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WO2011052161A1 - Composition de résine durcissable destinée à l'encapsulation d'un semi-conducteur optique, et produit durci composé de ladite composition - Google Patents

Composition de résine durcissable destinée à l'encapsulation d'un semi-conducteur optique, et produit durci composé de ladite composition Download PDF

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Publication number
WO2011052161A1
WO2011052161A1 PCT/JP2010/006217 JP2010006217W WO2011052161A1 WO 2011052161 A1 WO2011052161 A1 WO 2011052161A1 JP 2010006217 W JP2010006217 W JP 2010006217W WO 2011052161 A1 WO2011052161 A1 WO 2011052161A1
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WIPO (PCT)
Prior art keywords
formula
component
resin composition
optical semiconductor
curable resin
Prior art date
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Ceased
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PCT/JP2010/006217
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English (en)
Japanese (ja)
Inventor
義浩 川田
正人 鎗田
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2011538235A priority Critical patent/JPWO2011052161A1/ja
Priority to CN2010800492415A priority patent/CN102597042A/zh
Publication of WO2011052161A1 publication Critical patent/WO2011052161A1/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
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins

Definitions

  • the present invention relates to a curable resin composition for optical semiconductor encapsulation. More specifically, it can be manufactured only by the kneading process, suitable for transfer molding, reactivity and hardness at heat, mold release from mold, prevention of void entrainment, and removal of lead frame from runner resin after mold release (Hereinafter referred to as a gate break process) excellent in curable resin composition for encapsulating an optical semiconductor excellent in lead-free solder resistance after moisture absorption, when there is no resin leakage from the mold and when it is molded and cured, and its
  • the present invention relates to an optical semiconductor element sealed with a cured product.
  • transfer molding method a low-pressure transfer molding method (hereinafter referred to as transfer molding method) has been adopted as a method for sealing an optical semiconductor element from the viewpoint of mass productivity.
  • an epoxy resin has been adopted in terms of a balance of heat resistance, transparency, mechanical properties, and economy.
  • the combination of a bisphenol A type epoxy resin and an acid anhydride curing agent is excellent in terms of demoldability from a mold, which is an important item for transfer molding workability, and high heat hardness.
  • compositions using hexahydrophthalic anhydride, tetrahydrophthalic anhydride and the like as acid anhydride curing agents have been widely used.
  • Patent Document 1 Japanese Patent Laid-Open No. 3-3258
  • a metamorphic process or B-stage
  • a means for adjusting to mass productivity is provided separately.
  • the modification process is regarded as a problem that the economic efficiency is low in the production process of the resin composition. From the viewpoint of the production process of the resin composition, it is desired to obtain a composition suitable for mass productivity at the time of transfer molding only by kneading or mixing process.
  • polyfunctional acid anhydrides available on the market are crystalline compounds, and their melting points are usually higher than the temperature range (around 150 °) in which transfer molding is usually performed. Specific examples include TMEG100 (melting point: 178 ° C.) and Nippon Benikane tetracarboxylic acid anhydride (melting point: 190 ° C.). For this reason, when used as a curing agent, the crystals cannot be melted by heat at the transfer molding temperature (around 150 ° C.), and the curing agent that has not melted causes foreign matter.
  • the present condition is that examination which uses polyfunctional acid anhydride as a component for sealing materials for optical semiconductors is not fully carried out.
  • the polyfunctional acid anhydride curing agent has high adhesion. Therefore, there is a problem that the lead frame frame is difficult to come off from the runner portion. If removed by hand, the lead frame frame will be deformed.
  • the gate breakability in the case of using a polyfunctional acid anhydride has not been sufficiently studied.
  • it is also important to prevent resin leakage and void entrainment during transfer molding. The examination of the resin composition that can satisfy all of the above problems and workability at the time of transfer molding is still insufficient.
  • solder mounting process Fixing a large number of electronic components (including semiconductor elements) on a printed board or the like with solder is called a solder mounting process. Specifically, a semiconductor element sealed with an epoxy resin or the like is mounted on a printed circuit board pre-applied with a solder paste, and a lead-free solder melting furnace (usually called a solder reflow furnace) (The temperature reaches 220 ° C. to 270 ° C. above the melting point of the solder), and the semiconductor element is mounted on a printed circuit board or the like.
  • Lead-free solder means solder that does not use lead from the viewpoint of environmental conservation in recent years. Lead-free solder has a high melting temperature, and it is necessary to heat the reflow furnace to 240 ° C. or higher.
  • a filler such as silica is contained in an amount of 80% by weight (wt) or more, and means for reducing the moisture absorption amount is taken.
  • a sealing resin such as a photodiode or LED
  • the sealing material for optical semiconductor elements is more frequently peeled off in the lead-free solder mounting process performed in a moisture-absorbing state than the sealing material for semiconductor elements, and lead-free solder resistance (solder reflow, solder resistance, etc.) It has a very important problem of lowering.
  • a sealing material for a semiconductor element usually has a large property obtained by blending a silica filler.
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-27508
  • Patent Document 3 International Publication No. WO2004 / 0312557
  • a terpene skeleton phenol curing agent or biphenyl skeleton epoxy resin is used to improve solder resistance after moisture absorption.
  • an optical semiconductor encapsulating material containing There is an example of an optical semiconductor encapsulating material containing.
  • these patent documents describe that they are excellent in solder resistance, there is no description about workability at the time of transfer molding, which is a part of the object of the present invention, and demoldability from a mold. No mention is made of such things.
  • Patent Document 4 Japanese Patent Laid-Open No. 4-318023
  • Patent Document 5 Japanese Patent Laid-Open No. 4-318056
  • silica is an essential component, and it is obvious that the cited composition cannot be simply applied to the sealing material for optical semiconductors for the reason mentioned above.
  • These patent documents do not describe that they can be used as a sealing material for optical semiconductor elements.
  • the effect of filling with silica increases the elastic modulus of the sealing resin by high filling with silica, so that it can be removed from the mold. It is well known that it also works.
  • the epoxy resin composition described in Patent Documents 4 and 5 is for optical semiconductor elements as in Patent Documents 2 and 3 under the restriction that silica cannot be filled with a sealing material for optical semiconductor elements. As a sealing material, it does not satisfy market requirements.
  • a sealing material for an optical semiconductor element it can be manufactured only by a kneading process, is suitable for transfer molding, and has a mold workability such as mold release from a mold or after moisture absorption.
  • a resin composition for a sealing material that also has lead-free solder resistance.
  • JP-A-3-3258 Japanese Patent Laid-Open No. 2001-2758 WO2004 / 031257 pamphlet JP-A-4-318023 JP-A-4-318056
  • the present invention can be manufactured only by kneading or mixing process, is suitable for mass production at the time of transfer molding, does not cause resin leakage at the time of molding, suppresses entrainment of voids, has high heat hardness, and is released from the mold.
  • An object of the present invention is to provide a curable resin composition for encapsulating an optical semiconductor which is excellent in workability during transfer molding, such as the property of a resin and gate break, and also excellent in lead-free solder resistance after moisture absorption.
  • the present inventors have found that an epoxy resin composition for optical semiconductors satisfying the above problems can be obtained as a result of intensive studies to solve the above-mentioned problems. That is, the present invention relates to the following (1) to (11).
  • a curable resin composition for sealing an optical semiconductor comprising the following components (A) to (F):
  • (A) General formula (1) (Wherein R 1 s may be the same or different from each other, and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom. N is 0 to 10)
  • (B) General formula (2) (Wherein R 2 s may be the same as or different from each other, and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom.
  • R 3 represents Which may be the same or different from each other, each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom, and m is an average value of the number of repetitions of 0 to 10. .) An epoxy resin having an epoxy equivalent of 500 to 800 g / eq, (C) an epoxy resin represented by the general formula (2) and having an epoxy equivalent of 850 to 1500 g / eq, (D) A polyfunctional acid anhydride curing agent having two or more carboxyl groups and acid anhydride groups in one molecule, or two or more acid anhydride groups alone,
  • (E) At least one selected from the group consisting of compounds represented by the following formulas (15), (18) and (19) as a phenolic curing agent, Formula (15) ⁇ In the formula, o is an average value of the number of repetitions of 0 to 10, R 8 is the following formula (16) (Wherein R 9 may be the same as or different from each other, and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom) or the following formula ( 17) (Wherein R 10 s may be the same as or different from each other and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom). ⁇ ,
  • Formula (18) (Wherein R 11 s may be the same or different from each other, and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom).
  • Formula (19) (Wherein R 12 s may be the same as or different from each other, and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a halogen atom), and (F ) A (meth) acrylate having a phosphate group.
  • the curable resin composition for optical semiconductor encapsulation according to (1) further comprising (G) a curing accelerator.
  • the component (D) is at least one selected from the group consisting of compounds represented by the following formulas (3), (6) and (7)
  • the coupling position is not particularly limited. ),
  • Formula (6) (Wherein R 5 represents a linear or branched alkylene chain having 1 to 5 carbon atoms which may have a substituent, a cyclohexane skeleton or a benzene skeleton which may have a substituent), Formula (7) (Wherein R 6 represents a linear or branched alkylene group having 1 to 5 carbon atoms which may have a substituent, a cyclohexane skeleton or a benzene skeleton which may have a substituent).
  • the component (D) is a compound represented by the following formula (11), formula (12), formula (13) or formula (14)
  • the curable resin composition for optical semiconductor sealing of description is a compound represented by the following formula (11), formula (12), formula (13) or formula (14)
  • the curable resin composition for optical semiconductor sealing of description is a compound represented by the following formula (11), formula (12), formula (13) or formula (14)
  • the curable resin composition for optical semiconductor sealing of description is a compound represented by the following formula (11), formula (12), formula (13) or formula (14)
  • the compounding equivalent value of the curing agent component (D) is 0.30 to 0.80 and the compounding equivalent value of the component (E) is 0.20 to 0 with respect to 1 equivalent of epoxy group in the total amount of epoxy resin. Any one of (1) to (7) above, wherein the sum of the blending equivalent value of component (D) and the blending equivalent value of component (E) is in the range of 0.70 to 1.20.
  • the curable resin composition for optical semiconductor sealing of description. (9) The curable resin composition for optical semiconductor encapsulation according to any one of (3) to (7), further comprising (G) a curing accelerator.
  • the resin composition for encapsulating an optical semiconductor of the present invention can be produced only by kneading or mixing steps, and is excellent in mass productivity in transfer molding.
  • the optical semiconductor element sealed with the resin composition is excellent in lead-free solder resistance. That is, the composition has a high reactivity during transfer molding, a short gel time, no resin leakage from the mold, suppresses the entrainment of voids, and has a high hot hardness after molding, so that it can be removed from the mold. It is suitable for mass production because of its excellent moldability and gate breakability, and excellent workability during transfer molding.
  • the optical semiconductor element sealed with the resin composition is excellent in lead-free solder resistance after moisture absorption even though the filler is not blended in the resin composition. Therefore, the curable resin composition of the present invention is extremely useful as a sealing material for optical semiconductors.
  • the component (A) used in the present invention is a biphenol type epoxy resin represented by the general formula (1).
  • R 1 is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a straight or branched carbon number of 1 -8 alkyl groups, or halogen atoms such as chlorine, bromine and iodine.
  • a plurality of the functional groups of R 1 may be the same or different from each other, but all of them are particularly preferably hydrogen atoms.
  • n is an average value of the number of repetitions of 0 to 10.
  • the softening point of the biphenol type epoxy resin of the component (A) is preferably 50 ° C. or higher. If the softening point is too low, the heat hardness and reactivity are lowered. Moreover, the viscosity at the time of melting of the composition also decreases, and resin leakage or void entrainment occurs during transfer molding.
  • the softening point of the component (A) is more preferably 60 ° C. or higher. Although there is no particular upper limit, it is usually 150 ° C. or lower, preferably 120 ° C. or lower.
  • an epoxy resin for example, NC-3000, NC-3000H manufactured by Nippon Kayaku Co., Ltd., in which R 1 in the general formula (1) is a hydrogen atom, are commercially available.
  • R 1 in the general formula (1) is a hydrogen atom
  • a phenol resin is synthesized by condensing a substituted methylene biphenyl compound such as bishalogenomethylbiphenyl and a phenol under acidic conditions. Furthermore, the compound of General formula (1) can be obtained by making this phenol resin and epihalohydrins react in presence of an alkali metal hydroxide. Examples of phenols used in the above reaction include phenol, orthocresol, paracresol, and metacresol. These are preferable examples, but are not limited thereto.
  • Both the component (B) and the component (C) used in the present invention are bisphenol type epoxy resins represented by the general formula (2), and the epoxy equivalent of the component (B) is 500 to 800 g / eq, The epoxy equivalent of component (C) is 850 to 1500 g / eq. In the present invention, it is important to use the component (B) and the component (C) together with the component (A).
  • R 2 in the general formula (2) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a straight or branched carbon number of 1 -8 alkyl groups, or halogen atoms such as chlorine, bromine and iodine.
  • a plurality of R 2 functional groups present in the general formula (2) may be the same or different from each other, but those in which all are hydrogen atoms are particularly preferred.
  • R 3 in the general formula (2) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a straight or branched carbon number of 1 -8 alkyl groups, or halogen atoms such as chlorine, bromine and iodine.
  • a plurality of R 3 present in the general formula (2) may be the same or different from each other, but all of them are particularly preferably methyl groups.
  • M in the general formula (2) is an average value of the number of repetitions of 0 to 10.
  • such epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol A type epoxy resin, dimethyl bisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin, dimethyl bisphenol F type epoxy resin. Resins and the like are listed, and all are available from the market.
  • the resin in order to prevent the resin from being deformed by the eject pin used at the time of transfer molding demolding, it is required to exhibit a high heat hardness.
  • a bisphenol type epoxy resin of formula (2) having an epoxy equivalent in the range of 500 to 800 g / eq as component (B).
  • the epoxy equivalent is preferably in the range of 600 to 700 g / eq. If the epoxy equivalent is too low, even when high heat hardness can be exhibited, the viscosity at the time of melting of the composition tends to decrease, and resin leakage or void entrainment tends to occur during transfer molding.
  • an epoxy resin having an epoxy equivalent in the range of 500 to 800 g / eq for example, E1001 and E1002 manufactured by JER (Japan Epoxy Resin) in which R 2 in the general formula (2) is a hydrogen atom and R 3 is a methyl group
  • Toto Kasei Examples thereof include YD-012 and YD-902 manufactured by KK.
  • the epoxy equivalent of the component (C) bisphenol-type epoxy resin is in the range of 850 to 1500 g / eq, it is preferable because void entrainment is suppressed and other properties are not adversely affected. If the epoxy equivalent is too high, there is no problem in suppressing void entrainment, but it is not preferable because the hot hardness is significantly reduced. Furthermore, the softening point is too high and the handling workability tends to be inferior.
  • the above epoxy equivalent is 850 to 1200 g / eq, it is more preferable from the viewpoint of balance between hardness upon heating and suppression of voids.
  • the epoxy resin having an epoxy equivalent in the range of 850 to 1500 g / eq include Toto Kasei Co., Ltd. such as E1004 manufactured by JER (Japan Epoxy Resin) in which R 2 in the general formula (2) is a hydrogen atom and R 3 is a methyl group. Examples thereof include YD-904, YD-907, YD-014, YD-017 and the like manufactured by KK.
  • the total amount of the epoxy resin used in the composition is 100 wt%, and it is necessary to adjust and blend so that the content ratio of each component (A), component (B), and component (C) satisfies the following conditions. is there.
  • the total content of the component (B) and the component (C) is preferably 65 to 90 wt%, more preferably 70 to 90 wt%, still more preferably with respect to the total of the components (A) to (C). Is about 80 to 90 wt%.
  • the balance is component (A).
  • the amount of the component (A) is too small, the reactivity of the composition is lowered, and further, the hot hardness is lowered, so that the above-mentioned requirements tend not to be satisfied. Moreover, when there are too many components (A), the viscosity at the time of fusion
  • the hot hardness may be lowered.
  • each component (A), (B), (C) is adjusted within the above range, it is combined with the components (D) to (F) described later, so that reactivity, heat hardness, resin leakage, void entrainment, moisture absorption Since the resin composition of this invention which satisfy
  • the total amount of epoxy resin is usually the sum of components (A), (B), and (C). However, if necessary, when other epoxy resins to be described later are added, the total amount may be added.
  • the ratio of the total amount of the epoxy resin to the total amount of the curable resin composition of the present invention is about 40 to 90 wt%, preferably 50 to 85 wt%, and more preferably 60 to 85 wt%. It is more preferable when the content of these epoxy resins is the total amount of components (A), (B) and (C).
  • other resins can be added as long as the workability during the transfer molding is not adversely affected.
  • diglycidyl etherified products other than the above general formula (1) and general formula (2) specifically, polyfunctional epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl Examples thereof include ester-based epoxy resins, glycidylamine-based epoxy resins, and epoxy resins obtained by glycidylation of halogenated phenols.
  • the polyfunctional epoxy resin include glycidyl etherified products of polyphenol compounds and glycidyl etherified products of various novolak resins.
  • Examples of glycidyl etherified products of polyphenol compounds include bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1 -(4-Hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol ), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di-4- Full of hydroxyphenylfluorene Phenols having skeleton include glycidyl ethers of poly
  • Examples of glycidyl etherified products of various novolak resins include novolak resins made from various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, and xylylene skeletons
  • Examples thereof include glycidyl etherified products of various novolak resins such as phenol novolac resin, dicyclopentadiene skeleton-containing phenol novolak resin, and fluorene skeleton-containing phenol novolak resin.
  • alicyclic epoxy resin examples include alicyclic epoxy resins having an aliphatic skeleton such as cyclohexane such as 3,4-epoxycyclohexylmethyl 3 ′, 4′-cyclohexylcarboxylate.
  • aliphatic epoxy resin examples include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and xylylene glycol derivatives.
  • heterocyclic epoxy resin examples include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
  • glycidyl ester epoxy resin examples include epoxy resins obtained by glycidylation of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
  • Examples of the glycidylamine-based epoxy resins include epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, and diaminomethylbenzene derivatives.
  • Halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A are used as epoxy resins obtained by glycidylation of halogenated phenols. Examples thereof include epoxy resins obtained by glycidylation of phenols.
  • epoxy resins there are no particular restrictions on the use of these epoxy resins, but those with less colorability are more preferred from the viewpoint of transparency.
  • bisphenol S 4,4′-biphenylphenol, tetramethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, trishydroxyphenylmethane, resorcinol, 2,6-ditert-butylhydroquinone, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene Glycidylated polyfunctional epoxy resins; phenols, cresols, bisphenol A, bisphenol S, novolak resins made from various phenols such as naphthols, dicyclopentadiene skeleton-containing phenol novolac resins, biphenyl
  • these epoxy resins can be used in combination as one or a mixture of two or more as required. Those epoxy resins having an epoxy equivalent of 100 to 1700 g / eq, preferably 200 to 1000 g / eq can be used. Furthermore, the softening point of these epoxy resins is preferably 130 ° C. or lower in consideration of workability during production. These epoxy resins can be appropriately added within the range of 0 to 20 wt% with respect to the total amount of components (A) to (C), if necessary.
  • a high reactivity suitable for transfer molding only through a kneading or mixing production process without passing through an aging process, or high heat hardness, prevention of resin leakage and void entrainment, mold release from a mold In order to satisfy all of the subsequent gate breakability and to satisfy lead-free solder resistance after moisture absorption, two or more carboxyl groups and acid anhydride groups are combined in one molecule as component (D), or acid anhydride. It is important to use a polyfunctional acid anhydride curing agent having only two or more physical groups and a phenolic curing agent in combination as the component (E).
  • a polyfunctional acid anhydride is used as the component (D) in order to satisfy high reactivity suitable for transfer molding and high heat hardness. If it is a polyfunctional acid anhydride, there will be no restriction
  • the polyfunctional acid anhydride represented by Formula (14) is preferable.
  • R 4 in the compound of the formula (3) examples include a trivalent group of a cyclohexane ring of the formula (4) or a benzene ring of the formula (5).
  • the coupling position is not particularly limited.
  • R 4 is a cyclohexane ring of the formula (4), for example, 1,2,4 cyclohexane tricarboxylic acid-1,2 anhydride (manufactured by Mitsubishi Gas Chemical Co., Inc., H-TMA)
  • R 4 is a formula (5)
  • trimellitic anhydride manufactured by Mitsubishi Gas Chemical Co., Inc.
  • R 5 in formula (6) and R 6 in formula (7) a linear or branched alkylene chain having 1 to 8 carbon atoms, a divalent group of a cyclohexane skeleton having a substituent, or And a divalent group of a benzene skeleton.
  • substituent include a linear or branched alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group, or chlorine, bromine And halogen atoms such as iodine.
  • R 5 in formula (6) and R 6 in formula (7) a linear alkylene chain having 1 to 5 carbon atoms is preferable in consideration of workability.
  • examples of such a compound include ethylene glycol bis (anhydro trimellitate) (including trimellitic anhydride in part), such as Licacid TMEG-S (hereinafter simply referred to as TMEG-S) or Licacid.
  • TMEG-600 (hereinafter simply referred to as TMEG-600) and the like are available on the market as the Ricacid TMEG series (manufactured by Shin Nippon Rika Co., Ltd.).
  • at least one selected from the group consisting of formula (3), formula (6) and formula (7) is preferred.
  • examples of R 7 in the formula (8) include a tetravalent group of the cyclohexane ring in the formula (9) or a tetravalent group of the benzene ring in the formula (10).
  • examples of R 7 in the formula (8) include a tetravalent group of the cyclohexane ring in the formula (9) or a tetravalent group of the benzene ring in the formula (10).
  • the cyclohexane ring of the formula (9) pyromellitic anhydride nuclear hydrogenated product
  • the benzene ring of the formula (10) pyromellitic anhydride is obtained from the market. It is available.
  • the polyfunctional acid anhydride curing agent (D) compounds represented by the above formulas (11) to (14) can be used.
  • the compound of the formula (11) is a benzophenone tetracarboxylic acid anhydride
  • the compound of the formula (12) is Rikacide TMTA-C (manufactured by Shin Nippon Chemical Co., Ltd.)
  • the compound of the formula (13) is Rikacide
  • the compound of DSDA (manufactured by Shin Nippon Rika Co., Ltd.) and the compound of formula (14) can be obtained from the market as Jamaicacid TDA-100 (manufactured by Shin Nippon Rika Co., Ltd.).
  • R 8 in the formula (15) represents a biphenylene group which may have a substituent of the formula (16) or a phenylene group which may have a substituent of the formula (17).
  • o is an average value of the number of repetitions of 0 to 10.
  • R 9 in the formula (16), R 10 in the formula (17), R 11 in the formula (18), as R 12 in formula (19) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, A linear or branched alkyl group having 1 to 8 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group, or a halogen atom such as chlorine, bromine or iodine. When there are a plurality, they may be the same as or different from each other. Usually, these substituents are preferably hydrogen atoms.
  • the component (E) preferably has a softening point of 50 ° C. or higher and 130 ° C. or lower.
  • a curing agent examples include GPH-65 and GPH-103 (made by Nippon Kayaku Co., Ltd.) represented by the following formula (20), XYLOCK XEL-3L (produced by Mitsui Chemicals) represented by the following formula (21), YP90 (manufactured by Yasuhara Chemical Co., Ltd.), which is a mixture of the formula (22) and the following formula (23), is available from the market.
  • Formula (20) (specific structures of GPH-65 and GPH-103) (Wherein p represents an average value of the number of repetitions of 0 to 10) Formula (21) (Concrete structure of XYLOCK XEL-3L) (In the formula, q represents an average value of the number of repetitions of 0 to 10) Formula (22) Formula (23)
  • the curable resin composition of the present invention is used as an encapsulant for optical semiconductors, it is preferable to avoid hindering transparency.
  • Component (D) often has a melting point of 150 ° C. or higher. Therefore, when the composition is kneaded or mixed and used with the melting point of the component (D) being 150 ° C. or higher, the cured product is uneven due to the undissolved material of the component (D) or foreign matter remains. become. In order to avoid this problem, it is preferable to use the component (D) in a state where crystals are melted in advance.
  • the means is not particularly limited, and examples thereof include a method in which two or more kinds of compounds that can be used as the component (D) are once dissolved and mixed, and the melting point is lowered using the phenomenon of melting point lowering.
  • compounds that can be used as component (D) by dissolving component (E) in advance in an organic solvent (for example, methyl ethyl ketone (MEK)) that can dissolve component (E). Mix. Thereafter, the solvent is removed at a temperature close to the melting point of the component (D) with a vacuum heating device, and the melting point of the mixture can be adjusted to be equal to or lower than the transfer molding temperature.
  • MEK methyl ethyl ketone
  • the component (D) is produced, it is also possible to use a compound in which the compound has two or more kinds so that its melting point is lower than the transfer molding temperature due to the phenomenon of melting point drop.
  • the present invention it is an object to provide the resin composition excellent also in the gate break process.
  • the gate break process will be described in detail.
  • transfer molding there is a gate break process in which the lead frame frame is manually removed from the runner portion after demolding. At this time, it is important that the lead frame does not bend and can be removed easily by hand, and if it is good, the gate breakability is excellent. Conversely, if it cannot be removed unless a considerable force is applied and the lead frame is bent as a result, the gate breakability is inferior. If the lead frame is bent, it cannot proceed to the next process.
  • polyfunctional acid anhydride curing agent of component (D), phenolic curing of component (E) The above requirements may not be achieved by simply containing an agent. Therefore, with respect to 1 equivalent of epoxy group in the total amount of epoxy resin, the blending equivalent of polyfunctional acid anhydride curing agent (D) (equivalent of acid anhydride group and carboxyl group) and the blending equivalent of phenolic curing agent (E) ( It is more preferable to control (hydroxyl equivalent) under the following conditions.
  • the compounding equivalent value of component (D) is too small, the reactivity at the time of transfer molding is inferior, and further, the hardness at the time of heating is also reduced. Moreover, when the compounding equivalent value of a component (D) is too large, gate break property will be extremely inferior. If the blending equivalent value of component (E) is too large, it will cause a decrease in hardness during heating and a decrease in solder resistance after moisture absorption. Moreover, when the total of the compounding equivalent value of a component (D) and the compounding equivalent value of a component (E) is too small, a glass transition point (henceforth Tg) may become low. On the other hand, if the total is too large, Tg is increased and cracks are likely to occur in the solder mounting process.
  • the curing agent component it is preferable to use the curing agent components (D) and (E) together so that the amount becomes 100 wt%.
  • Other curing agents can be used as long as they do not cause harmful effects.
  • acid anhydride curing agents include aromatic carboxylic anhydrides such as phthalic anhydride, aliphatic carboxylic anhydrides such as azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydro Examples thereof include alicyclic carboxylic acid anhydrides such as phthalic acid anhydride, nadic acid anhydride, het acid anhydride, and hymic acid anhydride.
  • the blending amount of curing agents other than the curing agent components (D) and (E) is about 0 to 0.3 equivalents relative to 1 equivalent of epoxy groups in the total amount of epoxy resin.
  • the blending amount of all curing agent components including (D) and (E) is preferably in the range of 0.7 to 1.5 equivalents with respect to 1 equivalent of epoxy groups in the total amount of epoxy resin.
  • the purpose of the present invention is for optical semiconductor encapsulation, which is compatible with workability during transfer molding such as reactivity, mold release from mold, gate breakability, etc., and also has excellent lead-free solder resistance after moisture absorption It is to provide a curable resin composition.
  • the component (F) can be used by appropriately changing the amount of the composition constituted according to the present invention.
  • the object of the present invention can be better achieved by adding preferably within a certain range.
  • the content of the component (F) with respect to the total amount of the resin composition of the present invention is preferably in the range of 0.01 wt% to 5.0 wt%.
  • the adhesiveness may decrease and solder resistance after moisture absorption may be inferior. If the amount is too large, the adhesiveness may be improved, but the resin composition may have a negative effect on the curing acceleration, and curing after heat curing. A thing becomes fragile and the runner resin part breaks at the time of demolding by transfer molding, and the malfunction that it cannot finally demold may arise. From the viewpoint of the balance between the lead-free solder resistance and the mold release property, it is particularly preferably 0.1 wt% to 2.0 wt%, more preferably 0.1 wt% to 1.0 wt%, based on the total amount of the resin composition. It is good to contain a component (F).
  • component (F) may affect the acceleration of curing, the combined use of the component (G) described later is preferable.
  • component (G) is added in the range of 0.2 to 3.0, preferably 0.2 to 2.0, the balance between adhesion and curability is good.
  • a component (G) curing accelerator can be further used.
  • the resin composition of the present invention containing the component (G) is one of the preferred embodiments of the present invention.
  • the component (G) is not particularly limited as long as it has a function of promoting the reaction between the epoxy resin and the curing agent.
  • the gel time at 150 ° C. needs to be 60 seconds or less from the viewpoint of reactivity.
  • the reactivity is adjusted by providing a modification period by means of heating after the composition is adjusted, or adjusted by the amount of the curing accelerator (G). The method of doing etc. is mentioned.
  • the method of adjusting the reactivity by heating requires a certain amount of time. Furthermore, it is not preferable in terms of economics and technical difficulty, such as difficulty in determining the timing of metamorphosis.
  • the adjustment by the amount of the curing accelerator (G) is excellent in terms of economy and simplicity compared to the above-mentioned modification means because the reactivity can be adjusted only by the control by the addition amount. .
  • a gel time measuring machine can be used as an adjustment method based on the amount of the curing accelerator (G).
  • the gel time at 150 ° C. is preferably adjusted to 60 seconds or less, and preferably 50 seconds or less. At this time, if the gel time at 150 ° C. is long, the demoldability and tactability at the time of demolding are inferior, and furthermore, the hot hardness cannot be maintained high.
  • These accelerators are preferably added so that the gel time is within the range to be adjusted.
  • the total amount of the above components (D) to (G) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and still more preferably 15 to 40% by weight with respect to the total amount of the resin composition.
  • a colorant, a leveling agent, a coupling agent, a lubricant, an adhesion-imparting agent, and the like can be appropriately added to the epoxy resin composition of the present invention depending on the purpose.
  • the colorant and phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine series, infrared absorbers, ultraviolet absorbers, and other organic dyes, titanium oxide Inorganic pigments such as lead sulfate, chrome yellow, zinc yellow, chrome vermilion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chrome green, chromium oxide, cobalt green and the like.
  • Leveling agents include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, and titanium-based coupling agents. Can be mentioned.
  • Lubricants include hydrocarbon lubricants such as paraffin wax, micro wax, polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, stearylamide, palmitylamide, oleyl Higher fatty acid amide type lubricants such as amide, methylene bisstearamide, ethylene bisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra-) Higher fatty acid ester lubricants such as stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behe Acid, ricinoleic acid, such as magnesium naphthenate,
  • phosphite compounds and / or phosphate compounds include di-2-ethylhexyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, methyl acid phosphate, ethyl acid phosphate, isopropyl Acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate and the like.
  • the addition amount of the phosphite compound and / or phosphite compound is preferably set to 0.01 to 5 wt% in the composition from the viewpoint of adhesiveness, and more preferably in the range of 0.1 to 3 wt%. It is. If the addition amount is small, it is difficult to obtain an adhesive effect, and if the addition amount exceeds the above range, Tg (glass transition point) or the like may be lowered.
  • Specific examples of the compound containing S element include n-dodecanethiol, n-nonanethiol, n-pentanethiol, ethylene glycol-bis-3-mercaptopropionate, diethylene glycol-bis-3-mercaptopropionate.
  • Pionate triethylene glycol-bis-3-mercaptopropionate, tetraethylene glycol-bis-3-mercaptopropionate, propylene glycol-bis-3-mercaptopropionate, dipropylene glycol-bis-3-mercapto Propionate, tripropylene glycol-bis-3-mercaptopropionate, trimethylolpropane-tris-3-mercaptopropionate, tris- (ethyl-3-mercaptopropionate) isocyanurate, pentaerythris Tall-tetrakis-3-mercaptopropionate, dipentaerythritol-hex-3-mercaptopropionate, tris (3-mercaptopropioamino) -1,3,5-triazine, 3,3′-thiodipropion
  • acids dithiodipropionic acid, lauryl thiopropionic acid, thioglycolic acid, ammonium thioglycolate, thio
  • tetraethylene glycol-bis-3-mercaptopropionate trimethylolpropane-tris-3-mercaptopropionate, tris- (ethyl-3-mercaptopropionate) isocyanurate, pentaerythritol-tetrakis-3 -Mercaptopropionate and dipentaerythritol-hexa-3-mercaptopropionate, 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, thioglycolic acid, ammonium thioglycolate, thioglycol It is preferable to use acid monoethanolamine, diammonium dithiodiglycolate or the like alone or in combination.
  • the addition amount of the said specific thiol compound will not be specifically limited if it is a range which does not impair the characteristic of this invention. From the viewpoint of adhesiveness, it is preferably set to 0.01 to 10 wt% in the composition, and more preferably in the range of 0.1 to 5 wt%. If the addition amount is small, it is difficult to obtain an adhesive effect. If the addition amount exceeds the above range, Tg (glass point transfer) or the like may be lowered.
  • These adhesion-imparting agents can be used alone or in combination of two or more.
  • Component (A) is an epoxy resin in which R 1 is a hydrogen atom in the general formula (1), and n is an average value of the number of repetitions of 0 to 10,
  • component (B) in formula (2), R 2 is a hydrogen atom, R 3 is a methyl group, m is an average value of the number of repetitions of 0 to 10, and an epoxy equivalent is 500 to 800 g / eq.
  • Epoxy resin in component (C), in formula (2), R 2 is a hydrogen atom, R 3 is a methyl group, m is an average value of the number of repetitions of 0 to 10, and an epoxy equivalent is 850 to 1500 g / eq.
  • the polyfunctional anhydride curing agent of component (D) is the above formula (3), formula (6), formula (7), formula (8), formula (11), formula (12), formula (13) and formula ( 14) at least one acid anhydride selected from the group consisting of polyfunctional acid anhydrides,
  • the phenolic curing agent of component (E) has at least one selected from the group consisting of the compounds represented by formulas (15), (18) and (19), and component (F) a phosphate group (Meth) acrylate,
  • a curable resin composition for sealing an optical semiconductor 2.
  • the compound of formula (3) is trimellitic anhydride
  • the compound of formula (6) is ethylene glycol esterified trimellitic anhydride (R 5 in formula (6) is ethylene).
  • Compounding equivalent value of curing agent component (E): 0.20 to 0.60 equivalent 10.
  • the component (G) is a phosphine (preferably triphenylphosphine).
  • the components (A), (B), (C), (D), (E), (F), and (G) if necessary, and other Epoxy resins, other curing agents, other curing accelerators, and, if necessary, additive components such as coupling agents, coloring agents and leveling agents can be blended. If the compounding component is solid, after mixing using a compounding machine such as a Henschel mixer or Nauter mixer, knead at 80-130 ° C using a kneader, extruder, or heating roll, cool, pulverize, and form a powder. The curable resin composition of the invention is obtained.
  • a compounding machine such as a Henschel mixer or Nauter mixer
  • the compounding component when the compounding component is liquid, it is uniformly dispersed using a planetary mixer or the like to obtain the curable resin composition of the present invention.
  • the curable resin composition of the present invention thus obtained is solid, it is molded by a molding machine such as a transfer molding machine so as to seal the optical semiconductor element, and when it is liquid, the optical semiconductor element is sealed.
  • a molding machine such as a transfer molding machine
  • the optical semiconductor element is sealed.
  • After casting or dispensing into a mold it is heated to 100 to 200 ° C. and cured for 20 seconds to 5 hours, and sealed with a cured product of the curable resin composition of the present invention.
  • An optical semiconductor element can be obtained.
  • the optical semiconductor element of the present invention is an optical semiconductor element such as a light receiving element or a light emitting element sealed with the curable resin composition of the present invention.
  • a semiconductor device including the optical semiconductor element for example, DIP (dual Inline package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (think quad flat package), etc. It is done.
  • Hardness test Shore A measurement
  • Mold preheating temperature 150 ° C
  • Setting mold type ⁇ 50mm, thickness 5mm, retention time after injection of 4-chip disk mold: 180 seconds
  • Hardness meter Shore A rubber hardness meter measurement timing : After a holding time of 180 seconds, immediately after opening the upper mold, a Shore A measuring instrument was inserted into the surface of the ⁇ 50 mm disk resin, and the maximum value was taken as the Shore A value.
  • Tg measurement conditions using a sample molded into a bottom surface of 5 mm ⁇ 5 mm and a length of about 10 mm Measurement was performed in a compression mode using a temperature rising condition of 2 ° C./min using a TII apparatus manufactured by SII (Seiko Instruments). The change point of the linear expansion coefficient was defined as Tg.
  • Reflow test lead-free solder resistance
  • a 20-pin lead frame type simulated semiconductor element (lead frame material is made of copper, surface silver plated) is set in a transfer mold, and molding is performed so that unfilling does not occur in each sample. After demolding, it was post-cured at 150 ° C. for 4 hours to prepare a sample for a lead-free solder reflow test (hereinafter referred to as “reflow”).
  • the reflow test was performed by leaving the sample under high humidity conditions (the following moisture absorption conditions) and then immersing the sample in a lead-free solder melting furnace under the following conditions.
  • A-1 epoxy resin
  • C-1 bisphenol A type epoxy resin, epoxy equivalent 932 g / eq, manufactured by Toto Kasei Co., Ltd., YD-904 * D-1
  • Curing agent Multifunctional acid anhydride curing agent, TMEG-S (purity of trimellitic anhydride, 50% purity of trimellitic anhydride, ethylene glycol ester) 20%), melting point 60 ° C., acid anhydride equivalent 235 g / eq * D-2 (curing agent): polyfunctional acid anhydride curing agent, TMEG-S (purity of trimellitic anhydride, 50% purity of trimellitic anhydride, ethylene glycol ester) 20%), melting point 60 ° C., acid anhydride equivalent 235 g / eq * D-2 (curing agent
  • Comparative Examples 1 to 3 In order to confirm the reactivity in each resin using tetrahydrophthalic anhydride, which is a monofunctional acid anhydride used in the examples of Patent Document 1, a composition having the composition shown in Table 1 below was prepared. did. The kneading was melt-kneaded using an S1 kneader manufactured by Kurimoto Steel Co., Ltd., and the obtained kneaded product was cooled and pulverized. The gel time of 150 degreeC was measured with this ground material. Further, the pulverized product was formed into a necessary amount of tablets using a tablet machine, and then molded using a transfer molder with a disk mold preheated at 150 ° C. The results are also shown in Table 1.
  • Comparative Examples 4 and 5 Using the polyfunctional acid anhydride which is a component (D), it mix
  • compositions of the examples and comparative examples are the compositions shown in the respective tables, and are melt kneaded according to the melting temperature of the resin using a biaxial kneader, and the obtained kneaded material is pulverized and then transferred. It was set as the tablet for molding machines. Using the obtained tablet, a test optical semiconductor element was prepared under the above-described conditions using a transfer molding machine, and used as an evaluation sample. Examples 1, 2 and Comparative Example 6 are shown in Table 4, Examples 3, 4 and Comparative Example 7 are shown in Table 5, Example 5 is shown in Table 6, and Comparative Examples 8 and 9 are shown in Table 7, respectively. It should be noted that foreign matters and voids in the cured product not described in the table were not observed in any of Examples 1 to 5 and Comparative Examples 4 to 9 of the present invention.
  • Example of master batch preparation When using a component having a melting point of 150 ° C. or higher as component (D), it is necessary to dissolve and mix component (D) and component (E) in advance to lower the melting point below the transfer molding temperature. is there.
  • TMEG-600 melting point 165 ° C.
  • D-2 multifunctional curing agent component
  • Kajayard GPH-65 softening point 65 ° C.
  • Comparative Examples 8 and 9 Then, as Comparative Examples 8 and 9, a test sample was prepared using a resin composition obtained by adding the component (F) to the composition in which the combination of the epoxy resin and the curing agent was outside the scope of the present invention. The results are shown in Table 7 together with the composition.

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Abstract

La présente invention concerne une composition de résine durcissable destinée à l'encapsulation d'un semi-conducteur optique contenant : un composant de résine époxy novolaque biphényle multifonctionnel (A) ; une résine époxy bisphénol (B) ayant un poids d'équivalent époxy de 500 à 800 g/éq ; une résine époxy bisphénol (C) ayant un poids d'équivalent époxy de 850 à 1 500 g/éq ; un composant de durcissement anhydride multifonctionnel (D) ; un composant de durcissement phénolique (E) ayant un squelette biphényle ou un squelette alicyclique ; et un composant (méth)acrylate (F) ayant un groupe acide phosphorique. La composition de résine décrite présente une excellente réactivité pendant le moulage par transfert, un temps de gélification court, n'inclut/ne comprend pas de vides, présente une excellente dureté à des températures élevées pendant l'élimination du moule, et d'excellentes propriétés de cassure des orifices. De plus, l'élément semi-conducteur optique encapsulé résultant présente d'excellentes propriétés de re-circulation.
PCT/JP2010/006217 2009-10-29 2010-10-20 Composition de résine durcissable destinée à l'encapsulation d'un semi-conducteur optique, et produit durci composé de ladite composition Ceased WO2011052161A1 (fr)

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JP2012134446A (ja) * 2010-11-30 2012-07-12 Jnc Corp 光ナノインプリント用硬化性組成物および硬化性組成物から得られた硬化膜
JP2014094979A (ja) * 2012-11-07 2014-05-22 Panasonic Corp 半導体封止用エポキシ樹脂組成物および半導体装置
CN104080829A (zh) * 2012-09-28 2014-10-01 Won化学株式会社 耐冲击性优秀的热固性环氧树脂组合物
US20140335350A1 (en) * 2011-12-05 2014-11-13 Hitachi Chemical Company, Ltd. Method for forming protective film on electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
EP2774939A4 (fr) * 2011-10-31 2015-07-08 Toray Industries Composition de résine époxy en deux parties pour matériaux composites renforcés par fibres, et matériau composite renforcé par fibres
US10042254B2 (en) 2011-12-05 2018-08-07 Hitachi Chemical Company, Ltd. Method of forming protective film for touch panel electrode photosensitive resin composition and photosensitive element, and method of manufacturing touch panel
WO2019065248A1 (fr) 2017-09-29 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Composition de résine pour matériau composite renforcé par des fibres, et matériau composite renforcé par des fibres mettant en œuvre celle-ci
US10663861B2 (en) 2011-12-05 2020-05-26 Hitachi Chemical Company, Ltd. Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film
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US10663861B2 (en) 2011-12-05 2020-05-26 Hitachi Chemical Company, Ltd. Method for forming resin cured film pattern, photosensitive resin composition, photosensitive element, method for producing touch panel, and resin cured film
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WO2019065248A1 (fr) 2017-09-29 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Composition de résine pour matériau composite renforcé par des fibres, et matériau composite renforcé par des fibres mettant en œuvre celle-ci
KR20200081099A (ko) * 2018-12-27 2020-07-07 주식회사 케이씨씨 반도체 소자 언더필용 에폭시 수지 조성물
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