JP2012077257A - Method for producing cured product, and cured product - Google Patents
Method for producing cured product, and cured product Download PDFInfo
- Publication number
- JP2012077257A JP2012077257A JP2010226221A JP2010226221A JP2012077257A JP 2012077257 A JP2012077257 A JP 2012077257A JP 2010226221 A JP2010226221 A JP 2010226221A JP 2010226221 A JP2010226221 A JP 2010226221A JP 2012077257 A JP2012077257 A JP 2012077257A
- Authority
- JP
- Japan
- Prior art keywords
- curing
- epoxy resin
- resin composition
- cured product
- curable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000000203 mixture Substances 0.000 claims abstract description 50
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 38
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- 239000000463 material Substances 0.000 claims description 8
- 238000005457 optimization Methods 0.000 abstract 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- FEXXLIKDYGCVGJ-UHFFFAOYSA-N butyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OCCCC FEXXLIKDYGCVGJ-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- FIBARIGPBPUBHC-UHFFFAOYSA-N octyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCCC1OC1CCCCCCCC FIBARIGPBPUBHC-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JKXONPYJVWEAEL-UHFFFAOYSA-N oxiran-2-ylmethyl acetate Chemical compound CC(=O)OCC1CO1 JKXONPYJVWEAEL-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
-
- 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
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- 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
Landscapes
- 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)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、硬化物の製造方法及び硬化物、その硬化物を含む封止材、ならびにその封止材を含む光半導体装置に関する。 The present invention relates to a method for producing a cured product, a cured product, a sealing material including the cured product, and an optical semiconductor device including the sealing material.
光半導体装置に用いられる樹脂、特に光半導体の封止材には、高い光線透過率、光度保持率、ならびにヒートサイクル試験における優れた耐クラック性が要求される。従来、脂環式エポキシ樹脂によれば高い光線透過率、光度保持率が実現されるが、ヒートサイクル試験においてクラックが生じやすいという問題があった。この問題を解決するため、硬化触媒を用い硬化温度を何段階にも分けて段階的に硬化を進める方法や、脂環式エポキシ樹脂に芳香族環を有するビスフェノールＡ型のエポキシ樹脂などを混合する方法が採られている。しかしながら、前者の方法では作業性が悪く、十分な耐クラック性が得られず、後者の方法では、芳香族環に起因して光度保持率が低下するという欠点があった。 A resin used for an optical semiconductor device, particularly a sealing material for an optical semiconductor, is required to have high light transmittance, luminous intensity retention, and excellent crack resistance in a heat cycle test. Conventionally, according to the alicyclic epoxy resin, high light transmittance and luminous intensity retention were realized, but there was a problem that cracks were likely to occur in the heat cycle test. In order to solve this problem, a curing catalyst is used to divide the curing temperature into several stages and the curing proceeds in stages, or an alicyclic epoxy resin and a bisphenol A type epoxy resin having an aromatic ring are mixed. The method is taken. However, in the former method, workability is poor and sufficient crack resistance cannot be obtained, and in the latter method, there is a drawback in that the luminous intensity retention is reduced due to the aromatic ring.
特許文献１には、硬化触媒を含み、エポキシ樹脂として３，４−エポキシシクロヘキセニルメチル−３'，４'−エポキシシクロヘキセンカルボキシレートからなる脂環式エポキシ樹脂及び２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物からなる脂環式エポキシ樹脂の両方を含むとともに、下記式（Ａ）又は（Ｂ）で示される化合物の少なくとも一方を、上記透光性封止材料全質量に対して０．０１質量％〜１質量％含有してなる組成物を硬化させた硬化物が記載されている。この硬化物は、１２０℃で１時間の後、１５０℃で１時間の条件で硬化されており、耐クラック性が劣っている。 Patent Document 1 includes an alicyclic epoxy resin and 2,2-bis (hydroxymethyl) containing a curing catalyst and comprising 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate as an epoxy resin. It includes both alicyclic epoxy resins composed of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of -1-butanol and at least one of the compounds represented by the following formula (A) or (B) Is a cured product obtained by curing a composition containing 0.01% by mass to 1% by mass with respect to the total mass of the translucent sealing material. This cured product is cured at 120 ° C. for 1 hour and then at 150 ° C. for 1 hour, and has poor crack resistance.
特許文献２には、エポキシ樹脂としてビスフェノールＡジグリシジルエーテルを、酸無水物系硬化剤と硬化促進剤を用いて熱硬化したエポキシ樹脂が記載されている。特許文献２には、硬化物の内部応力を低減したい場合には、８０℃〜１３０℃程度で０．５時間〜５時間程度の条件で前硬化した後、１３０℃〜１８０℃程度で０．１時間〜１５時間程度の条件で後硬化することが好ましいとの記載があり、実施例では、１２０℃で１時間の前硬化後、１５０℃で３時間の後硬化により硬化物を作成しているが、このような条件では、得られた硬化物の耐クラック性は劣っている。また、上記エポキシ樹脂では、５ｍｍ厚の場合、１５０℃５日間熱処理後のイエローインデックスは１５．２増加しており、熱黄変が観られる。 Patent Document 2 describes an epoxy resin obtained by thermosetting bisphenol A diglycidyl ether as an epoxy resin using an acid anhydride curing agent and a curing accelerator. In Patent Document 2, when it is desired to reduce the internal stress of the cured product, it is precured at about 80 ° C. to 130 ° C. for about 0.5 hours to 5 hours, and then about 0.1 ° C. at about 130 ° C. to 180 ° C. There is a description that it is preferable to perform post-curing under conditions of about 1 hour to 15 hours. In the examples, after curing at 120 ° C. for 1 hour, a cured product is created by post-curing at 150 ° C. for 3 hours. However, under such conditions, the obtained cured product has poor crack resistance. In the case of the epoxy resin having a thickness of 5 mm, the yellow index after heat treatment at 150 ° C. for 5 days is increased by 15.2, and thermal yellowing is observed.
本発明の目的は、透明性、耐光性（光度保持性など）に優れ、かつヒートサイクル試験における耐クラック性に優れた硬化物であり、例えば、光半導体装置の封止材などとして適した硬化物の硬化方法を提供することにある。
本発明の他の目的は、該硬化方法により硬化した、透明性、耐光性に優れ、かつヒートサイクル試験における耐クラック性に優れた硬化物を提供することにある。
また、本発明の他の目的は、該硬化物を含む、透明性、耐光性に優れ、かつヒートサイクル試験における耐クラック性に優れた封止材、及び光半導体装置を提供することにある。
An object of the present invention is a cured product that is excellent in transparency, light resistance (lightness retention, etc.) and excellent in crack resistance in a heat cycle test, and is suitable for, for example, a sealing material for an optical semiconductor device. It is to provide a method for curing an object.
Another object of the present invention is to provide a cured product which is cured by the curing method and has excellent transparency and light resistance and excellent crack resistance in a heat cycle test.
Another object of the present invention is to provide a sealing material and an optical semiconductor device, which contain the cured product, which are excellent in transparency and light resistance and excellent in crack resistance in a heat cycle test.
本発明者らは、上記課題を解決するため鋭意検討した結果、脂環式エポキシ化合物を硬化性成分全量に対して６０重量％以上と、酸無水物などの硬化剤と、硬化促進剤とを含む硬化性樹脂組成物を、特定の硬化方法で硬化した場合に、透明性、耐光性に優れ、かつヒートサイクル試験における耐クラック性に優れた硬化物、封止材、並びに光半導体装置が得られることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have determined that the alicyclic epoxy compound is 60% by weight or more based on the total amount of the curable component, a curing agent such as an acid anhydride, and a curing accelerator. When the curable resin composition is cured by a specific curing method, a cured product, a sealing material, and an optical semiconductor device that are excellent in transparency and light resistance and crack resistance in a heat cycle test are obtained. The present invention has been found.
すなわち、本発明は、硬化性成分として脂環式エポキシ化合物（Ａ）と、硬化剤（Ｂ）と、硬化促進剤（Ｃ）とを含み、該脂環式エポキシ化合物（Ａ）の含有量が硬化性成分全量に対して６０重量％以上である硬化性エポキシ樹脂組成物を、温度９５℃以上１３５℃以下かつ４．５時間以上の硬化条件で硬化することを特徴とする硬化物の製造方法を提供する。
また、本発明は、上記硬化物の製造方法で製造された硬化物を提供する。
また、本発明は、上記硬化物を含む封止材を提供する。
さらに、本発明は、上記封止材を含む光半導体装置を提供する。
That is, this invention contains an alicyclic epoxy compound (A), a hardening | curing agent (B), and a hardening accelerator (C) as a sclerosing | hardenable component, and content of this alicyclic epoxy compound (A) is included. A method for producing a cured product, comprising curing a curable epoxy resin composition that is 60% by weight or more based on the total amount of the curable component under a curing condition of a temperature of 95 ° C. or higher and 135 ° C. or lower and 4.5 hours or longer. I will provide a.
Moreover, this invention provides the hardened | cured material manufactured with the manufacturing method of the said hardened | cured material.
Moreover, this invention provides the sealing material containing the said hardened | cured material.
Furthermore, this invention provides the optical semiconductor device containing the said sealing material.
本発明の硬化物の製造方法によれば、硬化条件における温度、時間を最適化することで、透明性に優れ、例えば光半導体装置の封止材として用いた場合に、耐光性、ヒートサイクル試験における耐クラック性に優れた硬化物、封止材、ならびに半導体装置を得ることができる。 According to the method for producing a cured product of the present invention, by optimizing the temperature and time under curing conditions, the transparency is excellent, for example, when used as a sealing material for an optical semiconductor device, light resistance, heat cycle test A cured product, a sealing material, and a semiconductor device excellent in crack resistance can be obtained.
＜硬化物の製造方法＞
本発明の硬化物の製造方法は、硬化性成分として脂環式エポキシ化合物（Ａ）と、硬化剤（Ｂ）と、硬化促進剤（Ｃ）とを含み、該脂環式エポキシ化合物（Ａ）の含有量が硬化性成分全量に対して６０重量％以上である硬化性エポキシ樹脂組成物を、温度９５℃以上１３５℃以下かつ４．５時間以上の硬化条件で硬化することを特徴とする。
<Method for producing cured product>
The manufacturing method of the hardened | cured material of this invention contains an alicyclic epoxy compound (A), a hardening | curing agent (B), and a hardening accelerator (C) as a sclerosing | hardenable component, and this alicyclic epoxy compound (A). A curable epoxy resin composition having a content of 60% by weight or more based on the total amount of the curable component is cured under curing conditions of a temperature of 95 ° C. or more and 135 ° C. or less and 4.5 hours or more.
＜硬化条件＞
本発明の硬化物の製造方法では、上記硬化性エポキシ樹脂組成物を、温度９５℃以上１３５℃以下かつ４．５時間以上の硬化条件で硬化する。本明細書において硬化は、硬化性エポキシ樹脂組成物を、例えば、所定の型に入れ、又は入れずに、所定温度で所定時間載置することにより行うことができる。硬化は、インターバルを置かずに続けて所定時間行ってもよいし、途中でインターバルを取ってもよい。インターバルを取る場合、硬化時間としては、インターバル前後で所定温度で処理した硬化時間の総合計の時間を指す。
<Curing conditions>
In the method for producing a cured product of the present invention, the curable epoxy resin composition is cured under curing conditions of a temperature of 95 ° C. or more and 135 ° C. or less and 4.5 hours or more. In the present specification, curing can be performed by placing the curable epoxy resin composition at a predetermined temperature for a predetermined time, for example, without putting it in a predetermined mold. Curing may be performed continuously for a predetermined time without an interval, or may be taken in the middle. When taking an interval, the curing time indicates a total time of curing times processed at a predetermined temperature before and after the interval.
硬化温度は温度９５℃以上１３５℃以下であり、好ましくは１００℃以上１３０℃未満、さらに好ましくは１００℃以上１２０℃以下である。硬化温度は上記温度範囲内であればよく、一定であっても、異なる数種類の温度でも良い。上記インターバルは、温度が９５℃を下回る温度となった時間を指し、室温付近（例えば２５℃程度）となってもよい。このインターバルにおいて、硬化性エポキシ樹脂組成物を型から外し、この型から外した硬化性エポキシ樹脂組成物をさらに上記硬化温度で硬化してもよい。硬化温度は、一定でもよく、温度９５℃以上１３５℃以下の範囲で変動してもよい。なかでも、硬化温度は、インターバルの有無に拘わらず一定であることが好ましい。 The curing temperature is 95 ° C or higher and 135 ° C or lower, preferably 100 ° C or higher and lower than 130 ° C, and more preferably 100 ° C or higher and 120 ° C or lower. The curing temperature may be in the above temperature range, and may be constant or several different temperatures. The interval refers to the time when the temperature is lower than 95 ° C., and may be near room temperature (for example, about 25 ° C.). In this interval, the curable epoxy resin composition may be removed from the mold, and the curable epoxy resin composition removed from the mold may be further cured at the curing temperature. The curing temperature may be constant or may vary within a temperature range of 95 ° C to 135 ° C. In particular, the curing temperature is preferably constant regardless of the presence or absence of an interval.
硬化時間は４．５時間以上（例えば４．５時間以上２４時間以下）であり、好ましくは５時間以上２０時間以下、さらに好ましくは５時間以上１６時間以下である。インターバルは、３０分以上（例えば３０分以上〜３０日）取ることができる。インターバルとしては、３０分〜１０日が好ましく、３０分〜３日がさらに好ましい。インターバルを取る場合、例えば、硬化性エポキシ樹脂組成物を所定の型に入れ、所定の温度で１時間〜２時間硬化し、続いて硬化性エポキシ樹脂組成物を室温付近まで放冷後、型から取り出し、続いて所定の温度で残りの時間を硬化することができる。本発明の硬化物の製造方法では、硬化性エポキシ樹脂組成物を上記の硬化条件で硬化することにより、ヒートサイクル試験における耐クラック性に優れた硬化物が得られる。 The curing time is 4.5 hours or more (for example, 4.5 hours or more and 24 hours or less), preferably 5 hours or more and 20 hours or less, more preferably 5 hours or more and 16 hours or less. The interval can be 30 minutes or longer (for example, 30 minutes to 30 days). The interval is preferably 30 minutes to 10 days, more preferably 30 minutes to 3 days. In the case of taking an interval, for example, the curable epoxy resin composition is put into a predetermined mold, cured at a predetermined temperature for 1 to 2 hours, and then the curable epoxy resin composition is allowed to cool to near room temperature, and then from the mold. Removal and subsequent curing at the predetermined temperature for the remaining time. In the manufacturing method of the hardened | cured material of this invention, the hardened | cured material excellent in the crack resistance in a heat cycle test is obtained by hardening | curing a curable epoxy resin composition on said hardening conditions.
＜硬化性エポキシ樹脂組成物＞
本発明の硬化物の製造方法に使用する硬化性エポキシ樹脂組成物は、硬化性成分として脂環式エポキシ化合物（Ａ）と、硬化剤（Ｂ）と、硬化促進剤（Ｃ）とを含み、該脂環式エポキシ化合物（Ａ）の含有量が硬化性成分全量に対して６０重量％以上である。
<Curable epoxy resin composition>
The curable epoxy resin composition used in the method for producing a cured product of the present invention includes an alicyclic epoxy compound (A), a curing agent (B), and a curing accelerator (C) as a curable component, Content of this alicyclic epoxy compound (A) is 60 weight% or more with respect to curable component whole quantity.
＜脂環式エポキシ化合物（Ａ）＞
本発明で用いられる脂環式エポキシ化合物（Ａ）としては、脂肪族環を有する化合物であれば特に限定されないが、（ｉ）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物、及び（ｉｉ）脂環にエポキシ基が直接単結合で結合している化合物であることが好ましい。
<Alicyclic epoxy compound (A)>
The alicyclic epoxy compound (A) used in the present invention is not particularly limited as long as it is a compound having an aliphatic ring. (I) Consists of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. The compound having an epoxy group and (ii) a compound in which the epoxy group is directly bonded to the alicyclic ring by a single bond are preferable.
（ｉ）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物としては、周知慣用のものの中から任意に選択して使用することができる。脂環エポキシ基としては、シクロヘキセンオキシド基が好ましい。 (I) The compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring can be arbitrarily selected from well-known ones. As the alicyclic epoxy group, a cyclohexene oxide group is preferable.
（ｉ）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物としては、特に、透明性、耐熱性の点で下記式（Ｉ）で表される脂環式エポキシ樹脂が望ましい。
２価の炭化水素基としては、炭素数が１〜１８の直鎖状又は分岐鎖状のアルキレン基、２価の脂環式炭化水素基等が挙げられる。炭素数が１〜１８の直鎖状又は分岐鎖状のアルキレン基としては、例えば、メチレン、メチルメチレン、ジメチルメチレン、エチレン、プロピレン、トリメチレン基等が挙げられる。２価の脂環式炭化水素基としては、例えば、１，２−シクロペンチレン、１，３−シクロペンチレン、シクロペンチリデン、１，２−シクロヘキシレン、１，３−シクロヘキシレン、１，４−シクロヘキシレン、シクロヘキシリデン基等の２価のシクロアルキレン基（シクロアルキリデン基を含む）などが挙げられる。 As a bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, And divalent cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.
連結基Ｘとしては、酸素原子を含有する連結基が好ましく、具体的には、−ＣＯ−，−Ｏ−ＣＯ−Ｏ−，−ＣＯＯ−，−Ｏ−，−ＣＯＮＨ−；これらの基が複数個連結した基；これらの基の１又は２以上と２価の炭化水素基の１又は２以上とが連結した基などが挙げられる。２価の炭化水素基としては前記の基が挙げられる。 As the linking group X, a linking group containing an oxygen atom is preferable. Specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—; A group in which one or two of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include the aforementioned groups.
式（Ｉ）で表される脂環式エポキシ化合物の代表的な例としては、下記式（Ｉ−１）〜（Ｉ−８）で表される化合物などが挙げられる。例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１（ダイセル化学工業製）等の市販品を使用することもできる。なお、下記式中、ｌ、ｍは、１〜３０の整数を表す。Ｒは炭素数１〜８のアルキレン基であり、メチレン、エチレン、プロピレン、イソプロピレン、ブチレン、イソブチレン、ｓ−ブチレン、ペンチレン、ヘキシレン、ヘプチレン、オクチレン基等の直鎖状又は分岐鎖状アルキレン基が挙げられる。これらのなかでも、メチレン、エチレン、プロピレン、イソプロピレン基等の炭素数１〜３の直鎖状又は分岐鎖状アルキレン基が好ましい。 Representative examples of the alicyclic epoxy compound represented by the formula (I) include compounds represented by the following formulas (I-1) to (I-8). For example, commercially available products such as Celoxide 2021P and Celoxide 2081 (manufactured by Daicel Chemical Industries) can also be used. In addition, in the following formula, l and m represent the integer of 1-30. R is an alkylene group having 1 to 8 carbon atoms, and linear or branched alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, s-butylene, pentylene, hexylene, heptylene, and octylene groups are included. Can be mentioned. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, propylene, and isopropylene group is preferable.
（ｉｉ）脂環にエポキシ基が直接単結合で結合している化合物としては、例えば下記式（ＩＩ）で表される化合物が挙げられる。 (Ii) Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).
脂環式エポキシ化合物（Ａ）としては、上記例示の化合物を、単独で又は２種類以上を組み合わせて使用することができ、例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１、ＥＨＰＥ ３１５０（ダイセル化学工業製）等の市販品を好ましく使用できる。 As the alicyclic epoxy compound (A), the above-exemplified compounds can be used singly or in combination of two or more kinds, such as Celoxide 2021P, Celoxide 2081, EHPE 3150 (manufactured by Daicel Chemical Industries), etc. Commercial products can be preferably used.
脂環式エポキシ化合物（Ａ）の含有量は、硬化性エポキシ樹脂組成物に含まれる硬化性成分全量に対して６０重量％以上（例えば６０〜１００重量％）である。硬化性成分とは、熱または放射線により硬化する硬化性化合物である。脂環式エポキシ化合物（Ａ）の含有量は、好ましくは、硬化性成分の全量に対して７０重量％（７０〜１００重量％）、さらに好ましくは８０重量％以上（８０〜１００重量％）とすることができる。なお、上記含有量は、脂環式エポキシ化合物（Ａ）を２種以上使用する場合には、その合計の含有量である。脂環式エポキシ化合物（Ａ）の含有量を上記範囲とすることにより、硬化性エポキシ樹脂組成物を硬化した場合に、光線透過率及び光度保持率に優れた硬化物が得られる。 Content of an alicyclic epoxy compound (A) is 60 weight% or more (for example, 60-100 weight%) with respect to the curable component whole quantity contained in a curable epoxy resin composition. The curable component is a curable compound that is cured by heat or radiation. The content of the alicyclic epoxy compound (A) is preferably 70% by weight (70 to 100% by weight), more preferably 80% by weight or more (80 to 100% by weight) with respect to the total amount of the curable component. can do. In addition, the said content is content of the sum total, when using 2 or more types of alicyclic epoxy compounds (A). By setting the content of the alicyclic epoxy compound (A) in the above range, when the curable epoxy resin composition is cured, a cured product having excellent light transmittance and luminous intensity retention is obtained.
本発明の硬化物の製造方法で用いる硬化性エポキシ樹脂組成物中の硬化性成分の合計含有量は、例えば３０〜９０重量％、好ましくは４０〜８０重量％、さらに好ましくは４０〜７０重量％である。硬化性エポキシ樹脂組成物中の硬化性成分の含有量を上記範囲とすることにより、硬化性に優れた樹脂組成物を得ることができる。 The total content of the curable components in the curable epoxy resin composition used in the method for producing a cured product of the present invention is, for example, 30 to 90% by weight, preferably 40 to 80% by weight, and more preferably 40 to 70% by weight. It is. By setting the content of the curable component in the curable epoxy resin composition within the above range, a resin composition having excellent curability can be obtained.
＜脂環式エポキシ化合物（Ａ）以外の硬化性成分＞
本発明で用いられる硬化性エポキシ樹脂組成物は、脂環式エポキシ化合物（Ａ）以外のエポキシ化合物を含んでいても良い。脂環式エポキシ化合物（Ａ）以外のエポキシ化合物としては、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ビス（２−エチルヘキシル）、１，４−ブタンジオールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル、プロピレングリコール、グリセリン等の脂肪族多価アルコールに１種または２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル、脂肪族長鎖二塩基酸脂肪族高級アルコールのモノグリシジルエーテルやフェノール、クレゾール、ブチルフェノール、またこれらにアルキレンオキサイドを付加することによって得られるポリエーテルアルコールのモノグリシジルエーテル、高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化アマニ油、エポキシ化ポリブタジエン、エチレンオキサイド、プロピレンオキサイド、スチレンオキサイド、メチルグリシジルエーテル、ブチルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、エチレングリコールグリシジルフェニルエーテル、エチレングリコールベンジルグリシジルエーテル、ジエチレングリコールグリシジルテトラヒドロピラニルエーテル、グリシジルメタクリレート、グリシジルアセテート等、または、これらのエポキシ化合物の水素原子の一部又は全てがフッ素で置換されたものも使用できる。
<Curable components other than alicyclic epoxy compound (A)>
The curable epoxy resin composition used in the present invention may contain an epoxy compound other than the alicyclic epoxy compound (A). Epoxy compounds other than the alicyclic epoxy compound (A) include dioctyl epoxyhexahydrophthalate, bis (2-ethylhexyl) epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol. Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, propylene glycol, glycerin Polyethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as Ricidyl ether, monoglycidyl ether of aliphatic long-chain dibasic aliphatic higher alcohol, phenol, cresol, butylphenol, polyether glycol monoglycidyl ether obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid Epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene, ethylene oxide, propylene oxide, styrene oxide, methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, Ethylene glycol glycidyl phenyl ether, ethylene glycol benzyl glycidyl ether, diethylene glycol Glycidyl tetrahydropyranyl ether, glycidyl methacrylate, glycidyl acetate, etc., or it may be used in which some or all of the hydrogen atoms of these epoxy compounds are substituted with fluorine.
また、上記に加えて、内部にエポキシ基を持つオリゴマータイプの放射線硬化性樹脂を使用することもできる。例えば、エポキシ化ポリブタジエン（製品名：エポリードＰＢ３６００、ＰＢ４７００、ダイセル化学工業株式会社）、エポキシ化スチレンブタジエンテレブロック共重合体（製品名 エポフレンドＡＴ５０１、ダイセル化学工業株式会社）等が挙げられる。また、ノボラック型エポキシ樹脂、例えば、フェノール、クレゾール、ハロゲン化フェノールおよびアルキルフェノール等のフェノール類とホルムアルデヒドとを酸性触媒下で反応して得られるノボラック類とエピクロルヒドリンおよび／またはメチルエピクロルヒドリンとを反応して得られるもの（製品名：ＥＯＣＮ−１０３、ＥＯＣＮ−１０４Ｓ、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０２７、ＥＰＰＮ−２０１、ＢＲＥＮ−Ｓ、日本化薬株式会社、製品名：ＤＥＮ−４３１、ＤＥＮ−４３９、ダウ・ケミカル社、および製品名：Ｎ−７３，ＶＨ−４１５０、大日本インキ化学工業株式会社）等がある。また、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ及びテトラブロムビスフェノールＡ等のビスフェノール類とエピクロルヒドリンとを反応させて得られるビスフェノール型エポキシ樹脂、或いは、ビスフェノールＡのジグリシジルエーテルと前記ビスフェノール類の縮合物とエピクロルヒドリンとを反応させ得られるビスフェノール型エポキシ樹脂（製品名：エピコート１００４、エピコート１００２、油化シェル株式会社、製品名：ＤＥＲ−３３０，ＤＥＲ−３３７、ダウ・ケミカル社）等がある。 In addition to the above, an oligomer-type radiation curable resin having an epoxy group inside can also be used. Examples thereof include epoxidized polybutadiene (product names: Epolide PB3600, PB4700, Daicel Chemical Industries, Ltd.), epoxidized styrene butadiene teleblock copolymer (product names Epofriend AT501, Daicel Chemical Industries, Ltd.), and the like. Also obtained by reacting novolak-type epoxy resins such as phenols, cresols, halogenated phenols and alkylphenols with phenols and formaldehyde in the presence of an acidic catalyst with epichlorohydrin and / or methyl epichlorohydrin. (Product names: EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S, Nippon Kayaku Co., Ltd., product names: DEN-431, DEN-439, Dow Chemical And product names: N-73, VH-4150, Dainippon Ink and Chemicals, Inc.). Also, a bisphenol type epoxy resin obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin, or a condensate of diglycidyl ether of bisphenol A and the bisphenols and epichlorohydrin. And bisphenol type epoxy resins (product names: Epicoat 1004, Epicoat 1002, Yuka Shell Co., Ltd., product names: DER-330, DER-337, Dow Chemical Co.).
脂環式エポキシ化合物（Ａ）以外のエポキシ化合物としては、上記例示の化合物を単独で又は２種以上を組み合わせて用いることができる。脂環式エポキシ化合物（Ａ）以外のエポキシ化合物としては、ビスフェノールＡ型エポキシ樹脂などの芳香族環を有するエポキシ化合物が好ましく使用できる。脂環式エポキシ化合物（Ａ）以外のエポキシ化合物は使用しなくても良い。 As an epoxy compound other than the alicyclic epoxy compound (A), the above-exemplified compounds can be used alone or in combination of two or more. As an epoxy compound other than the alicyclic epoxy compound (A), an epoxy compound having an aromatic ring such as a bisphenol A type epoxy resin can be preferably used. Epoxy compounds other than the alicyclic epoxy compound (A) may not be used.
＜硬化剤（Ｂ）＞
本発明の硬化物の製造方法で使用される硬化性エポキシ樹脂組成物は、硬化剤（Ｂ）を含有する。硬化剤（Ｂ）は、エポキシ基を有する化合物を硬化させる働きを有する。本発明における硬化剤（Ｂ）としては、エポキシ樹脂用硬化剤として周知慣用の硬化剤を使用することができる。本発明における硬化剤（Ｂ）としては、なかでも、２５℃で液状の酸無水物であることが好ましく、例えば、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルエンドメチレンテトラヒドロ無水フタル酸などを挙げることができる。また、例えば、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物などの常温（２５℃）で固体状の酸無水物は、常温（２５℃）で液状の酸無水物に溶解させて液状の混合物とすることで、本発明における硬化剤（Ｂ）として使用することができる。また、本発明においては、硬化剤（Ｂ）として、リカシッド ＭＨ−７００（新日本理化製）、ＨＮ−５５００（日立化成製）等の市販品を使用することもできる。
<Curing agent (B)>
The curable epoxy resin composition used in the method for producing a cured product of the present invention contains a curing agent (B). The curing agent (B) has a function of curing the compound having an epoxy group. As the curing agent (B) in the present invention, a conventionally known curing agent can be used as a curing agent for epoxy resin. In particular, the curing agent (B) in the present invention is preferably an acid anhydride that is liquid at 25 ° C., and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methyl endo. And methylenetetrahydrophthalic anhydride. Also, for example, acid anhydrides that are solid at room temperature (25 ° C.), such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, are liquid acid anhydrides at room temperature (25 ° C.) It can be used as the curing agent (B) in the present invention by dissolving in a product to form a liquid mixture. In the present invention, as the curing agent (B), commercially available products such as RIKACID MH-700 (manufactured by Nippon Nippon Chemical Co., Ltd.) and HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) can also be used.
硬化剤（Ｂ）は、一種でも、二種以上任意の割合で混合使用してもかまわない。その使用量としては、例えば、硬化性エポキシ樹脂組成物中に含有するエポキシ基を有する化合物の総量１００重量部に対して、５０〜１５０重量部、好ましくは１００〜１４５重量部、より具体的には、上記硬化性エポキシ樹脂組成物中に含有する全てのエポキシ基を有する化合物におけるエポキシ基１当量当たり、０．５〜１．５当量となる割合で使用することが好ましい。硬化剤（Ｂ）の使用量が５０重量部を下回ると、効果が不十分となり、硬化物の強靱性が低下する傾向があり、一方、硬化剤（Ｂ）の使用量が１５０重量部を上回ると、硬化物が着色して色相が悪化する場合がある。なお、上記使用量は、硬化剤（Ｂ）を２種以上使用する場合には、その合計の使用量である。 The curing agent (B) may be used singly or as a mixture of two or more kinds in an arbitrary ratio. The amount of use is, for example, 50 to 150 parts by weight, preferably 100 to 145 parts by weight, more specifically, with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable epoxy resin composition. Is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition. When the amount of the curing agent (B) used is less than 50 parts by weight, the effect becomes insufficient and the toughness of the cured product tends to be reduced, while the amount of the curing agent (B) used exceeds 150 parts by weight. When the cured product is colored, the hue may deteriorate. In addition, the said usage-amount is the usage-amount of the sum total, when using 2 or more types of hardening | curing agents (B).
本発明においては、硬化剤（Ｂ）を、好ましくは硬化性エポキシ樹脂組成物中に含有する全てのエポキシ基を有する化合物におけるエポキシ基１当量当たり、０．５〜１．５当量となる割合で使用するため、硬化の際の反応点が多く、また、硬化性エポキシ樹脂組成物を、温度９５℃以上１３５℃以下という低温で硬化するため、穏やかに且つ均一に硬化が進行し、ヒートサイクル試験における耐クラック性に優れた硬化物が製造されると考えられる。 In the present invention, the curing agent (B) is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition. Because it is used, there are many reaction points at the time of curing, and since the curable epoxy resin composition is cured at a low temperature of 95 ° C. or more and 135 ° C. or less, the curing proceeds gently and uniformly, and the heat cycle test It is considered that a cured product having excellent crack resistance is produced.
＜硬化促進剤（Ｃ）＞
本発明の硬化物の製造方法で使用される硬化性エポキシ樹脂組成物は硬化促進剤（Ｃ）を含有する。硬化促進剤（Ｃ）は、エポキシ基を有する化合物が硬化剤により硬化する際に、硬化速度を促進する機能を有する化合物である。本発明の硬化性エポキシ樹脂組成物に含まれていてもよい硬化促進剤（Ｃ）としては、周知慣用の硬化促進剤を使用することができ、例えば、１，８−ジアザビシクロ［５．４．０］ウンデセン−７（ＤＢＵ）、及びその塩（例えば、フェノール塩、オクチル酸塩、ｐ−トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩）；１，５−ジアザビシクロ［４．３．０］ノネン−５（ＤＢＮ）、及びその塩（例えば、ホスホニウム塩、スルホニウム塩、４級アンモニウム塩、ヨードニウム塩）；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ−ジメチルシクロヘキシルアミンなどの３級アミン；２−エチル−４−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾールなどのイミダゾール；リン酸エステル、トリフェニルホスフィンなどのホスフィン類；テトラフェニルホスホニウムテトラ（ｐ−トリル）ボレートなどのホスホニウム化合物；オクチル酸スズ、オクチル酸亜鉛などの有機金属塩；金属キレートなどが挙げられる。これらは、単独で又は２種以上を混合して使用することができる。
<Curing accelerator (C)>
The curable epoxy resin composition used in the method for producing a cured product of the present invention contains a curing accelerator (C). A hardening accelerator (C) is a compound which has a function which accelerates | stimulates a cure rate, when the compound which has an epoxy group hardens | cures with a hardening | curing agent. As the curing accelerator (C) that may be contained in the curable epoxy resin composition of the present invention, a well-known and commonly used curing accelerator can be used. For example, 1,8-diazabicyclo [5.4. 0] undecene-7 (DBU), and salts thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate); 1,5-diazabicyclo [4.3.0] Nonene-5 (DBN) and its salts (for example, phosphonium salt, sulfonium salt, quaternary ammonium salt, iodonium salt); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N- Tertiary amines such as dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole Phosphines such as phosphate ester and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organometallic salts such as tin octylate and zinc octylate; metal chelates and the like . These can be used alone or in admixture of two or more.
また、本発明においては、硬化促進剤（Ｃ）として、Ｕ−ＣＡＴ ＳＡ ５０６、Ｕ−ＣＡＴ ＳＡ １０２、Ｕ−ＣＡＴ ５００３、Ｕ−ＣＡＴ １８Ｘ、１２ＸＤ（開発品）（いずれもサンアプロ製）、ＴＰＰ−Ｋ、ＴＰＰ−ＭＫ（いずれも北興化学工業製）、ＰＸ−４ＥＴ（日本化学工業製）等の市販品を使用することもできる。 In the present invention, as the curing accelerator (C), U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD (developed product) (all manufactured by San-Apro), TPP Commercially available products such as -K, TPP-MK (both manufactured by Hokuko Chemical Co., Ltd.) and PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.
硬化促進剤（Ｃ）は、一種でも、二種以上任意の割合で混合使用してもかまわない。その使用量としては、例えば、硬化性エポキシ樹脂組成物中に含有するエポキシ基を有する化合物の総量１００重量部に対して、０．０５〜５重量部、好ましくは０．１〜３重量部、特に好ましくは０．２〜３重量部、最も好ましくは０．２５〜２．５重量部程度である。硬化促進剤（Ｃ）の使用量が０．０５重量部を下回ると、硬化促進効果が不十分となる場合があり、一方、硬化促進剤（Ｃ）の使用量が５重量部を上回ると、硬化物が着色して色相が悪化する場合がある。なお、上記使用量は、硬化促進剤（Ｃ）を２種以上使用する場合には、その合計の使用量である。 The curing accelerator (C) may be used singly or in combination of two or more in any ratio. The amount of use is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable epoxy resin composition. The amount is particularly preferably 0.2 to 3 parts by weight, and most preferably about 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (C) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when the amount of the curing accelerator (C) used exceeds 5 parts by weight, The cured product may be colored to deteriorate the hue. In addition, the said usage-amount is the usage-amount of the sum total, when using 2 or more types of hardening accelerators (C).
＜無機フィラー＞
本発明の硬化物の製造方法で使用される硬化性エポキシ樹脂組成物は、さらに、無機フィラーを含んでいてもよい。無機フィラーとしては、特に限定するものではないが、シリカ、アルミナ、マイカ、合成マイカ、タルク、酸化カルシウム、炭酸カルシウム、酸化ジルコニウム、酸化チタン、チタン酸バリウム、カオリン、ベントナイト、珪藻土、窒化ホウ素、窒化アルミ、炭化ケイ素、酸化亜鉛、酸化セリウム、酸化セシウム、酸化マグネシウム、ガラスビーズ、ガラス繊維、グラファイト、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、セルロースなどを1種類以上使用することができる。また、無機フィラーとしては、ナノシリカ、ナノチタニア、ナノジルコニア、カーボンナノチューブ等を挙げることができる。
<Inorganic filler>
The curable epoxy resin composition used in the method for producing a cured product of the present invention may further contain an inorganic filler. The inorganic filler is not particularly limited, but silica, alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, nitriding One or more kinds of aluminum, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fiber, graphite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, cellulose and the like can be used. Examples of the inorganic filler include nano silica, nano titania, nano zirconia, and carbon nanotube.
これらの無機フィラーは、例えば国際公開第９６／３１５７２号に記載されている火炎加水分解法や、火炎熱分解法、プラズマ法等の公知の方法で製造することができる。好ましい無機フィラーとしては、安定化されたコロイド状無機粒子のナノ分散ゾル類等を用いることができ、市販品としては、BAYER社製のシリカゾル、Goldschmidt社製のＳｎＯ2ゾル類、MERCK社製のＴｉＯ2ゾル類、Nissan Chemicals社製のＳｉＯ2、ＺｒＯ2、Ａ１2Ｏ3およびＳｂ2Ｏ3ゾルまたはDEGUSSA社製のAerosil分散物類などの市販品が入手可能である。 These inorganic fillers can be produced by a known method such as a flame hydrolysis method, a flame pyrolysis method, or a plasma method described in, for example, International Publication No. 96/31572. As preferred inorganic fillers, stabilized colloidal inorganic particle nano-dispersed sols and the like can be used, and commercially available products include BAYER silica sol, Goldschmidt SnO 2 sol, MERCK Commercially available products such as TiO 2 sols, SiO 2 , ZrO 2 , A1 2 O 3 and Sb 2 O 3 sols from Nissan Chemicals or Aerosil dispersions from DEGUSSA are available.
無機フィラーは、表面の改質によりこれらの粘度挙動を変化させることができる。粒子の表面改質は、公知の表面改質剤を用いて行うことができる。このような表面改質剤としては、例えば、無機フィラーの表面に存在する官能基と共有結合や錯形成等の相互作用が可能な化合物や、重合体マトリックスと相互作用可能な化合物を用いることができる。このような表面改質剤としては、例えば、分子内にカルボキシル基、（第１級、第２級、第３級）アミノ基、４級アンモニウム基、カルボニル基、グリシジル基、ビニル基、（メタ）アクリロキシ基、メルカプト基等の官能基を有する化合物等を用いることができる。このような表面改質剤としては、通常、標準温度および圧力条件下で液体であり、分子内の炭素数が例えば１５以下、好ましくは１０以下、特に好ましくは８以下の低分子有機化合物で構成される。前記低分子有機化合物の分子量は、例えば５００以下、好ましくは３５０以下、特に２００以下である。 Inorganic fillers can change their viscosity behavior by surface modification. The surface modification of the particles can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the inorganic filler such as a covalent bond or complex formation, or a compound capable of interacting with a polymer matrix may be used. it can. Examples of such surface modifiers include carboxyl groups, (primary, secondary, and tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, ) A compound having a functional group such as acryloxy group or mercapto group can be used. Such a surface modifier is usually a liquid under standard temperature and pressure conditions, and is composed of a low molecular organic compound having a carbon number in the molecule of, for example, 15 or less, preferably 10 or less, particularly preferably 8 or less. Is done. The molecular weight of the low molecular weight organic compound is, for example, 500 or less, preferably 350 or less, particularly 200 or less.
好ましい表面改質剤としては、例えば、ギ酸、酢酸、プロピオン酸、酪酸、ペンタン酸、ヘキサン酸、アクリル酸、メタクリル酸、クロトン酸、クエン酸、アジピン酸、コハク酸、グルタル酸、シュウ酸、マレイン酸およびフマル酸などの炭素数１〜１２の飽和または不飽和モノおよびポリカルボン酸類（好ましくは、モノカルボン酸類）；及びこれらのエステル類（好ましくはメタクリル酸メチル等のＣ1〜Ｃ4アルキルエステル類）；アミド類；アセチルアセトン、２，４−ヘキサンジオン、３，５−ヘプタンジオン、アセト酢酸およびＣ1〜Ｃ4アルキルアセト酢酸類などのβ−ジカルボニル化合物等が挙げられる。また、特に限定されないが、公知慣用のシランカップリング剤を表面改質剤として使用することもできる。 Preferred surface modifiers include, for example, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, malein acid and saturated or unsaturated mono- and polycarboxylic acids having 1 to 12 carbon atoms such as fumaric acid (preferably monocarboxylic acids); and C 1 -C 4 alkyl esters of these esters (preferably such as methyl methacrylate Amides; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C 1 -C 4 alkylacetoacetic acids. Moreover, although it does not specifically limit, a well-known and usual silane coupling agent can also be used as a surface modifier.
無機フィラーの粒径は、通常０．０１ｎｍ〜２００μｍ程度、好ましくは０．１ｎｍ〜１００μｍ、特に０．１ｎｍ〜５０μｍ程度である。 The particle size of the inorganic filler is usually about 0.01 nm to 200 μm, preferably 0.1 nm to 100 μm, and particularly about 0.1 nm to 50 μm.
無機フィラーの含有量は、硬化性成分の合計含有量を１００重量部とすると、１〜２０００重量部であることが好ましく、さらに好ましくは１０〜１０００重量部である。また、硬化性エポキシ樹脂組成物の全量に対する、無機フィラーの含有量は、例えば、５〜９５ｗｔ％、好ましくは１０〜９０ｗｔ％である。なお、上記含有量は、無機フィラーを２種以上使用する場合には、その合計の含有量である。 The content of the inorganic filler is preferably 1 to 2000 parts by weight, and more preferably 10 to 1000 parts by weight, where the total content of the curable components is 100 parts by weight. Moreover, content of the inorganic filler with respect to the whole quantity of a curable epoxy resin composition is 5-95 wt%, for example, Preferably it is 10-90 wt%. In addition, the said content is content of the sum total, when using 2 or more types of inorganic fillers.
＜ゴム粒子＞
本発明で使用する硬化性エポキシ樹脂組成物にはゴム粒子が含まれていても良い。ゴム粒子としては、例えば、粒子状ＮＢＲ（アクリロニトリル−ブタジエンゴム）、反応性末端カルボキシル基ＮＢＲ（ＣＴＢＮ）、メタルフリーＮＢＲ、粒子状ＳＢＲ（スチレン−ブタジエンゴム）等が挙げられる。ゴム粒子は、ゴム弾性を有するコア部分と、該コア部分を被覆する少なくとも１層のシェル層とから成る多層構造（コアシェル構造）を有し、表面に脂環式エポキシ樹脂と反応し得る官能基としてヒドロキシル基及び／又はカルボキシル基を有し、平均粒子径が１０ｎｍ〜５００ｎｍ、最大粒子径が５０ｎｍ〜１０００ｎｍであるゴム粒子であって、該ゴム粒子の屈折率と当該硬化性エポキシ樹脂組成物の硬化物の屈折率との差が±０．０２以内であるゴム粒子で有っても良い。ゴム粒子は、一種でも、二種以上任意の割合で混合使用してもかまわない。ゴム粒子の含有量は、硬化性成分の合計１００重量部に対して、例えば、０．５〜３０重量部であり、好ましくは１〜２０重量部、さらに好ましくは１〜１０重量部である。配合量が０．５重量部を下回ると、耐クラック性が低下する傾向があり、３０重量部を上回ると、耐熱性及び透明性が低下する傾向がある。なお、上記含有量は、ゴム粒子を２種以上使用する場合には、その合計の含有量である。
<Rubber particles>
The curable epoxy resin composition used in the present invention may contain rubber particles. Examples of the rubber particles include particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, particulate SBR (styrene-butadiene rubber), and the like. The rubber particle has a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion, and a functional group capable of reacting with an alicyclic epoxy resin on the surface. Rubber particles having a hydroxyl group and / or a carboxyl group, an average particle diameter of 10 nm to 500 nm, and a maximum particle diameter of 50 nm to 1000 nm, wherein the refractive index of the rubber particles and the curable epoxy resin composition It may be a rubber particle having a difference from the refractive index of the cured product within ± 0.02. The rubber particles may be used singly or in combination of two or more in any ratio. The content of the rubber particles is, for example, 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the curable component. If the blending amount is less than 0.5 parts by weight, the crack resistance tends to decrease, and if it exceeds 30 parts by weight, the heat resistance and transparency tend to decrease. In addition, the said content is content of the sum total, when using 2 or more types of rubber particles.
＜添加剤＞
本発明にかかる硬化性エポキシ樹脂組成物は、上記以外にも、本発明の効果を損なわない範囲内で各種添加剤を使用することができる。添加剤として、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、グリセリンなどの水酸基を有する化合物を使用すると、反応を緩やかに進行させることができる。その他にも、粘度や透明性を損なわない範囲内で、シリコーン系やフッ素系消泡剤、レベリング剤、γ−グリシドキシプロピルトリメトキシシランなどのシランカップリング剤、界面活性剤、難燃剤、着色剤、酸化防止剤、紫外線吸収剤、イオン吸着体、顔料、蛍光体、離型剤などの慣用の添加剤を使用することができる。
<Additives>
In addition to the above, the curable epoxy resin composition according to the present invention can use various additives within a range not impairing the effects of the present invention. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used as the additive, the reaction can be allowed to proceed slowly. In addition, as long as the viscosity and transparency are not impaired, silicone-based and fluorine-based antifoaming agents, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, surfactants, flame retardants, Conventional additives such as a colorant, an antioxidant, an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent can be used.
本発明の硬化物の製造方法で使用される硬化性エポキシ樹脂組成物は上記各成分を均一に混合することにより得られる。上記硬化性エポキシ樹脂組成物を得るには、各成分を自公転式攪拌脱泡装置、ホモジナイザー、プラネタリーミキサー、３本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用してなるべく均一になるように、攪拌、溶解、混合、分散等を行うことが望ましい。 The curable epoxy resin composition used in the method for producing a cured product of the present invention can be obtained by uniformly mixing the above components. In order to obtain the curable epoxy resin composition, each component is made as uniform as possible by using generally known mixing equipment such as a revolving type stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, etc.
＜硬化物＞
本発明では、上記硬化性エポキシ樹脂組成物を上記の硬化条件で硬化させることにより、透明性、耐光性（光度保持性など）に優れ、かつヒートサイクル試験における耐クラック性などの諸物性に優れた硬化物が得られる。
<Hardened product>
In the present invention, by curing the curable epoxy resin composition under the above-mentioned curing conditions, it is excellent in transparency and light resistance (such as light intensity retention) and various physical properties such as crack resistance in a heat cycle test. Cured product is obtained.
＜封止材＞
本発明の封止材は、上記硬化性エポキシ樹脂組成物を封止剤として使用し、上記の硬化条件で硬化させることにより、透明性、耐光性（光度保持性など）に優れ、かつヒートサイクル試験における耐クラック性などの諸物性に優れる。
<Encapsulant>
The encapsulant of the present invention uses the curable epoxy resin composition as an encapsulant and is cured under the above-mentioned curing conditions, so that it has excellent transparency and light resistance (such as light intensity retention) and a heat cycle. Excellent physical properties such as crack resistance in the test.
＜光半導体装置＞
本発明の光半導体装置は、上記硬化性エポキシ樹脂組成物で光半導体素子を封止し、上記の硬化条件で硬化させることにより得られる。光半導体素子の封止は、前述の方法で調製された硬化性エポキシ樹脂組成物を所定の成形型内に注入し、上記の硬化条件で加熱硬化して行う。本発明の光半導体装置は、透明性、耐光性（光度保持性など）に優れ、かつヒートサイクル試験における耐クラック性などの諸物性に優れている。
<Optical semiconductor device>
The optical semiconductor device of the present invention is obtained by sealing an optical semiconductor element with the curable epoxy resin composition and curing it under the curing conditions described above. The optical semiconductor element is sealed by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heat-curing under the above-described curing conditions. The optical semiconductor device of the present invention is excellent in transparency and light resistance (such as light intensity retention), and is excellent in various physical properties such as crack resistance in a heat cycle test.
本発明の硬化物の製造方法によれば、透明性、耐光性（光度保持性など）に優れ、かつヒートサイクル試験における耐クラック性などの諸物性に優れた光半導体封止材、接着材、電気絶縁材、積層板、コーティング、インク、塗料、シーラント、レジスト、複合材料、透明基材、透明シート、透明フィルム、光学素子、光学レンズ、光学部材、光造形、電子ペーパー、タッチパネル、太陽電池基盤、光導波路、導光板、ホログラフィックメモリなどが得られる。 According to the method for producing a cured product of the present invention, an optical semiconductor encapsulant, an adhesive, excellent in transparency, light resistance (such as light intensity retention), and various physical properties such as crack resistance in a heat cycle test, Electrical insulating material, laminated board, coating, ink, paint, sealant, resist, composite material, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, stereolithography, electronic paper, touch panel, solar cell base An optical waveguide, a light guide plate, a holographic memory, and the like can be obtained.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
製造例１
（エポキシ樹脂Ａ剤）
２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラル）シクロヘキサン付加物（ダイセル化学工業製 ＥＨＰＥ３１５０）と３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート（ダイセル化学工業製 セロキサイド２０２１Ｐ）もしくはビスフェノールＡ型エポキシ樹脂（新日鐵化学製 ＹＤ−１２８）を表１に示す配合処方（単位：重量部）に従って混合し、８０℃、１時間攪拌することで２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物を溶解させ、エポキシ樹脂（混合物）を得た。
Production Example 1
(Epoxy resin A agent)
1,2-epoxy-4- (2-oxyral) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE 3150, manufactured by Daicel Chemical Industries) and 3,4-epoxycyclohexylmethyl-3 ′, 4 '-Epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Chemical Industries) or bisphenol A type epoxy resin (YD-128 manufactured by Nippon Steel Chemical Co., Ltd.) was mixed according to the formulation (unit: parts by weight) shown in Table 1, By stirring for 1 hour, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol was dissolved to obtain an epoxy resin (mixture).
製造例２
（硬化剤と硬化促進剤と添加剤、可とう性付与剤の混合物、以下Ｂ剤と記載する）
Ｂ剤として、硬化剤（新日本理化製 リカシッド ＭＨ−７００；４−メチルヘキサヒドロ無水フタル酸／ヘキサヒドロ無水フタル酸＝７０／３０）：１００重量部、硬化促進剤（サンアプロ製 １８Ｘ）：０．５重量部、添加剤（和光純薬工業製 エチレングリコール）：１重量部、可とう性付与剤（新日本理化製 リカシッド ＨＦ−０８）：３重量部を、自公転式攪拌装置（あわとり練太郎ＡＲ−２５０ シンキー製）を使用して均一に混合し、脱泡してＢ剤を得た。
Production Example 2
(A mixture of curing agent, curing accelerator and additive, flexibility imparting agent, hereinafter referred to as B agent)
As the agent B, a curing agent (Rikacid MH-700 manufactured by Shin Nippon Chemical Co., Ltd .; 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30): 100 parts by weight, a curing accelerator (manufactured by SANAPRO 18X): 0. 5 parts by weight, additive (ethylene glycol manufactured by Wako Pure Chemical Industries): 1 part by weight, flexibility imparting agent (Rikacid HF-08, manufactured by Shin Nippon Rika Co., Ltd.): 3 parts by weight Taro AR-250 manufactured by Shinky Co., Ltd.) was used to uniformly mix and defoam to obtain B agent.
実施例１〜７、比較例１〜７
製造例１にて得たエポキシ樹脂Ａ剤と製造例２にて得たＢ剤を表１に示す配合処方（単位：重量部）に従って、各成分を自公転式攪拌装置（あわとり練太郎ＡＲ−２５０ シンキー製）を使用して均一に混合し、脱泡して硬化性エポキシ樹脂組成物を得た。
Examples 1-7, Comparative Examples 1-7
According to the compounding formulation (unit: parts by weight) shown in Table 1, the epoxy resin A agent obtained in Production Example 1 and the B agent obtained in Production Example 2 were subjected to a revolutionary stirring device (Awatori Kentaro AR) -250 made by Shinky Co., Ltd.) and uniformly defoamed to obtain a curable epoxy resin composition.
硬化条件（１）
実施例１、３で得た樹脂組成物を型（形状：ランプ形状、大きさ：φ３）に注入し、青色の発光ダイオード素子を実装したリードフレームを挿した後、オーブン（エスペック社製 ＧＰＨＨ−２０１）で１００℃で１５時間加熱硬化させ、樹脂で素子を封止した光半導体装置を得た。
Curing conditions (1)
The resin composition obtained in Examples 1 and 3 was poured into a mold (shape: lamp shape, size: φ3), a lead frame mounted with a blue light emitting diode element was inserted, and then an oven (GPH- manufactured by Espec Corp.) was inserted. 201) was cured by heating at 100 ° C. for 15 hours to obtain an optical semiconductor device in which the element was sealed with resin.
硬化条件（２）
実施例２、４〜７で得た樹脂組成物を型（形状：ランプ形状、大きさ：φ３）に注入し、青色の発光ダイオード素子を実装したリードフレームを挿した後、オーブン（エスペック社製 ＧＰＨＨ−２０１）で１２０℃で７時間加熱硬化させ、樹脂で素子を封止した光半導体装置を得た。
Curing conditions (2)
The resin compositions obtained in Examples 2, 4 to 7 were poured into a mold (shape: lamp shape, size: φ3), a lead frame on which a blue light emitting diode element was mounted was inserted, and then an oven (manufactured by Espec Corp.) GPHH-201) was heat-cured at 120 ° C. for 7 hours to obtain an optical semiconductor device in which the element was sealed with resin.
硬化条件（３）
比較例１、４で得た樹脂組成物を型（形状：ランプ形状、大きさ：φ３）に注入し、青色の発光ダイオード素子を実装したリードフレームを挿した後、オーブン（エスペック社製 ＧＰＨＨ−２０１）で１２０℃で４時間加熱硬化させ、樹脂で素子を封止した光半導体装置を得た。
Curing conditions (3)
After injecting the resin composition obtained in Comparative Examples 1 and 4 into a mold (shape: lamp shape, size: φ3) and inserting a lead frame mounted with a blue light-emitting diode element, an oven (GPH- manufactured by Espec Corp.) 201) was cured by heating at 120 ° C. for 4 hours to obtain an optical semiconductor device in which the element was sealed with resin.
硬化条件（４）
比較例２、５〜７で得た樹脂組成物を型（形状：ランプ形状、大きさ：φ３）に注入し、青色の発光ダイオード素子を実装したリードフレームを挿した後、オーブン（エスペック社製 ＧＰＨＨ−２０１）で１００℃で２時間加熱硬化した後、１４０℃で３時間加熱硬化することで、硬化した樹脂で素子を封止した光半導体装置を得た。
Curing conditions (4)
The resin composition obtained in Comparative Examples 2 and 5 to 7 was poured into a mold (shape: lamp shape, size: φ3), and after inserting a lead frame on which a blue light emitting diode element was mounted, an oven (manufactured by Espec Corp.) GPHH-201) was heat-cured at 100 ° C. for 2 hours, and was then heat-cured at 140 ° C. for 3 hours to obtain an optical semiconductor device in which the element was sealed with the cured resin.
硬化条件（５）
比較例３で得た樹脂組成物を型（形状：ランプ形状、大きさ：φ３）に注入し、青色の発光ダイオード素子を実装したリードフレームを挿した後、オーブン（エスペック社製 ＧＰＨＨ−２０１）で１５０℃で７時間加熱硬化することで、硬化した樹脂で素子を封止した光半導体装置を得た。
Curing conditions (5)
The resin composition obtained in Comparative Example 3 was poured into a mold (shape: lamp shape, size: φ3), a lead frame mounted with a blue light-emitting diode element was inserted, and then an oven (GPHH-201 manufactured by Espec Corp.) The optical semiconductor device in which the element was sealed with a cured resin was obtained by heat curing at 150 ° C. for 7 hours.
光線透過率
実施例及び比較例の配合処方による硬化前の硬化性エポキシ樹脂組成物を所定の型に注型し、上記硬化条件にて熱硬化して、厚さ３ｍｍのプレートを作製した。分光光度計（島津製作所製 分光光度計 ＵＶ−２４５０）を用いて４５０ｎｍの光線透過率を測定した。結果を表１に示す。
Light transmittance The curable epoxy resin composition before curing according to the formulation of Examples and Comparative Examples was cast into a predetermined mold and thermally cured under the above-described curing conditions to produce a plate having a thickness of 3 mm. The light transmittance at 450 nm was measured using a spectrophotometer (Spectrophotometer UV-2450 manufactured by Shimadzu Corporation). The results are shown in Table 1.
光度保持率
実施例及び比較例から得られた光半導体装置の全光束を全光束測定機（米国オプトロニックラボラトリーズ社製 マルチ分光放射測定システム ＯＬ７７１）を用いて測定した。さらに、２３℃、６０％ＲＨの恒温恒湿槽内で３００時間、光半導体装置に１００ｍＡの電流を流した後の全光束を測定した。次式から、光度保持率を算出した。結果を表１に示す。
｛光度保持率（％）｝＝｛３００時間後の全光束（ｌｍ）｝／｛０時間の全光束（ｌｍ）｝×１００
Luminance retention rate The total luminous flux of the optical semiconductor devices obtained from the examples and comparative examples was measured using a total luminous flux measuring machine (Multispectral Radiation Measurement System OL771 manufactured by Optronic Laboratories, USA). Further, the total luminous flux after a current of 100 mA was passed through the optical semiconductor device for 300 hours in a constant temperature and humidity chamber at 23 ° C. and 60% RH was measured. The luminous intensity retention was calculated from the following equation. The results are shown in Table 1.
{Luminance retention rate (%)} = {Total luminous flux after 300 hours (lm)} / {Total luminous flux after 0 hours (lm)} × 100
耐クラック性試験
実施例及び比較例から得た光半導体装置に、−４０℃・１５分及び１２０℃・１５分を１サイクルとした熱衝撃を、熱衝撃試験機（小型冷熱衝撃装置 ＴＳＥ−１１−Ａ エスペック社製）を用いて４００サイクルの試験を行った。その後、クラックの長さをデジタルマイクロスコープ（ＶＨＸ−９００ キーエンス製）を使用して観察し、光半導体装置５個のうち、発生したクラックの長さが９０μｍ以上のものを有する光半導体装置の個数を計測した。結果を表１に示す。
Crack resistance test The thermal shock with a cycle of −40 ° C. for 15 minutes and 120 ° C. for 15 minutes was applied to the optical semiconductor devices obtained from the examples and comparative examples, using a thermal shock tester (compact cold thermal shock device TSE-11). 400 cycles were tested using -A manufactured by ESPEC Corporation. Thereafter, the length of the crack is observed using a digital microscope (VHX-900, manufactured by Keyence), and the number of optical semiconductor devices having a crack length of 90 μm or more among the five optical semiconductor devices. Was measured. The results are shown in Table 1.
Claims (4)
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| JP2010226221A JP2012077257A (en) | 2010-10-06 | 2010-10-06 | Method for producing cured product, and cured product |
| CN2011800336021A CN102985458A (en) | 2010-10-06 | 2011-09-14 | Method for producing cured product and cured product |
| KR1020137001868A KR20130118298A (en) | 2010-10-06 | 2011-09-14 | Method for producing cured product and cured product |
| PCT/JP2011/070989 WO2012046552A1 (en) | 2010-10-06 | 2011-09-14 | Method for producing cured product and cured product |
| TW100135136A TW201217421A (en) | 2010-10-06 | 2011-09-29 | Production method for curing articles and curing articles |
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| JP2015108116A Division JP6072138B2 (en) | 2015-05-28 | 2015-05-28 | Method for producing cured product and cured product |
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| KR (1) | KR20130118298A (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014196431A (en) * | 2013-03-29 | 2014-10-16 | 三菱化学株式会社 | Epoxy resin, epoxy resin composition and hardened material |
| JP2016117802A (en) * | 2014-12-19 | 2016-06-30 | 株式会社ダイセル | Curable epoxy resin composition |
| JP2019023316A (en) * | 2013-06-03 | 2019-02-14 | 株式会社ダイセル | Curable epoxy resin composition |
| CN111406095A (en) * | 2018-01-11 | 2020-07-10 | 株式会社Lg化学 | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using same |
Families Citing this family (5)
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| CN104497486A (en) * | 2014-12-16 | 2015-04-08 | 浙江华正新材料股份有限公司 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
| CN107216613A (en) * | 2017-07-07 | 2017-09-29 | 东莞市德聚胶接技术有限公司 | Light curing resin composition and preparation method thereof |
| WO2019139354A1 (en) * | 2018-01-11 | 2019-07-18 | 주식회사 엘지화학 | Epoxy resin composition for semiconductor molding, and molding film and semiconductor package using same |
| WO2019155800A1 (en) * | 2018-02-08 | 2019-08-15 | 関西ペイント株式会社 | Resist composition and resist film |
| CN115124748A (en) * | 2022-07-28 | 2022-09-30 | 海南联塑科技实业有限公司 | Method for inhibiting degradation of plastic and precipitating micro plastic and application |
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| JP5154340B2 (en) * | 2008-08-27 | 2013-02-27 | 株式会社ダイセル | Resin composition for optical semiconductor encapsulation |
| JP5606752B2 (en) * | 2010-02-25 | 2014-10-15 | 株式会社ダイセル | Resin composition for optical semiconductor sealing and optical semiconductor device using the same |
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2011
- 2011-09-14 WO PCT/JP2011/070989 patent/WO2012046552A1/en active Application Filing
- 2011-09-14 KR KR1020137001868A patent/KR20130118298A/en not_active Withdrawn
- 2011-09-14 CN CN2011800336021A patent/CN102985458A/en active Pending
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| JPH06240001A (en) * | 1993-02-17 | 1994-08-30 | Nippon Kayaku Co Ltd | Organopolysiloxane and epoxy resin composition containing the same |
| JPH07288330A (en) * | 1994-04-18 | 1995-10-31 | Nitto Denko Corp | Photosemiconductor device |
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| JP2014196431A (en) * | 2013-03-29 | 2014-10-16 | 三菱化学株式会社 | Epoxy resin, epoxy resin composition and hardened material |
| JP2019023316A (en) * | 2013-06-03 | 2019-02-14 | 株式会社ダイセル | Curable epoxy resin composition |
| JP2016117802A (en) * | 2014-12-19 | 2016-06-30 | 株式会社ダイセル | Curable epoxy resin composition |
| CN111406095A (en) * | 2018-01-11 | 2020-07-10 | 株式会社Lg化学 | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using same |
| JP2021503033A (en) * | 2018-01-11 | 2021-02-04 | エルジー・ケム・リミテッド | Epoxy resin composition for semiconductor molding, molding film and semiconductor package using this |
| CN111406095B (en) * | 2018-01-11 | 2023-06-13 | 株式会社Lg化学 | Epoxy resin composition for molding semiconductor, molding film using the same, and semiconductor package |
| US11702520B2 (en) | 2018-01-11 | 2023-07-18 | Lg Chem, Ltd. | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same |
| JP7556506B2 (en) | 2018-01-11 | 2024-09-26 | エルジー・ケム・リミテッド | Epoxy resin composition for semiconductor molding, molding film and semiconductor package using same |
Also Published As
| Publication number | Publication date |
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| TW201217421A (en) | 2012-05-01 |
| WO2012046552A1 (en) | 2012-04-12 |
| CN102985458A (en) | 2013-03-20 |
| KR20130118298A (en) | 2013-10-29 |
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