TW201841968A - Epoxy resin, epoxy resin composition, and cured object obtained therefrom, use thereof, and production method therefor - Google Patents

Abstract

Provided are: an epoxy resin capable of forming cured objects excellent in terms of low-dielectric characteristics and adhesiveness to metals; an epoxy resin composition; and a cured object obtained therefrom, a use thereof, and a production method therefor. The epoxy resin comprises: (A) a structural unit derived from a hydrosilylated organic compound and formed by removing a hydrogen atom from the hydrosilyl group; (B) a structural unit derived from a compound containing no epoxy group but containing a carbon-carbon unsaturated bond and formed by converting the carbon-carbon unsaturated bond to a C=C bond or a C-C bond; and (C) a structural unit derived from a compound having both a carbon-carbon unsaturated bond and an epoxy group and formed by converting the carbon-carbon unsaturated bond to a C=C bond or a C-C bond.

Description

Epoxy resin, epoxy resin composition and cured product thereof, use and manufacturing method

The present invention relates to an epoxy resin, an epoxy resin composition, a cured product thereof, use thereof, and a method of producing the same.

Background Art In recent years, with the increase in performance and the reduction in size and speed of electronic devices, transmission signals have been moving toward higher frequencies. With high frequency, there is a strong demand for low dielectricization in high frequency regions for materials used in printed wiring boards and semiconductor packages. In this field, thermosetting resins such as epoxy resins are widely used as substrate materials or packaging materials.

It has been developed for the purpose of obtaining an epoxy resin having low dielectric properties and a composition containing the resin. For example, Patent Documents 1 and 2 disclose a dicyclopentadiene type epoxy resin and a composition having the resin. Further, Patent Document 3 discloses an epoxy resin composition characterized by containing an epoxy resin, an active ester compound, and three Cresol phenolic resin. However, the low dielectric properties of the above patent documents and the like are not sufficient.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei.

Disclosure of the Invention Problems to be Solved by the Invention An object of the present invention is to provide an epoxy resin composition which can form a cured product which is excellent in low dielectric properties and excellent in adhesion to metals.

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be attained by using a hydrogenated epoxy resin having a specific structure, and the present invention has been completed after repeated studies.

The present invention includes, for example, the subject matter described in the following. Item 1. An epoxy resin having: (A) a structural unit derived from an organic compound having a hydrogen group and removing a hydrogen atom of a hydrogen group; (B) derived from a carbon-carbon unsaturated bond And a structural unit which does not have an epoxy group compound and converts a carbon-carbon unsaturated bond into a C=C bond or a CC bond; and (C) is derived from a carbon-carbon unsaturated bond and an epoxy group a structural unit formed by converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond. Item 2. The epoxy resin according to Item 1, wherein (A) an organic compound having an anthracene hydrogen group is a compound represented by the formula (0): [Chemical Formula 1] Wherein R ^{1 is the} same or different and represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups may also be selected from a group of carbon atoms and At least one atom in the group consisting of nitrogen atoms is substituted, and the X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring are condensed, or A ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded, and n ^X represents 1, 2, 3 or 4). Item 3. The epoxy resin according to Item 1 or 2, wherein (B) a compound having a carbon-carbon unsaturated bond and having no epoxy group is a compound represented by the formula (8): [Chemical Formula 2] (wherein R ² represents an alkylene group having 1 to 8 carbon atoms, and the group may be substituted by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; and R ³ represents * -COO- or *-OCO- (the above "*" indicates the side bonded to R ² or L); R ⁴ represents an alkylene group having 1 to 4 carbon atoms, and the group may also be selected from a part of carbon atoms At least one atom in the group consisting of an oxygen atom and a nitrogen atom is substituted; R ⁵ represents a methyl group or a hydrogen atom; L represents a k-valent organic group; l each independently represents 0 or 1; m independently represents 0 or 1; n each independently represents 0 or 1; k represents an integer from 1 to 6; further, when there are a plurality of R ² , they may be the same group, or some or all of them are different groups; when there are a plurality of R ³ , They may be the same group, or some or all of them are different groups; when there are a plurality of R ⁴ , they may be the same group, or some or all of them may be different groups). The epoxy resin according to any one of items 1 to 3, wherein (C) a compound having a carbon-carbon unsaturated bond and an epoxy group is a compound represented by the formula (15): [Chemical Formula 3] (wherein R ^6A represents an alkenyl group or an alkynyl group having 2 to 18 carbon atoms, and the group may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ⁷ 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 also be selected from a group consisting of an oxygen atom and a nitrogen atom. At least one atom in the group is substituted; o represents an integer from 0 to 6; p represents an integer from 0 to 3. Item 5. The epoxy resin according to Item 4, Item 4 is attached to Items 1, 2 and 3, and the epoxy resin is represented by Formula (23): [Chemical Formula 4] (wherein R ⁶ represents an alkylene group having 2 to 18 carbon atoms, and the group may be selected from a group consisting of an oxygen atom and a nitrogen atom except for a carbon atom directly bonded to a carbon atom of the halogen atom. At least one atom is substituted; L ² represents a divalent group obtained by removing two hydrogen atoms from the following: a linear or branched alkane having a partial carbon atom which may be substituted by an oxygen atom, a saturated hydrocarbon ring, or unsaturated a hydrocarbon ring, a nitrogen-containing hetero ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or a structure having 2 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings bonded together a ring; q represents a positive number greater than 0 and 20 or less; X ² represents a divalent group obtained by removing two hydrogen atoms from the X ring; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , l, m, n, o, and p are synonymous with the foregoing). Item 6. An epoxy resin composition comprising the epoxy resin according to any one of items 1 to 5, a curing catalyst, and/or a curing agent. Item 7. A cured product which is a cured product of the epoxy resin composition according to Item 6. Item 8. A semiconductor package, a liquid package, a potting material, a sealing material, a printed substrate material or a composite material, comprising the epoxy resin composition according to item 6 or the cured product described in claim 7 as a constituent element. Item 9. A method for producing an epoxy resin composition, which comprises the step of producing an epoxy resin composition according to Item 6, which comprises mixing the epoxy resin with a curing catalyst and/or a curing agent.

Advantageous Effects of Invention The epoxy resin composition of the present invention can form a cured product which is excellent in low dielectric properties and excellent in adhesion to metals.

Embodiments for Carrying Out the Invention Hereinafter, each embodiment of the present invention will be described in detail. In addition, "include" in this specification also includes "the term "comprising" includes "consisting essentially of" and "consisting of.").

The epoxy resin of the present invention comprises: (A) a structural unit derived from an organic compound having a hydrazine group and removing a hydrogen atom of a hydrazine group; (B) derived from a carbon-carbon unsaturated bond and not a structural unit formed by a compound having an epoxy group and converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond; and (C) a compound derived from a carbon-carbon unsaturated bond and an epoxy group A structural unit formed by converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond.

The above epoxy resin may, for example, be (A) an organic compound having an anthracene hydrogen group, (B) a compound having no epoxy group and having a carbon-carbon unsaturated bond, and (C) having a carbon-carbon unsaturated bond and a ring The compound of the oxy group is obtained by a hydrazine hydrogenation reaction.

Further, in the following, (A) an organic compound having a hydrazine group, (B) a compound having no epoxy group and having a carbon-carbon unsaturated bond, and (C) having a carbon-carbon unsaturated bond and a ring The compounds of the oxy group are referred to as "component A", "component B" and "component C", respectively. Further, (A) a structural unit derived from an organic compound having a hydrazine group and removing a hydrogen atom of a hydrazine group, (B) is derived from a carbon-carbon unsaturated bond and having no epoxy a compound formed by converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond, and (C) a compound derived from a carbon-carbon unsaturated bond and an epoxy group and carbon The structural units formed by converting a carbon unsaturated bond into a C=C bond or a CC bond are simply referred to as an A component structural unit, a B component structural unit, and a C component structural unit, respectively.

The epoxy resin component A of the present invention is obtained by subjecting the component B and the component C to a hydrogenation reaction. Therefore, the epoxy resin of the present invention is an epoxy resin having a structure in which a carbon-carbon unsaturated bond is hydrogenated, and may be referred to as a hydrogenated epoxy resin. Further, as described in detail in the specification, the compound exemplified as the component A, the compound exemplified as the component B, and the compound exemplified as the component C are various. The epoxy resin of the present invention contains all combinations of the A component, the B component, and the C component described in the present specification. That is, the epoxy resin of the present invention contains all of the various epoxy resins obtained from all combinations of the compounds corresponding to the components A to C described in the present specification.

[(A) Organic compound having an anthracene hydrogen group] The A component is an organic compound having an anthracene hydrogen (Si-H) group and undergoing a hydrogenation reaction with a carbon-carbon unsaturated bond. The number of the hydrazine group is 1 or more, for example, preferably 1 to 12 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12), preferably 2, 3 or 4.

The component A is subjected to a hydrazine hydrogenation reaction with, for example, the component B and the component C, and a hydrogen atom is removed by the reaction to form an A component structural unit. The component A is preferably a compound having a structure in which a hydrazine group is bonded to the ring. For example, a compound represented by the following formula (0) can be exemplified. [Chemical Formula 5] (wherein R ¹ represents the same or different hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups may also be selected from the group consisting of oxygen atoms and At least one atom in the group consisting of nitrogen atoms is substituted, and the X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring are condensed, or A ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded, and n ^X represents 1, 2, 3 or 4).

More specifically, as the component A, for example, a compound having a structure of the formula (1) to (4) can be exemplified. [Chemical Formula 6] (In each formula, R ¹ and X ring systems are the same as defined above. That is, R ¹ represents the same or different hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the like. Further, 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, wherein the X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, and has 2 to 6 saturated hydrocarbon rings. And/or a ring having a structure in which an unsaturated hydrocarbon ring is condensed, or a ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked.

Although not particularly limited, it is preferably the case where R ¹ does not represent a hydrogen atom (that is, R ¹ represents the same or different alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 18 carbon atoms). Further, it is particularly preferred that in the formula (1), one R ¹ represents a hydrogen atom, and the other R ¹ represents the same or different alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group. Or aralkyl.

Further, in the formula (1), X represents a monovalent group (sometimes referred to as X ¹ ) obtained by removing one hydrogen atom from the X ring, and in the formula (2), X represents removal of two hydrogen atoms from the X ring. The obtained divalent group (sometimes referred to as X ² ), wherein X in the formula (3) represents a trivalent group (sometimes referred to as X ³ ) obtained by removing three hydrogen atoms from the X ring, in the formula (4) X is a tetravalent group (sometimes referred to as X ⁴ ) obtained by removing four hydrogen atoms from the X ring.

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

In the present specification, the saturated hydrocarbon ring is preferably a saturated hydrocarbon ring having 4 to 8 (4, 5, 6, 7, or 8 carbon atoms), and preferably a cyclopentane ring, a cyclohexane ring or the like.

Further, in the present specification, the unsaturated hydrocarbon ring is preferably a benzene ring or the like, for example, preferably an unsaturated hydrocarbon ring having 4 to 8 (4, 5, 6, 7, or 8 carbon atoms).

Further, in the present specification, the ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed is preferably 2, 3 or 4 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings. The condensed ring, more preferably a ring of 2 or 3 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring. More specifically, for example, a decahydronaphthalene ring, an adamantane ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a triphenylene ring, a tetrahydronaphthalene ring, 1, 2, 3, 4, 5, 6,7,8-octahydronaphthalene ring, drop Ene ring and the like.

a hydrogen atom bonded to a carbon atom constituting a carbon atom forming a hydrocarbon ring of the X ring and not bonded to a ruthenium atom, and may also be an alkane having 1 to 6 (1, 2, 3, 4, 5 or 6 carbon atoms) The group is substituted with an alkoxy group having 1 to 6 (1, 2, 3, 4, 5 or 6) carbon atoms or a halogen atom.

In the present specification, specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Further, examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

Further, the halogen atom-based fluorine atom, chlorine atom, bromine atom or iodine atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a bromine atom.

In the present specification, the ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked is preferably a structure represented by the following formula (5): [Chemical Formula 7]

In the formula (5), the X ^a ring and the X ^b ring represent the same or different saturated hydrocarbon ring or unsaturated hydrocarbon ring. That is, both the X ^a ring and the X ^b ring are saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring, and the other is an unsaturated hydrocarbon ring. In these, it is preferred that both the X ^a ring and the X ^b ring are saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings. For example, the X ^a ring and the X ^b ring are preferably both a benzene ring, a cyclohexane ring, or a benzene ring, and the other is a cyclohexane ring, and more preferably both are benzene rings.

In the formula (5), Y represents a bonding site, an alkylene 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 -. The alkylene group having 1 to 6 carbon atoms may, for example, be a methylene group, an exoethyl group, a n-propyl group, a n-butyl group or a n-hexyl group. Further, the alkyl group having 1 to 4 carbon atoms as 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. With respect to the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, 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 bonding site, an oxygen atom, a methylene group, a dimethylmethylene group (-C(CH ₃ ) ₂ -), -S-, -SO ₂ -, preferably a bonding site, a dimethyl group. Methylene, oxygen atom, -SO ₂ -.

With respect to the divalent, trivalent or tetravalent group (i.e., X ² , X ³ or X ⁴ ) in the group represented by X, specifically, for example, it is preferably a group represented by any one of the following formulas (wherein Y is the same as the above) , [Chemical Formula 8] Among them, a group represented by any one of the following formulas (wherein Y is the same as defined above) is preferred. [Chemical Formula 9]

Examples of the alkyl-based linear or branched alkyl group having 1 to 18 carbon atoms represented by the above R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Tertiary butyl, n-pentyl, neopentyl, third amyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, positive Sulfhydryl, n-dodecyl and the like. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

The cycloalkyl group represented by the above R ¹ may, for example, be a cycloalkyl group of a three to eight membered ring, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.

The aryl group represented by the above R ¹ may, for example, be 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. Among them, a phenyl group is preferred.

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

The alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 18 carbon atoms represented by R ¹ , as described above, may also be selected from a group consisting of an oxygen atom and a nitrogen atom. At least one of the atoms is substituted. When a part of carbon atoms are substituted, the number of substituted carbon atoms is, for example, 1 to 3, 1 or 2, or 1. The carbon atom may also be substituted by an oxygen atom or a nitrogen atom, preferably by an oxygen atom. Further, when the number of substituted carbon atoms is two or more, all of them may be substituted with the same atom (oxygen atom or nitrogen atom) or may be partially substituted with a different atom. R ^{1 is} preferably an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

More specifically, the component A can be exemplified by an organic compound having a total of one hydrogen atom directly bonded to a ruthenium atom in a molecule such as dimethylphenyl decane or triphenyl decane; methylphenyl decane; Molecules such as diphenyl decane, 1,2-bis(dimethyl decyl) benzene, 1,4-bis(dimethyl decyl) benzene, bis[(p-dimethyl decyl) phenyl] ether An organic compound having a total of two hydrogen atoms directly bonded to a ruthenium atom; an organic compound having a total of three hydrogen atoms directly bonded to a ruthenium atom in a molecule such as n-butyl decane or cyclopentyl decane; . Further, as the component A, specifically, bis(trimethyldecyloxy)methyl decane, bis(trimethyldecyloxy)ethyl decane, 3H, 5H-octamethyltetraoxane, 1H, 7H-octamethyltetraoxane, chloroethyl decane, 1,3-diphenyltetrakis(dimethylnonyloxy)dioxane, 1,3,5,7-tetramethylcyclotetraoxane 1,3,5,7-tetraethylcyclotetraoxane, pentamethylcyclopentaoxane, organically modified polyfluorene having a hydrazine group, and the like. The component A for preparing the epoxy resin may be one type or two or more types. In other words, the A-component structural unit contained in the epoxy resin may be one type or two or more types.

Among these, from the viewpoint that the cured product of the obtained epoxy resin composition easily has excellent low dielectric properties, the component A preferably has two or more hydrogen atoms directly bonded to the ruthenium atom in the molecule. The organic compound is particularly preferably an organic compound having two or more anthracene hydrogen groups in one molecule. Particularly preferred is a compound represented by the above formula (2) and having a total of two hydrogen atoms, a compound represented by the above formula (3) and having a total of three hydrogen atoms, and a hydrogen atom represented by the above formula (4). A total of four compounds, and among them, a compound represented by the above formula (2) and having a total of two hydrogen atoms is preferred.

More specifically, the component A is preferably 1,4-bis(dimethylindenyl)benzene having a structure represented by the following formula (6), and a double having the structure represented by the following formula (7). Methyl decyl) phenyl] ether.

[Chemical Formula 10]

From another viewpoint, the component A may be an organic compound having a total of one hydrogen atom directly bonded to the ruthenium atom in the molecule. At this time, the viscosity adjustment of the epoxy resin composition is easy.

When the component A contains an organic compound having a total number of hydrogen atoms directly bonded to a ruthenium atom in the molecule, the cured product of the obtained epoxy resin composition tends to have excellent low dielectric properties, and the content thereof is preferably The total mass of the component A is 30% by mass or less. That is, when the component A is an organic compound having a total number of hydrogen atoms directly bonded to a ruthenium atom in the molecule, the total number of hydrogen atoms directly bonded to the ruthenium atom in the molecule is not one (for example, two). The organic compound of three or four) is used in combination. In the total amount of the component A, the amount of the organic compound having one total of hydrogen atoms directly bonded to the ruthenium atom in the molecule is preferably 20 mol% or less.

[(B) Compound Containing No Epoxy Group and having Carbon-Carbon Unsaturated Bond] The B component is a compound having a carbon-carbon unsaturated bond and having no epoxy group. The carbon-carbon unsaturated bond can be reacted with a hydrazine group of the component A (hydrazine hydrogenation reaction).

The component B is subjected to a hydrazine hydrogenation reaction with the component A, and a carbon-carbon unsaturated bond is converted into a C-C bond or a C=C bond to form a component B structural unit. Further, when the carbon-carbon unsaturated bond is a C≡C bond, it can be converted into a C-C bond or a C=C bond, and when the carbon-carbon unsaturated bond is a C=C bond, it can be converted into a C-C bond.

Examples of the carbon-carbon unsaturated bond include a carbon-carbon unsaturated double bond (C=C bond) and a carbon-carbon unsaturated triple bond (C≡C bond). Among these, from the viewpoint that the cured product of the obtained epoxy resin composition easily has excellent low dielectric properties and the raw material is easily obtained, the carbon-carbon unsaturated bond is preferably a carbon-carbon unsaturated double bond. Further, in particular, the component B preferably has the following group: -CH=CH ₂ , -CH=CH(CH ₃ ), -C≡CH, or -C≡C-CH ₃ .

As the component B, for example, a compound represented by the following formula (8) can be exemplified: [Chemical Formula 11]

(wherein R ² represents an alkylene group having 1 to 8 carbon atoms, and the group may have a part of carbon atoms substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. R ³ represents * -COO- or *-OCO- (the above "*" indicates the side bonded to R ² or L). R ⁴ represents an alkylene group having 1 to 4 carbon atoms, and the group may also be selected from a part of carbon atoms. At least one atom in the group consisting of an oxygen atom and a nitrogen atom is substituted. R ⁵ represents a methyl group or a hydrogen atom, and L represents a k-valent organic group. l each independently represents 0 or 1. m each independently represents 0 or 1. n each independently represents 0 or 1. k represents an integer of 1 to 6. Further, when there are a plurality of R ² , they may be the same group, or some or all of them may be different groups. When there are a plurality of R ³ , They may be the same group, or some or all of them may be different groups. When there are a plurality of R ⁴ , they may be the same group, or some or all of them may be different groups).

Examples of the alkylene group having 1 to 8 (1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms represented by the above R ² include a methylene group, an exoethyl group, and a n-propyl group. It is butyl and so on.

The alkylene group having 1 to 4 (1, 2, 3 or 4) carbon atoms represented by the above R ⁴ may, for example, be a methylene group, an ethylidene group, a n-propyl group or a n-butyl group.

The k-valent organic group represented by the above L may, for example, be a linear or branched alkane, a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a nitrogen-containing heterocyclic ring, or have 2, from which a part of carbon atoms may be substituted by an oxygen atom. a ring of a structure in which a saturated hydrocarbon ring and/or an unsaturated hydrocarbon ring is condensed or a ring having a structure in which two saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring are bonded, respectively, and k hydrogen atoms are removed. base. The valence k of the organic group L is preferably 2 to 6 (2, 3, 4, 5 or 6), preferably 2 to 3.

l independently represent 0 or 1. When k is two or more, l also has two or more, and all of l may be the same value or different values. Preferably all l are the same value. m independently represents 0 or 1. When k is two or more, m may be two or more, and all m may be the same value or different values. Preferably all m are the same value. n independently represents 0 or 1. When k is two or more, n is also two or more, and all n may be the same value or different values. Preferably all l are the same value.

a hydrogen atom bonded to an alkane constituting the organic group L or a carbon atom constituting the ring, or a linear or branched alkyl group having 1 to 6 (1, 2, 3, 4, 5 or 6) carbon atoms, A linear or branched alkoxy group having a carbon number of 1 to 6, (1, 2, 3, 4, 5 or 6) is substituted with a halogen atom or a halogen atom. The number of hydrogen atoms which may be substituted may be, for example, 1 to 3, 1 or 2, or 1. Further, when the number of substituted hydrogen atoms is two or more, two hydrogen atoms bonded to the same carbon atom may be substituted, but it is preferred to substitute one hydrogen atom per carbon atom.

The linear or branched alkane constituting the organic group L is preferably a linear or branched alkane having 1 to 30 carbon atoms. The carbon number is preferably from 2 to 20, more preferably from 3 to 10. The alkane is preferably butane, 2,2-dimethylpropane or 2,2-dimethylbutane.

With respect to the saturated hydrocarbon ring constituting the aforementioned organic group L, for example, a saturated hydrocarbon ring having a carbon number of 4 to 8, (4, 5, 6, 7, or 8) is preferable, and more specifically, a cyclopentane ring or a cyclohexane is preferably exemplified. Alkane ring and the like. Further, examples of the unsaturated hydrocarbon ring constituting the organic group L include an aromatic hydrocarbon ring and a non-aromatic unsaturated hydrocarbon ring. The aromatic hydrocarbon ring is preferably, for example, a benzene ring. The non-aromatic unsaturated hydrocarbon ring is preferably an unsaturated hydrocarbon ring having 4 to 8 (4, 5, 6, 7, or 8 carbon atoms), and more preferably a cyclohexene ring or the like.

Regarding the nitrogen-containing hetero ring constituting the aforementioned organic group L, for example, it is preferably exemplified: three Ring, carbazole ring, and the like. About three Ring, preferably 1,2,3-three 1,2,4-three And 1,3,5-three More preferably 1,3,5-three . Further, the ring constituting the structure of the organic group L having 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings is preferably 2, 3 or 4 saturated hydrocarbon rings and/or unsaturated hydrocarbons. A ring formed by condensation of a ring, more preferably a ring of 2 or 3 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring. More specifically, for example, a decahydronaphthalene ring, an adamantane ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a triphenylene ring, a tricyclodecane ring, a tetrahydronaphthalene ring, 1, 2, 3,4,5,6,7,8-octahydronaphthalene ring, drop Ene ring and the like.

The ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded to each other in the organic group L is preferably a ring represented by the following formula (9): [Chemical Formula 12]

In the formula (9), L ^a and L ^b cycloalkyl ring represents the same or different saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, both the ring and L ^a L ^b are both cyclic saturated hydrocarbon ring or the unsaturated hydrocarbon ring both of which are, or are a saturated hydrocarbon ring and the other is unsaturated hydrocarbon ring. In these, preferably both the ring, and L ^a L ^b are both cyclic saturated hydrocarbon ring or the unsaturated hydrocarbon ring both of which are. For example, it is preferred that the L ^a ring and the L ^b ring are both a benzene ring, a cyclohexane ring, or a benzene ring, and the other is a cyclohexane ring, and more preferably both are benzene rings.

Further, in the formula (9), Q represents a bonding site, an alkylene 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-), and a sulfur atom (-S-). ), -SO-, or -SO ₂ -. The alkylene group having 1 to 6 carbon atoms may, for example, be a methylene group, an exoethyl group, a n-propyl group, a n-butyl group or a n-hexyl group. Further, the alkyl group having 1 to 4 carbon atoms as 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. With respect to the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, 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. Q is preferably a bonding site, an oxygen atom, a methylene group, a dimethylmethylene group (-C(CH ₃ ) ₂ -), -S-, -SO ₂ -, preferably a bonding site, a dimethyl group. Methylene, oxygen atom, -SO ₂ -.

Examples of the component B include vinylbenzene, vinylnaphthalene (1-vinylnaphthalene, 2-vinylnaphthalene), vinylcyclohexane, vinyl stearate, allylbenzene, and allyl group. An organic compound having one carbon-carbon unsaturated double bond in one molecule, such as a carbonate or an allyl phenyl ether; divinylbenzene (o-, m- or p-divinylbenzene), Divinyl dicarboxylate, diallyl phthalate, 5-vinyl-2-lower Alkene, vinyl cyclohexene (preferably 4-vinyl-1-cyclohexene), polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2'-diallyl double An organic compound having two carbon-carbon unsaturated double bonds in one molecule such as phenol A; triallyl cyanurate, triallyl 1,3,5-benzenetricarboxylate, and pentaerythritol An organic compound having three or more carbon-carbon unsaturated double bonds in one molecule, such as tetraacrylate or dipentaerythritol hexaacrylate. Other examples of the component B include allylic methoxymethyl decane, 1,4-bis(dimethylvinyl decyl) benzene, divinylmethyl phenyl decane, and diallyl Phenyl decane, dicyclopentadiene, ethylene drop Alkene, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, trimethylolpropanediallyl ether, divinylanthracene, having a carbon-carbon unsaturated double bond Organically modified polyfluorene oxide, polyethylene glycol diacrylate, and the like. The component B for modulating the epoxy resin may be one type or two or more types. In other words, the B-component structural unit included in the epoxy resin may be one type or two or more types.

Among these, from the viewpoint that the cured product of the obtained epoxy resin composition easily has excellent low dielectric properties, the component B is preferably an organic compound having two or more carbon-carbon unsaturated double bonds in the molecule, preferably. It is an organic compound having 2 or 3 carbon-carbon unsaturated double bonds in the molecule. More preferably, it is a compound in which k in the above formula (8) represents 2 or 3.

More specifically, the component B is preferably divinylbenzene represented by the following formula (10), divinyl adipate represented by the following formula (11), and phthalic acid represented by the following formula (12). Allyl ester, 5-vinyl-2-lower as shown in the following formula (13) Alkene, triallyl isocyanurate represented by the following formula (14).

[Chemical Formula 13]

From other viewpoints, the component B is also preferably an organic compound having one carbon-carbon unsaturated double bond in the molecule. At this time, the viscosity adjustment of the epoxy resin composition is easy.

The component B sometimes contains an organic compound having one carbon-carbon unsaturated double bond in the molecule. In this case, from the viewpoint that the cured product is likely to have excellent low dielectric properties, the content of the organic compound is preferably 30% by mass or less based on the total mass of the component B. When the component B is contained in an organic compound having one carbon-carbon unsaturated double bond in the molecule, it is preferred that the carbon-carbon unsaturated double bond in the molecule is two or more organic compounds (for example, k in the above formula (8) A compound of 2 to 6 integers) is used in combination. Further, in the total amount of the component B, the amount of the organic compound having one carbon-carbon unsaturated double bond in the molecule is preferably 20 mol% or less.

[(C) Compound having a Carbon-Carbon Unsaturated Bond and an Epoxy Group] The compound having a carbon-carbon unsaturated bond and an epoxy group as the component C has a carbon-carbon unsaturated bond and an epoxy group, and The organic compound which is subjected to hydrazine hydrogenation reaction with a hydrogen (Si-H) group may be used. The component C is a structural unit formed by subjecting a hydrogen (Si-H) group of the component A to a hydrogenation reaction to convert a carbon-carbon unsaturated bond into a C=C bond or a C-C bond. Further, when the carbon-carbon unsaturated bond is a C≡C bond, it is a structural unit formed by conversion to a CC bond or a C=C bond, and when the carbon-carbon unsaturated bond is a C=C bond, it is converted into a CC bond. And the structural unit formed.

Examples of the carbon-carbon unsaturated bond include a carbon-carbon unsaturated double bond and a carbon-carbon unsaturated triple bond. Among these, the carbon-carbon unsaturated bond is preferably a carbon-carbon unsaturated double bond from the viewpoint that the cured product easily has excellent low dielectric properties and the raw material is easily obtained.

The compound having a carbon-carbon unsaturated bond (double bond) and an epoxy group as the component C can be, for example, a compound represented by the following formula (15).

[Chemical Formula 14] (In the formula (15), R ^6A represents an alkenyl group or an alkynyl group having 2 to 18 carbon atoms, and the group may be substituted by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. R ⁷ 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 also be selected from an oxygen atom and a nitrogen atom. At least one atom in the group consisting of atoms is substituted. o represents an integer from 0 to 6, and p represents an integer from 0 to 3.

In the formula (15), the carbon number represented by R ^6A is 2 to 18 (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18). The alkenyl group is a linear or branched alkenyl group, preferably a linear chain. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Alkenyl, cyclohexenyl and the like. Preferred is an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, still 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 (i.e., an alkenyl group in which a terminal carbon atom forms a double bond with an adjacent carbon atom). In the formula (15), the carbon number represented by R ^6A is 2 to 18 (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18). The alkynyl group is a linear or branched alkynyl group, preferably a linear one. Specific examples thereof include an ethynyl group and a propargyl group. It is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 8 carbon atoms, still more preferably an alkynyl group having 2 to 6 carbon atoms, particularly preferably an ethynyl group or a propargyl group. Further, the alkynyl group is preferably an α-alkynyl group (i.e., an alkynyl group in which a terminal carbon atom forms a triple bond with an adjacent carbon atom).

The alkenyl group or alkynyl group having 2 to 18 carbon atoms may be substituted with a part of carbon atoms selected from 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 1 or a plurality (for example, 2, 3, 4, 5 or 6) carbon atoms, preferably 1 carbon atom. In the group, the alkenyl group having 2 to 18 carbon atoms, that is, a part of carbon atoms may be selected from a group substituted with at least one atom (preferably an oxygen atom) of a group consisting of an oxygen atom and a nitrogen atom. Examples thereof include an alkenyl group having 2 to 9 carbon atoms and an alkylene group having 1 to 8 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms and an alkyl group having 1 to 3 carbon atoms. Further, it is more preferably an alkenyl group having 2 to 4 carbon atoms and an alkylene group having 1 to 2 carbon atoms, and more preferably an alkenyl group -O-CH ₂ - having a carbon number of 3. More 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 -, etc., among these, preferably CH ₂ =CH-CH ₂ -O-CH ₂ -(allyloxymethyl) . Further, the alkynyl group having 2 to 18 carbon atoms, that is, a part of carbon atoms may be selected from a group substituted with at least one atom (preferably an oxygen atom) of a group consisting of an oxygen atom and a nitrogen atom, for example. The alkynyl group having 2 to 9 carbon atoms, the alkylene group having 1 to 8 carbon atoms, preferably the alkynyl group having 2 to 4 carbon atoms, and the alkyl group having 1 to 3 carbon atoms, More preferably, it is an alkynyl group having 2 to 4 carbon atoms, an alkylene group having 1 to 2 carbon atoms, and more preferably an alkynyl group -O-CH ₂ - having a carbon number of 3. More specifically, examples thereof _{include: CH≡CO-CH 2 -, CH≡C} -CH 2 -O-CH 2 -, CH≡C-CH 2 -O- (CH 2) 2 -, CH≡C- (CH ₂ ) ₃ -O-(CH ₂ ) ₄ - or the like, and among these, CH≡C-CH ₂ -O-CH ₂ - is preferred.

In the formula (15), R ⁷ represents the same or different 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 may also be a part of carbon atoms. It 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 three- to eight-membered ring or an epoxy ring. Further, the carbon atom which may be substituted may be 1 or a plurality (for example, 2, 3, 4, 5 or 6) carbon atoms, preferably 1 carbon atom. Examples of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group having 1 to 18 carbon atoms represented by R ⁷ are the same as the corresponding groups represented by the above R ¹ . Examples of the alkenyl-type linear or branched alkenyl group having 2 to 9 carbon atoms represented by R ⁷ include a vinyl group, an allyl group, a 2-propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. , heptenyl, octenyl, decenyl and the like. It is preferably an alkenyl group having 2 to 4 carbon atoms. R ^{7 is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

o is preferably 0 to 4 (0, 1, 2, 3 or 4), more preferably 0 or 4. p is preferably 0 or 1, more preferably 0. Further, when o is 0, the compound represented by the formula (15) is a compound represented by the following formula (15'). [Chemical Formula 15] (wherein R ^6A and R ⁷ and p are the same as defined above). When the component C contains a compound in which o is 0 (that is, a compound represented by the formula (15')), the B component is preferably an organic group L in the formula (8), and a part of carbon atoms may be a ring obtained by condensing an oxygen atom-substituted linear or branched alkane, an aromatic hydrocarbon ring, a non-aromatic unsaturated hydrocarbon ring, a nitrogen-containing hetero ring, a 2 to 6 saturated hydrocarbon ring, and/or an unsaturated hydrocarbon ring, Or a ring composed of two saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring, and the B component is more preferably an organic group L in the formula (8), which is an aromatic hydrocarbon ring or a non-aromatic unsaturated hydrocarbon ring. A nitrogen heterocycle or a ring of 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring is condensed. Further, when the component C contains a compound having a ratio of 4, the reaction is easy, and the component B is preferably a linear or branched chain in which the organic group L in the formula (8) is substituted by an oxygen atom. An alkane, an aromatic hydrocarbon ring, a nitrogen-containing hetero ring, or a ring of two saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring, and the B component is more preferably an organic group L in the formula (8). A hydrocarbon ring or a nitrogen-containing heterocyclic ring.

Specific examples of the component C include a 1,3-butadiene monoepoxide represented by the following formula (16), and 1,2-epoxy-5-hexene represented by the following formula (17). Epoxypropylpropargyl ether represented by formula (18), 1,2-epoxy-9-decene represented by the following formula (19), allyl epoxypropyl group represented by the following formula (20) Ether, 4-vinyl-1,2-epoxycyclohexane represented by the following formula (21), limonene oxide represented by the following formula (22), and the like.

[Chemical Formula 16]

Others, regarding the C component, specifically, exemplified by: glycidyl methacrylate, 1-allyl-3,5-diepoxypropyl isophthalocyanate, 4-hydroxybutyl acrylate epoxide Ether and the like. The C component may be one type or two or more types.

[Hydrazine Hydride Epoxy Resin] The epoxy resin (hydrazine hydride epoxy resin) of the present invention can be obtained, for example, by subjecting the A component, the B component, and the C component to a hydrazine hydrogenation reaction. More specifically, the hydrogenated epoxy resin has an epoxy resin having a structure derived from the A component, the B component, and the C component as a skeleton (that is, an A component structural unit, a B component structural unit, and a C component structural unit). .

The epoxy resin of the present invention is preferably an epoxy resin having a structure in which an A component structural unit and a B component structural unit are bonded one or more times (for example, an average of 1 to 20 times) at the interactive bonding. Each of the end portions is bonded to a C component structural unit. More specifically, for example, the component A is a divalent compound (for example, a compound represented by the formula (2)), the component B is a divalent compound (for example, a compound of k=2 in the formula (8)), and the component C is a formula (15). In the case of the compound shown, the epoxy resin represented by the formula (23) can be produced by the following reaction formula.

[Chemical Formula 17] (wherein R ⁶ represents an alkylene group having 2 to 18 carbon atoms or an extended alkenyl group having 2 to 18 carbon atoms, and the group may be selected from a carbon atom other than a carbon atom directly bonded to a halogen atom. Substituted by at least one atom in the group consisting of an oxygen atom and a nitrogen atom; L ² represents a linear or branched alkane, a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, or a part of a carbon atom which may be substituted by an oxygen atom. a nitrogen heterocycle, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, or a ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded to each other 2 a divalent group obtained by hydrogen atoms; q represents a positive number whose average value is greater than 0 and 20 or less; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6A , R ⁷ , X ² , l, m, n, o, and p are synonymous with the foregoing).

In the formula (23), R ⁶ represents an alkylene group having 2 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. The alkylene group is a linear or branched alkylene group, preferably a linear alkyl group. Examples thereof include: methylene, methylmethylene, ethyl methylene, dimethylmethylene, diethyl methylene, dimethylene (-CH ₂ CH ₂ -), trimethylene (-CH ₂ CH ₂ CH ₂ -), tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, hexamethylene, decamethylene, eleven Base, dodecamethylene, thirteen methylene and the like. Preferably, it is an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a carbon number of 2 to 5. alkyl. Further, the alkenyl group is a linear or branched alkenyl group, preferably a linear alkenyl group. For example, a vinyl group, a 1-extended propylene group, a 2-extended propylene group, a 1-butenbutenyl group, a 2-butenbutenyl group, a 1-extenylene group, a 2-extenylene group, and a 1- Hexyl, 2-hexenyl, 1-extenyl and the like. Preferably, it is 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 carbon number of 2 to 5. Alkenyl.

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

Specifically, when the side of the bond of R ⁶ to the ruthenium atom is (*), for example, (*) - a C 2 - 9 alkyl group - O - a carbon number 1 - 8 alkylene-, preferably (*)-carbon number 2 to 4 alkylene-O-carbon number 1 to 3 alkylene group - more preferably (*) - carbon number 2 to 4 An alkyl-O-alkylene group having 1 to 2 carbon atoms, more preferably a (*)-alkyl 3 alkylene group-O-methylene group. Further, for example, (*) - an alkenyl group having 2 to 9 carbon atoms - an alkyl group having 1 to 8 carbon atoms, preferably (*) - an alkenyl group having 2 to 4 carbon atoms - O-carbon number 1 to 3 alkylene group - more preferably (*) - carbon number 2 to 4 alkenyl group - O - carbon number 1 to 2 alkyl group -, especially preferably (*)- A carbon number of 3 alkenyl-O-methylene-.

More 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 -, etc., preferably (*)-(CH ₂ ) ₃ -O-CH ₂ -. Further, for example, (*)-CH=CH-O-CH ₂ -, (*)-CH=CH-CH ₂ -O-CH ₂ -, (*)-CH=CH-CH ₂ -O- (CH ₂ ) ₂ -, (*)-CH=CH-(CH ₂ ) ₃ -O-(CH ₂ ) ₄ -, etc., preferably (*)-CH=CH-CH ₂ -O- CH ₂ -.

In the hydrogenation reaction of the hydrazine, the amount of the component A, the component B, and the component C can be, for example, a hydrogen-carbon (Si-H) group in the component A per mole of the carbon-carbon unsaturated bond in the component B. The carbon-carbon unsaturated bond in the aromatic ring is 0.05 to 0.95 moles, preferably 0.1 to 0.9 moles, more preferably 0.2 to 0.8 moles. Further, the C component may be set such that the hydrazine hydrogen (Si-H) group in the component A is 1 mol, and the carbon-carbon unsaturated bond (excluding the carbon-carbon unsaturated bond in the aromatic ring) is 0.05 to 0.95. The ear is preferably 0.1 to 0.9 moles, more preferably 0.2 to 0.8 moles. Further, in the present specification, the number of hydrogen atoms bonded to a deuterium atom is counted as the number of hydrogen (Si-H) groups. For example, when two hydrogen atoms are bonded to a ruthenium atom, the number of ruthenium hydrogen (Si-H) groups is counted as two. q As described above, a positive number indicating that the average value is larger than 0 and 20 or less, a positive number having an average value of 0.1 to 15 is preferable, and a positive number having an average value of 0.2 to 10 is more preferable.

The rhodium hydrogenation reaction can be carried out by a known method, for example, the rhodium hydrogenation reaction can be carried out in the presence of a catalyst, in the presence or absence of a solvent. The hydrazine hydrogenation reaction allows the A component, the B component, and the C component to be simultaneously reacted. Further, after the component A and the component B are reacted, the reactant may be reacted with the component C, or the component A may be reacted with the component C, and then the reactant and the component B may be reacted. From the viewpoint of easiness of the production method and easy control of the reaction, it is preferred to react the component A with the component B, and then react the reactant with the component C.

In the hydrogenation reaction, a well-known catalyst for the hydrogenation reaction of hydrazine can be used. The catalyst may, for example, be a platinum-based catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenyl alkoxylate complex or platinum carbonyl complex; tris(triphenylphosphine) A ruthenium catalyst such as ruthenium; a ruthenium catalyst such as bis(cyclooctadienyl)dichloropurine. The catalyst may be in the form of a solvate (for example, a hydrate or an alcoholate), or may be in the form of a solution dissolved in an alcohol such as ethanol.

In the hydrogenation reaction of hydrazine, the amount of the catalyst used may be an amount which is an effective amount of the catalyst, that is, an amount capable of exhibiting the function of the catalyst. For example, the catalyst usage amount is 0.00001 to 20 parts by mass, preferably 0.0005 to 5 parts by mass, per 100 parts by mass of the component A.

The hydrazine hydrogenation reaction may be carried out without using a solvent, but the hydrazine hydrogenation reaction may be carried out under milder 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; and tetrahydrofuran and An ether solvent such as an alkane; an alcohol solvent such as ethanol or isopropyl alcohol; These solvents may be used singly or in combination of two or more.

The temperature of the hydrogenation reaction is, for example, 0 ° C to 150 ° C, preferably 10 ° C to 120 ° C. Further, the reaction time of the rhodium hydrogenation reaction is, for example, 5 minutes to 24 hours.

By the hydrogenation reaction, for example, the component A is reacted with the component B and the component C to form a hydrogenated epoxy resin.

The weight average molecular weight of the hydrogenated epoxy resin is preferably from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,000 to 30,000. When the weight average molecular weight of the hydrogenated epoxy resin is 500 or more, it is easy to exhibit more excellent low dielectric properties when a cured product is obtained. Further, since the weight average molecular weight of the hydrogenated epoxy resin is 500 or more, deterioration of solder heat resistance (heat proof bulging property) due to the low molecular weight epoxy resin can be suppressed. Further, since the weight average molecular weight of the hydrogenated epoxy resin is 100,000 or less, the solubility of the hydrogenated epoxy resin to the solvent and the low dielectric properties when the cured product is formed are not easily damaged. Here, the weight average molecular weight referred to herein means a weight average molecular weight measured by GPC measurement in terms of polystyrene.

[Epoxy Resin Composition] The oxime hydrogenated epoxy resin of the present invention can be combined with other components to prepare an epoxy resin composition containing the same. Examples of other components include an epoxy resin other than a hydrogenated epoxy resin, a curing catalyst, a curing agent, and an additive. The present invention also encompasses the epoxy resin composition.

The epoxy resin composition may also comprise an epoxy resin other than the hydrogenated epoxy resin of the present invention and the hydrogenated epoxy resin. Hereinafter, the hydrazine hydride epoxy resin may be referred to as "first epoxy resin", and the epoxy resin other than hydrazine hydrogenated epoxy resin may be referred to as "second epoxy resin".

Examples of the second epoxy resin include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a cresol novolac epoxy resin, and an alicyclic epoxy resin. Brominated epoxy resin, triglycidyl isocyanate, hydrogenated bisphenol A epoxy resin, aliphatic epoxy resin, epoxy propyl ether epoxy resin, bisphenol S epoxy resin , biphenyl type epoxy resin, double ring type epoxy resin, naphthalene type epoxy resin, and the like. The second epoxy resin may be used alone or in combination of two or more.

When the epoxy resin composition of the present invention contains the first epoxy resin and the second epoxy resin, the blending ratio of the two may be, for example, relative to the first epoxy resin and the second ring, within a range not inhibiting the effects of the present invention. The content of the second epoxy resin is set to 99% by mass or less based on the total mass of the oxygen resin. The content ratio of the second epoxy resin is preferably 80 to 1% by mass, preferably 50 to 1% by mass, and more preferably 30 to 1% by mass.

The epoxy resin composition may also be a hardening catalyst and/or a hardener comprising the epoxy resin of the present invention and as other components.

When the epoxy resin composition contains a hardening catalyst and/or a curing agent, the curing reaction rate of the cured product for obtaining the epoxy resin composition can be improved, and the strength of the obtained cured product can also be improved.

From the viewpoint of improving the electrical properties of the cured product of the epoxy resin composition, the imidazole catalyst, the phosphorus compound, the cation hardening catalyst, and the like can be exemplified as the hardening catalyst. Specific examples of the curing catalyst include imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; dicyandiamide and Derivative; 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, 2,4, a tertiary amine such as 6-tris(dimethylaminomethyl)phenol or dimethylaminopyridine; triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetra-p-tolylboronic acid, tetrabutyl a phosphorus-based compound such as o-o-diethyldithiophosphoric acid or a cationic hardening catalyst such as an aromatic sulfonium salt.

The amount of the curing catalyst is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total epoxy resin. In addition, all the epoxy resins are the first epoxy resin and the second epoxy resin, and the same applies hereinafter.

As the hardener, it is preferred to react with an epoxy resin to obtain a cured product of the epoxy resin composition. Examples of the curing agent include an amine curing agent, a guanamine curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, a cyanate curing agent, a thiol curing agent, and an isocyanate system. Hardener, etc.

Examples of the amine-based curing agent include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine and menthene diamine. , alicyclic amines such as bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane; m-phenylenediamine, diaminodiphenylmethane, diethyl Aromatic amines such as toluenediamine, diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2-(dimethylaminomethyl)phenol, 2,4 a secondary or tertiary amine such as 6-tris(dimethylaminomethyl)phenol or 1,8-diazabicyclo(5,4,0)-undecene-7.

Examples of the amide-based curing agent include dicyandiamide and a derivative thereof, and a polyamidamine resin (polyamine decylamine or the like).

Examples of the acid anhydride-based curing agent include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride; An alicyclic acid anhydride such as kinadiic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or 4-methylhexahydrophthalic anhydride.

Examples of the phenolic curing agent include a phenol novolak resin, a cresol novolak resin, a biphenyl type phenol resin, a triphenylmethane type phenol resin, a naphthol novolac resin, a phenol extending biphenyl resin, and a phenol type aralkyl resin. Biphenyl aralkyl type phenol resin, modified polyphenylene ether resin, having benzoic acid Ring compounds, etc.

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

Examples of the cyanate-based curing agent include a phenolic cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethyl bisphenol F type cyanate resin. Phenolic cyanate resin and the like.

Examples of the thiol-based curing agent include trimethylolpropane tris(3-mercaptopropionate) and tris-[(3-mercaptopropyloxy)-ethyl]-isopolycyanate. Pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3- Mercaptobutyloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethanetris(3-mercaptobutyrate), polysulfide polymer, and the like.

Examples of the isocyanate-based curing agent include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, leucine diisocyanate, and isophora. Ketone diisocyanate Alkane diisocyanate or the like.

The hardener is considered to have the required characteristics, and may be used alone or in combination of two or more. The curing agent preferably contains at least one of an acid anhydride-based curing agent, a phenol-based curing agent, an active ester-based curing agent, and an amine-based curing agent, and the electrical properties are easily improved by selecting the curing agent.

The amount of the hardener contained in the epoxy resin composition of the present invention can be, for example, 1 equivalent to the epoxy group in the epoxy resin composition of the present invention, and the amount of the reactive functional group in the hardener is set to 0.1. ~5 equivalents, preferably 0.3 to 3 equivalents, more preferably 0.5 to 2 equivalents.

The epoxy resin composition of the present invention may also contain other additives and the like. As the additive, a thermoplastic resin or a filler can be exemplified.

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, and polyacetal. Resin, such resin modified by acid, etc. 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, or the like is preferably modified by acid. Made of resin.

Examples of the filler include cerium oxide (more specifically, crystalline cerium oxide, molten cerium oxide, spherical molten cerium oxide, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, and 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. Further, examples of the filler include minerals such as montmorillonite, talc, mica, boehmite, kaolin, bentonite, hard calcite, vermiculite, and sericite. Examples of other fillers include carbides such as carbon black, acetylene black, ketjen black, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and various glass such as glass beads, glass sheets, and glass balloons. .

The filler may be in the form of a powder or may be dispersed in a resin.

The filler may be used alone or in combination of a plurality of types in consideration of fluidity, heat resistance, low thermal expansion property, mechanical properties, hardness, scratch resistance, and adhesion properties required for the epoxy resin composition or the cured product thereof.

Regarding other additives, for example, the epoxy resin composition may also include: an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a thermo-light stabilizer, an antistatic agent, a polymerization inhibitor, an antifoaming agent, Solvent, anti-aging agent, free radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleation A reagent, a coupling agent, a conductivity imparting agent, a phosphorus-based peroxide decomposing agent, a pigment, a metal deactivator, a physical property adjuster, and the like.

The epoxy resin composition of the present invention can be produced, for example, by a method comprising the steps of mixing a hydrazine hydrogenated epoxy resin (first epoxy resin) with a curing catalyst and/or a curing agent. When the hydrazine hydrogenated epoxy resin is mixed with the hardening catalyst and/or the curing agent, other additives such as the second epoxy resin and the filler may be blended as needed. The hydrogenated epoxy resin and the hardening catalyst and/or hardener may also be mixed while heating.

The method of mixing the hydrazine hydrogenated epoxy resin with the hardening catalyst and/or the hardening agent can be mixed, for example, using a commercially available mixer.

The cured product can be obtained by hardening the epoxy resin composition of the present invention.

A cured product of the epoxy resin composition can be obtained, for example, by heating the epoxy resin composition. The hardening temperature is, for example, room temperature (for example, 20 ° C) to 250 ° C. The hardening time can be appropriately adjusted depending on the composition, concentration, and blending ratio of the epoxy resin composition, and can be set, for example, from 10 minutes to 1 week. Further, the heating for hardening can be divided into several stages. For example, after heating at a predetermined temperature, the temperature is further increased, and heating is further performed for a predetermined time or the like, and the heating may be divided into stages to obtain a cured product.

The cured product thus obtained has excellent electrical characteristics such as low dielectric constant and low dielectric loss tangent. Further, the cured product has a high bonding strength to the metal. The cured product of the epoxy resin composition of the present invention has only an epoxy resin and a hardening catalyst and/or a hardener (ie, epoxy resin + hardening catalyst, epoxy resin + hardener, or epoxy resin + hardening catalyst + In the case of a hardener, the relative dielectric constant (1 GHz) of the cured product is preferably from 2.5 to 3.0, preferably from 2.5 to 2.8. Further, the cured product of the epoxy resin composition of the present invention preferably has a dielectric loss tangent (1 GHz) of about 0.001 to 0.009, preferably about 0.002 to 0.008, or about 0.002 to 0.007. More preferably, the above two conditions are met. Further, in the same manner, the cured epoxy resin of the present invention preferably satisfies the above relative dielectric constant (1 GHz) and/or dielectric loss tangent (1 GHz). Further, the relative dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz) herein were measured by a parallel plate capacitor method. The measurement by the parallel plate capacitor method can be carried out, for example, using a well-known dielectric constant measuring device.

The epoxy resin composition of the present invention can be suitably used, for example, in a wide range of applications such as a semiconductor package, a liquid package, a potting material, a sealing material, a printed substrate material, and a composite material. For example, in the above various applications, the epoxy resin composition of the present invention can be suitably used in order to improve electrical properties and metal adhesion.

Moreover, the cured product of the epoxy resin composition of the present invention can be applied to constituent elements (constituting members) such as a semiconductor package, a liquid package, a potting material, a sealing material, a printed substrate material, and a composite material.

[Examples] Hereinafter, the present invention will be more specifically described by way of examples.

(Production Examples 1 to 10) A hydrogenated epoxy resin was produced by using the component A, the component B, and the component C described below.

More specifically, the component A is prepared as A-1 or A-2 described below, and the component B is prepared as B-1, B-2, B-3 or B-4 described below, and the component C is prepared as follows: C-1 or C- 2. A-1: 1,4-bis(dimethylalkylalkyl)benzene (manufactured by Gelest) A-2: bis[(p-dimethyldecyl)phenyl]ether (manufactured by Gelest) B-1: two Vinylbenzene (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) B-2: Diallyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) B-3: Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) B -4:5-vinyl-2-down Alkene (manufactured by Tokyo Chemical Industry Co., Ltd.) C-1: 4-vinyl-1,2-epoxycyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) C-2: allylepoxypropyl ether (manufactured by Osaka SODA Co., Ltd.)

(Production Example 1) An epoxy resin was prepared as described below. Further, as shown in Table 1, A-1, B-2, and C-1 were used as the A component, the B component, and the C component, respectively. The components A and B were dissolved in 20 mL of toluene in the amounts shown in Table 1, and placed in a 10-neck flask having a volume of 100 mL equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel. Next, 20 mg of a platinum catalyst (manufactured by N.E. CHEMCAT Co., Ltd., Pt-VTS-IPA solution) was added at 25 ° C, and the mixture was stirred at 40 ° C for 2 hours. Then, the component C dissolved in 20 mL of toluene was added dropwise at 40 ° C, and the reaction liquid was stirred at 90 ° C for 4 hours while maintaining the reaction liquid. The composition of the reaction liquid was analyzed by high performance liquid chromatography (HPLC), and the completion of the reaction was confirmed by confirming the disappearance of the A component. Then, toluene was removed by evaporation, and the reaction liquid was concentrated, whereby epoxy resin 1 was obtained. The obtained epoxy resin 1 was a yellowish transparent liquid.

The epoxy resin 1 thus obtained was dissolved in tetrahydrofuran, and the weight average molecular weight converted into polystyrene was measured by GPC. The results are shown in Table 1. (Production Examples 2 to 10) The components A and B and the components C in the types and amounts shown in Table 1 were reacted in the same manner as in Production Example 1. The composition of the reaction liquid was analyzed by high performance liquid chromatography (HPLC), and the completion of the reaction was confirmed by confirming the disappearance of the A component. Then, toluene was removed by evaporation, and the reaction liquid was concentrated, whereby epoxy resins 2 to 10 were obtained (Table 1). The obtained epoxy resins 2 to 10 are all yellowish transparent liquids. Further, the weight average molecular weight of each epoxy resin was measured in the same manner as in Production Example 1. The results are shown in Table 1.

(Example 1) The epoxy resin 1 obtained in the production example 1 and the cation hardening catalyst (SAN-AID SI-100L, which is a product of Sanshin Chemical Industry Co., Ltd.; may be described as hardening catalyst A) are shown in Table 2 (mass ratio) was weighed in a measuring cup and stirred while heating to 30 ° C to uniformly mix and prepare an epoxy resin composition.

(Example 2) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 3 obtained in Production Example 3 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 3) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 5 obtained in Production Example 5 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 4) The epoxy resin obtained in Production Example 1, the curing catalyst 2-ethyl-4-methylimidazole (manufactured by Mitsubishi Chemical Corporation, EMI24; sometimes referred to as curing catalyst B), and the acid anhydride curing agent ( New Japan Chemical and Chemical Co., Ltd., MH-700; sometimes referred to as hardener A), weighed in a measuring cup according to the ratio (mass ratio) shown in Table 2, and heated while stirring to 30 ° C, thereby uniformly mixing and modulating epoxy Resin composition.

(Example 5) The epoxy resin composition was adjusted in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 2 obtained in Production Example 2 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 6) An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 3 obtained in Production Example 3 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 7) The epoxy resin composition was adjusted in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 4 obtained in Production Example 4 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 8) An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 5 obtained in Production Example 5 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 9) An epoxy resin composition was prepared in the same manner as in Example 4 except that the epoxy resin 1 was changed to the epoxy resin 6 obtained in Production Example 6 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 10) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 7 obtained in Production Example 7 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 11) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 8 obtained in Production Example 8 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 12) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 9 obtained in Production Example 9 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 13) An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 1 was changed to the epoxy resin 10 obtained in Production Example 10 and changed to the ratio (mass ratio) shown in Table 2. Things.

(Example 14) The epoxy resin 5 obtained in Production Example 5, triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.; sometimes referred to as a curing catalyst C) and a phenol resin-based curing agent ([phenol phenol type) Resin (made by DIC Corporation, TD-2131)]; sometimes referred to as hardener B), weighed in a measuring cup according to the ratio (mass ratio) shown in Table 2, and stirred while heating to 30 ° C, thereby uniformly mixing and modulating Epoxy resin composition.

(Example 15) The epoxy resin 5 obtained in Production Example 5, 4-dimethylaminopyridine as a curing catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.; sometimes referred to as a curing catalyst D), and an active ester-based curing agent (active) Ester resin, DIC company, EPICLON HPC-8000-65T; sometimes referred to as hardener C), weighed in a measuring cup according to the ratio (mass ratio) shown in Table 2, and stirred while heating to 30 ° C, thereby uniformly mixing , modulating the epoxy resin composition.

(Comparative Example 1) The epoxy resin 1 in the first embodiment was changed to a Bis-A type epoxy resin (JER 828, manufactured by Mitsubishi Chemical Corporation; sometimes referred to as epoxy resin 11), and was changed to the ratio shown in Table 3. The epoxy resin composition was prepared in the same manner as in Example 1 except for (mass ratio).

(Comparative Example 2) The epoxy resin composition was adjusted in the same manner as in Example 4 except that the epoxy resin 1 in Example 4 was changed to the epoxy resin 11 and changed to the ratio (mass ratio) shown in Table 3. Things.

(Comparative Example 3) The epoxy resin 1 in Example 1 was changed to 1,4-bis{[2-(3,4-epoxycyclohexyl)ethyl]dimethylammonio]}benzene (sometimes The epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin 12) was changed to the ratio (mass ratio) shown in Table 3.

(90-degree peeling strength of the copper foil) The epoxy resin composition prepared in each of the examples and the comparative examples was applied to an aluminum plate, and an electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) having a thickness of 35 μm was superposed thereon to form a laminate. body. The laminate was heated at 100 ° C for 1 hour, then heated at 120 ° C for 2 hours, and further heated at 150 ° C for 2 hours to form a cured product of the epoxy resin composition. After hardening, a slit having a width of 1 cm was formed by a cutter as a 90-degree peel strength test piece. For the obtained test piece, a 90-degree peel strength test was carried out using AGS-X (manufactured by Shimadzu Corporation) at a test speed of 50 mm/min.

(Electrical characteristics: relative dielectric constant and dielectric loss tangent) The epoxy resin composition prepared in each of the examples and the comparative examples was placed in a resin mold (thickness: 1 mm), and heated at 100 ° C for 1 hour, followed by 120. After heating at ° C for 2 hours and then at 150 ° C for 2 hours, a cured product of the epoxy resin composition was formed. Then, a size of 20 mm in width × 30 mm in length × 1 mm in thickness was cut out to obtain a test piece for measuring a dielectric constant. For the obtained test piece, a dielectric constant measuring device (E4991 ARF impedance/material analysis, manufactured by AGILEND) was used, and after calibrating with PTFE, the relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz were measured by a parallel plate capacitor method. ).

(Solder resistance heat resistance (heat swell resistance)) The epoxy resin composition prepared in each of the examples and the comparative examples was applied to an electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) having a thickness of 35 μm, and the electrolytic copper foil was superposed thereon. And a layered body is formed. The laminate was heated at 100 ° C for 1 hour, then heated at 120 ° C for 2 hours, and further heated at 150 ° C for 2 hours to form a cured product of the epoxy resin composition. After hardening, it was cut into a width of 1 cm by a cutter to obtain a heat-resistant embossing test piece. The obtained test piece was immersed in a solder bath of 280 ° C for 3 minutes to visually observe the change in appearance after the immersion. It was observed that the sweller was evaluated as "x" (bad), and the bulge was not observed as "○" (good). Further, an example of a test piece in which a bulge has occurred is shown in Fig. 1 .

Table 1 shows the blending amount of the components used in the respective production examples and the weight average molecular weight of the obtained epoxy resin. The mol in the parentheses in Table 1 represents the molar number of the functional group of the A group's anthracene hydrogen group, the B component carbon-carbon unsaturated bond group, or the C component unsaturated bond group.

Tables 2 and 3 show the results of the 90-degree peel strength and electrical properties (relative dielectric constant and dielectric loss tangent) and solder heat resistance of the copper foil. From these results, it is understood that the ruthenium hydrogenated epoxy resin obtained by the hydrazine hydrogenation reaction of the component A, the component B, and the component C (that is, the hydrazine hydrogenated epoxy resin having the component A, the component B, and the component C as a structural unit) The epoxy resin composition of the hardening catalyst is a cured product which is excellent in low dielectric properties and excellent in adhesion to metals. [Table 1] [Table 2] [table 3]

Fig. 1 shows an example of a test piece in which a bulge is generated.

Claims (9)

An epoxy resin having: (A) a structural unit derived from an organic compound having a hydrazine group and removing a hydrogen atom of a hydrazine group; (B) derived from a carbon-carbon unsaturated bond and having no a compound of an epoxy group and a structural unit formed by converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond; and (C) a compound derived from a carbon-carbon unsaturated bond and an epoxy group A structural unit formed by converting a carbon-carbon unsaturated bond into a C=C bond or a CC bond. An epoxy resin according to claim 1, wherein (A) an organic compound having an anthracene hydrogen group is a compound represented by the formula (0): [Chemical Formula 1] Wherein R ^{1 is the} same or different and represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups may also be selected from a group of carbon atoms and At least one atom in the group consisting of nitrogen atoms is substituted, and the X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring are condensed, or A ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are bonded, and n ^X represents 1, 2, 3 or 4). An epoxy resin according to claim 2, wherein (B) a compound having a carbon-carbon unsaturated bond and having no epoxy group is a compound represented by the formula (8): [Chemical Formula 2] (wherein R ² represents an alkylene group having 1 to 8 carbon atoms, and the group may be substituted by at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; and R ³ represents * -COO- or *-OCO- (the above "*" indicates the side bonded to R ² or L); R ⁴ represents an alkylene group having 1 to 4 carbon atoms, and the group may also be selected from a part of carbon atoms At least one atom in the group consisting of an oxygen atom and a nitrogen atom is substituted; R ⁵ represents a methyl group or a hydrogen atom; L represents a k-valent organic group; l each independently represents 0 or 1; m independently represents 0 or 1; n each independently represents 0 or 1; k represents an integer from 1 to 6; further, when there are a plurality of R ² , they may be the same group, or some or all of them are different groups; when there are a plurality of R ³ , They may be the same group, or some or all of them are different groups; when there are a plurality of R ⁴ , they may be the same group, or some or all of them may be different groups). An epoxy resin according to claim 3, wherein (C) a compound having a carbon-carbon unsaturated bond and an epoxy group is a compound represented by the formula (15): [Chemical Formula 3] (wherein R ^6A represents an alkenyl group or alkynyl group having 2 to 18 carbon atoms, and the group may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom; R ⁷ 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 also be selected from a group consisting of an oxygen atom and a nitrogen atom. At least one atom in the group is substituted; o represents an integer from 0 to 6; p represents an integer from 0 to 3. The epoxy resin of claim 4 is represented by the formula (23): [Chemical Formula 4] (wherein R ⁶ represents an alkylene group having 2 to 18 carbon atoms, and the group may be selected from a group consisting of an oxygen atom and a nitrogen atom except for a carbon atom directly bonded to a carbon atom of the halogen atom. At least one of the atoms is substituted; L ² represents a linear or branched alkane, a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, a nitrogen-containing heterocyclic ring, or 2 to 6 carbon atoms from which a part of carbon atoms may be substituted by an oxygen atom. a ring having a structure in which a saturated hydrocarbon ring and/or an unsaturated hydrocarbon ring is condensed or a ring having a structure in which two saturated hydrocarbon rings and/or an unsaturated hydrocarbon ring are bonded to each other to remove two hydrogen atoms; q represents a positive number whose average value is greater than 0 and 20 or less; X ² represents a divalent group obtained by removing two hydrogen atoms from the aforementioned X ring; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , l , m, n, o, and p are synonymous with the foregoing). An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 5, and a hardening catalyst and/or a hardener. A hardened material which is a cured product of the epoxy resin composition of claim 6. A semiconductor package, a liquid package, a potting material, a sealing material, a printed substrate material or a composite material, comprising the epoxy resin composition of claim 6 or the cured product of claim 7 as a constituent element. A method for producing an epoxy resin composition, which comprises the step of preparing an epoxy resin composition according to claim 6, which comprises the step of mixing the epoxy resin, the curing catalyst and/or the curing agent.