JP5326184B2 - NOVEL COMPOUND AND PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new compound useful as a curing promoter exhibiting excellent fluidity, reflow crack resistance and high-temperature aging resistance and excellent curabililty even during moisture absorption and to provide a method for producing the same. <P>SOLUTION: The new compound is represented by general formula (I) (R<SP>1</SP>s are each independently a hydrogen atom or a 1-18C substituted or nonsubstituted hydrocarbon group and two or more R<SP>1</SP>s may be mutually bonded to form a cyclic structure; R<SP>2</SP>and R<SP>3</SP>are each independently a hydrogen atom, a hydroxy group or a 1-18C substituted or nonsubstituted organic group and R<SP>2</SP>and R<SP>3</SP>may be the same or different and two or more R<SP>2</SP>and R<SP>3</SP>may be mutually bonded to form a cyclic structure; YH is a 0-18C organic group having one or more releasable protons (H+) and may be mutually bonded to one or more R<SP>2</SP>s to form a cyclic ring; m is an integer of 1-4; n is a number of &ge;0). <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a novel compound useful as a curing accelerator for a curable resin composition and a method for producing the same.

  Conventionally, curable resins such as epoxy resins have been widely used in fields such as molding materials, laminates, and adhesive materials. Since these curable resins are required to have fast curability from the viewpoint of improving productivity, a compound that accelerates the curing reaction, that is, a curing accelerator is generally used in the curable resin composition. For example, in the field of sealing technology relating to elements of electronic components such as transistors and ICs, compositions based on epoxy resins are widely used among curable resins. The reason for this is that epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, a combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance in the above-mentioned characteristics, and therefore has become the mainstream as a base resin for molding materials for IC sealing. And also in such an epoxy resin composition, generally hardening accelerators, such as amine compounds, such as tertiary amine and imidazole, and phosphorus compounds, such as phosphines and phosphonium, are used.

  On the other hand, in recent years, in the sealing technology for electronic component elements, the mounting of electronic components on a printed wiring board has been progressing, and along with this, surface mount packages have become the mainstream rather than conventional pin insertion packages. It's getting on. However, in the surface mount type package, the resistance against the package crack at the time of soldering, that is, the so-called reflow crack resistance tends to be reduced as compared with the pin insertion type package. That is, in surface-mounted ICs such as IC and LSI, the occupied volume of the element in the package gradually increases in order to increase the mounting density, and the thickness of the package is very thin. In addition, surface mount packages are subject to more severe conditions in the soldering process than pin insert packages. More specifically, in the pin insertion type package, since the soldering is performed from the back surface of the wiring board after the pins are inserted into the wiring board, the package is not directly exposed to a high temperature. On the other hand, in a surface-mounted IC, after temporarily fixing the surface of the wiring board, the package is directly exposed to a high soldering temperature because it is processed by a solder bath, a reflow device, or the like. As a result, when the IC package absorbs moisture, the moisture absorption moisture may rapidly expand during soldering, leading to package cracks, which is a major problem in package molding.

  Under such circumstances, an epoxy resin composition in which the content of the inorganic filler is increased has been reported in order to improve the reflow crack resistance in the surface mount package. However, as the content of the inorganic filler increases, the fluidity of the resin composition decreases, and defective molding during molding, such as defective filling, void formation, or poor conduction due to disconnection of the bonding wire of the IC chip. In many cases, the performance of the package is reduced. Therefore, there is a limit to the increase in the content of the inorganic filler, and as a result, it has been difficult to achieve a significant improvement in reflow crack resistance. In particular, such an epoxy resin composition is provided with a phosphorus curing accelerator such as triphenylphosphine and an amine curing accelerator such as 1,8-diazabicyclo [5.4.0] undecene-7 from the viewpoint of rapid curing. When added, the fluidity of the resin composition tends to decrease significantly. For this reason, in addition to improving the reflow crack resistance of the package, it is desired to improve the fluidity of the resin composition.

In order to improve the fluidity of an epoxy resin composition containing a high proportion of inorganic filler, for example, a method using an addition reaction product of triphenylphosphine and 1,4-benzoquinone as a curing accelerator has been proposed. (See Patent Document 1). As another method, a method using phosphoniophenolate as a curing accelerator has been proposed (see Patent Documents 2 and 3).
JP-A-9-157497 JP 2004-156035 A Japanese Patent Laid-Open No. 2004-156036

  However, in recent years, in the field of surface mount packages, there is a movement to regulate the content of halogen-containing flame retardant in the epoxy resin composition for sealing from the viewpoint of environmental problems. Therefore, the content of the inorganic filler tends to increase more and more in order to realize high flame resistance of the package without using these flame retardants and to further improve the thermal conductivity of the package. Under such circumstances, it is difficult to obtain sufficient fluidity even when the above-described phosphorus-based curing accelerator proposed for improving fluidity reduction in the epoxy resin composition for sealing is used. Tend to be. Therefore, further development of a good curing accelerator in various properties including fluidity is desired.

  Therefore, the present invention is useful as a curing accelerator for a curable resin composition, and exhibits excellent fluidity, reflow crack resistance, and high temperature storage characteristics, and imparts excellent curability even during moisture absorption. It is an object of the present invention to provide a novel compound that can be produced and a method for producing the same.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a specific phosphorus compound is useful as a curing accelerator, and have completed the present invention.

  The present invention relates to the following.

(1) A compound represented by the general formula (I)

(In the formula, each R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹ may be bonded to each other to form a cyclic structure;
R ² is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ² May be bonded together to form a ring structure,
R ³ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ³ May be bonded together to form a ring structure,
YH is an organic group having 0 to 18 carbon atoms having one or more releasable protons, and may combine with one or more R ² to form a cyclic structure;
m is an integer of 1 to 4, and p is a number of 0 or more)
(2) The compound according to (1) above, wherein YH in the general formula (I) is a monovalent organic group having a hydroxyl group or a phenolic hydroxyl group.

(3) The compound as described in (1) or (2) above, wherein at least one of R ¹ is a substituted or unsubstituted aromatic hydrocarbon group.

(4) The compound as described in (3) above, wherein all of R ¹ are phenyl groups.

(5) The compound according to any one of (1) to (4) above, wherein at least one of R ³ is a substituted or unsubstituted aromatic hydrocarbon group.

(6) The compound as described in any one of (1) to (5) above, wherein all of R ² are hydrogen atoms.

(7) A method for producing the compound described in (1) above, comprising reacting an intramolecular phosphonium salt represented by the following general formula (Ia) with a silanol compound represented by the following general formula (Ib): A featured manufacturing method.

(In the formula, each R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹ may be bonded to each other to form a cyclic structure;
R ² is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ² May be bonded together to form a ring structure,
Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms having one or more releasable protons, and is bonded to one or more R ² to form a cyclic structure. Also good)

(In the formula, each R ³ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different. The above R ³ may be bonded to each other to form a cyclic structure,
m represents an integer of 1 to 4)

  The novel compound according to the present invention is useful as a curing accelerator, and can exhibit excellent fluidity, curability, reflow crack resistance, and high-temperature storage properties in a curable resin composition. Therefore, a curable resin composition using a curing accelerator containing such a compound is excellent in curability at the time of moisture absorption and various properties such as fluidity. By sealing the elements of electronic components such as IC and LSI using such a curable resin composition, the reflow crack resistance and high-temperature storage characteristics are good and reliable as will be apparent from the examples described later. It is possible to provide an electronic component device having excellent performance, and its industrial value is high.

  The present invention will be described in detail below.

The novel compound according to the present invention is represented by the general formula (I).

(In the formula, each R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹ may be bonded to each other to form a cyclic structure;
R ² is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ² May be bonded together to form a ring structure,
R ³ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ³ May be bonded together to form a ring structure,
YH is an organic group having 0 to 18 carbon atoms having one or more releasable protons, and may combine with one or more R ² to form a cyclic structure;
m is an integer of 1 to 4, and p is a number of 0 or more)
The term “substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms” described as R ¹ in the above general formula (I) has 1 to 18 carbon atoms and may be substituted or unsubstituted. Is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

  More specifically, examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups, and these are substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. The thing which was done is mentioned.

  The substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group. Examples of the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group and tolyl group, alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, and tert-butylphenyl group. , Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, and the like, which further include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens, etc. May be substituted.

The term “two or more R ^1s may be bonded to each other to form a cyclic structure” described as R ^{1 in the} general formulas (I) and (Ia) means that two or three R ^1s are bonded to each other. As a bivalent or trivalent hydrocarbon group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene and hexylene, which can be bonded to a P atom to form a cyclic structure, an alkenyl group such as ethylenyl, propylenyl and butyrenyl groups, an aralkylene group such as a methylenephenylene group, phenylene and naphthylene And arylene groups such as anthracenylene, which may be substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogens, and the like.

The R ^{1 in the} general formula (I) is not particularly limited, but is preferably a monovalent substituent selected from the group consisting 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- Hydroxynaphthyl) group, 1- (4-hydroxynaphthyl) group, unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group Substituents selected from chain or cyclic alkyl groups such as sec-butyl group, tert-butyl group, octyl group and cyclohexyl group are more preferred. 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) And a non-substituted alkyl group or / and an alkoxy group or / and a hydroxyl group-substituted aryl group.

R ² in the above general formula (I) and ^(Ia), formula (I) and "substituted or unsubstituted organic group having 1 to 18 carbon atoms" refers described as R ³ of (Ib) are carbon atoms 1 Aliphatic hydrocarbon group, aromatic hydrocarbon group, aliphatic hydrocarbon or aromatic hydrocarbon oxy group, aliphatic hydrocarbon or aromatic which has ˜18 and may be substituted or unsubstituted It is meant to include those in which a hydrocarbon carbonyl group, an aliphatic hydrocarbon or an aromatic hydrocarbon oxycarbonyl group, and an aliphatic hydrocarbon or an aromatic hydrocarbon carbonyloxy group are bonded.

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

  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 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, etc. Substituted ones are mentioned. The aromatic hydrocarbon oxy group has a structure in which an oxygen atom is bonded to the above-described aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, or a phenoxyphenoxy group. Groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens and the like.

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

  Examples of the oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, allyloxycarbonyl group, cyclohexyloxycarbonyl group, and aromatic groups such as phenoxycarbonyl group and methylphenoxycarbonyl group. Examples include hydrocarbon oxycarbonyl groups and the like, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens and the like.

  Examples of the carbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, allylcarbonyloxy group, cyclohexylcarbonyloxy group and other aliphatic hydrocarbon carbonyloxy groups, phenylcarbonyloxy group, methylphenylcarbonyloxy And aromatic hydrocarbon carbonyloxy groups such as groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogens and the like.

The term “two or more R ² may be bonded to each other to form a cyclic structure” described as R ^{2 in the} above general formulas (I) and (Ia) means that 2 to 4 R ² are bonded, It means a case in which each becomes a divalent to tetravalent organic group as a whole. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure; an alkenyl group such as an ethylenyl, propylenyl, and butenyl group; an aralkylene group such as a methylenephenylene group; and an arylene group such as phenylene, naphthylene, and anthracenylene An oxy group or a dioxy group of these alkylene group, alkenyl group, aralkylene group, and arylene group, which are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen, or the like; Also good.

In addition, the term “two or more R ³ may be bonded to each other to form a cyclic structure” described as R ³ in the general formulas (I) and (Ib) means that two or three R ³ are bonded. , As a whole, means a case where each becomes a divalent or trivalent organic group. For example, an alkylene group such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure by combining with an Si atom; an alkenyl group such as an ethylenyl, propylenyl, and butenyl group; an aralkylene group such as a methylenephenylene group; a phenylene, naphthylene And arylene groups such as anthracenylene; these alkylene groups, alkenyl groups, aralkylene groups, oxy groups or dioxy groups of arylene groups, and further include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, It may be substituted with halogen or the like.

R ^{2 in the} general formulas (I) and (Ia) 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 availability of raw materials, a hydrogen atom; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group Aryloxy groups such as phenoxy group, p-tolyloxy group, m-tolyloxy group, o-tolyloxy group; phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, etc. Unsubstituted or alkyl group or / and alkoxy group or / and hydroxyl-substituted aryl group; methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. Substituents selected from linear or cyclic alkyl groups are more preferred. 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, etc., an unsubstituted or alkyl group or / and an alkoxy group or / and a hydroxyl group-substituted aryl group; Substituents selected from chain or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, octyl and cyclohexyl are more preferred. In the case where two or more R ² are bonded to each other to form a cyclic structure, it is not particularly limited, but together with the benzene ring to which R ² is bonded, a 1-(-2-hydroxynaphthyl) group, 1- ( Organic groups that form polycyclic aromatic groups such as a (-4-hydroxynaphthyl) group are preferred.

R ^{3 in the} general formulas (I) and (Ib) is not particularly limited, but is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, from the viewpoint of easy availability of raw materials, hydrogen atoms; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, p- Aryloxy groups such as tolyloxy group, m-tolyloxy group, o-tolyloxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, unsubstituted or alkyl group or / And alkoxy groups or / and hydroxyl-substituted aryl groups; linear or cyclic such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. A substituent selected from alkyl groups is more preferred. A hydrogen atom; a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group, etc., an unsubstituted or alkyl group or / and an alkoxy group or / and a hydroxyl group-substituted aryl group; a methyl group Substituents selected from chain or cyclic alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, and cyclohexyl group are more preferable.

  In the general formulas (I) and (Ib), m represents an integer of 1 to 4, and 1 or 2 is preferable from the viewpoint of easy availability of raw materials. In general formula (I), p represents a number of 0 or more, but p is a number arbitrarily determined depending on the starting material and the production method, and is not particularly limited from the viewpoint of the effect of the present invention.

YH in the general formula (I) is an organic group having 0 to 18 carbon atoms having one or more releasable protons (H ⁺ ), and is bonded to one or more R ² to form a cyclic structure. Also good. YH is, for example, a group in which a hydrogen atom is bonded to a group 16 atom such as a hydroxyl group, a mercapto group, or a hydroseleno group; a carbon having a carboxyl group such as a carboxyl group, a carboxymethyl group, a carboxyethyl group, or a carboxyphenyl group or a carboxynaphthyl group A monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxythienyl group, or a hydroxypyridyl group; Can be mentioned.

In addition, when YH in the formula (I) is bonded to one or more R ² to form a cyclic structure, for example, YH is combined with the benzene ring to which it is bonded to 2-(-6-hydroxynaphthyl). And a divalent organic group forming a hydroxy-substituted polycyclic aromatic group such as a group).

  Among the YHs exemplified above, although not particularly limited, a hydroxyl group in which an oxygen atom and a hydrogen atom are bonded, or a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group, a hydroxyfuryl group, a hydroxythienyl group, A monovalent organic group having a phenolic hydroxyl group such as a hydroxypyridyl group is preferred.

A preferred form of the compound represented by the formula (I) is not particularly limited, but at least one of R ¹ is a substituted or unsubstituted aromatic hydrocarbon group from the viewpoint of availability of raw materials. More preferably, all of R ¹ are substituted or unsubstituted aromatic hydrocarbon groups, more preferably all of R ¹ are phenyl groups, and at least one of R ² , more preferably all are hydrogen atoms. And at least one of R ³ is a substituted or unsubstituted aromatic hydrocarbon group, and YH is a monovalent organic group having a hydroxyl group or a phenolic hydroxyl group.

  The compound represented by the above general formula (I) is not particularly limited as long as the target compound can be produced. However, one embodiment of the present invention includes a production method by reacting an intramolecular phosphonium salt with a silanol compound. Intramolecular phosphonium salts and silanol compounds are readily available compounds, and the desired compounds can be easily produced by reacting them. Therefore, according to the production method of the present invention, it is possible to produce a compound useful as a curing accelerator on an industrial scale.

That is, the production method according to the present invention is for producing a compound represented by the above general formula (I), and comprises an intramolecular phosphonium salt represented by the following general formula (Ia) and the following general formula (Ib): It reacts with the silanol compound shown by characterized by the above-mentioned.

(In the formula, each R ¹ is independently selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, all of which may be the same or different. R ¹ may be bonded to each other to form a cyclic structure;
R ² is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different, and two or more R ² May be bonded together to form a ring structure,
Y ⁻ is an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms having one or more releasable protons, and is bonded to one or more R ² to form a cyclic structure. Also good)

(In the formula, each R ³ is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, and a substituted or unsubstituted organic group having 1 to 18 carbon atoms, all of which may be the same or different. The above R ³ may be bonded to each other to form a cyclic structure,
m represents an integer of 1 to 4)
Note that R ¹ and R ² in the general formula (Ia) and R ³ and m in the general formula (Ib) are as described above. Y in the general formula (Ia) ^- is one of the protons is an organic group desorbed from an organic group of 0-18 carbon atoms having one or more releasable protons (H ^+), one or more R ² May be combined with each other to form a ring 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, a hydroxy 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 thienyl group and a hydroxypyridyl group.

Moreover, when Y < ^- > in Formula (Ia) couple | bonds with one or more R < ² > and forms a cyclic structure, for example, Y < ^- > is 2-(-6) together with the benzene ring to which it couple | bonds. And a divalent organic group that forms a group in which a proton is eliminated from a hydroxyl group of a hydroxy polycyclic aromatic group such as a -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 group having an oxygen anion formed by elimination of a proton from a phenolic hydroxyl group such as a hydroxypyridyl group.

  The compound represented by the general formula (Ia) is not particularly limited, but addition reaction of tri-substituted phosphonioarylates and tri-substituted phosphines with substituted or unsubstituted 1,4-benzoquinones. Product (2-trisubstituted phosphonio (4-hydroxy) arylate) is preferred. For example, a tri-substituted phosphonioarylate can be prepared through a dehydrohalogenation step after reacting a tri-substituted phosphine with a halogenated hydroxyaryl compound using a metal catalyst as necessary. Further, for example, an addition reaction product (2-trisubstituted phosphonio (4-hydroxy) arylate) of tri-substituted phosphine and substituted or unsubstituted 1,4-benzoquinones is substituted or unsubstituted 1,4. -It can be prepared by addition reaction with benzoquinones. Such compounds and their production methods are described in Patent Documents 2 and 3.

  On the other hand, the compound represented by the general formula (Ib) is not particularly limited, but is triphenylsilanol, trimethylsilanol, trisubstituted silanols such as triethylsilanol, diphenylsilanediol, dimethylsilanediol, diethylsilanediol, Disubstituted silanediols such as methylphenylsilanediol are preferred. Such compounds are sold as reagents, and can be obtained from, for example, Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Sigma Aldrich Japan Co., Ltd., Shin-Etsu Chemical Co., Ltd., Amax Co., Ltd., etc. is there.

  In the production method according to the present invention, a solvent can be used when the compound of the general formula (Ia) is reacted with the compound of (Ib). The solvent that can be used is not particularly limited as long as the reaction proceeds. However, a solvent in which at least a part of the raw material is soluble in the solvent is preferable. When the raw material becomes insoluble in the solvent, the reaction tends to hardly proceed. Specifically, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol and diethylene glycol, ether solvents such as diethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran, N, N -Examples include amide solvents such as dimethylformamide and N, N-dimethylacetamide, ester solvents such as ethyl acetate and γ-butyrolactone, and solvents such as water. These may be used alone or in combination of two or more. May be used.

  The reaction temperature between the compounds represented by the general formulas (Ia) and (Ib) is not limited as long as the reaction proceeds and the product is stably maintained. The product can be obtained by removing all or part of the solvent from the resulting reaction mixture as necessary, followed by conventional treatments such as filtration and drying.

  As mentioned above, although the novel compound by this invention and its manufacturing method were demonstrated, the compound of this invention is useful as a hardening accelerator. Then, the curable resin composition which uses the compound by this invention as a hardening accelerator is demonstrated below.

  The curable resin composition contains (A) a curing accelerator and (B) a curable resin, and (A) the curing accelerator includes one or more compounds according to the present invention described above. It is characterized by including. Such a curable resin composition according to the present invention may further contain (C) a curing agent and (D) an inorganic filler in the components (A) and (B). Moreover, what added various additives, such as a coupling agent, an ion exchanger, a mold release agent, a stress relaxation agent, a flame retardant, and a coloring agent, may be added as needed. Hereinafter, main components constituting the curable resin composition according to the present invention will be described.

(A) Curing Accelerator In the curable resin composition according to the present invention, it is essential to use one or more curing accelerators according to the present invention as a curing accelerator. May be used in combination of one or more. There is no restriction | limiting in particular if the compounding quantity of the (A) hardening accelerator in a composition can achieve a hardening promotion effect. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the resin composition, the total amount of (A) the curing accelerator is preferably 0.1 to 100 parts by weight of the total (B) curable resin. It is desirable to blend 10 parts by weight, more preferably 1 to 7.0 parts by weight. When the blending amount is less than 0.1 parts by weight, it is difficult to cure in a short time, and when it exceeds 10 parts by weight, the curing rate is too fast and a good molded product may not be obtained.

  Known curing accelerators that can be used in combination with the curing accelerator according to the present invention include, for example, 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene- Cycloamidine compounds such as diazabicycloalkenes such as 7 and derivatives thereof; phenol novolak salts thereof and these compounds include 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-benzoquinone, phenyl-1,4-benzoquinone, etc. A compound having intramolecular polarization formed by adding a compound having a π bond such as a quinone compound or diazophenylmethane; Tertiary amines such as min, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole , Imidazoles such as 2-heptadecylimidazole, tetra-substituted phosphonium / tetra-substituted borates such as tetraphenylphosphonium / tetraphenyl borate; 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl borate, etc. Tetraphenylboron salts of: triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, (Alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris ( Organic phosphines such as tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; complexes of these organic phosphines and 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-ben Compounds having intramolecular polarization formed by adding a quinone compound such as quinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and a compound having a π bond such as diazophenylmethane; 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'-hydroxybiphenyl And compounds having intramolecular polarization obtained through a dehydrohalogenation step after reacting with a halogenated phenol compound such as ruthenium (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; from the viewpoint of curability, it has intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound and then dehydrohalogenating. Compounds are preferred.

  When the above-mentioned known curing accelerator is used in combination to constitute the (A) curing accelerator, the content of the one or more curing accelerators according to the present invention relative to the total amount of the (A) curing accelerator is preferably 30 in total. It is desirable that the content be at least 50% by weight, more preferably at least 50% by weight. When the content of the curing accelerator according to the present invention is less than 30% by weight, the curability and / or fluidity at the time of moisture absorption decreases, and the effect achievable by the present invention tends to decrease.

(B) Curable Resin The (B) curable resin that can be used in the present invention is not particularly limited as long as curing is accelerated by the (A) curing accelerator according to the present invention. For example, an epoxy resin, a phenol resin, a silicon resin, an amino resin, an unsaturated polyester resin, a diallyl phthalate resin, and an alkyd resin can be used. One of these resins can be used alone, or two or more can be used in combination. It doesn't matter. Especially, it is preferable to contain an epoxy resin as (B) curable resin from a viewpoint that the hardening acceleration effect by the (A) hardening accelerator by this invention is fully exhibited.

(B) When using an epoxy resin as a component of curable resin, the epoxy resin which has a 2 or more epoxy group in 1 molecule can be used. Such an epoxy resin is not particularly limited. For example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F including phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and the like. And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. A novolac-type epoxy resin obtained by epoxidizing a novolac resin obtained by heating;
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;
A sulfur atom containing epoxy resin is mentioned, These may be used independently or may be used in combination of 2 or more type.

  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, An epoxidized product of an aralkyl type phenol resin such as a salicylaldehyde type epoxy resin, a copolymer type epoxy resin of naphthols and phenols, a phenol aralkyl resin, or a naphthol aralkyl resin is preferable, and any one of them may be used alone. Two or more kinds may be used in combination. 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 atom is substituted in R ⁸ are 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.), which is a hydrogen atom, and 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 of 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. , Indicates a positive 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 others are hydrogen atoms 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 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; n is an average value; 10 indicates a positive number)

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, and n is an average value. 10 indicates a positive number)

Although it will not specifically limit if it is an epoxy resin containing a sulfur atom as a sulfur atom containing type epoxy resin, 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 6, 6 when the position where the oxygen atom is substituted in R ¹³ is 4 and 4 ', 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, Number)

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 novolac type phenol resin such as phenol novolak, cresol novolak, naphthol novolak or the like is glycidyl etherified or the like. Epoxy resins epoxidized using a technique are preferable, and for example, epoxy resins represented by the following general formula (VI) are more preferable. 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, and i is an integer of 0 to 3, n Is an average value and represents a positive 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 the epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) in which 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. And represents a positive 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.), and the like are available as commercial products.

(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, and i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value and represents a positive number from 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.) where i = 0, j = 0, and k = 0 are available as commercial products.

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, i is an integer of 0 to 3, j Is an integer of 0 to 2, k is an integer of 0 to 4, p is an average value of 0 to 1 and l and m are average values of 0 to 11 positive numbers (l + m) Represents a positive number from 1 to 11)
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.), which is an epoxy resin mixed with an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms in a weight ratio of 80:20, is available as a commercial product. is there. Further, among the epoxy resins represented by the following general formula (XI), ES21-R (trade name of Nippon Steel Chemical Co., Ltd.) in which R ²¹ is a methyl group, i = 1, j = 0, and k = 0. Etc. are available as commercial products.

(In the formulas (X) and (XI), R ^{37 to} R ^{41 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, and i is 0 to 3). , J is an integer from 0 to 2, and k is an integer from 0 to 4)

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ 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 ⁴¹ 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) needs to be in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the component (B) becomes high, so that of the curable resin composition Viscosity at the time of melt molding also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is preferably set in the range of 0-4.

  As mentioned above, although the specific example of the preferable epoxy resin which can be used for the curable resin composition by this invention was demonstrated along the said general formula (II)-(XI), as a more specific preferable epoxy resin, a reflow crack-proof From the viewpoint of properties, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is mentioned, and from the viewpoint of moldability and heat resistance, 4'-bis (2,3-epoxypropoxy) -biphenyl.

(C) Curing Agent In the curable resin composition according to the present invention, (C) a curing agent can be used as necessary. (B) When an epoxy resin is used as the curable resin, the usable curing agent is not particularly limited as long as it is a compound capable of curing 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. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint that the effect of the (A) curing accelerator is sufficiently exhibited, a phenol resin is preferable.

(C) There is no restriction | limiting in particular as a phenol resin which can be used as a hardening | curing agent. For example, it may be a phenol resin having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent, and in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol. A compound having two phenolic hydroxyl groups;
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 these 2 or more types is mentioned, These may be used independently or may be used in combination of 2 or more types.

  Among the above-mentioned phenol resins, from the viewpoint of reflow crack resistance, aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins are used. 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 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 phenol resin.

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, and all may be the same or different, and i is 0 to 3 , K is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a positive number of 0 to 10)
Among the phenol resins represented by the above general formula (XII), MEH-7851 (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 = 0, i = 0, k = 0, XLC (trade name, manufactured by Mitsui Chemicals), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), etc. 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. And represents a positive 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, and i is an integer of 0 to 3, k Is an integer from 0 to 4, n is an average value and represents a positive number from 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 available as a commercial product. .

(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, and i is an integer of 0 to 3, k Is an integer from 0 to 4, q is an integer from 0 to 5, l and m are each an average value and a positive number from 0 to 11 (l + m) is a positive number from 1 to 11)

  The novolac 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, k Is an integer from 0 to 4, n is an average value and represents a positive number from 0 to 10)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) is, for example, that all i ²² R ^{22 in} 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 needs to be in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curable resin component becomes high, so the curable resin composition The viscosity at the time of melt molding of the product also increases, 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 preferably set in the range of 0-4.

  When the epoxy resin is used as the (B) curable resin in the curable resin composition according to the present invention and the phenol resin is used as the (C) curing agent of the epoxy resin, the components (B) and (C) The blending ratio is preferably set in the range of 0.5 to 2.0 in terms of the ratio of hydroxyl equivalents of all phenol resins to the epoxy equivalents of all epoxy resins (number of hydroxyl groups in phenol resin / number of epoxy groups in epoxy resin). The ratio is more preferably 0.7 to 1.5, and still more preferably 0.8 to 1.3. When the ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the cured product tends to be inferior in heat resistance, moisture resistance, and electrical characteristics. On the other hand, when the ratio exceeds 2.0, the phenol resin 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 lowered. Tend.

(D) Inorganic filler (D) An inorganic filler can be further mix | blended with the curable resin composition of this invention as needed. In particular, when the curable resin composition is used as a molding material for sealing, it is preferable to blend (D) an inorganic filler. The (D) inorganic filler used in the present invention may be one generally used for a molding material for sealing, and is not particularly limited. For example, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, Examples include talc, clay, mica and other fine powders, or beads obtained by spheroidizing these. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  (D) Although there will be no restriction | limiting in particular if the compounding quantity of an inorganic filler will acquire the effect of this invention, It is preferable that it is the range of 55-90 volume% with respect to curable 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 is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the curable resin composition increases, the fluidity tends to decrease, and molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (D) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the curable 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 filling property to fall.

  From the viewpoint of fluidity, the particle shape of (D) inorganic filler is preferably spherical rather than square, and (D) the particle size distribution of inorganic filler is preferably distributed over a wide range. For example, when blending 75% by volume or more of the inorganic filler, it is preferable that 70% by weight or more of the filler be spherical particles and distributed over a wide range of 0.1 to 80 μm. Since such an inorganic filler tends to have a close-packed structure, a curable resin composition excellent in fluidity can be obtained with little increase in the viscosity of the material even when the blending amount is increased.

(Various additives)
In the curable resin composition according to the present invention, in addition to the above-described component (A) curing accelerator, (B) curable resin, (C) curing agent, and (D) inorganic filler as necessary, the following examples are given. Various additives such as a coupling agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a colorant may be added. However, the curable 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)
In the sealing curable resin composition of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, etc., as necessary, in order to enhance the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane 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 (D) 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-aminoethyl) ) Aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzyl) Silane coupling agents such as aminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; isopropyltriisostearoyl titanate, Isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditride) Ruphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate , Titanate cups such as isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate Ring agents, and two or more of these can be used alone. You may use it in combination. Among these, a coupling agent having a secondary amino group is preferable from the viewpoints of fluidity and wire flow.

(Ion exchanger)
An anion exchanger can be mix | blended with the curable resin composition of this invention as needed. In particular, when a curable resin composition is used as a molding material for sealing, an anion exchanger may be blended from the viewpoint of improving moisture resistance and high-temperature storage characteristics of an electronic component device including an element to be sealed. preferable. 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 is mentioned, These can be used individually or in combination of 2 or more types. Among these, hydrotalcite represented by the following general formula (XIX) is preferable.

(Chemical formula 21)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XIX)
(0 <X ≦ 0.5, m is a positive number)
The amount of these anion exchangers is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions, but is in the range of 0.1 to 30% by weight with respect to (B) curable resin. 1 to 5% by weight is more preferable.

(Release agent)
In the curable 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 thereof 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, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. It may be used in combination of two or more. Among them, an oxidized or non-oxidized polyolefin wax is 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 (B) the curable resin. 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. 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 a polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (B) curable resin, and 0.5 to 3 weight% is more preferable.

(Stress relaxation agent)
The curable resin composition of the present invention can contain a stress relaxation agent such as silicone oil and silicone rubber powder, if necessary. By blending 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 curable 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. The blending amount of the flame retardant is not particularly limited as long as the flame retardant effect is achieved. .

(Coloring agent)
Moreover, you may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara.

  The curable resin composition of the present invention described above 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, melted and kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. More specifically, for example, a method in which predetermined amounts of the above-described components are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooled, and pulverized. Can be obtained at The resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

  The above-mentioned curable resin composition according to the present invention can be suitably used as an element sealing material in an electronic component device. 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 curable resin composition of the present invention. More specifically, for example, after fixing a semiconductor element on a lead frame and connecting a terminal portion and a lead portion of an element such as a bonding pad by wire bonding or bump, the curable resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin) TCP (Tape Carrier), which is a general resin-encapsulated IC such as Small Outline Package (TQFP) and a semiconductor chip that is connected to a tape carrier with bumps by a curable resin composition of the present invention. Package), semiconductor chips connected to wiring formed on wiring boards and glass, wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid IC, multi-chip module in which active elements such as diestors, diodes, thyristors and / or passive elements such as capacitors, resistors and coils are sealed with the curable 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 on the back surface, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the curable resin composition of the present invention is used. Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed. 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 curable resin composition of the present invention, a low-pressure transfer molding method is most commonly used, 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 by the Example shown below.

(Preparation of curing accelerator)
Prior to the preparation of the curable resin composition, the compounds used as curing accelerators in each Example according to the present invention were prepared according to Synthesis Examples 1 to 9 shown below. In each synthesis example, 4-triphenylphosphoniophenolate, 2-triphenylphosphoniophenolate, 3-triphenylphosphoniophenolate, 2,6-dimethyl-4-triphenylphosphonate, which are starting materials, are used. Niophenolate, 3-tri-p-tolylphosphoniophenolate, and cyclohexyldiphenylphosphoniphenolate were synthesized according to the method described in JP-A No. 2004-156036, respectively.

Moreover, the analysis of the compound prepared by each synthesis example was implemented in accordance with the following method.
(1) ¹ H-NMR
The compound was dissolved in about 0.5 ml of heavy acetone, put into a φ5 mm sample tube, and measured with AV-300M manufactured by Bruker BioSpin. The shift value was based on CHD ₂ C (═O) CD ₃ (2.04 ppm) contained in a trace amount in the solvent.
(2) ³¹ P-NMR
The compound was dissolved in about 0.5 ml of deuterated methanol or deuterated acetone, put into a φ5 mm sample tube, and measured with AV-300M manufactured by Bruker BioSpin. The shift value was based on a phosphoric acid aqueous solution (0 ppm).
(3) IR
Using FTS 3000MX manufactured by Bio-Rad, measurement was performed according to the KBr method.

(Synthesis Example 1)
10.9 g (30.8 mmol) of 4-triphenylphosphoniophenolate was dispersed (partially dissolved) in 100 ml of acetone, and 10.0 g (46.2 mmol) of diphenylsilanediol was added to the solution while stirring. The pale yellow 4-triphenylphosphoniophenolate powder in the solution gradually turned white. Such a change is considered because diphenylsilanediol is soluble in acetone, and 4-triphenylphosphoniophenolate partially dissolved in acetone reacts with diphenylsilanediol and is gradually consumed. It is presumed to be caused by precipitation as a salt of -triphenylphosphoniophenolate and diphenylsilanediol. The reaction mixture was stirred at room temperature for 12 hours, then filtered and dried to give the product as 16.3 g white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, spectra shown in FIGS. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XX) (hereinafter referred to as “compound 1”). The yield was 93%.

(Synthesis Example 2)
4-Triphenylphosphoniophenolate (30.0 g, 84.6 mmol) was dispersed (partially dissolved) in 60 ml of acetone and 30 ml of distilled water, and 18.3 g (84.6 mmol) of diphenylsilanediol was stirred into the solution. Added. As diphenylsilanediol was added, 4-triphenylphosphoniophenolate once dissolved and immediately a white powder precipitated. The reaction mixture was stirred at room temperature for 30 minutes, and about 30 ml of acetone was distilled off with an evaporator, followed by filtration and drying to obtain a product as 43.5 g of a white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, the same spectrum as in Synthesis Example 1 was obtained. Therefore, the product is considered to have the structure represented by the formula (XX) shown earlier as in Synthesis Example 1 (hereinafter referred to as “Compound 1”). The yield was 90%.

(Synthesis Example 3)
10.9 g (30.8 mmol) of 4-triphenylphosphoniophenolate was dispersed (partially dissolved) in 100 ml of acetone, and 25.5 g (46.2 mmol) of triphenylsilanol was added to the solution while stirring. The pale yellow 4-triphenylphosphoniophenolate powder in the solution gradually turned white. This change is considered because triphenylsilanol is soluble in acetone, and 4-triphenylphosphoniophenolate partially dissolved in acetone reacts with triphenylsilanol and is gradually consumed. This is presumably due to precipitation as a salt of triphenylphosphoniophenolate and triphenylsilanol. The reaction mixture was stirred at room temperature for 12 hours, then filtered and dried to give the product as 25.3 g of a white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, spectra shown in FIGS. 4 to 6 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXI) (hereinafter referred to as “compound 2”). The yield was 91%.

(Synthesis Example 4)
4-Triphenylphosphoniophenolate (20.0 g, 56.4 mmol) was dissolved in acetone (40 ml) and distilled water (20 ml), and triphenylsilanol (31.2 g, 112.5 mmol) was added to the solution while stirring. As soon as triphenylsilanol was added, a white powder precipitated. The reaction mixture was stirred at room temperature for 30 minutes, and about 30 ml of acetone was distilled off by an evaporator, followed by filtration and drying to obtain 45.7 g of a product as a white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, the same spectrum as in Synthesis Example 3 was obtained. Therefore, the product is considered to have the structure represented by the formula (XXI) shown earlier as in Synthesis Example 3 (hereinafter referred to as “Compound 2”). The yield was 89%.

(Synthesis Example 5)
6.4 g (18.1 mmol) of 2-triphenylphosphoniophenolate was dissolved in 30 ml of acetone and 7.5 ml of distilled water, and 15.0 g (54.3 mmol) of triphenylsilanol was added to the solution with stirring. When triphenylsilanol was added, white powder gradually precipitated. The reaction mixture was stirred at room temperature for 2 hours, then filtered and dried to give the product as 13.8 g white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in heavy acetone), and IR measurement. As a result, spectra shown in FIGS. 7 to 9 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXII) (hereinafter referred to as “compound 3”). The yield was 84%.

(Synthesis Example 6)
6.4 g (18.1 mmol) of 3-triphenylphosphoniophenolate was dispersed (partially dissolved) in 60 ml of acetone, and 15.0 g (54.3 mmol) of triphenylsilanol was added to the solution while stirring. When triphenylsilanol was added, white powder precipitated immediately after the solubility of 3-triphenylphosphoniophenolate increased (the amount of undissolved powder decreased). The reaction mixture was stirred at room temperature for 2 hours, then filtered and dried to give 13.6 g of the product as a white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, spectra shown in FIGS. 10 to 12 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXIII) (hereinafter referred to as “compound 4”). The yield was 83%.

(Synthesis Example 7)
6.9 g (18.1 mmol) of 2,6-dimethyl-4-triphenylphosphoniophenolate was dissolved in 30 ml of acetone and 7.5 ml of distilled water, and 15.0 g (54. 3 mmol) was added. When triphenylsilanol was added, white powder gradually precipitated. The reaction mixture was stirred at room temperature for 2 hours, then filtered and dried to give 9.8 g of the product as a white solid.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in deuterated methanol), and IR measurement. As a result, spectra shown in FIGS. 13 to 15 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXIV) (hereinafter referred to as “compound 5”). The yield was 82%.

(Synthesis Example 8)
Disperse (partially dissolved) 7.2 g (18.1 mmol) of 3-tri-p-tolylphosphoniophenolate in 50 ml of acetone, and add 15.0 g (54.3 mmol) of triphenylsilanol to the solution while stirring. did. When triphenylsilanol was added, white powder precipitated immediately after the solubility of 3-tri-p-tolylphosphoniophenolate increased (the amount of undissolved powder decreased). The reaction mixture was stirred at room temperature for 2 hours, then filtered and dried to give the product as 15.8 g white solid.

The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in heavy acetone), and IR measurement. As a result, spectra shown in FIGS. 16 to 18 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXV) (hereinafter referred to as “compound 6”). The yield was 92%.

(Synthesis Example 9)
6.6 g (18.1 mmol) of cyclohexyldiphenylphosphoniophenolate was dispersed (partially dissolved) in 30 ml of acetone, and 15.0 g (54.3 mmol) of triphenylsilanol was added to the solution while stirring. Once triphenylsilanol was added, it dissolved once. Then, white powder gradually precipitated by adding 60 ml of hexane. After adding hexane and stirring for about 6 hours, the product was obtained as 9.1 g of a white solid by filtration and drying.
The obtained product was subjected to ¹ H-NMR measurement, ³¹ P-NMR measurement (measured in heavy acetone), and IR measurement. As a result, spectra shown in FIGS. 19 to 21 were obtained. When each spectrum was identified, the product is considered to have a structure represented by the following formula (XXVI) (hereinafter referred to as “compound 7”). The yield was 55%.

[Preparation of curable resin composition and evaluation of its properties]
(Examples 1-14 and Comparative Examples 1-10)
In each example, the following was used.

(Epoxy resin)
Epoxy resin 1: 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.)
Epoxy resin 2: Diphenylmethane skeleton epoxy resin having an epoxy equivalent of 192 and a melting point of 79 ° C. (trade name YSLV-80XY, manufactured by Nippon Steel Chemical Co., Ltd.)
Epoxy resin having flame retardancy (brominated epoxy resin): Brominated bisphenol A type epoxy resin (curing agent) having an epoxy equivalent of 393, a softening point of 80 ° C., and a bromine content of 48% by weight
Curing agent 1: Phenol aralkyl resin having a hydroxyl equivalent weight of 176 and a softening point of 70 ° C. (trade name: Millex XL-225, manufactured by Mitsui Chemicals, Inc.)
Curing agent 2: Biphenyl skeleton type phenol resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.)

(Curing accelerator)
Curing accelerator 1: Compound 1 prepared in Synthesis Example 1 or 2
Curing accelerator 2: Compound 2 prepared in Synthesis Example 3 or 4
Curing accelerator 3: Compound 3 prepared in Synthesis Example 5
Curing accelerator 4: Compound 4 prepared in Synthesis Example 6
Curing accelerator 5: Compound 5 prepared in Synthesis Example 7
Curing accelerator 6: Compound 6 prepared in Synthesis Example 8
Curing accelerator 7: Compound 7 prepared in Synthesis Example 9
Curing accelerator A: Triphenylphosphine (comparative curing accelerator)
Curing accelerator B: Addition reaction product of triphenylphosphine and 1,4-benzoquinone Curing accelerator C: 4-triphenylphosphoniophenolate Curing accelerator D: 2-triphenylphosphoniophenolate Additive 1: Diphenyl Silanediol Additive 2: Triphenylsilanol Note that Additives 1 and 2 corresponding to the curing accelerators A to D and the precursor of the curing accelerator according to the present invention were used for comparison.

Inorganic filler: Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation)
Release agent: Carnauba wax (manufactured by Celerica NODA)
Flame retardant: antimony trioxide By blending the above components in parts by weight shown in Tables 1 and 2, respectively, and kneading rolls under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, Examples 1 to 14, respectively And the curable resin composition of Comparative Examples 1-10 was obtained.

  Next, each curable resin composition obtained by Examples 1-14 and Comparative Examples 1-10 was evaluated by the various tests shown below. The evaluation results are shown in Tables 3 and 4. The curable 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) Spiral flow (fluidity index)
Using a spiral flow measurement mold in accordance with EMMI-1-66, the curable resin composition was molded under the above conditions, and the flow distance (cm) was measured.

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

(3) Hardness at the time of moisture absorption When the curable resin composition was allowed to stand for 72 hours under the condition of 25 ° C./50% RH, it was measured using a Shore D type hardness tester under the condition (2).

(4) Reflow crack resistance 1
A test silicon chip having dimensions of 8 × 10 × 0.4 mm was mounted on a 42 alloy frame using silver paste. Furthermore, a QFP80 pin package having an outer dimension of 14 × 20 × 2.0 mm was produced by molding and post-curing using the curable resin composition under the above conditions. The package was made to absorb moisture for 168 hours at 30 ° C. and 85% RH, and then reflowed at 215 ° C. for 90 seconds using a vapor phase reflow device to check for cracks and test The number of packages with crack generation relative to the number of packages (5) was evaluated.

(5) Reflow crack resistance 2
Evaluation was performed under the same conditions as in the above (4) except that moisture was absorbed for 168 hours at 85 ° C. and 60% RH.

(6) Reflow crack resistance 3
Evaluation was performed under the same conditions as in the above (4) except that moisture was absorbed for 168 hours under the conditions of 85 ° C. and 85% RH.

(7) High temperature storage characteristics A test element in which an aluminum wiring having a line / space of 10 μm was formed on a silicon substrate having an outer size of 5 × 9 mm and an oxide film of 5 μm was used. This test element was mounted on a 16-pin DIP (Dual Inline Package) 42 alloy lead frame partially silver-plated using silver paste. Next, the bonding pads of the element and the inner leads were connected by Au wires at 200 ° C. with thermonic wires. Further, a package was produced by molding and post-curing under the above conditions using a curable resin composition. After the package produced as described above is stored for 500 hours and 1000 hours at 200 ° C., it is taken out and subjected to a continuity test to determine the number of defective packages. Rated by the number of.

  As can be seen from Tables 3 and 4, Examples 1 to 14 containing the curing accelerator according to the present invention all have fluidity, heat hardness, heat hardness during moisture absorption, reflow crack resistance and high temperature storage characteristics. Excellent results.

  On the other hand, in Comparative Examples 1 to 10 containing a different type of curing accelerator from the curing accelerator according to the present invention, compared with Examples having the same resin composition except for the curing accelerator, the fluidity is inferior. Yes. In particular, Comparative Examples 4, 5, 9 and 10 in which the precursors of the curing accelerators used in the examples were added separately are inferior in fluidity as compared with the examples based on the present invention.

1 is a ¹ H-NMR spectrum of Compound 1 prepared as a curing accelerator according to the present invention. 3 is a ³¹ P-NMR spectrum of Compound 1 prepared as a curing accelerator according to the present invention. 2 is an IR spectrum of Compound 1 prepared as a curing accelerator according to the present invention. ¹ is a ¹ H-NMR spectrum of Compound 2 prepared as a curing accelerator according to the present invention. 3 is a ³¹ P-NMR spectrum of Compound 2 prepared as a curing accelerator according to the present invention. 2 is an IR spectrum of Compound 2 prepared as a curing accelerator according to the present invention. ¹ is a ¹ H-NMR spectrum of Compound 3 prepared as a curing accelerator according to the present invention. 3 is a ³¹ P-NMR spectrum of Compound 3 prepared as a curing accelerator according to the present invention. 2 is an IR spectrum of Compound 3 prepared as a curing accelerator according to the present invention. It is a ^{1 H-NMR} spectrum of Compound 4 was prepared as a curing accelerator according to the present invention. It is a ³¹ P-NMR spectrum of Compound 4 prepared as a curing accelerator according to the present invention. 4 is an IR spectrum of Compound 4 prepared as a curing accelerator according to the present invention. It is a ^{1 H-NMR} spectrum of compound 5 prepared as a curing accelerator according to the present invention. It is a ³¹ P-NMR spectrum of compound 5 prepared as a curing accelerator according to the present invention. FIG. 5 is an IR spectrum of Compound 5 prepared as a curing accelerator according to the present invention. FIG. It is a ^{1 H-NMR} spectrum of Compound 6 was prepared as a curing accelerator according to the present invention. It is a ³¹ P-NMR spectrum of compound 6 prepared as a curing accelerator according to the present invention. FIG. 5 is an IR spectrum of Compound 6 prepared as a curing accelerator according to the present invention. FIG. It is a ^{1 H-NMR} spectrum of compound 7 was prepared as a curing accelerator according to the present invention. 3 is a ³¹ P-NMR spectrum of Compound 7 prepared as a curing accelerator according to the present invention. FIG. 5 is an IR spectrum of Compound 7 prepared as a curing accelerator according to the present invention. FIG.

Claims (6)

A compound represented by the general formula (I):

(In the formula, R ¹ are each independently selected from the group consisting of Kaoru aromatic hydrocarbon radical alicyclic hydrocarbon group and C1-18 C1-18, all be the same or different You may,
R ² are each independently a hydrogen atom, a hydroxyl group, selected from the group consisting of an aromatic hydrocarbon group having alicyclic aliphatic hydrocarbon group and C1-18 C1-18, all be the same or different Or two or more R ² may be bonded to each other to form a cyclic structure,
R ³ are each independently a hydroxyl group, selected from the group consisting of an aromatic hydrocarbon group having alicyclic aliphatic hydrocarbon group and C1-18 C1-18, also all be the same or different Well, two or more R ³ may be bonded to each other to form a cyclic structure,
YH is a monovalent organic group having a hydroxyl group or a phenolic hydroxyl group having 1 to 18 carbon atoms,
m represents an integer of 1 to 4, and p represents a number of 0 or more. ) Each R ¹ is independently a 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) Selected from the group consisting of a group, 1- (4-hydroxynaphthyl) group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, and cyclohexyl group All may be the same or different,
Each R ² is independently a hydrogen atom, hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, methyl group, ethyl group, propyl group, isopropyl group, A 1- (2-hydroxynaphthyl) group in combination with a group consisting of a butyl group, a sec-butyl group, a tert-butyl group, an octyl group, and a cyclohexyl group, and a benzene ring to which ^two R ² are bonded. And 1- (4-hydroxynaphthyl) group, all may be the same or different,
Each R ³ independently represents a hydroxyl group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, The compound according to claim 1, which is selected from the group consisting of a sec-butyl group, a tert-butyl group, an octyl group, and a cyclohexyl group, all of which may be the same or different. The compound according to claim ¹ , wherein all of R ¹ are phenyl groups. All R ² is A compound according to claim 1, characterized in that a hydrogen atom.   YH is a hydroxyl group, The compound of any one of Claims 1-4 characterized by the above-mentioned. A method for producing the compound according to claim 1, wherein an intramolecular phosphonium salt represented by the following general formula (Ia) is reacted with a silanol compound represented by the following general formula (Ib). Method.

(In the formula, R ¹ are each independently selected from the group consisting of Kaoru aromatic hydrocarbon radical alicyclic hydrocarbon group and C1-18 C1-18, all be the same or different You may,
R ² are each independently a hydrogen atom, a hydroxyl group, selected from the group consisting of Kaoru aromatic hydrocarbon radical fat aliphatic hydrocarbon group and C1-18 C1-18, even all the same Two or more R ² may be bonded to each other to form a cyclic structure,
Y ^- is a monovalent one organic group proton is eliminated from the organic group having a phenolic hydroxyl group of the hydroxyl group or 1 to 18 carbon atoms. )

(Wherein, R ³ are each independently a hydroxyl group, selected from the group consisting of Kaoru aromatic hydrocarbon radical fat aliphatic hydrocarbon group and C1-18 C1-18, all the same However, they may be different, and two or more R ³ may be bonded to each other to form a cyclic structure,
m shows the integer of 1-4. )

Images