CN107250282A - Hot curing resin composition and Polycarboxylic acid resin containing polyol compound, anhydride compound and heat-curing resin and its hot curing resin composition is used and has used any of foregoing hot curing resin composition as encapsulating material or the optical semiconductor device of reflecting material - Google Patents
Hot curing resin composition and Polycarboxylic acid resin containing polyol compound, anhydride compound and heat-curing resin and its hot curing resin composition is used and has used any of foregoing hot curing resin composition as encapsulating material or the optical semiconductor device of reflecting material Download PDFInfo
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- CN107250282A CN107250282A CN201680008961.4A CN201680008961A CN107250282A CN 107250282 A CN107250282 A CN 107250282A CN 201680008961 A CN201680008961 A CN 201680008961A CN 107250282 A CN107250282 A CN 107250282A
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- Prior art keywords
- acid
- curing resin
- resin composition
- formula
- hot curing
- Prior art date
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- 238000001723 curing Methods 0.000 title claims abstract description 185
- 239000000463 material Substances 0.000 title claims abstract description 154
- 239000011342 resin composition Substances 0.000 title claims abstract description 145
- 229920005989 resin Polymers 0.000 title claims abstract description 115
- 239000011347 resin Substances 0.000 title claims abstract description 115
- -1 polyol compound Chemical class 0.000 title claims abstract description 114
- 238000013007 heat curing Methods 0.000 title claims abstract description 40
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
- 229920005862 polyol Polymers 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims description 59
- 230000003287 optical effect Effects 0.000 title claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 59
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 44
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 103
- 150000008065 acid anhydrides Chemical class 0.000 claims description 78
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000003822 epoxy resin Substances 0.000 claims description 48
- 229920000647 polyepoxide Polymers 0.000 claims description 48
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 47
- MNUSMUGFHGAOIW-UHFFFAOYSA-N cyclohexane-1,1,2-tricarboxylic acid Chemical compound OC(=O)C1CCCCC1(C(O)=O)C(O)=O MNUSMUGFHGAOIW-UHFFFAOYSA-N 0.000 claims description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 41
- 238000005984 hydrogenation reaction Methods 0.000 claims description 40
- 150000005846 sugar alcohols Polymers 0.000 claims description 37
- 230000009477 glass transition Effects 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 34
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 28
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 27
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 24
- 238000005227 gel permeation chromatography Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000009738 saturating Methods 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims 1
- 229920002601 oligoester Polymers 0.000 description 81
- 239000000203 mixture Substances 0.000 description 65
- 239000002904 solvent Substances 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 35
- 239000003795 chemical substances by application Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 27
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 26
- 238000004040 coloring Methods 0.000 description 23
- 238000002156 mixing Methods 0.000 description 23
- 239000004593 Epoxy Substances 0.000 description 19
- 238000007711 solidification Methods 0.000 description 19
- 230000008023 solidification Effects 0.000 description 19
- 238000006467 substitution reaction Methods 0.000 description 17
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 16
- 125000001424 substituent group Chemical group 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 229960003742 phenol Drugs 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 14
- 150000008064 anhydrides Chemical class 0.000 description 13
- 230000008859 change Effects 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 11
- 150000002460 imidazoles Chemical class 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 125000002723 alicyclic group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 150000002148 esters Chemical group 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 235000014692 zinc oxide Nutrition 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000007259 addition reaction Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 5
- 229960003019 loprazolam Drugs 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 4
- AORTZIIKTZPIQU-UHFFFAOYSA-N 3-butyl-4-methyloxolane-2,5-dione Chemical class CCCCC1C(C)C(=O)OC1=O AORTZIIKTZPIQU-UHFFFAOYSA-N 0.000 description 4
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
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- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
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- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
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- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003921 pyrrolotriazines Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 238000003856 thermoforming Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000005590 trimellitic acid group Chemical group 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical class C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical class N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GUYHYXFHXCHJFA-UHFFFAOYSA-N C(=O)(NN)NN.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 Chemical compound C(=O)(NN)NN.C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1 GUYHYXFHXCHJFA-UHFFFAOYSA-N 0.000 description 1
- QDZXJOMXPRWGFG-UHFFFAOYSA-N CCC1=NC=NC=N1.O=C1NC(=O)NC(=O)N1 Chemical compound CCC1=NC=NC=N1.O=C1NC(=O)NC(=O)N1 QDZXJOMXPRWGFG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AXNBHOOQHIIQFA-UHFFFAOYSA-N [S].C(F)(F)F Chemical compound [S].C(F)(F)F AXNBHOOQHIIQFA-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 210000000481 breast Anatomy 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- PBBJQDKWYWWATI-UHFFFAOYSA-N cyclohexene ethene Chemical class C1=CCCCC1.C=C PBBJQDKWYWWATI-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NQZLQSFXEXKXDE-UHFFFAOYSA-N docosanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCCCCCC(O)=O NQZLQSFXEXKXDE-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- SEIUOYFQDIJJEO-UHFFFAOYSA-N hexane-1,1,1-tricarboxylic acid Chemical class CCCCCC(C(O)=O)(C(O)=O)C(O)=O SEIUOYFQDIJJEO-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229940024423 isopropyl isobutyrate Drugs 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
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QCGKUFZYSPBMAY-UHFFFAOYSA-N methyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C(C(=O)OC)CCC2OC21 QCGKUFZYSPBMAY-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QKVIAQUPPCPXBX-UHFFFAOYSA-N n,n-dimethyl-1h-pyrrol-2-amine Chemical compound CN(C)C1=CC=CN1 QKVIAQUPPCPXBX-UHFFFAOYSA-N 0.000 description 1
- 125000005473 octanoic acid group Chemical class 0.000 description 1
- RVDPAMYCMNCDKC-UHFFFAOYSA-N octylphosphonic acid;zinc Chemical compound [Zn].CCCCCCCCP(O)(O)=O RVDPAMYCMNCDKC-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- KSOCVFUBQIXVDC-FMQUCBEESA-N p-azophenyltrimethylammonium Chemical compound C1=CC([N+](C)(C)C)=CC=C1\N=N\C1=CC=C([N+](C)(C)C)C=C1 KSOCVFUBQIXVDC-FMQUCBEESA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229960005480 sodium caprylate Drugs 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- 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
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Hot curing resin composition and following hot curing resin composition containing the polyol compound (A) with more than 3 hydroxyls, anhydride compound (B) and heat-curing resin (C) are provided, it is characterized in that, 0.01Pas~10Pas scope is in 100~200 DEG C of scope containing the polybasic carboxylic acid (A) and ICI Cone ＆ Plate viscosities shown in following formula (1), and provides and uses any of foregoing hot curing resin composition as encapsulating material or the semiconductor device of reflecting material.(in formula (1), R1Represent the alkylidene of carbon number 1~6, R2Represent the alkyl or carboxyl of hydrogen atom or carbon number 1~6.In formula (1), multiple R1、R2Can with it is mutually the same can also be different from each other.)
Description
Technical field
The present invention the first technical scheme (hereinafter referred to as the first invention) relate to suppress solidification when volatile quantity, to consolidate
The few heat-curing resin curing agent of coloring of compound, its hot curing resin composition is used and has used this
Hot curing resin composition is used as encapsulating material or the optical semiconductor device of reflecting material.In addition, the second skill of the present invention
Art scheme (hereinafter referred to as the second invention) relate to fully improve solidfied material glass transition temperature, have excellent formability, it is right
The few heat-curing resin curing agent of coloring of solidfied material, its hot curing resin composition is used and has used
The hot curing resin composition is used as encapsulating material or the optical semiconductor device of reflecting material.
Background technology
In the encapsulating material by the use of hot curing resin composition as semiconductor or it is used as semiconductor reflecting material
When, if containing the material that volatility is high in hot curing resin composition, in solidification, the material can volatilize, so as to produce
, there is the worry that reliability is reduced or deviation occurs for equivalent proportion and solidifies physical property reduction in space, it is therefore desirable that volatile quantity is few
Material.In addition, the problem of also there is bad smell when handling, it is therefore desirable that the few resin combination of volatile quantity.Enter
And, it is used as the encapsulating material of semiconductor, reflecting material, it is desirable to working life length, be difficult to the material that colours.Also, if heat cure
Property resin combination absorb the luminance reduction of light, then photosemiconductor that photosemiconductor is sent, therefore hot curing resin composition
Preferably there is high-transmission rate and the few resin combination of coloring.Therefore, it is compounded in consolidating in hot curing resin composition
Agent also requires that high-transmission rate and coloring are few.In addition, from the viewpoint of heat resistance, mouldability, reliability, the glass of solidfied material
Change transition temperature be certain temperature above is important, from the viewpoint of formability, the softening point of curing agent, viscosity are also at
Certain scope is important.
The heat resistance and the transparency of the acid anhydrides used as heat-curing resin curing agent are excellent, thus gradually by with
Used in optical semiconductor encapsulation etc..However, because volatility is high and fusing point is low, therefore only contain acid anhydrides as Thermocurable tree
The problem of there is physical property reduction, the bad smell that acid anhydrides volatilization is caused in the hot curing resin composition of fat curing agent.And then,
Due to for volatility and fusing point is low, therefore presence is the problem of can not be applied to die forming.
For tetracarboxylic anhydride, because fusing point is high (more than 150 DEG C), therefore as liquid resin composition be difficult to operate, into
Shape is poor, if therefore in view of for make liquid resin shape purposes degree of difficulty, be unsuitable for the present invention target use
On the way.
The example that carboxylic acid is used as to hardener for epoxy resin is it is known that, but fusing point is higher (more than 150 DEG C), exists
It is as described above the problem of, moreover, extremely difficult because easily being coloured when heating to ensure high-transmission rate, therefore this hair can not be suitable to
Bright intended applications.
Equally, for multi-carboxylic acid compounds, fusing point height (more than 150 DEG C), crystallinity are high, resin mixing is difficult and exists
Color also turns into problem, it is impossible to used in the intended applications of the present invention.
Therefore, as previously known material, not yet find to can solve the problem that the compound of above-mentioned problem.
Prior art literature
Patent document
Patent document 1：International Publication No. 2005/049597
Patent document 2：International Publication No. 2005/121202
The content of the invention
Problems to be solved by the invention
It is a first object of the present invention to provide when can fully improve the glass transition temperature of solidfied material, solidification
Volatile quantity is few, the coloring to solidfied material is few hot curing resin composition and used the hot curing resin composition
It is used as encapsulating material or the semiconductor device of reflecting material.
In addition, it is a second object of the invention to provide can fully improve the glass transition temperature of solidfied material, shaping
Property the much less first carboxylic acid of coloring excellent, to solidfied material, used its hot curing resin composition and used the heat
Hardening resin composition is used as encapsulating material or the semiconductor device of reflecting material.
The solution used to solve the problem
First invention is found：By making hardening resin composition contain the polyalcohol with more than 3 hydroxyls, so as to press down
Volatile quantity during system solidification, coloring when having excellent formability, being made solidfied material are few.
In addition, the second invention is found：By making hardening resin composition that there is specific viscosity and containing necessarily to compare
Example includes the change shown in aftermentioned formula (1) shown in polybasic carboxylic acid and aftermentioned formula (1a) and/or (1b) with isocyanuric acid ring
The Polycarboxylic acid resin of compound, so as to have sufficient glass transition temperature when solidfied material is made, have excellent formability, be made
Coloring during solidfied material is few.
I.e., the present invention relates to following (1)~(16).
(1) a kind of hot curing resin composition, it contains：Polyol compound (A) with more than 3 hydroxyls, acid
Anhydridization compound (B) and heat-curing resin (C).
(2) according to the hot curing resin composition described in (1), wherein, the foregoing polynary alcoholization with more than 3 hydroxyls
Compound (A) has includes more than 1 heteroatomic cyclic structure in intramolecular.
(3) hot curing resin composition according to (2), wherein, foregoing hetero atom is nitrogen-atoms.
(4) according to the hot curing resin composition described in (1), wherein, the foregoing polynary alcoholization with more than 3 hydroxyls
Compound (A) is the polyol compound shown in following formula (5).
(in formula (5), R1Represent the alkylidene of carbon number 1~6.In formula (5), multiple R1Can with it is mutually the same can also
It is different from each other.)
(5) hot curing resin composition according to any one of (1)~(4), wherein, foregoing anhydride compound
(B) it is selected from trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic acid
One kind or two or more compound in acid anhydride and methylhexahydrophthalic anhydride.
(6) hot curing resin composition according to any one of (1)~(5), it is characterised in that foregoing heat cure
Property resin (C) be epoxy resin.
(7) a kind of hot curing resin composition, it contains following Polycarboxylic acid resin,
The Polycarboxylic acid resin contains in the measure of gel permeation chromatography for more than 70 area %, following formula (1)
Shown polybasic carboxylic acid (A1), and contain in the measure of gel permeation chromatography for 0.5~10 area %, following formula (1a)
Carboxylic acid (A3) shown in shown polybasic carboxylic acid (A2) and/or following formula (1b),
(in formula (1), R1Represent alkylidene, the R of carbon number 1~62Represent the alkyl or carboxyl of hydrogen atom or carbon number 1~6.Formula
(1) in, multiple R1、R2Can with it is mutually the same can also be different from each other.)
(in formula (1a), R1、R2With the R in previously described formula (1)1、R2Represent identical implication.It is multiple in formula (1a)
R1、R2Can with it is mutually the same can also be different from each other.)
(in formula (1b), R1、R2With the R in previously described formula (1)1、R2Represent identical implication.It is multiple in formula (1b)
R1、R2Can with it is mutually the same can also be different from each other.)
(8) hot curing resin composition according to (7), wherein, foregoing polycarboxylic acids' resin contains to be oozed in gel
It is the acid anhydrides shown in 5~20 area %, following formula (6) in the measure of saturating chromatogram,
(in formula (6), R2With the R in previously described formula (1)2Represent identical implication.)
(9) according to the hot curing resin composition described in (7), wherein, foregoing polycarboxylic acids' resin is to make previously described formula (1)
Shown compound and compound obtained from the compound reaction shown in the formula (6) described in (8), and containing in gel infiltration color
It is 0.5~10 area %, the HMW body that retention time is shorter than compound shown in previously described formula (1) in the measure of spectrum.
(10) according to the hot curing resin composition any one of (7)~(9), its softening point be in 20 DEG C~
150 DEG C of scope.
(11) hot curing resin composition according to any one of (7)~(10), it contains foregoing polycarboxylic acids
Resin and selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenate equal benzene four
1 kind in acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Or two or more compound, selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid,
Hydrogenate pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methyl hexahydro O-phthalic
The summation of one kind or two or more compound in acid anhydrides accounts for the weight of 1 weight %~90 in foregoing hot curing resin composition
Measure %.
(12) hot curing resin composition according to any one of (7)~(11), it contains heat-curing resin.
(13) hot curing resin composition according to (12), wherein, consolidate foregoing hot curing resin composition
The glass transition temperature (Tg) for the solidfied material changed is more than 30 DEG C.
(14) a kind of solidfied material, it is to make (1)~(6), (12) and the heat-curing resin group any one of (13)
Compound heat cure.
(15) a kind of optical semiconductor device, it is encapsulated using the solidfied material described in (14).
(16) a kind of optical semiconductor device, it uses the solidfied material described in (14) as reflecting material.
The effect of invention
According to the first invention, using the teaching of the invention it is possible to provide volatile quantity when suppressing solidification, coloring when having excellent formability, being made solidfied material
Few hot curing resin composition and the hot curing resin composition has been used as encapsulating material or reflecting material
Optical semiconductor device.
In addition, according to the second invention, using the teaching of the invention it is possible to provide solidfied material have sufficient glass transition temperature, have excellent formability,
Colouring much less first carboxylic acid resin, having used its hot curing resin composition and used this when solidfied material is made
Hot curing resin composition is used as encapsulating material or the optical semiconductor device of reflecting material.And then, it can provide by suppression
Softening point processed and processing is become easily and can be fully kneaded, solidify the solidfied material of physical properties excellent.Additionally, it is provided solidification
The obdurability of thing, the reactive also excellent hot curing resin composition of resin.
Brief description of the drawings
Fig. 1 is to use the hot curing resin composition obtained by the present invention as schematic diagram during reflecting material.
Embodiment
The first invention is described in detail below.
The hot curing resin composition of first invention is characterised by, contains the polyalcohol (A) with more than 3 hydroxyls.
In first invention, if the known polyalcohol with more than 3 hydroxyls, then combine even in acid anhydrides (B)
In use, the composition for the volatile quantity that can be also inhibited when solidifying.Specifically, can include trimethylolpropane,
Pentaerythrite, glycerine, EO modified glycerols, PO modified glycerols, dipentaerythritol, polyalcohol shown in following formula (5) etc..Wherein,
It is preferably provided with containing heteroatomic cyclic structure, volatilization when especially the alcohol shown in following formula (5) can suppress to solidify in intramolecular
Amount, treatability is excellent under solid forms, so it is preferred that.
So, by using the polyalcohol (A) with more than 3 hydroxyls, so that even in the absence of curing accelerator
In the case of, volatile quantity during solidification is also inhibited, and can realize the addition for reducing curing accelerator, therefore can be suppressed
The resin combination of coloring, and the hot curing resin composition of working life length can be realized.
In formula (5), R1Represent the alkylidene of carbon number 1~6.
It is used as R1Concrete example, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, different Asia can be included
Propyl group, isobutylene, isopentylidene, neopentylidene, isohexylidene, cyclohexylidene etc., from the heat resistant transparent of gained solidfied material
From the viewpoint of, preferably methylene, ethylidene, propylidene, particularly preferred ethylidene.
In formula (5), multiple R1Respectively can with it is mutually the same can also be different from each other.
In compound shown in formula (5), the transparency from solidfied material, from the viewpoint of gas barrier property, preferably following formula (7)~
(9) compound shown in.
In first invention, used polyalcohol (A) can be that liquid can also be solid.It is excellent when polyalcohol is solid
It is less than 180 DEG C, more preferably less than 150 DEG C, particularly preferably less than 120 DEG C to select softening point.Because, softening point is higher than
At 180 DEG C, curing reaction can be rapidly promoted during mixing, it is impossible to obtain full and uniform composition.
In first invention, used polyalcohol (A) preferably functional equivalent is below 250g/eq., is more preferably
240g/eq. it is following.By the way that for such scope, the solidfied material of excellent heat resistance can be obtained.
The hot curing resin composition of polyol compound (A) and acid anhydrides with more than 3 hydroxyls in the first invention
In shared ratio be preferably：Relative to 1 mole of the hydroxyl of polyalcohol, acid anhydrides is 0.1~100 mole.Acid anhydrides is less than 0.1 mole
When, there is the worry that glass transition temperature will not be uprised fully, when acid anhydrides is more than 100 moles, there is volatile ingredient to become many, it is impossible to
To the worry of sufficient effect.It is further preferred that relative to 1 mole of the hydroxyl of polyalcohol, acid anhydrides is 0.5~10 mole.
The hot curing resin composition of first invention contains anhydride compound (B).Used anhydride compound (B) is excellent
It is below 250g/eq., more preferably below 240g/eq. to select functional equivalent.By that for such scope, can obtain heat-resisting
The excellent solidfied material of property.
As suitable anhydride compound (B), it can include selected from trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, equal benzene four
It is one kind or two or more in acid anhydrides, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Compound.
There is trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydro O-phthalic
When acid anhydrides and methylhexahydrophthalic anhydride, the high solidfied material of crosslink density is can obtain, therefore, it is possible to obtain with high glass
The solidfied material of glass transition temperature.
Trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride,
And among methylhexahydrophthalic anhydride, from the degree aspect for being difficult to colour, preferably cyclohexanetricarboxylic acid's acid anhydride, hydrogen
Change pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, further preferred cyclohexanetricarboxylic acid
Acid anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
As cyclohexanetricarboxylic acid's acid anhydride, hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydride, hexamethylene -1,2,3- tri- can be included
Carboxylic acid -1,2- acid anhydrides.In first invention, these acid anhydrides can also be applied in combination, but preferably hexamethylene -1,2,4- tricarboxylic acids -
1,2- acid anhydrides.
And then, wherein it is preferred that compound shown in following formula (6).
In formula (6), R2Represent hydrogen atom, the alkyl or carboxyl of carbon number 1~6.
In compound shown in formula (6), the compound shown in particularly preferred following (2)~(4).
On selected from trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, the adjacent benzene of hexahydro
The summation of one kind or two or more acid anhydrides in dicarboxylic acid anhydride and methylhexahydrophthalic anhydride is combined in heat-curing resin
Shared ratio in thing, relative to 1 mole of the hydroxyl of the polyol compound (A) with more than 3 hydroxyls, preferred anhydrides are
0.1~10 mole.When acid anhydrides is less than 0.1 mole, there is the worry that glass transition temperature will not be uprised fully, acid anhydrides rubs more than 10
At that time, volatile ingredient becomes worry many, that sufficient effect can not be obtained.It is more preferably sour relative to 1 mole of the hydroxyl of polyalcohol
Acid anhydride is 0.5~5 mole.
Hot curing resin composition in first invention contains heat-curing resin (C).It is used as heat-curing resin
(C) epoxy resin, phenolic resin, carbamide resin, melmac, unsaturated polyester resin etc., the first invention can, be included
In, it is generally desirable to use epoxy resin.
As epoxy resin, as long as it is usual as conventional hot curing resin composition, composition epoxy resin
The material of compounding, it is possible to use without particular limitation.It can such as include：With phenol novolak type epoxy resin, neighbour
It is headed by cresol novolak type epoxy resin, by material obtained from the novolac resin epoxidation of phenols and aldehydes, it is double
Phenol A, Bisphenol F, bisphenol S, the diglycidyl ether of alkyl substitution bis-phenol etc., diaminodiphenyl-methane, pass through isocyanuric acid etc.
Polyamines reacts obtained glycidyl amine type epoxy resin with epichlorohydrin, aoxidizes alkene key with peroxy acids such as peracetic acid and obtains
Alicyclic epoxy resin, the pyrrolotriazine derivatives asphalt mixtures modified by epoxy resin such as isocyanuric acid 2-glycidyl ester, triglycidyl isocyanurate
Fat, silesquioxane compound with epoxy radicals etc., these, which can be used alone, can also be applied in combination two or more.These
In epoxy resin, preferably with high-fire resistance, sunproof epoxy resin, therefore specifically, from melt viscosity, consolidating of obtaining
From the point of view of the viewpoint such as the coloring of compound and glass transition temperature, preferably without aromatic ring, diglycidyl ether type epoxy tree
The pyrrolotriazine derivatives asphalt mixtures modified by epoxy resin such as fat, alicyclic epoxy resin, isocyanuric acid 2-glycidyl ester, triglycidyl isocyanurate
Fat, the silesquioxane compound with epoxy radicals.
As alicyclic epoxy resin, it can include：1,2:8,9- diepoxies limonene, the oxidation of 4 vinyl cyclohexene list
Thing, vinyl cyclohexene dioxide, methylated ethylene cyclohexene dioxide, (3,4- epoxycyclohexyls) methyl -3,4-
Epoxycyclohexylcarboxylate, double-(3,4- epoxycyclohexyls) adipate ester, double-(3,4- epoxycyclohexyls methylene) adipic acid
Ester, double-(2,3- epoxycyclopentyls) ether, (2,3- epoxy -6- methylcyclohexylmethyls) adipate ester, dicyclopentadiene titanium dioxide
Cyclic aliphatic group and intramolecular with the yuan of rings of at least one 4~7 have the chemical combination of at least one epoxy radicals in thing equimolecular
Thing etc..As such alicyclic epoxy resin, preferably intramolecular has the alicyclic epoxy resin of more than 2 epoxy radicals.Point
The alicyclic epoxy resin with more than 2 epoxy radicals can be obtained as commercially available product in sub, for example, can include
CELLOXIDE 8000, CELLOXIDE 2021P, CELLOXIDE 2081, EHPE 3150 (are the strain of Daicel chemical industry
Formula commercial firm system) etc..
In addition, as triazine derivative epoxy resin, 1,3,5- tri- (oxiranylmethyl radical) -1,3,5- tri- can be included
Piperazine -2,4,6 (1H, 3H, 5H)-triketone etc..These triazine derivative epoxy resins can be obtained as commercially available product, for example, can arrange
Enumerate TEPIC-S, TEPIC-L, TEPIC-VL, TEPIC-PAS B22, TEPIC-UC (being Misao Kusano's system).
In addition, as the silesquioxane compound with epoxy radicals that can be used, preferably intramolecular have 2 with
The silesquioxane compound of upper epoxy radicals.There is the silesquioxane compound of more than 2 epoxy radicals as intramolecular, to bone
Frame is not particularly limited, for example, can include mixed structure more than chain, ring-type, scalariform or these at least two kinds of
There is glycidyl and/or the epoxy resin of 7-oxa-bicyclo[4.1.0 structure in siloxane structure.
There is the concrete example of the silesquioxane compound of more than 2 epoxy radicals as intramolecular, for example, can use day
The cage-type silsesquioxane with epoxide ring, Japanese Unexamined Patent Publication 2008-248169 publications described in this JP 2005-263869
Described in the silicones containing alicyclic epoxy group, having in a molecule described in Japanese Unexamined Patent Publication 2008-19422 publications
Organic polysilsesquioxane resins of at least two epoxy functional group etc..These intramoleculars have times of more than 2 epoxy radicals
Half silicone compounds can be obtained as commercially available product, can be included and be belonged to ring-type of the intramolecular with more than 2 epoxy radicals
Siloxanes, trade name " X-40-2670 " (Shin-Etsu Chemial Co., Ltd's system) etc..
Mix ratio on epoxy resin and anhydride compound (B), it is preferred that relative to the epoxy radicals in epoxy resin
1 equivalent, reacts it, particularly preferably in the way of the carboxyl that anhydride group and hydroxyl reaction are generated turns into the ratio of 0.5~1.5 equivalent
It is reacted in the way of as 0.5~1.2 equivalent.Relative to the equivalent of epoxy radicals 1, when carboxyl is less than 0.5 equivalent or carboxyl
During more than 1.5 equivalent, have solidification become not exclusively, the worry of solidification physical property that cannot be good, in addition with becoming appearance
The problem of easy coloring.
In addition, in hot curing resin composition, various composition can also be contained as other compositions.First can be used as
As long as the composition of the hot curing resin composition of invention and the known material of carboxylic acid contained, it is possible to be not particularly limited
Ground is used.Specifically, crosslinking can be obtained when there is trimellitic acid, cyclohexanetricarboxylic acid, pyromellitic acid, hydrogenation pyromellitic acid close
The high solidfied material of degree, therefore, it is possible to obtain the solidfied material with high glass-transition temperature.Trimellitic acid, cyclohexanetricarboxylic acid,
In pyromellitic acid, hydrogenation pyromellitic acid, from the degree aspect for being difficult to colour, preferably cyclohexanetricarboxylic acid, hydrogenation is equal
Benzenetetracarboxylic acid.
When the hot curing resin composition is contained above-mentioned carboxylic acid, it is characterised by, selected from trimellitic acid, hexamethylene tricarboxylic
Acid, pyromellitic acid, the summation for the one kind or two or more compound for hydrogenating pyromellitic acid are shared in hot curing resin composition
Ratio be the weight % of 1 weight %~90.During less than 1 weight %, glass transition temperature will not be uprised fully, higher than 90 weights
When measuring %, fusing point uprises, handles change difficulty.More preferably 10~60 weight %, more preferably 20~50 weight %.
In the hot curing resin composition of first invention, with weight ratio meter, the polyol with more than 3 hydroxyls
Thing (A)：(selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid and cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation
Pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
In one kind or two or more compound) be preferably 99:1~1:99th, 90 are more preferably:10~10:90th, 50 are particularly preferably:50
~10:90.By the way that for above-mentioned ratio, heat resistance is very excellent and viscosity is also low, can fully knead, therefore as solidfied material
Property also excellent hot curing resin composition.
In addition, the above-mentioned polyol compound (A) with more than 3 hydroxyls is with being selected from trimellitic anhydride, hexamethylene tricarboxylic
1 in acid anhydrides, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Kind or the summation ratio shared in hot curing resin composition of two or more compound be preferably the weight of 1 weight %~90
Measure %.By the way that for weight %, mixing property and mouldability are improved, as solidification physical property also excellent heat-curing resin combination
Thing.
And then, the oligoester for the terminal carboxylic that can be included in the hot curing resin composition of the first invention is for example following
Shown in formula (10).
(in formula, multiple P are represented optionally comprising 0~6 oxygen atom, nitrogen-atoms, phosphorus atoms, carbon number 2~20
The residue of polyalcohol, R represents the aliphatic alkyl of carbon number 2~20.Multiple n, k are individually present, 1 is represented in terms of averagely~
6.And n summation is 2 less than 12.)
As specific structural formula, for structure and intramolecular with formula (10) there is ester structure (to be preferably 2 ester knots
Structure) compound.And there is the compound of multiple carboxyls for end.
Wherein, the oligoester of the terminal carboxylic of previously described formula (10) is preferably by the polynary of 2~6 functions of carbon number more than 6
Alcohol and compound obtained from the esterification of representative examples of saturated aliphatic cyclic acid anhydride.
The oligoester of the terminal carboxylic recorded more particularly, for previously described formula (10), linking group R is preferably carbon number 4
~10 cycloalkanes hydrocarbon skeleton or norbornane skeleton, for cycloalkanes hydrocarbon skeleton, from the optical characteristics of its solidfied material, be preferably
Substituted or unsubstituted cyclohexane structure, the methyl cyclohexane alkyl structure for particularly possessing methyl.In addition, being used as norbornane bone
Frame, preferably norbornane, methyl norbornane structure.Here, as substituent applicatory in substituted material, it can arrange
Enumerate alkyl, carboxyl of carbon number 1~3 etc..
For the residue of polyalcohol of carbon number 2~10, (polyalcohol used from reaction removes hydroxyl to linking group P
Residue), the preferably crosslinked group or cycloalkyl of branched, P is particularly preferably by following (a) or (b) divalent defined
Crosslinked group.
(a) crosslinked group, it is the chain-like alkyl chain with branched structure of carbon number 6~20, and the chain-like alkyl chain has
The main chain of the straight chain of carbon number 3~12 and 2~4 side chains, and at least one of the side chain is carbon number 2~10；
Or,
(b) crosslinked group of divalent, it can have methyl on ring, from selected from Tricyclodecane Dimethanol or pentacyclopentadecandimethanol
2 hydroxyls are eliminated in the polycyclic glycol of at least one kind of crosslinking in dimethanol.
Wherein, when P is (b), in cycloalkanes hydrocarbon skeleton or norbornane skeleton of the preferred linking group R for carbon number 4~10
When, substituent R in formula (2A) more preferably described later3Represent the group beyond hydrogen atom.
It should be noted that the softening point of above-mentioned oligoester is usually more than 50 DEG C, preferably more than 60 DEG C, more preferably
More than 80 DEG C.Higher limit is not particularly limited, usually less than 500 DEG C, preferably less than 300 DEG C, more preferably 200 DEG C with
Under.
The oligoester of above-mentioned particularly preferred terminal carboxylic in first invention can be by making 2~6 officials of carbon number more than 6
The polyalcohol of energy carries out addition reaction with representative examples of saturated aliphatic cyclic acid anhydride and obtained.
The oligoester of terminal carboxylic in first invention can be the composition of the oligoester comprising 2 kinds of terminal carboxylics.Make
For obtain comprising at least two kinds of terminal carboxylics oligoester terminal carboxylic oligoester composition method, have following method：
The method for mixing the oligoester for the single terminal carboxylic that at least two kinds of above methods are obtained；Or in synthesis above-mentioned end carboxylic acid
Oligoester when, as above-mentioned representative examples of saturated aliphatic cyclic acid anhydride, using in the representative examples of saturated aliphatic cyclic acid anhydride of following middle selections
At least two kinds of mixtures or the method that carries out addition reaction using 2 kinds of foregoing polyols.
As the representative examples of saturated aliphatic cyclic acid anhydride used in the synthesis of the oligoester of terminal carboxylic, it can include following
Compound：With cyclohexane structure, and there is on the cyclohexane ring methyl substitution or carboxyl substitution or to be unsubstituted,
Intramolecular has the anhydride group that more than 1 (being preferably 1) is bonded with cyclohexane ring.
Specifically, it can include selected from by hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and hexamethylene
Alkane -1,2,4- tricarboxylic acids -1,2- acid anhydrides, trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride and hydrogenation pyromellitic acid
At least one kind of acid anhydrides in the group of acid anhydride composition.
2~6 functions used in synthesis as the oligoester of the terminal carboxylic in the first invention, carbon number more than 6
Polyalcohol, specifically, can include the end of the crosslinked group P in previously described formula (10) has the terminal carboxylic of hydroxyl
Oligoester.
In previously described formula (10), the crosslinked group shown in P is preferably the crosslinked group by foregoing (a) or (b) divalent defined,
They are specifically described below.
It is 2 with the branched structure yuan alcohol (glycol) from carbon number 6~20 by the crosslinked group of foregoing (a) divalent defined
In remove hydroxyl-removal obtained from divalent chain-like alkyl chain, be following structure：With the alkyl folded by 2 alcohol hydroxyl groups of glycol
Chain is main chain, with the alkyl chain (being referred to as side chain) gone out from the alkyl chain branch.The side chain can be from any carbon for constituting main chain
Atom branch, for example, also include the situation of carbon atom (terminal carbon of main chain) branch being bonded from alcohol hydroxyl group.As long as
It is that the crosslinked group with the structure is then any, following formula (a1) shows the concrete example of such crosslinked group.
In previously described formula, pass through the oxygen atoms bond of P both sides in mark * and formula (10).
As long as the above-mentioned alkylidene crosslinked group defined by (a) has the knot of alkyl branches (side chain) to main chain alkylidene
Structure is just not particularly limited, preferably main chain of the main chain carbon number for more than 3, the structure with least one alkyl side chain, in addition especially
It is preferred that main chain of the main chain carbon number for more than 3, the structure with more than 2 alkyl side chains.As preferred structure, it can include
The carbon number of the main chain of straight chain with carbon number 3~12 and 2~4 side chains and at least one side chain is 2~10 crosslinked group.
Now, the carbon number of more preferably at least 2 side chains is 2~10 crosslinked group.Furthermore it is preferred that difference of 2~4 side chains from main chain
Carbon atom branch.
As more specifically compound, it can include in the crosslinking group described in previously described formula (a1) in mark * position
It is bonded with the compound of hydroxyl.
Among the polyalcohol as raw material, preferably with least two at least two side chain and the side chain be carbon number 2~
The polyalcohol of 4 side chain.
As particularly preferred polyalcohol among such skeleton, 2,4- diethyl -1,5-PD, 2- second can be included
Base -2- butyl -1,3-PD, 2- ethyl -1,3- hexylene glycols etc., can especially include 2,4- diethyl -1,5-PD.
As the crosslinked group defined by foregoing (b), the group of the divalent shown in following formula (b1) can be included.
It is with tristane knot as by the polycyclic diol residue of crosslinking in the situation of foregoing (b) crosslinked group defined
Structure, pentacyclopentadecandimethanol structure as main framing diol residue, such as shown in following formula (b2).
In formula, multiple R2Independently represent hydrogen atom or methyl.Among these, preferably R2All hydrogen atoms
Crosslinked group.
Specifically, Tricyclodecane Dimethanol, methyl Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol can be included
Deng.
It is typically the addition reaction using sour, alkali as catalyst as the reaction of acid anhydrides and polyalcohol, but it is special in the first invention
Not preferably without using the reaction of catalyst.
During using catalyst, as workable catalyst, for example, it can include：Hydrochloric acid, sulfuric acid, Loprazolam, trifluoro
The acid compounds such as Loprazolam, p-methyl benzenesulfonic acid, nitric acid, trifluoracetic acid, trichloroacetic acid, sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change calcium, the metal hydroxides such as magnesium hydroxide, the amines, pyridine, dimethyl such as triethylamine, tripropylamine, tri-butylamine
The hetero ring type compounds, tetramethyl hydrogen such as the aminopyridine, -7- alkene of 1,8- diazabicyclos [5.4.0] 11, imidazoles, triazole, tetrazolium
Amine-oxides, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, trimethyl
Propyl group ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, tricaprylmethyl ammonium hydroxide, four
Quaternary ammonium salts such as ammonio methacrylate, 4 bromide, tetramethyl-ammonium iodide, tetramethyl ammonium acetate, tricaprylmethyl ammonium acetate etc..
These catalyst can be used a kind or be mixed with two or more.Among these, preferably triethylamine, pyridine, dimethylamino pyrrole
Pyridine.
The consumption of catalyst is not particularly limited, relative to the parts by weight of gross weight 100 of raw material, it is usually preferred to according to need
Use 0.001~5 parts by weight.
Preferably without the reaction of solvent in this reaction, but organic solvent can be used.As the consumption of organic solvent, relatively
In 1 part of foregoing acid anhydrides and the total amount of foregoing polyols as response matrix, using weight ratio meter as 0.005~1 part, be preferably
0.005~0.7 part, more preferably 0.005~0.5 part (i.e. below 50 weight %).The consumption of organic solvent is anti-relative to above-mentioned
When answering the parts by weight of matrix 1 with weight ratio meter more than 1 part, reacting into guild becomes extremely slow, and it is not preferable.It is used as having for can using
The concrete example of machine solvent, can use the paraffinics such as hexane, hexamethylene, heptane, the aromatic hydrocarbon compound such as toluene, dimethylbenzene,
The ketones such as MEK, methylisobutylketone, cyclopentanone, cyclohexanone (anon), the ethers, vinegar such as Anaesthetie Ether, tetrahydrofuran, dioxanes
Ester compounds such as acetoacetic ester, butyl acetate, methyl formate etc..
This reaction also can fully be reacted at a temperature of 20 DEG C or so.The problem of from the reaction time, preferably instead
It is 30~200 DEG C, particularly preferably more preferably 40~200 DEG C, 40~150 DEG C to answer temperature.Especially enter in no solvent
During this reaction of row, there is the volatilization of acid anhydrides, it is therefore preferable that the reaction below 100 DEG C, particularly preferably at 30~100 DEG C or 40
Reaction at~100 DEG C.
Equimolar reaction on the reactive ratio Optimization Theory of foregoing acid anhydrides and foregoing polyols, but can change as needed
Become.
As specific input ratio both when reacting it, in terms of its functional equivalent, work as relative to the anhydride group 1
Amount, preferably with the hydroxyl equivalent of the polyalcohol be calculated as 0.001~2 equivalent, more preferably 0.01~1.5 equivalent, further preferably
The polyalcohol is put into for the ratio of 0.1~1.2 equivalent.
The oligoester of the terminal carboxylic of preferred gained is solid in first invention, in order to obtain the resinous terminal carboxylic of solid
The oligoester of acid, preferably preferably using polyalcohol more than equimolar equivalent, but mobility becomes due to addition filler
It is important, in order to ensure the mobility, from its viscosity equilibrium, keeping scope (more than 50 DEG C of softening point) Nei Kelve of solid
Micro- destruction is balanced.
Specifically, relative to anhydride equivalent, the equivalent proportion of alcohol hydroxyl group is preferably 0.85~1.20 molar equivalent, especially
Preferably 0.90~1.10 molar equivalent.
Reaction time additionally depends on reaction temperature, catalytic amount etc., but from this viewpoint of industrial production, for a long time
Reaction can consume huge energy, and it is not preferable.In addition, the too short reaction time means the reaction acutely, from security side
Face is not preferred.It is 1~48 hour as preferred scope, preferably 1~36 hour, more preferably 1~24 hour, further
Preferably 2~10 hours or so.
After reaction terminates, in the case of using catalyst, catalyst is carried out by neutralization, washing, absorption etc. respectively
Remove, distillation removes solvent, so as to obtain the oligoester of target terminal carboxylic.On the other hand, carried out without using catalyst
During reaction, by distilling the oligoester for removing solvent and obtaining target terminal carboxylic as needed.In addition, in the feelings using solvent
Under condition, the oligoester of target terminal carboxylic is obtained by removing solvent.And then without using solvent, without using the feelings of catalyst
Under condition, directly take out and obtain target product.
As optimum manufacture method, there is following method：Under conditions of without using catalyst, in 40~150 DEG C
Make foregoing acid anhydrides, foregoing polyols reaction, remove solvent, then take out.
The mixture of the oligoester of so obtained aforementioned end carboxylic acid or the oligoester containing the terminal carboxylic is generally in
The resin-like (according to circumstances crystallization) of colourless~flaxen solid.The softening point of the oligoester of the terminal carboxylic is preferably 50
~190 DEG C, more preferably 55~150 DEG C, particularly preferably 60~120 DEG C.By by the end carboxylic with such softening point
The oligoester of acid is directly mixed into hot curing resin composition without being liquid, it is possible to provide with high reflectivity
Conservation rate, when carrying out heat resistant test, reflectivity is also difficult to the reflection part that reduces.
Generally, when crosslinked group serves as reasons the alkylidene with side chain that (a) define, colourless~flaxen solid is presented
Resin-like.
In first invention, the optimum used the hot curing resin composition of the oligoester containing terminal carboxylic
Method shaped for transmission, therefore, the oligoester of terminal carboxylic is the resin-like of solid.
In the case where crosslinked group serves as reasons the crosslinked group that (b) define, in the cycloalkanes that aliphatic alkyl is carbon number 4~10
When hydrocarbon skeleton or norbornane skeleton, the oligoester of the terminal carboxylic of all hydrogen atoms of substituent of ester ring type can be shown admittedly
Coloring during change, is unsuitable for especially harsh optical applications.It is the cycloalkanes hydrocarbon skeleton of carbon number 4~10 or drop ice in aliphatic alkyl
During piece alkane skeleton, such coloring is few for substituent is the compound of methyl or carboxyl, and its optical characteristics is improved.
It is also in the cycloalkanes that aliphatic alkyl is carbon number 4~10 foregoing in the compound of (a) crosslinked group defined
When hydrocarbon skeleton or norbornane skeleton, optical characteristics when substituent is the compound of methyl or carboxyl is improved, and is preferred.
That is, as the first invention terminal carboxylic oligoester composition, in the cycloalkanes hydrocarbon skeleton or drop for carbon number 4~10
Preferably it is preferably the terminal carboxylic of methyl or carboxyl or formula (9) with both comprising substituent during bornylane skeleton
The composition of oligoester.In the situation of the oligoester composition of the terminal carboxylic of the oligoester comprising two or more terminal carboxylic
Under, the composition being preferably as follows：Relative to the total amount of the oligoester of terminal carboxylic, it is comprising 50 moles of more than %, at least this take
Dai Ji be not the terminal carboxylic of the formula (1) of hydrogen atom oligoester (substituent be aforesaid alkyl, be preferably methyl or carboxyl
The oligoester of terminal carboxylic).More preferably comprising 70 moles of more than %, most preferably 90 moles of more than %, the substituent
It is not the oligoester composition of the terminal carboxylic of the oligoester of the terminal carboxylic of the formula (9) of hydrogen atom.Surplus is R3It is hydrogen atom
Following formula (2A) terminal carboxylic oligoester.
As the oligoester of terminal carboxylic suitable in the first invention, it can be used terminal carboxylic's shown in following formula (2A)
Oligoester.
(in above-mentioned formula, P represents implication same as described above, R3Represent hydrogen atom, the alkyl or carboxyl of carbon number 1~3.)
Herein, in above-mentioned formula (2A), the reasons why according to being noted as above, R3Can suitably using carbon number 1~3 alkyl or
Carboxyl.
Terminal carboxylic's oligoester preferred number average molecular weight Mn is the oligoester of more than 300 terminal carboxylic.
And then, as other curing agent that can be applied in combination, for example, it can include：Amine compound, with unsaturation
Acid anhydrides based compound, the acid anhydrides with organosiloxane skeleton, acid amides based compound, phenol system compound, the carboxylic serials of ring structure
Compound etc..As the concrete example for the curing agent that can be used, it can include：Diaminodiphenyl-methane, Diethylenetriamine, three second
Tetramine, diaminodiphenylsulfone, IPD, dicyandiamide, pass through the polyamide synthesized by linolenic 2 polymers and ethylenediamine
Resin, phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride,
Methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic acid anhydrides,
It is bicyclic [2.2.1] heptane -2,3- dicarboxylic anhydrides, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic anhydrides, bisphenol-A, Bisphenol F, double
Phenol S, fluorenes bis-phenol, terpene diphenol, 4,4 '-bis-phenol, 2,2 '-bis-phenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-xenyl] -4,4 '-two
Alcohol, hydroquinones, resorcinol, naphthalene glycol, three-(4- hydroxy phenyls) methane, 1,1,2,2- tetra- (4- hydroxy phenyls) ethane, phenol
Class (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzene first
Aldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, bicyclopentadiene, furfural, 4,4 '-
Double (chloromethyls) -1,1 '-biphenyl, 4,4 '-bis- (methoxies) -1,1 '-biphenyl, 1,4 '-bis- (chloromethyl) benzene, 1,4 '-it is bis-
Halogenated bisphenol class, imidazoles, the boron trifluoride-amine such as the condensation polymer of (methoxy) benzene etc. and their modifier, tetrabromobisphenol A
Complex compound, guanidine derivatives, condensation product of terpenes and phenols etc., but it is not limited to these materials.These can be used alone, also can group
Conjunction uses two or more.
Curing accelerator can be added in the hardening resin composition of first invention as needed.Promote as solidification
Agent, can be included：2-methylimidazole, 2- phenylimidazoles, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenyl -4- methyl
Imidazoles, 1- benzyl -2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyls -2-
Phenylimidazole, 1- cyano ethyl -2- undecyl imidazoles, 2,4- diaminourea -6 (2 '-methylimidazole (1 ')) ethyl-s-triazine,
2,4- diaminourea -6 (2 '-undecyl imidazole (1 ')) ethyl-s-triazine, 2,4- diaminourea -6 (2 '-ethyl, 4-methylimidazole
(1 ')) ethyl-s-triazine, (2 '-methylimidazole (1 ')) ethyl-s-triazine of 2,4- diaminourea -6 and isocyanuric acid adduct, 2-
The 2 of methylimidazole isocyanuric acid：3 addition products, 2- phenylimidazoles isocyanuric acid adduct, 2- phenyl -3,5- bishydroxymethyl miaows
Azoles, 2- phenyl -4- hydroxymethyl -5- methylimidazoles, 1- cyano ethyl -2- phenyl -3,5- dicyano ethoxyl methyl imidazoles
Various imidazoles, and these imidazoles and phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, equal benzene four
The salt of the oligoester of the terminal carboxylics such as acid, naphthalene dicarboxylic acids, maleic acid, oxalic acid, the amide-type, 1,8- bisazo-bis- such as dicyandiamide
The salt of tetraphenyl borate salts, the phenol novolacs of ring [5.4.0] endecatylene -7 grade bis-azo compound and these materials etc.
Class, the oligomeric esters of aforementioned end carboxylic acid or the salt with phosphonic acid, TBAB, cetyl trimethylammonium bromide,
The quaternary ammonium salts such as tricaprylmethyl ammonium bromide, cetyltrimethylammonium hydroxide (are preferably C1~C20 alkylammonium salts, triphenyl
Phosphine, phosphorus compound, the 2,4,6- such as phosphine, three (tolyl) phosphines, tetraphenyl phosphonium bromide, tetraphenylphosphonium tetraphenyl borate salts
The gold such as the phenols such as triamido methylphenol, amine adduct, tin octoate, octanesulfonic acid zinc, zinc stearate, copper naphthenate, cobalt naphthenate
Belong to compound etc., and microcapsule-type curing accelerator, the carbonyls zinc that microcapsules are obtained is made in these curing accelerators
Complex compound etc..It can be obtained according to such as heat resistance, curing rate, operating condition using any in these curing accelerators
To transparent resin composition required by characteristic come suitably select.As material preferred in the first invention, phosphorus can be included
Compound (more preferably quaternary phosphonium) or zinc stearate.
Curing accelerator is usual relative to 100 parts by weight epoxy resin in 0.001~15 parts by weight, preferably 0.01~5
Used in the range of parts by weight.
The asphalt mixtures modified by epoxy resin being generally commonly used can be added in the form of the additive in addition to above-mentioned additive as needed
Fat additive, such as pigment, dyestuff, fluorescent whitening agent, reinforcing material, filler, Chinese white, nucleator, surface-active
Agent, plasticizer, viscosity modifier, fluidity regulator, fire retardant, antioxidant, ultra-violet absorber, light stabilizer.
As above-mentioned filler, it can include：Crystalline silica, fused silica, antimony oxide, titanium oxide, oxygen
Change magnesium, zirconium oxide, aluminium hydroxide, magnesium hydroxide, aluminum oxide etc., but be not limited to these materials.These can be used alone, and also may be used
Two or more is applied in combination.
The compounding amount of inorganic filler is preferably 1~1000 relative to the parts by weight of total amount 100 of hardening resin composition
Parts by weight, more preferably 1~800 parts by weight.
As above-mentioned Chinese white, it is not particularly limited, for example, aluminum oxide, magnesia, antimony oxide, oxidation can be used
Titanium, zirconium oxide, zinc oxide, basic zinc carbonate, kaolin, calcium carbonate etc..Wherein, Chinese white can be hollow particle.In addition,
Suitably Chinese white can be surface-treated with silicon compound, aluminium compound, organic matter etc..These can be used alone,
It can be combined and use two or more.In addition, the average grain diameter of above-mentioned Chinese white is preferably 0.01~50 μm of scope.Less than 0.01 μ
During m, there is the tendency that particle is easily assembled, dispersiveness is deteriorated, during more than 50 μm, there is the reflection that can not fully obtain solidfied material
The tendency of characteristic.For example laser diffraction and scattering formula particles distribution instrument can be used to determine for above-mentioned average grain diameter.It is excellent in first invention
Choosing uses the powder of titanium oxide, particularly titanium dioxide.Because whiteness, light reflective and covering power are high, dispersiveness is steady
It is qualitative excellent, easily obtain.The crystal habit of titanium oxide is not particularly limited, can be rutile-type or rutile titania
Ore deposit type, can also be that both are mixed, but Detitanium-ore-type is because with photo-catalysis function, presence can make the worry that resin is deteriorated,
Therefore, it is preferably rutile-type in the first invention.
In addition, the content of Chinese white relative to the weight % of resin combination generally 10 weight %~95, more preferably
50~95% scope.When total content is less than 10 weight %, there is the tendency for the reflective character that can not fully obtain solidfied material,
During more than 95 weight %, the formability of resin combination is deteriorated, and there is the tendency that the making of substrate becomes difficult.
In the hot curing resin composition of first invention, usual ICI Cone ＆ Plate viscosities are preferably in 100~200 DEG C of scope
For 0.01~10Pas.During less than 0.01Pas, there is the worry for easily producing burr.Have when on the other hand, more than 10Pas
The worry of productivity ratio reduction.In present embodiment, the ICI viscosity of the hot curing resin composition at 150 DEG C is preferably
0.01Pas~10Pas, more preferably 0.05Pas~5Pas.In the hot curing resin composition of first invention
ICI Cone ＆ Plate viscosities are 0.01~10Pas in 100~200 DEG C of scope, and are high viscosity liquid or solid at room temperature
When, the mixing that can not possibly be carried out when being handled before not having pre-polymerization materialization etc. in the case of conventional anhydride curing agent becomes able to nothing
Carry out to pre-treatment, be preferred.In addition, the hot curing resin composition after mixing is solid at room temperature, therefore holding
The aspect easily shaped with lamellar morphology also has feature.Also, when being adjusted to the scope, compounded with fillers such as inorganic fillers
When composition under normal temperature (25 DEG C) be solid, therefore shaping become easy, volatile ingredient is few, it is thus possible to effectively prevent sky
A problem that gap, so it is preferred that.
, can be effectively compared with using the situation of common acid anhydrides in the hot curing resin composition of first invention
A problem that preventing space, therefore shaping becomes easy.
In addition, preferably softening point is in 20 DEG C~150 DEG C of scope to the hot curing resin composition of the first invention.
More specifically, it is preferably in 30 DEG C~130 DEG C of scope, is more preferably in 40 DEG C~120 DEG C of scope.By being adjusted to this
Scope, can easily be stirred by mixer etc., mix various composition, so can by mixing roll, extruder, kneader,
Roller, extruder (extruder) etc. are kneaded or melting mixing to it, and are cooled down, crushed.
The glass transition temperature of solidfied material is preferably above forming temperature.The glass transition temperature of solidfied material is shaping temperature
When below degree, solidfied material in a mold is the rubbery state of low elasticity, therefore, can become to take out rubber-like solidification from mould
Thing, when filling in aspiration pump (ejector), there is the worry for deforming etc. and producing unfavorable condition.Specifically, vitrifying turns
Temperature is preferably more than 30 DEG C, more preferably more than 40 DEG C, more preferably more than 50 DEG C.
Herein, in the present application, the glass transition temperature of solidfied material is preferably less than 150 DEG C, more preferably 140 DEG C
Below.
The hot curing resin composition of first invention is obtained by the above-mentioned various composition of dispersed mixing.To it
Method is not particularly limited, and can include following method：Sufficiently uniformly stirred by mixer etc., mix various composition, so
Kneaded or melting mixing using mixing roll, extruder, kneader, roller, extruder etc. afterwards, cooled down, crushed.Mixing or
The condition of melting mixing is determined according to the species of composition, compounding amount, is not particularly limited, more preferably at 20~200 DEG C
In the range of knead 5~40 minutes.When melting temperature is less than 20 DEG C, the dispersiveness reduction of each composition, it is difficult to make it fully knead,
During for temperature higher than 200 DEG C, the cross-linking reaction that there is resin combination drastically carries out, causes the load of resin composition
The heart.
The hot curing resin composition of first invention before thermoforming, at 0~30 DEG C it is desirable that at room temperature may be used
Pressurization (sheet) shaping.Press molding can be included for example in 0.01~10MPa, the side carried out under conditions of 1~5 second or so
Method.In addition, the mould used when being shaped to pressurization (sheet) is not particularly limited, for example, it is preferable to using by ceramic based material, fluorine
It is the mould being made up of pestle mould (mold) and mortar mould (lower mould) that resin material etc. is made.
The hot curing resin composition of first invention is partly led needing the light of high glass-transition temperature and high-transmission rate
It is useful in the purposes such as body encapsulating material, photosemiconductor reflecting material.
Purposes is being reflected in use, manufacture method is not particularly limited, for example, it is preferable to by transmitting into shape as light
Make the hot curing resin composition of the first invention.The hot curing resin composition of the first invention is injected in a mold, in example
As mold temperature be 150~190 DEG C, forming pressure be it is solidified 60~800 seconds under conditions of 2~20MPa, then from mould
Take out, made its heat cure through 1~3 hour at a temperature of 150 DEG C~180 DEG C of solidify afterwards.
(semiconductor device)
For the optical semiconductor device of the first invention, if illustrating concrete example, such as International Publication to representational structure
As No. 2012/124147 is recorded, light reflection of the configuration with cylindric hollow bulb prevents part on substrate, in circle
In the inner space of the hollow part of tubular, in configuring optical semiconductor on substrate.Also, with following structure：Connected with lead
The one end and substrate of optical semiconductor are connect, potting resin is enclosed in above-mentioned hollow bulb.
Pair suitably it can be described in detail using the reflecting material of the resin combination of the first invention.Pass through shaping
Obtained from reflecting material can suppress the discoloration that heat deterioration is caused.Reflecting material may be used as the LED illumination such as LED bulb utensil use
LED reflection device.The reflecting material obtained by the hot curing resin composition of the first invention may be constructed long lifespan and cheap
LED reflection device.
Fig. 1 has been shown with the one of the LED light device for the reflecting material that the shaping of being thermally cured property resin combination is obtained
Example.The reflecting material is LED reflection device 1.Reflecting material is formed as frame-shaped, has recess 2 and hole portion 3 in central portion.Recess 2 is set
It is set to the inclined face of wall.The wall of recess 2, which turns into, makes the reflecting surface that light reflects.Hole portion 3 is with through LED reflection device 1
Mode is arranged on the bottom of recess 2.The lead frame 4 being equipped with as the LED5 of light-emitting component is embedded with the hole portion 3.Lead frame
The wiring powered to LED5 can also be provided in 4.The luminous surface side (top of figure) of recess 2 is covered by transparent shield 6.
Thus, LED5 is protected.Shield 6 is engaged in the opening edge of recess 2 with LED reflection device 1.LED reflection device 1 is efficient as being used for
Ground reflection LED5 luminous reflecting plate plays a role.The shape of LED reflection device 1 is not limited to Fig. 1 shape, it may be considered that real
The LED5 of dress light quantity, color, directional properties etc. and it is appropriately designed.Above-mentioned light-reflecting article hot curing resin composition by
It is good in formability, therefore, it is possible to be readily derived the formed body of target shape.
Then, the second invention is described in detail.
The hot curing resin composition of second invention from improve glass transition temperature from the viewpoint of, be characterised by,
Containing following carboxylic acid resin, the carboxylic acid resin is contained in gel permeation chromatography (hereinafter referred to as GPC.) measure in be 70 faces
The polybasic carboxylic acid (A1) with isocyanuric acid ring shown in product more than %, following formula (1).Herein, 75 area % are preferably comprised
Above, more preferably more than 80 area %.The upper limit is not particularly limited, for example, below 99.9 area %.
In formula (1), R1Represent alkylidene, the R of carbon number 1~62Represent the alkyl or carboxyl of hydrogen atom or carbon number 1~6.
It is used as R1Concrete example, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, different Asia can be included
Propyl group, isobutylene, isopentylidene, neopentylidene, isohexylidene, cyclohexylidene etc., from the heat resistant transparent of gained solidfied material
From the viewpoint of, preferably methylene, ethylidene, propylidene, particularly preferred ethylidene.
It is used as R2In carbon number 1~6 alkyl concrete example, can include methyl, ethyl, propyl group, isopropyl, butyl,
Isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl, cyclopenta, hexyl, isohesyl, cyclohexyl etc., from the resistance to of gained solidfied material
From the viewpoint of the hot transparency, preferably methyl.
R2In, preferably methyl, carboxyl, from the room temperature (25 DEG C) of the hot curing resin composition containing polybasic carboxylic acid (A1)
Under viscosity will not be from the viewpoint of the transparency of excessively elevated viewpoint and gained solidfied material, preferably methyl is solid from gained
From the viewpoint of the gas barrier property of compound, high glass-transition temperature (Tg), hardness, particularly preferably carboxyl.
In formula (1), multiple R1、R2Respectively can with it is mutually the same can also be different from each other.
From improve the component such as encapsulating material or light reflecting material for having used hot curing resin composition reliability,
Solidify from the viewpoint of physical property, the hot curing resin composition of the second invention is characterised by, containing following carboxylic acid resin,
The carboxylic acid resin contains the carboxylic acid (A3) shown in polybasic carboxylic acid (A2) and/or following formula (1b) shown in following formula (1a), its
Ratio of the total amount in Polycarboxylic acid resin is 0.5~10 area % in GPC measure.Herein, 0.5~5 face is preferably comprised
Product %, further preferably 1~3 area %.
In formula (1a), R1Represent alkylidene, the R of carbon number 1~62Represent the alkyl or carboxyl of hydrogen atom or carbon number 1~6.
It is used as R1Concrete example, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, different Asia can be included
Propyl group, isobutylene, isopentylidene, neopentylidene, isohexylidene, cyclohexylidene etc., from the heat resistant transparent of gained solidfied material
From the viewpoint of, preferably methylene, ethylidene, propylidene, particularly preferred ethylidene.
It is used as R2In carbon number 1~6 alkyl concrete example, can include methyl, ethyl, propyl group, isopropyl, butyl,
Isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl, cyclopenta, hexyl, isohesyl, cyclohexyl etc., from the resistance to of gained solidfied material
From the viewpoint of the hot transparency, preferably methyl.
R2In, preferably methyl, carboxyl, from the room temperature (25 DEG C) of the hot curing resin composition containing Polycarboxylic acid resin
Under viscosity will not be from the viewpoint of the transparency of excessively elevated viewpoint and gained solidfied material, preferably methyl is solid from gained
From the viewpoint of the gas barrier property of compound, high glass-transition temperature (Tg), hardness, particularly preferably carboxyl.
In formula (1a), multiple R1、R2Respectively can with it is mutually the same can also be different from each other.
The hot curing resin composition of second invention preferably comprises following carboxylic acid resin, and the carboxylic acid resin is contained
The polybasic carboxylic acid (A2) shown in formula (1a) is stated, its ratio in Polycarboxylic acid resin is 0~10 face in GPC measure
Product %.Herein, further preferably 0~5 area %, further preferably 0~3 area %.
In formula (1b), R1Represent alkylidene, the R of carbon number 1~62Represent the alkyl or carboxyl of hydrogen atom or carbon number 1~6.
It is used as R1Concrete example, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, different Asia can be included
Propyl group, isobutylene, isopentylidene, neopentylidene, isohexylidene, cyclohexylidene etc., from the heat resistant transparent of gained solidfied material
From the viewpoint of, preferably methylene, ethylidene, propylidene, particularly preferred ethylidene.
It is used as R2In carbon number 1~6 alkyl concrete example, can include methyl, ethyl, propyl group, isopropyl, butyl,
Isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl, cyclopenta, hexyl, isohesyl, cyclohexyl etc., from the resistance to of gained solidfied material
From the viewpoint of the hot transparency, preferably methyl.
R2In, preferably methyl, carboxyl, from the room temperature (25 DEG C) of the hot curing resin composition containing Polycarboxylic acid resin
Under viscosity will not be from the viewpoint of the transparency of excessively elevated viewpoint and gained solidfied material, preferably methyl is solid from gained
From the viewpoint of the gas barrier property of compound, high glass-transition temperature (Tg), hardness, particularly preferably carboxyl.
In formula (1b), multiple R1、R2Respectively can with it is mutually the same can also be different from each other.
The hot curing resin composition of second invention preferably comprises following carboxylic acid resin, and the carboxylic acid resin is contained
The polybasic carboxylic acid (A2) shown in formula (1b) is stated, its ratio in Polycarboxylic acid resin is 0.5~10 face in GPC measure
Product %.Herein, further preferably 0.5~5 area %, further preferably 0.5~3 area %.
The hot curing resin composition of second invention preferably comprises following carboxylic acid resin, under the carboxylic acid resin is contained
The HMW body mixture that polybasic carboxylic acid (A4)~(A6) shown in formula (1c)~(1e) is represented is stated, their total amount is polynary
Ratio in carboxylic acid resin is 0.5~15 area % in GPC measure.Herein, further preferably 0.5~10 area %, enter
One step preferably comprises 1~5 area %.
In formula (1c)~(1e), R1Represent alkylidene, the R of carbon number 1~62Represent the alkyl or carboxylic of hydrogen atom or carbon number 1~6
Base.
It is used as R1Concrete example, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, different Asia can be included
Propyl group, isobutylene, isopentylidene, neopentylidene, isohexylidene, cyclohexylidene etc., from the heat resistant transparent of gained solidfied material
From the viewpoint of, preferably methylene, ethylidene, propylidene, particularly preferred ethylidene.
It is used as R2In carbon number 1~6 alkyl concrete example, can include methyl, ethyl, propyl group, isopropyl, butyl,
Isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl, cyclopenta, hexyl, isohesyl, cyclohexyl etc., from the resistance to of gained solidfied material
From the viewpoint of the hot transparency, preferably methyl.
R2In, preferably methyl, carboxyl, from the room temperature (25 DEG C) of the hot curing resin composition containing Polycarboxylic acid resin
Under viscosity will not be from the viewpoint of the transparency of excessively elevated viewpoint and gained solidfied material, preferably methyl is solid from gained
From the viewpoint of the gas barrier property of compound, high glass-transition temperature (Tg), hardness, particularly preferably carboxyl.
In formula (1c)~(1e), multiple R1、R2Respectively can with it is mutually the same can also be different from each other.
In formula (1c), * represents hydroxyl, hydroxyl present in above-mentioned formula (1a)~(1b) and previously described formula (1) and formula (1a)~
Hydroxyl present in the residue or following formula (6) of carboxyl reaction present in (1b) and previously described formula (1) and formula (1a)~
The residue of carboxyl reaction present in (1b).
For GPC retention time, above-mentioned HMW body (A4) is with the guarantor shorter than compound shown in the application formula (1)
Stay time dissolution.
Additionally, it is preferred that being following Polycarboxylic acid resin：It is to make the compound and the application formula shown in the application formula (1)
(6) shown in compound reaction obtained from compound and containing in the measure of gel permeation chromatography be 0.5~10 area %
, the HMW body that retention time is shorter than compound shown in the application formula (1).
The hot curing resin composition of second invention preferably comprises following carboxylic acid resin, under the carboxylic acid resin is contained
The acid anhydrides shown in formula (6) is stated, its ratio in Polycarboxylic acid resin is 5~20 area % in GPC measure.Herein, it is excellent
Choosing contains 5~15 area %.
In formula (6), R2The alkyl or carboxyl of hydrogen atom or carbon number 1~6 are represented respectively.
It is used as R2In carbon number 1~6 alkyl concrete example, can include methyl, ethyl, propyl group, isopropyl, butyl,
Isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl, cyclopenta, hexyl, isohesyl, cyclohexyl etc., from the resistance to of gained solidfied material
From the viewpoint of the hot transparency, preferably methyl.
R2In, preferably methyl, carboxyl, from the room temperature (25 DEG C) of the hot curing resin composition containing Polycarboxylic acid resin
Under viscosity will not be from the viewpoint of the transparency of excessively elevated viewpoint and gained solidfied material, preferably methyl is solid from gained
From the viewpoint of the gas barrier property of compound, high glass-transition temperature (Tg), hardness, particularly preferably carboxyl.
The Polycarboxylic acid resin of second invention can pass through the isocyanuric acid trihydroxy Arrcostab chemical combination shown in following formula (5)
The addition reaction of thing and the compound carboxylic acid anhydride shown in following formula (6) and obtain.
In formula (5), R1Represent implication as hereinbefore.
In compound shown in formula (5), the transparency from solidfied material, from the viewpoint of gas barrier property, preferably following formula (7)~
(9) compound shown in.
In compound shown in formula (6), the compound shown in particularly preferred following (2)~(4).
The manufacture of the Polycarboxylic acid resin of second invention can carry out carrying out under condition of no solvent in a solvent.
As solvent, as long as will not be with the carboxylic shown in the isocyanuric acid trihydroxy alkyl ester compound shown in previously described formula (5) and formula (6)
The solvent of anhydride compound reaction, it is possible to use without particular limitation.As the solvent that can be used, for example, it can include
The aprotic polar solvent of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, acetonitrile etc, first and second
Aromatic hydrocarbon of the ketone of ketone, cyclopentanone, methyl iso-butyl ketone (MIBK) etc, toluene, dimethylbenzene etc etc., among these, be preferably
Aromatic hydrocarbon, ketone.
These solvents can use a kind or be mixed with two or more.Using consumption during solvent relative to previously described formula (5)
Shown isocyanuric acid trihydroxy alkyl ester compound and the mass parts of summation 100 of the compound carboxylic acid anhydride shown in formula (6) are preferred
For 0.5~300 mass parts.
The Polycarboxylic acid resin of second invention is mostly solid under room temperature (25 DEG C), therefore from the point of view of operational viewpoint,
It is preferred that synthesizing in a solvent.
The Polycarboxylic acid resin of second invention can be manufactured without using catalyst, and catalyst can also be used to manufacture.
During using catalyst, as the catalyst that can be used, for example, it can include：Hydrochloric acid, sulfuric acid, Loprazolam, fluoroform sulphur
The acid compounds such as acid, p-methyl benzenesulfonic acid, nitric acid, trifluoracetic acid, trichloroacetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide,
The metal hydroxides such as magnesium hydroxide, the amines, pyridine, dimethylamino pyrrole such as triethylamine, tripropylamine, tri-butylamine
The hetero ring type compounds, tetramethyl hydroxide such as the pyridine, -7- alkene of 1,8- diazabicyclos [5.4.0] 11, imidazoles, triazole, tetrazolium
Ammonium, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, thmethylpropyl
Ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, tricaprylmethyl ammonium hydroxide, tetramethyl
Quaternary ammonium salt, the ortho-titanic acids such as ammonium chloride, 4 bromide, tetramethyl-ammonium iodide, tetramethyl ammonium acetate, tricaprylmethyl ammonium acetate
Ortho-titanic acid class, tin octoate, cobalt octoate, zinc octoate, manganese octoate, calcium octoate, Sodium Caprylate, the octanoic acids such as tetra-ethyl ester, the methyl esters of ortho-titanic acid four
The metal soaps such as potassium.
During using catalyst, a kind can be used or be mixed with two or more.
On using consumption during catalyst, relative to the isocyanuric acid trihydroxy Arrcostab chemical combination shown in previously described formula (5)
Thing and the mass parts of summation 100 of the compound carboxylic acid anhydride shown in formula (6), preferably 0.05~10 mass parts.
On the adding method of catalyst, can directly it add, or so that the state of its solvent for being dissolved in solubility etc.
Use.Now, can be anti-with the compound carboxylic acid anhydride shown in unreacted formula (6) using the solvent of the alcohol such as methanol, ethanol, water
Should, therefore preferably avoid as far as possible.
It is transparent, heat-resisting from improving for the solidfied material of the hot curing resin composition of gained in second invention
From the viewpoint of the transparency, preferably use the zinc polycarboxylates such as zinc octoate as catalyst, obtained by reduce Polycarboxylic acid resin or
From the viewpoint of the coloring of hot curing resin composition, preferably reacted without using catalyst.
Wherein, in order to obtain the solidfied material that the transparency, sulfidation-resistance are excellent, calcium stearate, carboxylic can particularly preferably be used
Sour zinc (2- ethyl hexyl alkanoic acids zinc, zinc stearate, behenic acid zinc, zinc myristate), phosphate zinc (octylphosphonic acid zinc, stearyl
Trbasic zinc phosphate etc.) etc. zinc compound.
Though the reaction temperature of the Polycarboxylic acid resin of the second invention during fabrication also depends on catalytic amount, using solvent,
But usually 20~160 DEG C, particularly preferably preferably 50~150 DEG C, 60~145 DEG C.In addition, total reaction time is usually 1
~20 hours, preferably 3~18 hours.Reaction can carry out 2 more than the stage, can for example make at 20~100 DEG C its react 1~
It is set to react after 8 hours, at 100~160 DEG C 1~12 hour etc..Compound carboxylic acid anhydride particularly shown in formula (6) is mostly
The high material of volatility, when using such material, makes after its reaction, at 100~160 DEG C at 20~100 DEG C in advance
It is reacted, thus can suppress volatilization.Thus, diffusion of the harmful substance into air is not only inhibited, can also obtain meeting setting
The Polycarboxylic acid resin of meter.
When being manufactured using catalyst, it can be quenched and/or be washed as needed to remove catalyst, but also may be used
Its former state is set to remain and consolidating as the composition epoxy resin containing Polycarboxylic acid resin and/or hot curing resin composition
Change accelerator to be utilized.
When carrying out washing step, the solvent that can be separated from water preferably is added according to the species of used solvent.As
It is preferred that solvent, can for example exemplify：The ketones such as MEK, methyl iso-butyl ketone (MIBK), cyclopentanone, ethyl acetate, butyl acetate, breast
The esters such as acetoacetic ester, isopropyl isobutyrate, the hydrocarbon such as hexane, hexamethylene, toluene, dimethylbenzene etc..
Reaction, washing in use solvent when, can by be concentrated under reduced pressure wait removal solvent.
The acid number (being determined by the JIS K-2501 methods recorded) of the Polycarboxylic acid resin of the second manufactured invention is excellent
Elect 150~415mgKOH/g, more preferably 185~375mgKOH/g, particularly preferably 200~320mgKOH/g as.If acid number
For more than 150mgKOH/g, then the mechanical property of solidfied material is improved, therefore it is preferred that, if acid number is below 415mgKOH/g, it is consolidated
Compound will not become really up to the mark, and modulus of elasticity becomes appropriate, be preferred.
In addition, the functional equivalent of the Polycarboxylic acid resin of the second invention is preferably 135~312g/eq, more preferably 150
~300g/eq, particularly preferably 180~280g/eq.
It is available to realize excellent durability and suitable for mixed by using the Polycarboxylic acid resin of the second invention
The hot curing resin composition of refining.
The hot curing resin composition of second invention is the Polycarboxylic acid resin comprising the second invention and other compositions
Resin combination.In the polycarboxylic acid compositions of second invention, heat-curing resin curing agent can be contained.As suitable
Heat-curing resin curing agent, can be included selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid and hexamethylene three
Carboxylic acid anhydrides, pyromellitic acid, hydrogenation pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and
One kind or two or more compound in methylhexahydrophthalic anhydride.
There is trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, the equal benzene of hydrogenation
, can when tetracid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
The high solidfied material of crosslink density is obtained, therefore, it is possible to obtain the solidfied material with high glass-transition temperature.However, inclined benzene three
Acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation pyromellitic acid, pyromellitic dianhydride, with
And hydrogenation pyromellitic dianhydride etc. carboxylic acid or acid anhydrides are due to crystallinity, thus softening point or fusing point are high, specific fusing point
For 150 DEG C~300 DEG C, therefore turn into problem in shaping sometimes.On the other hand, for hexahydrophthalic anhydride, methyl six
Hydrogen phthalic anhydride, problem is turned into because fusing point is below room temperature, therefore in shaping.Trimellitic acid, trimellitic anhydride, ring
Hexane tricarboxylic acids and cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride,
In hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, from the degree aspect for being difficult to colour, it is preferably
Cyclohexanetricarboxylic acid and cyclohexanetricarboxylic acid's acid anhydride, hydrogenation pyromellitic acid, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride,
And methylhexahydrophthalic anhydride, more preferably cyclohexanetricarboxylic acid's acid anhydride, hexahydrophthalic anhydride and methyl
Hexahydrophthalic anhydride.
As cyclohexanetricarboxylic acid's acid anhydride, it can include：Hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydrides, hexamethylene -1,2,3-
Tricarboxylic acids -1,2- acid anhydrides.In second invention, these acid anhydrides, but preferably hexamethylene -1,2 can also be applied in combination, 4- tricarboxylic acids -
1,2- acid anhydrides.
Selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid and cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation
Pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
In the summation of one kind or two or more compound the weight % of 1 weight %~90 is preferably accounted in hot curing resin composition.If
Less than 1 weight %, then glass transition temperature will not be improved fully, is had fusing point to uprise if 90 weight % are higher than, is operated change difficult
Worry.More preferably 10~60 weight %, more preferably 20~50 weight %.
And then, in the hot curing resin composition of the second invention, the polybasic carboxylic acid (A1) shown in above-mentioned formula (1) is with being selected from
Trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation pyromellitic acid, equal benzene four
It is one kind or two or more in acid anhydrides, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Functional equivalent in the mixture of compound is preferably below 250g/eq., more preferably below 240g/eq..By for this
The scope of sample, can effectively be played selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid and cyclohexanetricarboxylic acid's acid anhydride,
Benzenetetracarboxylic acid, hydrogenation pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methyl hexahydro are adjacent
The effect of the chemical combination object amount of one kind or two or more compound in phthalate anhydride, obtains the solidfied material of excellent heat resistance.
In addition, with weight ratio meter, the polybasic carboxylic acid (A1) shown in above-mentioned formula (1)：(selected from trimellitic acid, trimellitic anhydride,
Cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride,
One kind or two or more compound in hexahydrophthalic anhydride and methylhexahydrophthalic anhydride) it is preferably 99:1~
10:90th, 90 are more preferably:10~20:80th, 80 are particularly preferably:20~50:50.By the way that for above-mentioned ratio, heat resistance is very excellent
It is different and viscosity is also low, can fully it knead, therefore as solidification physical property also excellent hot curing resin composition.
In addition, the hot curing resin composition of the second invention includes the Polycarboxylic acid resin of the second invention and selected from inclined
Benzenetricarboxylic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenation pyromellitic acid, pyromellitic acid
One kind or two or moreization in acid anhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Compound, selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, the equal benzene four of hydrogenation
1 kind in acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Or the summation of two or more compound preferably accounts for the weight % of 1 weight %~90 in foregoing hot curing resin composition.By for
Weight %, thus improved as mixing property and mouldability, solidification physical property also excellent hot curing resin composition.
Hot curing resin composition in second invention is preferably to contain epoxy resin, phenolic resin, carbamide resin, trimerization
The composition of the heat-curing resins such as melamine resin, unsaturated polyester resin etc., in the second invention, it is generally desirable to use asphalt mixtures modified by epoxy resin
Fat.
As epoxy resin, as long as it is usual as conventional hot curing resin composition, composition epoxy resin
The material of compounding, it is possible to use without particular limitation.It can such as include：With phenol novolak type epoxy resin, neighbour
It is headed by cresol novolak type epoxy resin, by material obtained from the novolac resin epoxidation of phenols and aldehydes, it is double
Phenol A, Bisphenol F, bisphenol S, the diglycidyl ether of alkyl substitution bis-phenol etc., diaminodiphenyl-methane, pass through isocyanuric acid etc.
Polyamines and glycidyl amine type epoxy resin obtained from epichlorohydrin reaction, are obtained the oxidation of alkene key with peroxy acids such as peracetic acid
Alicyclic epoxy resin, isocyanuric acid 2-glycidyl ester, triglycidyl isocyanurate, silesquioxane compound
Deng these, which can be used alone, can also be applied in combination two or more.In these epoxy resin, the preferred ring with high-fire resistance
Oxygen tree fat, therefore specifically, come from the viewpoint of melt viscosity, the coloring of obtained solidfied material and glass transition temperature etc.
See, preferably diglycidyl ether type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate.
Mix ratio on epoxy resin and the heat-curing resin curing agent of the second invention, it is preferred that relative to
The equivalent of epoxy radicals 1 in epoxy resin, can be with the active group in the heat-curing resin curing agent of the epoxy reaction
(anhydride group, hydroxyl) is 0.5~1.5 equivalent (carboxylic acid is considered as into 1 function, acid anhydrides and is considered as 1 function), particularly preferably 0.5~1.2
Equivalent.Relative to the equivalent of epoxy radicals 1, when during less than 0.5 equivalent or more than 1.5 equivalent, have solidification become not exclusively,
The worry of solidification physical property that cannot be good, the problem of in addition with becoming easily to colour.
In addition, the terminal carboxylic's that can contain as the composition of the heat-curing resin curing agent of the second invention is low
Shown in polyester such as following formula (10).
(in formula, multiple P are represented optionally comprising 0~6 oxygen atom, nitrogen-atoms, phosphorus atoms, carbon number 2~20
The residue of polyalcohol, R represents the aliphatic alkyl of carbon number 2~20.Multiple n, k are individually present, 1 is represented in terms of averagely~
6.And n summation is 2 less than 12.)
As specific structural formula, for structure and intramolecular with formula (10) there is ester structure (to be preferably 2 ester knots
Structure) compound.And there is the compound of multiple carboxyls for end.
Wherein, the oligoester of the terminal carboxylic of previously described formula (10) is preferably by the polynary of 2~6 functions of carbon number more than 6
Alcohol and compound obtained from the esterification of representative examples of saturated aliphatic cyclic acid anhydride.
The oligoester of the terminal carboxylic recorded more particularly, for previously described formula (10), linking group R is preferably carbon number 4
~10 cycloalkanes hydrocarbon skeleton or norbornane skeleton, for cycloalkanes hydrocarbon skeleton, from the optical characteristics of its solidfied material, be preferably
Substituted or unsubstituted cyclohexane structure, the methyl cyclohexane alkyl structure for particularly possessing methyl.In addition, being used as norbornane bone
Frame, preferably norbornane, methyl norbornane structure.Here, as substituent applicatory in substituted material, it can arrange
Enumerate alkyl, carboxyl of carbon number 1~3 etc..
For the residue of polyalcohol of carbon number 2~10, (polyalcohol used from reaction removes hydroxyl to linking group P
Residue), the preferably crosslinked group or cycloalkyl of branched, P is particularly preferably by following (a) or (b) divalent defined
Crosslinked group.
(a) crosslinked group, it is the chain-like alkyl chain with branched structure of carbon number 6~20, and the chain-like alkyl chain has
The main chain of the straight chain of carbon number 3~12 and 2~4 side chains, and at least one of the side chain is carbon number 2~10；
Or,
(b) crosslinked group of divalent, it can have methyl on ring, from selected from Tricyclodecane Dimethanol or pentacyclopentadecandimethanol
2 hydroxyls are eliminated in the polycyclic glycol of at least one kind of crosslinking in dimethanol.
Wherein, when P is (b), in cycloalkanes hydrocarbon skeleton or norbornane skeleton of the preferred linking group R for carbon number 4~10
When, substituent R in formula (2A) more preferably described later3Represent the group beyond hydrogen atom.
It should be noted that the softening point of above-mentioned oligoester is usually more than 50 DEG C, preferably more than 60 DEG C, more preferably
More than 80 DEG C.Higher limit is not particularly limited, usually less than 500 DEG C, preferably less than 300 DEG C, more preferably 200 DEG C with
Under.
The oligoester of above-mentioned particularly preferred terminal carboxylic in second invention can be by making 2~6 officials of carbon number more than 6
The polyalcohol of energy carries out addition reaction with representative examples of saturated aliphatic cyclic acid anhydride and obtained.
The oligoester of terminal carboxylic in second invention can be the composition of the oligoester comprising 2 kinds of terminal carboxylics.Make
For obtain comprising at least two kinds of terminal carboxylics oligoester terminal carboxylic oligoester composition method, have following method：
Mix the method for the oligoester for the single terminal carboxylic that at least two kinds of above methods are obtained or in synthesis above-mentioned end carboxylic acid
Oligoester when, as above-mentioned representative examples of saturated aliphatic cyclic acid anhydride, using in the representative examples of saturated aliphatic cyclic acid anhydride of following middle selections
At least two kinds of mixtures or the method that carries out addition reaction using 2 kinds of foregoing polyols.
As the representative examples of saturated aliphatic cyclic acid anhydride used in the synthesis of the oligoester of terminal carboxylic, it can include following
Compound：With cyclohexane structure, and there is on the cyclohexane ring methyl substitution or carboxyl substitution or to be unsubstituted,
Intramolecular has the anhydride group that more than 1 (being preferably 1) is bonded with cyclohexane ring.
Specifically, it can include selected from by hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and hexamethylene
Alkane -1,2,4- tricarboxylic acids -1,2- acid anhydrides, trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride and hydrogenation pyromellitic acid
At least one kind of acid anhydrides in the group of acid anhydride composition.
2~6 functions used in synthesis as the oligoester of the terminal carboxylic in the second invention, carbon number more than 6
Polyalcohol, specifically, can include the end of the crosslinked group P in previously described formula (10) has the terminal carboxylic of hydroxyl
Oligoester.
In previously described formula (10), the crosslinked group shown in P is preferably the crosslinked group by foregoing (a) or (b) divalent defined,
They are specifically described below.
It is 2 with the branched structure yuan alcohol (glycol) from carbon number 6~20 by the crosslinked group of foregoing (a) divalent defined
In remove hydroxyl-removal obtained from divalent chain-like alkyl chain, be following structure：With the alkyl folded by 2 alcohol hydroxyl groups of glycol
Chain is main chain, with the alkyl chain (being referred to as side chain) gone out from the alkyl chain branch.The side chain can be from any carbon for constituting main chain
Atom branch, for example, also include the situation of carbon atom (terminal carbon of main chain) branch being bonded from alcohol hydroxyl group.As long as
It is that the crosslinked group with the structure is then any, following formula (a1) shows the concrete example of such crosslinked group.
In previously described formula, pass through the oxygen atoms bond of P both sides in mark * and formula (10).
As long as the above-mentioned alkylidene crosslinked group defined by (a) has the knot of alkyl branches (side chain) to main chain alkylidene
Structure is just not particularly limited, preferably main chain of the main chain carbon number for more than 3, the structure with least one alkyl side chain, in addition especially
It is preferred that main chain of the main chain carbon number for more than 3, the structure with more than 2 alkyl side chains.As preferred structure, it can include
The carbon number of the main chain of straight chain with carbon number 3~12 and 2~4 side chains and at least one side chain is 2~10 crosslinked group.
Now, the carbon number of more preferably at least 2 side chains is 2~10 crosslinked group.Furthermore it is preferred that difference of 2~4 side chains from main chain
Carbon atom branch.
As more specifically compound, it can include in the crosslinking group described in previously described formula (a1) in mark * position
It is bonded with the compound of hydroxyl.
Among the polyalcohol as raw material, preferably with least two at least two side chain and the side chain be carbon number 2~
The polyalcohol of 4 side chain.
As particularly preferred polyalcohol among such skeleton, 2,4- diethyl -1,5-PD, 2- second can be included
Base -2- butyl -1,3-PD, 2- ethyl -1,3- hexylene glycols etc., can especially include 2,4- diethyl -1,5-PD.
As the crosslinked group defined by foregoing (b), the group of the divalent shown in following formula (b1) can be included.
It is with tristane knot as by the polycyclic diol residue of crosslinking in the situation of foregoing (b) crosslinked group defined
Structure, pentacyclopentadecandimethanol structure as main framing diol residue, such as shown in following formula (b2).
In formula, multiple R2Independently represent hydrogen atom or methyl.Among these, preferably R2All hydrogen atoms
Crosslinked group.
Specifically, Tricyclodecane Dimethanol, methyl Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol can be included
Deng.
It is typically the addition reaction using sour, alkali as catalyst as the reaction of acid anhydrides and polyalcohol, but it is special in the second invention
Not preferably without using the reaction of catalyst.
During using catalyst, as workable catalyst, for example, it can include：Hydrochloric acid, sulfuric acid, Loprazolam, trifluoro
The acid compounds such as Loprazolam, p-methyl benzenesulfonic acid, nitric acid, trifluoracetic acid, trichloroacetic acid, sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change calcium, the metal hydroxides such as magnesium hydroxide, the amines, pyridine, dimethyl such as triethylamine, tripropylamine, tri-butylamine
The hetero ring type compounds, tetramethyl hydrogen such as the aminopyridine, -7- alkene of 1,8- diazabicyclos [5.4.0] 11, imidazoles, triazole, tetrazolium
Amine-oxides, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, trimethyl
Propyl group ammonium hydroxide, trimethyl butyl ammonium hydroxide, trimethyl cetyl ammonium hydroxide, tricaprylmethyl ammonium hydroxide, four
Quaternary ammonium salts such as ammonio methacrylate, 4 bromide, tetramethyl-ammonium iodide, tetramethyl ammonium acetate, tricaprylmethyl ammonium acetate etc..
These catalyst can be used a kind or be mixed with two or more.Among these, preferably triethylamine, pyridine, dimethylamino pyrrole
Pyridine.
The consumption of catalyst is not particularly limited, relative to the parts by weight of gross weight 100 of raw material, it is usually preferred to according to need
Use 0.001~5 parts by weight.
Preferably without the reaction of solvent in this reaction, but organic solvent can be used.As the consumption of organic solvent, relatively
In 1 part of foregoing acid anhydrides and the total amount of foregoing polyols as response matrix, using weight ratio meter as 0.005~1 part, be preferably
0.005~0.7 part, more preferably 0.005~0.5 part (i.e. below 50 weight %).The consumption of organic solvent is anti-relative to above-mentioned
When answering the parts by weight of matrix 1 with weight ratio meter more than 1 part, reacting into guild becomes extremely slow, and it is not preferable.It is used as having for can using
The concrete example of machine solvent, can use the paraffinics such as hexane, hexamethylene, heptane, the aromatic hydrocarbon compound such as toluene, dimethylbenzene,
The ketones such as MEK, methylisobutylketone, cyclopentanone, cyclohexanone (anon), the ethers, vinegar such as Anaesthetie Ether, tetrahydrofuran, dioxanes
Ester compounds such as acetoacetic ester, butyl acetate, methyl formate etc..
This reaction also can fully be reacted at a temperature of 20 DEG C or so.The problem of from the reaction time, preferably instead
It is 30~200 DEG C, particularly preferably more preferably 40~200 DEG C, 40~150 DEG C to answer temperature.Especially enter in no solvent
During this reaction of row, there is the volatilization of acid anhydrides, it is therefore preferable that the reaction below 100 DEG C, particularly preferably at 30~100 DEG C or 40
Reaction at~100 DEG C.
Equimolar reaction on the reactive ratio Optimization Theory of foregoing acid anhydrides and foregoing polyols, but can change as needed
Become.
As specific input ratio both when reacting it, in terms of its functional equivalent, work as relative to the anhydride group 1
Amount, preferably with the hydroxyl equivalent of the polyalcohol be calculated as 0.001~2 equivalent, more preferably 0.01~1.5 equivalent, further preferably
The polyalcohol is put into for the ratio of 0.1~1.2 equivalent.
The oligoester of the terminal carboxylic of preferred gained is solid in second invention, in order to obtain the resinous terminal carboxylic of solid
The oligoester of acid, preferably preferably using polyalcohol more than equimolar equivalent, but mobility becomes due to addition filler
It is important, in order to ensure the mobility, from its viscosity equilibrium, keeping scope (more than 50 DEG C of softening point) Nei Kelve of solid
Micro- destruction is balanced.
Specifically, relative to anhydride equivalent, the equivalent proportion of alcohol hydroxyl group is preferably 0.85~1.20 molar equivalent, especially
Preferably 0.90~1.10 molar equivalent.
Reaction time additionally depends on reaction temperature, catalytic amount etc., but from this viewpoint of industrial production, for a long time
Reaction can consume huge energy, and it is not preferable.In addition, the too short reaction time means the reaction acutely, from security side
Face is not preferred.It is 1~48 hour as preferred scope, preferably 1~36 hour, more preferably 1~24 hour, further
Preferably 2~10 hours or so.
After reaction terminates, in the case of using catalyst, catalyst is carried out by neutralization, washing, absorption etc. respectively
Remove, distillation removes solvent, so as to obtain the oligoester of target terminal carboxylic.On the other hand, carried out without using catalyst
During reaction, by distilling the oligoester for removing solvent and obtaining target terminal carboxylic as needed.In addition, in the feelings using solvent
Under condition, the oligoester of target terminal carboxylic is obtained by removing solvent.And then without using solvent, without using the feelings of catalyst
Under condition, directly take out and obtain target product.
As optimum manufacture method, there is following method：Under conditions of without using catalyst, in 40~150 DEG C
Make foregoing acid anhydrides, foregoing polyols reaction, remove solvent, then take out.
The mixture of the oligoester of so obtained aforementioned end carboxylic acid or the oligoester containing the terminal carboxylic is generally in
The resin-like (according to circumstances crystallization) of colourless~flaxen solid.The softening point of the oligoester of the terminal carboxylic is preferably 50
~190 DEG C, more preferably 55~150 DEG C, particularly preferably 60~120 DEG C.By by the end carboxylic with such softening point
The oligoester of acid is directly mixed into hot curing resin composition without being liquid, it is possible to provide with high reflectivity
Conservation rate, when carrying out heat resistant test, reflectivity is also difficult to the reflection part that reduces.
Generally, when crosslinked group serves as reasons the alkylidene with side chain that (a) define, colourless~flaxen solid is presented
Resin-like.
In second invention, the optimum used the hot curing resin composition of the oligoester containing terminal carboxylic
Method shaped for transmission, therefore, the oligoester of terminal carboxylic is the resin-like of solid.
In the case where crosslinked group serves as reasons the crosslinked group that (b) define, in the cycloalkanes that aliphatic alkyl is carbon number 4~10
When hydrocarbon skeleton or norbornane skeleton, the oligoester of the terminal carboxylic of all hydrogen atoms of substituent of ester ring type can be shown admittedly
Coloring during change, is unsuitable for especially harsh optical applications.It is the cycloalkanes hydrocarbon skeleton of carbon number 4~10 or drop ice in aliphatic alkyl
During piece alkane skeleton, such coloring is few for substituent is the compound of methyl or carboxyl, and its optical characteristics is improved.
It is also in the cycloalkanes that aliphatic alkyl is carbon number 4~10 foregoing in the compound of (a) crosslinked group defined
When hydrocarbon skeleton or norbornane skeleton, optical characteristics when substituent is the compound of methyl or carboxyl is improved, and is preferred.
That is, as the second invention terminal carboxylic oligoester composition, in the cycloalkanes hydrocarbon skeleton or drop for carbon number 4~10
Preferably it is preferably the terminal carboxylic of methyl or carboxyl or formula (10) with both comprising substituent during bornylane skeleton
Oligoester composition.In the feelings of the oligoester composition of the terminal carboxylic of the oligoester comprising two or more terminal carboxylic
Under condition, the composition being preferably as follows：It is comprising 50 moles of more than %, at least should relative to the total amount of the oligoester of terminal carboxylic
Substituent be not the terminal carboxylic of the formula (1) of hydrogen atom oligoester (substituent be aforesaid alkyl, be preferably methyl or carboxyl
Terminal carboxylic oligoester).More preferably comprising 70 moles of more than %, most preferably 90 moles of more than %, the substitution
Base is not the oligoester composition of the terminal carboxylic of the oligoester of the terminal carboxylic of the formula (10) of hydrogen atom.Surplus is R3It is that hydrogen is former
The oligoester of the terminal carboxylic of the following formula (2A) of son.
As the oligoester of terminal carboxylic suitable in the second invention, it can be used terminal carboxylic's shown in following formula (2A)
Oligoester.
(in above-mentioned formula, P represents implication same as described above, R3Represent hydrogen atom, the alkyl or carboxyl of carbon number 1~3.)
Herein, in above-mentioned formula (2A), the reasons why according to being noted as above, R3Can suitably using carbon number 1~3 alkyl or
Carboxyl.
Terminal carboxylic's oligoester preferred number average molecular weight Mn is the oligoester of more than 300 terminal carboxylic.
As the curing agent that can be applied in combination, for example, it can include：Amine compound, the acid with unsaturation ring structure
Acid anhydride based compound, the acid anhydrides with organosiloxane skeleton, acid amides based compound, phenol system compound, carboxylic acid based compound etc..Make
For the concrete example for the curing agent that can be used, it can include：Diaminodiphenyl-methane, Diethylenetriamine, three second tetramines, diaminourea
Diphenyl sulphone (DPS), IPD, dicyandiamide, pass through the polyamide synthesized by linolenic 2 polymers and ethylenediamine, adjacent benzene two
Formic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic acid
Acid anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic acid anhydrides, bicyclic [2.2.1]
Heptane -2,3- dicarboxylic anhydrides, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic anhydrides, bisphenol-A, Bisphenol F, bisphenol S, fluorenes bis-phenol,
Terpene diphenol, 4,4 '-bis-phenol, 2,2 '-bis-phenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-xenyl] -4,4 '-glycol, hydroquinones,
Resorcinol, naphthalene glycol, three-(4- hydroxy phenyls) methane, 1,1,2,2- tetra- (4- hydroxy phenyls) ethane, phenols (phenol, alkyl
Fortified phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, para hydroxybenzene first
Aldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, bicyclopentadiene, furfural, 4,4 '-bis- (chloromethyl) -1,
1 '-biphenyl, 4,4 '-bis- (methoxies) -1,1 '-biphenyl, 1,4 '-bis- (chloromethyl) benzene, 1,4 '-bis- (methoxy) benzene
Deng condensation polymer and the halogenated bisphenol class such as their modifier, tetrabromobisphenol A, imidazoles, boron trifluoride-amine complex, guanidine derive
Condensation product of thing, terpenes and phenols etc., but it is not limited to these materials.These can be used alone, also can be combined using 2 kinds with
On.
Curing accelerator can be added in the hot curing resin composition of second invention as needed.Promote as solidification
Enter agent, can include：2-methylimidazole, 2- phenylimidazoles, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenyl -4- first
Base imidazoles, 1- benzyl -2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyls -
2- phenylimidazoles, 1- cyano ethyl -2- undecyl imidazoles, 2,4- diaminourea -6 (2 '-methylimidazole (1 ')) ethyl-equal three
Piperazine, 2,4- diaminourea -6 (2 '-undecyl imidazole (1 ')) ethyl-s-triazine, 2,4- diaminourea -6 (2 '-ethyl, 4- methyl miaows
Azoles (1 ')) ethyl-s-triazine, 2,4- diaminourea -6 (2 '-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct,
The 2 of 2-methylimidazole isocyanuric acid：3 addition products, 2- phenylimidazoles isocyanuric acid adduct, 2- phenyl -3,5- bishydroxymethyls
Imidazoles, 2- phenyl -4- hydroxymethyl -5- methylimidazoles, 1- cyano ethyl -2- phenyl -3,5- dicyano ethoxyl methyl imidazoles
Various imidazoles, and these imidazoles and phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, equal benzene four
The salt of the oligoester of the terminal carboxylics such as acid, naphthalene dicarboxylic acids, maleic acid, oxalic acid, the amide-type, 1,8- bisazo-bis- such as dicyandiamide
The salt of tetraphenyl borate salts, the phenol novolacs of ring [5.4.0] endecatylene -7 grade bis-azo compound and these materials etc.
Class, the oligomeric esters of aforementioned end carboxylic acid or the salt with phosphonic acid, TBAB, cetyl trimethylammonium bromide,
The quaternary ammonium salts such as tricaprylmethyl ammonium bromide, cetyltrimethylammonium hydroxide (are preferably C1~C20 alkylammonium salts, triphenyl
Phosphine, phosphorus compound, the 2,4,6- such as phosphine, three (tolyl) phosphines, tetraphenyl phosphonium bromide, tetraphenylphosphonium tetraphenyl borate salts
The gold such as the phenols such as triamido methylphenol, amine adduct, tin octoate, octanesulfonic acid zinc, zinc stearate, copper naphthenate, cobalt naphthenate
Belong to compound etc., and microcapsule-type curing accelerator, the carbonyls zinc that microcapsules are obtained is made in these curing accelerators
Complex compound etc..Can be according to for example transparent, heat-resisting coloring, curing rate, behaviour using any in these curing accelerators
Make the characteristic required by the obtained transparent resin composition such as condition suitably to select.It is used as thing preferred in the second invention
Matter, can include phosphorus compound (more preferably quaternary phosphonium) or zinc stearate.
Curing accelerator is usual relative to 100 parts by weight epoxy resin in 0.001~15 parts by weight, preferably 0.01~5
Used in the range of parts by weight.
The asphalt mixtures modified by epoxy resin being generally commonly used can be added in the form of the additive in addition to above-mentioned additive as needed
Fat additive, such as pigment, dyestuff, fluorescent whitening agent, reinforcing material, filler, Chinese white, nucleator, surface-active
Agent, plasticizer, viscosity modifier, fluidity regulator, fire retardant, antioxidant, ultra-violet absorber, light stabilizer.
In the hot curing resin composition of second invention, it is generally desirable to, the Thermocurable under hot conditions during shaping
The ICI Cone ＆ Plate viscosities of resin curing agent are more contour than conventional anhydride curing agent, specifically, are 100 in forming temperature region
It is that 0.01~10Pas is preferable in the range of~200 DEG C.During less than 0.01Pas, burr is easily produced.On the other hand,
There is the worry that productivity ratio is reduced during more than 10Pas.
In present embodiment, heat-curing resin at 150 DEG C with the ICI viscosity of curing agent be preferably 0.01Pas~
10Pas, more preferably 0.05Pas~5Pas.
By being adjusted to the scope, in normal temperature, (25 DEG C) turn into solid, and shaping becomes easy, can effectively prevent space
A problem that.Further, since be solid at room temperature, therefore when being handled before there is no pre-polymerization materialization etc. in the case of liquid not
The mixing that may be carried out is carried out with becoming able to no pre-treatment, due to for solid, therefore is easily shaped with lamellar morphology.And then,
By being set as the hot curing resin composition of such low viscosity, in the past because of the softening point with crystallinity or fusing point
Each composition high, that mixing is difficult is fully melted and is distributed in curing agent, therefore crystal is defeated and dispersed, with the epoxy resin as host
Fully mixing, can obtain each composition and effectively arranges and the solidfied material with excellent physical property.
In addition, the preferred softening point of the hot curing resin composition of the second invention be 20~150 DEG C, more preferably 30 DEG C~
130 DEG C of scope, more preferably 40 DEG C~120 DEG C scope, particularly preferably 50~130 DEG C.
By being adjusted to the scope, it can easily be stirred by mixer etc., mix various composition, and then can be by grinding
Grinding roller, extruder, kneader, roller, extruder etc. are kneaded or melting mixing to it, and are cooled down, crushed.
Preferably the glass transition temperature (Tg) of solidfied material is higher than forming temperature.The glass transition temperature of solidfied material
(Tg) when for below forming temperature, solidfied material in a mold is the rubbery state of low elasticity, therefore, can become to take out from mould
Rubber-like solidfied material, when filling in stripper (ejector), there is the worry for deforming etc. and producing unfavorable condition.It is specific and
Speech, glass transition temperature (Tg) is preferably more than 30 DEG C, more preferably more than 40 DEG C, more preferably more than 50 DEG C.
Herein, in the second invention, the glass transition temperature (Tg) of solidfied material is preferably less than 150 DEG C, is more preferably 140
Below DEG C.
The hot curing resin composition of second invention is obtained by the above-mentioned various composition of dispersed mixing.To it
Method is not particularly limited, and can include following method：Sufficiently uniformly stirred by mixer etc., mix various composition, so
Kneaded or melting mixing using mixing roll, extruder, kneader, roller, extruder etc. afterwards, cooled down, crushed.Mixing or
The condition of melting mixing is determined according to the species of composition, compounding amount, is not particularly limited, more preferably at 20~100 DEG C
In the range of knead 5~40 minutes.When melting temperature is less than 20 DEG C, the dispersiveness reduction of each composition, it is difficult to make it fully knead,
During for temperature higher than 100 DEG C, exist and carry out the cross-linking reaction of resin combination, cause the worry of resin composition.
Preferably the hot curing resin composition of second invention at room temperature may be used before thermoforming, at 0~30 DEG C
Pressurization (sheet) shaping.Press molding can be included for example in 0.01~10MPa, the side carried out under conditions of 1~5 second or so
Method.In addition, the mould used when being shaped to pressurization (sheet) is not particularly limited, for example, it is preferable to using by ceramic based material, fluorine
It is the mould being made up of pestle mould (mold) and mortar mould (lower mould) that resin material etc. is made.
The hot curing resin composition of second invention is partly led needing the light of high glass-transition temperature and high-transmission rate
It is useful in the purposes such as body encapsulating material, photosemiconductor reflecting material.
Purposes is being reflected in use, manufacture method is not particularly limited, for example, it is preferable to by transmitting into shape as light
Make the hot curing resin composition of the second invention.The hot curing resin composition of the second invention is injected in a mold, in example
As mold temperature be 150~190 DEG C, forming pressure be it is solidified 60~800 seconds under conditions of 2~20MPa, then from mould
Take out, made its heat cure through 1~3 hour at a temperature of 150 DEG C~180 DEG C of solidify afterwards.
(semiconductor device)
For the optical semiconductor device of the second invention, if illustrating concrete example, such as International Publication to representational structure
As No. 2012/124147 is recorded, light reflection of the configuration with cylindric hollow bulb prevents part on substrate, in circle
In the inner space of the hollow part of tubular, in configuring optical semiconductor on substrate.Also, with following structure：Connected with lead
The one end and substrate of optical semiconductor are connect, potting resin is enclosed in above-mentioned hollow bulb.
Pair suitably it can be described in detail using the reflecting material of the resin combination of the second invention.Pass through shaping
Obtained from reflecting material can suppress the discoloration that heat deterioration is caused.Reflecting material may be used as the LED illumination such as LED bulb utensil use
LED reflection device.The reflecting material obtained by the hot curing resin composition of the second invention may be constructed long lifespan and cheap
LED reflection device.
Fig. 1 has been shown with the one of the LED light device for the reflecting material that the shaping of being thermally cured property resin combination is obtained
Example.The reflecting material is LED reflection device 1.Reflecting material is formed as frame-shaped, has recess 2 and hole portion 3 in central portion.Recess 2 is set
It is set to the inclined face of wall.The wall of recess 2, which turns into, makes the reflecting surface that light reflects.Hole portion 3 is with through LED reflection device 1
Mode is arranged on the bottom of recess 2.The lead frame 4 being equipped with as the LED5 of light-emitting component is embedded with the hole portion 3.Lead frame
The wiring powered to LED5 can also be provided in 4.The luminous surface side (top of figure) of recess 2 is covered by transparent shield 6.
Thus, LED5 is protected.Shield 6 is engaged in the opening edge of recess 2 with LED reflection device 1.LED reflection device 1 is efficient as being used for
Ground reflection LED5 luminous reflecting plate plays a role.The shape of LED reflection device 1 is not limited to Fig. 1 shape, it may be considered that real
The LED5 of dress light quantity, color, directional properties etc. and it is appropriately designed.Above-mentioned light-reflecting article hot curing resin composition by
It is good in formability, therefore, it is possible to be readily derived the formed body of target shape.
Embodiment
Hereinafter, the present invention is described in detail by embodiment, but the present invention is not limited by following record.
First, the first invention is described in detail by embodiment.
The preparation (embodiment 1-1~1-2, comparative example 1-1~1-2) of Thermocurable light reflection resin combination
Use EHPE-3150 (Daisel chemical industry Co., Ltd's alicyclic epoxy resin), THEIC-G (four countries
Into Industrial Co., Ltd's polyol compound), RIKACID MH-T (new Japan Chemical hardener for epoxy resin),
HISHICOLIN PX-4MP (Nippon Chemical Ind's curing catalysts), are compounded according to the formula table shown in table 1-1
Each composition, prepares embodiment 1-1~1-2 and comparative example 1-1~1-2 hot curing resin composition.It should be noted that table
The unit of the compounding amount of each composition in 1-1 is parts by weight, and empty column represents that the composition is not used.
The preparation (embodiment 1-3~1-4) of Thermocurable light reflection resin combination
Use EHPE-3150 (Daisel chemical industry Co., Ltd's alicyclic epoxy resin), two (trihydroxy methyls third
Alkane) (PERSTORP JAPAN CO., LTD polyol compound), RIKACID MH-T (new Japan Chemical epoxy resin use
Curing agent), HISHICOLIN PX-4MP (Nippon Chemical Ind's curing catalysts), according to matching somebody with somebody shown in table 1-2
Square table is compounded each composition, prepares embodiment 1-3~1-4 hot curing resin composition.It should be noted that in table 1-2
The unit of the compounding amount of each composition is parts by weight.
Hot curing resin composition Evaluation valencys
For the resin combination of each embodiment, the DMA, TMA, transmission of solidfied material are determined by following shown methods
Rate.It the results are shown in table 1-1.
(a) differential thermal-thermogravimetric determines (TG/DTA) simultaneously
(TG/DTA) is determined simultaneously on differential thermal-thermogravimetric, device (SII is determined simultaneously using differential thermal-heat
NanoTechnology Inc. Exstar TG/DTA7200), it is measured in following conditions.
(condition determination)
Determine temperature：40 DEG C~150 DEG C
Programming rate：20 DEG C/min
Retention time：150 DEG C 1 hour
Circulated gases：Nitrogen
Flow：200ml/ minutes
Planchet：Aluminum
Sample size：4~6mg
It should be noted that the embodiment 1~4 and comparative example 1~2 in table 1 below -1 and table 1-2 represent foregoing reality respectively
Apply a 1-1~1-4 and foregoing comparative example 1-1~1-2.
[table 1]
Table 1-1
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | ||
| Heat-curing resin | EHPE·3150 | 100.0 | 100.0 | 100 | 100 |
| Alcohol | THEIC-G | 29.4 | 29.4 | - | - |
| Acid anhydrides | RIKACID MH-T | 74.1 | 74.1 | 69.6 | 69.6 |
| Curing accelerator | PX-4MP | - | 2.0 | - | 1.7 |
| Volatile quantity (%) | 1.99 | 0.55 | 24.92 | 2.43 |
[table 2]
Table 1-2
| Embodiment 3 | Embodiment 4 | ||
| Heat-curing resin | EHPE-3150 | 100.0 | 100.0 |
| Alcohol | Two (trimethylolpropanes) | 25.3 | 25.3 |
| Acid anhydrides | RIKACID MH-T | 88.3 | 88.3 |
| Curing accelerator | PX-4MP | - | 2.1 |
| Volatile quantity (%) | 4.01 | 0.55 |
It can be seen from result above, the hot curing resin composition of the first invention has the few spy of volatilization during solidification
Levy.
Then, the second invention is described in detail by embodiment.
Herein, in synthesis example, gel permeation chromatography (hereinafter referred to as " GPC "), ICI viscosity, each measure of softening point are such as
Carry out as described belowly.
1)GPC
By Shodex SYSTEM-21 posts (KF-803L, KF-802.5 (× 2), KF-802) of post, link eluent be
Tetrahydrofuran, flow velocity are 1ml/ minutes, column temperature is 40 DEG C and be detected as RI (Reflective index) condition and enter
OK, standard curve uses Shodex polystyrene standards.In addition, functional equivalent is calculated by the ratio calculated by GPC,
Carboxylic acid, acid anhydrides are set to 1 equivalent and obtain numerical value.
2) ICI viscosity
Determine the melt viscosity in the cone-plate method at 150 DEG C.
3) softening point
It is measured by the method based on JIS K-7234.
Synthesis example 2-1 (heat-curing resin curing agent A-1)
In the flask for possessing agitator, reflux condensing tube, agitating device, implement nitrogen purging while adding isocyanide urea
261.2 parts of sour three (2- hydroxy methacrylates), methylhexahydrophthalic anhydride (the new Japan Chemical system of Co., Ltd., RIKACID MH-
T) 504.6 parts, MEK766.0 parts, 7 hours heating stirrings is carried out at 70 DEG C, the MEK solution of inclusion compound is thus obtained.To
153.2 parts of methylhexahydrophthalic anhydride (the new Japan Chemical system of Co., Ltd., RIKACID MH-T) is wherein added, at 70 DEG C
1 hour heating stirring of lower progress.Then, 150 DEG C were warming up to from 70 DEG C with about 1 hour, are removed under conditions of 150 DEG C, 1 hour
Solvent, obtains heat-curing resin curing agent.
Obtained curing agent is colorless solid.In addition, functional equivalent is 232g/eq..ICI viscosity is at 150 DEG C
0.38Pa·s.Softening point is 82.6 DEG C.
In addition, being that 81.1%, 2 substitution bodies are 3.04%, 1 substitution as 3 substitution bodies of principal component on GPC areas ratio
Body is 1.04%.
[table 3]
Synthesis example 2-2 (heat-curing resin curing agent A-2)
In the reactive tank for possessing agitator, reflux condensing tube, agitating device, implement nitrogen purging while adding isocyanide
7840 parts of urea acid three (2- hydroxy methacrylates), methylhexahydrophthalic anhydride (the new Japan Chemical system of Co., Ltd., RIKACID
MH-T) 15140 parts, 23000 parts of MEK (MEK), 7 hours heating stirrings are carried out at 70 DEG C, are thus obtained containing compound
MEK solution.The temperature of the MEK solution is reduced to room temperature, adding methylhexahydrophthalic anhydride, (Co., Ltd. is newly Japanese
Physics and chemistry system, RIKACID MHT) 4600 parts, 1 hour heating stirring is carried out at 40 DEG C.Then, it is slow with about 5 hours from 40 DEG C
Carry out decompression and be warming up to 150 DEG C, remove solvent under conditions of 150 DEG C, 1 hour, obtain heat-curing resin curing agent.
Obtained curing agent is colorless solid.In addition, functional equivalent is 234g/eq..ICI viscosity is at 150 DEG C
0.40Pa·s.Softening point is 82.9 DEG C.
In addition, being that 82.59%, 2 substitution bodies are 0.00%, 1 substitution as 3 substitution bodies of principal component on GPC areas ratio
Body is 1.25%.
[table 4]
[table 5]
Table 2-1
Embodiment 1~2 in above-mentioned table 2-1 is represented by the GPC of the obtained curing agent of foregoing synthesis example 2-1~2-2 respectively
The result of analysis.In addition, in above-mentioned table 2-1,1 substitution body refers to the compound of above-mentioned formula (5) by the chemical combination of 1 above-mentioned formula (6)
The product of thing substitution, 2 substitution bodies refer to what the compound of above-mentioned formula (5) was replaced by the compound of 2 above-mentioned formulas (6)
Product, 3 substitution bodies refer to the product that the compound of above-mentioned formula (5) is replaced by the compound of 3 above-mentioned formulas (6).
According to the second invention, using the teaching of the invention it is possible to provide coloring when having excellent formability, solidfied material is made less, can provide with abundant glass
The Polycarboxylic acid resin of the solidfied material of glass transition temperature, its hot curing resin composition is used and has used this
Hot curing resin composition is used as encapsulating material or the optical semiconductor device of reflecting material.And then, by suppressing polynary carboxylic
Acid resin or the softening point for having used its hot curing resin composition, the processing of hot curing resin composition become to hold
Easily, and can fully it knead, using the teaching of the invention it is possible to provide the solidfied material of solidification physical properties excellent.In addition, using the teaching of the invention it is possible to provide the reactivity of resin
The excellent solidfied material of excellent hot curing resin composition, obdurability.
The present invention is described in detail with reference to specific embodiment, but those skilled in the art understand and are not departing from the present invention
Various changes and modifications can be done in the case of spirit and scope.
It should be noted that the application was based on 2 months 2015 Japanese patent application (Japanese Patent Application 2015- filed in 5 days
021450 and Japanese Patent Application 2015-021668), quote entire contents by quoting.In addition, cited all referring to whole
Body is included in the application.
Industrial applicability
The volatile quantity of the heat-curing resin curing agent of first invention is low, have excellent formability, and has used foregoing heat cure
Property resin curing agent hot curing resin composition the solidfied material that glass transition temperature is fully high, coloring is few can be provided,
Therefore the hot curing resin composition of the first invention is as the encapsulating material of photosemiconductor or the material of light reflecting material
Useful.Glass transition temperature fully height is important for formability and reliability.In addition, making as reflecting material
Used time, it is possible to increase reflectivity.
In addition, the melt viscosity of the heat-curing resin curing agent of the second invention is low, have excellent formability, use foregoing
The hot curing resin composition of heat-curing resin curing agent can provide the abundant height of glass transition temperature, colour few consolidate
Compound, therefore, the hot curing resin composition of the second invention as photosemiconductor encapsulating material or light reflecting material
Material is useful.Glass transition temperature fully height is important for formability and reliability.In addition, coloring exists less
Transmissivity can be improved when being used as encapsulating material, as reflecting material in use, reflectivity can be improved.
Description of reference numerals
1 LED reflection device, 2 reflecting materials, 3 hole portions, 4 lead frames, 5 LED, 6 shields.
Claims (16)
1. a kind of hot curing resin composition, it contains：Polyol compound (A), acid anhydrides chemical combination with more than 3 hydroxyls
Thing (B) and heat-curing resin (C).
2. hot curing resin composition according to claim 1, wherein, the polyalcohol with more than 3 hydroxyls
Compound (A) has includes more than 1 heteroatomic cyclic structure in intramolecular.
3. hot curing resin composition according to claim 2, wherein, the hetero atom is nitrogen-atoms.
4. hot curing resin composition according to claim 1, wherein, the polyalcohol with more than 3 hydroxyls
Compound (A) is the polyol compound shown in following formula (5),
In formula (5), R1Represent in the alkylidene of carbon number 1~6, formula (5), multiple R1Can with it is mutually the same can also be each other
It is different.
5. according to hot curing resin composition according to any one of claims 1 to 4, wherein, the anhydride compound (B)
For selected from trimellitic anhydride, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride, with
And the one kind or two or more compound in methylhexahydrophthalic anhydride.
6. according to hot curing resin composition according to any one of claims 1 to 5, wherein, the heat-curing resin
(C) it is epoxy resin.
7. a kind of hot curing resin composition, it contains following Polycarboxylic acid resin,
The Polycarboxylic acid resin contains in the measure of gel permeation chromatography shown in more than 70 area %, following formula (1)
Polybasic carboxylic acid (A1), and containing in the measure of gel permeation chromatography for 0.5~10 area %, shown in following formula (1a)
Polybasic carboxylic acid (A2) and/or following formula (1b) shown in carboxylic acid (A3),
In formula (1), R1Represent the alkylidene of carbon number 1~6, R2Represent in the alkyl or carboxyl of hydrogen atom or carbon number 1~6, formula (1),
Multiple R1、R2Can with it is mutually the same can also be different from each other；
In formula (1a), R1、R2With the R in the formula (1)1、R2Represent in identical implication, formula (1a), multiple R1、R2Can
With it is mutually the same can also be different from each other；
In formula (1b), R1、R2With the R in the formula (1)1、R2Represent in identical implication, formula (1b), multiple R1、R2Can
With it is mutually the same can also be different from each other.
8. hot curing resin composition according to claim 7, wherein, the Polycarboxylic acid resin contains oozes in gel
It is the acid anhydrides shown in 5~20 area %, following formula (6) in the measure of saturating chromatogram,
In formula (6), R2With the R in the formula (1)2Represent identical implication.
9. hot curing resin composition according to claim 7, wherein, the Polycarboxylic acid resin is to make the formula
(1) compound shown in and compound obtained from the compound reaction shown in the formula (6) described in claim 8, and contain
It is 0.5~10 area %, the high score that retention time is shorter than compound shown in the formula (1) in the measure of gel permeation chromatography
Son amount body.
10. the hot curing resin composition according to any one of claim 7~9, its softening point is in 20 DEG C~150
DEG C scope.
11. the hot curing resin composition according to any one of claim 7~10, it contains the polybasic carboxylic acid tree
Fat and selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid, hydrogenate equal benzene four
1 kind in acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Or two or more compound, selected from trimellitic acid, trimellitic anhydride, cyclohexanetricarboxylic acid, cyclohexanetricarboxylic acid's acid anhydride, pyromellitic acid,
Hydrogenate pyromellitic acid, pyromellitic dianhydride, hydrogenation pyromellitic dianhydride, hexahydrophthalic anhydride and methyl hexahydro O-phthalic
The summation of one kind or two or more compound in acid anhydrides accounts for the weight of 1 weight %~90 in the hot curing resin composition
Measure %.
12. the hot curing resin composition according to any one of claim 7~11, it contains heat-curing resin.
13. hot curing resin composition according to claim 12, wherein, consolidate the hot curing resin composition
The glass transition temperature (Tg) for the solidfied material changed is more than 30 DEG C.
14. a kind of solidfied material, it is to make the thermosetting any one of claim 1~6, claim 12 and claim 13
The property changed resin combination heat cure.
15. a kind of optical semiconductor device, it is encapsulated using the solidfied material described in claim 14.
16. a kind of optical semiconductor device, it uses the solidfied material described in claim 14 as reflecting material.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-021668 | 2015-02-05 | ||
| JP2015-021450 | 2015-02-05 | ||
| JP2015021450A JP2016141799A (en) | 2015-02-05 | 2015-02-05 | Thermosetting resin composition containing polyhydric alcohol compound, acid anhydride compound and thermosetting resin and optical semiconductor device using the thermosetting resin composition as encapsulation material or reflector |
| JP2015021668A JP2016141806A (en) | 2015-02-05 | 2015-02-05 | Polycarboxylic acid resin, thermosetting resin composition using the same and optical semiconductor device using the thermosetting resin composition as encapsulation material or reflector |
| PCT/JP2016/053430 WO2016125874A1 (en) | 2015-02-05 | 2016-02-04 | Thermosetting resin composition including polyhydric alcohol compound, acid anhydride compound and thermosetting resin, polycarboxylic acid resin, thermosetting resin composition using same, and photosemiconductor device using either one of the thermosetting resin compositions as sealing material or reflective material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107250282A true CN107250282A (en) | 2017-10-13 |
Family
ID=56564213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680008961.4A Withdrawn CN107250282A (en) | 2015-02-05 | 2016-02-04 | Hot curing resin composition and Polycarboxylic acid resin containing polyol compound, anhydride compound and heat-curing resin and its hot curing resin composition is used and has used any of foregoing hot curing resin composition as encapsulating material or the optical semiconductor device of reflecting material |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN107250282A (en) |
| TW (1) | TW201702298A (en) |
| WO (1) | WO2016125874A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51124197A (en) * | 1975-04-22 | 1976-10-29 | Dainippon Ink & Chem Inc | A resin composition |
| JPH0193317A (en) * | 1987-10-05 | 1989-04-12 | Sumitomo Heavy Ind Ltd | Injection molding method |
| JPH03121155A (en) * | 1989-10-04 | 1991-05-23 | New Japan Chem Co Ltd | Epoxy resin composition |
| JP2001059017A (en) * | 1999-08-24 | 2001-03-06 | Nitto Denko Corp | Epoxy resin composition for flow casting |
| JP2007099901A (en) * | 2005-10-04 | 2007-04-19 | Nippon Steel Chem Co Ltd | Epoxy resin and epoxy resin composition |
| US20100164127A1 (en) * | 2007-05-17 | 2010-07-01 | Nitto Denko Corporation | Epoxy resin composition for photosemiconductor element encapsulation and cured product thereof, and photosemiconductor device using the same |
| CN102365309A (en) * | 2009-04-03 | 2012-02-29 | 库克复合材料和聚合物公司 | Thermosetting compositions containing isocyanurate rings |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2058239T3 (en) * | 1987-11-27 | 1994-11-01 | Enichem Sintesi | LIQUID COMPOSITION THERMOFRAGUANTE CONTAINING A POLYEPOXIDE. |
| CN104684960B (en) * | 2012-09-27 | 2017-05-10 | 日本化药株式会社 | polycarboxylic acid resin and epoxy resin composition |
| JP2015096602A (en) * | 2013-10-07 | 2015-05-21 | 株式会社ダイセル | Curable epoxy resin composition |
| WO2016013257A1 (en) * | 2014-07-24 | 2016-01-28 | 日本化薬株式会社 | Polycarboxylic acid, polycarboxylic acid composition, epoxy resin composition and heat-curable resin composition each containing said polycarboxylic acid, cured products of said compositions, and optical semiconductor device |
-
2016
- 2016-02-04 WO PCT/JP2016/053430 patent/WO2016125874A1/en active Application Filing
- 2016-02-04 CN CN201680008961.4A patent/CN107250282A/en not_active Withdrawn
- 2016-02-05 TW TW105104023A patent/TW201702298A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51124197A (en) * | 1975-04-22 | 1976-10-29 | Dainippon Ink & Chem Inc | A resin composition |
| JPH0193317A (en) * | 1987-10-05 | 1989-04-12 | Sumitomo Heavy Ind Ltd | Injection molding method |
| JPH03121155A (en) * | 1989-10-04 | 1991-05-23 | New Japan Chem Co Ltd | Epoxy resin composition |
| JP2001059017A (en) * | 1999-08-24 | 2001-03-06 | Nitto Denko Corp | Epoxy resin composition for flow casting |
| JP2007099901A (en) * | 2005-10-04 | 2007-04-19 | Nippon Steel Chem Co Ltd | Epoxy resin and epoxy resin composition |
| US20100164127A1 (en) * | 2007-05-17 | 2010-07-01 | Nitto Denko Corporation | Epoxy resin composition for photosemiconductor element encapsulation and cured product thereof, and photosemiconductor device using the same |
| CN102365309A (en) * | 2009-04-03 | 2012-02-29 | 库克复合材料和聚合物公司 | Thermosetting compositions containing isocyanurate rings |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201702298A (en) | 2017-01-16 |
| WO2016125874A1 (en) | 2016-08-11 |
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Application publication date: 20171013 |