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WO2003082976A1 - Composition de resine thermodurcissable et materiau de moulage de resine epoxyde utilisant cette composition et dispositif semi-conducteur - Google Patents

Composition de resine thermodurcissable et materiau de moulage de resine epoxyde utilisant cette composition et dispositif semi-conducteur Download PDF

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Publication number
WO2003082976A1
WO2003082976A1 PCT/JP2002/003104 JP0203104W WO03082976A1 WO 2003082976 A1 WO2003082976 A1 WO 2003082976A1 JP 0203104 W JP0203104 W JP 0203104W WO 03082976 A1 WO03082976 A1 WO 03082976A1
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group
monovalent
atom
general formula
resin composition
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English (en)
Inventor
Yoshiyuki Goh
Akiko Okubo
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority to PCT/JP2002/003104 priority Critical patent/WO2003082976A1/fr
Publication of WO2003082976A1 publication Critical patent/WO2003082976A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • 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

  • the present invention relates to a thermosetting resin composition and an epoxy resin molding material using the composition and a semiconductor device. More particularly, it relates to a thermosetting resin composition, having good characteristics regarding curing property, fluidity and storage stability at an ordinary room temperature, which can be used suitably for a material in the fields of electric and electronic industries. Furthermore, it relates to an epoxy resin molding material using the composition and a semiconductor device encapsulated with a cured product of the epoxy resin molding material, having excellent soldering resistance and humidity resistance reliability.
  • An object of the present invention is to provide a thermosetting resin composition, having good characteristics regarding curing property, fluidity and storage stability at an ordinary room temperature, which is useful in the fields of electric and electronic industries, and an epoxy resin molding material prepared therefrom, and furthermore a semiconductor device encapsulated with a cured product of the epoxy resin molding material, having excellent soldering resistance and humidity resistance reliability.
  • thermosetting resin composition having combined characteristics of excellent curing property, fluidity and storage stability by using a compound having 2 or more epoxy groups in one molecule and a compound having 2 or more phenolic hydroxyl groups in one molecule, together with a phosphonium compound having the specific structure, and an epoxy resin molding material, and further the present inventors have found the fact that a semiconductor device having high soldering resistance and humidity resistance reliability can be obtained by using said epoxy resin molding material. As the result the present invention has been completed.
  • the present invention provides thermosetting resin compositions stated in the following items (1) to (12) , an epoxy resin molding material stated in the following item (13) and a semiconductor device stated in the following item (14).
  • thermosetting resin composition comprising, as the essential ingredients, (A) a compound having 2 or more epoxy groups in one molecule, (B) a compound having 2 or more phenolic hydroxyl groups in one molecule, and (C) a phosphonium compound represented by the general formula (1) :
  • R ⁇ r R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond;
  • P is phosphorus atom;
  • H is hydrogen atom;
  • Y is a group formed by releasing 1 proton from a proton donor having trivalency or a higher valency; and n means a value of 0.2 to 2.
  • thermosetting resin composition stated in the above item (1) , wherein the phosphonium compound (C) represented by the general formula (1) is a phosphonium compound represented by the general formula (2) :
  • R ⁇ r R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond;
  • P is phosphorus atom;
  • H is hydrogen atom;
  • 0 is oxygen atom;
  • Ar is an organic group having a valency of p, containing aromatic group or heterocyclic group;
  • p is an integer of at least 3; and q means a value of 0.2 to 2.
  • thermosetting resin composition stated in the above item (1) , wherein the phosphonium compound (C) represented by the general formula (1) is a phosphonium compound represented by the general formula (3) :
  • R-, R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond;
  • P is phosphorus atom;
  • H is hydrogen atom;
  • 0 oxygen atom;
  • Ar is an organic group having a valency of (r+1) , containing aromatic group or heterocyclic group;
  • r is an integer of at least 2; and s means a value of 0.2 to 2.
  • P is phosphorus atom
  • R-, R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond
  • Ar is an aromatic group or a heterocyclic group having a valency of (t+u)
  • X is hydrogen atom or a monovalent organic group
  • t is an integer of 3 to 5
  • u is an integer of 1 to 3.
  • thermosetting resin composition as stated in the above item (4), wherein the phosphonium compound (C) represented by the general formula (4) is a phosphonium compound represented by the general formula (5) or (6) :
  • R l R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond, or
  • R lf R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond; and R 5 is hydrogen atom or a monovalent alkyl group having 1 to 18 carbon atoms.
  • thermosetting resin composition stated in the above item (3) , wherein the phosphonium compound (C) represented by the general formula (3) is a phosphonium compound represented by the general formula
  • R x , R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond;
  • P is phosphorus atom;
  • H is hydrogen atom;
  • 0 is oxygen atom; and
  • y means a value of 0.2 to 2, or
  • R l R 2 , R 3 and R 4 may be the same as or different from one another and each is a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group and is bonded to the phosphorus atom to form a P-C bond; p is phosphorus atom; H is hydrogen atom; 0 is oxygen atom; and z means a value of 0.2 to 2.
  • thermosetting resin composition stated in any one of the above items (1) to (6), wherein the cation portion of phosphonium compound (C) represented by any one of the general formulas (1) to (8) is tetraphenyl phosphonium cation.
  • thermosetting resin composition stated in any one of the above items (1) to (7), wherein the compound (A) having 2 or more epoxy groups in one molecule is a crystalline epoxy resin having a melting point of 50 to 150°C.
  • thermosetting resin composition stated in the above item (8), wherein the crystalline epoxy resin having a melting point of 50 to 150°C is at least one epoxy resin represented by the general formula (9) :
  • R 6 , R 7 , R 8 and R 9 are each an organic group or a atom selected from hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, phenyl group and a halogen atom, each of which may be the same or different from one another.
  • thermosetting resin composition stated in any one of the above items (1) to (7) , wherein the compound (A) having 2 or more epoxy groups in one molecule is a biphenylaralkyl type epoxy resin represented by the general formula (10) :
  • R 10 to R 17 are each an organic group or an atom selected from hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, each of which may be the same or different from one another; and a means an average value of 1 to 5.
  • thermosetting resin composition stated in any one of the above items (1) to (7), wherein the compound (A) having 2 or more epoxy groups in one molecule contains, as the essential ingredients, a crystalline epoxy resin having a melting point of 50 to 150°C represented by the general formula (9) and a biphenylaralkyl type epoxy resin represented by the general formula (10) .
  • thermosetting resin composition stated in any one of the above items (1) to (11), wherein the compound (B) having 2 or more phenolic hydroxyl groups in one molecule is selected from aralkyl type phenolic resins represented by the general formulas (11) to (12) :
  • R 18 to R 21 are each an organic group or an atom selected from hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, each of which may be the same or different from one another; and b means an average value of 1 to 5, and
  • R 22 to R 29 are each an organic group or an atom selected from hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, each of which may be the same or different from one another; and c means an average value of 1 to 5.
  • An epoxy resin molding material comprising, as the essential ingredients, the thermosetting resin composition as stated in any one of the above items (1) to (12), and (D) an inorganic filler.
  • the compound (A) having 2 or more epoxy groups in one molecule, used in the present invention is not restricted and any compound having 2 or more epoxy groups in one molecule may be used.
  • a bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol type epoxy resin and the like, a biphenyl type epoxy resin represented by the general formula (9), a stilene type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl aralkyl type epoxy resin represented by the general formula (10) , a naphthalene type epoxy resin, other epoxy resins prepared by reacting the hydroxyl groups contained in phenols, phenolic resins, naphthols and the like, with epichlorohydrin, epoxy compounds and the like are exemplified.
  • an alicyclic epoxy resin which has been epoxidized by oxidizing an olefin with a peroxy acid epoxy resins which have been prepared by epoxidizing dihydroxybenzenes such as catechol, resorcinol, hydroquinone or the like, or a phenolic resin obtained by reacting dicyclopentadiene with a phenol, with epichlorohydrin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin and the like can be exemplified.
  • epoxy resins especially, crystalline epoxy resins having a melting point of 50 to 150°C, which have biphenyl type skelton, tetra-substituted bisphenol F type skeleton, stilbene type skeleton or the like, and epoxy resins having biphenyl aralkyl type skelton are preferable.
  • the crystalline epoxy resin has stiff structure in its main chain, and shows crystallizability because it has relatively low molecular structure, and it is a crystalline solid at an ordinary room temperature, but is melted rapidly and changed into a liquid state with low viscosity at a temperature region not lower than the melting point.
  • the melting point of a crystalline epoxy resin is determined by the heat absorption peak temperature with crystal fusion when it is heated from an ordinary room temperature at a heating-up speed of 5°C/minute by using a differential scanning calorimeter.
  • Preferable melting point of the crystalline epoxy resin is within 50 to 150°C, in view of storage stability at an ordinary room temperature and curing property due to melting property of the epoxy resin when it is molded.
  • a biphenyl type epoxy resin represented by, for example, the general formula (9) is preferable ' in view of storage stability of the resin composition or the molding material, and low melting viscosity at molding.
  • the substituent groups of R 5 to R 9 in the bisphenyl type epoxy resin represented by the general formula (9) are each an organic group or atom selected from hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, phenyl group and a halogen atom, each of which may be same as or different from one another.
  • methyl group, ethyl group, propyl group, butyl group, chlorine atom, bromine atom and the like can be exemplified, and especially methyl group is preferable in view of low melting viscosity of the epoxy resin and low water absorption of cured product of the resin.
  • the biphenyl aralkyl type epoxy resins are preferable in view of the fluidity in molding, low water absorption of the cured product of the resin, and soldering crack resistance, because this resin contains only a small portion of epoxy groups in the molecule, and so the amount of hydroxyl groups formed by reacting with a curing agent becomes small, and hence water absorption rate of the cured product is lowered, and because the molecule possesses suitable flexing property, and so good reactivity is shown in the curing reaction, and hence viscosity can be decreased.
  • epoxy resins can be used singly or in combination of 2 or more kinds of the resins, and epoxy resins used in combination of crystalline epoxy resin with biphenylaralkyl type epoxy resin are particularly preferable, in view of the balance among storage stability, low melting viscosity in shaping operation, and soldering crack resistance.
  • the substituent groups of R 10 to R 17 in the biphenylaralkyl type epoxy resin represented by the general formula (10) are each an organic group or an atom selected from hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, each of which may be same as or different from one another.
  • methyl group, ethyl group, propyl group, butyl group, chlorine atom, bromine atom and the like can be exemplified, and especially hydrogen atom or methyl group is preferable in view of low melting viscosity of the epoxy resin and low water absorption of cured product of the resin.
  • a means an average number of repeating epoxy resin units, and the value is preferably in the range of 1 to 5 in view of melting viscosity of the epoxy resin and fluidity characteristics of the resin composition.
  • Compound (B) having 2 or more phenolic hydroxyl groups in 1 molecule is used as a curing agent for the compound (A) having 2 or more epoxy groups in 1 molecule.
  • phenol novolak resin, cresol novolak resin, aralkyl type phenolic resin as represented by the general formulas (11) and (12) bisphenolic resin, trisphenolic resin, xylylene- modified novolak resin, terpene-modified novolak resin, dicyclopentadiene-modified phenolic resin, bisphenols and the like are exemplified, and among these compounds aralkyl type phenolic resins represented by the general formulas (11) and (12) are particularly preferable.
  • the aralkyl type phenolic resins contain less portion of hydroxyl groups in the molecule, and so water absorption rate of the cured product is small, and moreover good reactivity is shown in the curing reaction because the molecule possesses suitable flexing property, and hence viscosity can be decreased.
  • the resins are particularly preferable in view of the fluidity in molding, low water absorption of the cured resin product, and soldering crack resistance.
  • the substituent groups of R 18 to R 21 , and R 22 to R 29 in the aralkyl type phenolic resins represented by the general formulas (11) and (12) are each, an organic group and atom selected from hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, each of which may be same as or different from one another.
  • hydrogen atom, methyl group, ethyl group, propyl group, or butyl group, chlorine atom, bromine atom and the like can be exemplified, and especially hydrogen atom or methyl group is preferable in view of low melting viscosity of the phenolic resin, low water absorption of the cured resin product, and soldering crack resistance.
  • b and c mean an average repeating number of phenolic resin unit, and the number is preferably in the range of 1 to 5, in view of suitably low melting viscosity of the phenolic resin and fluidity characteristics of the resin composition.
  • the phosphonium compound (C) acting as a curing accelerator is a complex salt of tetra-substituted phosphonium with polyproton donor represented by the general formula (1), or the general formulas (2) to (3), or further the general formulas (4) to (8) .
  • This phosphonium compound forms a stable complex salt wherein one tetra- substituted onium cation and an organic anion formed by releasing one proton from a polyproton donor form an ionic pair, and further the anionic molecular portion is bonded to other proton donor molecules through molecular interaction such as hydrogen bonding.
  • the activity at low temperature is inhibited, so that good storage stability can be given to the resin composition.
  • the supermolecular type of complex salt structure, formed by hydrogen bonding is rapidly thermally decomposed dissociatively and activated, and rapidly accelerates curing reaction similarly to the action shown by the conventional phosphonium salts, to realize good curing property.
  • the catalytic activity of the present phosphonium compound is more inhibited until reaching the temperature for molding, and hence the product having better fluidity can be obtained in the molding. Therefore, use of the present specific phosphonium compound (C) can provide the product having excellent resin characteristics and material characteristics, which satisfy all of good storage stability, curing property and fluidity.
  • the phosphonium cation which composes the phosphonium compound (C) used in the present invention is a tetra-substituted phosphonium ion having substituent groups such as a monovalent, organic group having an aromatic ring or a heterocyclic ring or a monovalent, aliphatic group which is bonded to the phosphorus atom to form a P-C bond, and concretely, a tetraaryl-substituted phosphonium ion, such as tetraphenyl phosphonium, tetratolyl phosphonium, tetranaphthyl phosphonium or the like; a triarylmonoalkyl phosphonium ion which is produced from a phosphonium halide synthesized from a triaryl phosphine and an alkyl halide, such as ethyltriphenyl phosphonium, benzyltriphenyl phosphonium,
  • trihydroxybenzene derivatives such as 1, 2, 3-trihydroxybenzene, 1,3,5- trihydroxybenzene, 2, 3, 4-trihydroxybenzophenone, 2,3,4- trihydroxyacetophenone, 2,4, 6-trihydroxypropiophenone, 1, 8, 9-trihydroxyanthracene, 1,2,4- trihydroxyanthraquinone, 1,4,9, 10- tetrahydroxyanthracene, 2,3,4,4'- tetrahydroxyphenylmethane, gallic acid, methyl gallate, ethyl gallate, n-butyl gallate, n-octyl gallate, n- lauryl gallate, stearyl gallate and the like; trimesic acid, trimellitic acid, pyromellitic acid, citrazinic acid, barbituric acid, tannic acid, cyanuric
  • a trihydroxybenzene derivative such as 1,2,3- trihydroxybenzene, 1, 3, 5-trihydroxybenzene, 2,3,4- trihydroxybenzophenone or the like
  • a polyhydroxy type carboxylic acid such as gallic acid, citrazinic acid, tannic acid or the like
  • a gallic acid ester such as methyl gallate, ethyl gallate, n-octyl gallate, n- lauryl gallate, stearyl gallate or the like are particularly preferable.
  • JP 58-39838B states a tetrahydrocarbyl phosphonium phenoxide salt and a compound prepared by complexing the tetrahydrocarbyl phosphonium phenoxide salt with at least 1 mole of polyphenol H m X wherein X means phenoxide anion per mole of the phosphonium phenoxide salt, which compound is useful as a catalyst for the reaction of a compound containing vicinal epoxide groups, with a polyphenol.
  • H m X corresponding to the above-mentioned phenoxide of phosphonium phenoxide and a polyphenol as a complexing agent
  • resorcinol hydroquinone
  • phenolphthalein 2, ' , 4" -tris (hydroxyphenyl) -methane and the like
  • further unsubstituted or chloro- or bromo-substituted bisphenols are stated in detail as specifically preferable examples in Examples of the JP publication.
  • a compound having hydroxyl groups and carboxyl groups which are hydrogen bond-forming functional groups, substituted on the same aromatic nucleus, the total number of these groups being 3 or more, is preferable.
  • Such a compound is substantially different from the polyphenols as exemplified in JP 58-39838B;
  • a polyphenol compound in which the total number of hydroxyl group and carboxyl group substituted on the same aromatic nucleus is smaller than 3 molecular interaction on the basis of hydrogen bonding is weaker, so that the stability of the complex anion portion of phosphonium compound (C) is lower, and the phosphonium compound tends to develop the activity at low temperature.
  • the polyphenols as exemplified in JP 58-39838B are used as the polyproton donor to compose the phosphonium compound (C) , then the improvement in storage stability of the resin composition, which is one of the objects of the present invention, cannot be obtained.
  • the total number of hydrogen bond-forming functional groups consisting of hydroxyl groups and carboxyl groups is 3 or more, and the larger number causes stronger intermolecular hydrogen bonding which gives stable complex salt, and improves the storage stability of the resin composition.
  • the molar ratio n of proton donor YH composing the complex anion portion to the phosphonium cation is preferable in the range of 0.2 to 2 in view of the stability of phosphonium compound (C) .
  • n is less than 0.2, then the stability of the complex salt due to hydrogen bonding is decreased, and the complex salt would be easily decomposed dissociatively at low temperature, and hence sufficient storage stability of the resin composition or molding material cannot be obtained.
  • values of the molar ratios q, s, y and z of the proton donor YH composing the complex anion portion of the phosphonium compounds represented by the general formulas (2) and (3) , and the phosphonium compounds represented by the general formulas (7) and (8), to the phosphonium cation are preferably in the range of 0.2 to 2.
  • the phosphonium compound (C) used in the present invention can be synthesized according to a method which comprises dissolving a proton donor having trivalency or a higher valency as mentioned previously, and a basic compound which assists finally dehydrohalogenation, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like in a solvent such as alcohol, and adding the above-mentioned tetra-substituted phosphonium halide dissolved in a suitable solvent to carry out their reaction, and finally recovering the desired product as a solid product through operations such as recrystallization and reprecipitation; or a method which comprises reacting a tetra-substituted phosphonium tetra-substituted borate with a proton donor under heating, and further reacting in a solvent such as an alcohol under heating.
  • a basic compound which assists finally dehydrohalogenation for example, an alkali metal hydroxide such as sodium hydroxide
  • the amount of the phosphonium compound (C) which functions as a curing accelerator, used in the present invention is preferable in the range of 0.5 to 20 parts by weight, when the total weight of compound (A) having 2 or more epoxy groups in one molecule, and compound (B) having 2 or more phenolic hydroxyl groups in one molecule as a curing agent is 100 parts by weight. Further, with regard to the ratio of compound (C) having 2 or more epoxy groups in one molecule, and compound (B) having 2 or more phenolic hydroxyl groups in one molecule as a curing agent is 100 parts by weight. Further, with regard to the ratio of compound (C) which functions as a curing accelerator, used in the present invention is preferable in the range of 0.5 to 20 parts by weight, when the total weight of compound (A) having 2 or more epoxy groups in one molecule, and compound (B) having 2 or more phenolic hydroxyl groups in one molecule as a curing agent is 100 parts by weight. Further, with regard to the ratio of compound (C) which
  • the inorganic filler (D) used in the present invention there is no specific restriction to the kind thereof, and any one of those generally used in encapsulating materials can be used.
  • fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary coagulated silica powder, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber and the like can be exemplified, and particularly, fused spherical silica powder is preferable.
  • Preferable shape of the filler is infinitely spherical, and the filling amount can be increased by mixing particles having different sizes.
  • the amount of the inorganic filler 200 to 2,400 parts by weight of the filler is preferable to the total amount, 100 parts by weight of compound (A) having 2 or more epoxy groups in one molecule and compound (B) having 2 or more phenolic hydroxyl groups in one molecule.
  • the amount of the filler is less than 200 parts by weight, it is feared that reinforcing effect due to the inorganic filler may not be sufficiently developed.
  • the amount is more than 2,400 parts by weight, then fluidity of the resin composition is decreased and it is feared that insufficient filling may be caused in molding, which is not preferable.
  • the amount of the inorganic filler is 250 to 1,400 parts by weight per 100 parts by weight in the total amount of the above-mentioned compounds (A) and (B) , then coefficient of moisture absorption of cured product of the molding material is decreased and generation of soldering cracks can be prevented. Additionally, under such a condition, it is more preferable that gold wire deformation in the semiconductor device would not be caused because the viscosity of molding material decreases in melting operation.
  • the powders having spherical shape and wide particle size distribution are effective.
  • the epoxy resin molding material of the present invention can contain various additives, for example, coupling agent such as ⁇ -glycidoxypropyl- trimethoxysilane or the like; coloring agent such as carbon black or the like; flame retardant such as brominated epoxy resin, antimony oxide, phosphorus compound or the like; low stress ingredient such as silicone oil, silicone rubber or the like; releasing agent such as natural wax, synthetic wax, higher fatty acid or metallic salts thereof, paraffine or the like; oxidation inhibitor and the like.
  • coupling agent such as ⁇ -glycidoxypropyl- trimethoxysilane or the like
  • coloring agent such as carbon black or the like
  • flame retardant such as brominated epoxy resin, antimony oxide, phosphorus compound or the like
  • low stress ingredient such as silicone oil, silicone rubber or the like
  • releasing agent such as natural wax, synthetic wax, higher fatty acid or metallic salts thereof, paraffine or the like
  • oxidation inhibitor and the like for example, coupling agent such as ⁇
  • phosphonium compound (C) which functions as a curing accelerator in the present invention
  • other well-known catalysts such as triphenylphosphine, 1,8- diazabicyclo [5, 4 , 0] -7-undecene, 2-methylimidazole and the like can be used without any problem, together with the compound (C) in the range where characteristics of the compound (C) are not damaged.
  • the epoxy resin molding material of the present invention is obtained by mixing the ingredients (A) to (D) , and other additives by using a mixer at an ordinary room temperature, then kneading the mixture under heating by use of a heated roller or a heated kneader, and cooling and cruching the kneaded mixture.
  • the molding material can be cured and molded by a molding method such as transfer molding, compression molding, injection molding or the like.
  • the semiconductor device encapsulated with cured product of the epoxy resin molding material of the present invention is included within the technical scope of the present invention, and shows excellent humidity resistance.
  • Footnote (*) Calculated from the integrated strength ratio of ⁇ -NMR data.
  • Synthesized phosphonium compound (C) was added to compound (A) having 2 or more epoxy groups in one molecule and compound (B) having 2 or more phenolic hydroxyl groups in one molecule, and this mixture was mixed and crushed, and further this mixture was melted and kneaded on a hot plate at 100°C for 5 minutes, and then cooled and crushed to prepare a sample of the composition, which was evaluated. Evaluation methods are described as follows. (1) Curing torque
  • the initial curing heat release value just after the preparation and the curing heat release value after treatment of storage at 40°C for 3 days were measured.
  • Percentage of the curing heat release value after treatment of storage (mJ/mg) against the initial curing heat release value (mJ/mg) was calculated .
  • the curing heat release value was measured by differential thermal analysis under the condition of heating-up rate of 10°C/min . The larger percentage shows smaller change with time in curing heat release value, and thus means better storage stability .
  • thermosetting resin compositions were prepared by the above-mentioned method in accordance with the formulations shown in Table 2 - 3 and evaluated.
  • well-known curing accelerators triphenylphosphine, 1,8- diazabicylo [5, 4, 0] -7-undecene, 2-methylimidazole, and tetra-n-butylphosphonium salicylate were used in place of the compounds (C) used in Examples. Evaluation results of thus obtained thermosetting resin compositions are shown in Tables 2 - 3. (-0
  • Phenolic aralkyl resin manufactured by Mitsui Toatsu Chemicals, Inc.
  • Footnotes Notes of l), 2), 3), 4), 5) and 6) are the same as defined in the footnotes under Table 2.
  • Thermosetting resin compositions of the present invention prepared in Examples 1 - 10 showed both good curing properties and good storage stability, while the compositions prepared in Comparative Examples 1 - 6 showed poor storage stability and slightly lower curing properties .
  • Phenol aralkyl resin XLC-LL 48 (manufactured by Mitsui Toatsu Chemical, Inc. )
  • Fused spherical silia 500 (average particle diameter: 15 ⁇ m)
  • spiral flow was measured at 175°C as mold temperature, under 6.8 MPa as injection pressure, and for 2 minutes as curing time.
  • the spiral flow is a parameter of fluidity, and the larger value means better fluidity.
  • curing torque was measured at 175°C and after 45 seconds. The larger value means better curing property.
  • a sample of 16pDIP was molded at 175°C as mold temperature, under 6.8 MPa as pressure, and for 2 minutes as curing time, and thus obtained molded sample was cured at 175°C for 8 hours, and then disconnection failure was examined by applying electric voltage of 20V to the sample of l ⁇ pDIP in steam at 125°C and relative humidity of 100%.
  • Disconnection time was defined as a time until disconnection was caused in more than 8 packages among 15 packages. The unit thereof is hour. Measurement was conducted for at most 500 hours, and when the number of defective packages was less than 8 at that time, then the disconnection time was defined as longer than 500 hours. The longer disconnection time means better humidity resistance reliability.
  • Footnotes Notes of l), 2), 3), 4), 5) and 6) are the same as defined in the footnotes under Table 2,
  • Epoxy resin molding materials of Examples 11 - 20 of the present invention were quite excellent on curing property, fluidity and storage stability, and additionally semiconductor devices encapsulated with cured products of the epoxy resin molding materials showed good humidity resistance reliability.
  • the epoxy resin molding materials according to Comparative Examples 7 - 12 could not satisfy all of curing property, fluidity, storage stability and humidity resistance reliability.
  • thermosetting resin composition and the epoxy resin molding material of the present invention possess excellent curing property, storage stability and fluidity, and can be used suitably in electric and electronic material industries . Additionally, a semiconductor device encapsulated with cured product of the epoxy resin molding material is excellent on soldering resistance and humidity resistance reliability, and hence extremely useful.

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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)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine thermodurcissable, qui présente des caractéristiques combinées de propriété de séchage rapide et de haute stabilité au stockage à fluidité élevée, et un matériau de moulage de résine époxyde, ainsi qu'un dispositif semi-conducteur utilisant ce matériau. Plus précisément, l'invention concerne une composition de résine thermodurcissable comprenant, comme ingrédient essentiel, (A) un composé ayant au moins 2 groupes époxydes dans 1 molécule, (B) un composé ayant au moins 2 groupes hydroxyle phénolique dans 1 molécule, et (C) un composé de phosphonium représenté par la formule générale (1), et un matériau de moulage de résine époxyde contenant ces ingrédients, ainsi qu'un dispositif semi-conducteur encapsulé avec un produit séché de celui-ci. R1, R2, R3 et R4 peuvent être identiques ou différents les uns des autres, chacun représentant un groupe organique monovalent possédant un cycle aromatique ou hétérocyclique, ou un groupe aliphatique monovalent et étant lié à l'atome de phosphore pour former une liaison P-C; P représente l'atome de phosphore; H représente l'atome d'hydrogène; Y représente un groupe formé par la libération de 1 proton d'un donneur de protons possédant une trivalence ou une valence plus élevée; et n représente une valeur située entre 0,2 et 2.
PCT/JP2002/003104 2002-03-28 2002-03-28 Composition de resine thermodurcissable et materiau de moulage de resine epoxyde utilisant cette composition et dispositif semi-conducteur Ceased WO2003082976A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG131750A1 (en) * 2002-09-18 2007-05-28 Sumitomo Bakelite Co Thermosetting resin composition, epoxy resin molding material and semiconductor device
JP2013216871A (ja) * 2012-03-12 2013-10-24 San Apro Kk エポキシ樹脂硬化促進剤
JP2015063661A (ja) * 2013-08-29 2015-04-09 北興化学工業株式会社 エポキシ樹脂系組成物
WO2016121356A1 (fr) * 2015-01-30 2016-08-04 パナソニックＩｐマネジメント株式会社 Composition de résine époxyde pour étanchéité, produit durci et dispositif semi-conducteur
EP2746287B1 (fr) * 2012-12-24 2017-05-24 Cheil Industries Inc. Sel de phosphonium quaternaire, composition de résine époxy pour encapsulation d'un dispositif semi-conducteur comprenant le sel de phosphonium quaternaire et dispositif à semi-conducteur encapsulé avec cette composition de résine époxy
US11319406B2 (en) * 2017-11-14 2022-05-03 Eneos Corporation Prepreg, fiber-reinforced composite material, and molded article

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Publication number Priority date Publication date Assignee Title
US4395574A (en) * 1980-05-12 1983-07-26 The Dow Chemical Co. Phosphonium phenoxide catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
JP2000007761A (ja) * 1998-06-25 2000-01-11 Sumitomo Bakelite Co Ltd 熱硬化性樹脂組成物
JP2001089636A (ja) * 1999-07-22 2001-04-03 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
EP1130041A1 (fr) * 1999-07-22 2001-09-05 Sumitomo Bakelite Co., Ltd. Composition de resine epoxyde et dispositif semi-conducteur
JP2002105171A (ja) * 2000-09-29 2002-04-10 Sumitomo Bakelite Co Ltd 積層板用エポキシ樹脂組成物、並びにこれを用いたプリプレグおよび積層板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395574A (en) * 1980-05-12 1983-07-26 The Dow Chemical Co. Phosphonium phenoxide catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
JP2000007761A (ja) * 1998-06-25 2000-01-11 Sumitomo Bakelite Co Ltd 熱硬化性樹脂組成物
JP2001089636A (ja) * 1999-07-22 2001-04-03 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物及び半導体装置
EP1130041A1 (fr) * 1999-07-22 2001-09-05 Sumitomo Bakelite Co., Ltd. Composition de resine epoxyde et dispositif semi-conducteur
JP2002105171A (ja) * 2000-09-29 2002-04-10 Sumitomo Bakelite Co Ltd 積層板用エポキシ樹脂組成物、並びにこれを用いたプリプレグおよび積層板

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG131750A1 (en) * 2002-09-18 2007-05-28 Sumitomo Bakelite Co Thermosetting resin composition, epoxy resin molding material and semiconductor device
JP2013216871A (ja) * 2012-03-12 2013-10-24 San Apro Kk エポキシ樹脂硬化促進剤
EP2746287B1 (fr) * 2012-12-24 2017-05-24 Cheil Industries Inc. Sel de phosphonium quaternaire, composition de résine époxy pour encapsulation d'un dispositif semi-conducteur comprenant le sel de phosphonium quaternaire et dispositif à semi-conducteur encapsulé avec cette composition de résine époxy
JP2015063661A (ja) * 2013-08-29 2015-04-09 北興化学工業株式会社 エポキシ樹脂系組成物
WO2016121356A1 (fr) * 2015-01-30 2016-08-04 パナソニックＩｐマネジメント株式会社 Composition de résine époxyde pour étanchéité, produit durci et dispositif semi-conducteur
JP6023992B1 (ja) * 2015-01-30 2016-11-09 パナソニックＩｐマネジメント株式会社 封止用エポキシ樹脂組成物、硬化物、及び半導体装置
US9633922B2 (en) 2015-01-30 2017-04-25 Panasonic Intellectual Property Management Co., Ltd. Sealing epoxy resin composition, hardened product, and semiconductor device
US11319406B2 (en) * 2017-11-14 2022-05-03 Eneos Corporation Prepreg, fiber-reinforced composite material, and molded article

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