WO2006112396A1 - 硬化促進性化合物-シリカ複合体、硬化促進性化合物-シリカ複合体の製造方法、硬化促進剤、硬化性樹脂組成物及び電子部品装置 - Google Patents
硬化促進性化合物-シリカ複合体、硬化促進性化合物-シリカ複合体の製造方法、硬化促進剤、硬化性樹脂組成物及び電子部品装置 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- Curing accelerating compound-silica composite method for producing curing accelerating compound-silica composite, curing accelerator, curable resin composition, and electronic component device
- the present invention relates to a curing accelerating compound silica composite, a curing accelerator containing the curing accelerating compound silica composite, a curable resin composition containing the curing accelerator, and a sealing material Curable resin composition suitable for various electronic and electrical component uses such as laminates, molding materials, paint materials or adhesive materials, and an element sealed using the curable resin composition
- the present invention relates to an electronic component device.
- curable resins such as epoxy resins are widely used. Since these curable resin is required to be fast curable 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.
- a curing accelerator is generally used in the curable resin composition.
- compositions based on epoxy resins are widely used. The reason is that epoxy resin is balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.
- the combination of orthocresol novolac type epoxy resin and phenol novolac hardener has the above characteristics.
- V has become the mainstream base resin for molding materials for IC encapsulation.
- epoxy resin compositions generally also contain nitrogen such as tertiary amine, quaternary ammonia, 1,8 diazabicyclo [5.4.0] undecene-7 (DBU), imidazole, etc.
- Curing accelerators such as compounds and phosphorus compounds such as phosphines and phosphonium salts are used.
- microcapsules do not show any potential if the capsule breaks during the production of the rosin composition, and if it is strengthened so that it does not break during production, it will break gradually during the curing reaction, so it will cure quickly. There was a problem. Under such circumstances, the present situation is that storage and transportation of the resin composition are carried out at a low temperature by using a curing accelerator that is prioritized for practically important fast curability.
- the package is not directly exposed to a high temperature, whereas in the surface mounting type package, the wiring is performed. After temporarily fixing the surface of the board, the package is directly exposed to a high soldering temperature because it is processed with a solder bath or reflow equipment. As a result, if the knocker absorbs moisture, the moisture absorption may rapidly expand during soldering, leading to package cracks, which is a major problem in knocker molding.
- such epoxy resin composition has a phosphorus-based curing accelerator such as triphenylphosphine and nitrogen-containing curing such as 1,8 diazabicyclo [5.4.0] undecene-7.
- a phosphorus-based curing accelerator such as triphenylphosphine
- nitrogen-containing curing such as 1,8 diazabicyclo [5.4.0] undecene-7.
- the present invention provides a curing accelerator capable of exhibiting excellent storage stability, a curable resin composition containing the same, and an electronic device including an element sealed with the curable resin composition. It is an object to provide a component device.
- the present invention relates to the following (1) to (13).
- Curing accelerating property obtained by sol-gel reaction of at least one compound selected from the compound represented by the following general formula (I 1) and its partial condensate in the presence of a curing accelerating compound and water.
- Compound Silica composite obtained by sol-gel reaction of at least one compound selected from the compound represented by the following general formula (I 1) and its partial condensate in the presence of a curing accelerating compound and water.
- n 0 or 1
- R 1 is selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and may combine with one or more R 2 to form a cyclic structure.
- R 2 represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms. Selected from the group consisting of an amino group and a substituted or unsubstituted carbo-oxy group having 2 to 18 carbon atoms, all of which may be the same or different, and two or more R 2 are bonded to each other to form a cyclic structure May be. )
- the curing accelerating compound is a phosphine compound, a phosphonium salt compound, a cyclic amidin compound, a cyclic amidium salt compound, an aminic compound, or an ammonium salt compound.
- the curing accelerating compound silica composite according to (1), which is at least one compound selected.
- each R 3 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. 2 or more R 3 may combine with each other to form a cyclic structure
- R 4 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. 4 may be bonded to each other to form a cyclic structure,
- a curing accelerator comprising at least one type of the curing accelerating compound-silica composite according to any one of (1) to (4).
- a curable resin composition comprising (A) the curing accelerator according to (5) and (B) a curable resin.
- the epoxy resin contained in the curable resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolak.
- the curable resin composition according to any one of to (10).
- (C) Hardener power aralkyl-type phenolic resin, dicyclopentagen-type phenolic resin, salicylaldehyde-type phenolic resin, benzaldehyde-type phenolic resin and aralkyl-type phenolic resin The curable resin composition according to any one of the above (7) to (11), which contains at least one resin selected from the group consisting of:
- An electronic component device including an element sealed with the curable resin composition according to any one of (7) to (12).
- FIG. 1 is an IR ⁇ vector of the compound prepared in Preparation Example 1 as a curing accelerating compound-silica composite according to the present invention.
- FIG. 2 is an IR ⁇ vector of the compound prepared in Preparation Example 2 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 3 is an IR ⁇ vector of the compound prepared in Preparation Example 3 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 4 is an IR ⁇ vector of the compound prepared in Preparation Example 4 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 5 is an IR ⁇ vector of the compound prepared in Preparation Example 5 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 6 is an IR ⁇ vector of the compound prepared in Preparation Example 6 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 7 is an IR ⁇ vector of the compound prepared in Preparation Example 7 as a curing accelerating ICH compound silica composite according to the present invention.
- FIG. 8 shows the preparation of a curing-accelerating ichigo compound silica composite according to the present invention in Preparation Example 8.
- FIG. 9 is an IR ⁇ vector of the compound prepared in Preparation Example 109 as a curing-accelerating compound silica composite according to the present invention.
- FIG. 10 is an IR ⁇ vector of the compound prepared in Preparation Example 10 as a curing-accelerating composite silica composite according to the present invention.
- FIG. 11 is an IR ⁇ vector of the compound prepared in Preparation Example 11 as a curing accelerating compound-silica composite according to the present invention.
- FIG. 12 is an IR vector of the compound prepared in Preparation Example 12 as a curing-accelerating composite silica composite according to the present invention.
- FIG. 13 is an IR vector of the compound prepared in Preparation Example 13 as a curing accelerating compound-silica composite according to the present invention.
- FIG. 14 is an IR ⁇ vector of the compound prepared in Preparation Example 14 as a curing accelerating compound-silica composite according to the present invention.
- the curing accelerator according to the present invention can be effectively used for accelerating the curing of the curable resin, and is represented by the following general formula (I 1) in the presence of a curing accelerating compound and water.
- a curing accelerating compound obtained by subjecting at least one compound selected from a compound and a partial condensate thereof to a sol-gel reaction and a silica composite is characterized.
- n 0 or 1
- R 1 is selected from the group consisting of a hydrogen atom and a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and may combine with one or more R 2 to form a cyclic structure.
- R 2 represents a functional group capable of reacting with a phenolic hydroxyl group, and each independently represents a halogen atom, a hydroxyl group, a substituted or unsubstituted oxy group having 1 to 18 carbon atoms, or a substituted or unsubstituted group having 0 to 18 carbon atoms.
- Amino group and substituted or unsubstituted carbo-loxy group having 2 to 18 carbon atoms Two or more R 2 s may be selected from the group of force and may be all the same or different, and may form a cyclic structure by bonding to each other.
- the "substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms" described as R 1 in the general formula (1-1) has 1 to 18 carbon atoms and is substituted. It is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be substituted or unsubstituted.
- 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, Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, aryl group, vinyl group and other aliphatic hydrocarbon groups, and alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, halogens Examples thereof include those substituted with an atom, a group containing an epoxy group such as a glycidyloxy group, an epoxycyclohexyl group, and an epoxy group, a metatalyloxy group, a mercapto group, an imino group, a ureido group, and an isocyanate group.
- the substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group.
- the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and the like.
- Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as a phenyl group and a tolyl group, a dimethylphenol group, an ethylphenol group, a butylphenol group, and a tert-butylphenol.
- Alkyl group-substituted aryl groups such as alkenyl groups, methoxyphenyl groups, ethoxyphenol groups, butoxyphenyl groups, tert-butoxyphenyl groups such as tert-butoxyphenyl groups, etc., and further include alkyl groups, alkoxy groups , Aryl group, aryloxy group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, metathaloxy group, mercapto group, imino group , A ureido group, an isocyanate group or the like.
- R 1 in the general formula (I-1) is not particularly limited, but is a monovalent substituent selected from the group consisting of an optionally substituted alkyl group and aryl group. It is preferable that Among these, from the viewpoint of easy availability of raw materials, a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group.
- the “halogen atom” described as R 2 in the general formula (1-1) includes a fluorine atom, a chlorine atom, an odor atom, and an iodine atom.
- the “substituted or unsubstituted oxy group having 1 to 18 carbon atoms” described as R 2 in the general formula (1-1) includes, for example, “substituted or unsubstituted having 1 to 18 carbon atoms”.
- an “aliphatic hydrocarbon oxy group” and a “substituted or unsubstituted aromatic hydrocarbon oxy group having 1 to 18 carbon atoms” and the like More specific examples are as follows.
- Examples of the above-mentioned "substituted or unsubstituted aliphatic hydrocarbonoxy group having 1 to 18 carbon atoms” include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec butoxy group , tert-butoxy group, a cyclopropyl O alkoxy group, Kishiruokishi group cyclohexylene, cyclopentylene Ruo alkoxy group, Ariruokishi group, Okishi structures aliphatic hydrocarbon groups described above is an oxygen atom bonded as R 1 such Biniruokishi group And groups in which they are substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.
- Examples of the "substituted or unsubstituted aromatic hydrocarbonoxy group having 1 to 18 carbon atoms” include, for example, a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, Butoxyphenoxy group, phenoxyphenoxy group, etc., such as an oxy group having a structure in which an oxygen atom is bonded to the aromatic hydrocarbon group described above as R 1 , and the like, and an alkyl group, an alkoxy group, an aryl group , An aryloxy group, an amino group, a halogen atom and the like.
- the "substituted or unsubstituted amino group having 0 to 18 carbon atoms" described as R 2 in the general formula (I-1) includes, for example, an unsubstituted amino group and a substituted group having 1 to 18 carbon atoms. Or an unsubstituted aliphatic hydrocarbon amino group, aromatic hydrocarbon amino group, dialiphatic hydrocarbon amino group, diaromatic hydrocarbon amino group, aliphatic hydrocarbon aromatic hydrocarbon amino group, and carbon number 0 to 18 substituted or unsubstituted silylamino groups are included. More specific examples are as follows.
- Examples of the "substituted or unsubstituted aliphatic hydrocarbon amino group having 1 to 18 carbon atoms" include, for example, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, an n-butylamino group, sec- Butylamino group, tert-Butylamino group, Pentylamino group, Hexylamino group, Octylamino group, Decylamino group, Dodecylamino group, Cyclopentylamino group, Cyclohexylamino group, Cycloheptylamino group, Arylamino group, Buruamino group, Cyclopentenylamino Group, an amino group substituted by the aliphatic hydrocarbon group described above as R 1 such as a cyclohexenylamino group, and the aliphatic hydrocarbon group part thereof are an alkyl
- Examples of the "substituted or unsubstituted aromatic hydrocarbon amino group having 1 to 18 carbon atoms” include, for example, a phenylamino group, a naphthylamino group, a tolylamino group, a dimethylphenylamino group, an ethylphenolamino group, a butylphenol.
- Substituted with the aromatic hydrocarbon group described above as R 1 such as -lamino group, tert-butylphenylamino group, methoxyphenylamino group, ethoxyphenylamino group, butoxyphenylamino group, tert-butoxyphenylamino group, etc.
- Examples include amino groups, and those obtained by substituting these aromatic hydrocarbon groups with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, and the like.
- dialiphatic hydrocarbon amino group having 1 to 18 carbon atoms dimethylamino group, jetylamino group, dipropylamino group, diisopropylamino group, di-n-butylamino group, di-sec —Butylamino group, di-tert-Butylamino group, dicyclopen Tyramino group, dicyclohexylamino group, dicycloheptylamino group, ethylmethylamino group, methylisopropylamino group, methyl-n-butylamino group, methyl-sec-butylamino group, methyl-tert-butylamino group, methylcyclohexylamino group, diarylamino group, Amino group substituted by two aliphatic hydrocarbon groups described above as R 1 such as dibutylamino group, dicyclopentalumino group, dicyclohex
- Examples of the "substituted or unsubstituted diaromatic hydrocarbon amino group having 1 to 18 carbon atoms" include diphenylamino group, dinaphthylamino group, ditolylamino group, bis (dimethylphenol) amino group, bis ( Ethylphenol) amino group, bis (butylphenol) amino group, bis (tert-butylphenol) amino group, bis (methoxyphenyl) amino group, bis (ethoxyphenyl) amino group, bis (butoxyphenol) A) an amino group, a bis (tert-butoxyphenyl) amino group, etc., and an amino group substituted by two aromatic hydrocarbon groups described above as R 1 , and an alkyl group, an alkoxy group, an aryl group, Examples include those substituted with an aryloxy group, amino group, halogen atom, or the like.
- Examples of the "substituted or unsubstituted aliphatic hydrocarbon aromatic hydrocarbon amino group having 1 to 18 carbon atoms" include, for example, methylphenolamino group, methylnaphthylamino group, butylphenolamino group and the like.
- R 1 may be an amino group substituted by the aliphatic hydrocarbon group or aromatic hydrocarbon group described above.
- Examples of the "substituted or unsubstituted silylamino group having 0 to 18 carbon atoms” include, for example, an unsubstituted silylamino group, trimethylsilylamino group, triethylsilylamino group, triphenylsilylamino group, methyl (trimethylsilyl) Aliphatic groups described above as R 1 for silyl groups such as amino groups, methyl (triphenylsilyl) amino groups, phenyl (trimethylsilyl) amino groups, and phenyl (triphenylsilyl) amino groups, and Z or amino groups
- Examples include silylamino groups substituted with hydrocarbon groups and Z or aromatic hydrocarbon groups, and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. It is done.
- the "substituted or unsubstituted carbonyloxy group having 2 to 18 carbon atoms" described as R 2 in the general formula (I-1) includes, for example, "substituted or unsubstituted carbon atoms having 2 to 18 carbon atoms”.
- Aliphatic hydrocarbons A “carbonyloxy group” and a “substituted or unsubstituted aromatic hydrocarbon group having 2 to 18 carbon atoms”. More specific examples are as follows.
- Examples of the above-mentioned "substituted or unsubstituted aliphatic hydrocarbon carbooxy group having 2 to 18 carbon atoms" include, for example, a methyl carbo oxy group, an eth yl carbo oxy group, a propyl force carbonyl oxy group, an isopropyl carbo oxy group.
- the aliphatic hydrocarbon carbo-oxy group described above as R 1 such as a bululcarboxoxy group, and those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, etc. Is mentioned.
- Examples of the above-mentioned "substituted or unsubstituted aromatic hydrocarbon carbooxy group having 2 to 18 carbon atoms" include, for example, a phenyl-carboxyl group, a methyl-phenyl-carboxyl group, and an ethyl-phenyl-carboxyl group.
- R 1 such as a ruoxy group, a methoxyphenyl carboxy group, a butoxy phen carboxy group, a phenoxy phen carboxy group, etc., and the aromatic hydrocarbon carboxy group described above as an alkyl group, Examples thereof include those substituted with a alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom and the like.
- R 2 in the general formula (1-1) and "2 or more R 2 may be bonded to each other to form a cyclic structure" is 2 or more R 2 are bonded to each other This means that the whole is an organic group with two or more valences.
- an alkylene group such as ethylene, propylene, butylene, pentylene, hexylene, etc., which can form a cyclic structure by bonding with a Si atom
- an alkyl group such as an ethylene, propylene, butylene group
- a dioxy group of an aralkylene group such as a methylenephenol group, which may be substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen, or the like.
- R 2 in the above general formula (I-1) is not particularly limited, but is easily available, and therefore is substituted or unsubstituted having a chlorine atom, a hydroxyl group, or a carbon number of 1 to 8.
- a monovalent oxy group is preferred.
- the viewpoint power of reactivity is more preferably a chlorine atom, a hydroxyl group or an oxy group.
- at least one of R 2 is a hydroxyl group or an oxy group having 1 to 8 carbon atoms. More preferably.
- ⁇ amino propyl trimethoxy silane, gamma-ureidopropyl trimetrexate Kishishiran, .gamma. black port trimethoxysilane, ⁇ - Aniri Silane combination of ⁇ 1 such as propyltrimethoxysilane, j8 (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, etc. Things. These specific examples are all available as industrial products or reagents.
- the compound represented by the general formula (1-1) may be a commercially available compound as an industrial product or a reagent, or a compound synthesized by a known method.
- silane compounds in which R 2 is an oxy group are preferred from the viewpoints of long-term stability of cured products and long-term reliability of electronic components.
- a compound obtained by self-condensing one compound represented by 1) or two or more compounds The compound produced by the reaction and condensation is included.
- the condensation reaction can be carried out using water if necessary, and adding a known substance that promotes the condensation reaction such as acid or alkali as necessary.
- the following reaction formula (
- R 2 is common to general formula (I-1).
- the degree of condensation can be adjusted according to the reaction conditions. In general, the concentration of a substance that promotes the reaction, such as strong alkali or strong acid, is high, the reaction temperature is high! However, the degree of condensation tends to increase, and the degree of condensation tends to decrease under weak conditions such as low concentrations of substances that promote reactions such as weak alkalis and weak acids and low reaction temperatures.
- the number of molecules of the compound that can be condensed is not particularly limited, but on average it is preferably 1.5 or more molecules, more preferably 2 to 50 molecules, and 2 to 20 molecules. It is even more preferable.
- Silane compounds that can be used in the present invention include compounds in which they are partially condensed as described above, and some of them remain as compounds represented by the above general formula (I 1) without condensation. But ...
- the partial condensate of the silane compound represented by the general formula (I 1) used in the present invention is used by condensing the silane compound represented by the general formula (1-1).
- commercially available products may be used, or these may be combined.
- the compound represented by the general formula (I 1) and the partial condensate power thereof are selected as the at least one compound selected from the above formula (I 1 ) Is preferably a partial condensate of the compound represented by
- the curing accelerating compound of the present invention used in the silica composite is not limited, and examples thereof include the following.
- Cyclic amidine compounds such as 2-methylimidazole, 2-phenolimidazole, 2-phenol 4-methylimidazole, 2-heptadecylimidazole, and their derivatives, ⁇ cyclic amidium salt compounds>
- a salt such as a phenol novolak salt of the cyclic amidine compound and
- These compounds include maleic anhydride, 1,4 monobenzoquinone, 2,5 toluquinone, 1,4-naphthoquinone, 2,3 dimethylbenzoquinone, 2,6 dimethylbenzoquinone, 2,3 dimethoxy 5-methyl-1,4
- Intramolecular polarization with addition of ⁇ -bonded compounds such as monobenzoquinone, 2,3 dimethoxy-1,4 monobenzoquinone, ferro 1,4 monobenzoquinone, diazophenol methane, etc.
- DBU tetraphenolate salt DBN tetraphenolate salt, 2-ethyl-4-methylimidazole tetraphenolate salt, ⁇ ⁇ Cyclic amidium salt compounds such as methylmorpholine tetraphenolate salt,
- Tertiary amines such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives,
- Triphenylphosphine diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl'alkoxyphenyl) phosphine, tris (dialkylphenyl) Phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) Phosphine compounds such as phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, complexes of these phosphines with organic borons,
- Tetraphenyl phospho-umu 'Tetra-substituted phospho-mums such as'tetra-phenol' Tetra-substituted borate
- Phosphorus salt compounds such as salts of tetra-phenyl phospho-um and phenol compounds, Etc.
- a tertiary phosphine and Z or a phosphorous salt compound V it is preferable to use a tertiary phosphine and Z or a phosphorous salt compound V, and the phosphorous represented by the general formula (1-2) is preferred. It is more preferable to use a compound or an intermolecular salt thereof.
- each R 3 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. 2 or more R 3 may combine with each other to form a cyclic structure
- R 4 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. 4 forces S may be bonded to each other to form a cyclic structure,
- the "substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms" described as R 3 in the above general formula (1-2) has 1 to 18 carbon atoms and may be substituted. Or, it is meant to include an aliphatic hydrocarbon group and an aromatic hydrocarbon group which may be unsubstituted.
- 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, Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, aryl group, vinyl group and other aliphatic hydrocarbon groups, and alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, amino groups, and the like Examples thereof include those substituted with a halogen atom or the like.
- the substituted or unsubstituted aliphatic hydrocarbon group also includes a substituted or unsubstituted alicyclic hydrocarbon group.
- the substituted or unsubstituted alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and the like.
- Examples of the substituted or unsubstituted aromatic hydrocarbon group include aryl groups such as phenyl group and tolyl group, dimethylphenol group, ethylphenol group, butylphenol group, and tert-butylphenol.
- Alkyl group-substituted aryl groups such as alkenyl groups, methoxyphenyl groups, ethoxyphenol groups, butoxyphenyl groups, tert-butoxyphenyl groups such as tert-butoxyphenyl groups, etc., and further include alkyl groups, alkoxy groups , An aryl group, an aryloxy group, an amino group, a halogen atom or the like may be substituted.
- R 3 may be bonded to each other to form a cyclic structure” described as R 3 in the general formula (I-2) means that 2 or 3 R 3 are bonded. In this case, it means that each becomes a divalent or trivalent hydrocarbon group as a whole.
- alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene that can be bonded to Si atoms to form a cyclic structure
- alkyl groups such as ethylene, propylene, and butylene groups
- alkyl groups such as ethylene, propylene, and butylene groups
- aralkylene groups such as a lenylene group
- arylene groups such as phenylene, naphthylene, and anthracerene
- alkyl groups alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms, and the like. It's replaced.
- R 3 in the general formula (I 2) is not particularly limited, but may be a monovalent substituent selected from the group consisting of an optionally substituted alkyl group and aryl group. Preferably there is. Among these, from the viewpoint of easy availability of raw materials, a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group.
- unsubstituted such as — (4-hydroxynaphthyl)
- the "substituted or unsubstituted organic group having 1 to 18 carbon atoms" described as R 4 in the above general formula (1-2) has 1 to 18 carbon atoms and may be substituted or non-substituted.
- An optionally substituted aliphatic hydrocarbon group, aromatic hydrocarbon group, and aliphatic hydrocarbon or aromatic hydrocarbon oxy group, carbol group, oxycarbol group, and carboloxy group are bonded. Means to include things.
- Examples of the aliphatic hydrocarbonoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec butoxy group, a tert butoxy group, a cyclopropyloxy group, and a cyclohexyloxy group.
- An oxygen group having a structure in which an oxygen atom is bonded to the above-described aliphatic hydrocarbon group such as a cyclopentyloxy group, a aryloxy group, and a vinyloxy group, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group.
- aromatic hydrocarbonoxy group examples include an oxygen atom in the above aromatic hydrocarbon group such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, and a phenoxyphenoxy group.
- an oxy group having a structure in which is bonded and those substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.
- Examples of the carbol group include a formyl group, a acetyl group, and an ethyl carbol.
- aromatic hydrocarbon carbonyl group such as arylcarbonyl
- aromatic hydrocarbon carbonyl group such as phenol group, methyl furol group, etc.
- Examples of the oxycarbonyl group include, for example, aliphatic carbonization such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a allyloxycarbonyl group, a cyclohexyloxyl group, and the like.
- Aromatic hydrocarbon oxycarbonyl groups such as hydrogenoxycarbonyl group, phenoxycarbonyl group, methylphenoxycarbonyl group, etc., and alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups , Halogen atoms and the like are substituted.
- Examples of the carboxoxy group include, for example, an aliphatic hydrocarbon carbonyloxy group such as a methylcarboxoxy group, an ethylcarbonyloxy group, a butylcarboxoxy group, a arylcarboxoxy group, a cyclohexylcarbonyloxy group, and the like.
- Aromatic hydrocarbon carboxy-oxy groups such as phenylcarbonyloxy group, methylphenylcarbonyloxy group, etc., and those substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc. Things.
- the general formula (I - 2) terms described as R 4 and "2 or more R 4 are each other, bonded may form a cyclic structure in the" a two to four R 4 Are combined to form divalent to tetravalent organic groups as a whole.
- aralkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene that can form a cyclic structure, alkenyl groups such as ethylenyl, propylenyl, and butylene groups, aralkylene groups such as methylene phenylene groups, and phenols.
- arylene groups such as lene, naphthylene, anthracene, and the like, alkylene groups, alkenyl groups, aralkylene groups, oxy groups or dioxy groups of the arylene groups, and these include alkyl groups, alkoxy groups, aryl groups, It may be substituted with an aryloxy group, amino group, hydroxyl group, halogen atom or the like.
- R 4 in the general formula (1-2) is not particularly limited, but may be a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, aryl group, alkoxy group, aryloxy group. Groups are preferred.
- substituents that can be 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.
- R 5 In the case where two or more R 5 are bonded to each other to form a cyclic structure, there is no particular limitation, but in combination with the benzene ring to which R 4 is bonded, a 1- (1-2 hydroxynaphthyl) group, 1 (1-4 An organic group that forms a polycyclic aromatic group such as a (hydroxy naphthyl) group is preferred.
- an organic group in which one proton is eliminated from an organic group having 0 to 18 carbon atoms and having one or more releasable protons (H +), R 4 may be bonded to each other to form a cyclic structure.
- monovalent organic radicals in which hydrogen atoms are bonded to group 16 atoms such as sesame hydroxyl groups, mercapto groups, and hyde-opened seleno groups Proton-eliminated groups, carboxyl groups, carboxymethyl groups, carboxyethyl groups, carboxy groups C1-C18 monovalent organic group having a carboxyl group such as a phenyl group carboxynaphthyl group, a group from which a proton of a carboxylic acid is eliminated, a hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl group
- a monovalent organic group having 1 to 18 carbon atoms having a phenolic hydroxyl group such as a hydroxy group, a hydroxyfuryl group, a hydroxy chayl group, and a hydroxy pyridyl group, and the like, and a group in which a phenolic proton is eliminated.
- Y— in the general formula (I 2) is bonded to one or more R 4 to form a cyclic structure, for example, in combination with the benzene ring to which it is bonded.
- the hydroxyl group protons from which a proton is eliminated, or a hydroxyphenol group, a hydroxyphenylmethyl group, a hydroxynaphthyl group. It is preferably a monovalent organic group having an oxygen ion formed by elimination of a phenolic hydroxyl group proton such as a hydroxyfuryl group, a hydroxycell group, or a hydroxypyridyl group.
- Y— in the general formula (I 2) is bonded to one or more R 4 to form a cyclic structure
- a group in which a hydroxyl group proton of a hydroxy polycyclic aromatic group such as a 2-(-6-hydroxynaphthyl) group is eliminated together with a benzene ring to which it is bonded is preferable.
- the intermolecular salt of the phosphonium compound represented by the general formula (I2) is not limited, but the phosphonium compound represented by the formula (I2) and phenol, naphtho A compound having a phenolic hydroxyl group, such as a compound previously exemplified as a phenol compound having two or more phenolic hydroxyl groups in the molecule, a silanol such as triphenylsilanol, diphenolsilanediol, trimethylsilanol, etc.
- Examples thereof include compounds having a group, organic acids such as oxalic acid, acetic acid and benzoic acid, and intermolecular salt compounds with inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid and nitric acid.
- Specific examples of the phosphonium compound represented by the general formula (I2) are not limited to the following, but include tertiary phosphine, 1,4 benzoquinone, methyl-1,4 benzoquinone, 2 , 3 Dimethoxy-1,4 benzoquinone, 2,5 Dimethoxy-1,4 benzoquinone, Methoxy-1,4 benzoquinone, 2,3 Dimethyl-1,4 benzoquinone, 2,5-Dimethyl-1,4 benzoquinone, Methyl-1, 4 Monobenzoquinone, 2,5-di-t-butyl-1,4 monobenzoquinone, tert-butinole 1,4 monobenzoquinone, pheninole 1,4 monobenzoquinone, 1,4 naphthoquinone, etc. .
- Tertiary (p-methoxyphenyl) phosphine tris- (o-methoxyphenyl) phosphine, tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, bis (p-) Methoxyphenyl) phenylphosphine, bis (o-methoxyphenyl) phosphine, di-p-tolylphenylphosphine, di-o-tolylphenolphosphine, di-m-tolylphenolphosphine, diphenyl- ( Triarylphosphine such as p-methoxyphenyl) phosphine, diphenyl- (o-methoxyphenyl) phosphine, diphenyl-p-tolylphosphine, diphenyl-2-o-tolylphosphine, diphenyl-2-m-tolylphosphine, triphen
- Trialkylphosphine such as tricyclohexylphosphine, tributylphosphine, trioctylphosphine,
- dialkyl aryl phosphines such as dibutyl phenyl phosphine, dicyclohexyl phenyl phosphine, and dioctyl phenyl phosphine.
- the curing accelerating compound of the present invention is composed of at least one compound selected from the compound represented by the above general formula (I1) and its partial condensate in the presence of the curing accelerating compound and water. If it is a hardening acceleration
- the ratio of the curing accelerating compound and silica of the silica composite is within the range where the effects of the present invention can be obtained. If it is, it will not specifically limit, but 0.0-50 force S is preferable, 0.1-10 is more preferable 0.5-5 is still more preferable. When the ratio of the curing accelerating compound and silica is less than 0.02, the rapid curability tends to be lowered, and when it is more than 50, the storage stability as the effect of the present invention tends to be lowered.
- the method for producing a silica composite includes a curing accelerating compound.
- the silica composite is characterized by subjecting at least one compound selected from the compound represented by the general formula (I 1) and a partial condensate thereof in the presence of a curing accelerating compound and water to a sol-gel reaction. To do.
- the compound represented by the above general formula (I 1) and its partial condensate force The reaction of at least one selected compound produces a curing accelerating compound silica composite. If it is a method, there is no restriction
- the solvent that can be used in the present invention is not particularly limited as long as it does not adversely affect the formation of the curing accelerating compound-silica composite, and is an aromatic hydrocarbon solvent such as toluene or xylene.
- Aromaphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, etc.
- Alcohol solvents such as jetyl ether, diethylene glycol dimethyl ether and tetrahydrofuran, amide solvents such as N, N dimethylformamide and N, N-dimethylacetamide, ester solvents such as ethyl acetate and y butyrolataton , Solvents such as water, and those alone May be used in combination or two or more may be used in combination.
- ether solvents such as jetyl ether, diethylene glycol dimethyl ether and tetrahydrofuran
- amide solvents such as N, N dimethylformamide and N, N-dimethylacetamide
- ester solvents such as ethyl acetate and y butyrolataton
- Solvents such as water, and those alone May be used in combination or two or more may be used in combination.
- the solvent is preferably removed by filtration, distillation, drying or the like after the reaction from the viewpoint of voidless properties.
- the reaction temperature is limited as long as the reaction proceeds and the curing accelerating compound is stably held. is not.
- the reaction rate of the compound represented by the general formula (I1) and the partial condensate thereof is particularly limited.
- the number of unreacted R 2 groups may be 30% or less based on the total number of R 2 groups in the compound represented by the above general formula (I 1) and its partial condensate at the start of the reaction. It is more preferably 10% or less, and even more preferably 5% or less. Based on the total R 2 groups at the start reaction, it tends to cause the number of R 2 groups of more than 30% the unreacted deterioration of occurrence and the long-term reliability of the voids of the cured product.
- R is generated as a by-product of the condensation reaction of the compound represented by the general formula (1-1) and a partial condensate thereof. Become. Therefore, the production method according to the present invention is preferably provided with a step of removing R from the reaction product by heating as necessary. More specific examples are as follows:
- a by-product may be obtained by heating, Z or distillation under reduced pressure, washing, filtration, etc. as necessary. Removing hydrogen halide from
- a by-product may be obtained by heating, Z or distillation under reduced pressure, washing, filtration, etc. as necessary. Removing any alcohol or allylol;
- a secondary reaction may be carried out by heating and Z or distillation under reduced pressure, washing, filtration, etc. as necessary.
- the product carboxylic acid is removed.
- the curable resin composition according to the present invention comprises (A) a curing accelerator and (B) a curable resin, and (A) the curing accelerator according to the present invention described above.
- Curing acceleration compound It is characterized by containing at least one silica composite.
- the curable resin composition according to the present invention may further contain (C) a curing agent and (D) an inorganic filler in addition to the components (A) and (B).
- various additives such as a coupling agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a coloring agent may be added.
- a coupling agent such as a coupling agent, an ion exchanger, a release agent, a stress relaxation agent, a flame retardant, and a coloring agent may be added.
- one or more curing accelerator compounds according to the present invention are used as a curing accelerator.
- one or more known curing accelerators are used in combination. May be.
- the blending amount of the (A) curing accelerator in the composition is not particularly limited as long as the curing promoting effect can be achieved. However, from the viewpoint of improving the curability and fluidity of the greave composition when it absorbs moisture, (A) the curing accelerator is used as the net hardening accelerator for 100 parts by weight of the total (B) curable fat.
- the total amount is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight.
- the net amount of curing accelerator is an amount obtained by removing the silica content of the curing accelerating compound-silica composite of the present invention from the amount of curing accelerator.
- Curing accelerating compound according to the present invention examples include, for example, 1,5 diazabicyclo [4.3.0] nonene 5, 1,8 diazabicyclo Cyclic amidine compounds such as [5. 4. 0] undecene-7 diazabicycloalkene, 2-methylimidazole, 2-phenolimidazole, 2-ferro-l-methylimidazole, 2-heptadecylimidazole, etc. ,
- These compounds include maleic anhydride, 1,4 monobenzoquinone, 2,5 toluquinone, 1,4-naphthoquinone, 2,3 dimethylbenzoquinone, 2,6 dimethylbenzoquinone, 2,3 dimethoxy 5-methyl-1,4 Intramolecular polarization with addition of ⁇ -bonded compounds such as monobenzoquinone, 2,3 dimethoxy-1,4 monobenzoquinone, ferro 1,4 monobenzoquinone, diazophenol methane, etc.
- a compound having, Cyclic amidonium compounds such as DBU tetraphenolate, DBN tetraphenolate, 2-ethyl-4-methylimidazole tetraphenolate, N-methylmorpholine tetraphenolate,
- Tertiary amines such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives,
- Ammonia such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetra-ethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrabutylhydroxide hydroxide Um salt compounds,
- Triphenylphosphine diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl'alkoxyphenyl) phosphine, tris (dialkylphenyl) Phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) Phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine,
- Phosphinic compounds such as complexes of these phosphines and organic borons
- phosphine compounds and maleic anhydride 1,4 monobenzoquinone, 2,5 toluquinone, 1,4 naphthoquinone, 2,3 dimethylbenzoquinone, 2,6 dimethylbenzoquinone, 2,3-dimethoxy-5-methyl 1,4 benzoquinone
- 'Tetra-substituted phosphonium such as tetraphenols' Tetra-substituted borates, phospho-um salt compounds such as salts of tetraphenyl phosphonium and phenolic compounds, and the like.
- phospho-um salt compounds such as salts of tetraphenyl phosphonium and phenolic compounds, and the like.
- it is preferable to use tertiary phosphine and Z or a phospho-um salt compound it is more preferable to use a phospho-um compound represented by the general formula (I 2) or an intermolecular salt thereof. I like it.
- the curing accelerator is constituted in combination with the above-mentioned known curing accelerator
- the total amount is preferably 30% by weight or more, more preferably 50% by weight or more.
- the content is less than 30% by weight, the storage stability is lowered and the effect achievable by the present invention tends to be lowered.
- the (B) curable resin usable in the present invention is not particularly limited as long as the resin is cured by the (A) curing accelerator according to the present invention.
- epoxy resin, phenol resin, cage resin, amino resin, unsaturated polyester resin, diallyl phthalate resin, alkyd resin, etc. one of these resins is used alone. Even if you use two or more types in combination, Among them, the viewpoint power that the curing acceleration effect by the (A) curing accelerator according to the present invention is sufficiently exhibited is preferably (B) containing epoxy resin as a curable resin.
- epoxy resin having two or more epoxy groups in one molecule can be used.
- epoxy resin is not particularly limited, and examples thereof include phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenol, cresol, xylenol, resorcin, catechol, bis Phenols such as phenol A and bisphenol F, and naphthols such as Z or ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and compounds having an aldehyde group such as formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde With an acidic catalyst or Novolac type epoxy resin obtained by co-condensation of novolac resin; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, stilbene
- Glycidyl ester type epoxy resin of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid;
- Glycidyl-type or methyldaricidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom, such as a phosphorus or isocyanuric acid, is substituted with a glycidyl group;
- Burecyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3, 4 epoxycyclohexylmethyl- 3, 4-epoxycyclohexanecarboxylate, 2— (3, 4 epoxy) cyclohexyl 5, 5— Alicyclic epoxy resin such as spiro (3,4 epoxy) cyclohexane m-dioxane;
- Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin Glycidyl ether of terpene modified phenolic resin
- Trimethylolpropane type epoxy resin Linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; Diphenylmethane type epoxy resin;
- Epoxidized aralkyl-type phenols such as phenol aralkyl resin and naphthol aralkyl resin;
- Sulfur atom-containing epoxy resin These may be used alone or in combination of two or more.
- epoxy resins biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolac type in terms of reflow crack resistance and fluidity Epoxy resin, dicyclopentagen-type epoxy resin, salicylaldehyde-type epoxy resin, copolymerization of naphthols and phenols, type epoxy resin, phenol aralkyl resin, naphthol aralkyl resin, etc.
- Those that are preferred for epoxy resins of aralkyl-type phenol resin may be used alone or in combination of two or more. However, in order to exert their performance, 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. Examples of preferred epoxy resin 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 ( ⁇ ) is preferred.
- V an epoxy resin represented by the following general formula ( ⁇ )
- R 8 is a 3, 3 ', 5, 5 standing cate group when the oxygen atom substitution positions are 4 and 4' positions.
- YX—4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), all of which are hydrogen atoms, 4, 4'-bis (2,3-epoxypropoxy) biphenyl, all R, where R 8 is a hydrogen atom 8 '3 when the position, 3' oxygen atom positions 4 and 4 are replaced out of the case and R 8 a hydrogen atom, 5, 5 other in Tatsuryoku methyl groups are hydrogen atoms
- YL-6121H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), which is a mixed product, is available as a commercial product.
- 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. Value, 0 ⁇ Indicates a positive number of 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 ( ⁇ ) is preferable.
- R 9 is a 3, 3 ', 5, 5 cation group when the oxygen atom substitution positions are 4 and 4' positions.
- the other is a hydrogen atom and all of R 1G is a hydrogen atom, and the three-force methyl group, one-force tert-butyl group of 3, 3 ', 5, 5 and the others are hydrogen atoms.
- ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixture when all of R 1C) are hydrogen atoms, is available as a commercial product.
- R 9 and R 1G represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, each of which may be the same or different, and n is an average value
- the diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but it is represented by the following general formula (IV). Epoxy resin is preferred.
- R 11 are hydrogen atoms, and oxygen atoms in R 12 are substituted, and the positions are 4 and 4 ′ positions 3 and 3 5,5 YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), which is a hydrogen atom and other hydrogen atoms, is commercially available.
- R 11 and R ′′ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different, and n is an average value, Indicates a positive number from 0 to 10.
- the sulfur atom-containing epoxy resin is not particularly limited as long as it is a sulfur atom-containing epoxy resin, and examples thereof include an epoxy resin represented by the following general formula (V): .
- an epoxy resin represented by the following general formula (V): 3 when the position where oxygen atom is substituted in R 13 is 4 and 4 is tert-butyl group 6, 6 YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), which has a S-methyl group and is otherwise a hydrogen atom, is commercially available.
- the novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a novolak type such as phenol novolak, cresol novolak, naphthol novolak, etc.
- An epoxy resin obtained by epoxidizing phenol resin using a technique such as Daricidyl etheri is preferable.
- an epoxy resin represented by the following general formula (VI) is more preferable.
- R 14 and R 15 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different; i is an integer of 0 to 3 , N is an average value and represents a positive number between 0 and 0.)
- the dicyclopentagen-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentagen skeleton as a raw material, but the following general formula (VII)
- the epoxy resin shown is preferred.
- R lb represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different.
- I is an integer of 0 to 3
- n is an average. Value, indicating a positive number between 0 and 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, and a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group.
- the epoxy resin represented by the following general formula (VIII) is preferred, which is preferred to a salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl ether of a salicylaldehyde type phenol resin such as a novolak type phenol resin. preferable.
- R 1 ′ and are 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.
- the copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin prepared from a compound having a naphthol skeleton and a compound having a phenol skeleton, but the naphthol skeleton is not limited.
- R iy to R 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 from 0 to 2, k is from 0 to 4 P represents an integer with a positive value between 0 and 1, 1 and m are average values with 0 to: L 1 positive (1 + m) is 1 to: L 1 positive Indicates. )
- the epoxy resin represented by the general formula (IX) includes a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regularly. And block copolymers containing in block form, any one of which may be used alone or in combination of two or more.
- Epoxidation products of aralkyl type phenolic resins such as phenolic aralkyl resin, naphthol aralkyl resin, biphenol type aralkyl resin, etc.
- Naphthols and dimethoxyparaxylene and bis (methoxymethyl) biphenyl derivatives thereof are not particularly limited as long as they are epoxy resins made from phenolic resins synthesized.
- phenols such as phenol and talesol
- naphthols such as Z or naphthol and dimethylnaphthol
- dimethoxyparaxylene and bis (methoxymethyl) biphenyl are synthesized as glycidyl ethers.
- the epoxy resin represented by the following general formulas (X) and (XI) is more preferable.
- R 37 to R 41 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be all the same or different.
- J is an integer from 0 to 2
- k is an integer from 0 to 4.
- R 8 to R 21 and R 37 to R 41 in the general formulas ( ⁇ ) to (XI) “all may be the same or different” means, for example, the formula ( ⁇ ) This means that all of the 8 to 88 R 8 s may be the same or different. For the other R 9 to R 21 and R 37 to R 41 , it means that all of them may be the same or different depending on the number of each contained in the formula. R 8 to R 21 and R 37 to R 41 may be the same or different. For example, all of R 9 and R 1G may be the same or different.
- ⁇ is in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the component ( ⁇ ) increases, so that the curable resin composition The viscosity at the time of melt molding of the product also increases, which tends to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead).
- the average ⁇ per molecule is preferably set in the range of 0-4.
- the usable curing agent is not particularly limited as long as it is a compound capable of curing epoxy resin.
- phenol compounds such as phenol resin, amine compounds such as diamine and polyamine, organic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, carboxylic acids such as dicarboxylic acid and polycarboxylic acid
- phenol resin is preferable from the viewpoint of (A) the effect of sufficiently exerting the effect of the curing accelerator.
- phenolic resin that can be used as a curing agent.
- resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted which is a phenol resin having two or more phenolic hydroxyl groups in one molecule generally used as a hardener.
- Biphenol and other compounds having two phenolic hydroxyl groups in one molecule phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol 8, bisphenol F, phenol-phenol, and aminophenol Novolac type obtained by condensation or cocondensation of naphthols such as Z or ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene and the like with aldehydes such as formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst Phenol resin;
- phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol 8, bisphenol F, phenol-phenol, and aminophenol Novolac type obtained by condensation or cocondensation of naphthols such as Z or ⁇ -naphthol,
- Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins which are also synthesized with phenols and cocoons or naphthols and dimethoxyparaxylene and bis (methoxymethyl) biphenol;
- Noraxylylene and / or metaxylylene-modified phenolic resin Noraxylylene and / or metaxylylene-modified phenolic resin
- Dicyclopentagen-type phenolic resin dicyclopentagen-type naphthol resin synthesized by copolymerization with phenols and ⁇ or naphthols and dicyclopentagen; cyclopentagen-modified phenolic resin;
- Biphenol type phenolic resin Triphenylmethane phenol resin
- phenolic resins from the viewpoint of reflow crack resistance, aralkyl type phenolic resins, dicyclopentagen type phenolic resins, salicylaldehyde type phenolic resins, and benzaldehyde type and aralkyl type copolymeric phenols. Preferred are rosin and novolac phenolic rosin.
- aralkyl-type phenol resin, dicyclopentagen-type phenol resin, salicylaldehyde-type phenol resin, benzaldehyde- and aralkyl-type copolymer type phenol resin, and novolak-type phenol resin Whether used alone or in combination of two or more, in order to exert their performance, it is necessary to use a total of 30% by weight or more based on the total amount of phenolic resin. It is more preferable to use 50% by weight or more.
- the aralkyl type phenolic resin is not particularly limited as long as it is synthesized from phenols and / or naphthols and dimethyparaxylene or bis (methoxymethyl) biphenyl or a derivative thereof.
- phenolic resin represented by the following general formulas ( ⁇ ) to (XI V) is preferred U.
- R to R are hydrogen atoms or monovalent organic compounds having 1 to 18 carbon atoms. Each may be the same or different, i is an integer from 0 to 3, k is an integer from 0 to 4, j is an integer from 0 to 2, n is an average value, and 0 to 10 Indicates a positive number.
- the dicyclopentagen type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentagen skeleton as a raw material, but the following general formula (XV ) Is preferred.
- XV phenolic resins represented by the following general formula (XV)
- DPP trade name, manufactured by Nippon Petrochemical Co., Ltd.
- 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
- n is an average. Value, indicating a positive number between 0 and 10.
- the salicylaldehyde type phenolic resin is not particularly limited as long as it is a phenolic resin using a compound having a salicylaldehyde skeleton as a raw material, but is represented by the following general formula (XVI) I prefer phenolic rosin.
- R dU and R 31 represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may be all the same or different. Integer, k is an integer from 0 to 4, n is an average value, and represents a positive number from 0 to 10.
- Benzaldehyde-type and aralkyl-type copolymer type phenol resins are particularly limited as long as they are copolymer type phenol resins made from a compound having a benzaldehyde skeleton as a raw material and aralkyl-type phenol resin. Although it is not preferred, phenol resin represented by the following general formula (XVII) is preferred.
- R to 4 each represents 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 from 0 to 3, k Is an integer from 0 to 4, q is an integer from 0 to 5, 1, and m are average values, 0 to: L 1 is a positive number (1 + m) is 1 to: L 1 is a positive number .)
- the novolac type phenol resin includes phenols and / or naphthols and alfa. There is no particular limitation as long as it is a phenolic resin obtained by condensation or cocondensation with a aldehyde under an acidic catalyst, but a phenolic resin represented by the following general formula (XVIII) is preferable.
- R db represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, which may be all 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.
- R 22 to R 36 in the general formula (XII) ⁇ (XVIII) may all respectively be the same or different", for example, the formula (XII) in the i-number of R 22 of It means that all may be the same or different from each other.
- R 23 to R 36 it means that all of them may be the same or different from each other depending on the number of each contained in the formula.
- R 22 to R 36 may be the same as or different from each other.
- all of R 22 and R 23 may be the same or different.
- All of R 3G and R 31 may be the same or different.
- n is in the range of 0 to 10, and when it exceeds 10, (B) the melt viscosity of the curable resin component increases, The viscosity at the time of melt molding of the fat composition 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.
- the blending ratio of the above components (B) and (C) is the total phenolic resin to the epoxy equivalent of all epoxy resin. It is preferable to set the ratio in the range of 0.5 to 2.0 in terms of the ratio of hydroxyl group equivalents (number of hydroxyl groups in phenolic resin Z number of epoxy groups in epoxy resin). 5 is more preferable. 0.8 to 1.3 is still more preferable. If the ratio is less than 0.5, the epoxy resin is insufficiently cured, and the cured product tends to be inferior in heat resistance, moisture resistance and electrical properties.
- the curable resin composition of the present invention may further contain (D) an inorganic filler as required.
- an inorganic filler used in the present invention is not particularly limited as long as it is generally used for molding materials for sealing.
- examples of the inorganic filler having a flame-retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, magnesium-zinc composite hydroxide, and zinc borate. It is done.
- fused silica is preferred from the viewpoint of reducing the linear expansion coefficient
- alumina is preferred from the viewpoint of high thermal conductivity.
- These inorganic fillers may be used alone or in combination of two or more.
- the blending amount of the (D) inorganic filler is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably in the range of 55 to 90% by volume with respect to the curable resin composition. ,.
- These inorganic fillers are formulated 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, the improvement of these properties tends to be insufficient. If the blending amount exceeds 90% by volume, the viscosity of the curable resin composition increases, the fluidity decreases, and molding becomes impossible. It tends to be difficult.
- the average particle size of the (D) inorganic filler is preferably 1 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
- Below L m the viscosity of the curable resin composition rises, and when it exceeds 50 m, the resin component and the inorganic filler are easily separated, resulting in non-uniform cured product and cured product characteristics. Tend to vary, or the filling ability to narrow gaps tends to decrease.
- the particle shape of (D) inorganic filler is preferably spherical rather than square (D)
- the particle size distribution of inorganic filler is preferably distributed over a wide range.
- 70% by weight or more of them be spherical particles and distributed in a wide range of 0.1 to 80 m.
- Such an inorganic filler can easily form a close-packed structure, so that a curable resin composition excellent in fluidity with little increase in the viscosity of the material can be obtained even if the amount is increased.
- curable resin composition in addition to the above-described components (A) curing accelerator, (B) curable resin, (C) curing agent, (D) inorganic filler, if necessary, Various additives such as coupling agents, ion exchangers, mold release agents, stress relieving agents, flame retardants, and coloring agents may be added. However, various additives known in the art may be added to the curable resin composition according to the present invention as needed without being limited to the following additives.
- an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, a ureido may be used as necessary in order to increase the adhesion between the resin component and the inorganic filler.
- Known coupling agents such as various silane compounds such as silane and bur silane, titanium compounds, aluminum chelates, and aluminum Z zirconium compounds can be added.
- the amount of coupling agent is preferably 0.1 to 2.5 wt 0/0 and more preferably from 05 to 5% by weight 0.1 relative to (D) an inorganic filler. Is less than 0.05 wt 0/0 tend to adhesion to the frame is lowered, tends to package formability decreases when more than 5 wt% is there.
- Examples of the coupling agent include vinyltrichlorosilane, butyltriethoxysilane, butyrris (j8-methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, j8 (3,4-epoxycyclohexene).
- An anion exchanger can be blended in the curable resin composition of the present invention as necessary.
- an anion exchanger should be blended from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device having an element to be sealed. Is preferred ⁇ .
- the anion exchanger used in the present invention is not particularly limited but can be a conventionally known one.
- talcite an element selected from magnesium, aluminum, titanium, zirconium and bismuth. These can be used alone or in combination of two or more. Of these, the iodo-talcite represented by the following general formula (XIX) is preferred.
- the amount of these anion exchangers is not particularly limited as long as it is sufficient to capture anions such as halogen ions, but it is in the range of 0.1 to 30% by weight based on (B) curable resin. 1 to 5% by weight is preferable.
- a mold release agent may be blended in order to give good mold releasability from the mold during molding.
- a mold release agent used in this invention A conventionally well-known thing can be used. Examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as acid-polyethylene and non-acidic polyethylene. One of these may be used alone, or two or more may be used in combination. Among them, acid-type or non-acid-type polyolefin waxes are preferred.
- the blending amount is preferably from 0.01 to L0% by weight with respect to (B) curable resin. 1-5% by weight is more preferred. If the blended amount of 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 polyolefin waxes include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series made of hextone. Also, When other release agents are used in combination with the polyolefin-based wax, the blending amount is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight, based on (B) the curable resin.
- the curable resin composition of the present invention can be blended with a stress relaxation agent such as silicone oil or silicone rubber powder, if necessary.
- a stress relaxation agent such as silicone oil or silicone rubber powder
- 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, thermoplastic elastomers such as silicones, styrenes, polyolefins, urethanes, polyesters, polyetherols, polyamides, polybutadienes, NR (natural Rubber), NBR (Atari-tolyl-butadiene rubber), rubber particles such as acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, Examples thereof include rubber particles having a core-shell structure such as a methyl methacrylate-butyl acrylate copolymer, and these may be used alone or in combination of two or more.
- examples of silicone-based flexible agents that are preferred for silicone-based flexible agents include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.
- the curable resin composition of the present invention can be blended with a flame retardant as necessary to impart flame retardancy.
- the flame retardant used in the present invention is not particularly limited, and examples thereof include known organic or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, metal hydroxides, and the like. One kind may be used alone, or two or more kinds may be used in combination.
- the amount of flame retardant added is not particularly limited as long as the flame retardant effect is achieved, but 1 to 30% by weight is preferable to (B) curable resin such as epoxy resin 2 to 15% % Is more preferable.
- the curable resin composition of the present invention described above can be prepared by any technique as long as various components can be uniformly dispersed and mixed.
- a general technique there can be mentioned a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll or an extruder, and then cooled and pulverized.
- a predetermined amount of the above-mentioned components are uniformly stirred and mixed, and then kneaded, cooled, and pulverized with a neater, roll, etastruder or the like that has been heated to 70 to 140 ° C in advance. It can be obtained by a method such as The resin composition is easy to handle if it is tableted with dimensions and weight that match the molding conditions of the knocker.
- An electronic component device includes an element sealed with the above-described curable resin composition.
- Electronic component devices include, for example, lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils And the like, and those in which the element portions are 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 part and a lead part of an element such as a bonding pad with wire bonding bumps, the curable resin composition of the present invention is used.
- DIP Device Inline Package
- PLCC Physical Leaded Chip Carrier
- QFP Quad Flat Package
- SOP Small Outline Package
- SOJ Small Outline J -lead package
- TSOP Thin Small Outline Package
- TQFP Thin Quad Flat Package
- other common resin-encapsulated ICs and semiconductor chips connected to tape carriers with bumps are sealed with the curable resin composition of the present invention.
- Stopped TCP Tape Carrier Package
- active elements such as semiconductor chips, transistors, diodes, thyristors, etc. connected to wiring formed on wiring boards and glass by wire bonding, flip chip bonding, solder, etc.
- COB Chip On Board
- hybrid multi-chip module
- wiring board connected to the back side
- passive elements such as Z or capacitors, resistors, coils, etc. sealed with the curable resin composition of the present invention
- a device is mounted on the surface of an organic substrate on which a terminal is formed for bump or wire bonding. Examples include BGA (Ball Grid Array), CSP (Chip Size Package), etc., in which the element is connected to the wiring formed on the organic substrate and then the element is encapsulated with the curable resin composition of the present invention.
- the curable resin composition of the present invention can also be used effectively for printed circuit boards.
- a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like is used. May be.
- Tetraphenylphosphonium phenoxide was synthesized according to the methods of Synthesis Examples 1 to 7 below.
- Ratio power of preparation It is considered that the ratio of curing acceleration compound-silica is 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. From the measurement of IR ⁇ vector, there is a peak shifted from 4-triphenylphospho-offenolate, which is the raw material, and it is assumed that the structure is changed from 4-triphenylphospho-offenolate. .
- Ratio power of preparation It is considered that the ratio of curing acceleration compound-silica is 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. From the IR ⁇ vector measurement, there is a peak shifted from 2-triphenylphospho-offenolate, which is a raw material, and it is assumed that the structure is changed from 2-triphenylphospho-offenolate. .
- the ratio of curing accelerator compound silica is considered to be 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. 1 From the measurement of the vector, there is a peak shifted from the raw material 2, 6-dimethyl-4 triphenyl phosphophenolate, so there is a change from 2, 6-dimethyl-4-triphenylphosphophenolate. It is assumed that it exists in the structure.
- the ratio of the curing accelerating compound-silica ratio is considered to be 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. From the measurement of IR ⁇ vector, there is a peak shifted from 3- (tri-p-tolylphospho-o) phenolate, which is the raw material, so the structure changed from 3- (tri-p-tolylphospho-o) phenolate. Presumed to exist! / ⁇ .
- Ratio power of preparation Curing acceleration compound The ratio of silica is considered to be 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. From the measurement of IR ⁇ vector, there is a peak shifted from the raw material cyclohexyl diphenyl phospho-offenolate, so that it exists in a structure modified from cyclohexyl diphenyl phospho-off enolate. Guessed.
- Ratio power of preparation It is considered that the ratio of curing acceleration compound-silica is 1: 1. This was pulverized using a mortar, and the IR ⁇ vector was measured in the same manner as in Preparation Example 1. As a result of IR ⁇ vector measurement, there is a peak shifted from 6-triphenylphospho--2-naphtholate, which is a raw material, and therefore there is a structure changed from 6-triphenylphospho--2-naphtholate. I guess that.
- the ratio of curing accelerating compound silica is considered to be 1: 1. This was pulverized to an average particle size of about 4 m using a jet mill, and 1 vector was measured in the same manner as in Preparation Example 1. From the IR spectrum measurement, there is a peak shifted from the starting material, 4-triphenylphosphonophenolate, so it is presumed that it exists in a structure changed from 4-triphenylphospho-phenolate.
- the ratio of curing accelerator compound silica is considered to be 1: 2. This was pulverized to an average particle size of about 4 m using a jet mill, and 1 vector was measured in the same manner as in Preparation Example 1. From the IR spectrum measurement, there is a peak shifted from the starting material, 4-triphenylphosphonophenolate, so it is presumed that it exists in a structure changed from 4-triphenylphospho-phenolate.
- Tetrabutylamine acetate lOg (mmol) was dissolved in 10 g of distilled water and 20 g of acetone, and 20 g of the above-mentioned M silicate 51 (trade name of Tama Chemical Co., Ltd.) was added while stirring at room temperature. Within a few minutes, the solution turned into a gel. While heating this reaction mixture in an oil bath at 30 to 40 ° C., water, the acetone product used as a solvent, and by-product methanol were distilled off under reduced pressure using an aspirator. Finally, the remaining water was dried at 80 ° C. with a dryer to obtain 19.8 g of a white solid compound. It is considered that the ratio of the charge-accelerating property and the compound-silica is 1: 1. This was pulverized using a mortar, and the IR spectrum was measured in the same manner as in Preparation Example 1.
- IR (KBr method) spectra of the compounds obtained in Preparation Examples 1 to 14 are shown in Figs. 1 to 14, respectively.
- the compounds obtained in Preparation Examples 1 to 14 are cured according to the present invention. It is considered that it is a curing acceleration compound silica composite used as an accelerator.
- phenol aralkyl resin having a hydroxyl equivalent weight of 176 and a softness point of 70 ° C (curing agent 1: trade name Mirlex XL-225, manufactured by Mitsui Engineering Co., Ltd.), a hydroxyl equivalent of 199, softening Point 89
- Curing agent 2 trade name MEH — 7851, manufactured by Meiwa Kasei Co., Ltd.
- the compound obtained in Preparation Example 1 (curing accelerator 1), the compound obtained in Preparation Example 2 (curing accelerator 2), obtained in Preparation Example 3 above.
- spherical fused silica having an average particle diameter of 17.5 m and a specific surface area of 3.8 m 2 Zg was prepared.
- epoxy silane ⁇ -dalicydoxypropyltrimethoxysilane
- carbon black product name ⁇ -100, manufactured by Mitsubishi Chemical Corporation
- release agent Carnauba wax (manufactured by Celerica NODA) and flame retardant antimony trioxide were prepared.
- Examples 1 to 26 and Comparative Example 1 were prepared by blending the above-described components in parts by weight shown in Tables 1 to 5 and performing roll kneading under conditions of a kneading temperature of 80 ° C and a kneading time of 15 minutes, respectively. A curable resin composition of ⁇ 22 was obtained. [0153] [Table 1] Table 1 Composition table
- 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. Post-curing was performed at 175 ° C for 6 hours.
- Spiral flow index of liquidity
- a curable resin composition that was allowed to stand for 72 and 144 hours in a constant temperature bath at 25 ° C. was molded under the condition (1) above, and the flow distance was measured.
- the residual ratio was determined as a ratio from the initial flow distance.
- the curable resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, it was measured using a Shore D-type hardness meter.
- Table 6 ⁇ As shown in the component force from LO, Examples 1-26 containing the curing accelerator according to the present invention resulted in excellent storage stability even in terms of V and deviation.
- Comparative Examples 1 to 22 including a different type of curing accelerator from the curing accelerator according to the present invention are inferior in storage stability.
- the curing accelerator according to the present invention can exhibit excellent storage stability in the curable resin composition, the curable resin composition using the curing accelerator is cured. Compared to the comparative example, which is the same except for the accelerator, the storage stability in terms of fluidity is excellent.
- the method of the present invention is effective for any curing accelerating compound.
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Abstract
Description
Claims
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CN2006800118115A CN101155854B (zh) | 2005-04-15 | 2006-04-14 | 固化促进性化合物-硅石复合体、固化促进性化合物-硅石复合体的制造方法、固化促进剂、固化性树脂组合物及电子零件装置 |
JP2007526859A JP5157444B2 (ja) | 2005-04-15 | 2006-04-14 | 硬化促進性化合物−シリカ複合体、硬化促進性化合物−シリカ複合体の製造方法、硬化促進剤、硬化性樹脂組成物及び電子部品装置 |
US11/911,267 US8129467B2 (en) | 2005-04-15 | 2006-04-14 | Curing accelerating compound-silica composite material, method for producing curing accelerating compound-silica composite material, curing accelerator, curable resin composition, and electronic component device |
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CN102200367B (zh) * | 2007-04-20 | 2015-01-28 | 松下电器产业株式会社 | 冷藏库以及除菌装置 |
JP2010138372A (ja) * | 2008-11-13 | 2010-06-24 | Seiko Epson Corp | 樹脂組成物 |
KR101095136B1 (ko) * | 2009-04-23 | 2011-12-16 | 삼성전기주식회사 | 인쇄회로기판용 수지 조성물 및 이를 이용한 인쇄회로기판 |
CN102666683B (zh) * | 2009-09-28 | 2015-12-16 | 三菱丽阳株式会社 | 纤维强化复合材料 |
US9176259B2 (en) | 2011-03-04 | 2015-11-03 | Intermolecular, Inc. | Sol-gel based antireflective (AR) coatings with controllable pore size using organic nanocrystals and dendrimers |
US9441119B2 (en) * | 2011-03-28 | 2016-09-13 | Intermolecular, Inc. | Sol-gel transition control of coatings by addition of solidifiers for conformal coatings on textured glass |
JP6060904B2 (ja) | 2011-09-29 | 2017-01-18 | 日立化成株式会社 | エポキシ樹脂組成物及び電子部品装置 |
CN103865379A (zh) * | 2012-12-11 | 2014-06-18 | 深圳富泰宏精密工业有限公司 | 聚二甲基硅氧烷溶胶,应用该聚二甲基硅氧烷溶胶对金属基体进行表面处理的方法及制品 |
US8753021B1 (en) * | 2013-02-12 | 2014-06-17 | Corning Cable Systems Llc | Adhesives for securing optical fibers to ferrules of optical connectors and methods for use thereof |
CN106397740A (zh) * | 2015-07-30 | 2017-02-15 | 肯特催化材料股份有限公司 | 环氧树脂固化促进剂及其制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5337799A (en) * | 1976-09-18 | 1978-04-07 | Merck Patent Gmbh | Composite containing silicone dioxide and process for producing same |
JPH02300229A (ja) * | 1989-05-16 | 1990-12-12 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JPH03122114A (ja) * | 1989-10-06 | 1991-05-24 | Somar Corp | 硬化剤組成物、その製造方法及び熱硬化性エポキシ樹脂組成物 |
JPH0625470A (ja) * | 1992-07-10 | 1994-02-01 | Nippon Kayaku Co Ltd | マイクロカプセル型硬化促進剤及びこれを含む樹脂組成物 |
JPH06184283A (ja) * | 1992-12-21 | 1994-07-05 | Sumitomo Bakelite Co Ltd | 半導体封止用樹脂組成物 |
JPH0977959A (ja) * | 1995-09-14 | 1997-03-25 | Toshiba Corp | マイクロカプセル型硬化促進剤および樹脂組成物 |
JP2000186132A (ja) * | 1998-12-22 | 2000-07-04 | Toshiba Corp | マイクロカプセル型硬化触媒およびそれを用いた半導体封止用樹脂組成物 |
JP2004149437A (ja) * | 2002-10-30 | 2004-05-27 | Sumikin Air Water Chemical Inc | トリアリールホスホニオフェノラートの製造方法 |
JP2004156035A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | 硬化性樹脂の硬化促進剤、硬化性樹脂組成物及び電子部品装置 |
JP2004156036A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | 硬化性樹脂の硬化促進剤、硬化性樹脂組成物、電子部品装置、及びホスフィン誘導体の製造方法 |
JP2004277511A (ja) * | 2003-03-13 | 2004-10-07 | Sumitomo Bakelite Co Ltd | 硬化促進剤 |
JP2004300071A (ja) * | 2003-03-31 | 2004-10-28 | Air Water Chemical Inc | ヒドロキシアリールトリアリールホスホニウムアイオダイド、その製法及びその誘導体の製造方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5124399B2 (ja) | 1973-03-19 | 1976-07-23 | ||
JPH078899B2 (ja) | 1987-03-12 | 1995-02-01 | 田岡化学工業株式会社 | 硬化性組成物 |
JP3513835B2 (ja) * | 1993-03-09 | 2004-03-31 | 日立化成工業株式会社 | 接着フィルム |
JP2912193B2 (ja) | 1995-06-14 | 1999-06-28 | 日東電工株式会社 | マイクロカプセル型硬化剤または硬化促進剤、およびそれを含有するエポキシ樹脂組成物、並びに硬化方法およびエポキシ樹脂硬化物 |
JP3478315B2 (ja) | 1995-12-06 | 2003-12-15 | 日立化成工業株式会社 | 半導体封止用エポキシ樹脂組成物及び該樹脂組成物で封止した半導体装置 |
JP3217266B2 (ja) | 1996-06-11 | 2001-10-09 | 住友ベークライト株式会社 | 潜伏性触媒及び該触媒を配合してなる熱硬化性樹脂組成物 |
DE69716218T2 (de) * | 1996-11-20 | 2003-04-17 | Jsr Corp., Tokio/Tokyo | Härtbare Harzzusammensetzung und gehärtete Produkte |
JPH115829A (ja) | 1997-06-19 | 1999-01-12 | Sumitomo Bakelite Co Ltd | 熱硬化性樹脂組成物 |
US6303149B1 (en) | 1998-08-13 | 2001-10-16 | Sol-Gel Technologies, Ltd. | Method for the preparation of oxide microcapsules loaded with functional molecules and the products obtained thereof |
JP2000181632A (ja) | 1998-12-17 | 2000-06-30 | Funai Electric Co Ltd | 映像機器のタッチ入力装置 |
JP2001114872A (ja) | 1999-08-06 | 2001-04-24 | Hitachi Chem Co Ltd | 封止用エポキシ樹脂組成物及び電子部品装置 |
JP4148685B2 (ja) | 2002-02-18 | 2008-09-10 | ソニーケミカル&インフォメーションデバイス株式会社 | 潜在性硬化剤、潜在性硬化剤の製造方法及び接着剤 |
JP4569076B2 (ja) | 2002-06-05 | 2010-10-27 | 住友ベークライト株式会社 | 硬化促進剤、エポキシ樹脂組成物および半導体装置 |
US6753373B2 (en) * | 2002-06-20 | 2004-06-22 | Kris W. Winowiecki | Polyolefin compositions and method of use thereof in molded products |
KR100524820B1 (ko) * | 2003-06-17 | 2005-10-31 | 한국화학연구원 | 실리카 마이크로캡슐의 제조방법 |
JP4329426B2 (ja) | 2003-06-24 | 2009-09-09 | 日立化成工業株式会社 | 封止用エポキシ樹脂成形材料及び電子部品装置 |
CN101133097B (zh) * | 2005-01-26 | 2011-11-09 | 日立化成工业株式会社 | 固化促进剂、固化性树脂组合物及电子器件装置 |
-
2006
- 2006-04-14 KR KR1020077026328A patent/KR101005994B1/ko active IP Right Grant
- 2006-04-14 CN CN2006800118115A patent/CN101155854B/zh not_active Expired - Fee Related
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Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5337799A (en) * | 1976-09-18 | 1978-04-07 | Merck Patent Gmbh | Composite containing silicone dioxide and process for producing same |
JPH02300229A (ja) * | 1989-05-16 | 1990-12-12 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JPH03122114A (ja) * | 1989-10-06 | 1991-05-24 | Somar Corp | 硬化剤組成物、その製造方法及び熱硬化性エポキシ樹脂組成物 |
JPH0625470A (ja) * | 1992-07-10 | 1994-02-01 | Nippon Kayaku Co Ltd | マイクロカプセル型硬化促進剤及びこれを含む樹脂組成物 |
JPH06184283A (ja) * | 1992-12-21 | 1994-07-05 | Sumitomo Bakelite Co Ltd | 半導体封止用樹脂組成物 |
JPH0977959A (ja) * | 1995-09-14 | 1997-03-25 | Toshiba Corp | マイクロカプセル型硬化促進剤および樹脂組成物 |
JP2000186132A (ja) * | 1998-12-22 | 2000-07-04 | Toshiba Corp | マイクロカプセル型硬化触媒およびそれを用いた半導体封止用樹脂組成物 |
JP2004156035A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | 硬化性樹脂の硬化促進剤、硬化性樹脂組成物及び電子部品装置 |
JP2004156036A (ja) * | 2002-10-18 | 2004-06-03 | Hitachi Chem Co Ltd | 硬化性樹脂の硬化促進剤、硬化性樹脂組成物、電子部品装置、及びホスフィン誘導体の製造方法 |
JP2004149437A (ja) * | 2002-10-30 | 2004-05-27 | Sumikin Air Water Chemical Inc | トリアリールホスホニオフェノラートの製造方法 |
JP2004277511A (ja) * | 2003-03-13 | 2004-10-07 | Sumitomo Bakelite Co Ltd | 硬化促進剤 |
JP2004300071A (ja) * | 2003-03-31 | 2004-10-28 | Air Water Chemical Inc | ヒドロキシアリールトリアリールホスホニウムアイオダイド、その製法及びその誘導体の製造方法 |
Also Published As
Publication number | Publication date |
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KR20070120193A (ko) | 2007-12-21 |
JP5157444B2 (ja) | 2013-03-06 |
CN101155854B (zh) | 2011-09-07 |
KR101005994B1 (ko) | 2011-01-05 |
JPWO2006112396A1 (ja) | 2008-12-11 |
TWI325437B (ja) | 2010-06-01 |
CN101155854A (zh) | 2008-04-02 |
TW200643100A (en) | 2006-12-16 |
US8129467B2 (en) | 2012-03-06 |
US20090062460A1 (en) | 2009-03-05 |
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