JP5040510B2 - Epoxy resin composition and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin composition and an electronic component device including an element sealed by the epoxy resin composition.

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs, and LSIs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. In recent years, in order to achieve high performance and high functionality of electronic component devices, high-density mounting of elements, miniaturization of wiring, multilayering, increase in the number of pins, increase in the occupied area of an element package, and the like have been advanced. Also, in electronic devices in the automotive field and the like, an increase in so-called power-related elements that consume a large amount of power is observed, and in addition to the high-density mounting of the elements, the problem of heat generation of the elements is closed up. High heat resistance and heat dissipation are also required for the epoxy resin molding material for fixing.

As a method for increasing the heat dissipation of the epoxy resin molding material for sealing, crystalline silica (for example, see Patent Document 1), alumina (for example, see Patent Document 2), silicon nitride (for example, see Patent Document 3), aluminum nitride ( For example, a method of adding a highly heat-conductive inorganic filler such as Patent Document 4) has been reported. However, crystalline silica has a small heat conduction effect, and there is a problem that reliability such as moisture resistance reliability of the package is lowered when silicon nitride or aluminum nitride is used. Therefore, at present, alumina, which has higher thermal conductivity than crystalline silica and does not lower the reliability, is generally used as an inorganic filler with high thermal conductivity.
Japanese Patent No. 2811933 Japanese Patent No. 2874089 Japanese Patent Publication No. 6-57744 JP-A-11-147936

  However, in order to increase the heat dissipation of the package, there is a problem that fluidity and curability etc. are reduced when blending high thermal conductivity inorganic fillers such as alumina into the epoxy resin molding material for sealing. This tendency becomes more prominent as the value increases. In particular, when a resin having high heat resistance, that is, a polyfunctional resin is used, the fluidity tends to further decrease.

  As described above, when a polyfunctional resin is used to increase heat resistance and a highly heat-conductive inorganic filler such as alumina is used to further improve heat dissipation, moldability is lowered as a result. That is, the present condition is that the method of obtaining the epoxy resin hardened | cured material which has high heat resistance and heat dissipation and was excellent in the moldability etc. using the present epoxy resin composition is not yet shown.

  The present invention has been made in view of such circumstances, and an epoxy resin composition that provides a cured product having excellent moldability, heat resistance, heat dissipation, and reliability, and an electronic component device including an element sealed thereby It is an issue to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use a curing agent containing a compound obtained by reacting a specific silane compound and a phenol compound with an inorganic filler containing alumina. As a result, it was found that the intended purpose can be achieved, and the present invention has been completed.

The present invention is an epoxy resin composition comprising (1) (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler,
The (B) curing agent is obtained by reacting at least one compound (d1) selected from a silane compound represented by the following general formula (I-1) and a partial condensate thereof with a phenol compound (d2). A compound (D) obtained,
And (C) It is related with the epoxy resin composition characterized by the inorganic filler containing an alumina.

(In the formula (I-1), n is an integer of 0 to 2, R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, All may be the same or different, and R ² is a halogen atom, a hydroxyl group, a monovalent oxy group having 1 to 18 carbon atoms that may have a substituent, or a carbon number that may have a substituent. have an amino group and a substituent of 0-18 also selected from the group consisting of optionally carbonyloxy group having 2 to 18 carbon atoms may be all the same or different, 2 selected from R ¹ and R ² The above may combine to form a ring structure.)
The invention also relates to (2) the compound (D), the reaction at the start of the silane compound and unreacted R ^2, based on the R ² groups in which the portion of at least one compound selected from the condensation product (d1) It is related with the epoxy resin composition as described in said (1) characterized by the content rate of base being 10% or less.

  The present invention is also characterized in that (3) 80% by weight or more of the phenol compound (d2) based on the total weight of the phenol compound is a divalent phenol compound. ).

  The present invention also provides (4) at least one compound (d1) wherein 50% by weight or more of the phenol compound (d2) is selected from the silane compound and a partial condensate thereof based on the total weight of the phenol compound. It is related with the epoxy resin composition as described in any one of said (1)-(3) characterized by being a cyclizable phenol compound.

The invention also relates to (5) the silane compound and at least one compound selected from the partial condensate in (d1), R ² is a hydroxyl group or a substituent of the optionally also good number 1-18 carbon has The epoxy resin composition according to any one of (1) to (4), wherein the epoxy resin composition is a monovalent oxy group.

The present invention also provides an epoxy resin composition comprising (6) (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The (B) curing agent is obtained by reacting at least one compound (e1) selected from a silane compound represented by the following general formula (I-2) and a partial condensate thereof with a phenol compound (e2). A compound (E) obtained,
And (C) It is related with the epoxy resin composition characterized by the inorganic filler containing an alumina.

(In Formula (I-2), m is 0 or 1, n is an integer of 2 or more, and R ^{1 ′} is an n-valent organic group having 0 to 18 carbon atoms that may have a substituent. , Two or more SiR ^{2 ′} _m R ^{3 ′} _(3-m) groups bonded to R ^{1 ′} may all be the same or different, and R ^{2 ′} may have a hydrogen atom and a substituent. It is selected from the group consisting of good hydrocarbon groups having 1 to 18 carbon atoms, and may be bonded to R ^{1 ′} or R ^{3 ′} to form a cyclic structure. R ^{3 ′} represents a halogen atom, a hydroxyl group or a substituent. C1-C18 monovalent oxy group that may have, C2-C18 amino group that may have a substituent, and C2-C18 that may have a substituent selected from the group consisting of carbonyl group, all may be the same or different, two or more R ^{3 'are} be bonded to each other to form a cyclic structure .)
In the present invention, (7) the compound (E) is an unreacted R based on the number of R ^{3 ′} groups in at least one compound (e1) selected from a silane compound and a partial condensate thereof at the start of the reaction. The content rate of ^{3 'group} is 10% or less, It is related with the epoxy resin composition as described in said (6) characterized by the above-mentioned.

  Further, in the present invention, (8) In the phenol compound (e2), 80% by weight or more of the phenol compound (e2) based on the total weight of the phenol compound is a divalent phenol compound. It relates to the epoxy resin composition described in 1.

  The present invention also relates to (9) at least one compound (e1) in which 50% by weight or more of the phenol compound (e2) is selected from the silane compound and a partial condensate thereof based on the total weight of the phenol compound. It is related with the epoxy resin composition as described in any one of said (6)-(8) characterized by being a cyclizable phenol compound.

In the present invention, (10) in at least one compound (e1) selected from the silane compounds and partial condensates thereof, R ^{3 ′} may have a hydroxyl group or a substituent having 1 to 18 carbon atoms. It relates to the epoxy resin composition according to any one of (6) to (9) above, which is a monovalent oxy group.

In addition, the present invention provides: (11) the compound (D) and / or the compound (E) having a structural moiety represented by the following general formula (I-3) and a structure represented by the following general formula (I-4): It has at least one of the site | parts, It is related with the epoxy resin composition as described in any one of said (1)-(10) characterized by the above-mentioned.

(In the formula (I-3), Ar represents a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides.)

(In the formula (I-4), Ar represents a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides, and n is 0 or more. Indicates the number.)
In addition, the present invention provides: (12) the compound (D) and / or the compound (E) having a structural moiety represented by the general formula (I-3) and a structure represented by the general formula (I-4). Including at least one of the sites, and the structural site represented by the general formula (I-3) and / or the total number of aryloxysilyl (ArO-Si) bonds in the compound (D) and / or the compound (E) and / or The epoxy resin according to any one of (1) to (11) above, wherein the number of aryloxysilyl bonds in the structural moiety represented by the general formula (I-4) is 30% or more. Relates to the composition.

  In the present invention, (13) the content of the inorganic filler (C) is 80% by weight or more based on the total weight of the epoxy resin composition, and 75% by weight or more of the inorganic filler (C). It is an alumina, It is related with the epoxy resin composition as described in any one of said (1)-(12) characterized by the above-mentioned.

  In the present invention, (14) the content of the inorganic filler (C) is 85% by weight or more based on the total weight of the epoxy resin composition, and 80% by weight or more of the inorganic filler (C). It is an alumina, It is related with the epoxy resin composition as described in any one of said (1)-(12) characterized by the above-mentioned.

  Moreover, this invention relates to the epoxy resin composition as described in any one of said (1)-(14) characterized by containing (F) hardening accelerator further (15).

  In the present invention, (16) the (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, or a dicyclopentadiene type epoxy resin. And at least one epoxy resin selected from the group consisting of a salicylaldehyde type epoxy resin, a epoxide resin copolymerized with naphthols and phenols, and an epoxidized aralkyl type phenol resin. It is related with the epoxy resin composition as described in any one of (1)-(15).

  The present invention also relates to (17) an electronic component device comprising an element sealed with the epoxy resin composition according to any one of (1) to (16).

  The epoxy resin composition according to the present invention is excellent in moldability, and can provide a cured product excellent in heat resistance, heat dissipation and reliability. In addition, an electronic component device including an element sealed with the epoxy resin composition according to the present invention has high reliability and high industrial value.

  Hereinafter, the present invention will be described in detail.

The epoxy resin composition of the present invention is an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and the (B) curing agent is represented by the following general formula ( A compound (D) obtained by reacting at least one compound (d1) selected from the silane compound represented by I-1) and a partial condensate thereof with a phenol compound (d2), and (C ) The inorganic filler contains alumina.

(In the formula (I-1), n is an integer of 0 to 2, R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, All may be the same or different, and R ² is a halogen atom, a hydroxyl group, a monovalent oxy group having 1 to 18 carbon atoms that may have a substituent, or a carbon number that may have a substituent. have an amino group and a substituent of 0-18 also selected from the group consisting of optionally carbonyloxy group having 2 to 18 carbon atoms may be all the same or different, 2 selected from R ¹ and R ² The above may combine to form a ring structure.)
In the epoxy resin composition of the present invention, the (B) curing agent is at least one compound (d1) selected from the silane compound represented by the general formula (I-1) and a partial condensate thereof, and a phenol compound. It is important to contain the compound (D) obtained by reacting with (d2).
(D1) Silane compound and partial condensate thereof (silane compound)
The silane compound used in the present invention is represented by the above general formula (I-1), and in formula (I-1), R ¹ has 1 to 18 carbon atoms which may have a hydrogen atom and a substituent. Selected from the group consisting of the following hydrocarbons, all of which may be the same or different.

The “optionally substituted hydrocarbon group having 1 to 18 carbon atoms” described as R ¹ is an aliphatic hydrocarbon having 1 to 18 carbon atoms that may be substituted or unsubstituted. Group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

  More specifically, examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-butyl. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and these aliphatic hydrocarbon groups as alkyl groups , Alkoxy group, aryl group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group, and isocyanate group And the like substituted with a substituent such as.

  Examples of the alicyclic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group. Alicyclic hydrocarbon groups and alicyclic hydrocarbon groups such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, epoxy groups, etc. And groups substituted with a substituent such as a group containing a group, a methacryloxy group, a mercapto group, an imino group, a ureido group, and an isocyanate group.

  Examples of the aromatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include aryl groups such as phenyl group and tolyl group, methylphenyl group, dimethylphenyl group, and ethylphenyl group. Alkyl group-substituted aryl groups such as butylphenyl group and tert-butylphenyl group, aromatic hydrocarbon groups such as alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group and tert-butoxyphenyl group These are further groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group, a methacryloxy group, a mercapto group. Groups, imino groups, ureido groups, isocyanate groups, etc. Or it may be substituted with substituent.

In addition, as R < ¹ > of the said general formula (I-1), although it does not specifically limit, The monovalent hydrocarbon chosen from the group which consists of the alkyl group and aryl group which may have a substituent. It is preferably a group. Among them, from the viewpoint of easy availability of raw materials, aryl such as phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, etc. Group: methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, epoxycyclohexylethyl group, glycidoxypropyl group, chloropropyl group, methacryloxy A chain or cyclic alkyl group such as propyl group, mercaptopropyl group, aminopropyl group, N-phenylaminopropyl group, N-aminopropylaminopropyl group, ureidopropyl group, isocyanatepropyl group; preferable.

In the general formula (I-1), R ² is a halogen atom, a hydroxyl group, a monovalent oxy group having 1 to 18 carbon atoms which may have a substituent, or a carbon number which may have a substituent. It is selected from the group consisting of a C 2-18 carbonyloxy group which may have a 0-18 amino group and a substituent, and all may be the same or different.

The “halogen atom” described as R ² includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The “monovalent oxy group having 1 to 18 carbon atoms which may be substituted” described as R ² is an aliphatic group having 1 to 18 carbon atoms which may be substituted or unsubstituted. It is meant to include a hydrocarbon oxy group, an alicyclic hydrocarbon oxy group, and an aromatic hydrocarbon oxy group.

Examples of the aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec- An aliphatic hydrocarbon oxy group having a structure in which an oxygen atom is bonded to the aliphatic hydrocarbon group described above as R ¹ such as butoxy group, tert-butoxy group, allyloxy group, vinyloxy group, and the like, and these aliphatic hydrocarbon oxy groups Are substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen atom.

Examples of the alicyclic hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include a cyclopropyloxy group, a cyclohexyloxy group, a cyclopentyloxy group, an allyloxy group, a vinyloxy group and the like. R ¹ of the alicyclic hydrocarbon oxy group having a structure in which an oxygen atom is bonded to the alicyclic hydrocarbon group described above, and these alicyclic hydrocarbon oxy groups are alkyl groups, alkoxy groups, aryl groups, aryl Examples thereof include those substituted with a substituent such as an oxy group, an amino group, or a halogen atom.

Examples of the aromatic hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxy An aromatic hydrocarbon oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group described above as R ¹ such as a phenoxy group and the like, and the aromatic hydrocarbon oxy group as an alkyl group, an alkoxy group, an aryl group, Examples thereof include those substituted with a substituent such as an aryloxy group, an amino group, and a halogen atom.

The “optionally substituted amino group having 0 to 18 carbon atoms” described as R ² includes, for example, an unsubstituted amino group, an optionally substituted or unsubstituted carbon group having 1 carbon atom. ~ 18 aliphatic hydrocarbon amino group, alicyclic hydrocarbon amino group, aromatic hydrocarbon amino group, dialiphatic hydrocarbon amino group, dialicyclic hydrocarbon amino group, diaromatic hydrocarbon amino group, An aliphatic hydrocarbon aromatic hydrocarbon amino group and a silylamino group are included. More specific examples are as follows.

Examples of the aliphatic hydrocarbon amino group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, and an n-butylamino group. , sec- butylamino group, tert- butylamino group, pentylamino group, hexylamino group, octyl amino group, decylamino group, a dodecyl group, an arylamino group, an aliphatic described above as R ¹ and vinyl amino group carbonized Aliphatic hydrocarbon amino groups substituted by hydrogen groups, and those aliphatic hydrocarbon groups substituted with substituents such as alkyl groups, alkoxy groups, aralkyl groups, aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. Is mentioned.

Examples of the alicyclic hydrocarbon amino group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclopentenylamino group, and a cyclohexenyl. An alicyclic hydrocarbon amino group substituted by the alicyclic hydrocarbon group described above as R ¹ such as an amino group, etc., and an alkyl group, alkoxy group, aralkyl group, aryl on these alicyclic hydrocarbon group parts And those substituted by a substituent such as a group, a hydroxyl group, an amino group, or a halogen atom.

Examples of the aromatic hydrocarbon amino group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a phenylamino group, a naphthylamino group, a tolylamino group, a dimethylphenylamino group, an ethylphenylamino group, Substituted by the aromatic hydrocarbon group described above as R ¹ such as butylphenylamino group, tert-butylphenylamino group, methoxyphenylamino group, ethoxyphenylamino group, butoxyphenylamino group, tert-butoxyphenylamino group, etc. And aromatic hydrocarbon amino groups, and those obtained by substituting substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, and halogen atoms in the aromatic hydrocarbon group portions.

Examples of the dialiphatic hydrocarbon amino group having 1 to 18 carbon atoms which may be substituted or unsubstituted include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, and di-n-butylamino. Group, di-sec-butylamino group, di-tert-butylamino group, ethylmethylamino group, methylisopropylamino group, methyl-n-butylamino group, methyl-sec-butylamino group, methyl-tert-butylamino group A dialiphatic hydrocarbon amino group substituted by two aliphatic hydrocarbon groups described above as R ¹ such as a group, a methylcyclohexylamino group, a diallylamino group, a divinylamino group, an allylmethylamino group, and the like; Aliphatic hydrocarbon amino groups can be substituted with alkyl groups, alkoxy groups, aralkyl groups, aryl groups, hydroxyl groups, Examples include those in which a substituent such as a mino group or a halogen atom is substituted.

Examples of the C1-C18 dialicyclic hydrocarbon amino group which may be substituted or unsubstituted include a dicyclopentylamino group, a dicyclohexylamino group, a dicycloheptylamino group, a dicyclopentenylamino group, A dialicyclic hydrocarbon amino group substituted by two alicyclic hydrocarbon groups described above as R ¹ such as a dicyclohexenylamino group, etc., and an alkyl group, an alkoxy group on these dialicyclic hydrocarbon amino groups And a group substituted with a substituent such as a group, an aralkyl group, an aryl group, a hydroxyl group, an amino group, and a halogen atom.

Examples of the C1-C18 diaromatic hydrocarbon amino group which may be substituted or unsubstituted include, for example, a diphenylamino group, a dinaphthylamino group, a ditolylamino group, a bis (dimethylphenyl) amino group, Bis (ethylphenyl) amino group, bis (butylphenyl) amino group, bis (tert-butylphenyl) amino group, bis (methoxyphenyl) amino group, bis (ethoxyphenyl) amino group, bis (butoxyphenyl) amino group, A diaromatic hydrocarbon amino group substituted by two aromatic hydrocarbon groups described above as R ¹ such as a bis (tert-butoxyphenyl) amino group, and an alkyl group on these diaromatic hydrocarbon amino groups; Those substituted with a substituent such as an alkoxy group, aryl group, aryloxy group, amino group, or halogen atom Can be mentioned.

Examples of the C1-C18 aliphatic hydrocarbon aromatic hydrocarbon amino group which may be substituted or unsubstituted include, for example, a methylphenylamino group, a methylnaphthylamino group, a butylphenylamino group, Examples of R ¹ include aliphatic hydrocarbon aromatic hydrocarbon amino groups substituted with the aliphatic hydrocarbon groups and aromatic hydrocarbon groups described above.

Examples of the silylamino group having 0 to 18 carbon atoms which may be substituted or unsubstituted include, for example, an unsubstituted silylamino group, trimethylsilylamino group, triethylsilylamino group, triphenylsilylamino group, methyl (trimethylsilyl) A silyl group such as an amino group, a methyl (triphenylsilyl) amino group, a phenyl (trimethylsilyl) amino group, a phenyl (triphenylsilyl) amino group, and / or an aliphatic hydrocarbon group described above as R ¹ for the amino group or And / or a silylamino group substituted with an aromatic hydrocarbon group, and those having a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen atom substituted on the silylamino group.

Examples of the “optionally substituted carbonyloxy group having 2 to 18 carbon atoms” described as R ² include, for example, an aliphatic group having 2 to 18 carbon atoms that may be substituted or unsubstituted. A hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group are included. More specific examples are as follows.

Examples of the aliphatic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, n-butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, allylcarbonyloxy group, carbonyloxy group of the aliphatic hydrocarbon group described above as R ¹ such as vinylcarbonyloxy group, and the like, and These aliphatic hydrocarbon carbonyloxy groups are substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen atom.

Examples of the alicyclic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms that may be substituted or unsubstituted include R ¹ such as a cyclopropylcarbonyloxy group, a cyclohexylcarbonyloxy group, and a cyclopentylcarbonyloxy group. As described above, the carbonyloxy group of the alicyclic hydrocarbon group and the alicyclic hydrocarbon carbonyloxy group are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like. Substituted ones are mentioned.

Examples of the aromatic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms which may be substituted or unsubstituted include, for example, phenylcarbonyloxy group, methylphenylcarbonyloxy group, ethylphenylcarbonyloxy group, methoxyphenylcarbonyl An oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group described above as R ¹ such as an oxy group, a butoxyphenylcarbonyloxy group, and a phenoxyphenylcarbonyloxy group, and the aromatic hydrocarbon carbonyloxy group. Examples thereof include those substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, and a halogen atom.

R ^{2 in the} general formula (I-1) is not particularly limited, but is easily available, and therefore has 1 to 8 carbon atoms which may have a chlorine atom, a hydroxyl group, or a substituent. A monovalent oxy group is preferred. Among these, from the viewpoint of reactivity, a chlorine atom, a hydroxyl group, or a monovalent oxy group having 1 to 8 carbon atoms is more preferable, and a cured product obtained by using the compound (D) according to the present invention as an epoxy resin curing agent. Considering the influence on long-term reliability, it is more preferable that at least one of R ² is a hydroxyl group or a monovalent oxy group having 1 to 8 carbon atoms.

In addition, “two or more selected from R ¹ and R ² may combine to form a cyclic structure” described in the general formula (I-1) means that R ¹ and R ² are bonded to each other, It means the case where each becomes a divalent or higher organic group as a whole. For example, when two R ¹ are bonded to an Si atom to form a cyclic structure, an alkylene group such as an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group; an alkenyl such as an ethylenyl group, a propylenyl group, or a butyrenyl group Groups: aralkylene groups such as methylenephenylene groups; arylene groups such as phenylene groups, naphthylene groups, anthracenylene groups, and the like. When one R ¹ and one R ² are bonded to a Si atom to form a cyclic structure, the alkylene group, alkenyl group, aralkylene group, and arylene group oxy group are exemplified. When two R ² are bonded to the Si atom to form a cyclic structure, the alkylene group, alkenyl group, and dioxy group of aralkylene group are exemplified. These organic groups include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, epoxy group-containing groups, methacryloxy groups, mercapto groups, etc. May be substituted with a substituent such as a group, an imino group, a ureido group or an isocyanate group.

  “N” in the general formula (I-1) is not particularly limited as long as it is an integer of 0 to 2. However, n = 0 or 1 is preferable from the viewpoint of heat resistance, and n = 1 is more preferable from the viewpoint of fluidity. Moreover, it is preferable that it is n = 2 from a viewpoint of the low stress property of the hardened | cured material to produce | generate.

  Although the specific compound of the said general formula (I-1) is illustrated below, it is not restricted to them. Examples of silane compounds with n = 0 include tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrakis (ethoxyethoxy) silane, tetrakis (methoxyethoxy) silane, tetrapropoxysilane, tetraallyloxysilane, tetrachlorosilane, and tetrabromosilane. , Tetraacetoxysilane, tetrakis (dimethylamino) silane, and the like.

  Examples of silane compounds with n = 1 include phenyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltrifluorosilane, phenyltriacetoxysilane, phenylbis (dimethylamino) chlorosilane, methyltriethoxysilane, and methyltrimethoxysilane. , Methyltrichlorosilane, methyltriacetoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, n- Propyltriethoxysilane, n-propyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylto Limethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxy Silane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Examples include triethoxysilane.

  Examples of n = 2 silane compounds include substituted or unsubstituted diaryl dialkoxysilanes such as diphenyldimethoxysilane, diphenyldiethoxysilane, and dimesityldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldipropoxysilane. , Diethyldiethoxysilane, decylmethyldiethoxysilane, dicyclopentyldimethoxysilane, divinyldiethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycid Substituted or unsubstituted dialkyl dialkoxysilane such as xylpropylmethyldiethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, vinylphenyl Arylalkyldialkoxysilanes such as ethoxysilane, substituted or unsubstituted diarylsilanediols such as diphenylsilanediol, diphenyldichlorosilane, ditolyldichlorosilane, dimesityldichlorosilane and other substituted or unsubstituted diaryldichlorosilanes, dimethyldi Substituted or unsubstituted dialkyldichlorosilane, phenylethyldichlorosilane, phenylmethyldichlorosilane, etc. substituted or unsubstituted arylalkyldichlorosilane, dimethyldiacetoxysilane, such as chlorosilane, dodecylmethyldichlorosilane, divinyldichlorosilane, diisopropyldichlorosilane Substituted or unsubstituted dia, such as dialkyldiacetoxysilane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) diethylsilane, etc. Substituted or unsubstituted diaryldiaminosilanes such as killed diaminosilane and bis (dimethylamino) diphenylsilane, cyclic silane compounds such as phenylmethylbis (dimethylamino) silane and hexamethylcyclotrisilazane, and dialkylalkoxychlorosilanes such as dimethylmethoxychlorosilane Etc.

  All of the above-described specific examples are available as industrial products or reagents. The compound represented by the general formula (I-1) may be a commercially available compound as an industrial product or a reagent, or a compound synthesized by a known method.

(Partial condensate of silane compound)
The “partial condensate of the silane compound represented by the general formula (I-1)” is a compound obtained by self-condensing one kind of the silane compound represented by the general formula (I-1), or two or more kinds. Means a compound formed by reacting and condensing with each other. Although not particularly limited, the condensation reaction can be carried out using water if necessary, and adding a known substance that promotes the condensation reaction such as acid or alkali as necessary. In a normal condensation reaction, one molecule of water is consumed, one condensation reaction occurs, and two molecules of R ² H are generated as by-products (2≡Si—R ² + H ₂ O → ≡Si—O—). Si≡ + 2R ² H).

  The degree of condensation can be adjusted according to the reaction conditions, and the number of molecules of the compound formed by condensation is not particularly limited, but is preferably 1.5 or more on average. More preferably, it is 50 molecules, and further preferably 2-20 molecules.

  The silane compounds that can be used in the present invention may include compounds in which they are partially condensed as described above, and some of them remain as silane compounds represented by the above general formula (I-1) without condensation. It may be.

(D1) The partial condensate of the silane compound represented by the general formula (I-1) used in the present invention may be condensed at the same time when reacted with a phenol compound, even if the silane compound is condensed in advance. Also, commercially available products may be used, or these may be combined. As a specific example of the partial condensate of the silane compound represented by the general formula (I-1) available as a commercial product, R ^{2 in} the formula (I-1) is a methoxy group, n = 0, average condensation M silicate 51 (trade name, manufactured by Tama Chemical Co., Ltd.) having 3 to 5 molecules, M silicate 56 (Tama Chemical Co., Ltd.) having R = ^{2 and a} methoxy group, n = 0 and an average number of condensed molecules of 8 to 12 Company name, R ² is an ethoxy group, n = 0, silicate 40 (trade name, manufactured by Tama Chemical Co., Ltd.) having an average number of condensed molecules of about 5, R ² is an ethoxy group, and n = 0 Silicate 45 having an average number of condensed molecules of 6 to 8 (trade name, manufactured by Tama Chemical Co., Ltd.), R ¹ is a methyl group and R ² is a methoxy group, n = 1, and the average number of condensed molecules is 3 to 5. MTMS-A (trade name, manufactured by Tama Chemical Co., Ltd.), R ¹ is a methyl group , R ² is a methoxy group, n = 1, 1,3-dimethyltetramethoxydisiloxane (reagent sold by AMAX Co., Ltd.) having 2 condensation molecules, R ¹ is an n-octyl group, and R ² is an ethoxy group Yes, 1,3-di-n-octyltetraethoxydisiloxane (reagent sold by AMAX Co., Ltd.) having n = 1 and 2 condensed molecules is included.

The epoxy resin composition of the present invention is an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The (B) curing agent is obtained by reacting at least one compound (e1) selected from a silane compound represented by the following general formula (I-2) and a partial condensate thereof with a phenol compound (e2). A compound (E) obtained,
And the said (C) inorganic filler contains an alumina, The epoxy resin composition characterized by the above-mentioned.

(In Formula (I-2), m is 0 or 1, n is an integer of 2 or more, and R ^{1 ′} is an n-valent organic group having 0 to 18 carbon atoms that may have a substituent. , Two or more SiR ^{2 ′} _m R ^{3 ′} _(3-m) groups bonded to R ^{1 ′} may all be the same or different, and R ^{2 ′} may have a hydrogen atom and a substituent. It is selected from the group consisting of good hydrocarbon groups having 1 to 18 carbon atoms, and may be bonded to R ^{1 ′} or R ^{3 ′} to form a cyclic structure. R ^{3 ′} represents a halogen atom, a hydroxyl group or a substituent. C1-C18 monovalent oxy group that may have, C2-C18 amino group that may have a substituent, and C2-C18 that may have a substituent selected from the group consisting of carbonyl group, all may be the same or different, two or more R ^{3 'are} be bonded to each other to form a cyclic structure .)
In the epoxy resin composition of the present invention, the (B) curing agent is at least one compound (e1) selected from the silane compound represented by the general formula (I-2) and a partial condensate thereof, and a phenol compound. It is important to contain the compound (E) obtained by reacting with (e2).
(E1) Silane compound and partial condensate thereof (silane compound)
The silane compound used in the present invention is represented by the above general formula (I-2), and in the formula (I-2), R ^{1 ′} may have a substituent n having 0 to 18 carbon atoms. Valent organic group.

The “optionally substituted n-valent organic group having 0 to 18 carbon atoms (n is an integer of 2 or more)” described as R ^{1 ′} has 1 carbon atom which may have a substituent. It means that an n-valent heteroatom group having 0 to 18 carbon atoms that may have a substituent and a n-valent hydrocarbon group of -18. The “optionally substituted n-valent hydrocarbon group having 1 to 18 carbon atoms” is an n-valent aliphatic carbonized group having 1 to 18 carbon atoms which may be substituted or unsubstituted. It is meant to include a hydrogen group, an n-valent alicyclic hydrocarbon group and an n-valent aromatic hydrocarbon carbon group.

  More specifically, examples of the n-valent aliphatic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Hexylene group, octylene group, decylene group, dodecylene group, vinylene group, ethylidene group, vinylidene group, propenylene group, butadienylene group, etc., divalent aliphatic hydrocarbon group, methylidene group, ethylidene group, 1,2,3- A trivalent aliphatic hydrocarbon group such as a propanetriyl group, a butanediylidene group, a tetravalent aliphatic hydrocarbon group such as 1,3-propanediyl-2-ylidene and the like, an alkyl group, an alkoxy group, an aryl group, Hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacrylate Oxy group, a mercapto group, an imino group, a ureido group, an isocyanate group include those substituted with a substituent such as a nitro group.

  Examples of the n-valent alicyclic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclopentenylene group. A divalent alicyclic hydrocarbon group such as a cyclohexenylene group or a cyclohexylidene group, a trivalent alicyclic hydrocarbon group such as a cyclopentanetriyl group or a cyclohexanetriyl group, and an alkyl group thereof, Alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group, The thing substituted by substituents, such as an isocyanate group and a nitro group, is mentioned.

  In addition, the n-valent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted includes a heteroatom-containing aliphatic hydrocarbon group, for example, 2-oxa Propylene group, 2-oxabutylene group, 3-oxapentylene group, 2-thiopropylene group, 2-thiobutylene group, 3-thiopentylene group, 4-thioheptylene group, 2,3-dithiobutylene group, 4,5-dithiooctylene Group, divalent heteroatom-containing aliphatic hydrocarbon group such as 4,5,6,7-tetrathiononylene group, 4-azaheptylene group, 2-azapropanediyl-2-methylene group, 3-azapentanediyl -3-trivalent heteroatom-containing aliphatic hydrocarbon groups such as ethylene group and alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogens And a group substituted with a substituent such as a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group or a nitro group. .

  Examples of the n-valent aromatic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include divalent aromatic hydrocarbons such as a phenylene group, a biphenylene group, and a terphenylene group Group, benzenetriyl group, trivalent aromatic hydrocarbon group such as biphenyltriyl group and the like, and alkyl group, alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, Examples thereof include those substituted with a substituent such as an epoxy group such as an epoxycyclohexyl group and an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group, and a nitro group.

  In addition, the n-valent aromatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted includes a polycyclic aromatic hydrocarbon group, such as a naphthylene group and anthracenylene. A divalent polycyclic aromatic hydrocarbon group such as a group, a trivalent polycyclic aromatic hydrocarbon group such as a naphthalenetriyl group and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group , Halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group, isocyanate group, nitro group, etc. Can be mentioned.

  The n-valent aromatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted includes a heteroatom-containing aromatic hydrocarbon group, for example, diphenylene oxide. Groups, divalent heteroatom-containing aromatic hydrocarbon groups such as diphenylene sulfide groups, trivalent heteroatom-containing aromatic hydrocarbon groups such as triphenyleneamino groups and the like, alkyl groups, alkoxy groups, aryl groups, aryloxy Group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group, isocyanate group, nitro group, etc. And those substituted with a group.

  The heteroatom-containing aliphatic hydrocarbon group or / and the heteroatom-containing aromatic hydrocarbon group also include a heterocycle-containing group, for example, frangiyl group, thiophene diyl group, pyrrole diyl group, imidazole diyl group, Divalent heterocyclic ring-containing groups such as morpholine diyl group, furantriyl group, thiophene triyl group, pyrrole triyl group, imidazole triyl group, morpholine triyl group, triazine triyl group, isocyanurate triyl group, isocyanurate tri A trivalent heterocyclic ring-containing group such as a propylene group, and an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group -Containing groups, methacryloxy groups, mercapto groups, Amino group, a ureido group, an isocyanate group include those substituted with a substituent such as a nitro group.

  The n-valent aliphatic hydrocarbon group having 1 to 18 carbon atoms and the n-valent aromatic hydrocarbon group which may be substituted or unsubstituted may include an aliphatic portion and an aromatic portion. In addition, for example, a divalent substituent such as a methylene bisphenylene group, a propylene bisphenylene group, a phenylene bismethylene group, a phenylene bisethylene group, a phenylenemethylene group, a benzenetriyltrismethylene group, etc. Trivalent substituents, and groups containing an epoxy group such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group; Those substituted with substituents such as oxy group, mercapto group, imino group, ureido group, isocyanate group, nitro group It is below.

  The “n-valent hetero atom group having 0 to 18 carbon atoms which may have a substituent” is a divalent hetero atom such as an oxygen atom or a sulfur atom, or a sulfur atom derivative such as a disulfide group or a tetrasulfide group. , Trivalent hetero atoms such as nitrogen atom and phosphorus atom and those containing an epoxy group such as alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen group, glycidyloxy group, epoxycyclohexyl group, epoxy group, etc. And a group substituted with a substituent such as a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group or a nitro group.

R ^{1 ′ in the} general formula (I-2) is not particularly limited, but is preferably a divalent or trivalent hydrocarbon group. Among these, from the viewpoint of easy availability of raw materials, an aliphatic hydrocarbon group consisting only of divalent carbon atoms and hydrogen atoms such as methylene group, ethylene group, propylene group, butylene group, phenylene group, and phenylenebisethylene group. Divalent heteroatom-containing aliphatic hydrocarbon group such as 2-thiopropylene group, 4-thioheptylene group, 4,5-dithiooctylene group, 4,5,6,7-tetrathiononylene group, 4-azaheptylene group, etc. A trivalent heterocyclic ring-containing group such as an isocyanurate tripropylene group is more preferable.

In the general formula (I-2), R ^{2 ′} is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent.

The “optionally substituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{2 ′} is an aliphatic carbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted. It is meant to include a hydrogen group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. More specifically, in the silane compound represented by the general formula (I-1), the substituent described as R ¹ can be given.

In the general formula (I-2), R ^{3 ′} is a halogen atom, a hydroxyl group, a monovalent oxy group having 1 to 18 carbon atoms which may have a substituent, and a carbon which may have a substituent. It is selected from the group consisting of an amino group having 0 to 18 carbon atoms and a carbonyloxy group having 2 to 18 carbon atoms which may have a substituent.

The “halogen atom” described as R ^{3 ′} includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The “monovalent oxy group having 1 to 18 carbon atoms which may be substituted” described as R ^{3 ′} is a fatty acid having 1 to 18 carbon atoms which may be substituted or unsubstituted. Means containing an aromatic hydrocarbonoxy group, an alicyclic hydrocarbonoxy group, and an aromatic hydrocarbonoxy group. More specifically, in the silane compound represented by the general formula (I-1), “monovalent oxy group having 1 to 18 carbon atoms which may have a substituent” exemplified as R ² may be mentioned. It is done.

Examples of the “optionally substituted amino group having 0 to 18 carbon atoms” described as R ^{3 ′ in} formula (I-2) include an unsubstituted amino group, a substituted or C1-C18 aliphatic hydrocarbon amino group, alicyclic hydrocarbon amino group, aromatic hydrocarbon amino group, dialiphatic hydrocarbon amino group, dialicyclic hydrocarbon amino which may be unsubstituted Groups, diaromatic hydrocarbon amino groups, aliphatic hydrocarbon aromatic hydrocarbon amino groups, and silylamino groups. More specifically, in the silane compound represented by the general formula (I-1), “amino group having 0 to 18 carbon atoms which may have a substituent” exemplified as R ² may be mentioned.

The “optionally substituted carbonyloxy group having 2 to 18 carbon atoms” described as R ^{3 ′ in} formula (I-2) is, for example, substituted or unsubstituted. And an aliphatic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group. More specifically, in the silane compound represented by the above general formula (I-1), “an optionally substituted carbonyloxy group having 2 to 18 carbon atoms” exemplified as R ² can be mentioned.

Moreover, “two or more R ^{3 ′} may be bonded to each other to form a cyclic structure” described as R ^{3 ′ in} formula (I-2) means that two or more R ^{3 ′} are bonded to each other. , Meaning that each becomes a divalent or higher organic group as a whole. For example, divalent radicals of the divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group exemplified above as R ^{1 ′} which can be bonded to a Si atom to form a cyclic structure, R ^{1 ′} As the trivalent aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the trioxy group of the aromatic hydrocarbon group exemplified above, these include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group. It may be substituted with a substituent such as a group, a hydroxyl group and a halogen.

R ^{3 ′ in the} general formula (I-2) is not particularly limited, but since it is easily available, it may have a chlorine atom, a hydroxyl group, or a substituent and may have 1 to 8 carbon atoms. These monovalent oxy groups are preferred. Among these, from the viewpoint of reactivity, a chlorine atom, a hydroxyl group, or a monovalent oxy group having 1 to 8 carbon atoms is more preferable, and has an influence on the ease of production of a compound obtained by reacting a silane compound and a phenol compound. In consideration, at least one of R ^{3 ′} is more preferably a hydroxyl group or a monovalent oxy group having 1 to 8 carbon atoms.

  “M” in the general formula (I-2) is not particularly limited as long as it is 0 or 1, and is determined according to the required performance. From the viewpoint of heat resistance, m = 0 is preferable, and from the viewpoint of low stress property of the cured product to be generated, m = 1 is preferable.

  “N” in the general formula (I-2) is not particularly limited as long as it is an integer of 2 or more, but n is preferably 2 or 3 from the viewpoint of viscosity.

  Examples of specific compounds of the general formula (I-2) are not limited to the following. For example, as a silane compound of m = 1, substituted or unsubstituted bis (alkyl) such as bis (dichlorosilyl) methane, bis (methyldichlorosilyl) methane, bis (methyldichlorosilyl) ethane, bis (methyldifluorosilyl) ethane, etc. Examples thereof include substituted or unsubstituted bis (alkyldialkoxysilylalkyl) amines such as dihalosilyl) alkane, bis (methyldiethoxysilylpropyl) amine, and bis (methyldimethoxysilylpropyl) amine. As silane compounds of m = 0, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, 1,3-bis (trichlorosilyl) propane, 1,6-bis (trichlorosilyl) hexane, , 8-bis (trichlorosilyl) octane and other substituted or unsubstituted bis (trihalosilyl) alkyl, bis (trichlorosilyl) ethylene and other substituted or unsubstituted bis (trihalosilyl) alkenes, bis (trichlorosilyl) acetylene and other substitutions Or unsubstituted bis (trihalosilyl) alkyne, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, 1,8-bis (triethoxysilyl) octane, 1,2- Substituted or unsubstituted bis (trial, such as bis (trimethoxysilyl) decane Bis (alkoxysilyl) arene such as substituted or unsubstituted bis (trialkoxysilyl) alkene such as xylsilyl) alkane, bis (triethoxysilyl) ethylene, 1,4-bis (triethoxysilyl) benzene, 1,4- Substituted or unsubstituted bis (trialkoxy) such as bis (trimethoxysilylmethyl) benzene, bis (alkoxysilylalkyl) arene such as 1,4-bis (trimethoxysilylpropyl) benzene, and bis (trimethoxysilylpropyl) amine Examples thereof include substituted or unsubstituted bis (trialkoxysilylalkyl) sulfides such as (silylalkyl) amine, bis (triethoxysilylpropyl) disulfide, and bis (triethoxysilylpropyl) tetrasulfide. All of these specific examples are available as industrial products or reagents. The compound represented by the general formula (I-2) may be a commercially available compound as an industrial product or a reagent, or a compound synthesized by a known method.

(Partial condensate of silane compound)
The “partial condensate of the silane compound represented by the general formula (I-2)” is a compound obtained by self-condensing one kind of the silane compound represented by the general formula (I-2), or two or more kinds. Means a compound formed by reacting and condensing with each other. Although not particularly limited, the condensation reaction can be carried out using water if necessary, and adding a known substance that promotes the condensation reaction such as acid or alkali as necessary. In a normal condensation reaction, one molecule of water is consumed, one condensation reaction occurs, and two molecules of R ^{3 ′} H are generated as by-products (2≡Si—R ^{3 ′} + H ₂ O → ≡Si— O—Si≡ + 2R ^{3 ′} H).

  The degree of condensation can be adjusted depending on the reaction conditions, and the number of molecules of the compound formed by condensation is not particularly limited, but is preferably larger than 1 molecule on average, and is preferably 1.05 to 50 It is more preferably a molecule, and even more preferably 1.1 to 20 molecules.

  The silane compound that can be used in the present invention only needs to contain a compound in which they are partially condensed as described above, and a part of the silane compound does not condense and is a silane compound represented by the above general formula (I-2). May remain.

  (E1) The partial condensate of the silane compound represented by the general formula (I-2) used in the present invention may be condensed at the same time when reacted with the phenol compound, even if it is used by condensing the silane compound in advance. Also, commercially available products may be used, or these may be combined.

(D2) (e2) Phenol compound In the present invention, the phenol compound (d2), which is a synthesis raw material of the compound (D), and the phenol compound (e2), which is a synthesis raw material of the compound (E), are the same, The case of the phenol compound (d2) will be described below as a representative.

The phenol compound (d2) that can be used in the present invention is not particularly limited as long as it has one or more phenolic hydroxyl groups in the molecule. For example, one phenolic per molecule such as phenol, cresol, xylenol, cumylphenol, phenylphenol, aminophenol and other phenols, α-naphthol, β-naphthol, methylnaphthalene, naphthols such as dimethylnaphthalene, etc. A compound having a hydroxyl group (that is, a monohydric phenol compound);
Compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol (ie, divalent phenol compound);
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
And a phenol compound having two or more phenolic hydroxyl groups in the molecule, such as a triphenylmethane type phenol resin; and a phenol resin obtained by copolymerizing two or more of the above resins. One of the above phenol compounds may be used alone, or two or more of these compounds may be used in combination.

  The phenol compound (d2) that can be used in the present invention is preferably a phenol compound having two or less phenolic hydroxyl groups in one molecule of the phenol compound from the viewpoint of the viscosity of the compound (D). The greater the number of phenolic hydroxyl groups in one molecule of the phenol compound, the higher the viscosity of the resulting compound (D), which tends to make it difficult to manufacture and / or handle after manufacturing. In particular, when a novolac-type phenol resin or a resol-type phenol resin is used, gelation tends to occur because there are many phenolic hydroxyl groups in one molecule and the molecular weight between reaction points is small.

  On the other hand, the phenol compound (d2) that can be used in the present invention includes two or more phenolic hydroxyl groups in one molecule of the phenol compound from the viewpoint of heat resistance of the epoxy resin composition containing the compound (D) according to the present invention. Phenol compounds having are preferred. However, in view of the above-mentioned viscosity, the content of the dihydric phenol compound is preferably 70% by weight or more, more preferably 80% by weight or more, and further preferably 85% by weight or more based on the total weight of the phenol compound. It is. For example, a compound obtained by reacting when the content of a dihydric phenol compound is less than 70% by weight and the content of a phenol compound having 3 or more phenolic hydroxyl groups in one molecule is 30% by weight or more. The viscosity of (D) tends to be high and the handleability tends to be poor.

  The dihydric phenol compound is not particularly limited. Examples thereof include hydroquinone, resorcin, catechol, bisphenol A, bisphenol F, dihydroxynaphthalene, substituted or unsubstituted biphenol, and one of these compounds may be used alone, or two or more thereof may be used in combination.

Of the dihydric phenol compounds, phenol compounds capable of cyclization with at least one compound (d1) selected from silane compounds and condensates thereof are preferred. Such a compound is not particularly limited, and examples thereof include phenol compounds as shown in the following general formulas (I-1a) to (I-1d), and one of them is used alone. Or you may use combining 2 or more types.

(In the formula, each R ⁶ is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. The above R ⁶ may combine to form a cyclic structure)
The phenol compound represented by the general formula (I-1a) is not particularly limited, and examples thereof include catechol and 2,3-dihydroxynaphthalene.

Wherein R ⁷ is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. The above R ⁷ may combine to form a cyclic structure)
The phenol compound represented by the general formula (I-1b) is not particularly limited, and examples thereof include 2,2′-biphenol and 1,1′-bi-2-naphthol.

(In the formula, each R ⁸ is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. The above R ⁸ may combine to form a cyclic structure, and R ⁹ represents a divalent organic group having 0 to 18 carbon atoms)
Although it does not specifically limit as a phenolic compound shown by the said general formula (I-1c), For example, 2,2'- dihydroxydiphenylmethane, 2,2'-dihydroxy-5,5'-dimethyldiphenylmethane, 2,2′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylmethane, 2,2′-dihydroxydiphenyl sulfide, 2,2′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenylsulfone, 1,1 '-Methylenedi-2-naphthol.

(In the formula, each R ¹⁰ is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 18 carbon atoms which may have a substituent, and all may be the same or different. The above R ¹⁰ may combine to form a cyclic structure)
Although it does not specifically limit as a phenol compound shown by the said general formula (I-1d), For example, 1, 8- dihydroxy naphthalene is mentioned.

The term “an organic group having 1 to 18 carbon atoms which may have a substituent” described as R ⁶ , R ⁷ , R ⁸ and R ^{10 in the} above general formulas (I-1a) to (I-1d) Is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an alicyclic Hydrocarbon oxy group, aromatic hydrocarbon oxy group, aliphatic hydrocarbon carbonyl group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group , An aromatic hydrocarbon oxycarbonyl group, an aliphatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, and an aromatic hydrocarbon carbonyloxy group bonded to each other.

  Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl. Group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and these aliphatic hydrocarbon groups as alkyl groups, alkoxy groups, Examples thereof include those substituted with a substituent such as an aryl group, a hydroxyl group, an amino group, and a halogen.

  Examples of the alicyclic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group. And those obtained by substituting these alicyclic hydrocarbon groups with substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, and halogens.

  Examples of the aromatic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, and butylphenyl. Groups, alkyl group-substituted aryl groups such as tert-butylphenyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, and the like. It may be substituted with a substituent such as a group, an aryl group, an aryloxy group, an amino group, or a halogen.

  Examples of the aliphatic hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec A group having a structure in which an oxygen atom is bonded to the above-described aliphatic hydrocarbon group such as a butoxy group, a tert-butoxy group, an allyloxy group, a vinyloxy group, and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, Examples thereof include those substituted with a substituent such as amino group and halogen.

  Examples of the alicyclic hydrocarbon oxy group having 1 to 18 carbon atoms that may be substituted or unsubstituted include the above-mentioned fatty acids such as a cyclopropyloxy group, a cyclohexyloxy group, and a cyclopentyloxy group. Groups having a structure in which an oxygen atom is bonded to an aromatic hydrocarbon group, and those substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen.

  Examples of the aromatic hydrocarbon oxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include phenoxy group, methylphenoxy group, ethylphenoxy group, methoxyphenoxy group, butoxyphenoxy group, phenoxyphenoxy group. A group having a structure in which an oxygen atom is bonded to the above-described aromatic hydrocarbon group such as a group, and those substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen. Can be mentioned.

  Examples of the aliphatic hydrocarbon carbonyl group having 1 to 18 carbon atoms, which may be substituted or unsubstituted, alicyclic hydrocarbon carbonyl group or aromatic hydrocarbon carbonyl group include formyl group, acetyl group, An aliphatic hydrocarbon carbonyl group such as an ethylcarbonyl group, a butyryl group, an allylcarbonyl group, an alicyclic hydrocarbon carbonyl group such as a cyclohexylcarbonyl group, an aromatic hydrocarbon carbonyl group such as a phenylcarbonyl group, a methylphenylcarbonyl group; and The thing substituted by substituents, such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, and halogen, is mentioned.

  As the aliphatic hydrocarbon oxycarbonyl group having 1 to 18 carbon atoms, which may be substituted or unsubstituted, alicyclic hydrocarbon oxycarbonyl group or aromatic hydrocarbon oxycarbonyl group, a methoxycarbonyl group , Ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group and other aliphatic hydrocarbon oxycarbonyl groups, cyclohexyloxycarbonyl group and other alicyclic hydrocarbon oxycarbonyl groups, phenoxycarbonyl group, methylphenoxycarbonyl group and other aromatics Examples thereof include hydrocarbon oxycarbonyl groups and those substituted with substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, and halogens.

  Examples of the aliphatic hydrocarbon carbonyloxy group, alicyclic hydrocarbon carbonyloxy group or aromatic hydrocarbon carbonyloxy group having 1 to 18 carbon atoms which may be substituted or unsubstituted include methylcarbonyloxy Group, ethylcarbonyloxy group, butylcarbonyloxy group, aliphatic hydrocarbon carbonyloxy group such as allylcarbonyloxy group, alicyclic hydrocarbon carbonyloxy group such as cyclohexylcarbonyloxy group, phenylcarbonyloxy group, methylphenylcarbonyloxy And an aromatic hydrocarbon carbonyloxy group such as a group and those substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, and a halogen.

Furthermore, “may form a cyclic structure” described as R ⁶ , R ⁷ , R ⁸ , and R ¹⁰ means that two or more R ⁶ , R ⁷ , R ⁸ , or R ¹⁰ are bonded together, As a case where each becomes a divalent to tetravalent organic group. For example, a group that forms a polycyclic aromatic ring such as a naphthalene ring, anthracene ring, or phenanthrene ring in combination with a benzene ring to which they are bonded is exemplified. These include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and the like. Substituents such as a group, a hydroxyl group, an amino group, and halogen may be substituted.

R ⁶ , R ⁷ , R ⁸ , and R ¹⁰ in the general formulas (I-1a) to (I-1d) are not particularly limited, but have a hydrogen atom, a hydroxyl group, and a substituent. An alkyl group, an aryl group, an alkoxy group, and an aryloxy group, which may be a monovalent organic group, are preferable. Among these, from the viewpoint of easy availability of raw materials, an unsubstituted or alkyl group such as a hydrogen atom, a hydroxyl group, a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group, or the like Chain structure or cyclic such as // alkoxy group or / and hydroxyl group-substituted aromatic group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. An organic group selected from alkyl groups is more preferable, and an organic group selected from a hydrogen atom, a hydroxyl group, a phenyl group, a methyl group, an ethyl group, and a tert-butyl group is more preferable. When two or more R ⁶ , R ⁷ , R ⁸ , or R ¹⁰ are bonded to form a cyclic structure, it is preferably combined with a benzene ring to which they are bonded to form a naphthalene ring.

Moreover, although R < ⁶ >, R < ⁷ >, R < ⁸ > and R < ¹⁰ > of said general formula (I-1a)-(I-1d) are not specifically limited, R < ⁶ >, R from a heat resistant viewpoint. ⁷ , R ⁸ , and R ¹⁰ are each preferably 50% or more of hydrogen atoms, more preferably 75% or more of hydrogen atoms.

R ^{9 in the} general formula (I-1c) represents a divalent organic group having 0 to 18 carbon atoms. The divalent organic group having 0 to 18 carbon atoms is not particularly limited, and examples thereof include a divalent organic group having 0 carbon atoms such as an oxygen atom, a sulfur atom, a sulfoxide group, and a sulfonyl group, A bivalent hydrocarbon group etc. are mentioned. There is no restriction | limiting in particular as a C1-C18 bivalent hydrocarbon group, For example, aliphatic hydrocarbon groups, such as a methylene group, ethylene group, a propylene group, fats, such as a cyclohexylene group, a cyclopentylene group Cyclic hydrocarbon groups and those substituted with substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens, aromatic hydrocarbon groups such as phenylene groups, naphthylene groups, anthracenylene groups, and the like, and These include those substituted with substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, and halogens.

  Among these, from the viewpoint of availability, an oxygen atom, a sulfur atom, a sulfoxide group, a sulfonyl group, an alkylene group, a cyclohexylene group, a cyclopentylene group, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group Is preferably substituted. Oxygen, sulfur, sulfoxide, sulfonyl, methylene, methylmethylene, isopropylmethylene, phenylmethylene, cyclohexylmethylene, dimethylmethylene, methyldiisopropylmethylene, methylphenylmethylene, cyclohexylene Group, cyclopentylene group, and cyclopentylene group are more preferable.

  The phenol compound (d2) preferably has a small amount of ionic impurities in the phenol compound in consideration of the effect on the long-term reliability of the cured product obtained by using the compound (D) according to the present invention as an epoxy resin curing agent. It is preferable to purify the phenol compound as necessary.

(Volatile component)
In the present invention, the reaction of at least one compound (d1) selected from the silane compound represented by the general formula (I-1) and a partial condensate thereof with the phenol compound (d2) and / or the general formula (I) -2) Water, alcohol, ammonia, amine, carboxylic acid, hydrogen halide produced by the reaction of at least one compound (e1) selected from the silane compound and partial condensate thereof with phenol compound (e2) A by-product such as a solvent, a solvent optionally used in the reaction, and a solvent optionally contained for the purpose of adjusting the resin viscosity are treated as “volatile components”. In addition, the unreacted R ² group and / or R ^{3 ′} group present in the compound (D) and / or compound (E) obtained by the above reaction is also regarded as a potential volatile component. " That is, when the compound (D) and / or compound (E) having an unreacted R ² group and / or R ^{3 ′} group is used as an epoxy resin curing agent, water, alcohol, ammonia, amine, carvone during the curing reaction It will produce volatile components such as acids or hydrogen halides.

In the present invention, the content of the volatile component is preferably 10% by weight or less based on the total weight of the compound (D) and / or the compound (E) obtained by the above reaction. From the viewpoint of suppression of voids in the cured product and moldability, the content of the volatile component is more preferably 5% by weight or less, and particularly preferably less than 3% by weight. When unreacted R ² group and / or R ^{3 ′} group is present, the weight of the unreacted R ² group and / or R ^{3 ′} group reacts with each other, for example, volatile components such as water, alcohol, ammonia, amine, carboxylic acid or hydrogen halide. Calculated assuming that

In addition, the compound obtained by reacting at least one compound selected from the silane compound and its partial condensate according to the present invention with a phenol compound is used for applications other than molding materials such as laminates, adhesives, and coatings. In the case, it may contain a by-product and a solvent used as necessary. In these applications, by setting conditions, it is easy to remove the by-products and the solvent so that no voids are generated, but the reaction and compound of the unreacted R ² group and / or unreacted R ^{3 ′} group Since (D) and / or compound (E) is cured under substantially the same conditions, it is caused by R ² H and / or R ^{3 ′} H generated from unreacted R ² group and / or unreacted R ^{3 ′} group. It is difficult to avoid the generation of voids. From such a viewpoint, in the compound (D) and / or compound (E), R ² in at least one compound (d1) and / or (e1) selected from the silane compound at the start of the reaction and the condensate thereof. ^'relative to the base, unreacted R ² groups and / or unreacted R ^3' groups and / or R ³ preferably radix content of 10% or less, more preferably 5% or less, 3 More preferably, it is% or less.

(Structural site contained in compound (D) and / or compound (E))
The compound (D) and / or the compound (E) has an aryloxysilyl (ArO—Si) bond. As one form of the said compound (D) and / or the said compound (E), it has at least one of the structural site shown by the following general formula (I-3), and the structural site shown by the following general formula (I-4) It is preferable. The compound having the structural moiety is a phenol having a compound (d1) and / or (e1) selected from a silane compound and a partial condensate thereof and two or more cyclizable phenolic hydroxyl groups in the molecule. It is obtained by using compound (d2) and / or (e2). The structural site represented by the following general formula (I-3) originates from the silane compound itself represented by the above general formula (I-1) and the above general formula (I-2). The structural site represented by (I-4) originates from a site that is partially condensed in the silane compound.

(In the formula (I-3), Ar represents a divalent organic group having a group derived from a cyclic compound having 2 to 30 carbon atoms and having aromaticity on both sides)

(In the formula (I-4), Ar represents a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides, and n is 0 or more. Indicates the number.)
Here, “a divalent organic group having a group derived from a cyclic compound having 2 to 30 carbon atoms and having aromaticity” described as Ar is not particularly limited, For example, an aryl group such as a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, a binaphthylene group, a methylenebisphenylene group, a methylenebisnaphthylene group, an oxybisphenylene group, a sulfonylbisphenylene group, or a thiobisphenylene group is provided on both sides. Divalent organic groups and divalent organic groups having heterocyclic groups on both sides, such as furanylene, thiophenylene, imidazolylene, methylene bisfurylene, methylene bisthiophenylene, methylene bis imidazolylene, etc. On the other hand, an organic group such as a divalent organic group having a heterocyclic group is included.

  “N” in the formula (I-4) represents a number of 0 or more, but from the viewpoint of easy formation of a cyclic structure, n is preferably in the range of 0 to 10, more preferably 0 to 5. It is desirable that it is in the range, more preferably in the range of 0-3.

  The above-mentioned compound (D) and / or compound (E) having the structural moiety represented by the above general formula (I-3) and / or general formula (I-4) has a relatively small molecular weight. And tends to be easy to manufacture and handle after manufacture. Moreover, since it becomes possible to raise content of the at least 1 sort (s) of compound (d1) and / or (e1) chosen from the silane compound and its condensate in compound (D) and / or compound (E), this book The cured product obtained from the epoxy resin composition according to the invention tends to have improved heat resistance. From such a viewpoint, on the basis of the total number of aryloxysilyl (ArO-Si) bonds present in the compound (D) and / or the compound (E), the compound (D) and / or the compound (E) in the present invention, The number of aryloxysilyl bonds in the structural moiety represented by the general formula (I-3) and / or the general formula (I-4) is 30% or more, preferably 50% or more.

(Production Method of Compound (D) and / or Compound (E))
The method for producing the compound (D) comprises reacting at least one compound (d1) selected from the silane compound represented by the general formula (I-1) and a partial condensate thereof with a phenol compound (d2). Have

  Moreover, the manufacturing method of the said compound (E) reacts at least 1 sort (s) of compounds (e1) chosen from the silane compound shown by the said general formula (I-2), and its partial condensate, and a phenol compound (e2). A step of causing

  In the production method of the above compound (D) or compound (E), there is no particular limitation on the reaction means and the like as long as the target compound (D) or compound (E) is produced. May be used. The solvent is removed by filtration, distillation or the like after the reaction. Solvents that can be used are those that do not adversely affect the reaction of at least one compound (d1) or (e1) selected from the silane compound and its partial condensate compound with the phenol compound (d2) or (e2). It is not particularly limited as long as it is an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, an alicyclic hydrocarbon solvent such as cyclohexane, acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, ether solvents such as diethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, ester systems such as ethyl acetate and γ-butyrolactone Use a known solvent such as a solvent. It can be.

The ratio of at least one compound (d1) or (e1) selected from the silane compound and its partial condensate compound and the phenol compound (d2) or (e2) is such that the reaction proceeds and the desired compound is obtained. The range is not particularly limited. For example, the R ² group in at least one compound (d1) selected from a silane compound and a partial condensate compound thereof and / or R ³ in at least one compound (e1) selected from a silane compound and a partial condensate compound thereof. ^'and groups, the equivalent ratio of phenolic hydroxyl groups in the phenol compound (d2) and / or (e2) (i.e., [phenol compound (d2) and / or phenolic hydroxyl group number of (e2)] / [silane compound and The number of R ² groups in at least one compound (d1) selected from partial condensate compounds and / or the number of R ^{3 ′} groups in at least one compound (e1) selected from silane compounds and partial condensate compounds]) It is preferably in the range of 0.1 to 10, more preferably in the range of 0.5 to 5.0, 0 It is more preferably in the range of 9 to 3.0. In particular, the equivalent ratio is most preferably around 1. When the equivalent ratio is less than 0.1, unreacted R ² groups and / or R ^{3 ′} groups tend to remain. On the other hand, when the equivalent ratio is greater than 10, the usefulness of the compound obtained by reacting at least one compound selected from the silane compound and its partial condensate compound with a phenol compound as an epoxy curing agent decreases. However, the heat resistance of the cured product tends to decrease. The “equivalent ratio” is not a charging ratio but means a ratio of the number of phenolic hydroxyl groups and the number of R ² groups and / or R ^{3 ′} groups contained in the product after production. For example, when the R ² group and / or the R ^{3 ′} group react to form a by-product and are removed by volatilization, filtration, etc., they are not included. In addition, the equivalence ratio “near 1” means that it may actually deviate slightly from 1.0 due to a weighing error, a deviation in purity, or the like. Specifically, the equivalent ratio is preferably 0.9 to 1.1, and more preferably 0.95 to 1.05.

Further, the reaction rate of at least one compound (d1) and / or (e1) selected from the silane compound and its partial condensate compound with the phenol compound (d2) and / or (e2) is particularly limited. It is not something. For example, based on the total number of R ² groups and / or the total number of R ^{3 ′} groups in the specific silane compound at the start of the reaction, the number of unreacted R ² groups and / or the total number of R ^{3 ′} groups may be 10% or less. Preferably, it is 5% or less, more preferably 1% or less. ^'Relative to the base, the number of R ² groups and / or R ³ of more than ^10%' total R ² groups and / or all R ³ at the beginning of the reaction when the group becomes unreacted the silane compound and its partial condensation product Usefulness of the compound obtained by reacting at least one compound selected from the compound and a phenol compound as an epoxy curing agent tends to decrease, leading to generation of voids in the cured product and a decrease in long-term reliability.

In the above production method, R ² H and / or R ^{3 ′} H is used as a by-product of the reaction of at least one compound selected from the silane compound and its partial condensate compound with a phenol compound together with the target compound. Will be generated. Therefore, it is preferable that the manufacturing method includes a step of removing R ² H or R ^{3 ′} H from the reaction product by heating as necessary. More specific examples are as follows:
When at least one compound selected from a silane compound in which R ² and / or R ^{3 ′} is a halogen atom and a partial condensate compound thereof is reacted with a phenol compound, heating and / or decompression is performed as necessary. Removing by-product hydrogen halide by evaporation, washing, filtration, etc .;
When at least one compound selected from a silane compound in which R ² and / or R ^{3 ′} is a hydroxyl group and a partial condensate compound thereof is reacted with a phenol compound, heating and / or reduced pressure distillation is performed as necessary. Removing by-product water by leaving, washing, filtering, etc .;
When at least one compound selected from a silane compound in which R ² and / or R ^{3 ′} is an oxy group and a partial condensate compound thereof is reacted with a phenol compound, heating and / or decompression is performed as necessary. By-product alcohol or arylol is removed by evaporation, washing, filtration, etc .;
When at least one compound selected from a silane compound in which R ² and / or R ^{3 ′} is an amino group and a partial condensate compound thereof is reacted with a phenol compound, heating and / or decompression is performed as necessary. By-product ammonia or amine is removed by evaporation, washing, filtration, etc .;
When at least one compound selected from a silane compound in which R ² and / or R ^{3 ′} is a carbonyloxy group and a partial condensate compound thereof and a phenol compound are reacted, heating and / or as necessary By-product carboxylic acid is removed by distillation under reduced pressure, washing, filtration and the like.

  In the said manufacturing method, in order to accelerate | stimulate reaction with the at least 1 sort (s) of compound chosen from the said silane compound and its partial condensate compound, and a phenol compound, you may use a catalyst as needed. Examples of usable catalysts include cycloamidines such as diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7. Compounds, derivatives thereof, phenol novolac salts thereof and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone , A quinone compound such as 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a π bond such as diazophenylmethane Compounds with intramolecular polarization formed by adding compounds, pyridine, triethylamine, triethylenediamine, benzine Tertiary amines such as dimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, tetrasubstituted phosphonium tetrasubstituted borate such as tetraphenylphosphonium tetraphenylborate, tetraphenyl such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate Boron salt, triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl al Coxiphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine Organic phosphines such as trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc., complexes of these organic phosphines with organic borons, organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5- Toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3- Quinone compounds such as methoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane, these organic phosphines and 4-bromo Phenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2 -Methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4 -Chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol And compounds having intramolecular polarization obtained through a dehydrohalogenation step after reacting with a halogenated phenol compound such as 4-bromo-4′-hydroxybiphenyl (see Japanese Patent Application Laid-Open No. 2004-156036) and the like. Can be mentioned.

In the above production method, the combination of at least one compound selected from a silane compound and a partial condensate compound thereof and a catalyst is not particularly limited, but curing achieved by the simplicity of the reaction and the use of the reaction product. From the viewpoint of long-term stability of the product, a phosphonium compound represented by the following general formula (I-5) or an intermolecular salt thereof is used as a catalyst, and a phenol compound and a silane compound in which R ² and / or R ^{3 ′} are oxy groups It is preferable to carry out the reaction by reacting at least one compound selected from the partial condensate compounds thereof and heating to 80 ° C. to 300 ° C. to remove the by-product alcohol. From the viewpoint of easy removal of R ² H and / or R ^{3 ′} H as a by-product, R ² and / or R ^{3 ′} is more preferably an alkoxy group having 1 to 3 carbon atoms.

(In formula (I-5), each R ⁴ is independently selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, all of which are the same. Two or more R ^{4 s} may be bonded to each other to form a cyclic structure, and each R ⁵ independently represents a hydrogen atom, a hydroxyl group, and a carbon number that may have a substituent. Selected from the group consisting of 1 to 18 organic groups, all may be the same or different, and two or more R ⁵ may be bonded to each other to form a cyclic structure, and Y ⁻ is one or more releasable An organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms having an active proton (H ⁺ ), and may be bonded to one or more R ⁵ to form a cyclic structure)
The “optionally substituted hydrocarbon group having 1 to 18 carbon atoms” described as R ^{4 in the} general formula (I-5) may be substituted or unsubstituted. It means containing an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

  Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , Tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and these aliphatic hydrocarbon groups as alkyl groups, alkoxy groups, aryl groups , Hydroxyl groups, amino groups, and those substituted with a substituent such as a halogen atom.

  Examples of the alicyclic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group. And those obtained by substituting these alicyclic hydrocarbon groups with substituents such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, and halogen atoms.

  Examples of the aromatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group Alkyl group-substituted aryl groups such as tert-butylphenyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, and tert-butoxyphenyl group. It may be substituted with a substituent such as a group, an aryl group, an aryloxy group, an amino group, or a halogen atom.

The term “two or more R ^4s may be bonded to each other to form a cyclic structure” described as R ^{4 in} formula (I-5) means that two or three R ^4s are bonded to each other as a whole. The case where it becomes a bivalent or trivalent hydrocarbon group is meant. For example, alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene, etc., alkenyl groups such as ethylenyl, propylenyl, butyrenyl groups, aralkylene groups such as methylenephenylene groups, phenylene, naphthylene, etc. And arylene groups such as anthracenylene, which may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

In addition, as R < ⁴ > of the said general formula (I-5), although it does not specifically limit, It is preferable that it is a monovalent substituent selected from the group which consists of an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p- Hydroxyphenyl group, m-hydroxyphenyl group, o-hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2- (Hydroxy naphthyl) group, 1- (4-hydroxy naphthyl) group, etc., unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl group-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, Substituents selected from linear or cyclic alkyl groups such as sec-butyl group, tert-butyl group, octyl group, and cyclohexyl group More preferable. Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, p-hydroxyphenyl group, m-hydroxyphenyl group, o- Hydroxyphenyl group, 2,5-dihydroxyphenyl group, 4- (4-hydroxyphenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 1- (2-hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) It is more preferable that the aryl group is unsubstituted or substituted with an alkyl group and / or an alkoxy group and / or a hydroxyl group.

The “organic group having 1 to 18 carbon atoms which may have a substituent” described as R ^{5 in the} general formula (I-5) may be substituted or unsubstituted. To 18 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon oxy group, alicyclic hydrocarbon oxy group, aromatic hydrocarbon oxy group, aliphatic hydrocarbon carbonyl Group, alicyclic hydrocarbon carbonyl group, aromatic hydrocarbon carbonyl group, aliphatic hydrocarbon oxycarbonyl group, alicyclic hydrocarbon oxycarbonyl group, aromatic hydrocarbon oxycarbonyl group, fat having 2 to 18 carbon atoms Means containing an aromatic hydrocarbon carbonyloxy group, an alicyclic hydrocarbon carbonyloxy group, or an aromatic hydrocarbon carbonyloxy group.

More specifically, the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group are as described above for R ⁴ .

  Examples of the aliphatic hydrocarbon oxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, cyclopropyloxy group, cyclohexyloxy group, and cyclopentyl. A group having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group such as an oxy group, an allyloxy group, a vinyloxy group, and the like, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, etc. And those substituted with. Examples of the aromatic hydrocarbon oxy group include a structure in which an oxygen atom is bonded to the above aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group. And a group in which they are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

  Examples of the carbonyl group include aliphatic hydrocarbon carbonyl groups such as formyl group, acetyl group, ethylcarbonyl group, butyryl group, cyclohexylcarbonyl group, and allylcarbonyl, and aromatic hydrocarbons such as phenylcarbonyl group and methylphenylcarbonyl group. Examples thereof include carbonyl groups and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms and the like.

  Examples of the oxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group and other aliphatic hydrocarbon oxycarbonyl groups, phenoxycarbonyl group, methylphenoxycarbonyl group and the like. Aromatic hydrocarbon oxycarbonyl groups and those substituted with an alkyl group, alkoxy group, aryl group, aryloxy group, amino group, or halogen atom can be mentioned.

  Examples of the aliphatic hydrocarbon carbonyloxy group, alicyclic hydrocarbon carbonyloxy group and aromatic hydrocarbon carbonyloxy group having 2 to 18 carbon atoms which may be substituted or unsubstituted include, for example, methyl Aliphatic hydrocarbon carbonyloxy groups such as carbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, and allylcarbonyloxy group, alicyclic hydrocarbon carbonyloxy groups such as cyclohexylcarbonyloxy group, phenylcarbonyloxy group, methylphenyl An aromatic hydrocarbon carbonyloxy group such as a carbonyloxy group and those substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, or a halogen atom can be mentioned.

The "may also form a 2 or more R ⁵ is ring structure by bonding with each other" the general formula (I-5) and terms described as R ⁵ in, bonded to two to four R ^5, as a whole It means a case where each becomes a divalent to tetravalent organic group. For example, alkylene groups such as ethylene, propylene, butylene, pentylene and hexylene that can form a cyclic structure, alkenyl groups such as ethylenyl, propylenyl, and butyrenyl groups, aralkylene groups such as methylenephenylene groups, and arylenes such as phenylene, naphthylene, and anthracenylene Groups, and alkylene groups, alkenyl groups, aralkylene groups, and arylene groups in which an oxy group or a dioxy group is bonded. These include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, It may be substituted with a halogen atom.

R ^{5 in the} general formula (I-5) is not particularly limited, but is preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, an unsubstituted or alkyl group such as a hydrogen atom, a hydroxyl group, a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group, and / or Alkoxy groups and / or aryl groups substituted with hydroxyl groups, and chain or cyclic alkyls such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, octyl, and cyclohexyl groups A substituent selected from the group is more preferable. In the case where two or more R ⁵ are bonded to each other to form a cyclic structure, there is no particular limitation, but in combination with the benzene ring to which R ⁵ is bonded, a 1-(-2-hydroxynaphthyl) group, 1- ( Organic groups that form polycyclic aromatic groups such as a (-4-hydroxynaphthyl) group are preferred.

Y ⁻ in the general formula (I-5) is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H ⁺ ). R ⁵ may be bonded to each other to form a cyclic structure. For example, Y ^- represents a hydroxyl group, a mercapto group, a monovalent group proton is eliminated from the organic group having a hydrogen atom bonded to the Group 16 atoms such as hydro seleno group, a carboxyl group, a carboxymethyl group, a carboxyethyl group, carboxyphenyl A group in which a proton of a carboxylic acid is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a carboxyl group such as a carboxynaphthyl group, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, Examples thereof include groups in which a phenolic proton is eliminated from a monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as a hydroxythienyl group and a hydroxypyridyl group.

In addition, when Y ⁻ in the general formula (I-5) is bonded to one or more R ⁵ to form a cyclic structure, for example, Y ⁻ is 2 together with the benzene ring to which it is bonded. Examples thereof include divalent organic groups that form a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a-(-6-hydroxynaphthyl) group.

Previously illustrated Y ^- among, but are not limited to, oxygen anion proton from the hydroxyl group is eliminated, or hydroxyphenyl group, hydroxyphenyl methyl group, hydroxynaphthyl group, hydroxy furyl group, hydroxy thienyl group And a monovalent organic group having an oxygen anion formed by elimination of a proton from a phenolic hydroxyl group such as a hydroxypyridyl group.

Moreover, when Y < ^- > in the said general formula (I-5) couple | bonds with one or more R < ⁵ > and forms a cyclic structure, Y < ^- > is 2 together with the benzene ring to which it has couple | bonded, for example. A group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a-(-6-hydroxynaphthyl) group is preferable.

  Further, the intermolecular salt of the phosphonium compound represented by the general formula (I-5) is not limited, but the phosphonium compound represented by the formula (I-5) and phenol, naphthol, 2 in the molecule. Compounds having phenolic hydroxyl groups such as the compounds exemplified above as phenol compounds having the above phenolic hydroxyl groups, compounds having silanol groups such as triphenylsilanol, diphenylsilanediol, trimethylsilanol, oxalic acid, acetic acid, benzoic acid, etc. And intermolecular salt compounds with organic acids, inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid and nitric acid.

  Specific examples of the phosphonium compound represented by the general formula (I-5) are not limited, but include tris- (p-methoxyphenyl) phosphine, tris- (o-methoxyphenyl) phosphine, -P-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, bis- (p-methoxyphenyl) phenylphosphine, bis- (o-methoxyphenyl) phosphine, di-p-tolylphenylphosphine, di -O-tolylphenylphosphine, di-m-tolylphenylphosphine, diphenyl- (p-methoxyphenyl) phosphine, diphenyl- (o-methoxyphenyl) phosphine, diphenyl-p-tolylphosphine, diphenyl-o-tolylphosphine, diphenyl -M-tolylphosphine, tri Triarylphosphine such as phenylphosphine, trialkylphosphine such as tricyclohexylphosphine, tributylphosphine, trioctylphosphine, alkyldiarylphosphine such as cyclohexyldiphenylphosphine, octyldiphenylphosphine, dibutylphenylphosphine, dicyclohexylphenylphosphine, dioctyl Tertiary phosphine such as phenylphosphine and the like, 1,4-benzoquinone, methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone , Methoxy-1,4-benzoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, Addition of til-1,4-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, t-butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone, 1,4-naphthoquinone, etc. Reaction products, and these tertiary phosphines and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodination Phenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromine A compound having intramolecular polarization obtained through a dehydrohalogenation step after reacting with a halogenated phenol compound such as mo-2-naphthol or 4-bromo-4'-hydroxybiphenyl (Japanese Patent Laid-Open No. 2004-156035) Gazette and JP 2004-156036 A).

  Among these, from the availability of raw materials and the stability of the phosphonium compound represented by the above general formula (I-5), an addition reaction product of triphenylphosphine and 1,4-benzoquinone, tri-p-tolylphosphine, 1,4-benzoquinone addition reaction product, tris- (p-methoxyphenyl) phosphine and 1,4-benzoquinone addition reaction product, diphenyl-p-tolylphosphie and 1,4-benzoquinone addition reaction product, tributylphosphine and 1 , 4-Benzoquinone addition reaction product, tricyclohexylphosphine and 1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product, dicyclohexylphenylphosphine and 1,4-benzoquinone addition reaction product Synthesis examples described in JP-A No. 2004-156035 Compound represented by the structure according to Formula prepared in ~9 (XXVII) ~ (XXXVII) is preferred.

(Epoxy resin composition)
A compound obtained by reacting at least one compound (d1) selected from the group consisting of the silane compound represented by the general formula (I-1) and a partial condensate thereof according to the present invention with a phenol compound (d2) ( D) and / or obtained by reacting at least one compound (e1) selected from the group consisting of the silane compound represented by the general formula (I-2) and a partial condensate thereof with a phenol compound (e2). The compound (E) can be used in various applications as a curable resin that can be cured by itself or by reacting with another resin. For example, it can be used for applications such as molding materials such as sealing materials, laminated plate materials, various adhesive materials, various electronic and electrical component materials, and coating materials. The compound (D) and / or the compound (E) includes an epoxy resin, a phenol resin, an isocyanate resin, a urethane resin, an unsaturated polyester resin, a melamine resin, a silicone resin, an allyl resin, an alkyd resin, and the like. It is also possible to use in combination. Moreover, since the said compound (D) and / or compound (E) are useful as an epoxy resin hardening | curing agent, it is curable resin combining with an epoxy resin and the other component which accelerates | stimulates hardening of an epoxy resin as needed. It can also be a composition.

  The epoxy resin composition according to the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and the (B) curing agent is the compound (D) and / or The compound (E) is included, and the inorganic filler (C) includes alumina. The epoxy resin composition according to the present invention may further contain (F) a curing accelerator. Moreover, what added various additives, such as a coupling agent, an ion exchanger, a mold release agent, a stress relaxation agent, and a coloring agent, may be added as needed. Hereinafter, main components constituting the epoxy resin composition according to the present invention will be described.

(A) Epoxy Resin The (A) epoxy resin that can be used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, phenols such as phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β-naphthol, dihydroxynaphthalene A novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of a naphthol compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like with an aldehyde group compound under an acidic catalyst;
Bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene phenols (bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin),
Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol;
Glycidyl ester type epoxy resins of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid;
Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group;
Vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
Sulfur atom-containing epoxy resin;
Naphthalene type epoxy resins may be mentioned, and these may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin in terms of reflow crack resistance and fluidity, Salicylaldehyde type epoxy resins, copolymerized epoxy resins of naphthols and phenols, phenol aralkyl resins, epoxidized aralkyl type phenol resins such as naphthol aralkyl resins, and naphthalene type phenol resins are preferred, and any one of them is used. It may be used alone or in combination of two or more. However, in order to exhibit these performances, it is preferable to use them in total of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of epoxy resin. Specific examples of preferable epoxy resins are shown below.

  The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following general formula (II) is preferable.

Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) in which all are hydrogen atoms, 4,4′-bis (2,3-epoxypropoxy) biphenyl in which all R ⁸ are hydrogen atoms, and all R ⁸ are In the case of a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.

(In the formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value, Shows a number from 0 to 10)
The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), 3, ⁹ ′, 5 ′ and 5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, one is a tert-butyl group, and the other is a hydrogen atom and R ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all ¹⁰ are hydrogen atoms, is available as a commercial product.

(In the formula (III), ^{R 9} and ^{R 10} represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value, 0 Indicates the number of
The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ¹² are 3, 3 ′, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), in which the 5,5′-position is a methyl group and the others are hydrogen atoms, is commercially available.

(In the formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and 0 to 10 Indicates the number of
Although it will not specifically limit as a sulfur atom containing type epoxy resin if it is an epoxy resin containing a sulfur atom, For example, the epoxy resin shown by the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the tert-butyl group is the tert-butyl group when the positions where the oxygen atom substitution positions in R ¹³ are the 4 and 4 'positions, and 6, 6 YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) in which the '-position is a methyl group and the other is a hydrogen atom is commercially available.

(In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, Show)
The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified. Epoxy resins epoxidized using the above method are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.), in which all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group and i = 1. Etc. are available as commercial products.

(In the formula (VI), R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is (It is an average value and indicates a number from 0 to 10)
The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) where i = 0 is available as a commercial product.

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. Yes, indicates a number from 0 to 10)
The salicylaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a salicylaldehyde skeleton, but a novolak type phenol resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a salicylaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Among epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc., where i = 0 and k = 0. It is available as a commercial product.

(In the formula (VIII), R ¹⁷ and R ¹⁸ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and k is An integer of 0 to 4, n is an average value and represents a number of 0 to 10)
The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, but a compound having a naphthol skeleton And a novolak-type phenol resin using a compound having a phenol skeleton, which is glycidyl etherified, and more preferably an epoxy resin represented by the following general formula (IX). Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0, etc. It is available as a commercial product.

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, j is An integer of 0 to 2, k represents an integer of 0 to 4, p represents an average value of 0 to 1, l and m each represents an average value of 0 to 11 (l + m) represents 1 to 1 11 indicates the number)
As the epoxy resin represented by the general formula (IX), a random copolymer containing 1 structural unit and m structural units randomly, an alternating copolymer containing alternately, a copolymer containing regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.

Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. The epoxy resin is not particularly limited as long as it is made of a phenol resin synthesized from the above derivatives. For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following general formulas (X) and (XI) are more preferable. Among epoxy resins represented by the following general formula (X), i = 0, R ⁴⁰ is a hydrogen atom, NC-3000S (trade name, manufactured by Nippon Kayaku Co., Ltd.), i = 0, R ⁴⁰ is a hydrogen atom. CER-3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), in which an epoxy resin and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a weight ratio of 80:20, is available as a commercial product. is there. Among epoxy resins represented by the following general formula (XI), ESN-175 (trade name of Nippon Steel Chemical Co., Ltd.) where j = 0 and k = 0 are available as commercial products.

(In the formulas (X) and (XI), R ^{37 to} R ⁴¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and i is 0 to 3) An integer, j is an integer from 0 to 2, and k is an integer from 0 to 4)
The naphthalene type epoxy resin is not particularly limited as long as it is an epoxy compound containing a naphthalene ring. For example, a naphthol compound synthesized from a naphthol derivative such as naphthol, dihydroxynaphthalene, or dimethylnaphthol is preferably glycidyl etherified, and an epoxy resin represented by the following general formula (XI-a) is more preferable. Among the epoxy resins represented by the following general formula (XI-a), EXA-4700, EXA-4701 wherein n = 1, all of R ⁴¹ and R ⁴² are hydrogen atoms, and all of R ⁴³ are glycidyloxy groups. (Dainippon ink chemical Co., Ltd. trade name), n = ^0, all ^{R 41} and ^{R 42} are hydrogen ^{atoms, R 43} is HP-4032 (Dainippon ink chemical Co., Ltd. trade name glycidyl group ), N = 1, R ⁴¹ and R ⁴² are all hydrogen atoms, one of R ⁴³ is a hydrogen atom, and the other is a glycidyloxy group EXA-4750 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) Etc. are available as commercial products.

(In the formula (XI-a), R ⁴¹ and R ⁴² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R ⁴³ represents a hydrogen atom or a glycidyloxy group, and they are all the same or different. And n is an average value and represents a number from 0 to 10.)
About R < ⁸ > -R < ²¹ > and R < ³⁷ > -R < ⁴³ > in said general formula (II)-(XI) and (XI-a), "all may be the same or different, respectively" means, for example, formula ( It means that all ^{8 to} 88 R ^{8 in} II) may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴³ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴³ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.

  “N” in the above general formulas (II) to (XI) and (XI-a) is preferably in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curing agent is high. Therefore, the viscosity at the time of melt molding of the epoxy resin composition is also increased, and it is easy to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is more preferably set in the range of 0-4.

(B) Curing Agent The epoxy resin composition according to the present invention is characterized in that the (B) curing agent contains the compound (D) and / or the compound (E) shown above. In the epoxy resin composition according to the present invention, the blending ratio of (A) the epoxy resin to the compound (D) and / or the compound (E) is the number of all epoxy groups in the (A) epoxy resin and the compound (D). And / or the ratio of the number of —ArO—Si bonds in compound (E) and the total number of unreacted phenolic hydroxyl groups in compound (D) and / or compound (E), ie, [(compound (D) And / or the number of —ArO—Si bonds in compound (E)) + (number of unreacted phenolic hydroxyl groups in compound (D) and / or compound (E))] / [number of all epoxy groups in epoxy resin] Therefore, it is preferably set in the range of 0.5 to 2.0. The blending ratio is more preferably set in the range of 0.7 to 1.5, and still more preferably set in the range of 0.8 to 1.3. When the said mixture ratio becomes less than 0.5, hardening of an epoxy resin will become inadequate and it exists in the tendency for the heat resistance of a hardened | cured material, moisture resistance, and an electrical property to fall. On the other hand, if the blending ratio exceeds 2.0, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are reduced. It tends to decrease.

  In the epoxy resin composition according to the present invention, as the (B) curing agent, a curing agent other than the compound (D) and / or the compound (E) shown above may be included. The compound that can be used in combination as the curing agent is not particularly limited as long as it is a compound that can cure the epoxy resin. For example, phenol compounds such as phenol resin, amine compounds such as diamine and polyamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and other organic acids, dicarboxylic acids, and carboxylic acid compounds such as polycarboxylic acids. One or more of these resins may be used in combination. Among these, it is preferable to use a compound having two or more phenolic hydroxyl groups in one molecule.

  In addition, in the epoxy resin composition of the present invention, in the case where a phenol compound is used as a curing agent in addition to the component (D) and / or the component (E) according to the present invention, the total amount of the component serving as the curing agent (B) As a reference, the blending amount of the component (D) and / or the component (E) according to the present invention is preferably 30% by weight or more, and more preferably 50% by weight or more. (B) When the content of the component (D) and / or the component (E) according to the present invention in the curing agent is less than 30% by weight, the low water-absorbing property is lowered, and the effect achievable by the present invention tends to be reduced. There is.

  Furthermore, in the epoxy resin composition of the present invention, when a compound having two or more phenolic hydroxyl groups in one molecule is used as a curing agent, (A) an epoxy resin and (B) (D) of the present invention as a curing agent. The blending ratio of the component and / or the component (E) and the phenol compound used in combination is as follows: (A) the number of all epoxy groups in the epoxy resin, (B) the number of functional groups capable of reacting with the epoxy groups of the curing agent, the present invention The ratio of the number of -ArO-Si bonds in component (D) and / or (E) and the sum of the number of unreacted phenolic hydroxyl groups in component (D) and / or (E) according to the present invention, That is, [((B) number of functional groups capable of reacting with epoxy group in curing agent) + (number of —ArO—Si bonds in component (D) and / or (E) according to the present invention) + (according to the present invention) (D A component and / or (E) unreacted phenolic hydroxyl group number in component)] / [total number of epoxy groups in the epoxy resin, is preferably set in a range of 0.5 to 2.0. The blending ratio is more preferably set in the range of 0.7 to 1.5, and still more preferably set in the range of 0.8 to 1.3. When the said mixture ratio becomes less than 0.5, hardening of an epoxy resin will become inadequate and it exists in the tendency for the heat resistance of a hardened | cured material, moisture resistance, and an electrical property to fall. On the other hand, if the blending ratio exceeds 2.0, the curing agent component becomes excessive and not only the curing efficiency is lowered, but also a large amount of phenolic hydroxyl group remains in the cured resin, so that the electrical characteristics and moisture resistance of the package are reduced. It tends to decrease.

In the above-mentioned range, the phenol compound that can be used in combination with the component (D) and / or the component (E) according to the present invention as a curing agent is not particularly limited, and 2 in one molecule generally used as a curing agent. It may be a phenol compound having one or more phenolic hydroxyl groups. For example, a compound having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
The phenol resin obtained by copolymerizing 2 or more types of these resin is mentioned, These may be used independently or may be used in combination of 2 or more type.

  Among the above-mentioned phenol compounds, aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins are used from the viewpoint of reflow crack resistance. preferable. These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination of two types. A combination of the above may also be used. However, in order to exert the effect of the compound (D) and / or the compound (E) according to the present invention, the above-mentioned phenol resin is preferably 70% by weight or less, more preferably based on the total amount of the curing agent. It is desirable to use together at 50% by weight or less, more preferably 30% by weight or less.

The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. Phenol resins represented by (XII) to (XIV) are preferred.

(In the formulas (XII) to (XIV), R ^{22 to} R ^{28 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different; An integer, k is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a number of 0 to 10)
Among the phenol resins represented by the above general formula (XII), ME = 07851 (trade name of Meiwa Kasei Co., Ltd.) in which i = 0 and R ²³ are all hydrogen atoms is commercially available. Among the phenol resins represented by the above general formula (XIII), XL-225, XLC (trade name, manufactured by Mitsui Chemicals, Inc.), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc., where i = 0 and k = 0. Is commercially available. Among the phenol resins represented by the above general formula (XIV), SN-170 (trade name of Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁷ k = 0, and R ²⁸ k = 0 is a commercial product. Is available as

The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (trade name, manufactured by Nippon Petrochemical Co., Ltd.) where i = 0 is available as a commercial product.

(In the formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and n is an average value. Yes, indicates a number from 0 to 10)
The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.

Among phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) where i = 0 and k = 0 is available as a commercial product.

(In the formula (XVI), R ³⁰ and R ³¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and k is An integer of 0 to 4, n is an average value and represents a number of 0 to 10)
The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the following general formula (XVII) is preferable.

Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having i = 0, k = 0, and q = 0 is commercially available. .

(In the formula (XVII), R ^{32 to} R ³⁴ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and k is An integer of 0 to 4, q is an integer of 0 to 5, l and m are each an average value of 0 to 11 (l + m) represents a number of 1 to 11)
The novolak type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but the following general formula (XVIII ) Is preferred.

I = 0 Among phenolic resin represented by the following general formula ^{(XVIII), R 35} are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), HP-850N (manufactured by Hitachi Chemical Co., Ltd. Product Name) etc. are commercially available.

(In the formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, i is an integer of 0 to 3, and k is An integer of 0 to 4, n is an average value and represents a number of 0 to 10)
“All may be the same or different” described for R ^{22 to} R ³⁶ in the general formulas (XII) to (XVIII) means that, for example, all i R ^{22s in} the formula (XIV) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above general formulas (XII) to (XVIII), “n” is preferably in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curing agent is increased, so that the epoxy resin composition Viscosity at the time of melt molding is increased, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is more preferably set in the range of 0-4.

(C) Inorganic filler The epoxy resin composition according to the present invention is characterized in that (C) the inorganic filler contains alumina.

  The blending amount of the inorganic filler is not particularly limited as long as the effect of the present invention is obtained, but is preferably in the range of 55 to 90% by volume with respect to the total weight of the epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount of the inorganic filler is less than 55% by volume, these properties are not improved. When the amount exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and the molding tends to be difficult.

  In order to realize high heat dissipation, it is preferable to increase the weight ratio of (C) inorganic filler, particularly alumina, to the entire epoxy resin composition. Specifically, the content of (C) inorganic filler is 80% by weight or more with respect to the total weight of the epoxy resin composition, and 75% by weight or more of (C) inorganic filler is alumina. Preferably, the content of (C) inorganic filler is 85% by weight or more with respect to the total weight of the epoxy resin composition, and (C) 80% by weight or more of the inorganic filler is alumina. More preferably, all of the inorganic filler may be alumina.

  From the viewpoint of fluidity, it is preferable to use spherical alumina as the alumina, and it is not particularly limited as long as it is spherical alumina. For example, it is preferable that the particle size distribution of alumina is distributed over a wide range. For example, it is preferable to use in combination those having a maximum particle size distribution of 0.1 to 3 μm and those having 3 to 50 μm. Moreover, 1-60 micrometers is preferable and, as for the average particle diameter of spherical alumina, 3-50 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.

  In the present invention, inorganic fillers other than alumina can be used in combination. Inorganic fillers that can be used in combination may be those generally used for molding materials for sealing, and are not particularly limited. For example, fused silica, crystalline silica, silica gel, porous silica, glass, zeolite, calcium carbonate, calcium oxide, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, Examples thereof include fine particles such as steatite, spinel, mullite, titania, talc, clay and mica, or beads obtained by spheroidizing these. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient. One of these inorganic fillers may be used alone, or two or more thereof may be used in combination. From the viewpoint of reducing fluidity and linear expansion coefficient, it is preferable to use crystalline silica and fused silica, more preferably fused silica, and even more preferably spherical fused silica. Furthermore, you may use together metal hydroxide type fillers, such as aluminum hydroxide, magnesium hydroxide, and a composite metal hydroxide, which have a flame-retardant effect.

  The average particle diameter of the inorganic filler other than the alumina is preferably 1 to 50 μm, more preferably 10 to 30 μm. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.

  From the viewpoint of fluidity, the particle shape of the inorganic filler other than alumina is preferably spherical rather than rectangular, and the particle size distribution of the inorganic filler other than alumina is preferably distributed over a wide range. For example, when 75 volume% or more of inorganic fillers other than the alumina are blended, it is preferable that 70 weight% or more of them be spherical particles and distributed in a wide range of 0.1 to 80 μm. Since such an inorganic filler can easily have a close-packed structure, even if the amount is increased, an increase in the viscosity of the material is small, and an epoxy resin composition excellent in fluidity can be obtained.

(F) Curing accelerator In the epoxy resin composition by this invention, you may mix | blend a curing accelerator as needed. Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 and 1,8-diazabicyclo [5.4.0] undecene-7. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having a triethylenediamine, benzyldimethylamine, Tertiary amines such as liethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Imidazoles such as tetraphenylphosphonium and tetraphenylborate, tetrasubstituted phosphonium and tetrasubstituted borates, tetraethylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate, Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phos Sphin, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, tris Organic phosphines such as alkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, or complexes of these organic phosphines with organic borons, these organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4 Quinone compounds such as benzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane, these organic phosphines and 4-bromophenol, 3-bromophenol 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4- Bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4 Examples thereof include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as' -hydroxybiphenyl and then dehydrohalogenating (described in JP-A No. 2004-156036). When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. Later, a compound having intramolecular polarization obtained by dehydrohalogenation, and from the viewpoint of curability, intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound, followed by a dehydrohalogenation step. A compound having is preferred. In particular, it is preferable to use a phosphine compound represented by the following general formula (I-5) or an intermolecular salt thereof. In the formula, R ⁴ , R ⁵ and Y ⁻ are as described above.

  The blending amount of the (F) curing accelerator in the epoxy resin composition according to the present invention is not particularly limited as long as a curing acceleration effect is achieved. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the epoxy resin composition, the total amount of the (F) curing accelerator is preferably 0.1 to 100 parts by weight of the total (A) epoxy resin. It is desirable to blend 10 parts by weight, more preferably 1 to 7.0 parts by weight. If the blending amount of the curing accelerator is less than 0.1 parts by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing rate may be too high to obtain a good molded product.

(Various additives)
In the epoxy resin composition according to the present invention, in addition to the above-described component (A) epoxy resin, (B) curing agent, (C) inorganic filler, and (F) curing accelerator, the following difficulty may be exemplified as necessary. You may add various additives, such as a flame retardant, a coupling agent, an ion exchanger, a mold release agent, a stress relaxation agent, and a coloring agent. However, the epoxy resin composition according to the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

(Coupling agent)
The epoxy resin composition of the present invention includes various silanes such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Known coupling agents such as compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.

  The blending amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight with respect to (C) the inorganic filler. If it is less than 0.05% by weight, the adhesion to the frame tends to be lowered, and if it exceeds 5% by weight, the moldability of the package tends to be lowered.

  Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane , Γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-amino Til) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinyl) Silane coupling agents such as (benzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate , Isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditri Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl triocta Titanates such as noyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate Coupling agents, etc., and these can be used alone It may be used in combination on. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are mentioned, These can be used individually or in combination of 2 or more types. Especially, the hydrotalcite shown by the following general formula (XIX) is preferable.

(0 <X ≦ 0.5, m is a positive number)
The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by weight with respect to (A) the epoxy resin. 1 to 5% by weight is more preferable.

(Release agent)
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used. Examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It may be used alone or in combination of two or more. Among these, higher fatty acids, oxidized or non-oxidized polyolefin-based waxes are preferable, and the blending amount thereof is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight with respect to (A) the epoxy resin. preferable. If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesiveness may be inhibited. As a higher fatty acid, for example, carnauba wax manufactured by Celerica NODA Co., Ltd. may be mentioned as a commercially available product. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (A) epoxy resin, and 0.5 to 3 weight% is more preferable.

(Stress relaxation agent)
The epoxy resin composition of the present invention may contain a stress relaxation agent such as silicone oil or silicone rubber powder as required. By adding a stress relaxation agent, the amount of warp deformation and package cracking of the package can be reduced. The stress relaxation agent that can be used is not particularly limited as long as it is a known flexible agent (stress relaxation agent) that is generally used. Commonly used flexible agents include, for example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR, and the like. (Acrylonitrile-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples thereof include rubber particles having a core-shell structure such as a copolymer, and these may be used alone or in combination of two or more. Among these, silicone-based flexible agents are preferable, and examples of silicone-based flexible agents include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

(Flame retardants)
In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound and metal hydroxide containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom are mentioned, These 1 type is mentioned. It may be used alone or in combination of two or more. Although there will be no restriction | limiting in particular if the flame-retardant effect is achieved, the compounding quantity of a flame retardant is 1-30 weight% with respect to (A) epoxy resin, and 2-15 weight% is more preferable.

(Coloring agent)
The epoxy resin composition of the present invention may contain known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, bengara and the like.

(Preparation of epoxy resin composition)
The epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-described components, kneading with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooling, pulverizing, etc. Can be obtained at The epoxy resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

(Electronic component equipment)
An electronic component device according to the present invention includes an element sealed with the epoxy resin composition of the present invention. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc. And those in which the element portion is sealed with the epoxy resin composition of the present invention. More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding or bump, the transfer is performed using the epoxy resin composition of the present invention. Sealed by molding or the like, DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-Tap) Common resin-sealed ICs such as Outline Package (TQFP) and TQFP (Thin Quad Flat Package), half connected to the tape carrier by bumps A semiconductor chip, a transistor, and a semiconductor chip connected to a wiring formed on a TCP (Tape Carrier Package), a wiring board or glass sealed with the epoxy resin composition of the present invention by wire bonding, flip chip bonding, solder, etc. A COB (Chip On Board) module, a hybrid IC, a multichip module, and a back surface in which active elements such as diodes and thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the epoxy resin composition of the present invention. The element is mounted on the surface of the organic substrate on which the terminals for connecting the wiring board are formed, the element and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the element is sealed with the curable resin composition of the present invention. Stopped BGA (Ball Grid Array), CSP ( hip Size Package) and the like. Among them, the curable resin composition of the present invention is less likely to have a decrease in elastic modulus at high temperatures, and thus can be suitably used for applications requiring heat resistance, high-temperature operation guarantees, and the like. Specifically, a power module package, an in-vehicle package, a semiconductor package that operates even at high temperatures, such as SiC, and the like can be given. Moreover, the curable resin composition of this invention can be used effectively also in a printed circuit board.

  As a method for sealing an electronic component device using the epoxy resin composition of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited to these Examples.

(Synthesis example)
(Synthesis Example 1)
A 500 ml separable flask was charged with 100 g (0.54 mol) of 2,2′-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 152 ml of toluene, and dissolved by heating to about 100 ° C. While maintaining the temperature at about 100 ° C., 55 g of a methyltrimethoxysilane partial condensate (MTMS-A manufactured by Tama Chemical Industry Co., Ltd.) was dropped into the solution over about 30 minutes, followed by triphenylphosphine and 1,4 -0.50 g (0.0013 mol) of an adduct with benzoquinone was added, and the reaction was continued at 110 to 120 ° C for about 12 hours. At that time, methanol as a by-product was removed from the reaction system as an azeotrope with toluene used as a solvent. After completion of the reaction, toluene was removed under reduced pressure at about 80 ° C. using an aspirator, put into a fluororesin-coated metal container, and cooled to room temperature (25 ° C.) to obtain 112 g of a solid product.

The obtained product was subjected to ¹ H-NMR measurement and IR measurement.

The ¹ H-NMR spectrum of the product obtained in this synthesis example is shown in FIG. ^From the result of ¹ H-NMR measurement, a signal derived from the methoxy group of the partial condensate of methyltrimethoxysilane as a raw material and methanol as a by-product was not confirmed.

The results of IR measurement are shown in FIGS. FIG. 2 is an IR spectrum of 2,2′-biphenol as a raw material, and FIG. 3 is an IR spectrum of the product obtained in this example. From the result of IR measurement of the product, the presence of an absorption band characteristic of the Si—OAr group was confirmed at 920 to 970 cm ⁻¹ . From the above results, the product is presumed to have a unit structure represented by the following general formula (XX) and the following general formula (XXI).

(Synthesis Example 2)
A 300 ml separable flask was charged with 100 g (0.54 mol) of 2,2′-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 ml of toluene, and heated to about 100 ° C. to dissolve a solid component to obtain a solution. . While maintaining the solution at about 100 ° C., 59 g (0.26 mol) of 1,3-dimethyltetramethoxydisiloxane (reagent sold by AMAX Co.) was dropped into the solution over about 20 minutes, followed by triphenylphosphine. 0.50 g (0.0013 mol) of an adduct of 1,4-benzoquinone was added, and the reaction was continued at 120 to 130 ° C. for about 20 hours. At that time, methanol as a by-product was removed from the reaction system as an azeotrope with toluene used as a solvent. After completion of the reaction, 117 g of the product is obtained by removing toluene from the reaction solution under reduced pressure at about 80 ° C. using an aspirator, and then discharging the remainder into a metal container coated with Teflon and cooling to room temperature. Obtained as a solid.

The obtained product was subjected to ¹ H-NMR measurement and IR measurement.

The ¹ H-NMR spectrum of the product obtained in this synthesis example is shown in FIG. ^From the result of ¹ H-NMR measurement, it was confirmed that the signal derived from the methoxy group of 1,3-dimethyltetramethoxydisiloxane as a raw material was 0.9% based on the start of the reaction.

The IR spectrum of the product obtained in this synthesis example is shown in FIG. From the results of IR measurement, there is a characteristic absorption band in the Si—OAr group at 920 to 970 cm ⁻¹ and a peak of O—H of the phenolic hydroxyl group derived from the raw material (see FIG. 2). It was confirmed that it had disappeared. From the above results, the product is presumed to contain a curable resin having a structural unit represented by the general formula (XX) and the general formula (XXI).

(Synthesis Example 3)
In a 300 ml separable flask, 155 g (0.83 mol) of 2,2′-biphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 222 ml of toluene were added and dissolved by heating to about 100 ° C. While maintaining the temperature at about 100 ° C., 1 g of an addition reaction product of triphenylphosphine and 1,4-benzoquinone was added to the solution, followed by 110 g of phenyltrimethoxysilane (AY43-040 manufactured by Toray Dow Corning Co., Ltd.) .55 mol) was added dropwise over about 60 minutes. Methanol as a by-product is removed from the reaction system as an azeotrope with toluene used as a solvent. When the amount of toluene in the reaction system decreases, toluene is further added to the reaction system as an azeotrope. While removing, the reaction was continued for 42 hours at about 120-130 ° C. After completion of the reaction, 197 g of the product was obtained by removing toluene from the reaction solution under reduced pressure using an aspirator at about 80 ° C., and then discharging the remainder into a metal container coated with Teflon and cooling to room temperature. Obtained as a solid.

The obtained product was subjected to ¹ H-NMR measurement and IR measurement.

The ¹ H-NMR spectrum of the product obtained in this synthesis example is shown in FIG. ^From the result of ¹ H-NMR measurement, it was confirmed that the signal derived from the methoxy group of the raw material phenyltrimethoxysilane was 0.6% on the basis of the start of the reaction.

The IR spectrum of the product obtained in this synthesis example is shown in FIG. From the results of IR measurement, there is a characteristic absorption band in the Si—OAr group at 920 to 970 cm ⁻¹ and a peak of O—H of the phenolic hydroxyl group derived from the raw material (see FIG. 2). It was confirmed that it had disappeared. From the above results, the product is presumed to contain a curable resin having the structural unit represented by the general formula (XX) shown above.

(Synthesis Example 4)
A 1000 ml separable flask was charged with 580 ml of methanol, cooled to 10 ° C. with ice, and 90 g (1.66 mol) of sodium methoxide (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was charged and dissolved to obtain a solution. While maintaining the solution at 10 ° C., a solution in which 101 g (0.414 mol) of 1,2-bis (methyldichlorosilyl) ethane (reagent sold by Amax Co.) was dissolved in 200 ml of methanol was added to the solution over about 90 minutes. The solution was dropped, the temperature was raised stepwise, and the mixture was refluxed for about 20 hours. The reaction solution was left overnight at room temperature, the by-product was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 93 g of 1,2-bis (methyldimethoxysilyl) ethane as a liquid.

  Subsequently, 146 g (0.78 mol) of 2,2′-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 160 ml of toluene were charged into a 500 ml separable flask, and heated to 100 ° C. to dissolve it to obtain a solution. While maintaining the solution at 100 ° C., 93 g (0.39 mol) of 1,2-bis (methyldimethoxysilyl) ethane synthesized by the above reaction was dropped into the solution over about 50 minutes. Further, 0.73 g (0.0020 mol) of an adduct of triphenylphosphine and 1,4-benzoquinone was added to the solution and continued at 110 to 120 ° C. for about 8 hours. At that time, methanol as a by-product was removed from the reaction system as an azeotrope with toluene used as a solvent. After completion of the reaction, 181 g of the product was obtained by removing the toluene from the reaction solution under reduced pressure at about 80 ° C. using an aspirator, and then discharging the remainder into a metal container coated with Teflon and cooling to room temperature. Obtained as a solid.

The obtained product was subjected to ¹ H-NMR measurement and IR measurement.

The ¹ H-NMR spectrum of the product obtained in this synthesis example is shown in FIG. ^From the result of ¹ H-NMR measurement, it was confirmed that the signal derived from the methoxy group of 1,2-bis (methyldimethoxysilyl) ethane as a raw material was 0.6% based on the start of the reaction.

FIG. 9 shows the IR spectrum of the product obtained in this synthesis example. From the results of IR measurement, there is a characteristic absorption band in the Si—OAr group at 920 to 970 cm ⁻¹ and a peak of O—H of the phenolic hydroxyl group derived from the raw material (see FIG. 2). It was confirmed that it had disappeared. From the above results, the product is presumed to contain a curable resin having the structural unit represented by the general formula (XX) shown above.

(Synthesis Example 5)
A 500 ml separable flask was charged with 150 g (0.804 mol) of 2,2′-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 180 ml of toluene, and dissolved by heating to about 100 ° C. While maintaining the temperature at about 100 ° C., 1 g of an addition reaction product of triphenylphosphine and 1,4-benzoquinone was added to the solution, and then 95 g (0.268 mol) of bis (triethoxysilyl) ethane (reagent sold by Amax Co., Ltd.). ) Was added dropwise over about 30 minutes. Ethanol as a by-product is removed from the reaction system as an azeotrope with toluene used as a solvent. When the amount of toluene in the reaction system decreases, further toluene is added to the reaction system as an azeotrope. While removing, the reaction was continued for about 26 hours. After completion of the reaction, toluene was removed under reduced pressure at about 80 ° C. using an aspirator, put into a metal container coated with fluororesin, and cooled to room temperature to obtain 163 g of a solid product.

The obtained product was subjected to ¹ H-NMR measurement and IR measurement. The ¹ H-NMR spectrum of the product obtained in this example is shown in FIG. ^From the result of ¹ H-NMR measurement, it was confirmed that the signal derived from the ethoxy group of bis (triethoxysilyl) ethane as a raw material and ethanol as a by-product was 2.7% based on the start of the reaction. .

An IR spectrum of the product obtained in this synthesis example is shown in FIG. From the results of IR measurement, an absorption band characteristic of the Si—OAr group was confirmed in the product at 850 to 1000 cm ⁻¹ . From the above results, the product is presumed to have a unit structure of the general formula (XX).

  In addition, 2,2'-biphenol used in Synthesis Examples 1 to 5 is a reagent manufactured by Tokyo Chemical Industry Co., Ltd., but as a result of measuring the cation concentration and the anion concentration by ion chromatography, the sodium ion was 600 ppm. The potassium ions were 380 ppm, the chloride ions were 610 ppm, the phosphate ions were 130 ppm, and the nitrate ions were 10 ppm. The 2,2'-biphenol used in Synthesis Examples 1 to 5 was obtained by purifying a reagent manufactured by Tokyo Chemical Industry Co., Ltd. The cation concentration and the anion concentration after purification were 60 ppm for sodium ions and 9.0 ppm for chloride ions, and no other ions detected before purification were detected. A specific method for purifying 2,2'-biphenol will be described below.

(Purification of 2,2'-biphenol)
Into a 3000 ml separable flask, 1500 g of 2,2′-biphenol (reagent made by Tokyo Chemical Industry Co., Ltd.), 500 ml of toluene, and 1000 ml of distilled water are added, and these are heated to about 90 ° C. to dissolve the solid components, and a solution It was. The solution was heated and stirred for 2.5 hours while maintaining at about 90 ° C., and then left overnight, and the precipitated solid was filtered and washed (1500 ml of distilled water). The solid was again put into a 3000 ml separable flask, 500 ml of toluene and 1000 ml of distilled water were added, and the mixture was heated to about 90 ° C. to dissolve it to obtain a solution. The solution was heated and stirred for 2.5 hours while maintaining the temperature at about 90 ° C., and then left overnight, and the precipitated solid was filtered and washed (1500 ml of distilled water). The obtained solid was vacuum-dried at 70 ° C., put into a 2000 ml separable flask, 500 ml of toluene was added, heated to dissolve, and a trace amount of water was removed azeotropically. Subsequently, the solution was allowed to stand overnight, and the precipitated solid was filtered and dried to obtain 1340 g of purified 2,2′-biphenol.

  Details of various measurements of the reaction products (hereinafter referred to as “curable resins”) obtained in Synthesis Examples 1 to 5 are as follows.

(1) ¹ H-NMR
About 10 mg of curable resin was dissolved in about 1 ml of heavy acetone to form a solution. The solution was placed in a φ5 mm sample tube and measured using AV-300M manufactured by Bruker BioSpin. The shift value was based on (CD ₃ ) ₂ CO (2.05 ppm) contained in a trace amount in the solvent.

(2) IR
Measurement was carried out using Bio-Rad FTS 3000MX according to the KBr method.

(3) Ion chromatograph 5 g of 2,2′-biphenol and 50 g of distilled water pulverized using a mortar are placed in a polypropylene container, heated at 95 ° C. for 20 hours, filtered for the extracted water, and subjected to the following method. And measured. From this measured value, 50 g of distilled water was put into a polypropylene container in the same manner as above, and the measured value of water prepared by heating at 95 ° C. for 20 hours was subtracted to obtain various ion values contained in 2,2′-biphenol. Conversion was made to the ion concentration.

(3-1) A cation guard column (Shim-pack IC-GC3) and a separation column (Shim-pack IC-C3) equipped with Shimadzu HIC-6A ion chromatograph, eluent: 1 mM oxalic acid Measurement was performed under the conditions of aqueous solution / acetonitrile = 5/1, flow rate: 1.1 ml / min, column temperature: 30 ° C.

(3-2) Anion: Using an IC20 ion chromatograph manufactured by DIONEX equipped with a guard column (IonPac AG9-HC) and a separation column (IonPac AS9-HC), eluent: 9 mM aqueous sodium carbonate, flow rate: 1. Measurement was performed under the conditions of 0 ml / min and column temperature: 30 ° C.

[Preparation of epoxy resin composition and evaluation of properties]
(Examples 1-8, Comparative Examples 1-4)
(A) Epoxy resin Epoxy resin 1: Salicylaldehyde type epoxy resin having an epoxy equivalent of 168 and a softening point of 62 ° C. (trade name “1032H60” manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.)
(B) Curing Agent Curing Agent 1: Curing Resin Obtained in Synthesis Example 1 Curing Agent 2: Curing Resin Obtained in Synthesis Example 2 Curing Agent 3: Curing Resin Obtained in Synthesis Example 3 Curing Agent 4: Synthesis Example Curing resin obtained in 4 Curing agent 5: Curing resin obtained in Synthesis Example 5 Curing agent A: Salicylaldehyde type phenol resin having a hydroxyl equivalent of 103 and a softening point of 86 ° C (trade name “MEH-7500, manufactured by Meiwa Kasei Co., Ltd.) ")
Curing agent B: phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (trade name: Millex XLC, manufactured by Mitsui Chemicals, Inc.)
(C) Inorganic filler Spherical alumina: Spherical alumina having an average particle size of 12.5 μm and a specific surface area of 2.1 m ² / g (trade name DAB-10SI manufactured by Electrochemical Co., Ltd.)
Fused silica: spherical fused silica (F) curing accelerator having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g addition reaction product of triphenylphosphine and 1,4-benzoquinone (other various additives)
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (trade name “MA-100” manufactured by Mitsubishi Chemical Corporation)
Mold release agent: Carnauba wax (manufactured by Celerica NODA)
By blending the above-mentioned components in parts by weight shown in Tables 1 and 2, respectively, and performing roll kneading under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, Examples 1 to 8 and Comparative Examples 1 to 4 respectively. An epoxy resin composition was obtained.

  Next, each epoxy resin composition obtained by Examples 1-8 and Comparative Examples 1-4 was evaluated by each test shown below. The evaluation results are shown in Tables 1 and 2. The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.

(1) The spiral flow epoxy resin composition was molded using a spiral flow measurement mold according to EMMI-1-66 under the above conditions, and the flow distance (cm) was determined.

(2) Hardness upon heating The epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and measured immediately using a Shore D hardness meter.

(3) Glass transition temperature The epoxy resin composition was molded into a size of 80 mm length × 10 mm width × 3 mm thickness under the above conditions and post-cured. Next, it is cut into a length of 55 mm with a diamond cutter, using a viscoelasticity measuring device ARES (manufactured by Rheometric Scientific FE Co., Ltd.) in a dynamic mode under conditions of a heating rate of 5 ° C. and a frequency of 6.28 rad / s. The glass transition temperature (° C.) was determined from the measurement of tan δ.

(4-1) Elastic modulus at high temperature (240 ° C)
From the measurement in the above (3), the storage elastic modulus (× 10 ⁸ Pa) at 240 ° C. was determined.

(4-2) Elastic modulus at high temperature (270 ° C.)
The storage elastic modulus (× 10 ⁸ Pa) at 270 ° C. was determined from the measurement in (3) above.

(5) Thermal conductivity The epoxy resin composition was molded into a size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions and post-cured. Then cut to a length of 10mm with a diamond cutter, the thermal diffusivity measuring apparatus LFA447 Nanoflash (NETZSCH-Geratebau Inc.) using thermal diffusivity D of ^(m 2/2), the electronic hydrometer SD-200L (alpha Mirage stock The specific gravity ρ (kg / m ³ ) using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elma), the specific heat Cp (J / kgK) is obtained, the thermal diffusivity D, the specific gravity ρ, and the specific heat. The thermal conductivity λ (W / mK) was calculated from the product of Cp.

  Examples 1 to 8 containing the compound (D) and / or the compound (E) as the curing agent and alumina as the inorganic filler all have high elastic modulus and high thermal conductivity at high temperatures, and normal molding conditions So, it has fluidity without problems. On the other hand, Comparative Examples 1 to 4 which do not contain the compound (D) component and / or the compound (E) as a curing agent have a low elastic modulus at a high temperature and do not contain alumina as an inorganic filler. 3 has low thermal conductivity. Therefore, the epoxy resin composition of the present invention containing the compound (D) component and / or the compound (E) as a curing agent and alumina as an inorganic filler exhibits excellent heat resistance and heat dissipation. It is a curable resin excellent in moldability.

1 is a ¹ H-NMR spectrum of a curable resin according to the present invention (Synthesis Example 1). It is IR spectrum of 2,2'-biphenol used in the synthesis example of the curable resin according to the present invention. It is IR spectrum of curable resin by this invention (Synthesis example 1). ^{1 is} a ¹ H-NMR spectrum of a curable resin according to the present invention (Synthesis Example 2). It is IR spectrum of curable resin by this invention (Synthesis example 2). ^{1 is} a ¹ H-NMR spectrum of a curable resin according to the present invention (Synthesis Example 3). It is IR spectrum of curable resin by this invention (Synthesis example 3). ^{1 is} a ¹ H-NMR spectrum of a curable resin according to the present invention (Synthesis Example 4). It is IR spectrum of curable resin by this invention (Synthesis example 4). ^{1 is} a ¹ H-NMR spectrum of a curable resin according to the present invention (Synthesis Example 5). It is IR spectrum of curable resin by this invention (Synthesis example 5).

Claims (17)

An epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The (B) curing agent is obtained by reacting at least one compound (d1) selected from a silane compound represented by the following general formula (I-1) and a partial condensate thereof with a phenol compound (d2). A compound (D) obtained,
In the phenol compound (d2), 70% by weight or more based on the total weight of the phenol compound is a divalent phenol compound,
And the said (C) inorganic filler contains an alumina, The epoxy resin composition characterized by the above-mentioned.

(In the formula (I-1), n is 0 or 1, R ¹ is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and all are R ² may be the same or different, and R ² is a halogen atom, a hydroxyl group, a monovalent hydrocarbon oxy group having 1 to 18 carbon atoms that may have a substituent, or a carbon number that may have a substituent. have an amino group and a substituent of 0-18 also selected from the group consisting of optionally carbonyloxy group having 2 to 18 carbon atoms may be all the same or different, 2 selected from R ¹ and R ² The above may combine to form a ring structure.) The compound (D) is at least one compound (d1) in R ² R ² groups content of unreacted groups as a reference at 10% or less selected from the reaction starting silane compound and its partial condensation product The epoxy resin composition according to claim 1, wherein the epoxy resin composition is present. Oite the phenol compound (d2), the epoxy resin composition according to claim 1 or claim 2 that 80 wt% or more based on the total weight, wherein the divalent phenol compound of the phenol compound.   In the phenol compound (d2), 50% by weight or more based on the total weight of the phenol compound is a phenol compound that can be cyclized with at least one compound (d1) selected from the silane compound and a partial condensate thereof. The epoxy resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. In at least one compound (d1) selected from the silane compound and its partial condensate, R ² is a monovalent hydrocarbon oxy group having 1 to 18 carbon atoms which may have a hydroxyl group or a substituent. The epoxy resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. An epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The (B) curing agent is obtained by reacting at least one compound (e1) selected from a silane compound represented by the following general formula (I-2) and a partial condensate thereof with a phenol compound (e2). A compound (E) obtained,
In the phenol compound (e2), 70% by weight or more based on the total weight of the phenol compound is a divalent phenol compound,
And the said (C) inorganic filler contains an alumina, The epoxy resin composition characterized by the above-mentioned.

(In Formula (I-2), m is 0, n is an integer of 2 or more, R ^{1 ′} is an optionally substituted n-valent organic group having 0 to 18 carbon atoms, and R ^{1 ′} Two or more SiR ^{2 ′} _m R ^{3 ′} _(3-m) groups bonded to ^{1 ′} may be all the same or different, and R ^{2 ′} may be a carbon atom optionally having a hydrogen atom and a substituent. It is selected from the group consisting of hydrocarbon groups of 1 to 18 and may combine with R ^{1 ′} or R ^{3 ′} to form a cyclic structure, and R ^{3 ′} has a halogen atom, a hydroxyl group, and a substituent. A monovalent hydrocarbon oxy group having 1 to 18 carbon atoms which may have, an amino group having 0 to 18 carbon atoms which may have a substituent, and 2 to 18 carbon atoms which may have a substituent. selected from the group consisting of carbonyl group, all may be the same or different, two or more R ^{3 'are} bonded to each other to form a cyclic structure It has.) The compound (E) is a silane compound at the beginning of the reaction and R ³ groups content of ^{'R 3} unreacted groups ^based' 10% at its portion at least one compound selected from the condensation product (e1) The epoxy resin composition according to claim 6, wherein:   8. The epoxy resin composition according to claim 6, wherein 80% by weight or more of the phenol compound (e2) is a dihydric phenol compound based on the total weight of the phenol compound.   In the phenol compound (e2), 50% by weight or more based on the total weight of the phenol compound is a phenol compound that can be cyclized with at least one compound (e1) selected from the silane compound and a partial condensate thereof. The epoxy resin composition according to any one of claims 6 to 8, wherein the composition is an epoxy resin composition. In at least one compound (e1) selected from the silane compound and a partial condensate thereof, R ^{3 ′} is a monovalent hydrocarbon oxy group having 1 to 18 carbon atoms which may have a hydroxyl group or a substituent. It is, The epoxy resin composition as described in any one of Claims 6-9 characterized by the above-mentioned. The compound (D) and / or the compound (E) has at least one of a structural moiety represented by the following general formula (I-3) and a structural moiety represented by the following general formula (I-4). The epoxy resin composition according to any one of claims 1 to 10.

(In the formula (I-3), Ar represents a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides.)

(In the formula (I-4), Ar represents a divalent organic group having 2 to 30 carbon atoms and a group derived from an aromatic cyclic compound on both sides, and n is 0 or more. Indicates the number.)   The compound (D) and / or the compound (E) includes at least one of a structural moiety represented by the general formula (I-3) and a structural moiety represented by the general formula (I-4), D) and / or, based on the total number of aryloxysilyl (ArO—Si) bonds in compound (E), the structural moiety represented by the general formula (I-3) and / or the general formula (I-4) 12. The epoxy resin composition according to claim 1, wherein the number of aryloxysilyl bonds in the structural site shown is 30% or more.   The content of the (C) inorganic filler is 80% by weight or more based on the total weight of the epoxy resin composition, and 75% by weight or more of the (C) inorganic filler is alumina. Item 13. The epoxy resin composition according to any one of Items 1 to 12.   The content of the (C) inorganic filler is 85% by weight or more based on the total weight of the epoxy resin composition, and 80% by weight or more of the (C) inorganic filler is alumina. Item 13. The epoxy resin composition according to any one of Items 1 to 12.   Furthermore, (F) hardening accelerator is contained, The epoxy resin composition as described in any one of Claims 1-14 characterized by the above-mentioned.   The (A) epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols. 16. The resin composition according to claim 1, comprising at least one epoxy resin selected from the group consisting of a copolymerization type epoxy resin of a phenol and a phenol, and an epoxidized product of an aralkyl type phenol resin. The epoxy resin composition described in 1.   An electronic component device comprising an element sealed with the epoxy resin composition according to claim 1.

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