WO2018131564A1 - 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, a use of the composition, and the like.

Epoxy resins are widely used in various applications such as adhesives, electronic materials and composite materials. However, there is a constant demand for higher performance of epoxy resin materials. For example, with the energy saving of the manufacturing process, a rapidly curing epoxy resin material is required. In the field of electronic materials, further improvement in electrical characteristics is desired.

For example, Patent Document 1 describes an epoxy resin composition excellent in rapid curability by combining an epoxy resin and a cationic polymerization initiator. In the epoxy resin composition described in Patent Document 1, curability is improved by using a sulfonium borate salt as a cationic polymerization initiator. However, electrical properties and water resistance are still not sufficient.

International Publication Number 2012/042796 British Patent No. 1123960

Therefore, an object of the present invention is to provide an epoxy resin composition having not only fast curability but also excellent electrical properties and water resistance after curing, and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventor has found that an epoxy resin composition containing a specific epoxy resin containing a silicon atom and a thermal cationic polymerization initiator has excellent rapid curability. The present inventors have found that an epoxy resin composition having low dielectric properties and water resistance can be obtained after curing. Based on this knowledge, further research was conducted and the present invention was completed.

The present invention encompasses the subject matter described in the following sections.
Item 1.
Formula (1):

(In the formula, the ring X 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 connected,
R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):

(In the formula, 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. The carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R ² represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. May be substituted with
R ^{3 s} are the same or different and each 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 these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
m represents an integer of 0 to 6,
n represents an integer of 0 to 3. )
However, at least one of R ^Xa , R ^Xb , R ^Xc , and R ^Xd is a group represented by the formula (3),
A hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R ^Xa , R ^Xb , R ^Xc , and R ^Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom. )
The epoxy resin composition containing the epoxy resin represented by these, and a thermal cationic polymerization initiator.
Item 2.
A ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected,
Formula (2):

(Wherein, ring X ^{1 and} ring X ² are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO ₂ —). The epoxy resin composition described in 1.
Item 3.
The saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
The unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms;
Item 3. The epoxy resin composition according to Item 1 or 2.
Item 4.
Formula (1-ia):

( ^Wherein X ⁱⁱ 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, to two hydrogen atoms A divalent group obtained by removing or a formula (2 ^g -ia):

(Wherein Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), -SO- or -SO _2- )).
R ^{1 s} are the same or different and each 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 these groups have a part of 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 and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. Optionally substituted with at least one atom
R ^{3 s} are the same or different and each 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 these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
m represents an integer of 0 to 6,
n represents an integer of 0 to 3. )
And an epoxy resin represented by the formula (1-iiia):

(In the formula, X ⁱⁱⁱ 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, to 3 hydrogen atoms A trivalent group obtained by removing or a formula (2 ^g -iiia):

(Wherein Y represents the same as described above),
R ¹ , R ² , R ³ , m, and n are the same as described above. )
Item 2. The epoxy resin composition according to item 1, comprising at least one epoxy resin selected from the group consisting of epoxy resins represented by: and a thermal cationic polymerization initiator.
Item 5.
Item 5. The epoxy resin composition according to any one of Items 1 to 4, wherein the thermal cationic polymerization initiator is at least one selected from the group consisting of a sulfonium salt, a boron compound, and a mixture of a boron compound and a Lewis base.
Item 6.
Item 6. The epoxy resin composition according to any one of Items 1 to 5, comprising 0.01 to 50 parts by mass of a thermal cationic polymerization initiator with respect to 100 parts by mass of the epoxy resin.
Item 7.
Item 7. A cured product of the epoxy resin composition according to any one of Items 1 to 6.
Item 8.
A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, wherein the epoxy resin composition according to any one of Items 1 to 6 or the cured product according to Item 7 is used, Coverlay film, electromagnetic shielding film, printed circuit board material or composite material.
Item 9.
Any one of Items 1 to 6, which is used for a semiconductor encapsulant, a liquid encapsulant, a potting material, a seal material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic shielding film, a printed circuit board material, or a composite material Item 8. The epoxy resin composition according to Item 8, or the cured product according to Item 7.
Item 10.
Any one of Items 1 to 6 for producing a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic wave shielding film, a printed circuit board material, or a composite material Use of the epoxy resin composition according to Item 8 or the cured product according to Item 7.

Since the epoxy resin composition of the present invention contains a specific epoxy resin and a thermal cationic polymerization initiator, it has excellent fast curability, and the cured product has electrical properties (low dielectric properties) and heat resistance. is doing. Moreover, it is excellent also in water resistance. Therefore, the epoxy resin composition of the present invention includes, 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 lay film, an electromagnetic wave shielding film, a printed board material, and a composite material. It can be suitably used for a wide range of uses.

Hereinafter, each embodiment of the present invention will be described in more detail.

The epoxy resin composition included in the present invention has the formula (1):

And a thermal cationic polymerization initiator.

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

(Hereinafter sometimes referred to as “group of formula (3)”). Hereinafter, the lower alkyl group, the lower alkoxy group, and the lower alkenyl group may be collectively referred to as “lower carbon substituent”. In the present invention, among the lower carbon substituents, a lower alkyl group or a lower alkoxy group is more preferable.

However, at least one of R ^Xa , R ^Xb , R ^Xc , and R ^Xd is a group of the formula (3). In other words, R ^Xa , R ^Xb , R ^Xc , and R ^Xd are three hydrogen atoms or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen atoms or halogen atoms or Two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or lower carbon substituent and three are groups of formula (3), or all are of formula (3) It is a group. More specifically, for example, among R ^Xa , R ^Xb , R ^Xc , and R ^Xd , (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 (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 formula (3), or (iii) R ^Xa Is a hydrogen atom or a halogen atom or a lower carbon substituent, and R ^Xb , R ^Xc , and R ^Xd are groups of the formula (3), or (iv) all of R ^Xa , R ^Xb , R ^Xc , and R ^Xd Can be a group of formula (3). Of R ^Xa , R ^Xb , R ^Xc , and R ^Xd , those that are not the group of formula (3) are more 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. Therefore, (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 group of the formula (3), R ^Xa , R ^Xb and R ^Xc may be the same or different, and (ii) R ^Xa and R ^Xb are a hydrogen atom, a halogen atom or a lower carbon substituent. When R ^Xc and R ^Xd are a group of the formula (3), R ^Xa and R ^Xb may be the same or different, R ^Xc and R ^Xd may be the same or different, and (iii) R ^Xa is a hydrogen atom or When R ^Xb , R ^Xc , and R ^Xd are a group of formula (3) with a halogen atom or lower carbon substituent, R ^Xb , R ^Xc , and R ^Xd may be the same or different, and (iv) R ^Xa , ^{R Xb, Xc,} and when all ^{R Xd} is a group of formula (3) ^{is, R Xa, R Xb, R} Xc, and ^{R Xd} may be the same or different. In any of these cases, the groups of the formula (3) are preferably the same.

In addition, when 2 or 3 of R ^Xa , R ^Xb , R ^Xc , and R ^Xd are halogen atoms or lower carbon substituents, these halogen atoms or lower carbon substituents may be the same or different. . In this case, 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 refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group. Here, “lower” means 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Of the lower carbon substituents, a lower alkyl group or a lower alkoxy group is preferred. Specific examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Preferred examples of the lower alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

In this 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 connected. . In the present specification, as the saturated hydrocarbon ring, for example, a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a cyclopentane ring, a cyclohexane ring and the like are particularly preferable. In the present specification, as the unsaturated hydrocarbon ring, for example, an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a benzene ring or the like is particularly preferable. Further, in the present specification, as the ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, the saturated hydrocarbon ring and / or unsaturated hydrocarbon ring is 2, 3, Alternatively, a ring having 4 condensed rings is preferable, and a ring having 2 or 3 condensed rings is more preferable. More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- Examples include an octahydronaphthalene ring and a norbornene ring.

In this 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 collectively referred to as a “hydrocarbon ring”. May be called.

As a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, the formula (2):

The ring represented by is preferable.

In the formula (2), the X ¹ ring and the X ² ring are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X ¹ ring and the X ² ring are both saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. It is preferable that both the X ¹ ring and the X ² ring are saturated hydrocarbon rings or both are unsaturated hydrocarbon rings. For example, the X ¹ ring and the X ² ring are preferably both benzene rings, both cyclohexane rings, or one is a benzene ring and the other is a cyclohexane ring, and more preferably both are benzene rings.

Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO. -Or -SO ₂ -is shown. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Preferred examples of the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms include —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH ₂ CH (CH ₃ ) CH. Examples thereof include _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—, —SO ₂ —, and more preferably a bond, a dimethylmethylene group, an oxygen atom, —SO ₂ —.

The ring represented by formula (2) is substituted with R ^Xa , R ^Xb , R ^Xc , and R ^Xd . The ring X in the formula (1) is a ring represented by the formula (2), wherein 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). In some cases, either X ¹ ring or X ² ring may be substituted with a group of formula (3). In this case, when the ring represented by formula (2) is substituted with 0, 1, 2, or 3 halogen atoms or a lower-carbon substituent group, substituted (X ¹ ring halogen atom or a lower carbon substituent Number: X ² ring substitution number) is (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 are groups of the formula (3), either the X ¹ ring or the X ² ring is a group of the formula (3) in may be substituted, X ¹ ring and X ² rings may be substituted by one by one group of the formula (3), X ¹ ring and X ² ring group of the formula (3) one by one It is preferably substituted with. In this case, the ring represented by the formula (2) is substituted with 0, 1, or 2 halogen atoms or lower carbon substituents, and the halogen atom or lower carbon substituent (X ¹ ring substitution number: X ² The number of ring substitutions can 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 groups of the formula (3), either the X ¹ ring or the X ² ring is a group of the formula (3) May be substituted with two X ¹ rings, one X ² ring may be substituted with one group of formula (3), one X ¹ ring and two X ² rings with formula (3) In which two X ¹ rings are substituted with one X ² group or ^one X ¹ ring and two X ² rings are represented by formula (3). It is preferably substituted with a group of In this case, the ring represented by the formula (2) is substituted with 0 or 1 halogen atom or a lower carbon substituent, and the halogen atom or lower carbon substituent (the number of substitution of X ¹ ring: substitution of X ² ring) The number) can be (1: 0) or (0: 1). When all of R ^Xa to R ^Xd are groups of the formula (3), either the X ¹ ring or the X ² ring may be substituted with four groups of the formula (3), and the X ¹ ring is 3 One X ² ring may be substituted with one group of formula (3), one X ¹ ring may be substituted with three X ² rings with three groups of formula (3), and X ¹ ring There may be substituted with two X ² rings two formulas (3) group, it is preferred that X ¹ ring are two X ² ring is substituted by two groups of formula (3).

Formula (1 '), which is a group that is part of Formula (1):

(In formula (1 ′), ring X is the same as above.)
As the tetravalent group represented by the formula, a group represented by the following formula is particularly preferable. That is,

Or

Or

(In formula (2 ^g ), Y is the same as above.)
It is group represented by these.

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. Part of the 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 partial carbon atoms are preferably carbon atoms that are not directly bonded to a silicon atom. The part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. Incidentally, R ¹ bonded to the same silicon atom in view like the simplicity of the synthesis is preferably the same. Moreover, it is more preferable that all R ¹ existing in the formula (1) is the same.

The alkyl group having 1 to 18 carbon atoms represented by R ¹ is a linear or branched alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- Nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned. An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable.

The alkenyl group having 2 to 9 carbon atoms represented by R ¹ is a linear or branched alkenyl group such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, etc. are mentioned. An alkenyl group having 2 to 4 carbon atoms is preferred.

Examples of the cycloalkyl group represented by R ¹ include a 3- to 8-membered cycloalkyl group, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.

Examples of the aryl group represented by R ¹ include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Preferably, it is a phenyl group.

Examples of the aralkyl group represented by R ¹ include an alkyl group having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group). For example, benzyl group, α-phenethyl group, β-phenethyl group, β- Examples thereof include a methylphenethyl group.

R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more 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, preferably a linear alkylene group. For example, methylene, methylmethylene, ethylmethylene, dimethylmethylene, diethylmethylene, dimethylene (—CH ₂ CH ₂ —), trimethylene (—CH ₂ CH ₂ CH ₂ —), tetramethylene, penta Examples include a methylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a tridecamethylene group. For example, an alkylene group having 2 to 18 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms. And particularly preferably an alkylene group having 2 to 5 carbon atoms.

In the alkylene group having 1 to 18 carbon atoms, some 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 partial carbon atom is preferably a carbon atom that is not directly bonded to any of a silicon atom and a 3- to 8-membered ring or an epoxy ring. The part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.

Examples of the group include, when the side bonded to the silicon atom of R ² is (*), for example, (*)-alkylene having 2 to 9 carbon atoms-O-alkylene having 1 to 8 carbon atoms, preferably (*)-C2-C4 alkylene-O-C1-C3 alkylene-, more preferably (*)-C2-C4 alkylene-O-C1-C2 alkylene-, especially Preferably, (*)-C3 alkylene-O-methylene- is used.

Specifically, for example, (*) — (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- and the like, among which (*)-(CH ₂ ) ₃ -O-CH _2- preferable.

In the formula (3), m represents an integer of 0 to 6 (that is, 0, 1, 2, 3, 4, 5, or 6). N represents an integer of 0 to 3 (that is, 0, 1, 2, or 3). Here, a group to which R ^{2 of} formula (3) is bonded (side not bonded to a silicon atom) is represented by formula (4) (hereinafter, sometimes referred to as “group of formula (4)”). It becomes as follows.

For the group of formula (4), when m is an integer of 1 to 6, specifically described by the structural formula,
When m = 1

When m = 2

When m = 3

When m = 4

When m = 5

When m = 6

It is indicated.

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

In the formula (3), R ² and R ³ are bonded to a 3- to 8-membered ring or an epoxy ring. Note that n represents the number of R ³ bonded to a 3- to 8-membered ring or an 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. 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. The partial carbon atom is preferably a carbon atom that is not directly bonded to a 3- to 8-membered ring or an epoxy ring. The part of carbon atoms which may be substituted may be 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.

Alkyl group R ³ having 1 to 18 carbon atoms represented by an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, each aryl group and aralkyl group, those similar to the corresponding substituents represented by R ¹ Can be mentioned.

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

Among these, as preferred examples of the group of the formula (3), R ¹ , R ² , R ³ , m, and n are the same as described above, and all of R ¹ are the same, and R ³ is present in a plural number. In some cases) groups that are all identical are mentioned. The group is present in the epoxy resin represented by the formula (1) in 1, 2, 3 or 4, and each group may be the same or different, and is preferably the same.

Further, as a particularly preferred specific example of the group of formula (4), R ³ is the same as above, and m is 0, 1, 2, 3 or 4, and n is 0, 1 or 2. Among them, more preferred are the following groups (all of which R ³ is as defined above).

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

In addition, a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R ^Xa , R ^Xb , R ^Xc , and R ^Xd are not bonded is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent). That is, when the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, these rings are constituted. And a hydrogen atom bonded to a carbon atom to which R ^Xa , R ^Xb , R ^Xc , and R ^Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent) And when the X ring is a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, these connected saturated hydrocarbon rings and / or unsaturated hydrocarbon rings and R ^Xa a carbon atom constituting the hydrocarbon ^{ring, R} Xb, ^{R Xc,} and hydrogen atoms bonded to the carbon atom to which R ^Xd is not bound is a lower carbon substituent or a halogen atom (preferably lower carbon location It may be substituted by a group). The case where the X ring is a ring represented by the formula (2) will be described more specifically. The carbon atoms constituting the X ¹ ring and the X ² ring, and R ^Xa , R ^Xb , R ^Xc , And a hydrogen atom bonded to a carbon atom to which R ^Xd is not bonded may be substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent).

In this specification, a carbon atom that constitutes a hydrocarbon ring constituting the X ring and to which R ^Xa , R ^Xb , R ^Xc , and R ^Xd are not bonded is referred to as “R ^Xa-d non-bonded”. Sometimes called a "carbon atom."

R ^Xa-d non-bonded hydrogen atoms bonded to carbon atoms may be substituted lower carbon substituent group or a halogen atom, it is preferable to only one single R ^Xa-d unbound carbon atoms bonds. That is, when the hydrogen atom attached to R ^Xa-d unbound carbon atoms is substituted, one hydrogen atom have a lower carbon substituent or a halogen of the hydrogen atoms bonded to R ^Xa-d unbound carbon atoms It is preferably substituted with an atom. Further, the number of substitutions (that is, the total of the lower carbon substituent and the halogen atom) is preferably smaller than the number of R ^Xa-d non-bonded carbon atoms. More specifically, the number of the substitution is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, and still more preferably 1 to 2. In particular, when the X ring is a ring represented by the formula (2), the hydrogen atom to be substituted is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.

When at least one of R ^Xa , R ^Xb , R ^Xc , and R ^Xd is a lower carbon substituent and at least one lower carbon substituent is bonded to an R ^Xa-d unbonded carbon atom, It is preferred that the carbon substituents are the same. That is, ^if there is a lower carbon substituent in R ^Xa , R ^Xb , R ^Xc , and R ^{Xd and} there is a lower carbon substituent bonded to an R ^Xa-d unbonded carbon atom, all lower carbon substitutions It is preferred that the groups are the same. 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 the R ^Xa-d non-bonded carbon atom. It is preferred that all halogen atoms are the same. That is, when a halogen atom is present in R ^Xa , R ^Xb , R ^Xc , and R ^Xd and a halogen atom bonded to an R ^Xa-d unbonded carbon atom is present, all halogen atoms are the same. Is preferred.

More specifically, for example, a tetravalent group represented by the above formula (1 ') is

In the case where the epoxy resin represented by the formula (1) is represented by the formula (1-X1)

(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 and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group. An epoxy resin represented by a group or a lower alkenyl group is preferred. In the formula (1-X1), it is more preferable that R ^Xa , R ^Xb , R ^Xc , R ^Xd , R ^Xg1 and R ^Xg2 are bonded to different carbon atoms on the benzene ring, respectively. Among the epoxy resins represented by the formula (1-X1), those in which R ^Xg1 and R ^Xg2 are hydrogen atoms are preferable.

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

(In the formula (1-X1a), R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same as described above, and R ^Xg1 and R ^Xg2 are the same as described above), (1-X1b):

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

Among the epoxy resins represented by the formula (1-X1a), for example, R ^Xa and R ^Xb are hydrogen atoms, R ^Xc and R ^Xd are groups of the formula (3), and R ^Xg1 and R ^Xg2 are hydrogen atoms. In some cases, R ^Xa and R ^Xc are hydrogen atoms, R ^Xb and R ^Xd are groups of the formula (3), and R ^Xg1 and R ^Xg2 are more preferably hydrogen atoms.

Also, among the epoxy resins represented by the formula (1-X1b), for example, R ^Xa is a hydrogen atom, R ^Xb , R ^Xc and R ^Xd are groups of the formula (3), and R ^Xg1 and R ^Xg2 are hydrogen. More preferably, it is an atom.

In addition, the tetravalent group represented by the above formula (1 ')

(In formula (2 ^g ), Y is the same as above.)
In the case of a group represented by formula (1), the epoxy resin represented by formula (1) is

(In the formula (1-X2), Y is the same as defined above; R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same as defined above; R ^X11 , R ^X12 , R ^X13 , and R ^X21 , R ^X22 and R ^X23 may be the same or different and each represents 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 more preferably bonded to different carbon atoms, and R ^Xb , R ^Xd , R ^X21 , More preferably, R ^X22 and R ^X23 are bonded to different carbon atoms. Also, 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 carbon atom to which Y is bonded.

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

(In the formula (1-X2a), Y is the same as defined above; R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same as defined above; R ^X11 , R ^X12 , and R ^X13 and R ^X21 , R ^X22 and R ^X23 are the same or different and each represents 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):

(In the formula (1-X2b), Y is the same as defined above; R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same as defined above; R ^X11 , R ^X12 , R ^X13 , and R ^X21 , R ^X22 and R ^X23 are the same or different and each represents 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):

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

Among the epoxy resins represented by the formula (1-X2a), for example, R ^Xa , R ^Xb , R ^Xc , and R ^Xd are groups of the formula (3), and R ^X11 and R ^X21 are lower carbon substituents. ^Yes , it is preferable that R ^X12 , R ^X13 , R ^X22 , and R ^X23 are hydrogen atoms. Among them, Y is an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms (particularly —C (CH ₃ ) ₂ —), and R ^Xa , R ^Xb , R ^Xc , And R ^Xd is 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 particularly preferably hydrogen atoms. In these cases, it is more preferable that 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 the same.

Among the epoxy resins represented by the formula (1-X2b), for example, R ^Xa and R ^Xb are hydrogen atoms, R ^Xc and R ^Xd are groups of the formula (3), and R ^X11 , R ^X12 , R ^X13 , R ^X21 , R ^X22 , and R ^X23 are preferably a hydrogen atom. In this case, it is more preferable that the groups of the formula (3) of R ^Xc and R ^Xd are the same.

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

In the present specification, the explanation regarding the X ring, R ^Xa , R ^Xb , R ^Xc , and R ^Xd in formula (1), and R ¹ , R ² , R ³ , m, and n in the group of formula (3) In addition, any combination including the description of the group of the formula (4) can be arbitrarily combined, and any epoxy resin represented by the combination can be used in the present invention.

In the formula ^{(1), (iia) R} Xa-d -bonded hydrogen atom has not been substituted in the non-bonded carbon atom, ^and, R ^Xa, R ^Xb, of ^{R Xc,} and ^{R Xd, R Xa} and R ^Xb is a hydrogen atom and R ^Xc and R ^Xd are groups of the formula (3), or (iii) the hydrogen atom bonded to the R ^Xa-d non-bonded carbon atom is not substituted, and R ^Xa , R ^{Among Xb} , R ^Xc , and R ^Xd , R ^Xa is a hydrogen atom and R ^Xb , R ^Xc , and R ^Xd are groups of the formula (3), or (iva) R ^{Xa-d is} bonded to a non-bonded carbon atom. The bonded hydrogen atoms are not substituted and all of R ^Xa , R ^Xb , R ^Xc , and R ^Xd can be groups of formula (3).

In the case of (ia), the epoxy resin represented by the formula (1) is represented by the following formula (1-ia):

[Wherein X ⁱⁱ represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a formula (2 ^g -ia):

(Wherein Y is the same as defined above),
R ¹ , R ² , R ³ , m, and n are the same as described above. ]
The epoxy resin represented by these is preferably included. Note that R ¹ , R ² , R ³ , m, and n may all be the same or different, and are preferably the same.

As divalent group represented by X ^ii, preferably cyclohexane-1,4-diyl group, a 1,4-phenylene group, more preferably a 1,4-phenylene group.

Of the divalent groups represented by the formula (2 ^g -ia), the formula (2 ^g -ia ') is preferable:

(Wherein Y is the same as above)
It is group represented by these.

In the formula (2 ^g -ia ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO ₂ — is particularly preferable.

As X ^ii, among them preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, the formula ⁽² g ^-iia ') can be mentioned, more preferably a 1,4-phenylene group.

For example, in the formula (1-ia), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R ³ is a ring X ⁱⁱ is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R ¹ is the same and has 1 to 3 carbon atoms. A group of ² to 6 carbon atoms in which R ² is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.

In the case of (iii), the epoxy resin represented by the formula (1) is represented by the following formula (1-iii):

[Wherein X ⁱⁱⁱ is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or a compound represented by the formula (2 ^g -iii):

(Wherein Y is the same as above), and R ¹ , R ² , R ³ , m, and n are the same as above. ]
The epoxy resin represented by these is preferably included. Note that R ¹ , R ² , R ³ , m, and n may all be the same or different, and are preferably the same.

The trivalent group represented by X ⁱⁱⁱ is preferably the following group:

Is mentioned.

Of the trivalent groups represented by the formula (2 ^g -iiia), the formula (2 ^g -iii ') is preferable.

(Wherein Y is the same as above)
It is group represented by these.

In the formula (2 ^g -iii ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO ₂ — is particularly preferable.

For example, in the formula (1-iii), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4), and n is the same 0 (ie, R ^{3 represents a} ring X ⁱⁱⁱ is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R ¹ is the same and has 1 to 3 carbon atoms. A group of ² to 6 carbon atoms in which R ² is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.

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

[Wherein, X ^iv represents a tetravalent group represented by the above (1 ′) and a hydrogen atom bonded to an R ^Xa-d non-bonded carbon atom in the X ring is not substituted, R ¹ , R ² , R ³ , m, and n are the same as described above. ]
The epoxy resin represented by these is included. Note that R ¹ , R ² , R ³ , m, and n may all be the same or different, and are preferably the same.

The tetravalent group represented by X ^iv is preferably the following group:

Is mentioned.

The tetravalent group represented by X ^iv is preferably a tetravalent group represented by the formula (2 ^g ), wherein a hydrogen atom bonded to an R ^Xa-d non-bonded carbon atom is not substituted. Is the formula (2 ^g -iva ′):

(Wherein Y is the same as above)
The group represented by these is mentioned.

In the formula (2 ^g -iva ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO ₂ — is particularly preferable.

For example, in the formula (1-iva), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R ³ is a ring X ^iv is a tetravalent group obtained by removing four hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R ¹ is the same and has 1 to 3 carbon atoms. A group of ² to 6 carbon atoms in which R ² is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.

Of the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIa):

(In the formula, R ¹ , R ² and X ⁱⁱ are the same as above.)
The compound represented by these is mentioned.

Among the compounds represented by the formula (1-IIa), X ⁱⁱ is a 1,4-phenylene group or a group represented by the formula (2 ^g- ia ′) (preferably a 1,4-phenylene group). R ¹ is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and R ² is the same or different (preferably the same) an alkylene having 2 to 6 carbon atoms Group (*) — (CH ₂ ) ₂ —O—CH ₂ —, (*) — (CH ₂ ) ₃ —O—CH ₂ —, (*) — (CH ₂ ) ₃ —O— (CH ₂ ) _A compound which is _2- or (*)-(CH ₂ ) ₅ -O- (CH ₂ ) _4- is preferred. The above same, (*) indicates the side bonded to the silicon atoms of R ^2.

Of the epoxy resins represented by the above formula (1-IIa), more preferred are those represented by the formula (1-IIa1):

(Wherein R ¹ and X ⁱⁱ are the same as above).
Or formula (1-IIa2):

(Wherein R ¹ and X ⁱⁱ are the same as above).
The epoxy resin represented by these can be illustrated. Note that R ¹ may be the same or different, and is preferably the same.

In the formula (1-IIa1) or (1-IIa2), R ¹ is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and X ⁱⁱ is 1, More preferred is a 4-phenylene group or a group represented by the formula (2 ^g -ia ′).

Further, among the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIb):

(In the formula, R ¹ , R ² , R ³ , X ⁱⁱ , and n are the same as above.)
The epoxy resin represented by these can also be mentioned. Note that R ¹ , R ² , R ³ , and n may all be the same or different, and are preferably the same.

In the formula (1-IIb), X ⁱⁱ is a 1,4-phenylene group or a group represented by the formula (2 ^g -ia ′) (preferably a 1,4-phenylene group), and R ¹ is the same or different. (Preferably the same) is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), n is both 0 (that is, the ring is not substituted with R ³ ), and R ² is the same or different ( More preferably, it is the same and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH ₂ ) ₂ —).

Further, among the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIIa):

(Wherein R ¹ , R ² , R ³ , X ⁱⁱⁱ and n are the same as above)
The epoxy resin represented by these can also be mentioned. Note that R ¹ , R ² , R ³ , and n may all be the same or different, and are preferably the same.

In the formula (1-IIIa), X ⁱⁱⁱ is

Or

Or a group represented by the formula (2 ^g -iii ′), R ¹ is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and both n are 0 (That is, the ring is not substituted with R ³ ), and R ² is the same or different (preferably the same) and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH ₂ ) ₂ —) Is more preferable.

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

The epoxy resin represented by the formula (1) can be produced based on or according to a known method, for example, based on or according to the description of Patent Document 2 (UK Patent No. 1123960). Also, for example, an epoxy resin represented by the formula (1-ia) can be produced by a reaction represented by the following reaction formula.

(In the formula, R ^2A is an alkenyl group having 2 to 18 carbon atoms, and in this group, some carbon atoms are 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 the same as 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 straight chain. Specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a norbornenyl group, and a cyclohexenyl group. An alkenyl group having 2 to 10 carbon atoms is preferred, an alkenyl group having 2 to 8 carbon atoms is more preferred, an alkenyl group having 2 to 6 carbon atoms is more preferred, and a vinyl group, allyl group or It is a butenyl group. The alkenyl group is preferably an α-alkenyl group.

In these alkenyl groups having 2 to 18 carbon atoms, some 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 some carbon atoms are preferably carbon atoms not directly bonded to the epoxy ring. The part of carbon atoms that may be substituted is 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. Examples of the group include 2 to 9 alkenyl-O-carbon having 1 to 8 carbon atoms, preferably 2 to 4 alkenyl-O carbon atoms having 1 to 3 carbon atoms, more preferably 2 to 3 carbon atoms. Examples thereof include 4 alkenyl-O-alkylene having 1 to 2 carbon atoms, particularly preferably 3 alkenyl-O—CH ₂ —. Specifically, for example, 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 - is like, among these _{CH 2 = CH-CH 2 -O} -CH 2 - ( allyloxymethyl group).

The epoxy resin represented by the formula (1-ia) can be produced by subjecting the compound represented by the formula (5-ia) and the compound represented by the formula (6) to a hydrosilylation reaction. The hydrosilylation reaction can usually be carried out in the presence of a catalyst, in the presence or absence of a solvent. Further, in place of the compound represented by the formula (5-ia), the formula (5-iii):

(Wherein R ¹ and X ⁱⁱⁱ are the same as above)
Or the formula (5-iva):

(Wherein R ¹ and X ⁱⁱⁱ are the same as above)
Or formula (5-ia):

(In the formula, X ⁱ represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring, and R ¹ is the same as above.)
An epoxy resin represented by the above formula (1-iii) or (1-iva) or an epoxy having a structure in which one group of the formula (3) is bonded to a hydrocarbon ring. Resins can also be produced. In the structures of these compounds, X ⁱ to X ^iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring. Use a compound having a structure substituted with a valent group, a trivalent group obtained by removing three hydrogen atoms from the X ring, or a tetravalent group obtained by removing four hydrogen atoms from the X ring Thus, various compounds represented by the formula (1) can be produced.

The catalyst used in the hydrosilylation reaction may be a known catalyst such as platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .; Fin) rhodium and other rhodium catalysts; and iridium catalysts such as bis (cyclooctadienyl) dichloroiridium. The above catalyst may be in the form of a solvate (for example, hydrate, alcohol solvate, etc.). In use, the catalyst may be dissolved in an alcohol (for example, ethanol) and used in the form of a solution. it can. In addition, a catalyst can be used individually or in combination of 2 or more types.

The amount of the catalyst used may be an effective amount as a catalyst. For example, the compound represented by the above formula (5-ia), (5-ia), (5-iiia), or (5-iva) and the formula ( The amount is 0.00001 to 20 parts by weight, preferably 0.0005 to 5 parts by weight, based on 100 parts by weight in total with the compound represented by 6).

The hydrosilylation reaction proceeds without using a solvent, but the reaction can be performed under mild conditions by using a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.

The amount of the compound represented by the formula (6) is, for example, Si— in the compound represented by the formula (5-ia), (5-ia), (5-iii), or (5-iva). The amount is usually 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of the H group.

The reaction temperature is usually 0 ° C. to 150 ° C., preferably 10 ° C. to 120 ° C., and the reaction time is usually 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 isolation method such as distilling off the solvent from the reaction solution.

The thermal cationic polymerization initiator generates an acid species capable of cationic polymerization of a cationically polymerizable compound by heat. As the thermal cationic polymerization initiator used in the present invention, known ones that are used as thermal cationic polymerization initiators for epoxy resins can be appropriately selected and used. For example, iodonium salts, sulfonium salts, phosphonium salts, boron compounds, ferrocenes, Lewis acids, mixtures of boron compounds and Lewis bases, and the like can be used. A thermal cationic polymerization initiator can be used individually or in combination of 2 or more types.

For example, as the boron compound, a Lewis acid disclosed in WO2012 / 060449 can be preferably used. Further, for example, as a mixture of a boron compound and a Lewis base, a cationic curing catalyst comprising 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, and the like can be used, and among them, an amine compound can be preferably used. For example, as a mixture of a boron compound and an amine compound, a mixture composed 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 WO2012 / 060449 are incorporated herein by reference.

Commercially available products can be used for the thermal cationic polymerization initiator. Commercially available products of thermal cationic polymerization initiators include CP-66 and CP-77 manufactured by ADEKA, CI-2855 and CI-2639 manufactured by Nippon Soda Co., Ltd., Sun Aid SI-60, SI-60L and SI manufactured by Sanshin Chemical Industry Co., Ltd. Preferred examples include -80, SI-80L, SI-100, SI-100L, and aromatic fluorine-based acid generators TPB, TEPBD and FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd.

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

As the sulfonium salt, the following formula:

(In the formula, R ⁴ represents a hydrogen atom, halogen, or an alkyl group having 1 to 12 carbon atoms, and R ^5a and R ^5b are the same or different and each represents an alkyl group having 1 to 12 carbon atoms, a benzyl group, or halogenobenzyl. Group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, dichlorobenzyl group, trichlorobenzyl group, nitrobenzyl group, dinitrobenzyl group, trinitrobenzyl group, naphthylmethyl group (α-naphthyl) Methyl group, β-naphthylmethyl group), vinylbenzyl group, or cinnamyl group,
R ⁶ represents a hydrogen atom, halogen, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, or —O—R ⁷ , and R ⁷ represents a methyl group, an acetyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzoyl group, A phenoxycarbonyl group, a chloroacetyl group, a dichloroacetyl group, a trichloroacetyl group, or a trifluoroacetyl group;
Z represents PF ₆ , SbF ₆ , a halogen atom (eg, 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. In the case where Z represents (C ₆ F ₅ ) ₄ B, Z ⁻ represents tetrakispentafluorophenyl borate. )
The sulfonium salt represented by these is preferable. In the formula, the alkyl group having 1 to 12 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) is more preferably an alkyl group having 1 to 8 carbon atoms. An alkyl group having 1 to 6 carbon atoms is more preferable. Further, it may be a linear or branched alkyl group. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl Group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n-dodecyl group 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, benzyl group, halogenobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl. Group, methoxybenzyl group, chlorobenzyl group, dichlorobenzyl group, trichlorobenzyl group, nitrobenzyl group, dinitrobenzyl group, trinitrobenzyl group, α-naphthylmethyl group, β-naphthylmethyl group, vinylbenzyl group, or cinnamyl group R ^5b represents an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a naphthylmethyl group, R ⁶ represents a hydrogen atom, a hydroxyl group, or —O—R ⁷ , and R ⁷ represents a methyl group or acetyl group It is more preferable to show a group.

Examples of commercially available sulfonium salts represented by the formula include San-Aid SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L and the like manufactured by Sanshin Chemical Industry Co., Ltd. Illustrated.

Furthermore, as a sulfonium salt, for example, the following formula:

(Wherein Z is the same as above)
Or

(Wherein Z is the same as above)
The compound represented by can also be used preferably.

Also, as a boron compound (including a boron compound in a mixture of a boron compound and a Lewis base), the following formula:

(Wherein R is the same or different and represents a hydrocarbon group which may have a substituent. H is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. J is an integer of 1 or more, k is an integer of 0 or more, and j + k = 3 is satisfied)).

The hydrocarbon group here is preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be an unsubstituted group or a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom. Other organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group corresponds to an unsubstituted alkyl group as a whole), An aryl group, an alkenyl group, an alkoxy group, a hydroxyl group, etc. are mentioned.

H in the above formula is 1, 2, 3, 4, or 5, and is the same or different and represents the number of fluorine atoms bonded to the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. h is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.

J is an integer of 1 or more, k is an integer of 0 or more, and satisfies j + k = 3. That is, the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom. j is more preferably 2 or more, and further preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.

Among the boron compounds, specific boron compounds include, for example, tris (pentafluorophenyl) borane (TPB), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, and tris (4-fluorophenyl) borane. Among them, TPB is preferable.

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

As the boron compound contained in the mixture, for example, the above-described boron compound can be preferably used, and tris (pentafluorophenyl) borane is particularly preferable. Moreover, as an amine compound contained in the said mixture, the compound described in each following item described in WO2012 / 036164 other than piperidine etc. is illustrated preferably. Carbon numbers 1 to 6 indicate carbon numbers 1, 2, 3, 4, 5 or 6, and carbon numbers 1 to 20 indicate carbon numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; 3 to 10 carbon atoms represents 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms; 6 to 14 carbon atoms indicate 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms.

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

[Wherein R ^1N to R ^5N are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]
Item 2n.
The amine compound according to Item 1n, wherein the amine compound has a piperidine structure represented by the following formula.

[Wherein R ^1N to R ^5N are as defined above; X ^N represents an —O— group, — (C═O) — group, —NR ^7N — group (R ^7N represents a hydrogen atom or 1 to 6 represents an alkyl group), —O (C═O) — group, — (C═O) O— group, —NH (C═O) — group or — (C═O) NH— group] Item 3n.
The amine compound according to Item 1n, wherein the amine compound is represented by the following formula.

[Where:
R ^1N to R ^5N are as defined above;
X ^N and Z ^N are the same or different and are —O— group, — (C═O) — group, —NR ^7N — group (R ^7N represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), Represents —O (C═O) — group, — (C═O) O— group, —NH (C═O) — group or — (C═O) NH— group;
Y ^N represents an optionally substituted alkylene group having 1 to 20 carbon atoms;
R ^6N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the above-mentioned piperidine structure;
The substituent that the alkylene group having 1 to 20 carbon atoms may have 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 a substituent. One or more selected from the group consisting of aryl groups having 6 to 14 carbon atoms;
The substituent that the aryl group having 6 to 14 carbon atoms may have is one or more 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 Show]
Item 4n.
The amine compound according to Item 1n, wherein the amine compound is represented by the following formula.

[Wherein, at least one of R ^8N to R ^11N (that is, 1, 2, 3 or 4) represents the above-mentioned piperidine structure, and the rest represents an alkyl group having 1 to 20 carbon atoms]
Item 5n.
The amine compound according to Item 1n, wherein the amine compound is a polymer.
Item 6n.
The amine compound according to Item 1n, wherein the amine compound is represented by the following formula.

[Wherein R ^1N to R ^5N are as defined above]
Among them, examples of preferred specific amine compounds are shown below by structural formulas. For example, the following compound is mentioned as a preferable example of the amine compound of said item 3n.

Moreover, the following compound is mentioned as a preferable example of the amine compound of said item 4n.

Moreover, the following compound is mentioned as a preferable example of the amine compound of the said item 5n.

Moreover, the following compound is mentioned as a preferable example of the amine compound of the said item 6n.

Among these, particularly preferable amine compounds include the amine compounds described in Table 1 below.

As the mixture of the boron compound and the amine compound, a commercially available product can be used. For example, FX-TP-BC-PC series manufactured by Nippon Shokubai Co., Ltd. can be used.

Examples of more specific preferred thermal cationic polymerization initiators include diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, tris (pentafluorophenyl) borane (TPB), and bis (pentafluorophenyl). ) Phenylborane, pentafluorophenyl-diphenylborane, tris (4-fluorophenyl) borane, tetrakis (pentafluorophenyl) borate salt, the aforementioned sulfonium 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 the effects of the present invention can be exhibited. For example, the amount is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin, the lower limit is more preferably 0.05 parts by weight or more, further preferably 0.1 parts by weight or more, and 0.5 parts by weight or more Even more preferred is 1 part by weight or more. Moreover, 30 mass parts or less are more preferable, as for an upper limit, 10 mass parts or less are more preferable, and 5 mass parts or less are more preferable.

The epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) as long as the curing of the present invention is not impaired. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, triglycidyl isocyanurate, hydrogenated Examples thereof include bisphenol A type epoxy resins, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, dicyclo type epoxy resins, and naphthalene type epoxy resins. These epoxy resins may be used alone or in combination of two or more.

When blending an epoxy resin other than the epoxy resin represented by formula (1), the blending ratio of the epoxy resin represented by formula (1) and the epoxy resin other than the epoxy resin represented by formula (1) is The mass ratio is, for example, 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 40:60.

The epoxy resin composition of the present invention may contain a filler, a curing agent, a curing catalyst, a thermoplastic resin, an additive, and the like as necessary within a range that does not impair the object and effect of the present invention.

Examples of the filler include silica (more specifically, crystalline silica, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate. Inorganic compounds such as calcium silicate, potassium titanate, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO). Moreover, metals, such as gold | metal | money, silver, copper, aluminum, nickel, iron, zinc, stainless steel, are mentioned. In addition, minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite can be mentioned. 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; various glasses such as glass beads, glass flakes and glass balloons Can be mentioned. Further, the filler may be used as it is, or a filler dispersed in a resin may be used. As the filler, considering the fluidity, heat resistance, low thermal expansion, mechanical properties, hardness, scratch resistance and adhesiveness required for the composition and the cured product, alone or in combination of two or more kinds. Can be used.

Examples of the curing agent include an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, a mercaptan curing agent, an isocyanate curing agent, an active ester curing agent, and a cyanate ester curing. Agents and the like. A hardening | curing agent may be used independently, and can be used properly according to the characteristic to request | require, and may use 2 or more types together.

Examples of amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, benzenediamine, bis (4-aminocyclohexyl) methane, and bis (aminomethyl) cyclohexane. Alicyclic amines such as diaminodicyclohexylmethane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2- (dimethylaminomethyl) phenol, 2 , 4,6-Tris (dimethylaminomethyl) phenol, DBU (1,8-diazabicyclo (5,4,0) -undecene-7), DBN (1, - diazabicyclo (4,3,0) - nonene-5), and a secondary and tertiary amines, such as.

Examples of amide-based curing agents include dicyandiamide and its derivatives, polyamide resins (polyaminoamide, etc.), and the like.

Examples of acid anhydride curing agents include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; methyl nadic anhydride And alicyclic acid anhydrides such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.

Examples of phenolic curing agents include phenol novolak resins, cresol novolak resins, biphenyl type novolak resins, triphenylmethane type phenol resins, naphthol novolak resins, phenol biphenylene resins, phenol aralkyl resins, biphenyl aralkyl type phenol resins, and modified polyphenylene ether resins. And compounds having a benzoxazine ring.

Examples of mercaptan curing agents include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), Tetraethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate) , Trimethylol ethane tris (3-mercaptobutyrate), polysulfide polymer and the like.

Examples of the isocyanate curing agent include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.

Examples of the active ester curing agent include compounds having at least one ester group that reacts with an epoxy resin in one molecule, such as phenol ester, thiophenol ester, N-hydroxyamine ester, and heterocyclic hydroxy compound ester. Can be mentioned.

Examples of the curing catalyst include imidazole compounds, dicyandiamides, tertiary amines, phosphorus compounds, Lewis acid compounds, and the like. A curing catalyst may be used independently and can be used properly according to the characteristic to require, and may use 2 or more types together.

Examples of the thermoplastic resin include polyolefin resin, acrylic resin, phenoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyurethane resin, polyarylate resin, polyphenylene ether resin, polyacetal resin, and those obtained by acid modification. Is mentioned. From the viewpoint of compatibility with the epoxy resin composition according to the present invention and heat resistance, polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, and those obtained by acid modification are preferred, among these More preferred are polyolefin resins and acid-modified polyolefin resins. A thermoplastic resin can be used individually or in combination of 2 or more types.

Examples of the additive include an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a heat and light stabilizer, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a solvent, an antiaging agent, a radical inhibitor, and an adhesive. Property improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide Examples include decomposing agents, pigments, metal deactivators, and physical property modifiers.

The epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1), a thermal cationic polymerization initiator, and, if necessary, other components. The mixing method is not particularly limited as long as it can be uniformly mixed. A solvent (for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.) may be added to the epoxy resin composition of the present invention as long as the effects of the present invention are not adversely affected.

A cured product (that is, a cured product of the epoxy resin composition) can be obtained by curing the epoxy resin composition of the present invention. The curing method is not particularly limited, and can be carried out, for example, by heat curing the composition. The curing temperature is usually from room temperature to 250 ° C., and the curing time varies depending on the composition, and can usually be set widely from 30 minutes to 1 week.

In this specification, “including” also includes “consisting essentially of” and “consisting of” (The term “comprising” “includes” “consisting” essentially “of” “and” “consisting” of.).

Hereinafter, the present invention will be described more specifically, but the present invention is not limited to the following examples.

Production Example 1 (Production of Epoxy Resin A)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser, under a nitrogen atmosphere, 5.9 g of allyl glycidyl ether, 0.05 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate, and 100 g of toluene were added. First, the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 4 hours. After removing toluene by concentration, 10.3 g (epoxy equivalent 211 g / eq) of 1,4-bis [(2,3-epoxypropyloxypropyl) dimethylsilyl] benzene (epoxy resin A) as a colorless transparent liquid was obtained.

Production Example 2 (Production of Epoxy Resin B)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, 5.0 g of 1,2-epoxy-5-hexene, 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate 0 0.05 g and 100 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 5 hours. After removing toluene by concentration, 9.5 g (epoxy equivalent 195 g / eq) of 1,4-bis [(2,3-epoxybutyl) dimethylsilyl] benzene (epoxy resin B) as a colorless transparent liquid was obtained.

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

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

Production Example 5 (Production of epoxy resin E)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 7.4 g of 1,2-epoxy-4-vinylcyclohexane and a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate in a nitrogen atmosphere 0.05 g and 250 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,3,5-tris (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 6 hours. After removing the toluene by concentration, 11.8 g of an colorless transparent liquid 1,3,5-tris {[2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl} benzene (epoxy resin E) (epoxy equivalent 208 g / eq) ).

Examples, Comparative Examples Each component of the blending amounts described in Table 2 and Table 3 was weighed into a cup and stirred with a magnetic stirrer at room temperature (25 ° C.) for 5 minutes to prepare an epoxy resin composition.

Each component in Table 2 and Table 3 is as follows. In addition, the numerical value of each component of Table 2 and Table 3 shows a mass part.

Epoxy resin F: Bis-A type epoxy resin (grade 828) manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 189 g / eq)
Epoxy resin G: Alicyclic epoxy resin manufactured by Daicel (Celoxide 2021P; generic name is 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) (epoxy equivalent 137 g / eq)
-Cationic polymerization initiator A: San-Aid SI-60L manufactured by Sanshin Chemical Industry Co., Ltd.
Cationic polymerization initiator B: FX-TP-BC-PC-AD-57103 manufactured by Nippon Shokubai Co., Ltd.

Test example 1
(1) Fast Curing Epoxy resin compositions obtained in Examples and Comparative Examples were heated in an oven at 140 ° C. and cured within 30 seconds, ◎ cured within 2 minutes, and 2 What did not harden within minutes was set as x. The results are shown in Tables 2 and 3.

(2) 90 degree peel strength with respect to copper foil The epoxy resin compositions obtained in the examples and comparative examples were applied to an aluminum plate, and an electrolytic copper foil (made by Furukawa Electric Co., Ltd.) having a thickness of 35 μm was laminated thereon. It was. It was cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. After curing, a cut was made with a cutter so that the width became 1 cm, and a 90-degree peel strength test piece was obtained. The obtained test piece was subjected to a 90 degree peel strength test using AGS-X (manufactured by Shimadzu Corporation) at a test speed of 50 mm / min. The results are shown in Tables 2 and 3.

(3) Electrical characteristics (dielectric constant, dielectric loss tangent)
Each epoxy resin composition obtained in Examples and Comparative Examples was poured into a resin mold (thickness 2 mm), and cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. Next, the cured product was cut into a size of width 20 mm × length 30 mm × thickness 2 mm to obtain a dielectric constant measurement test piece.

The obtained test piece was measured for dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) at 25 ° C. using a dielectric constant measuring device (impedance analyzer, manufactured by Agilent). The dielectric constant measuring apparatus was calibrated using PTFE. The results are shown in Tables 2 and 3.

(4) Water resistance (elasticity change rate before and after water absorption test)
Each epoxy resin composition obtained in Examples and Comparative Examples was poured into a resin mold (thickness 2 mm), and cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. Next, the cured product was cut into a size of width 20 mm × length 30 mm × thickness 2 mm to obtain a test piece for water resistance evaluation. The obtained test piece was immersed in pure water at room temperature for one week and subjected to water absorption treatment. The storage modulus of the test piece was measured using a dynamic viscoelasticity measuring device (RSG-G2, manufactured by TA Instruments) at a tensile mode and a temperature increase rate of 10 ° C./min.
The change rate of the elastic modulus before and after water absorption was calculated from the following formula.
(Storage elastic modulus at 30 ° C. after water absorption test / Storage elastic modulus at 30 ° C. before water absorption) × 100
The results are shown in Tables 2 and 3.

　

Claims (8)

1. Formula (1):
   

   

   (In the formula, ring X is a saturated hydrocarbon ring or 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 connected,
   R ^Xa , R ^Xb , R ^Xc , and R ^Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):
   

   

   (In the formula, 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. The carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
   R ² represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. May be substituted with
   R ^{3 s} are the same or different and each 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 these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
   m represents an integer of 0 to 6,
   n represents an integer of 0 to 3. )
   However, at least one of R ^Xa , R ^Xb , R ^Xc , and R ^Xd is a group represented by the formula (3),
   A hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R ^Xa , R ^Xb , R ^Xc , and R ^Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom. )
   The epoxy resin composition containing the epoxy resin represented by these, and a thermal cationic polymerization initiator.
2. A ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected,
   Formula (2):
   

   

   (Wherein, ring X ^{1 and} ring X ² are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO ₂ —). 2. The epoxy resin composition according to 1.
3. The saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
   The unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms;
   The epoxy resin composition according to claim 1 or 2.
4. Formula (1-ia):
   

   

   ( ^Wherein X ⁱⁱ 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, to two hydrogen atoms A divalent group obtained by removing or a formula (2 ^g -ia):
   

   

   (Wherein Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), -SO- or -SO _2- )).
   R ^{1 s} are the same or different and each 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 these groups have a part of 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 and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. Optionally substituted with at least one atom
   R ^{3 s} are the same or different and each 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 these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
   m represents an integer of 0 to 6,
   n represents an integer of 0 to 3. )
   And an epoxy resin represented by the formula (1-iiia):
   

   

   (In the formula, X ⁱⁱⁱ 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, to 3 hydrogen atoms A trivalent group obtained by removing or a formula (2 ^g -iiia):
   

   

   (Wherein Y represents the same as described above),
   R ¹ , R ² , R ³ , m, and n are the same as described above. )
   The epoxy resin composition of Claim 1 containing the at least 1 sort (s) of epoxy resin selected from the group which consists of epoxy resin represented by these, and a thermal cationic polymerization initiator.
5. The epoxy resin composition according to any one of claims 1 to 4, wherein the thermal cationic polymerization initiator is at least one selected from the group consisting of a sulfonium salt, a boron compound, and a mixture of a boron compound and a Lewis base.
6. The epoxy resin composition according to any one of claims 1 to 5, comprising 0.01 to 50 parts by mass of a thermal cationic polymerization initiator with respect to 100 parts by mass of the epoxy resin.
7. A cured product of the epoxy resin composition according to any one of claims 1 to 6.
8. A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive, wherein the epoxy resin composition according to any one of claims 1 to 6 or the cured product according to claim 7 is used. Layer, coverlay film, electromagnetic shielding film, printed circuit board material or composite material.