoxy resin represented by the formula (1-X1b):

[Chemical Formula 27]

(In the formula (1-X1b), R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as ^defined above, and R ^Xg1 and R ^{Xg2 are the} same as ^defined above).

In the epoxy resin represented by the formula (1-X1a), it is preferable that R ^Xa and R ^Xb are a hydrogen atom, R ^Xc and R ^Xd are a group of the formula (3), and R ^Xg1 and R ^Xg2 are a hydrogen atom. Or R ^Xa and R ^Xc are a hydrogen atom, R ^Xb and R ^Xd are a group of the formula (3), and R ^Xg1 and R ^Xg2 are a hydrogen atom.

Further, in the epoxy resin represented by the formula (1-X1b), it is preferable that R ^Xa is a hydrogen atom, R ^Xb , R ^Xc and R ^Xd are a group of the formula (3) and R ^Xg1 and R ^Xg2 are A hydrogen atom.

Further, when the tetravalent group represented by the above formula (1') is a group shown below:

[Chemical Formula 28]

(Y in the formula (2 ^g ) is the same as the above); the epoxy resin represented by the formula (1) can also be preferably exemplified by the epoxy resin represented by the following formula (1-X2):

[Chemical Formula 29]

(In the formula (1-X2), Y is the same as the above, R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as described above, and R ^X11 , R ^X12 and R ^X13 and R ^X21 , R ^X22 and R ^{X23 are the} same or different, and represent A hydrogen atom, a lower alkyl group, a lower alkoxy group or a lower alkenyl group). In the formula (1-X2), R ^Xa , R ^Xc , R ^X11 , R ^X12 and R ^X13 are preferably bonded to different carbon atoms, respectively, and R ^Xb , R ^Xd , R ^X21 , R ^X22 and R ^X23 are respectively different from each other. Carbon atom bonding is preferred. Further, R ^Xa , R ^Xb , R ^Xc , R ^Xd , R ^X11 , R ^X12 , R ^X13 , R ^X21 , R ^X22 and R ^X23 are not bonded to the Y-bonded carbon atom.

Among the epoxy resins represented by the formula (1-X2), a more preferable one is an epoxy resin represented by the formula (1-X2a):

[Chemical Formula 30]

(In the formula (1-X2a), Y is the same as the above, R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as described above, and R ^X11 , R ^X12 and R ^X13 and R ^X21 , R ^X22 and R ^{X23 are the} same or different, and represent A hydrogen atom, a lower alkyl group, a lower alkoxy group or a lower alkenyl group; or an epoxy resin represented by the formula (1-X2b):

[Chemical Formula 31]

(In the formula (1-X2b), Y is the same as the above, R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as described above, and R ^X11 , R ^X12 and R ^X13 and R ^X21 , R ^X22 and R ^{X23 are the} same or different from each other, and represent A hydrogen atom, a lower alkyl group, a lower alkoxy group or a lower alkenyl group; or an epoxy resin represented by the formula (1-X2c):

[Chemical Formula 32]

(In the formula (1-X2c), Y is the same as the above, R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same as described above, and R ^X11 , R ^X12 and R ^X13 and R ^X21 , R ^X22 and R ^{X23 are the} same or different, and represent A hydrogen atom, a lower alkyl group, a lower alkoxy group or a lower alkenyl group).

The epoxy resin represented by the formula (1-X2a) is preferably in the case where R ^Xa , R ^Xb , R ^Xc and R ^Xd are a group of the formula (3), and R ^X11 and R ^X21 are lower carbon substituents. R ^X12 , R ^X13 , R ^X22 and R ^X23 are a hydrogen atom. Among them, it is particularly preferable that Y is an alkylene group having 1 to 6 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms (especially -C(CH ₃ ) ₂ -), R ^Xa , R ^Xb R ^Xc and R ^Xd are a group of the formula (3), R ^X11 and R ^X21 are lower alkoxy groups, and R ^X12 , R ^X13 , R ^X22 and R ^X23 are a hydrogen atom. In these cases, the groups of the formula (3) of R ^Xa , R ^Xb , R ^Xc and R ^{Xd are} all the same and the lower carbon substituents of R ^X11 and R ^X21 are preferably the same.

Further, in the epoxy resin represented by the formula (1-X2b), it is preferred that R ^Xa and R ^Xb are a hydrogen atom, R ^Xc and R ^Xd are a group of the formula (3), and R ^X11 , R ^X12 , R ^X13 , R ^X21 , R ^X22 and R ^X23 are a hydrogen atom. At this time, the groups of the formula (3) of R ^Xc and R ^Xd are preferably the same.

Further, in the epoxy resin represented by the formula (1-X2c), it is preferred that R ^Xa is a hydrogen atom, R ^Xb , R ^Xc and R ^Xd are a group of the formula (3) and R ^X11 , R ^X12 , R ^X13 , R ^X21 , R ^X22 and R ^X23 are a hydrogen atom. In this case, the groups of the formula (3) of R ^Xb , R ^Xc and R ^Xd are preferably the same.

In the present specification, the relevant descriptions of the X ring, R ^Xa , R ^Xb , R ^Xc and R ^Xd of the formula (1) and R ¹ , R ² , R ³ , m and n of the group of the formula (3) include 4) The relevant description of the groups can be arbitrarily combined, and any of the epoxy resins shown in the combination can also be used in the present invention.

In the formula (1), it may be: (iia) the hydrogen atom to which the carbon atom of the unbonded R ^Xa-d is unsubstituted, and R ^Xa , R ^Xb , R ^Xc and R ^Xd , wherein R ^Xa and R ^Xb are hydrogen An atom and R ^Xc and R ^Xd are a group of the formula (3); (iiia) a hydrogen atom bonded to a carbon atom which is not bonded to R ^Xa-d is unsubstituted and R ^Xa , R ^Xb , R ^Xc and R ^Xd R ^Xa is a hydrogen atom and R ^Xb , R ^Xc and R ^Xd are a group of the formula (3); or, (iva) a hydrogen atom to which a carbon atom which is not bonded to R ^Xa-d is unsubstituted and R ^Xa , R ^Xb , R ^Xc and R ^{Xd are} all groups of the formula (3).

In the case of (iia), the epoxy resin represented by the formula (1) preferably contains an epoxy resin represented by the following formula (1-iia):

[Chemical Formula 33]

[wherein, X ⁱⁱ represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring or a divalent group represented by the following formula (2 ^{g -} iia):

[Chemical Formula 34]

(wherein Y is the same as defined above); and R ¹ , R ² , R ³ , m and n are the same as defined above. Further, R ¹ , R ² , R ³ , m and n may be the same or different from each other, and the same is preferred.

The divalent group represented by X ^{ii is} preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, and more preferably a 1,4-phenylene group.

Formula (2 ^g -iia) 2 monovalent group shown, should the following formula (2 ^g -iia ') a group represented by:

[Chemical Formula 35]

(where Y is the same as above).

Among the formulas (2 ^g -iia'), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom or -SO ₂ - is particularly preferable.

Further, X ⁱⁱ is preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, a formula (2 ^g -iia'), and more preferably a 1,4-phenylene group.

For example, in the formula (1-iia), an epoxy resin is preferably used in the present invention in the form of the following: m is 0, 1, 2, 3 or 4 (m is 0 or 4 in particular) And n is 0 (ie, the ring is not substituted by R ³ ); X ⁱⁱ is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (especially a benzene ring); R ^{1 is} also a carbon number of 1 to 3 And the R ² is an alkylene group having 2 to 6 carbon atoms, and the carbon atom of the base is not directly bonded to the ruthenium atom and any one of the 3 to 6 member rings or the epoxy ring. Can be replaced by an oxygen atom.

In the case of (iiia), the epoxy resin represented by the formula (1) preferably contains an epoxy resin represented by the following formula (1-iiia):

[Chemical Formula 36]

Wherein X ⁱⁱⁱ represents a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring or a trivalent group represented by the following formula (2 ^{g -} iiia):

[Chemical Formula 37]

(wherein Y is the same as defined above); and R ¹ , R ² , R ³ , m and n are the same as defined above. Further, R ¹ , R ² , R ³ , m and n may be the same or different from each other, and the same is preferred.

The trivalent group represented by X ^{iii is} ideally exemplified by the following:

[Chemical Formula 38]

The basis of the above.

Formula (2 ^g -iiia) 3 divalent group shown, over a group represented by the following formula (2 ^g -iiia '):

[Chemical Formula 39]

(where Y is the same as above).

Among the formulas (2 ^{g -} iiia'), a group in which Y is a bonding bond, a dimethylmethylene group, an oxygen atom or -SO ₂ - is particularly preferable.

For example, in the formula (1-iiia), an epoxy resin is preferably used in the present invention in the form of the following: m is 0, 1, 2, 3 or 4 (m is 0 or 4 in particular) Preferably, n is 0 (ie, the ring is not substituted by R ³ ); X ⁱⁱⁱ is a trivalent group obtained by removing 3 hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring); R ^{1 is} also a carbon number of 1 to 3 And the R ² is an alkylene group having 2 to 6 carbon atoms, and the carbon atom of the base is not directly bonded to the ruthenium atom and any one of the 3 to 6 member rings or the epoxy ring. Can be replaced by an oxygen atom.

In the case of (iva), the epoxy resin represented by the formula (1) contains an epoxy resin represented by the following formula (1-iva):

[Chemical Formula 40]

[wherein, X ^iv represents a tetravalent group represented by the above (1') and a hydrogen atom to which the carbon atom to which the carbon atom of the X ring is not bonded to R ^Xa-d is unsubstituted, R ¹ , R ² , R ³ , m and n are the same as above]. Further, R ¹ , R ² , R ³ , m and n may be the same or different from each other, and the same is preferred.

The 4-valent group represented by X ^{iv is} ideally exemplified by the following:

[Chemical Formula 41]

The basis of the above.

The group which is a tetravalent group represented by X ^iv , a tetravalent group represented by the formula (2 ^g ) and a hydrogen atom to which the carbon atom to which the carbon atom of R ^Xa-d is not bonded is unsubstituted, is preferably as follows. (2 ^g -iva') group:

[Chemical Formula 42]

(where Y is the same as above).

Among the formulas (2 ^g -iva'), a group in which Y is a bonding bond, a dimethylmethylene group, an oxygen atom or -SO ₂ - is particularly preferable.

For example, in the formula (1-iva), an epoxy resin is preferably used in the present invention in the form of the following: m is 0, 1, 2, 3 or 4 (m is 0 or 4 in particular) Preferably, and n is 0 (ie, the ring is not substituted by R ³ ); X ^iv is a tetravalent group obtained by removing 4 hydrogen atoms from a hydrocarbon ring (especially a benzene ring); R ^{1 is} also a carbon number of 1 to 3 And the R ² is an alkylene group having 2 to 6 carbon atoms, and the carbon atom of the base is not directly bonded to the ruthenium atom and any one of the 3 to 6 member rings or the epoxy ring. Can be replaced by an oxygen atom.

In the epoxy resin represented by the formula (1), a more preferable one is specifically a compound represented by the following formula (1-IIa):

[Chemical Formula 43]

(wherein R ¹ , R ² and X ^{ii are the} same as defined above).

In the compound of the formula (1-IIa), X ⁱⁱ is a 1,4-phenylene group or a group represented by the formula (2 ^g -iia') (preferably 1,4-phenylene group), and R ^{1 is the} same Or mutually different (should be the same) and are alkyl groups having 1 to 3 carbon atoms (especially methyl groups), and R ^{2 is the} same or different (suitable for the same) and is an alkylene group having a carbon number of 2 to 6, (*) -(CH ₂ ) ₂ -O-CH ₂ -, (*)-(CH ₂ ) ₃ -O-CH ₂ -, (*)-(CH ₂ ) ₃ -O-(CH ₂ ) ₂ - or (* A compound of -(CH ₂ ) ₅ -O-(CH ₂ ) ₄ - is preferred. Further, the symbol (*) in the same manner as described above indicates the side of R ² bonded to the ruthenium atom.

Among the epoxy resins represented by the above formula (1-IIa), a more preferred one is an epoxy resin represented by the formula (1-IIa1):

[Chemical Formula 44]

(wherein R ¹ and X ^{ii are the} same as defined above); or an epoxy resin of the formula (1-IIa2):

[Chemical Formula 45]

(wherein R ¹ and X ^{ii are the} same as above). Alternatively, R ¹ may be the same or different and the same.

In the formula (1-IIa1) or (1-IIa2), the R ^{1 group} is the same or different (suitable for the same) and is an alkyl group having 1 to 3 carbon atoms (particularly methyl group) and X ⁱⁱ is 1,4- It is preferred to extend the phenyl group or the base represented by the formula (2 ^{g -} iia').

Further, among the epoxy resins represented by the formula (1), an epoxy resin represented by the following formula (1-IIb) may be preferably used:

[Chemical Formula 46]

(wherein R ¹ , R ² , R ³ , X ⁱⁱ and n are the same as defined above). Further, any of R ¹ , R ² , R ³ and n may be the same or different from each other, and the same is preferred.

In the formula (1-IIb), X ⁱⁱ is a 1,4-phenylene group or a group represented by the formula (2 ^g -iia') (preferably 1,4-phenylene group), and R ^{1 is the} same or mutually Isopy (same) and is an alkyl group having 1 to 3 carbon atoms (especially methyl), n is 0 (ie, the ring is not substituted by R ³ ), and R ^{2 is the} same or different (should be the same) and is The alkylene group having 2 to 6 carbon atoms (preferably dimethylene: -(CH ₂ ) ₂ -) is preferred.

Further, among the epoxy resins represented by the formula (1), an epoxy resin represented by the following formula (1-IIIa) may be further preferably used:

[Chemical Formula 47]

(wherein R ¹ , R ² , R ³ , X ⁱⁱⁱ and n are the same as defined above). Further, any of R ¹ , R ² , R ³ and n may be the same or different from each other, and the same is preferred.

In formula (1-IIIa), X ⁱⁱⁱ is

[Chemical Formula 48]

or

[Chemical Formula 49]

Or a group represented by the formula (2 ^g -iiia'), R ^{1 is the} same or different (suitably the same) and is an alkyl group having 1 to 3 carbon atoms (especially methyl), and n is 0 (ie, ring is not Preferably, R ^{3 is} substituted, and R ^{2 is the} same or different (preferably the same) and is an alkylene group having 2 to 6 carbon atoms (preferably dimethylene: -(CH ₂ ) ₂ -).

In the epoxy resin composition of the present invention, the epoxy resin represented by the formula (1) may be used singly or in combination of two or more kinds.

The epoxy resin represented by the formula (1) can be produced according to or according to a known method, and can be produced, for example, according to the description of Patent Document 2 (British Patent No. 1123960). Further, for example, an epoxy resin represented by the formula (1-iia) can be produced by a reaction represented by the following reaction formula.

[Chemical Formula 50]

(wherein R ^2A is an alkenyl group having 2 to 18 carbon atoms, and a part of the carbon atoms of the group may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ¹ , R ² , R ³ and X ^{ii are} as defined above).

The alkenyl group having 2 to 18 carbon atoms represented by R ^2A is a linear or branched alkenyl group, and is preferably a linear chain. Specifically, it may, for example, be a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group or an octenyl group. Alkenyl, cyclohexenyl and the like. It is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group, an allyl group or a butenyl group. Further, the alkenyl group is preferably an α-alkenyl group.

The carbon atom of the alkenyl group having 2 to 18 carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The carbon atom is preferably a carbon atom which is not directly bonded to the epoxy ring. Further, the carbon atom which may be substituted may be one or a plurality of (e.g., 2, 3, 4, 5 or 6) carbon atoms, and is preferably one carbon atom. The group may be, for example, a carbon number of 2 to 9 alkenyl-O-carbon number 1 to 8 alkylene group-, preferably a carbon number of 2 to 4 alkenyl-O-carbon number of 1 to 3 alkylene group-, preferably The carbon number is 2 to 4 alkenyl-O-carbon number 1 to 2 alkylene group-, and particularly preferably a carbon number 3 alkenyl-O-CH ₂ -. Specifically, it can be exemplified by CH ₂ =CH-O-CH ₂ -, CH ₂ =CH-CH ₂ -O-CH ₂ -, CH ₂ =CH-CH ₂ -O-(CH ₂ ) ₂ -, CH ₂ =CH-(CH ₂ ) ₃ -O-(CH ₂ ) ₄ -etc., wherein CH ₂ =CH-CH ₂ -O-CH ₂ -(allyloxymethyl) is preferred.

The epoxy resin represented by the formula (1-iia) can be produced by subjecting a compound represented by the formula (5-iia) and a compound represented by the formula (6) to a hydrogenation reaction. The hydrazine hydrogenation reaction can usually be carried out in the presence of a catalyst, in the presence of a solvent or in the absence of a solvent. Further, the compound of the formula (5-iia) may be changed to a compound represented by the following formula: a compound represented by the formula (5-iiia):

[Chemical Formula 51]

(wherein R ¹ and X ^{iii are the} same as defined above), or a compound of the formula (5-iva):

[Chemical Formula 52]

(wherein R ¹ and X ^{iii are the} same as defined above), or a compound of the formula (5-ia):

[Chemical Formula 53]

(wherein, X ⁱ represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring, and R ¹ is the same as defined above) to produce an epoxy resin represented by the above formula (1-iiia) or (1-iva) or has An epoxy resin having a structure in which a group of formula (3) is bonded to a hydrocarbon ring. Further, by using a monovalent group obtained by removing one hydrogen atom from the X ring and a two-valent group removing two hydrogen atoms from the X ring in the structure of the compounds, X ⁱ ~ X ^iv is removed from the X ring. A compound of the formula (1) can be produced by a compound having a structure in which a trivalent group derived from a hydrogen atom or a tetravalent group obtained by removing four hydrogen atoms from the X ring is substituted.

The catalyst for the rhodium hydrogenation reaction may be a known catalyst, such as platinum carbon, chloroplatinum (IV) acid, platinum olefin complex, platinum alkenyl alkoxylate complex, platinum carbonyl complex. Platinum-based catalyst; ruthenium-based catalyst such as bis(triphenylphosphine) ruthenium; ruthenium-based catalyst such as bis(cyclooctadienyl)phosphonium dichloride. The above catalyst may be in the form of a solvate (such as a hydrate or an alcoholate), and may be used in the form of a solution by dissolving the catalyst in an alcohol (e.g., ethanol or the like) each time. Further, the catalyst may be used singly or in combination of two or more.

The amount of the catalyst used may be an effective dose based on the catalyst, for example, a compound and a formula represented by the above formula (5-ia), (5-iia), (5-iiia) or (5-iva). 6) The total amount of the compound shown is 0.00001 to 20 parts by mass, and preferably 0.0005 to 5 parts by mass.

The above hydrogenation reaction can be carried out without using a solvent, but the reaction can be carried out under mild conditions by using a solvent. The solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic hydrocarbon solvent such as hexane or octane; tetrahydrofuran or An ether solvent such as an alkoxide; an alcohol solvent such as ethanol or isopropyl alcohol; and the like may be used alone or in combination of two or more.

The compound of the formula (6) is used in an amount of, for example, Si-H group 1 mol in the compound represented by the formula (5-ia), (5-iia), (5-iiia) or (5-iva). Usually 0.5 to 2 moles, preferably 0.6 to 1.5 moles, and more preferably 0.8 to 1.2 moles.

The reaction temperature is usually from 0 ° C to 150 ° C, preferably from 10 ° C to 120 ° C, and the reaction time is usually from about 1 hour to 24 hours.

After completion of the reaction, the epoxy resin represented by the formula (1) can be obtained by using a known separation method such as distilling off a solvent or the like from the reaction liquid.

The thermal cationic polymerization initiator is an acid species which can be used for cationic polymerization of a cationically polymerizable compound by heat. As the thermal cationic polymerization initiator to be used in the present invention, a known one which has been used as a thermal cationic polymerization initiator of an epoxy resin can be appropriately selected and used. For example, a phosphonium salt, a phosphonium salt, a phosphonium salt, a boron compound, a ferrocene, a Lewis acid, a mixture of a boron compound and a Lewis base, or the like can be used. The thermal cationic polymerization initiator may be used singly or in combination of two or more.

For the boron compound, for example, the Lewis acid disclosed in WO2012/060449 can be suitably used. Further, as for the mixture of the boron compound and the Lewis base, a cationic hardening catalyst composed of a Lewis acid (boron compound) and a Lewis base disclosed in WO2012/060449 can be used. As the Lewis base, for example, an amine compound, a phosphine compound, a sulfide compound or the like can be used, and an amine compound can be suitably used. Further, for example, in the case of a mixture of a boron compound and an amine compound, a mixture of a Lewis acid disclosed in WO2012/060449 and an amine compound described below can also be used. The contents described in the specification and/or drawings of WO 2012/060449 are also incorporated herein by reference.

The thermal cationic polymerization initiator can also be purchased from commercially available products. A commercially available product of a thermal cationic polymerization initiator is preferably exemplified by CP-66 and CP-77 manufactured by ADEKA Co., Ltd.; CI-2855 and CI-2639 manufactured by Japan Soda Co., Ltd.; SAN-AID SI-60, SI manufactured by Sanshin Chemical Industry Co., Ltd. -60L, SI-80, SI-80L, SI-100, SI-100L; aromatic fluorine-based acid generators TPB, TEPBD, and FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd.

Among these, from the viewpoints of water resistance and low dielectric properties of the cured product of the obtained epoxy resin composition, it is particularly preferable to use a cerium salt, a boron compound or a mixture of a boron compound and a Lewis base, and it is preferable to use hydrazine. a salt or a mixture of a boron compound and an amine compound.

The barium salt is preferably a barium salt of the following formula:

[Chemical Formula 54]

(wherein R ⁴ represents a hydrogen atom, a halogen or an alkyl group having 1 to 12 carbon atoms; and R ^5a and R ^{5b are the} same or different from each other, and represent an alkyl group having 1 to 12 carbon atoms, a benzyl group, a halogenated benzyl group, and a group Benzyl, dimethylbenzyl, trimethylbenzyl, methoxybenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, naphthylmethyl α- naphthylmethyl, [beta] naphthylmethyl), vinylbenzyl or basal Gui; R ⁶ represents a hydrogen atom, a halogen, an alkyl group having 1 to 12 carbon atoms, the hydroxyl group or -OR ^7; R ⁷ represents a methyl Base, ethyl hydrazino, methoxycarbonyl, ethoxycarbonyl, benzhydryl, phenoxycarbonyl, chloroethyl, chloroethane, trichloroethyl or trifluoroethenyl; Z represents PF ₆ , SbF ₆ , halogen atom (such as F, Cl, Br), (C ₆ F ₅ ) ₄ B, (C ₂ F ₅ ) ₂ F ₄ P, (C ₂ F ₅ ) ₃ F ₃ P or (C ₂ F _{5) 4} F ₂ P; another, Z when Z represents _{(C 6 F 5) 4 B} - represents a store pentafluorophenyl borate). The alkyl group having 1 to 12 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms in the formula is preferably an alkyl group having 1 to 8 carbon atoms, and carbon. Alkyl groups of 1 to 6 are more preferred. It may be a linear or branched alkyl group. Specifically, it may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, tertiary pentyl, n-hexyl, or Heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl and the like.

Further, for example, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R ^5a represents an alkyl group having 1 to 4 carbon atoms, a benzyl group, a halogenated benzyl group, a methylbenzyl group, a dimethyl benzyl group, and a trimethyl group. Benzyl, methoxybenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, alpha-naphthylmethyl, beta-naphthylmethyl, Vinylbenzyl or cinnamyl; R ^5b represents an alkyl group having 1 to 4 carbon atoms, benzyl or naphthylmethyl; R ⁶ represents a hydrogen atom, a hydroxyl group or -OR ⁷ ; and R ⁷ represents a methyl group or an ethyl fluorenyl group.

The commercial product of the onium salt represented by this formula may be, for example, SAN-AID SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, etc. manufactured by Sanshin Chemical Industry Co., Ltd.

Further, the phosphonium salt can also be suitably used as the compound of the following formula:

[Chemical Formula 55]

(where Z is the same as above); or

[Chemical Formula 56]

(wherein Z is the same as above).

Further, in the case of a boron compound (a boron compound which also contains a mixture of a boron compound and a Lewis base), a compound represented by the following formula is an ideal example:

[Chemical Formula 57]

(wherein R is the same or different from each other, and represents a hydrocarbon group which may have a substituent; h is an integer of 1 to 5, and is the same or different from each other, and represents the number of fluorine atoms bonded to the aromatic ring; j is an integer of 1 or more , k is an integer of 0 or more and satisfies j+k=3).

The hydrocarbon group herein is preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited as long as the carbon atom is 1 to 20 as a whole, and is preferably an alkyl group, an aryl group or an alkenyl group. The alkyl group, the aryl group and the alkenyl group may be an unsubstituted group, or may be one in which one or more hydrogen atoms are substituted by another organic group or a halogen atom. In this case, the other organic group may, for example, be an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the entire substituted hydrocarbon group corresponds to an unsubstituted alkyl group), an aryl group, an alkenyl group, an alkoxy group, a hydroxyl group or the like.

In the above formula, h is 1, 2, 3, 4 or 5, and is the same or different from each other, and represents the number of fluorine atoms bonded to the aromatic ring. The bonding position of the fluorine atom of the aromatic ring is not particularly limited. h should be 2~5, preferably 3~5, most preferably 5.

Further, j is an integer of 1 or more, and k is an integer of 0 or more and satisfies j + k = 3. That is, at least one of the aromatic acid groups in which the Lewis acid is bonded to the fluorine atom is bonded to the boron atom. j is preferably 2 or more, more preferably 3, that is, an aromatic ring bonded with a fluorine atom has three forms bonded to a boron atom.

Among the boron compounds, specific boron compounds may be exemplified by hexafluorophenyl)borane (TPB), bis(pentafluorophenyl)phenylborane, pentafluorophenyl-diphenylborane, and ginseng ( 4-fluorophenyl)borane and the like, wherein TPB is preferred.

The mixture of the boron compound and the Lewis base is preferably a mixture of a boron compound and an amine compound, and the mixture is preferably a mixture of an amine compound such as quinone (pentafluorophenyl)borane and piperidine. Further, for example, a boron compound and an amine compound mixture described in WO2012/036164 can be suitably used. The contents of the specification and/or drawings of WO 2012/036164 are also incorporated herein by reference.

As the boron compound contained in the mixture, for example, the above boron compound can be suitably used, and ginseng (pentafluorophenyl)borane is particularly preferable. Further, the amine compound contained in the mixture is preferably a compound contained in the following items described in WO2012/036164, in addition to piperidine or the like. In addition, carbon numbers 1 to 6 represent carbon numbers 1, 2, 3, 4, 5 or 6, and carbon numbers 1 to 20 represent carbon numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, carbon number 3 to 10 means carbon number 3, 4, 5, 6, 7, 8, 9 or 10, carbon number 6 to 14 The carbon number is 6, 7, 8, 9, 10, 11, 12, 13 or 14.

Item 1n. An amine compound having a piperidine structure represented by the following formula.

[Chemical Formula 58]

[wherein, R ^1N to R ^{5N are the} same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]. The amine compound according to Item 1n, wherein the amine compound has a piperidine structure represented by the following formula.

[Chemical Formula 59]

^Wherein R ^1N to R ^5N have the same meaning as defined above; X ^N represents -O- group, -(C=O)- group, -NR ^7N - group (R ^7N represents a hydrogen atom or a carbon number of 1 to 6) Alkyl), -O(C=O)-yl, -(C=O)O-yl, -NH(C=O)-yl or -(C=O)NH-yl]. The amine compound according to Item 1n, wherein the amine compound is a compound represented by the following formula.

[Chemical Formula 60]

^Wherein R ^1N to R ^{5N are} synonymous with the above: X ^N and Z ^{N are the} same or different, and represent an -O- group, a -(C=O)- group, a -NR ^7N - group (R ^7N represents a hydrogen atom) Or an alkyl group having 1 to 6 carbon atoms, -O(C=O)- group, -(C=O)O- group, -NH(C=O)- group or -(C=O)NH- group Y ^N represents an alkylene group having 1 to 20 carbon atoms which may have a substituent; R ^6N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or the above piperidine structure; and may have a carbon number of 1 to 20 The substituent of the alkyl group is selected from the group consisting of a halogen atom, a hydroxyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms which may also have a substituent. One or more of the constituent groups; a substituent having an aryl group having 6 to 14 carbon atoms is selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The base group constitutes one or more of the groups]. The amine compound according to Item 1n, wherein the amine compound is a compound represented by the following formula.

[Chemical Formula 61]

[wherein, at least 1 (i.e., 1, 2, 3 or 4) of R ^8N to R ^11N represents the above piperidine structure, and the remainder represents an alkyl group having 1 to 20 carbon atoms]. The amine compound according to Item 1n, wherein the above amine compound is a polymer. The amine compound according to Item 1n, wherein the amine compound is a compound represented by the following formula.

[Chemical Formula 62]

[wherein, R ^1N to R ^{5N are} synonymous with the above expression]. Among them, a desirable specific example of the amine compound is represented by the following structural formula. For example, a preferred example of the amine compound described in the above item 3n is exemplified by the following compounds.

[Chemical Formula 63]

Further, a preferred example of the amine compound described in the above item 4n is as follows.

[Chemical Formula 64]

Further, a preferred example of the amine compound described in the above item 5n is as follows.

[Chemical Formula 65]

Further, a preferred example of the amine compound described in the above item 6n is as follows.

[Chemical Formula 66]

Among these, particularly preferred amine compounds are the amine compounds described in Table 1 below.

[Table 1]

Commercially available materials can also be used as the mixture of the boron compound and the amine compound. For example, the FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd. can be used.

More specific examples of the thermal cationic polymerization initiator include diphenylphosphonium hexafluoroantimonate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium tetrafluoroborate, and hexafluorophenyl)borane. (TPB), bis(pentafluorophenyl)phenylborane, pentafluorophenyl-diphenylborane, cis(4-fluorophenyl)borane, quinone (pentafluorophenyl)borate, the above hydrazine a salt, a mixture of the above boron compound and the above amine compound, and the like.

The blending ratio of the thermal cationic polymerization initiator used in the present invention is not particularly limited as long as it can exhibit the effects of the present invention. For example, it is preferably 0.01 to 50 parts by mass, more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the epoxy resin. . Further, the upper limit is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

The epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the above formula (1) within a range not impairing the effects of the present invention. For the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin can be used. , tripolyglycidyl isocyanate, hydrogenated bisphenol A epoxy resin, aliphatic epoxy resin, epoxy propyl ether epoxy resin, bisphenol S epoxy resin, biphenyl type Epoxy resin, bicyclic epoxy resin, naphthalene epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more.

When the epoxy resin other than the epoxy resin represented by the formula (1) is blended, the blend ratio of the epoxy resin represented by the formula (1) to the epoxy resin other than the epoxy resin represented by the formula (1) is in terms of mass ratio For example, it is 100:0~20:80, and it should be 100:0~30:70, preferably 100:0~40:60.

The epoxy resin composition of the present invention may contain a filler, a hardener, a hardening catalyst, a thermoplastic resin, an additive, etc., as needed, within a range not impairing the object and effect of the present invention.

The foregoing filler may, for example, be cerium oxide (more specifically, crystalline cerium oxide, molten cerium oxide, spherical molten cerium oxide, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium nitride, Inorganic carbide such as niobium carbide, boron nitride, calcium carbonate, calcium niobate, potassium titanate, aluminum nitride, indium oxide, aluminum oxide, antimony oxide, antimony oxide, magnesium oxide, iron oxide, tin-doped indium oxide (ITO), etc. Compound. Further, metals such as gold, silver, copper, aluminum, nickel, iron, zinc, and stainless steel may be mentioned. Other examples include minerals such as montmorillonite, talc, mica, boehmite, kaolin, bentonite, hard calcite, vermiculite, and sericite. Examples of the other fillers include carbon compounds such as carbon black, acetylene black, Ketjen black, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and various glasses such as glass beads, glass chips, and glass hollow spheres. Further, the filler may be used as it is or may be dispersed in the resin. The filler may be used singly or in combination of a plurality of kinds in consideration of the fluidity, heat resistance, low thermal expansion property, mechanical properties, hardness, scratch resistance, and adhesion property required for the composition and the cured product.

Examples of the curing agent include an amine curing agent, a guanamine curing agent, an acid anhydride curing agent, a phenol curing agent, a thiol curing agent, an isocyanate curing agent, an active ester curing agent, and a cyanate ester curing. Agents, etc. The hardener may be used alone or in a differentiated manner depending on the desired characteristics, and may be used in combination of two or more.

The amine-based hardener may, for example, be a chain aliphatic amine such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraamethylenetetraamine; isophoronediamine, phenylenediamine, bis(4- An alicyclic amine such as aminocyclohexyl)methane, bis(aminomethyl)cyclohexane or diaminodicyclohexylmethane; m-phenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, An aromatic amine such as diaminodiethyldiphenylmethane; dimethylbenzylamine, triethylenediamine, piperidine, 2-(dimethylaminomethyl)phenol, 2,4,6-gin (dimethyl) Aminomethyl)phenol, DBU (1,8-diazabicyclo(5,4,0)-undecene-7), DBN (1,5-diazabicyclo (4,3,0) ) - terpenes-5) and other secondary amines and tertiary amines.

The amide-based curing agent may, for example, be dicyandiamide or a derivative thereof, or a polyamide resin (polyamine amide or the like).

Examples of the acid anhydride-based curing agent include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acids such as phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, and 1,2,4,5-benzenetetracarboxylic anhydride; An acid anhydride; an alicyclic acid anhydride such as methyl nadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or 4-methylhexahydrophthalic anhydride.

The phenolic curing agent may, for example, be a phenol novolac resin, a cresol novolac resin, a biphenyl type phenol resin, a triphenylmethane type phenol resin, a naphthol novolac resin, a phenol coexisting phenyl resin, a phenol aralkyl resin, or a biphenyl aryl group. Alkyl phenol resin, modified polyphenylene ether resin, with benzo Ring compounds, etc.

Examples of the thiol-based hardener include trimethylolpropane ginseng (3-propionate), ginseng-[(3-propionyloxy)-ethyl]-trimeric isocyanate, and neopentyl pentoxide (3). -propionate), tetraethylene glycol bis(3-propionate), pentaerythritol bismuth (3-butyrate), 1,4-bis(3-indolyloxy) butyl Alkane, trimethylolpropane ginseng (3-butyrate), trishydroxymethyl ginseng (3-butyrate), polysulfide polymer, and the like.

The isocyanate-based curing agent may, for example, be hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, ammonium diisocyanate or isophorone diisocyanate. , norbornane diisocyanate, and the like.

The active ester-based curing agent is, for example, a compound having one or more ester groups capable of reacting with an epoxy resin in one molecule, and examples thereof include phenol ester, thiophenolate ester, N-hydroxylamine ester, and heterocyclic hydroxy compound ester. .

The hardening catalyst may, for example, be an imidazole compound, a dicyandiamide, a tertiary amine, a phosphorus compound or a Lewis acid compound. The hardening catalyst can be used alone or in accordance with the desired characteristics, and two or more types can be used in combination.

The thermoplastic resin may, for example, be a polyolefin resin, an acrylic resin, a phenoxy resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyurethane resin, a polyarylate resin, a poly(phenylene ether) resin, A polyacetal resin, such an acid-modified substance, and the like. From the viewpoint of compatibility with the epoxy resin composition of the present invention and heat resistance, a polyolefin resin, an acrylic resin, a phenoxy resin, a polyarylate resin, a polyphenylene ether resin, and the like are modified by acid. It is preferable that the polyolefin resin or the acid-modified polyolefin resin is more preferable. The thermoplastic resin may be used singly or in combination of two or more.

The foregoing additives may, for example, be antioxidants, inorganic phosphors, slip agents, ultraviolet absorbers, thermo-light stabilizers, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, radical inhibitors, adhesions Improver, flame retardant, surfactant, storage stability improver, ozone aging agent, thickener, plasticizer, radiation shielding agent, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide A decomposing agent, a pigment, a metal inerting agent, a physical property adjuster, and the like.

The epoxy resin composition of the present invention can be produced by mixing an epoxy resin represented by the formula (1) and a thermal cationic polymerization initiator, and further mixing other components as needed. The mixing method is not particularly limited as long as it is a method of uniform mixing. The epoxy resin composition of the present invention may be added with a solvent (for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, or the like insofar as it does not adversely affect the effects of the present invention. Cyclohexane, etc.).

By hardening the epoxy resin composition of the present invention, a cured product (i.e., a cured product of the epoxy resin composition) can be obtained. The curing method is not particularly limited, and for example, the composition can be heat-cured. The hardening temperature is usually from room temperature to 250 ° C, and the hardening time varies depending on the composition. Usually, the setting range can be as wide as 30 minutes to 1 week.

In addition, the term "contains" as used in this specification also includes "the term "comprising" includes "consisting essentially of" and "consisting of."). Example

The invention will be more specifically described below, but the invention is not limited by the following examples.

Production Example 1 (Production of Epoxy Resin A) In a four-necked flask of 200 mL capacity equipped with a stirrer, a thermometer, and a cooler, 5.4 g of allyl epoxypropyl ether and hexachloroplatinic acid hexahydrate were fed under a nitrogen atmosphere. After 0.05 g of a 2 wt% ethanol solution and 100 g of toluene, the temperature of the liquid was raised to 70 °C. Thereafter, 5.0 g of 1,4-bis(dimethylindenyl)benzene was added dropwise thereto over 15 minutes, followed by stirring at 90 ° C for 4 hours. After removing toluene by concentration, 1,4-bis[(2,3-epoxypropyloxypropyl)dimethylmethyl]benzene (epoxy resin A) 10.3 g (epoxy) was obtained as a colorless transparent liquid. Equivalent 211 g/eq).

Production Example 2 (Production of Epoxy Resin B) In a four-necked flask of 200 mL capacity equipped with a stirrer, a thermometer, and a cooler, 5.0 g of 1,2-epoxy-5-hexene and hexachlorobenzene were fed under a nitrogen atmosphere. After 0.05 g of a 2 wt% ethanol solution of platinum acid hexahydrate and 100 g of toluene, the liquid temperature was raised to 70 °C. Thereafter, 5.0 g of 1,4-bis(dimethylindenyl)benzene was added dropwise thereto over 15 minutes, followed by stirring at 90 ° C for 5 hours. After removing toluene by concentration, 9.5 g of 1,4-bis[(2,3-epoxybutyl)dimethylamyl]benzene (epoxy resin B) was obtained as a colorless transparent liquid (epoxy equivalent: 195 g/eq). ).

Production Example 3 (Production of Epoxy Resin C) In a four-necked flask of 200 mL capacity equipped with a stirrer, a thermometer, and a cooler, 1,2-epoxy-4-vinylcyclohexane was fed under a nitrogen atmosphere to 6.4 g. After 0.05 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate and 100 g of toluene, the liquid temperature was raised to 70 °C. Thereafter, 5.0 g of 1,4-bis(dimethylindenyl)benzene was added dropwise thereto over 15 minutes, followed by stirring at 90 ° C for 4 hours. After removing toluene by concentration, 1,4-bis{[2-(3,4-epoxycyclohexyl)ethyl]dimethylmethyl}benzene (epoxy resin C) 10.8 g (colorless transparent liquid) was obtained. Epoxy equivalent of 221 g/eq).

Production Example 4 (Production of Epoxy Resin D) In a four-necked flask of 200 mL capacity equipped with a stirrer, a thermometer, and a cooler, 1,2-epoxy-4-vinylcyclohexane was fed under a nitrogen atmosphere to 4.3 g. After adding 0.05 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate and 250 g of toluene, the temperature of the liquid was raised to 70 °C. Thereafter, 5.0 g of bis[(p-dimethylindenyl)phenyl]ether was added dropwise thereto over 15 minutes, followed by stirring at 90 ° C for 6 hours. After removing toluene by concentration, 4,4'-bis{[2-(3,4-epoxycyclohexyl)ethyl]dimethylamyl}diphenyl ether (epoxy resin D) was obtained as a colorless transparent liquid. ) 8.9 g (epoxy equivalent: 267 g/eq).

Production Example 5 (Production of Epoxy Resin E) In a four-necked flask of 200 mL capacity equipped with a stirrer, a thermometer, and a cooler, 7.4 g of 1,2-epoxy-4-vinylcyclohexane was fed under a nitrogen atmosphere. After adding 0.05 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate and 250 g of toluene, the temperature of the liquid was raised to 70 °C. Thereafter, 5.0 g of 1,3,5-gin(dimethylindenyl)benzene was added dropwise thereto over 15 minutes, followed by stirring at 90 ° C for 6 hours. After removing toluene by concentration, a 1,3,5-parade {[2-(3,4-epoxycyclohexyl)ethyl]dimethylmethyl}benzene (epoxy resin E) 11.8 was obtained as a colorless transparent liquid. g (epoxy equivalent: 208 g/eq).

EXAMPLES AND COMPARATIVE EXAMPLES Each component of the blending amounts shown in Tables 2 and 3 was weighed in a measuring cup, and stirred at room temperature (25 ° C) for 5 minutes using a magnetic stirrer to prepare an epoxy resin composition.

The components in Table 2 and Table 3 are as follows. In addition, the numerical values of the respective components of Tables 2 and 3 indicate the parts by mass.

・Epoxy resin F: Bis-A type epoxy resin (Grade 828) made by Mitsubishi Chemical Corporation (epoxy equivalent 189g/eq) ・Epoxy resin G: DAICEL CO. alicyclic epoxy resin (CELLOXIDE 2021P; general 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) (epoxy equivalent: 137 g/eq) ・Cation polymerization initiator A: SAN-made by Sanshin Chemical Industry Co., Ltd. AID SI-60L ・Cationic polymerization initiator B: FX-TP-BC-PC-AD-57103 manufactured by Nippon Shokubai Co., Ltd.

Test Example 1 (1) Rapid Curability The epoxy resin compositions obtained in the examples and the comparative examples were heated in an oven at 140 ° C, and evaluated as ◎ in the case of hardening within 30 seconds, and evaluated as ○ in 2 minutes. Those who have not hardened within minutes are evaluated as ×. The results are shown in Table 2 and Table 3.

(2) 90-degree peel strength with respect to copper foil The epoxy resin composition obtained by the Example and the comparative example was apply|coated on the aluminum board, and the electrolytic copper foil of 35 micrometers thick was laminated|stacked from it. system). The mixture was heated at 100 ° C for 1 hour, at 120 ° C for 2 hours, and at 150 ° C for 2 hours to be hardened. After hardening, a slit having a width of 1 cm was placed with a cutting blade to prepare a 90-degree peel strength test piece. For the obtained test piece, AGS-X (manufactured by Shimadzu Corporation) was used, and a 90-degree peel strength test was carried out under the conditions of a test speed of 50 mm/min. The results are shown in Table 2 and Table 3.

(3) Electrical characteristics (relative dielectric constant, dielectric loss tangent) Each epoxy resin composition obtained in the examples and the comparative examples was poured into a resin mold (thickness: 2 mm), and heated at 100 ° C for 1 hour. The mixture was heated at 120 ° C for 2 hours and at 150 ° C for 2 hours to be hardened. Next, the cured product was cut into a size of 20 mm in width × 30 mm in length × 2 mm in thickness to prepare a test piece for measuring the dielectric constant.

The relative dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) of the obtained test piece were measured at 25 ° C using a dielectric constant measuring device (impedance analyzer, manufactured by Agilent Co., Ltd.). In addition, the calibration of the dielectric coefficient measuring device was performed using PTFE. The results are shown in Table 2 and Table 3.

(4) Water resistance (change rate of elastic modulus before and after water absorption test) Each epoxy resin composition obtained in the examples and the comparative examples was poured into a resin mold (thickness: 2 mm), and heated at 100 ° C for 1 hour. The mixture was heated at 120 ° C for 2 hours and at 150 ° C for 2 hours to be hardened. Next, the cured product was cut into a size of 20 mm in width × 30 mm in length × 2 mm in thickness to prepare a test piece for evaluation of water resistance. The obtained test piece was immersed in pure water at room temperature for one week, and subjected to water absorption treatment. The storage elastic modulus was measured in a tensile mode and a temperature increase rate of 10 ° C/min using a dynamic viscoelasticity measuring apparatus (RSG-G2, manufactured by TA Instruments). The rate of change of the elastic modulus before and after water absorption was calculated by the following formula, and the water resistance of 95% or more was evaluated as ◎, and the water resistance of 90% or more and less than 95% was evaluated as ○, and when it was less than 90%, the water resistance was evaluated as ×. (Storage modulus at 30 ° C after storage test / storage modulus at 30 ° C before water absorption) × 100 The results are shown in Table 2 and Table 3.

[Table 2]

[table 3]

Claims (8)

An epoxy resin composition containing an epoxy resin represented by the following formula (1) and a thermal cationic polymerization initiator: [Chemical Formula 1] (wherein the X ring is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or having 2 saturated hydrocarbon rings and/or Or a ring of a structure of an unsaturated hydrocarbon ring; wherein R ^Xa , R ^Xb , R ^Xc and R ^{Xd are the} same or different, and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom or the following a group represented by the formula (3): [Chemical Formula 2] (wherein R ^{1 is the} same or different from each other, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part of carbon atoms It is selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ² represents an alkylene group having a carbon number of 1 to 18, and the group is bonded to a carbon atom directly bonded to a ruthenium atom. A part of the carbon atoms may be selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{3 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms and a carbon number of 2 to 9 An alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have a part of carbon atoms substituted by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; m represents 0 to 6 An integer of n; an integer of 0 to 3; wherein, at least one of R ^Xa , R ^Xb , R ^Xc and R ^Xd is a group represented by the formula (3), and constitutes a hydrocarbon ring for forming an X ring; ^Further , the hydrogen atom to which the carbon atoms of R ^Xa , R ^Xb , R ^Xc and R ^Xd are bonded may be substituted by a lower alkyl group, a lower alkoxy group, a lower alkenyl group or a halogen atom). The epoxy resin composition of claim 1, wherein the ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded is a ring represented by the following formula (2): [Chemical Formula 3] (wherein the X ¹ ring and the X ² ring are the same or different from each other, and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y represents a bond bond, and may also be substituted with a carbon number of 1 to 4 carbon atoms 1 to 6 An alkyl group, an oxygen atom (-O-), a sulfur atom (-S-), -SO- or -SO ₂ -). The epoxy resin composition according to claim 1 or 2, wherein the saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms, and the unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms. An epoxy resin composition according to claim 1, which comprises at least one epoxy resin selected from the group consisting of epoxy resins and a thermal cationic polymerization initiator; a ring represented by the formula (1-iia) Oxygen resin: [Chemical Formula 4] (wherein, X ⁱⁱ represents a divalent group obtained by removing a hydrogen atom from a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or a ring having a structure in which a ring of 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring is condensed. The divalent group represented by the formula (2 ^g -iia): [Chemical Formula 5] (wherein Y represents a bond bond, an alkyl group having 1 to 6 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), - SO- or -SO ₂ -); R ^{1 is the} same or different, and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the groups A part of the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{2 is the} same or different from each other, and represents an alkylene group having 1 to 18 carbon atoms, and the base is excluded. A part of the carbon atoms outside the carbon atom directly bonded to the ruthenium atom may be selected from at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ^{3 is the} same or different from each other, and represents a carbon number of 1 to 18 An alkyl group, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the group may have at least a part of carbon atoms selected from the group consisting of an oxygen atom and a nitrogen atom. 1 atomic substitution; m represents an integer from 0 to 6; n represents an integer from 0 to 3; and an epoxy resin of the formula (1-iiia): [Chemical Formula 6] (wherein, X ⁱⁱⁱ represents a trivalent group obtained by removing three hydrogen atoms from a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or a ring having a structure in which a ring of 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring is condensed or the following a trivalent group represented by the formula (2 ^{g -} iiia): [Chemical Formula 7] (wherein Y is the same as the above); and R ¹ , R ² , R ³ , m and n are the same as defined above. The epoxy resin composition according to any one of claims 1 to 4, wherein the thermal cationic polymerization initiator is selected from the group consisting of a phosphonium salt, a boron compound, and a mixture of a boron compound and a Lewis base. . The epoxy resin composition according to any one of claims 1 to 5, which contains 0.01 to 50 parts by mass of a thermal cationic polymerization initiator based on 100 parts by mass of the epoxy resin. A hardened material, which is a cured product of the epoxy resin composition according to any one of claims 1 to 6. A semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover film, an electromagnetic wave shielding film, a printed substrate material or a composite material, which is used according to any one of claims 1 to 6. An epoxy resin composition or a cured product as claimed in claim 7.