Classifications

• • 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
• • 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
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/226—Mixtures of di-epoxy compounds
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • 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
  • C08G59/686—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 containing nitrogen
• • 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
  • C08G59/688—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 containing phosphorus
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether

Definitions

• the present invention relates to a latent catalyst for epoxy resin, an epoxy resin composition, and a semiconductor device.
• transfer molding with an epoxy resin composition is suitable as it is inexpensive and applicable to industrial mass production of the devices, and is widely employed in the art.
• the properties and the reliability of semiconductor devices are being improved by improving epoxy resin and its curing agent, phenolic resin.
• the materials for encapsulating semiconductor chips are required to have high flowability that is not detracted from by the inorganic filler to be added thereto in a large amount for improving the rapid curability thereof so as to improve the production efficiency and for improving the heat resistance and the reliability of encapsulated semiconductors.
• An addition reaction product of a tertiary phosphine and a quinone that has good rapid curability is added as a curing accelerator to epoxy resin compositions for use in the filed of electric and electronic materials, for the purpose of accelerating the curing reaction of the curing resins (see, e.g., Patent Document 1).
• the curing accelerator of such a type may exhibit its curing acceleration effect even at relatively low temperatures. Therefore, though slightly, the curing reaction is accelerated even in the initial stage thereof, and because of this reaction, the resin composition shall have an increased molecular weight.
• the increased molecular weight thereof causes an increase in the resin viscosity, and, as a result, the resin composition that contains a large amount of a filler for reliability improvement may be problematic in that its flowability is poor and therefore its moldability is also poor.
• An object of the invention is to provide a latent catalyst useful for epoxy resin.
• Another object of the invention is to provide an epoxy resin composition of good curability, flowability and storability.
• a still other object of the invention is to provide a semiconductor device having excellent solder-cracking resistance and excellent moisture-resistant reliability.
• the present inventors made extensive studies so as to solve the above-mentioned problems. As a result, the inventors obtained the following findings (a) to (c) and have completed the present invention based thereon.
• a latent catalyst for epoxy resin comprising:
• An epoxy resin composition comprising:
• the latent catalyst of the invention is extremely useful for epoxy resin curing acceleration, and when mixed in an epoxy resin composition, an epoxy resin composition that satisfies all of good flowability, good storability and good curability can be obtained.
• the semiconductor device of the invention has good solder-cracking resistance and good moisture resistance, even when exposed to high temperatures.
• the latent catalyst of the invention has a cation moiety capable of accelerating curing reaction of epoxy resin, and a silicate anion moiety having the ability to suppress the curing reaction-accelerating activity of the cation moiety.
• the silicate anion is not dissociated in a temperature range lower than a desired reaction temperature, and this makes it possible to suppress the curing reaction-accelerating activity of the cation moiety.
• the silicate anion structure that has an extremely low nucleophilicity does not readily initiate and accelerate curing reaction in a low-temperature range, and therefore it can imparts both properties of excellent flowability and excellent storage stability to epoxy resin at the same time.
• Adducts of tertiary phosphine and p-benzoquinone as in the related art, and intramolecular or intermolecular salts of onium cation and phenoxide anion such as ordinary onium-phenoxide salts readily induce curing acceleration owing to the high nucleophilicity of the phenoxide anion therein, and therefore they lower the flowability of resin compositions.
• the silicate anion structure of extremely low nucleophilicity cuts its chelate bond during curing reaction, for example, under heat and dissociates itself, so that the silicate moiety is taken in a resin and loses the function of suppressing the curing reaction-accelerating activity of the cation moiety, and as a result, the released cation moiety accelerates curing reaction. Accordingly, the catalyst imparts both excellent flowability and excellent curability of resin composition at the same time.
• Intramolecular or intermolecular salts of onium cation and borate anion such as ordinary borate salts in the related art keep the borate anion of extremely low nucleophilicity therein all the time during curing reaction, and therefore could not attain satisfactory curability.
• the structure (molecular form) of the latent catalyst of the invention may be any so far as it comprises a cation moiety capable of accelerating curing reaction of epoxy resin and an anion moiety having the ability to suppress the curing reaction-accelerating activity of the cation moiety, and examples thereof include, for example, complexes or complex salts comprising an excess anion or cation moiety coordinating therein, and other known molecular forms formed through non-covalent bonding such as molecular compounds, as well as simple salts comprising an anion moiety and a cation moiety that bond to each other through ion-bonding at a ratio of 1/1.
• the cation moiety includes, for example, a nitrogen atom, a phosphorus atom, a sulfur atom or an iodine atom. From the aspect of the reaction activity, the cation moiety preferably contains a nitrogen atom or a phosphorus atom.
• employable are phosphines, tertiary amines and onium salts that are used for accelerating curing reaction of epoxy resin, and preferred are onium salts.
• the latent catalyst of the invention is preferably an onium silicate in which the cation moiety contains a nitrogen or phosphorus atom, and the onium silicate includes those of formula (1).
• the atom A 1 is a nitrogen or phosphorous atom; and the substituents R 1 , R 2 , R 3 and R 4 bonding to the atom A 1 each are an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or are a substituted or unsubstituted aliphatic group, and they may be the same or different from one another.
• substituents R 1 to R 4 include, for example, phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl and cyclohexyl groups.
• substituted or unsubstituted aromatic groups such as phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups.
• the substituent X 1 is an organic group that bonds to the substituents Y 1 and Y 2 .
• the substituent X 2 is an organic group that bonds to the substituents Y 3 and Y 4 .
• the substituents Y 1 and Y 2 each are a group resulting from a proton-donating substituent through release of a proton, and the substituents Y 1 and Y 2 bond to the silicon atom to form a chelate structure.
• Y 3 and Y 4 each are a group resulting from a proton-donating substituent through release of a proton, and the substituents Y 3 and Y 4 bond to the silicon atom to form a chelate structure.
• the substituents X 1 and X 2 may be the same or different from each other; and the substituents Y 1 , Y 2 , Y 3 and Y 4 may be the same or different from one another.
• the groups of Y 1 X 1 Y 2 and Y 3 X 2 Y 4 in formula (1) result from divalent or more polyvalent proton donors through release of two protons.
• the divalent or more polyvalent proton donors include, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin.
• catechol 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene from the aspect of the storage stability and the moisture-resistant reliability.
• Z 1 is an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or is a substituted or unsubstituted aliphatic group.
• aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl and octyl groups
• aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl groups
• reactive substituents such as glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl groups.
• preferred are methyl, phenyl, naphthyl and biphenyl groups from the aspect of the heat stability.
• onium silicates as the latent catalyst according to the invention are extremely superior to conventional curing accelerators in the point of its properties as curing accelerators, especially the curability, the flowability and the storability thereof.
• latent catalysts include those of formula (2) shown above having a phosphonium cation.
• the substituents R 5 , R 6 and R 7 bonding to the phosphorus atom each are an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or are a substituted or unsubstituted aliphatic group, and they may be the same or different from one another.
• substituents R 5 to R 7 include, for example, phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl and cyclohexyl groups.
• substituents R 5 , R 6 and R 7 in formula (2) it is preferable that each of substituents R 5 , R 6 and R 7 is a substituted or unsubstituted aromatic group, such as phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups.
• Latent catalysts with such preferred substituents have especially excellent reactivity of curing and stability of chemical structure.
• the substituent Ar is a substituted or unsubstituted aromatic group.
• the substituent Ar includes, for example, phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl and hydroxynaphthyl groups.
• preferred examples of the substituent Ar include phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl and hydroxynaphthyl groups.
• Latent catalysts with such preferred substituents have especially excellent reactivity of curing and stability of chemical structure.
• the substituent X 3 is an organic group that bonds to the substituents Y 5 and Y 6 .
• the substituent X 4 is an organic group that bonds to the substituents Y 7 and Y 8 .
• the substituents Y 5 and Y 6 each are a group resulting from a proton-donating substituent through release of a proton, and the substituents Y 5 and Y 6 bond to the silicon atom to form a chelate structure.
• the substituents Y 7 and Y 8 each are a group resulting from a proton-donating substituent through release of a proton, and the substituents Y 7 and Y 8 bond to the silicon atom to form a chelate structure.
• the substituents X 3 and X 4 may be the same or different from each other; and Y 5 , Y 6 , Y 7 and Y 8 may be the same or different from one another.
• the groups of Y 5 X 3 Y 6 and Y 7 X 4 Y 8 in formula (2) result from divalent or more polyvalent proton donors through release of two protons.
• the divalent or more polyvalent proton donors include, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin.
• catechol 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene from the aspect of the storage stability and the moisture-resistant reliability.
• Z 2 is an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or is a substituted or unsubstituted aliphatic group.
• aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl and octyl groups
• aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl groups
• reactive substituents such as glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl groups.
• preferred are methyl, phenyl, naphthyl and biphenyl groups from the aspect of the heat stability.
• more preferred latent catalysts include those of formula (3) shown above having a phosphonium cation in which the organic groups bonding to the phosphorus atom each are a substituted or unsubstituted phenyl group.
• the substituents R 8 , R 9 and R 10 on the phenyl groups are selected from a hydrogen atom, a methyl group, a methoxy group and a hydroxyl group, and they may be the same or different from each other.
• the substituent X 5 is an organic group that bonds to the substituents Y 9 and Y 10 .
• the substituents Y 9 and Y 10 each are a group resulting from a proton-donating substituent through release of a proton, and they may be the same or different from each other, and the substituents Y 9 and Y 10 bond to the silicon atom to form a chelate structure.
• the group of Y 9 X 5 Y 10 in formula (3) results from divalent or more polyvalent proton donors through release of two protons.
• the divalent or more polyvalent proton donors include, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin.
• catechol 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene from the aspect of the storage stability and the moisture-resistant reliability.
• Z 3 is an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or is a substituted or unsubstituted aliphatic group.
• aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl and octyl groups
• aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl groups
• reactive substituents such as glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl groups.
• preferred are methyl, phenyl, naphthyl and biphenyl groups from the aspect of the heat stability.
• the phosphonium silicates of formula (3) are preferred as their synthesis can be made simple since the two proton-donating substituents constituting the chelate are the same.
• the latent catalyst of the invention it is preferable that contacting an onium halide with an alkali metal salt of a silicate.
• the alkali metal salt of a silicate is obtained by neutralizing, with an alkali hydroxide such as sodium hydroxide, a trialkoxysilane and a proton donor that can make a chelate bonding with a silicon atom.
• the synthesis scheme is represented by the reaction formula shown below. According to the synthesis method, the intended latent catalyst can be easily synthesized at a high yield.
• the trialkoxysilane includes, for example, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.
• the onium halide compound includes those having an organic group having an optionally-substituted, aromatic or heterocyclic ring and those having an optionally-substituted aliphatic group.
• Specific examples thereof include, for example, triphenylsulfonium bromide, methyltrioctylammonium bromide, tetraphenylammonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, triphenyl(2-hydroxyphenyl)phosphonium bromide, triphenyl(3-hydroxyphenyl)phosphonium bromide, triphenyl(6-hydroxy-2-naphthalene)phosphonium bromide, tris(4-methylphenyl)(2-hydroxyphenyl)phosphonium bromide and tris(4-methoxyphenyl)(2-hydroxyphenyl)phosphonium bromide, each of which may be optionally-substituted.
• A represents a phosphorus or nitrogen atom
• R represents an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or represents a substituted or unsubstituted aliphatic group
• X represents a monovalent anion
• R′ represents an aliphatic group
• Y and Z each represent a group resulting from a proton-donating substituent through release of one proton
• R′′ represents an organic group that bonds to the proton-donating substituents YH and ZH
• R′′′ represents an organic group having a substituted or unsubstituted, aromatic or heterocyclic ring or represents a substituted or unsubstituted aliphatic group.
• the onium silicate can be easily obtained by adding dropwise a solution of the onium halide compound to a solution of the silicate complex that is formed by neutralizing a solution of the trialkoxysilane and the proton donor with an alkali such as sodium hydroxide, at room temperature.
• the solvent for use in the reaction is, for example, preferably an alcohol solvent such as methanol, ethanol or propanol.
• the solvent may be optionally mixed with a re-precipitation solvent such as water.
• the above-mentioned synthetic route is one general method for synthesizing the latent catalyst of formula (1), but the invention is not limited thereto.
• the epoxy resin composition of the invention comprises (A) a compound having at least two epoxy groups in one molecule, (B) a compound having at least two phenolic hydroxyl groups in one molecule, (C) the latent catalyst of the invention, and (c) an inorganic filler, and optionally (D) an inorganic filler.
• the epoxy resin composition has excellent curability, flowability and storability.
• the compound (A) having at least two epoxy groups in one molecule for use in the invention may be any so far as it has at least two epoxy groups in one molecule, and there is no particular limitation posed thereon.
• the compound (A) includes, for example, bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins and bromobisphenol-type epoxy resins; biphenyl-type epoxy resins, biphenylaralkyl-type epoxy resins, stilbene-type epoxy resins, phenol-novolak-type epoxy resins, cresol-novolak-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, dihydroxybenzene-type epoxy resins; epoxy compounds that are produced by reacting epichlorohydrin on the hydroxyl group of phenols, phenolic resins or naphthols; epoxy resins produced through oxidative epoxydation of olefins with peracids; glycidyl ester-type epoxy resins and glycidylamine-type epoxy resins. These compounds may be used either singly or in combination of two or more thereof.
• the compound (B) for use in the invention has at least two phenol hydroxyl groups in one molecule, and it acts or functions as a curing agent for the compound (A).
• the compound (B) includes phenol-novolak resins, cresol-novolak resins, bisphenol resins, phenolaralkyl resins, biphenylaralkyl resins, trisphenol resins, xylylene-modified novolak resins, terpene-modified novolak resins and dicyclopentadiene-modified phenol resins. These compounds may be used either singly or in combination of two or more thereof.
• the latent catalyst (C) for use in the epoxy resin composition of the invention is the above-mentioned latent catalyst.
• onium silicates are preferred, including, for example, sulfonium silicate, ammonium silicate, pyridinium silicate, phosphonium silicate, iodonium silicate, and selenium silicate. These compounds may be used either singly or in combination of two or more thereof.
• the inorganic filler (D) may be blended with the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor devices.
• the inorganic filler (D) may be blended with the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor devices.
• the inorganic filler (D) includes, for example, fused and crushed silica, fused silica, crystalline silica, secondary aggregated silica, alumina, titanium white, aluminium hydroxide, talc, clay and glass fibers. They may be used either singly or in combination of two or more thereof.
• the content (blending amount) of the latent catalyst (C) in the epoxy resin composition of the invention is preferably about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight.
• the epoxy resin composition has well-balanced properties among curability, flowability, storability, and properties of its cured products.
• the blending ratio of the compound (A) having at least two epoxy groups in one molecule to the compound (B) having at least two phenolic hydroxyl groups in one molecule is preferably such that the phenolic hydroxyl group of the compound (B) is about 0.5 to 2 mol, more preferably about 0.7 to 1.5 mol per 1 mol of the epoxy group of the compound (A).
• the epoxy resin composition keep a suitable balance among various properties, and the various properties are further improved.
• the content (blending amount) of the inorganic filler (D) is preferably about 200 to 2400 parts by weight, more preferably about 400 to 1400 parts per 100 parts by weight of the sum of the compound (A) and the compound (B). If the content thereof is less than the lower limit of the range, then the inorganic filler (D) may have insufficient reinforcing effect; on the other hand, if the content of the inorganic filler (D) is more than the upper limit of the range, then the flowability of the epoxy resin composition may lower and may therefore cause filling insufficiency upon molding the epoxy resin composition (for example, upon manufacturing semiconductor devices).
• the content (blending amount) of the inorganic filler (D) falls between 400 and 1400 parts by weight per 100 parts by weight of the sum of the compound (A) and the compound (B), then the moisture absorption of the cured products of the epoxy resin composition becomes lower and the occurrence of solder cracks can be prevented.
• the epoxy resin composition of this type has good flowability upon heat-melting, and therefore the occurrence of wire deformation inside semiconductor devices can be effectively prevented.
• the content (blending amount) of the inorganic filler (D) in terms of parts by weight may be dealt with by converting it to % by volume taking into account the specific gravity of the compound (A), the compound (B) and the inorganic filler (D) itself.
• the epoxy resin composition of the invention may optionally contain various additives of, for example, coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane, colorant such as carbon black, flame retardant such as bromoepoxy resin, antimony oxide or phosphorus compound, a low-stress component such as silicone oil or silicone rubber, lubricant such as natural wax, synthetic wax, higher fatty acid or its metal salt or paraffin, and antioxidant.
• coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane
• colorant such as carbon black
• flame retardant such as bromoepoxy resin
• a low-stress component such as silicone oil or silicone rubber
• lubricant such as natural wax, synthetic wax, higher fatty acid or its metal salt or paraffin, and antioxidant.
• the epoxy resin composition may contain any other known catalyst such as triphenyl phosphine, 1,8-diazabicyclo(5.4.0)-7-undecene or 2-methylimidazole.
• the epoxy resin composition of the invention may be obtained by mixing the compounds (A) to (C) and optionally the compound (D) along with any other additives by the use of a mixer at room temperature, then heating and kneading the mixture with a hot roll, a heating kneader or the like, and cooling and grinding the resulting mixture.
• the thus obtained epoxy resin composition for use as a molding resin is molded and cured by a molding method such as transfer molding, compression molding, injection molding or the like to encapsulate electronic parts such as semiconductor elements. In this way, a semiconductor device of the present invention can be obtained.
• the thus obtained semiconductor device of the invention has excellent solder-cracking resistance and excellent moisture-resistant reliability.
• the latent catalyst (C) of the invention especially the compound of formula (I) is thermally stable and the silicate anion moiety therein is bulky. Accordingly, the ion mobility of the free ion derived from the latent catalyst through dissociation during curing reaction is low. This makes the solder-cracking resistance and the moisture-resistant reliability of the semiconductor device of the invention excellent.
• the epoxy resin composition of the invention is used as an encapsulating material for semiconductor devices.
• the application of the epoxy resin composition of the invention is not limited thereto.
• the addition of the inorganic filler may be omitted.
• Epoxy resin compositions each containing any of the above-mentioned compounds C1 to C11 and triphenyl phosphine were prepared, and these were used in manufacturing semiconductor devices.
• Biphenyl-type epoxy resin (YX-4000HK manufacture by Japan Epoxy Resins Co., Ltd.) of the formula (16) shown below as the compound (A); phenolaralkyl resin (XLC-LL manufactured by Mitsui Chemicals Corp.) of the formula (17) shown below (in which the number of repetitive units of 3 is a mean value) as the compound (B); the compound C1 as the latent catalyst (C); fused spherical silica (having a mean particle size of 15 ⁇ m) as the inorganic filler (D); carbon black, bromobisphenol A-type epoxy resin and carnauba wax as the other additives were prepared.
• Physical Data of Compound of Formula (16) Melting point: 105 ° C. Epoxy equivalent: 193 ICI melt viscosity at 150° C.: 0.15 poises
• 100-pin TQFP was manufactured in a mode of transfer molding at a mold temperature of 175° C. under an injection pressure of 7.4 MPa and for a curing time of 2 minutes, followed by post-curing at 175° C. for 8 hours.
• the package size of the 100-pin TQFP was 14 ⁇ 14 mm, its thickness was 1.4 mm; the silicon chip (semiconductor chip) size was 8.0 ⁇ 8.0 mm; and the lead frame was formed of 42-alloy.
• 16-pin DIP was manufactured in a mode of transfer molding at a mold temperature of 175° C. under an injection pressure of 6.8 MPa and for a curing time of 2 minutes, followed by post-curing at 175° C. for 8 hours.
• the package size of the 16-pin DIP was 6.4 ⁇ 19.8 mm, its thickness was 3.5 mm; the silicon chip (semiconductor chip) size was 3.5 ⁇ 3.5 mm; and the lead frame was formed of 42-alloy.
• Biphenylaralkyl-type epoxy resin (NC-3000P manufactured by Nippon Kayaku Co., Ltd.) of the formula (18) shown below (in which the number of repetitive units of 3 is a mean value) as the compound (A); biphenylaralkyl-type phenol resin (MEH-7851SS manufactured by Meiwa Kasei K.
• packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.64 parts by weight of the compound C2 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.64 parts by weight of the compound C2 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 2.28 parts by weight of the compound C3 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 2.28 parts by weight of the compound C3 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.00 parts by weight of the compound C4 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.00 parts by weight of the compound C4 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.48 parts by weight of the compound C5 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.48 parts by weight of the compound C5 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 2.57 parts by weight of the compound C6 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 2.57 parts by weight of the compound C6 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.63 parts by weight of the compound C7 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.63 parts by weight of the compound C7 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.57 parts by weight of the compound C8 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.57 parts by weight of the compound C8 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.31 parts by weight of the compound C9 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.31 parts by weight of the compound C9 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 4.31 parts by weight of the compound C10 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 4.31 parts by weight of the compound C10 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.97 parts by weight of the compound C11 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.97 parts by weight of the compound C11 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• thermosetting resin composition thermosetting resin composition
• package semiconductor device
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 1.85 parts by weight of triphenyl phosphine-benzoquinone adduct was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 1.00 part by weight of triphenyl phosphine was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 1.00 part by weight of triphenyl phosphine was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 2.57 parts by weight of C12 of the formula (20) shown below was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 2.57 parts by weight of C12 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 2.81 parts by weight of C13 of the formula (21) shown below was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 2.81 parts by weight of C13 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 1 except that 3.29 parts by weight of C14 of the formula (22) shown below was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 1.
• An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 2 except that 3.29 parts by weight of C14 was used in place of the compound C1. Using the epoxy resin composition, packages (semiconductor device) were manufactured in the same manner as in Example 2.
• each resin composition was examined at a mold temperature of 175° C. under an injection pressure of 6.8 MPa for a curing time of 2 minutes.
• the spiral flow is a parameter of resin flowability. Larger values indicate better flowability.
• the epoxy resin compositions were stored in air at 30° C. for 1 week, and their spiral flow was measured in the same manner as in the above item (1). The percentage (%) of the spiral flow of the stored sample relative to that of the fresh sample is obtained.
• 100-pin TQFE was left in an atmosphere at 85° C. and 85% RH for 168 hours, and then dipped in a solder bath at 260° C. for 10 seconds.
• a voltage of 20 V was applied to 16-pin DIP in a water vapor at 125° C. and 100% RH, and the samples were checked for interconnection failure. The time required until 8 of 15 packages tested showed some interconnection failure was taken as the failure time.
• the test time was at most 500 hours. When the number of failed packages was less than 8 at lapse of time of 500 hours, then the failure time of the sample is indicated as over 500 hours (>500).
• test data of (1) to (5) are given in Table 1 and Table 2.
• TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 11 12 Com- Compo- YX-4000HK 52 52 52 52 52 52 52 posi- nent (A) NC-3000 57 57 57 57 57 57 57 tion Compo- XLC-LL 48 48 48 48 48 (wt.
• the epoxy resin compositions of Examples 1 to 22 (that are the epoxy resin compositions of the invention) all had good curability and good flowability, and, in addition, the packages of the Examples encapsulated with the cured product of the resin composition (that are the semiconductor devices of the invention) all had good solder-cracking resistance and good moisture-resistant reliability.
• the epoxy resin compositions of Comparative Example 1 and Comparative Example 2 were both poor in flowability, and the packages of these Comparative Examples were not resistant to solder-cracking and their moisture-resistant reliability was extremely low.
• the epoxy resin compositions of Comparative Example 3 and Comparative Example 4 both had remarkably poor curability and flowability, and the packages of these Comparative Examples were not resistant to solder-cracking.
• the epoxy resin compositions of Comparative Example 5 and Comparative Example 6 were both poor in flowability.
• the epoxy resin compositions of Comparative Example 7, Comparative Example 8, Comparative Example 9 and Comparative Example 10 were all deteriorated in curability, and could not bring about good cracking resistance and reliability.
• Epoxy resin compositions thermosetting resin compositions
• thermosetting resin compositions were produced in the same manner as in Examples 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, and Comparative Examples 1, 3, 5, 7, 9, respectively, except that 26 parts by weight of the biphenyl-type epoxy resin of formula (16) and 28.5 parts by weight of the biphenylaralkyl-type epoxy resin of formula (18) were used as the compound (A), and 45.5 parts by weight of the phenolaralkyl resin of formula (17) was used as the compound (B).
• packages semiconductor device
• Epoxy resin compositions thermosetting resin compositions
• thermosetting resin compositions were produced in the same manner as in Examples 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, and Comparative Examples 1, 3, 5, 7, 9, respectively, except that 54.5 parts by weight of the biphenyl-type epoxy resin of formula (16) was used as the compound (A), and 24 parts by weight of the phenolaralkyl resin of formula (17) and 21.5 parts by weight of the biphenylaralkyl-type phenol resin of formula (19) were used as the compound (B).
• packages semiconductor device
• the latent catalyst of the invention Using the latent catalyst of the invention, epoxy resin compositions having good curability, flowability and storability can be obtained.
• the latent catalyst is suitable for thermosetting resin compositions that contains a phosphine or phosphonium salt as a curing accelerator.
• the resin composition of the invention is suitable for the field of electric and electronic materials.

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• Epoxy Resins (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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