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WO2003080726A1 - Materiau de moulage en resine epoxy destine a l'encapsulation et aux dispositifs et composants electroniques - Google Patents

Materiau de moulage en resine epoxy destine a l'encapsulation et aux dispositifs et composants electroniques Download PDF

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Publication number
WO2003080726A1
WO2003080726A1 PCT/JP2002/012974 JP0212974W WO03080726A1 WO 2003080726 A1 WO2003080726 A1 WO 2003080726A1 JP 0212974 W JP0212974 W JP 0212974W WO 03080726 A1 WO03080726 A1 WO 03080726A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
molding material
resin molding
borate
zinc borate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2002/012974
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English (en)
Japanese (ja)
Inventor
Ryouichi Ikezawa
Hidenori Abe
Masanobu Fujii
Tomohiro Hayashi
Tomohiro Miyata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to AU2002354468A priority Critical patent/AU2002354468A1/en
Priority to JP2003578465A priority patent/JPWO2003080726A1/ja
Publication of WO2003080726A1 publication Critical patent/WO2003080726A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • 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

  • Epoxy resin molding compound for sealing and electronic component device This application is a Japanese patent application filed earlier by the same applicant, that is, Japanese Patent Application No. 2002-81347 (filing date: March 22, 2002), Japanese Patent Application These are accompanied by priority claims based on Japanese Patent Application No. 2002-81363 (filed on March 22, 2002) and Japanese Patent Application No. 2002-81386 (filed on March 22, 2002). Incorporated here for reference.
  • Technical field is a Japanese patent application filed earlier by the same applicant, that is, Japanese Patent Application No. 2002-81347 (filing date: March 22, 2002), Japanese Patent Application These are accompanied by priority claims based on Japanese Patent Application No. 2002-81363 (filed on March 22, 2002) and Japanese Patent Application No. 2002-81386 (filed on March 22, 2002). Incorporated here for reference. Technical field
  • the present invention relates to a sealing epoxy resin molding material, particularly a halogen-free, non-antimony, flame-retardant sealing epoxy resin molding material required from the viewpoint of environmental friendliness.
  • the present invention relates to a molding material suitable for stopping and an electronic component device provided with an element sealed with the molding material.
  • epoxy resin molding materials have been widely used.
  • epoxy resin balances various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products.
  • the flame retardancy of these epoxy resin molding materials for sealing is mainly achieved by a combination of a brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide.
  • JP-A-9-227765 red phosphorus
  • JP-A-9-227765 an ester phosphate compound
  • JP-A-235449 a method using a phosphazene compound
  • JP-A-8-225714 a method using a metal hydroxide
  • JP-A-9-241483 a method using a metal hydroxide and a metal oxide.
  • a method using a combination thereof Japanese Patent Application Laid-Open No.
  • these non-halogen and non-antimony flame retardants have not achieved moldability and reliability equivalent to those of sealing epoxy resin molding materials using both a brominated resin and antimony oxide.
  • the present invention has been made in view of such circumstances, and is a halogen-free and non-antimony epoxy resin material for encapsulation which has good flame retardancy without deteriorating reliability such as moldability, fluidity, moisture resistance, and the like.
  • the purpose of the present invention is to provide an electronic component device having an element sealed by the above.
  • the inventors of the present invention have studied the mechanism of flame retardation by zinc borate in order to solve the above-mentioned problems.
  • zinc borate has an endothermic It is said that the flame retardancy is achieved by the effect and the glass vitrification effect of boric acid.However, when a sufficient amount is used to secure the flame retardancy, the water of crystallization of zinc borate causes the hardening reaction. It has been found that it inhibits and lowers moldability.
  • zinc borate has an endothermic amount of about 600 J / g due to release (and thermal decomposition) of water of crystallization, and about 160 J / g of magnesium hydroxide and water. Low compared to about 180 J / g of aluminum oxide (2001: Issued by N.T.S. Inc., "Fire-retardant technology using non-halogen flame-retardant materials") The contribution of the endothermic effect of the release of water of crystallization to the combustion is small, and the contribution of the vitrification due to the melting of the boron oxide generated after decomposition is large. It has been found that flame retardancy can be achieved by using anhydrous zinc borate containing no water.
  • anhydrous borate obtained by treating anhydrous zinc borate with a predetermined amount of an inorganic or organic substance was used as a flame retardant. It has been found that in addition to the effect, the fluidity in the low shear region can be improved.
  • M represents a metal element
  • m, n, x, and y are each independently a positive number.
  • the amount of the boric acid-based flame retardant is less than that of the epoxy resin molding compound for encapsulation.
  • Y is a divalent organic group having a substituted or unsubstituted aromatic ring
  • R is a hydrogen atom or a substituted or unsubstituted organic group having 1 to 6 carbon atoms, and R is different even if all are the same.
  • M and n each represent an integer of 0 to 3.
  • R 1 , R 2 and R 3 represent a substituted or unsubstituted alkyl group, aryl group, aralkyl group and hydrogen atom having 1 to 10 carbon atoms, all of which may be the same or different. Except when it is an atom.)
  • the epoxy resin is a biphenyl type epoxy resin, a bisphenol F type epoxy tree J3, a stilbene type epoxy resin, a sulfur atom containing epoxy resin,
  • the epoxy resin (A) used in the present invention is not particularly limited as it is generally used for an epoxy resin molding material for encapsulation.
  • examples thereof include a phenol nopolak epoxy resin, an orthocresol nopolak epoxy resin, and a trif.
  • Phenols such as phenols, cresols, xylenols, resorcinols, phenols, such as epoxy resins having an enylmethane skeleton, and phenols such as bisphenol A and pisphenol F and / or ⁇ -naphthol and ⁇ -naphthol
  • Noplac resin obtained by condensation or co-condensation of naphthols such as dihydroxynaphthylene and a compound having an aldehyde group such as formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in the presence of an acidic catalyst.
  • Diglycidyl ethers such as bisphenol ⁇ , bisphenol F, bisphenol, alkyl-substituted or unsubstituted biphenol, stilbene-type epoxy resin, hydroquinone-type epoxy resin, polybasic acids such as phthalic acid, dimer acid and epichlor Daricidyl ester type epoxy resin obtained by the reaction of hydrin, glycidylamine type epoxy resin obtained by the reaction of polyamines such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, dicyclopentene phenol and phenols Epoxy compound of co-condensation resin, Epoxy resin having naphthylene ring, epoxide of aralkyl-type phenol resin such as phenol-aralkyl resin, naphthol-aralkyl resin, trimethylolpropane-type epoxy resin, terpene Sex epoxy resin, Orefu fin coupling obtained by oxidizing with a peracid
  • biphenyl epoxy resin, bisphenol F epoxy resin, stilbene epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of reflow resistance, and novolak epoxy resin is preferable from the viewpoint of curability.
  • a dicyclopentene-type epoxy resin is preferred.
  • a naphthalene-type epoxy resin and a triphenylmethyl-type epoxy resin are preferred, and at least one of these epoxy resins is contained. Is preferred.
  • bifunctional epoxy resins which are highly reliable and can be highly filled, are also advantageous in flame retardancy, are more preferable.
  • Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (III), and examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (XXXXXIV).
  • Examples of the type epoxy resin include an epoxy resin represented by the following general formula (IV), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (V).
  • Ri to R 8 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different; n is 0 to Indicates an integer of 3.
  • ⁇ - 8 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 10 carbon atoms Selected from 10 aralkyl groups, all of which may be the same or different, and n is an integer of 0 to 3. Indicates a number.
  • Ri to R8 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different; n is 0
  • Ri to R 8 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different; n is 0 to
  • biphenyl type epoxy resin represented by the general formula (III) examples include 4,4′-bis (2,3-epoxypropoxy) biphenyl and 4,4′-bis (2,3-epoxy). Propoxy) —3,3 ', 5,5'-tetramethylbiphenyl-based epoxy resin, epichlorohydrin and 4,4'-biphenol or 4,4,-(3,3' , 5,5'-tetramethyl) biphenol and an epoxy resin obtained by the reaction. Above all, 4, 4 'one screw
  • the stilbene-type epoxy resin represented by the general formula (IV) can be obtained by reacting styrene-based phenols, which are raw materials, and epichlorohydrin in the presence of a basic substance.
  • the stilbene phenols, which are the raw materials include For example, 3_t-butyl-4,4'-dihydroxy-3 ', 5,5'_trimethylstilbene, 3-t_butyl-4,4'dihydroxy-3', 5 ', 6-trimethylstilbene, 4,4 '-Dihydroxy-3,3', 5,5, -tetramethylstilbene, 4,4, -dihydroxy-3,3, di-t-butyl-5,5,1-dimethylstilbene, 4,4'- Dihydroxy-3,3, di-t-butyl-6,6'-dimethylstilbene, etc., among which 3-t-butyl-4,4'-dihydroxy-1-3 ', 5,5'-trimethylstilbene, and ⁇ 4,4'-dihydroxy-1,3,3,5,5'
  • Ri to R 8 are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted carbon group having 1 to 10 carbon atoms.
  • Epoxy resins selected from alkoxy groups of 10 to 10 are preferred, and epoxy resins in which Ri, R 4 , R 5 and R 8 are hydrogen atoms and R 2 , R 3 , R 6 and R 7 are alkyl groups are preferred. More preferred is an epoxy resin in which RR 4 , R 5 and Rs are hydrogen atoms, R 2 and R 7 are methyl groups, and R 3 and R 6 are t-butyl groups.
  • YSLV-12TE manufactured by Toto Kasei Co., Ltd.
  • any of these epoxy resins may be used alone or in combination of two or more.
  • the amount of the epoxy resin is 20 to the total amount of the epoxy resin in order to exhibit its performance. %, More preferably at least 30% by weight, even more preferably at least 50% by weight.
  • Examples of the nopolak type epoxy resin include an epoxy resin represented by the following general formula (VI).
  • R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.
  • the nopolak-type epoxy resin represented by the general formula (VI) can be easily obtained by reacting nopolak-type phenol resin with epichlorohydrin.
  • R in the general formula (VI) is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group, a propoxy group.
  • n is preferably an integer of 0 to 3.
  • nopolak epoxy resins represented by the general formula (VI) orthocresol nopolak epoxy resins are preferred.
  • a nopolak type epoxy resin When a nopolak type epoxy resin is used, its amount is preferably at least 20% by weight, more preferably at least 30% by weight, based on the total amount of the epoxy resin in order to exhibit its performance.
  • Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (VII).
  • Ri and R 2 are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 10, m Represents an integer of 0 to 6.
  • Ri in the above formula (VII) includes, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and a t-butyl group, a vinyl group, an aryl group, a butenyl group, and the like.
  • a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms such as an alkenyl group, a halogenated alkyl group, an amino group-substituted alkyl group, or a mercapto group-substituted alkyl group; Preferred are an alkyl group such as a methyl group and a hydrogen atom, and more preferred are a methyl group and a hydrogen atom.
  • R 2 includes, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t_butyl group; an alkenyl group such as a vinyl group, an aryl group and a butenyl group; Alkyl group, amino-substituted alkyl group, Examples thereof include a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as a mercapto group-substituted alkyl group, with a hydrogen atom being preferred.
  • an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t_butyl group
  • an alkenyl group such as a vinyl group, an aryl group and a butenyl group
  • a dicyclopentadiene-type epoxy resin When a dicyclopentadiene-type epoxy resin is used, its amount is preferably at least 20% by weight, more preferably at least 30% by weight, based on the total amount of the epoxy resin in order to exhibit its performance.
  • Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (VHI), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (IX).
  • the naphthalene type epoxy resin represented by the following general formula (VIII) includes a random copolymer containing one structural unit and m structural units at random, an alternating copolymer containing alternately, and a copolymer containing regularly. Examples thereof include block copolymers containing in a united or block form, and any one of these may be used alone, or two or more may be used in combination. Further, the triphenylmethane-type epoxy resin represented by the following general formula (IX) is not particularly limited, but a salicylaldehyde-type epoxy resin is preferable.
  • Ri to R 3 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different.
  • p is 1 or 0, 1 and m are integers from 0 to 11 respectively, (1 + m) is an integer from 1 to 11 and (1 + p) is an integer from 1 to 12 Is chosen.
  • i is an integer of 0-3, j is an integer of 0-2, and k is an integer of 0-4.
  • R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10).
  • the amount of the epoxy resin is 20% by weight or more based on the total amount of the epoxy resin in order to exhibit its performance. It is preferably at least 30% by weight, more preferably at least 50% by weight.
  • the above biphenyl-type epoxy resin, stilbene-type epoxy resin, sulfur-atom-containing epoxy resin, nopolak-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthylene-type epoxy resin and triphenylmethane-type epoxy resin are: Any one of them may be used alone or two or more of them may be used in combination. However, the compounding amount is preferably 50% by weight or more based on the total amount of epoxy resin, and 60% by weight or more. More preferably, the content is 80% by weight or more.
  • the curing agent (B) used in the present invention is not particularly limited, and is generally used for an epoxy resin molding material for sealing.
  • examples thereof include phenol, cresol, resorcinol, catechol, bisphenol A, and bisphenol.
  • F phenols such as phenylphenol and aminophenol, and / or naphthols such as ⁇ _naphthol, / 3-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde.
  • Nopolak phenolic resin obtained by condensation or cocondensation in the presence of an acidic catalyst phenols and phenols synthesized from phenols and ⁇ ⁇ or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol aralkyl Resin-based aralkyl-type phenolic resins, phenols and / or naphthols and cyclopentadiene, and synthesized by copolymerization from cyclopentadiene, such as diclopen-phenol-type phenol nopolak resin and naphthol-no-polak resin, etc. And terbene-modified phenolic resins. These may be used alone or in combination of two or more.
  • biphenyl-type phenol resins are preferable from the viewpoint of flame retardancy, and aralkyl-type phenol resins are preferable from the viewpoint of reflow resistance and curability.
  • dispersing pen-type pen-type phenol resin is preferable.
  • triphenyl methane-type phenol resin is preferable, and from the viewpoint of curability. Therefore, a nopolak type phenol resin is preferable, and it is preferable to contain at least one of these phenol resins.
  • biphenyl type phenol resin examples include a phenol resin represented by the following general formula (X).
  • All R i ⁇ R 9 in the formula (X) is well be the same or different, a hydrogen atom, a methyl group, Echiru group, propyl group, butyl group, an isopropyl group, carbon number 1 to 1, such as an isobutyl group
  • An alkyl group having 0 to 10 carbon atoms such as an alkoxyl group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenyl group, a tolyl group, and a aryl group having 6 to 10 carbon atoms such as a xylyl group; and
  • aralkyl groups having 6 to 10 carbon atoms, such as benzyl group and phenethyl group, and among them, a hydrogen atom and a methyl group are preferable.
  • n shows the integer of 0-10.
  • Examples of the biphenyl type phenolic resin represented by the general formula (X) include compounds in which all of Ri to R 9 are hydrogen atoms. Among them, from the viewpoint of melt viscosity, n is 1 or more. A mixture of the condensate containing 50% by weight or more of the condensate is preferable. As such a compound, MEH-7885 (trade name of Meiwa Kasei Co., Ltd.) is available as a commercial product.
  • its blending amount is preferably at least 30% by weight, more preferably at least 50% by weight, and more preferably at least 50% by weight, in order to exert its performance. % By weight or more is more preferable.
  • aralkyl-type phenolic resin examples include a phenol-aralkyl resin and a naphthol-aralkyl resin.
  • the phenol-aralkyl resin represented by the following general formula (XI) is preferable, and R in the general formula (XI) is a hydrogen atom.
  • the phenol aralkyl resin having an average value of n of 0 to 8 is more preferable.
  • Specific examples include p-xylylene-type phenol-aralkyl resin, m-xylylene Type phenols and aralkyl resins.
  • the compounding amount thereof is preferably at least 30% by weight, more preferably at least 50% by weight, based on the total amount of the curing agent in order to exhibit the performance. No.
  • R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.
  • dicyclopentene-type phenol resin examples include a phenol resin represented by the following general formula (XII).
  • Ri and R 2 are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 10, m Is
  • a dicyclopentene phenolic resin When a dicyclopentene phenolic resin is used, its amount is preferably at least 30% by weight, more preferably at least 50% by weight, based on the total amount of the curing agent in order to exhibit its performance.
  • triphenylmethane-type phenolic resins examples include, for example,
  • the triphenylmethane type phenolic resin represented by (XIII) is not particularly limited, and examples thereof include salicylaldehyde type phenolic resin, o-hydroxybenzaldehyde type phenolic resin, m-hydroxybenzaldehyde type phenolic resin and the like. These may be used alone or in combination of two or more. Among them, salicylaldehyde type phenol resins are preferred.
  • a triphenylmethane-type phenol resin represented by the following general formula (XIV) There is no particular limitation, but if necessary, a resin copolymerized with a P-xylylene type phenol-aralkyl resin may be used.
  • R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10;
  • R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10).
  • triphenylmethane-type phenol resin When a triphenylmethane-type phenol resin is used, its blending amount is preferably at least 30% by weight, more preferably at least 50% by weight, based on the total amount of the curing agent in order to exhibit its performance.
  • the nopolak-type phenol resin examples include a phenol nopolak resin, a cresol nopolak resin, and a naphthol nopolak resin. Among them, a phenol nopolak resin is preferable.
  • a nopolak type phenol resin when used, its amount is preferably at least 30% by weight, more preferably at least 50% by weight, based on the total amount of the curing agent in order to exhibit its performance.
  • biphenyl-type phenolic resin, aralkyl-type phenolic resin, dicyclopentene-type phenolic resin, triphenylmethane-type phenolic resin and nopolak-type phenolic resin can be used alone or in combination of two or more. May be used, but the compounding amount is 60 times the total amount of the curing agent. % Or more, more preferably 80% by weight or more.
  • the equivalent ratio of (A) the epoxy resin to (B) the curing agent is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the curing agent and the number of epoxy groups in the epoxy resin) is Although there is no particular limitation, it is preferably set to a range of 0.5 to 2, and more preferably 0.6 to 1.3, in order to minimize the amount of each unreacted component. In order to obtain an epoxy resin molding material for sealing excellent in moldability and reflow resistance, it is more preferable to set the ratio in the range of 0.8 to 1.2.
  • (C) boric acid-based flame retardant used in the present invention (C 1) boric anhydride, (C2) zinc borate and (C3) zinc borate anhydride can be used.
  • the (C 1) anhydrous borate used in the present invention acts as a flame retardant, and is not particularly limited as long as the effects of the present invention can be obtained.
  • it is represented by the following formula (I) And metal salts of boric anhydride.
  • M represents a metal element
  • m, n, x, and y are each independently a positive number.
  • Examples of the metal borate anhydride represented by the composition formula (I) include, for example, organic acid salts of boric anhydride such as melamine anhydride borate, ammonium borate anhydride, and complex acid metal salts of anhydrous boric acid such as zinc phosphate.
  • One of these may be used alone, or two or more thereof may be used in combination.
  • boric anhydride in order to improve the properties of the extract when used as a sealing material, boric anhydride
  • the solubility of the salt in water at 25 ° C. is preferably lg or less, more preferably 0.1 g or less, per 100 g of water.
  • the solubility in water is determined by adding 10 g of anhydrous borate to 100 ml of pure water, stirring at 25 ° C for 30 minutes, sucking 10 cc of the supernatant with a pipette, and incubating at 100 ° C for 24 hours. This is the value obtained by weighing the residue and converting it to 10 Oml (100 g) of pure water.
  • a metal borate anhydride in which M in the composition formula (I) is a metal element selected from a group other than an alkali metal and an alkaline earth metal is preferable. If the solubility in water is high, the extraction liquid characteristics of the sealing material are deteriorated. In particular, since the electrical conductivity of the extract increases, there is a concern that the reliability of the semiconductor device in a bias test or the like may decrease.
  • the classification of metal elements is based on the long-period periodic table with the typical element being subgroup A and the transition element being subgroup B. (Source: Chemical Dictionary 4 by Kyoritsu Shuppan Co., Ltd., February 15, 1987) 30th printing).
  • the “metal element selected from other than the alkali metal and the alkaline earth metal” representing M in the composition formula (I) refers to the long-period type periodic table (Source: Kyoritsu Shuppan Co., Ltd.) Published “Chemical Encyclopedia 4”, a reduced edition of February 15, 1987, No. 30), a transition metal element belonging to Group ⁇ to Group IB and a typical metal element belonging to Group ⁇ to Group VIA.
  • a transition metal element belonging to Group ⁇ to Group IB and a typical metal element belonging to Group ⁇ to Group VIA.
  • elements other than the typical metal elements that is, alkali metals and alkaline earth metals belonging to. Specifically, it refers to a metal element having an atomic number of 13, 21 to 32, 39 to 51, 57 to 84, and 89 to 102.
  • a metal borate anhydride in which M in the composition formula (I) is a metal element selected from Co, Zn, A 1 and Bi is preferable.
  • Anhydrous zinc borate represented by (XXII), etc. anhydrous aluminum borate represented by the following composition formulas (XXIII), (XXIV), (XXV), etc., and anhydrous boron borate represented by the following composition formula (XXVI), etc.
  • Bismuth acid and the like.
  • anhydrous zinc borate represented by the following composition formula (II) is preferable from the viewpoints of economy, supplyability and boric acid content.
  • anhydrous bismuth borate represented by the following composition formula (XXVI) is preferable.
  • Commercial products include FB-500 (trade name, manufactured by BORAX) as anhydrous zinc borate represented by the following composition formula (II), and Shikoku Chemicals Corporation as aluminum borate anhydride, represented by the following composition formula (II): The name alpolite PF 08 T is available respectively.
  • the method for producing the anhydrous borate is not particularly limited, but a method in which boric acid is directly produced by reacting a carbonate or an oxide of a partner salt, or a method in which these materials are heated (fired). A method in which the hydrated borate is heated (calcined) to remove water of crystallization, and the like.
  • the (C 2) zinc borate used in the present invention acts as a flame retardant, and is not particularly limited as long as the effects of the present invention can be obtained.
  • zinc borate represented by the following composition formula (XXVII) And the like.
  • zinc borate represented by the composition formula (XIII) include the following composition formulas (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), and one of these. May be used alone or in combination of two or more.
  • zinc borate represented by the following composition formula (XXVIII) is preferable from the viewpoint of flame retardancy.
  • ZB trade name of US BORAX
  • FRF-30 trade name of Mizusawa Chemical Industry Co., Ltd.
  • As the zinc borate represented by (XXXII), FB_415 (trade name, manufactured by US BORAX) is commercially available.
  • anhydrous zinc borate used in the present invention acts as a flame retardant, and is not particularly limited as long as the effects of the present invention can be obtained.
  • anhydrous boron represented by the following composition formula (XIX) Zinc acid and the like.
  • anhydrous zinc borate represented by the composition formula (XXXIII) include the following composition formulas (II), (XIX), (XX), (XXI), and (XXII). They may be used alone or in combination of two or more. It may be used in combination with zinc borate. Of these, anhydrous zinc borate represented by the following composition formula (II) is preferable from the viewpoint of flame retardancy.
  • FB-500 (trade name, manufactured by US BORA) is commercially available.
  • the method for producing anhydrous zinc borate is not particularly limited, but a method in which boric acid is directly produced by reacting a carbonate or oxide of a partner salt, or a method in which hydrated borate is heated to form water of crystallization. A removal method and the like can be mentioned.
  • (C) Boric acid-based flame retardants have improved flame retardancy or fluidity due to improved dispersibility.
  • D) At least one of an inorganic substance and an organic substance may be treated for the purpose of improving the quality. In that case, it is preferable that (D) the surface treatment is performed with at least one of an inorganic substance and an organic substance.
  • the boric acid-based flame retardant is used for the treatment.
  • the inorganic or organic substance is not particularly limited. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, Silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, zinc oxide, zinc stannate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentane
  • metal elements such as genenyl iron, composite metal hydroxides, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide, talcites at the mouth, magnesium, aluminum, titanium, and zirconium Hydrogenation of elements selected from iron and bismuth Products, vinyltrichlorosilane, vinyltriethoxy
  • (D) As a method of treating at least one of an inorganic substance and an organic substance, for example, a method of treating a resin such as an acrylic resin, a phenol resin, an epoxy resin, and a melamine resin by a suspension emulsion polymerization method or a mechanochemical method; Examples thereof include a method of treating the surface with a silane-based, titanate-based, or aluminum-based coupling agent such as stearic acid, and a method of treating the surface with an inorganic substance such as aluminum hydroxide, magnesium hydroxide, or silica by a mechanochemical method. From the viewpoints of improving dispersibility and thermal stability, treatment with a metal hydroxide is preferable, and treatment with magnesium hydroxide is more preferable.
  • a resin such as an acrylic resin, a phenol resin, an epoxy resin, and a melamine resin by a suspension emulsion polymerization method or a mechanochemical method
  • a resin such as an acrylic resin, a
  • the processing may be performed alone or a plurality of processings may be performed.
  • the processing may be performed alone or a plurality of processings may be performed.
  • the effect of zinc borate or anhydrous zinc borate due to boric acid is reduced, the wettability with the resin is improved, the dispersibility of zinc borate or anhydrous zinc borate is improved, and the flame retardancy is improved. And the fluidity in the low shear region are improved.
  • the processing amount is increased, Not only does zinc borate or treated anhydrous zinc borate easily aggregate, but also the flame retardancy and curability decrease.
  • (C 1) anhydrous borate is used as the flame retardant
  • (D) The amount of inorganic or organic substances to be treated is ((CI) / ((C 1) + (D))) by weight. Is preferably less than 0.02, and more preferably less than 0.01. For the same reason, (C2) zinc borate or
  • (D) The amount of inorganic or organic material to be treated is ((C2) Z ((C2) + (D) :)) or ((C3) Z ((C 3) +
  • the average particle size of (C 1) anhydrous borate, (C 2) zinc borate or (C 3) zinc borate as the (C) boric acid flame retardant is not particularly limited. In light of the above, 0.01 to 50 im is preferable, 0.1 to 30 / m is more preferable, and 0.5 to 20 im is more preferable. Anhydroborate having an average particle size of less than 0.01 zm is difficult to produce, and if it exceeds 50 m, the flame retardant effect may be insufficient or the gate may be clogged during molding.
  • the amount of (C 1) anhydrous borate, (C 2) zinc borate or (C 3) zinc borate as the (C) boric acid flame retardant is not particularly limited. It is preferably 0.01 to 20% by weight, more preferably 0.05 to 5% by weight, and still more preferably 0.1 to 0.5% by weight, based on the resin molding material. If it is less than 0.01% by weight, the flame retardancy tends to be insufficient, and if it exceeds 20% by weight, the moldability tends to decrease.
  • the blending amount of (C2) zinc borate or (C 3) anhydrous zinc borate is preferably less than 0.5% by weight, more preferably less than 0.3% by weight, based on the epoxy resin molding material for sealing. . It has been found that even at a compounding amount of less than 0.5% by weight, the effect of vitrifying the charcoal is exhibited and flame retardancy can be achieved. Unless (C2) zinc borate or (C3) anhydrous zinc borate is blended, the flame retardancy tends to be insufficient. At 0.5% by weight or more, (C2) zinc borate However, the curability and fluidity in the low shear region tend to decrease, and (C 3) In the case of anhydrous zinc borate, the fluidity in the low shear region tends to decrease.
  • the compounding amount may be 0.5% by weight or more, but especially when untreated. Is preferably less than 0.5% by weight.
  • the epoxy resin molding material for sealing of the present invention uses (C) an anhydrous borate as the (C) boric acid-based flame retardant, it is added to the (C 1) anhydrous borate.
  • Conventionally known non-halogen and non-antimony flame retardants can be blended as required.
  • the epoxy resin molding material for encapsulation according to the present invention comprises: (C) zinc borate or (C 3) anhydrous zinc borate as a boric acid-based flame retardant; ) In addition to zinc borate or (C 3) anhydrous zinc borate, conventionally known non-halogen and non-antimony flame retardants can be blended as required.
  • coated or uncoated red phosphorus an ester compound having a phosphorus atom, triphenylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, 2,2-[(2- (diphenylphosphinyl) ) 1,1,4-phenylene) bis (oxymethylene)] bis-oxysilane, phosphine compounds such as tri-n-octylphosphine oxide, phosphorus and nitrogen-containing compounds such as cyclophosphazene, etc.
  • Phosphorus-based flame retardants melamine, melamine derivatives, melamine-modified phenolic resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives, isocyanuric acid derivatives, zinc oxide, zinc stannate, iron oxide, molybdenum oxide, molybdic acid
  • nitrogen-containing compounds such as cyanuric acid derivatives, isocyanuric acid derivatives, zinc oxide, zinc stannate, iron oxide, molybdenum oxide, molybdic acid
  • metal elements such as zinc and dicyclopentene genenyl iron
  • metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide
  • those metal hydroxides as resins, coupling agents, stearic acid And the like, a composite metal hydroxide, and the like.
  • One of these may be used alone, or two or more may be used in combination.
  • (E) a phosphorus-based flame retardant is highly effective in combination, and (C 1) anhydrous borate, (C 2) zinc borate or When used in combination with a (C) boric acid-based flame retardant such as (C 3) anhydrous zinc borate, the amount required for flame retardancy can be reduced.
  • Examples of the composite metal hydroxide include a compound represented by the following composition formula (XXXIV).
  • Mi and M 2 indicate different metal elements, and a, b, c, d, m, n, and 1 indicate positive numbers.
  • Mi and M 2 in the above composition formula (XXXIV) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, Mi and M 2 are different from each other so that Element, selected from group IV alkaline earth metal elements, group IVB, IIB, VHI, IB, group ⁇ and IVA group metal elements, M 2 selected from ⁇ ⁇ : QB group transition metal elements
  • Mi is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and more preferably, M 2 is selected from iron, cobalt, nickel, copper and zinc.
  • magnesium Mi of preferably M 2 is zinc or nickel
  • the molar ratio of m and n is not particularly limited, it is preferable that mZn is from 99Z1 to 50/50.
  • the metal elements are classified according to the long-period type periodic table with the typical element being the A sub-group and the transition element being the B sub-group. (Source: Chemical Dictionary 4 j 1987 Two This was done on the 15th of March, the 30th edition.
  • the shape of the composite metal hydroxide is not particularly limited, but from the viewpoint of fluidity, a polyhedral shape having an appropriate thickness is preferable to a flat shape. In the composite metal hydroxide, polyhedral crystals are easily obtained as compared with the metal hydroxide.
  • the compounding amount of the composite metal hydroxide is not particularly limited, but is preferably 0.05 to 20% by weight, more preferably 0.01 to 15% by weight, based on the molding epoxy resin molding material. , 0.05 to 12% by weight. If it is less than 0.05% by weight, the flame retardancy tends to be insufficient, and if it exceeds 20% by weight, the fluidity and the reflow resistance tend to decrease.
  • the epoxy resin molding material for encapsulation of the present invention further comprises, as an optional component, (E) phosphorus in addition to (A) the epoxy resin, (B) a curing agent, and (C) a boric acid-based flame retardant.
  • a flame retardant, (F) an inorganic filler and (G) other components may be contained.
  • One of these optional components may be used alone, or two or more of them may be used in combination.
  • the phosphorus-based flame retardant is not particularly limited as long as the effects of the present invention can be obtained. Coated or uncoated red phosphorus, phosphorus and a nitrogen-containing compound such as cyclophosphazene, tricalcium ditrilotrismethylene phosphonate, etc.
  • Phosphonates such as methane-11-hydroxy-11,1-diphosphonic acid dicalcium salt, triphenylphosphine, 21- (diphenylphosphinyl) octahydroquinone, 2,2-1 ([2- (Diphenylphosphinyl) -1,4-phenylene) bis (oxomethylene)] bis-oxosilane, phosphine compounds such as tri-n-octylphosphinoxide, ester compounds having a phosphorus atom, cyclophosphazene And phosphorus- and nitrogen-containing compounds such as butane. One of these may be used alone, or two or more may be used in combination.
  • an ester compound having a phosphorus atom and a phosphine compound are preferable from the viewpoint of hydrolysis resistance and fluidity.
  • Red phosphorus acts as a flame retardant, and is not particularly limited as long as the effects of the present invention can be obtained.
  • examples of red phosphorus coated with a thermosetting resin red phosphorus coated with an inorganic compound and an organic compound, and the like. Coated red phosphorus is preferred.
  • the thermosetting resin used for the red phosphorus coated with the thermosetting resin is not particularly limited. Examples thereof include an epoxy resin, a phenol resin, a melamine resin, a urethane resin, a cyanate resin, and a urea-formalin resin.
  • ananiline-formalin resin furan resin, polyamide resin, polyamide-imide resin, polyimide resin, and the like. These may be used alone or in combination of two or more. Further, coating and polymerization may be performed simultaneously using monomers or oligomers of these resins, and the thermosetting resin produced by polymerization may be coated. The thermosetting resin may be cured after coating. Is also good. Above all, epoxy resin, phenolic resin and melamine resin are preferable from the viewpoint of compatibility with the base resin blended in the sealing epoxy resin molding material.
  • the inorganic compound used for the red phosphorus coated with the inorganic compound and the organic compound is not particularly limited.
  • examples thereof include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, and zirconium oxide.
  • examples include dimethyl, bismuth hydroxide, barium carbonate, calcium carbonate, zinc oxide, titanium oxide, nickel oxide, iron oxide, and the like.One of these may be used alone, or two or more may be used in combination. Is also good.
  • zirconium hydroxide, hydrous zirconium oxide, aluminum hydroxide and zinc oxide which are excellent in the effect of capturing phosphate ions, are preferred.
  • the organic compound used for the red phosphorus coated with the inorganic compound and the organic compound is not particularly limited.
  • a low molecular weight compound used for surface treatment such as a coupling agent or a chelating agent, or a thermoplastic resin And high molecular weight compounds such as thermosetting resins.
  • One of these compounds may be used alone, or two or more of them may be used in combination.
  • a thermosetting resin is preferable from the viewpoint of the coating effect, and an epoxy resin, a phenol resin, and a melamine resin are more preferable from the viewpoint of compatibility with the base resin blended in the epoxy resin molding material for sealing.
  • red phosphorus is coated with an inorganic compound and an organic compound
  • the order of the coating treatment is not particularly limited.Either coating with an inorganic compound and then coating with an organic compound, or coating with an organic compound and then coating with an inorganic compound can be used. However, using a mixture of both, Sometimes it may be coated.
  • the coating form is not particularly limited, and may be physically adsorbed, chemically bonded, or other forms. Further, the inorganic compound and the organic compound may be present separately after coating, or may be in a state where a part or the whole of both is bonded.
  • the amounts of the inorganic compound and the organic compound are not particularly limited as long as the effects of the present invention can be obtained.
  • the weight ratio of the inorganic compound and the organic compound may be as follows. Is preferably, 10/90 to 95Z5 is more preferable, and 30/70 to 90Z10 is more preferable, and an inorganic compound and an organic compound or a raw material thereof so as to have such a weight ratio. It is preferable to adjust the amount of the monomer or oligomer used.
  • the method for producing coated red phosphorus such as red phosphorus coated with a thermosetting resin and red phosphorus coated with an inorganic compound and an organic compound is not particularly limited.
  • the thickness of the coating film is not particularly limited as long as the effects of the present invention can be obtained, and the coating may be a uniform coating on the red phosphorus surface or a non-uniform coating.
  • the particle size of red phosphorus is not particularly limited as long as the effects of the present invention can be obtained, but the average particle size (the particle size at which 50% by weight is accumulated in the particle size distribution) is preferably from 1 to 100 m, and from 5 to 100 m. 50 m is more preferred. If the average particle size is less than 1 tm, the molded product has a high phosphate ion concentration and tends to have poor moisture resistance. If the average particle size exceeds 100 m, high integration of narrow pad pitch In such a case, there is a tendency that defects such as deformation, short-circuiting, and cutting of the wire are likely to occur.
  • Phosphorus and nitrogen-containing compounds act as flame retardants and are not particularly limited as long as the effects of the present invention can be obtained.
  • the following formula (XXXV) and Z or the following formula (XXXVI) may be repeated in the main chain skeleton.
  • m in the formulas (XXXV) and (XXXVII) is an integer of 1 to 10
  • R i to R 4 are an alkyl group having 1 to 12 carbon atoms and an aryl group which may have a substituent. And all may be the same or different, but at least one is a group having a hydroxyl group
  • A represents an alkylene group having 1 to 4 carbon atoms or an arylene group.
  • N in the formulas (XXXVI) and (XXXVIII) is an integer of 1 to L 0, and R 5 to R 8 are selected from an alkyl group or an aryl group having 1 to 12 carbon atoms which may have a substituent.
  • A represents an alkylene group or an arylene group having 1 to 4 carbon atoms.
  • m RR 2, R 3, and R 4 may all be the same or different, and n R 5 , R 6 , R 7 , and R 8 may be different even if all n are the same. May be.
  • XXXV alkyl group or aryl group having 1 to 12 carbon atoms which may have a substituent represented by a length of 1 to! ⁇ 8 .
  • alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group, phenyl group, aryl groups such as 11-naphthyl group and 2-naphthyl group , O-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, o—
  • alkyl-substituted aryl groups such as cumenyl group, m-cumenyl group, p-cumenyl group, and mesityl group
  • aryl-substituted alkyl groups such as benzyl group and phenethyl group.
  • an aryl group is preferable from the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material, and a phenyl group or a hydroxyphenyl group is more preferable.
  • at least one of 1 to! ⁇ 4 is preferably a hydroxyphenyl group, and all of R i to R 8 may be a hydroxyphenyl group, but one of R i R 4 is a hydroxyphenyl group. The case is more preferred. !
  • ⁇ ⁇ 8 tends to be brittle Epokishi cured resin in the case of all hydro Kishifueniru group, because if R 1 - R 8 are all by phenyl group is not incorporated into the crosslinked structure of the epoxy resin, E port carboxymethyl resin curing The heat resistance of the material tends to decrease.
  • the alkylene or arylene group having 1 to 4 carbon atoms represented by ⁇ in the above formulas (XXXV) to (XXXVIII) is not particularly limited.
  • an arylene group is preferable. Groups are more preferred.
  • the cyclic phosphazene compound is a polymer of any one of the above formulas (XXXV) to (XXXVIII), a copolymer of the above formula (XXXV) and the above formula (XXXVI), or a mixture of the above formula (XXXVII) and the above formula (XXXVIII) ), But in the case of a copolymer, any of a random copolymer, a block copolymer, and an alternating copolymer may be used.
  • the copolymerization molar ratio mZn is not particularly limited, but is preferably 1/0 to 1 Z4, more preferably 1 Z0 to: 1 / 1.5 from the viewpoint of improving the heat resistance and strength of the epoxy resin cured product. . Further, the degree of polymerization m + n is 1 to 20, preferably 2 to 8, and more preferably 3 to 6.
  • Preferred examples of the cyclic phosphazene compound include a polymer represented by the following formula (XXXIX) and a copolymer represented by the following formula (XXXX).
  • m in the formula (XXXIX) is an integer of 0 to 9, and 1 to! ⁇ 4 each independently represent hydrogen or a hydroxyl group.
  • n is an an integer from 0 to 9
  • R 1! ⁇ 4 is at least one selected from hydrogen or hydroxyl in, respectively it independently is hydroxyl
  • R 5 ⁇ R 8 is independently selected from hydrogen or a hydroxyl group.
  • the cyclic phosphazene compound represented by the above formula (XXXX) can be a compound containing the following m repeating units (a) and n repeating units (b) alternately, a block containing it, and a random. Any of these may be included, but those that include randomly are preferred.
  • One of ⁇ to 4 is mainly composed of a polymer having a hydroxyl group and m of 3 to 6, or one of Ri to R 4 in the above formula (XXXX) is a hydroxyl group, and all of R 5 to R 8 are Hydrogen or one having a hydroxyl group, m / n of lZ2 to l / 3 and m + n of 3 to 6 as a main component is preferable.
  • SPE-100 trade name of Otsuka Chemical Co., Ltd.
  • ester compound having a phosphorus atom examples include phosphoric acid ester, o-ester, ester phosphite, hypophosphite, and the like. From the viewpoint of hydrolysis resistance, an ester compound having a phosphorus atom Is more preferably a compound having an aromatic ring.
  • the compound having an aromatic ring examples include a compound having a skeleton represented by the following general formula (XXXXI), and among them, a compound represented by the following general formula ( ⁇ ⁇ ⁇ ⁇ ) is preferable.
  • Y is a divalent organic group having a substituted or unsubstituted aromatic ring
  • R is a hydrogen atom or a substituted or unsubstituted organic group having 1 to 6 carbon atoms, and R is different even if all are the same.
  • M and n each represent an integer of 0 to 3.
  • ester compound having a phosphorus atom examples include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylendiphenyl.
  • the following structural formula ( ⁇ ) Compounds having an aromatic ring represented by (XXXXVI) are preferred, and compounds represented by structural formulas (XXXXVII) to (XXXXIX) are more preferred.
  • a phosphine oxide compound represented by the following general formula (XXXXXI ID) is preferable from the viewpoint of chemical stability.
  • R 1 R 2 and R 3 represent a substituted or unsubstituted alkyl group, aryl group, aralkyl group and hydrogen atom having 1 to 10 carbon atoms, all of which may be the same or different. Except when it is an atom.)
  • R to Sha 3 be a substituted or unsubstituted aryl group, and particularly preferable is phenyl. Group.
  • the amount of the phosphorus-based flame retardant such as an ester compound having a phosphorus atom and a phosphine compound is not particularly limited.However, (F) the amount of the phosphorus atom relative to all the other components except the inorganic filler is 0.1%. It is preferably from 0.1 to 50% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.5 to 3% by weight. If the amount is less than 0.01% by weight, the flame retardancy tends to be insufficient, and if it exceeds 50% by weight, the moldability and the moisture resistance tend to decrease.
  • the epoxy resin molding material for sealing of the present invention may optionally contain (F) an inorganic filler.
  • F The inorganic filler is blended for the purpose of absorbing moisture, reducing the coefficient of linear expansion, improving the thermal conductivity and improving the strength, and is generally used in epoxy resin molding materials for sealing.
  • fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, while fused silica is preferred from the viewpoint of high thermal conductivity.
  • Is preferably alumina, and the shape of the filler is preferably spherical in terms of fluidity during molding and mold abrasion.
  • the mixing amount of the inorganic filler is 70 to 98 weight based on the epoxy resin molding material for sealing from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and improvement of strength. %, Preferably from 80 to 95% by weight, more preferably from 85 to 93% by weight. If the amount is less than 70% by weight, the flame retardancy and reflow resistance tend to decrease. If the amount exceeds 98% by weight, the fluidity tends to be insufficient.
  • a curing accelerator can be used if necessary.
  • the curing accelerator is not particularly limited, and is generally used in molding epoxy resin molding materials.
  • 1,8-diaza-visit (5,4,0) pendene-7,1,1, Cycloamidine compounds such as 5-diazabicyclo (4,3,0) nonene, 5,6dibutylamino-1,8-diazabicyclo (5,4,0) indene, and maleic anhydride, 1 , 4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylpenzoquinone, 2,6-dimethylpentazoquinone, 2,3-dimethoxy-1-5-methyl-1,4-benzoquinone Quinone compounds such as 2,3-dimethoxy-11,4-benzoquinone, phenyl_1,4-benzoquinone, and diazophenylmethane, phenolic resin
  • Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine; A phosphorus compound having an intramolecular polarization obtained by adding a compound having a ⁇ bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or phenol resin to these phosphine compounds; tetraphenylphosphonium tetra Phenylprolate, triphenylphosphinetetraphenyl
  • phosphine compounds and adducts of phosphine compounds with quinone compounds are preferable, and tertiary phosphine compounds such as triphenylphosphine and adducts of triphenylphosphine with quinone compounds are preferable. More preferred. When a tertiary phosphine compound is used, it is preferable to further contain a quinone compound.
  • an adduct of a cycloamidine compound and a phenol resin is preferable, and a phenolnopolak resin salt of diazapicicloundecene is more preferable.
  • the amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.05 to 2% by weight based on the epoxy resin molding material for sealing. , 0.01 to 0.5% by weight is more preferable. If the amount is less than 0.05% by weight, the curability in a short time tends to be inferior. If the amount exceeds 2% by weight, the curing speed tends to be too fast to obtain a good molded product.
  • An ion trapping agent can be further added to the encapsulating epoxy resin molding material of the present invention, if necessary, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of semiconductor elements such as IC.
  • the ion trapping agent there is no particular limitation on the ion trapping agent, and any known ion trapping agent can be used. These may be used alone or in combination of two or more. Among them, the talcite at the mouth represented by the following composition formula (XXXXX) is preferable.
  • the compounding amount of the ion trapping agent is not particularly limited as long as it is a sufficient amount to capture anion such as octylogen ion.
  • the amount of the ion trapping agent relative to (A) epoxy resin It is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 10% by weight, even more preferably from 1 to 5% by weight.
  • the epoxy resin molding material for encapsulation of the present invention may further include epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, if necessary, in order to enhance the adhesion between the resin component and the inorganic filler.
  • coupling agents such as silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds.
  • These include, for example, vinylyltrichlorosilane, vinyltriethoxysilane, pinyl tris (/ 3-methoxyethoxy) silane, acryloxypropyltrimethoxysilane,] 3- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, acrylicoxyfifoxypyrmethyldimethoxysilane, vinyltriacetoxysilane, amercaptopropyltrimethoxysilane, araminopropyltriethoxysilane, ⁇ - anilinopropyltrimethoxysilane, avalilinopropylmethyldimethoxysilane, 7- [bis (] 3-hydroxyethyl)] aminopropyltriethoxysilane, N-J3-
  • the amount of the coupling agent is preferably from 0.05 to 5% by weight, more preferably from 0.1 to 2.5% by weight, based on the inorganic filler (F). If it is less than 0.05% by weight, the adhesiveness to the frame tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.
  • the epoxy resin molding material for encapsulation according to the present invention may further comprise, as other additives, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin resins, polyethylene, and polyethylene oxide, and carbon black.
  • release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin resins, polyethylene, and polyethylene oxide, and carbon black.
  • a coloring agent such as, a stress relieving agent such as silicone oil or silicone rubber powder and the like can be added as required.
  • the epoxy resin molding compound for encapsulation of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed, but as a general method, a predetermined amount of raw materials are mixed with a mixer. After sufficient mixing by mixing, etc., melt kneading with a mixing nozzle, an extruder or the like, then cooling and pulverizing may be mentioned. It is easy to use if it is made into a tablet with dimensions and weight that match the molding conditions. (Electronic component equipment)
  • the electronic component device provided with the element sealed with the sealing epoxy resin molding material obtained by the present invention includes a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, and a semiconductor chip. , Active elements such as transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc., were mounted, and the necessary parts were sealed with the sealing epoxy resin molding material of the present invention. And electronic component devices. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion of an element such as a bonding pad and a lead portion are connected by wire bonding and bumps.
  • DIP Device Inline Package
  • PLCC Plastic Leaded Chip Carrier
  • epoxy resin molding material for General resin sealing such as QFP (Quad Flat Package), SOP (Small Outline Package), S ⁇ J (Small Outline J-lead package), TS ⁇ P (Thin Small Outline Package), TQFP (Thin Quad Flat Package)
  • QFP Quad Flat Package
  • SOP Small Outline Package
  • S ⁇ J Small Outline J-lead package
  • TS ⁇ P Thin Small Outline Package
  • TQFP Thin Quad Flat Package
  • the semiconductor chip connected by bumps to the fixed-type IC and tape carrier is connected to the TCP (Tape Carrier Package) sealed with the epoxy resin molding material for sealing of the present invention, and the wiring formed on the wiring board and glass.
  • Active elements such as semiconductor chips, transistors, diodes, thyristors and the like, and / or passive elements such as capacitors, resistors, coils, etc., connected by wire bonding, flip chip bonding, soldering, etc., are encapsulated with the epoxy resin molding material of the present invention.
  • the device is mounted on the surface of an encapsulated COB (Chip On Board) module, Hybrid I (:, multi-chip module, and an organic substrate with terminals for wiring board connection on the back, and bumps and BGA (Ball Grid Array), CSP (Chip Size Package) in which the device is connected to the wiring formed on the organic substrate by wire bonding and then the device is sealed with the epoxy resin molding material for sealing of the present invention.
  • COB Chip On Board
  • Hybrid I :, multi-chip module, and an organic substrate with terminals for wiring board connection on the back
  • bumps and BGA (Ball Grid Array), CSP (Chip Size Package) in which the device is connected to the wiring
  • a low pressure transfer molding method is the most common, but an injection molding method, a shrink molding method, or the like may be used.
  • Tables 4 and 5 show the evaluation results of the molded epoxy resin molding materials of the examples and comparative examples.
  • the molding of the sealing epoxy resin molding material was performed by a transfer molding machine under the conditions of a mold temperature of 180 ° (molding pressure of 6.9 MPa and a curing time of 90 seconds. 5 hours at C.
  • Table 4
  • Comparative Examples A1 to A6 in which a borate was used instead of the anhydrous borate of the component (CI) of the present invention had extremely low hardness when heated and were inferior in moldability. Comparative Examples A7 and A8, which used a phosphorus-based flame retardant alone, were inferior in flame retardancy.
  • the fluidity, the hardness at the time of heating, the reflow resistance, the moisture resistance, and the high-temperature storage characteristics were all good, and V-0 was achieved in the UL-94 test. It showed flame retardancy.
  • Examples A1 to A8 and A10 to A15 using a metal borate anhydride other than the alkaline earth metal the extract liquid conductivity was small and the reliability was good.
  • the evaluation results of the prepared epoxy resin molding materials for sealing in Examples ⁇ and Comparative Example ⁇ ⁇ are shown in Table 10, Table 11 and Table 12.
  • the molding of the sealing epoxy resin molding material was carried out using a transfer molding machine at a mold temperature of 180 ° (: molding pressure of 6.9 MPa, transfer time of 5 seconds, and curing time of 90 seconds. Post-curing was performed at 180 ° C. for 5 hours.
  • the treatment amount of (C2) zinc borate or (C 3) anhydrous zinc borate treated with the inorganic or organic substance (D) of the present invention is ((C2) / ((C2) + (D))) by weight ratio. ) Or ((C3) / ((C3) I (D)))) is 0.02 or more. Poor sex. Comparative Examples B2 B4 B5 also had reduced flame retardancy. (D) Comparative example using zinc borate or (C3) anhydrous zinc borate not treated with inorganic or organic substances B 6 B 9 B 11 has a large number of voids and is inferior in moldability. Was. Comparative Examples B12 and B13 using the phosphorus-based flame retardant alone had poor flame retardancy.
  • Example B 1 B 19 showed good fluidity, hot hardness, reflow resistance, moisture resistance, high-temperature storage characteristics and moldability, and a V-94 test in the UL-94 test. And achieved flame retardancy.
  • Treated anhydrous zinc borate 1 5.0 10.0 Triphenylphosphine 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
  • Trifenylphosphine oxide 10.0 Trifenylphosphine 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
  • the evaluation results of the epoxy resin molding materials for sealing of the produced examples and comparative examples are shown in Tables 16, 17 and 18.
  • the molding of the epoxy resin molding compound for sealing was performed using a transfer molding machine under the conditions of a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, a transfer time of 5 seconds, and a curing time of 90 seconds. Post-curing was performed at 180 ° C for 5 hours. Table 16
  • Comparative Examples C1 to C4 containing (C 2) zinc borate of the present invention in an amount of 0.5% by weight or more based on the epoxy resin molding material for sealing have extremely low hardness and a large number of voids generated. Poor moldability.
  • Comparative Examples 5 and 6, in which (C 3) anhydrous zinc borate was contained in an amount of 0.5% by weight or more based on the epoxy resin molding compound for encapsulation the number of generated voids was large, and the moldability was high. Inferior.
  • Comparative Examples C7 and C8 using the phosphorus-based flame retardant alone had inferior flame retardancy.
  • Examples C1 to C22 showed good fluidity, hot hardness, reflow resistance, moisture resistance, high-temperature storage characteristics and moldability, and V-94 in the UL-94 test. Achieved 0, indicating flame retardancy.
  • Epoxy molding materials for sealing were prepared in Examples A, B, and C and Comparative Examples A, B, and C using the components listed below.
  • Biphenyl-type epoxy resin with an epoxy equivalent of 192 and a melting point of 105 ° C (Yuka Shell Epoxy Co., Ltd. Pico YX-4000H), an epoxy equivalent of 245 and a sulfur atom-containing epoxy with a melting point of 113 ° C
  • O-cresol nopolak type epoxy resin (trade name: ES CN-190, manufactured by Sumitomo Chemical Co., Ltd.) having an epoxy equivalent of 195 and a softening point of 65 ° C;
  • Aralkyl type phenol tree with a hydroxyl equivalent of 172 and a softening point of 70 ° C as a curing agent Fat (Mitsui Chemicals Co., Ltd. trade name MILEX XL-225), hydroxyl equivalent 198, biphenyl type phenolic resin with softening point 75 ° C (Meiwa Kasei Co., Ltd.
  • ME H-785 1), hydroxyl equivalent 104, softening Triphenylmethane type phenol resin with a point of 88 ° C (MEH-7500 manufactured by Meiwa Kasei Co., Ltd.), a hydroxyl equivalent of 154, and a triphenylmethane type phenol resin with a softening point of 73 ° C 2 (Sumikin Chemical Co., Ltd.)
  • Phenol nopolak resin brand name HE510
  • hydroxyl equivalent 103 softening point 83 ⁇ (brand name ⁇ -100 manufactured by Meiwa Kasei Co., Ltd.);
  • anhydrous borate As anhydrous borate, anhydrous borate 1 (composition formula (XV), average particle size 3 zm, solubility in water 0.668 water 1001111), anhydrous borate 2 (composition formula (XVI), average particle size) Diameter 12 m, solubility in water 0.08 g / water 100 m 1), anhydrous borate 3 (composition formula (II) below, average particle size 8 / im, solubility in water 0.Olg / water 100 ml, BORA brand name FB-500), anhydrous borate 6 (the following composition formula (XXIII), average particle size 7 im, solubility in water 0.02 g / water 100 ml, brand name from Shikoku Chemicals Co., Ltd.) Arborite PF 08T), anhydrous borate 7 (the following composition formula (XXVI), average particle size 8 ⁇ m, solubility in water 0.0200 ml), and anhydrous borate 8 (the following composition formula (XXXXX
  • zinc borate 1 zinc borate of the following composition formula (XXVIII), average particle size 3 m, FRF-30 manufactured by Mizusawa Chemical Industry Co., Ltd.
  • zinc borate 2 the following composition formula ( XXVIII) zinc borate, average particle size 8 / im, FR-50 manufactured by Mizusawa Chemical Industry Co., Ltd.
  • zinc borate 3 zinc borate of the following composition formula (XXVIII), average particle size 9 / im, US (BORA FB-ZB), zinc borate 4 (zinc borate of the following composition formula (XXXII), average particle size 5 / im, US BORAX FB—415)
  • anhydrous zinc borate 1 (zinc borate of the following composition formula (II), average particle size 8 ⁇ m, US BORA FB-500),
  • XXXIV composite metal hydroxides
  • Mi magnesium
  • M2 is zinc
  • m 0.8
  • n 0.2
  • 1 1, a, b
  • Triphenyl phosphine oxide as a phosphine compound
  • triphenyl phosphine as a hardening accelerator
  • Epoxy silane coupling agents Shin 'Koshi Chemical Industry Co., Ltd.
  • an epoxy resin molding material for sealing was molded under the above conditions and post-cured, and the flame retardancy was evaluated according to the UL-94 test method.
  • the epoxy resin molding material for sealing was molded into a disk having a diameter of 50111111 and a thickness of 3111111 under the above conditions, and measured immediately after molding using a Shore D hardness meter.
  • a package (QFP) is formed by molding and post-curing using the epoxy resin molding compound for sealing under the above conditions, and after performing pre-treatment, humidifying to prevent disconnection failure due to aluminum wiring corrosion every predetermined time. The humidification time when the ratio of defective packages to the number of test packages (10) reached 50% was evaluated.
  • the flat package was humidified at 85 ° C and 85% RH for 72 hours, and then subjected to vapor phase reflow treatment for 215 and 90 seconds. Subsequent humidification was performed under the conditions of 0.2 MPa and 121 ° C.
  • a 5 m m x 9 mm x 0.4 mm test silicon chip with a 10 m / m and 1 m thick aluminum wiring line on a 5 m thick oxide film is mounted on a 42 alloy lead frame with a partial silver plating.
  • a test piece for measuring impurities was finely pulverized, and a 5 g sample was put into an Acom-made Niseal (extraction jig) together with 50 ml of distilled water, and extracted in a thermostat at 12 l ° C / 20 hours. The extract was filtered to obtain a test solution. Using the test solution, electric conductivity was measured with an electric conductivity meter CM-115 manufactured by Kyoto Electronics Co., Ltd.
  • the epoxy resin molding material for encapsulation according to the present invention can achieve flame retardancy with non-halogen and non-antimony as shown in the examples, has excellent moldability such as curability, reflow resistance, moisture resistance and high temperature.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La présente invention concerne un matériau de moulage en résine époxy destiné à l'encapsulation qui comprend (A) une résine époxy, (B) un agent de durcissement et (C) un agent d'ignifugation borate comme composants essentiels, l'agent d'ignifugation borate (C) étant (C1) un sel de borate anhydre, (c2) un borate de zinc, ou (c3) un borate de zinc anhydre. Cette invention concerne aussi des composants ou des dispositifs électroniques comprenant des éléments encapsulés avec ce matériau. Cette invention concerne un matériau de résine époxy non halogène et non antimoine destiné à l'encapsulation dont l'ignifugation est améliorée sans dégrader la fiabilité des propriétés de moulage, la fluidité, la résistance à l'humidité etc.. Cette invention concerne aussi des composants et des dispositifs électroniques comprenant des éléments encapsulés avec ce matériau.
PCT/JP2002/012974 2002-03-22 2002-12-11 Materiau de moulage en resine epoxy destine a l'encapsulation et aux dispositifs et composants electroniques Ceased WO2003080726A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006052391A (ja) * 2004-07-13 2006-02-23 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2007099808A (ja) * 2005-09-30 2007-04-19 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
JP2007177150A (ja) * 2005-12-28 2007-07-12 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
US7585443B2 (en) 2004-05-20 2009-09-08 Albemarle Corporation Pelletized brominated anionic styrenic polymers and their preparation and use
JP2012025964A (ja) * 2004-07-13 2012-02-09 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116598054B (zh) * 2023-07-18 2023-09-12 创进电缆有限公司 一种高阻燃防火电缆及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5342553A (en) * 1991-11-22 1994-08-30 U. S. Borax Inc. Process of making zinc borate and fire-retarding compositions thereof
EP0812883A1 (fr) * 1995-12-28 1997-12-17 Toray Industries, Inc. Composition de resine epoxy
JPH11124480A (ja) * 1997-10-24 1999-05-11 Matsushita Electric Works Ltd 半導体封止用樹脂組成物およびその製造方法、ならびにこの半導体封止用樹脂組成物を用いた半導体装置
JP2001131393A (ja) * 1999-10-29 2001-05-15 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2001181522A (ja) * 1999-12-28 2001-07-03 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、及び、成形品
JP2001335708A (ja) * 2000-05-26 2001-12-04 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、並びに半導体素子収納用パッケージ
JP2002038005A (ja) * 2000-07-26 2002-02-06 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、並びに半導体素子収納用パッケージ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5342553A (en) * 1991-11-22 1994-08-30 U. S. Borax Inc. Process of making zinc borate and fire-retarding compositions thereof
EP0812883A1 (fr) * 1995-12-28 1997-12-17 Toray Industries, Inc. Composition de resine epoxy
JPH11124480A (ja) * 1997-10-24 1999-05-11 Matsushita Electric Works Ltd 半導体封止用樹脂組成物およびその製造方法、ならびにこの半導体封止用樹脂組成物を用いた半導体装置
JP2001131393A (ja) * 1999-10-29 2001-05-15 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2001181522A (ja) * 1999-12-28 2001-07-03 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、及び、成形品
JP2001335708A (ja) * 2000-05-26 2001-12-04 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、並びに半導体素子収納用パッケージ
JP2002038005A (ja) * 2000-07-26 2002-02-06 Matsushita Electric Works Ltd 熱可塑性樹脂組成物、その製造方法、並びに半導体素子収納用パッケージ

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7585443B2 (en) 2004-05-20 2009-09-08 Albemarle Corporation Pelletized brominated anionic styrenic polymers and their preparation and use
JP2006052391A (ja) * 2004-07-13 2006-02-23 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2012025964A (ja) * 2004-07-13 2012-02-09 Hitachi Chem Co Ltd 封止用エポキシ樹脂成形材料及び電子部品装置
JP2007099808A (ja) * 2005-09-30 2007-04-19 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
JP2007177150A (ja) * 2005-12-28 2007-07-12 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置

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JPWO2003080726A1 (ja) 2005-07-21
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