JP4114464B2 - Phenol derivative and method for producing the same - Google Patents
Phenol derivative and method for producing the same Download PDFInfo
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- JP4114464B2 JP4114464B2 JP2002338431A JP2002338431A JP4114464B2 JP 4114464 B2 JP4114464 B2 JP 4114464B2 JP 2002338431 A JP2002338431 A JP 2002338431A JP 2002338431 A JP2002338431 A JP 2002338431A JP 4114464 B2 JP4114464 B2 JP 4114464B2
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- phenol derivative
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- 150000002989 phenols Chemical class 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- -1 phenol compound Chemical class 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 10
- 150000004662 dithiols Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001400 nonyl 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])[H] 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 238000003756 stirring Methods 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 125000002947 alkylene group Chemical group 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002313 adhesive film Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012778 molding material Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 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 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- OOJYPCDXFPWXFL-UHFFFAOYSA-N [C].OC1=CC=CC=C1 Chemical compound [C].OC1=CC=CC=C1 OOJYPCDXFPWXFL-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000002228 disulfide group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000010680 novolac-type phenolic resin Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011907 photodimerization Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 125000005591 trimellitate group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、フェノール誘導体、フェノール誘導体の製造方法、熱可塑性樹脂組成物、感光性樹脂組成物、接着力向上方法及び耐湿性向上方法に関する。
【０００２】
【従来の技術】
電気・電子部品の液晶表示器（ＬＣＤ）や半導体パッケージの接着及び封止のための材料としてフェノール樹脂が広く用いられている。また、電気・電子部品の種々の特性を高めるために特定構造のフェノール誘導体が適用され、難接着面への接着力向上のため、含イオウ化合物の添加を行う場合がある。
【０００３】
例えば、導電性接着剤では、基材樹脂としてのエポキシ樹脂の他に、硬化剤としてのポリアリルフェノール樹脂を配合している（特許文献１）。
【０００４】
また、ＴＡＢ用接着剤付きテープにおいては、接着剤の構成成分であるポリアミド樹脂の他に、フェノール炭素−フェノール炭素間に硫黄原子や酸素原子を導入したフェノール誘導体を含有させて、接着性及び絶縁性の改良を図っている（特許文献２）。
【０００５】
フレキシブル印刷回路基板用接着剤においては、添加成分であるアクリロニトリルブタジエンゴムの酸化防止剤として、特定構造の含硫黄フェノール誘導体が配合される場合がある（特許文献３）。
【０００６】
また、封止用樹脂組成物では、接着性向上のための添加剤として、テトラスルフィド構造を有する化合物（特許文献４）やジスルフィド構造を有する化合物（特許文献５、特許文献６）が用いられている。
【０００７】
一方、液晶表示器（ＬＣＤ）や半導体パッケージの小型化・軽量化に伴い、高密度実装技術が要求されており、最近の異方導電性フィルム（ＡＣＦ）やダイボンドフィルム等の接着剤に対する被接着対象物の表面層の材料として、銅の他に、銀、金、パラジウム、金パラジウム合金、あるいは窒化珪素等が多く用いられるようになってきている。
【０００８】
【特許文献１】
特開平６−３２２３５０号公報
【特許文献２】
特開平１１−２６０８６５号公報
【特許文献３】
特開平７−２４５４７８号公報
【特許文献４】
特開２０００−１３６２９０号公報
【特許文献５】
特開２００２−３７０４号公報
【特許文献６】
特開２００２−２４９５４８号公報
【０００９】
【発明が解決しようとする課題】
しかしながら、銅、銀、金、パラジウム、金パラジウム合金等の金属材料、あるいは窒化珪素等の材料は難接着素材であり、これらの材料で基材が被覆された表面は汚染の影響も受けやすいことから、表面層が上記材料で構成される基材に対して樹脂を接合するにあたり、高い接着性及び優れた安定性を得ることは困難であった。
【００１０】
そこで、本発明の目的は、熱硬化性樹脂や感光性樹脂等の樹脂に添加剤として用いることができ、添加後の樹脂に、金、銀、銅、パラジウム、金パラジウム合金、窒化珪素等で被覆された基材に対する高い接着力を付与させることが可能で、接着後の接合物の耐湿性をも向上可能な化合物を提供することを目的とする。
【００１１】
【課題を解決するための手段】
本発明者らは、上記の目的を達成すべく鋭意研究を重ねた結果、新規化合物である所定構造のフェノール誘導体により、上記目的が達成可能であることを見出し、本発明を完成させた。
【００１２】
すなわち、本発明のフェノール誘導体（ジスルフィド構造及びチオエーテル構造を有するフェノール誘導体であり、フェノリックジスルフィドとも称される。）は、下記一般式（１）で表されることを特徴とするものである。かかるフェノール誘導体は、熱硬化性樹脂や感光性樹脂等の樹脂に添加剤として用いることができ、添加後の樹脂に、金、銀、銅、パラジウム、金パラジウム合金、窒化珪素等で被覆された基材に対する高い接着力を付与させることができるのみならず、接着後の接合物の耐湿性を向上することも可能である。
【化６】
本発明は、また下記一般式（１１）で表される新規化合物たるフェノール誘導体（メルカプト基及びチオエーテル構造を有するフェノール誘導体であり、フェノリックモノチオールとも称される。）を提供し、上記一般式（１）で表されるフェノール誘導体は、下記一般式（１１）で表されるフェノール誘導体のジスルフィド化反応により得られるものであることが好ましい。
【化７】
ここで、上記一般式（１１）で表されるフェノール誘導体は、下記一般式（２１）で表されるフェノール化合物（アリル基を有するフェノール化合物）又は一般式（２２）で表されるフェノール化合物（ビニル基を有するフェノール化合物）と、下記一般式（３１）で表されるジチオールと、を反応させる方法により製造可能である。
【化８】
なお、上記一般式において、Ｒ１はエチレン基又は直鎖状のプロピレン基を示し、Ｒ２及びＲ３はそれぞれ独立にメチレン基、エチレン基、直鎖状のプロピレン基又はフェニレン基を示し、Ｇは水素原子、メチル基、エチル基、ブチル基、ノニル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミノ基又はフェニル基を示す。
【００１６】
本発明は上記に加え、上記一般式（１）で表されるフェノール誘導体と、熱硬化性樹脂と、を含むことを特徴とする熱硬化性樹脂組成物、並びに、上記一般式（１）で表されるフェノール誘導体と、感光性樹脂と、を含むことを特徴とする感光性樹脂組成物を提供する。かかる樹脂は、銅、銀、金、金パラジウム合金、窒化珪素等で被覆された基材に対して高い接着力を発揮し、接着後の接合物の耐湿性を向上させることができる。
【００１７】
したがって、本発明により、被着体に対する樹脂の接着力向上方法であって、当該樹脂に上記一般式（１）で表されるフェノール誘導体を含有させることを特徴とする方法が提供可能となり、更に、被着体と該被着体に接着した樹脂とを備える樹脂接合物の耐湿性向上方法であって、当該樹脂に上記一般式（１）で表されるフェノール誘導体を含有させることを特徴とする方法が提供可能となる。
【００１８】
上記接着力向上方法においては、上記被着体は、金、銀、銅、パラジウム、金パラジウム合金及び窒化ケイ素からなる群より選ばれる材料で基材が被覆された被着体であり、上記樹脂は上記被着体の上記材料面に接着すべき樹脂であることが好ましく、同様に上記耐湿性向上方法においては、上記被着体は、金、銀、銅、パラジウム、金パラジウム合金及び窒化ケイ素からなる群より選ばれる材料で基材が被覆された被着体であり、上記樹脂は上記被着体の上記材料面に接着したものであることが好ましい。
【００１９】
【発明の実施の形態】
先ず、一般式（１）で表されるフェノール誘導体及び一般式（１１）で表されるフェノール誘導体について、好適な実施形態を説明する。
【００２０】
一般式（１）及び（１１）において、Ｒ１は炭素数２〜３のアルキレン基であり、炭素数３のアルキレン基には直鎖状及び分岐状アルキレン基が含まれるが、アルケニル基へのチオールの付加反応により合成する場合を考慮すれば、R１はエチレン基（−ＣＨ２−ＣＨ２−）又は直鎖状のプロピレン基（−ＣＨ２−ＣＨ２−ＣＨ２−）が好ましい。なお、ベンゼン環上の水酸基に対するR１の位置は、オルト位、メタ位、パラ位のいずれであってもよい。
【００２１】
一般式（１）、（１１）及び（３１）において、Ｒ２及びＲ３はそれぞれ独立に炭素数１〜１０のアルキレン基又はフェニレン基であり、アルキレン基は炭素数１〜１０の直鎖状アルキレン基が好ましい。Ｒ２及びＲ３は、炭素数１〜６の直鎖状アルキレン基又はフェニレン基であることが好ましく、炭素数１〜４の直鎖状アルキレン基又はフェニレン基であることがより好ましい。アルキレン基としてはメチレン基（−ＣＨ２−）、エチレン基（−ＣＨ２−ＣＨ２−）又は直鎖状のプロピレン基（−ＣＨ２−ＣＨ２−ＣＨ２−）が好ましい。
【００２２】
一般式（１）、（１１）、（２１）及び（２２）において、Ｇは水素原子、メチル基、エチル基、ブチル基、ノニル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミノ基、フェニル基、ベンジル基又はハロゲン原子である。接着性及び耐湿性付与の観点から、これらの中では、水素原子、メチル基、エチル基、ブチル基、ノニル基、メトキシ基、エトキシ基、ブトキシ基、水酸基、カルボキシル基、ニトロ基、アミノ基又はフェニル基が好ましく、メチル基、エチル基、ブチル基、ノニル基、メトキシ基、エトキシ基、ブトキシ基がより好ましい。なお、ベンゼン環上の水酸基に対するＧの位置は、オルト位、メタ位、パラ位のいずれであってもよい。
【００２３】
一般式（１）で表されるフェノール誘導体の具体例としては、下記一般式（１ａ）で表されるフェノール誘導体（Ｒ１が炭素数３のアルキレン基、Ｇがメトキシ基である誘導体）、下記一般式（１ｂ）で表されるフェノール誘導体（Ｒ１が炭素数３のアルキレン基、Ｇが水素原子である誘導体）が挙げられる。なお、Ｒ２及びＲ３については上記と同義である。
【化１０】
また、一般式（１１）で表されるフェノール誘導体の具体例としては、下記一般式（１１ａ）で表されるフェノール誘導体（Ｒ１が炭素数３のアルキレン基、Ｇがメトキシ基である誘導体）、下記一般式（１１ｂ）で表されるフェノール誘導体（Ｒ１が炭素数３のアルキレン基、Ｇが水素原子である誘導体）が挙げられる。なお、Ｒ２及びＲ３については上記と同義であり、後述のように下記一般式（１１ａ）で表されるフェノール誘導体は、一般式（１ａ）で表されるフェノール誘導体の製造に用いることができ、下記一般式（１１ｂ）で表されるフェノール誘導体は、一般式（１ｂ）で表されるフェノール誘導体の製造に用いることができる。
【化１２】
次に、一般式（１）で表されるフェノール誘導体及び一般式（１１）で表されるフェノール誘導体の製造方法について説明する。
【００２６】
一般式（１１）で表されるフェノール誘導体は、一般式（２１）又は一般式（２２）で表されるフェノール化合物に対して、一般式（３１）で表されるジチオールを付加反応させることにより得ることができる。この場合において、一般式（２１）で表されるフェノール化合物を用いた場合はＲ１が炭素数３のアルキレン基である一般式（１１）のフェノール誘導体が得られ、一般式（２２）で表されるフェノール化合物を用いた場合はＲ１が炭素数２のアルキレン基である一般式（１１）のフェノール誘導体が得られる。
【００２７】
一般式（２１）又は一般式（２２）で表されるフェノール化合物と上記一般式（３１）で表されるジチオールを反応させるに当たり、上記フェノール化合物に対してジチオールを等モル量以上用いることが好ましい。ジチオールを過剰に用いることにより、生成物における一般式（１１）で表されるフェノール誘導体の割合（純度）を向上させることができる。
【００２８】
反応温度や反応時間等の条件は、上記反応が充分に進行する条件を選べばよく、反応温度は１００℃〜２００℃、反応時間は３０分〜７時間程度とすることができる。
【００２９】
より詳しくは、上記反応は、上記フェノール化合物とジチオールとを反応容器に導入し、当該反応容器中にて撹拌、還流させながら加熱して実施することが好ましい。反応は、空気中で行うことができるが、窒素ガス等の不活性ガス雰囲気中で行うのが好適である。所定の時間の経過により、一般式（１１）のフェノール誘導体が生成するので、過剰なジチオールは減圧留去するか、適当な溶媒を加えて分取する。得られたフェノール誘導体は、反応物混合系から単離・精製してもよいが、単離・精製することなくこれを原料として、式（１）のフェノール誘導体の製造に供してもよい。
【００３０】
一般式（１）で表されるフェノール誘導体は、上述の製造方法等により得られた一般式（１１）で表されるフェノール誘導体のジスルフィド化反応（一般式（１１）で表されるフェノール誘導体２分子の酸化反応）により得ることができる。
【００３１】
かかる反応は、ジメチルスルホキシド（ＤＭＳＯ）を酸化剤及び溶媒として用いることにより実施することが好ましい。この場合において、ＤＭＳＯの使用量は、一般式（１１）で表されるフェノール誘導体に対し２倍モル量が基本であるが、２倍モル以上に過剰に加えておくことが好適である。
【００３２】
上記反応における、反応温度や反応時間等の条件は、酸化反応が充分に進行する条件を選べばよく、例えば、反応温度は５０℃〜７０℃、反応時間は４時間〜８時間程度とすることができる。
【００３３】
より詳しくは、上記反応は、一般式（１１）で表されるフェノール誘導体を反応容器に秤量し、ＤＭＳＯ中に添加して、攪拌しながら５０℃〜７０℃で加熱して実施することが好適である。反応の進行過程及び終点は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で確認することができ、反応終了後、純水にて再沈澱を行い、反応生成物を収集して一般式（１）のフェノール誘導体を得ることができる。
【００３４】
次に、一般式（１）で表されるフェノール誘導体と熱硬化性樹脂とを含む熱硬化性樹脂組成物（以下単に「熱硬化性樹脂組成物」という。）、並びに、一般式（１）で表されるフェノール誘導体と感光性樹脂とを含む感光性樹脂組成物（以下単に「感光性樹脂組成物」という。）について、好適な実施形態を説明する。
【００３５】
熱硬化性樹脂組成物を構成する熱硬化性樹脂としては、公知の熱硬化性樹脂、例えば、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、アミノ樹脂（尿素樹脂、メラミン樹脂）、ポリイミド樹脂等を用いることができる。
【００３６】
熱硬化性樹脂組成物は、一般式（１）で表されるフェノール誘導体及び熱硬化性樹脂の他、当該熱硬化性樹脂の硬化促進剤や反応触媒、フィラー、強化繊維（ガラス繊維、炭素繊維等）、増量剤、着色剤等を更に含有するものであってもよい。また、一般式（１）で表されるフェノール誘導体の含有量は、熱硬化性樹脂１００重量部に対して、０．０１〜５０重量部が好ましく、０．０５〜３０重量部がより好ましく、０．１〜１０重量部が更に好ましい。
【００３７】
感光性樹脂組成物を構成する感光性樹脂としては、公知の感光性樹脂、例えば、エチレン性不飽和結合等の光ラジカル重合性の基を有したポリマー、光二量化を生じる基を有したポリマー、光カチオン重合開始剤を含有させたエポキシ樹脂等のカチオン重合性樹脂を用いることができる。
【００３８】
光ラジカル重合性の基を有したポリマーは、光ラジカル重合性開始剤や光ラジカル重合性モノマーを含有していてもよく、光二量化を生じる基を有したポリマーは光重合性モノマーを含有していてもよい。また、感光性樹脂組成物には、増感剤、発色剤、フィラー、強化繊維（ガラス繊維、炭素繊維等）、増量剤等を添加することができる。
【００３９】
なお、一般式（１）で表されるフェノール誘導体の含有量は、感光性樹脂組成物１００重量部に対して、０．０１〜５０重量部が好ましく、０．０５〜３０重量部がより好ましく、０．１〜１０重量部が更に好ましい。
【００４０】
以上説明した一般式（１）で表されるフェノール誘導体を樹脂に添加することにより、当該樹脂の被着体に対する接着力を向上させることができ、当該樹脂が被着体に接着した樹脂接合物の耐湿性を向上させることができる。
【００４１】
ここで用いられる樹脂としては、上述の熱硬化性樹脂組成物及び感光性樹脂組成物が挙げられ、被着体としては、金、銀、銅、パラジウム、金パラジウム合金又は窒化ケイ素で基材が被覆された被着体が挙げられる。金、銀、銅、パラジウム、金パラジウム合金又は窒化ケイ素は難接着素材であるために、通常の樹脂では良好な接着性（はく離強度等）や耐湿性（プレッシャークッカー試験（ＰＣＴ）における耐性等）が得られないのに対して、一般式（１）で表されるフェノール誘導体を樹脂に添加することにより、これらの特性を顕著に向上させることができる。
【００４２】
【実施例】
以下、本発明の好適な実施例についてさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００４３】
［一般式（１１）で表されるフェノール誘導体の合成］
＜実施例１＞
２−メトキシ−４−アリルフェノール（オイゲノール）１３．３ｇ（０．０８１０ｍｏｌ）をセパラブルフラスコに秤量し、これに下記式（３１ａ）に示す２，２’−チオジエタンチオール５０．０ｇ（０．３２４ｍｏｌ）を添加した。
【化１４】
【化１５】
＜実施例２＞
２−メトキシ−４−アリルフェノール（オイゲノール）８．２１ｇ（０．０５００ｍｏｌ）をセパラブルフラスコに秤量し、これに下記式（３１ｂ）に示す４，４’−チオビスベンゼンチオール５０．０ｇ（０．２００ｍｏｌ）を添加した。
【化１６】
【化１７】
［一般式（１）で表されるフェノール誘導体の合成］
＜実施例３＞
実施例１で得られた式（１１ａ’）で表されるフェノール誘導体２０ｇ（０７８５ｍｏｌ）をセパラブルフラスコに秤量し、１０倍モル量のジメチルスルホキシド（ＤＭＳＯ）を加え、攪拌しながら約７０℃で加熱した。ＧＰＣで反応の進行を追い、反応終了を確認後、蒸留水にて反応生成物を再沈澱し回収した。これにより、一般式（１ａ）においてＲ２及びＲ３がエチレン基である下記式（１ａ’）で表されるフェノール誘導体を得た。なお、ＧＰＣとしては島津製作所製Ｃ−Ｒ４Ａを用い、溶離液にテトラヒドロフラン（ＴＨＦ）、測定濃度は２．０ｇ／Ｌとした。また、カラムは東ソー社製ＴＳＫ ｇｅｌ Ｇ３０００ＨｘＬ＋ＴＳＫ ｇｅｌ Ｇ２０００ＨｘＬ、ＲＩモニタは日立製作所製Ｌ−３３００、ポンプには日立製作所製Ｌ−６０００を用いた。
【化１８】
＜実施例４＞
実施例２で得られた式（１１ａ’’）で表されるフェノール誘導体２０ｇ（０．０３８６ｍｏｌ）をセパラブルフラスコに秤量し、１０倍モル量のジメチルスルホキシド（ＤＭＳＯ）を加えた後、攪拌しながら約７０℃で加熱した。実施例３と同様の条件で、ＧＰＣにより反応の進行を追い、反応終了を確認後、蒸留水にて反応生成物を再沈澱し回収した。これにより、一般式（１ａ）においてＲ２及びＲ３がフェニレン基である下記式（１ａ’’）で表されるフェノール誘導体を得た。
【化１９】
［接着剤への応用］
＜実施例５＞
（ポリイミド樹脂の合成）
攪拌装置、窒素導入管、乾燥管を備えた１リットルの４つ口フラスコに、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパンを４１．０ｇ（０．１０モル）を入れ、窒素気流下、ＮＭＰ（Ｎ−メチルピロリドン）２５０ｇを加えて溶液とした。フラスコを水浴上に移し、激しく攪拌させながら１，２−（エチレン）ビス（トリメリテート二無水物）４１．０ｇ（０．１０モル）を少量ずつ加えた。酸二無水物がほぼ溶解したら、ゆっくりと攪拌しながら６時間反応させ、ポリアミド溶液を得た。
【００４８】
次に、上記ポリアミド溶液が入った４つ口フラスコに蒸留装置を装着し、キシレン２２０ｇを加えた。窒素気流下、１８０℃の油浴上で激しく攪拌しながら、イミド化により生成する縮合水をキシレン共に共沸留去した。その反応液を水中に注ぎ、沈殿したポリマーを濾別乾燥してポリイミド樹脂を得た。
【００４９】
（ワニスの調合）
得られたポリイミド樹脂１００重量部に対してＤＭＡｃ（ジメチルアセトアミド）５００重量部とＴＣＧ−１（フィラー）２００重量部とを配合してポリイミドワニスを調合すると共に、この時点で、実施例３で得られた式（１ａ’）で表されるフェノール誘導体を５重量部配合した。
【００５０】
（接着フィルムの作成）
ポリプロピレンフィルム基材上に上記ワニスを３０〜５０μｍの厚さに塗布し、８０℃で１０分、続いて１５０℃で３０分、加熱乾燥し、室温で冷やした後、乾燥物を基材から剥がして接着フィルムを得た。
【００５１】
＜比較例１＞
式（１ａ’）で表されるフェノール誘導体を添加しなかった他は、実施例５と同様にして、接着フィルムを得た。
【００５２】
（接着フィルムの評価）
実施例５及び比較例１の接着フィルムについて、ピール強度（はく離強度）を測定した。すなわち、接着フィルムを５ｍｍ×５ｍｍの大きさに切断し、これを５ｍｍ×５ｍｍのシリコンチップと銅リードフレームの間に挟み、１ｋｇの加重をかけて、１８０℃または２５０℃で圧着させた後、１８０℃で一時間加熱して接着フィルムを硬化させた。そして、２４５℃または２７５℃、２０秒加熱時の引き剥がし強さをプッシュプルゲージで測定した。測定結果を表１に示した。
【表１】
［封止材への応用］
＜実施例６＞
（実施例６−１）
クレゾールノボラックエポキシ樹脂（エポキシ当量２１５）が１９重量％、ノボラック型フェノール樹脂（フェノール当量１０７）が９重量％、実施例３で得られた式（１ａ’）で表されるフェノール誘導体が０．２重量％、溶融シリカ粉末が７１．２重量％、硬化促進剤が０．３重量％、エステル系ワックス類が０．３重量％となるように、これらを常温で混合し、更に９０〜９５℃で混練した後、冷却粉砕して成形材料を製造した。
【００５４】
（実施例６−２）
クレゾールノボラックエポキシ樹脂（エポキシ当量２１５）が１９重量％、ノボラック型フェノール樹脂（フェノール当量１０７）が９重量％、実施例４で得られた式（１ａ’’）で表されるフェノール誘導体が０．２重量％、溶融シリカ粉末が７１．２重量％、硬化促進剤が０．３重量％、エステル系ワックス類が０．３重量％となるように、実施例６−１と同様にして、混合した後に混練及び粉砕して成形材料を製造した。
【００５５】
（比較例２）
式（１ａ’）で表されるフェノール誘導体を用いなかった他は、実施例６−１と同様にして（フェノール誘導体以外の材料の比率は実施例６−１と同様）、成形材料を製造した。
【００５６】
（接着強度の評価）
実施例６−１、６−２及び比較例２の成形材料を１７０℃に加熱した金型内にトランスファー注入し、接着面積４ｍｍ２の成形品をＰｄ又はＰｄ−Ａｕプレプレーティングされた基材上に成形し、１７５℃で８時間放置した後、せん断接着強度を求めた。
【００５７】
（耐湿性の評価）
実施例６−１、６−２及び比較例２の成形材料を用いて、２本以上のアルミニウム配線を有するシリコン製チップ（テスト用素子）をＰｄプレプレーティングフレームに接着し、１７５℃２分間トランスファー成形して、成形品を作製し、これに対して１７５℃８時間の後硬化を行った。得られた成形品に対し４０℃、９０％ＲＨ、１００時間の吸湿処理を行い、最高温度２４０℃のＩＲリフロー炉を４回通過させた。その後、１２７℃、２．５気圧の飽和水蒸気中でＰＣＴ試験を行い、アルミニウムの腐食による断線を不良とした。ＰＣＴ試験は成形品数２０で行い、１００時間、３００時間及び５００時間後の不良品数を調べた。
【００５８】
以上の結果を表２にまとめて示す。なお、表２における耐湿性の欄の数値は、不良品数／成形品数を示すものである。
【表２】
【発明の効果】
以上説明したように、本発明によれば、熱硬化性樹脂や感光性樹脂等の樹脂に添加剤として用いることができ、添加後の樹脂に、金、銀、銅、パラジウム、金パラジウム合金、窒化珪素等で被覆された基材に対する高い接着力を付与させることが可能で、接着後の接合物の耐湿性をも向上可能な化合物を提供することが可能になる。かかる化合物は、半導体実装技術に有用な添加剤として用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phenol derivative, a method for producing a phenol derivative, a thermoplastic resin composition, a photosensitive resin composition, a method for improving adhesion, and a method for improving moisture resistance.
[0002]
[Prior art]
Phenolic resin is widely used as a material for bonding and sealing liquid crystal displays (LCD) of electrical and electronic parts and semiconductor packages. In addition, a phenol derivative having a specific structure is applied to enhance various characteristics of electric / electronic parts, and a sulfur-containing compound may be added to improve the adhesion to difficult-to-bond surfaces.
[0003]
For example, in a conductive adhesive, a polyallyl phenol resin as a curing agent is blended in addition to an epoxy resin as a base resin (Patent Document 1).
[0004]
In addition, in a tape with an adhesive for TAB, in addition to the polyamide resin which is a constituent component of the adhesive, a phenol derivative in which a sulfur atom or an oxygen atom is introduced between phenol carbon and phenol carbon is contained so as to have adhesiveness and insulation. The improvement of property is aimed at (patent document 2).
[0005]
In the adhesive for flexible printed circuit boards, a sulfur-containing phenol derivative having a specific structure may be blended as an antioxidant for acrylonitrile butadiene rubber, which is an additive component (Patent Document 3).
[0006]
Moreover, in the sealing resin composition, a compound having a tetrasulfide structure (Patent Document 4) or a compound having a disulfide structure (Patent Document 5, Patent Document 6) is used as an additive for improving adhesiveness. Yes.
[0007]
On the other hand, with the miniaturization and weight reduction of liquid crystal display (LCD) and semiconductor packages, high-density mounting technology is required, and adhesion to adhesives such as recent anisotropic conductive films (ACF) and die bond films is required. As a material for the surface layer of the object, silver, gold, palladium, gold-palladium alloy, silicon nitride, and the like are often used in addition to copper.
[0008]
[Patent Document 1]
JP-A-6-322350 [Patent Document 2]
Japanese Patent Laid-Open No. 11-260865 [Patent Document 3]
JP-A-7-245478 [Patent Document 4]
JP 2000-136290 A [Patent Document 5]
Japanese Patent Laid-Open No. 2002-3704 [Patent Document 6]
Japanese Patent Laid-Open No. 2002-249548
[Problems to be solved by the invention]
However, metal materials such as copper, silver, gold, palladium, gold-palladium alloy, or materials such as silicon nitride are difficult-to-adhere materials, and the surface on which the substrate is coated with these materials is also susceptible to contamination. Therefore, it has been difficult to obtain high adhesiveness and excellent stability when the resin is bonded to the substrate whose surface layer is made of the above material.
[0010]
Therefore, the object of the present invention can be used as an additive to a resin such as a thermosetting resin or a photosensitive resin, and the resin after the addition is made of gold, silver, copper, palladium, gold-palladium alloy, silicon nitride, etc. An object of the present invention is to provide a compound capable of imparting a high adhesive force to a coated substrate and improving the moisture resistance of a bonded product after bonding.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by a phenol derivative having a predetermined structure, which is a novel compound, and completed the present invention.
[0012]
That is, the phenol derivative of the present invention (a phenol derivative having a disulfide structure and a thioether structure and also referred to as phenolic disulfide) is characterized by being represented by the following general formula (1). Such a phenol derivative can be used as an additive to a resin such as a thermosetting resin or a photosensitive resin, and the resin after the addition is coated with gold, silver, copper, palladium, gold-palladium alloy, silicon nitride, or the like. Not only can a high adhesive force be applied to the substrate, it is also possible to improve the moisture resistance of the bonded product after bonding.
[Chemical 6]
The present invention also provides a phenol derivative (a phenol derivative having a mercapto group and a thioether structure, also referred to as phenolic monothiol), which is a novel compound represented by the following general formula (11). The phenol derivative represented by 1) is preferably obtained by disulfide reaction of a phenol derivative represented by the following general formula (11).
[Chemical 7]
Here, the phenol derivative represented by the general formula (11) is a phenol compound represented by the following general formula (21) (phenol compound having an allyl group) or a phenol compound represented by the general formula (22) ( It can be produced by a method of reacting a phenol compound having a vinyl group) with a dithiol represented by the following general formula (31).
[Chemical 8]
In the above general formula, R 1 represents an ethylene group or a linear propylene group , R 2 and R 3 each independently represent a methylene group, an ethylene group, a linear propylene group or a phenylene group, and G Represents a hydrogen atom, methyl group, ethyl group, butyl group, nonyl group, methoxy group, ethoxy group, butoxy group, hydroxyl group, carboxyl group, nitro group, amino group or phenyl group.
[0016]
In addition to the above, the present invention includes a thermosetting resin composition comprising a phenol derivative represented by the general formula (1) and a thermosetting resin, and the general formula (1). The photosensitive resin composition characterized by including the phenol derivative represented and photosensitive resin is provided. Such a resin exhibits a high adhesive force to a base material coated with copper, silver, gold, gold-palladium alloy, silicon nitride or the like, and can improve the moisture resistance of the bonded product after bonding.
[0017]
Therefore, according to the present invention, it is possible to provide a method for improving the adhesion of a resin to an adherend, characterized in that the resin contains the phenol derivative represented by the general formula (1). A method for improving the moisture resistance of a resin bonded article comprising an adherend and a resin adhered to the adherend, wherein the resin contains a phenol derivative represented by the general formula (1). Can be provided.
[0018]
In the method for improving adhesion, the adherend is an adherend having a base coated with a material selected from the group consisting of gold, silver, copper, palladium, gold-palladium alloy and silicon nitride, and the resin Is preferably a resin to be adhered to the material surface of the adherend. Similarly, in the moisture resistance improving method, the adherend is made of gold, silver, copper, palladium, gold-palladium alloy, and silicon nitride. It is preferable that the substrate is coated with a material selected from the group consisting of: and the resin is bonded to the material surface of the adherend.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
First, suitable embodiment is described about the phenol derivative represented by General formula (1) and the phenol derivative represented by General formula (11).
[0020]
In the general formulas (1) and (11), R 1 is an alkylene group having 2 to 3 carbon atoms, and the alkylene group having 3 carbon atoms includes linear and branched alkylene groups. Considering the case of synthesis by addition reaction of thiol, R 1 is preferably an ethylene group (—CH 2 —CH 2 —) or a linear propylene group (—CH 2 —CH 2 —CH 2 —). The position of R 1 with respect to the hydroxyl group on the benzene ring may be any of the ortho position, meta position, and para position.
[0021]
In the general formulas (1), (11) and (31), R 2 and R 3 are each independently an alkylene group having 1 to 10 carbon atoms or a phenylene group, and the alkylene group is a straight chain having 1 to 10 carbon atoms. An alkylene group is preferred. R 2 and R 3 are preferably a linear alkylene group having 1 to 6 carbon atoms or a phenylene group, and more preferably a linear alkylene group having 1 to 4 carbon atoms or a phenylene group. The alkylene group is preferably a methylene group (—CH 2 —), an ethylene group (—CH 2 —CH 2 —) or a linear propylene group (—CH 2 —CH 2 —CH 2 —).
[0022]
In the general formulas (1), (11), (21) and (22), G represents a hydrogen atom, a methyl group, an ethyl group, a butyl group, a nonyl group, a methoxy group, an ethoxy group, a butoxy group, a hydroxyl group, a carboxyl group, A nitro group, an amino group, a phenyl group, a benzyl group or a halogen atom; Among these, from the viewpoint of imparting adhesiveness and moisture resistance, among them, hydrogen atom, methyl group, ethyl group, butyl group, nonyl group, methoxy group, ethoxy group, butoxy group, hydroxyl group, carboxyl group, nitro group, amino group or A phenyl group is preferable, and a methyl group, an ethyl group, a butyl group, a nonyl group, a methoxy group, an ethoxy group, and a butoxy group are more preferable. In addition, the position of G with respect to the hydroxyl group on the benzene ring may be any of ortho, meta, and para positions.
[0023]
Specific examples of the phenol derivative represented by the general formula (1) include a phenol derivative represented by the following general formula (1a) (a derivative in which R 1 is an alkylene group having 3 carbon atoms and G is a methoxy group), Examples thereof include phenol derivatives represented by the general formula (1b) (derivatives in which R 1 is an alkylene group having 3 carbon atoms, and G is a hydrogen atom). R 2 and R 3 have the same meaning as described above.
[Chemical Formula 10]
Specific examples of the phenol derivative represented by the general formula (11) include a phenol derivative represented by the following general formula (11a) (a derivative in which R 1 is an alkylene group having 3 carbon atoms and G is a methoxy group). And phenol derivatives (derivatives in which R 1 is an alkylene group having 3 carbon atoms and G is a hydrogen atom) represented by the following general formula (11b). In addition, about R < 2 > and R < 3 >, it is synonymous with the above, and the phenol derivative represented by the following general formula (11a) is used for manufacture of the phenol derivative represented by general formula (1a) as mentioned later. The phenol derivative represented by the following general formula (11b) can be used for the production of the phenol derivative represented by the general formula (1b).
Embedded image
Next, the manufacturing method of the phenol derivative represented by General formula (1) and the phenol derivative represented by General formula (11) is demonstrated.
[0026]
The phenol derivative represented by the general formula (11) is obtained by adding a dithiol represented by the general formula (31) to the phenol compound represented by the general formula (21) or the general formula (22). Obtainable. In this case, when the phenol compound represented by the general formula (21) is used, a phenol derivative of the general formula (11) in which R 1 is an alkylene group having 3 carbon atoms is obtained, and is represented by the general formula (22). When the phenol compound to be used is used, a phenol derivative of the general formula (11) in which R 1 is an alkylene group having 2 carbon atoms is obtained.
[0027]
In reacting the phenol compound represented by the general formula (21) or the general formula (22) with the dithiol represented by the general formula (31), it is preferable to use the dithiol in an equimolar amount or more with respect to the phenol compound. . By using dithiol excessively, the ratio (purity) of the phenol derivative represented by the general formula (11) in the product can be improved.
[0028]
Conditions such as reaction temperature and reaction time may be selected so that the reaction proceeds sufficiently. The reaction temperature can be 100 ° C. to 200 ° C., and the reaction time can be about 30 minutes to 7 hours.
[0029]
More specifically, the reaction is preferably carried out by introducing the phenol compound and dithiol into a reaction vessel, and heating while stirring and refluxing in the reaction vessel. The reaction can be carried out in air, but is preferably carried out in an inert gas atmosphere such as nitrogen gas. Since the phenol derivative of the general formula (11) is formed with the passage of a predetermined time, excess dithiol is distilled off under reduced pressure or is collected by adding an appropriate solvent. The obtained phenol derivative may be isolated and purified from the reactant mixture system, but it may be used as a raw material for the production of the phenol derivative of the formula (1) without isolation and purification.
[0030]
The phenol derivative represented by the general formula (1) is a disulfide reaction of the phenol derivative represented by the general formula (11) obtained by the above-described production method (phenol derivative 2 represented by the general formula (11)). Molecular oxidation reaction).
[0031]
Such a reaction is preferably carried out by using dimethyl sulfoxide (DMSO) as an oxidizing agent and a solvent. In this case, the amount of DMSO used is basically a 2-fold molar amount relative to the phenol derivative represented by the general formula (11), but it is preferable to add it excessively to a 2-fold mole or more.
[0032]
Conditions such as reaction temperature and reaction time in the above reaction may be selected such that the oxidation reaction proceeds sufficiently. For example, the reaction temperature is 50 ° C. to 70 ° C., and the reaction time is about 4 hours to 8 hours. Can do.
[0033]
More specifically, the reaction is preferably carried out by weighing the phenol derivative represented by the general formula (11) into a reaction vessel, adding it to DMSO, and heating at 50 ° C. to 70 ° C. with stirring. It is. The progress and end point of the reaction can be confirmed by gel permeation chromatography (GPC). After completion of the reaction, reprecipitation is performed with pure water, the reaction product is collected, and the phenol of the general formula (1) is collected. Derivatives can be obtained.
[0034]
Next, a thermosetting resin composition containing a phenol derivative represented by the general formula (1) and a thermosetting resin (hereinafter simply referred to as “thermosetting resin composition”), and the general formula (1) A preferred embodiment of a photosensitive resin composition (hereinafter simply referred to as “photosensitive resin composition”) containing a phenol derivative represented by formula (I) and a photosensitive resin will be described.
[0035]
Examples of the thermosetting resin constituting the thermosetting resin composition include known thermosetting resins such as epoxy resins, phenol resins, unsaturated polyester resins, polyurethane resins, amino resins (urea resins, melamine resins), polyimides. Resin or the like can be used.
[0036]
The thermosetting resin composition includes a phenol derivative represented by the general formula (1) and a thermosetting resin, a curing accelerator, a reaction catalyst, a filler, a reinforcing fiber (glass fiber, carbon fiber) of the thermosetting resin. Etc.), bulking agents, colorants and the like. Moreover, 0.01-50 weight part is preferable with respect to 100 weight part of thermosetting resins, and, as for content of the phenol derivative represented by General formula (1), 0.05-30 weight part is more preferable, 0.1-10 weight part is still more preferable.
[0037]
As the photosensitive resin constituting the photosensitive resin composition, a known photosensitive resin, for example, a polymer having a radically polymerizable group such as an ethylenically unsaturated bond, a polymer having a group causing photodimerization, A cationically polymerizable resin such as an epoxy resin containing a photocationic polymerization initiator can be used.
[0038]
The polymer having a radical photopolymerizable group may contain a radical photopolymerizable initiator or a radical photopolymerizable monomer, and the polymer having a group that causes photodimerization contains a photopolymerizable monomer. May be. In addition, a sensitizer, a color former, a filler, a reinforcing fiber (glass fiber, carbon fiber, etc.), an extender, and the like can be added to the photosensitive resin composition.
[0039]
In addition, 0.01-50 weight part is preferable with respect to 100 weight part of photosensitive resin compositions, and, as for content of the phenol derivative represented by General formula (1), 0.05-30 weight part is more preferable. 0.1 to 10 parts by weight is more preferable.
[0040]
By adding the phenol derivative represented by the general formula (1) described above to the resin, the adhesive strength of the resin to the adherend can be improved, and the resin bonded product in which the resin adheres to the adherend. The moisture resistance of can be improved.
[0041]
Examples of the resin used here include the thermosetting resin composition and the photosensitive resin composition described above, and examples of the adherend include gold, silver, copper, palladium, gold-palladium alloy, or silicon nitride. Examples include coated adherends. Since gold, silver, copper, palladium, gold-palladium alloy or silicon nitride is a difficult-to-adhere material, good adhesiveness (peeling strength, etc.) and moisture resistance (resistance in pressure cooker test (PCT), etc.) with ordinary resins However, these characteristics can be remarkably improved by adding a phenol derivative represented by the general formula (1) to the resin.
[0042]
【Example】
EXAMPLES Hereinafter, although the preferable Example of this invention is described in detail, this invention is not limited to these Examples.
[0043]
[Synthesis of Phenol Derivative Represented by General Formula (11)]
<Example 1>
13.3 g (0.0810 mol) of 2-methoxy-4-allylphenol (eugenol) was weighed into a separable flask, and 50.0 g of 2,2′-thiodiethanethiol represented by the following formula (31a) (0 .324 mol) was added.
Embedded image
Embedded image
<Example 2>
8.21 g (0.0500 mol) of 2-methoxy-4-allylphenol (eugenol) was weighed into a separable flask, and 50.0 g of 4,4′-thiobisbenzenethiol represented by the following formula (31b) (0 .200 mol) was added.
Embedded image
Embedded image
[Synthesis of phenol derivative represented by general formula (1)]
<Example 3>
20 g (0785 mol) of the phenol derivative represented by the formula (11a ′) obtained in Example 1 was weighed into a separable flask, 10-fold molar amount of dimethyl sulfoxide (DMSO) was added, and the mixture was stirred at about 70 ° C. Heated. Following the progress of the reaction by GPC and confirming the completion of the reaction, the reaction product was reprecipitated and recovered with distilled water. Thus, a phenol derivative represented by the following formula (1a ′) in which R 2 and R 3 in the general formula (1a) are ethylene groups was obtained. Note that C-R4A manufactured by Shimadzu Corporation was used as GPC, tetrahydrofuran (THF) was used as an eluent, and the measurement concentration was 2.0 g / L. Further, TSK gel G3000HxL + TSK gel G2000HxL manufactured by Tosoh Corporation was used as the column, L-3300 manufactured by Hitachi Ltd. was used as the RI monitor, and L-6000 manufactured by Hitachi Ltd. was used as the pump.
Embedded image
<Example 4>
20 g (0.0386 mol) of the phenol derivative represented by the formula (11a ″) obtained in Example 2 was weighed into a separable flask, 10-fold molar amount of dimethyl sulfoxide (DMSO) was added, and the mixture was stirred. While heating at about 70 ° C. Under the same conditions as in Example 3, the progress of the reaction was followed by GPC, and after the completion of the reaction was confirmed, the reaction product was reprecipitated and recovered with distilled water. As a result, a phenol derivative represented by the following formula (1a ″) in which R 2 and R 3 in the general formula (1a) are phenylene groups was obtained.
Embedded image
[Application to adhesives]
<Example 5>
(Synthesis of polyimide resin)
Into a 1 liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a drying tube was placed 41.0 g (0.10 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane. In a nitrogen stream, 250 g of NMP (N-methylpyrrolidone) was added to prepare a solution. The flask was transferred to a water bath, and 41.0 g (0.10 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little with vigorous stirring. When the acid dianhydride was almost dissolved, the mixture was reacted for 6 hours with slow stirring to obtain a polyamide solution.
[0048]
Next, a distillation apparatus was attached to the four-necked flask containing the polyamide solution, and 220 g of xylene was added. Condensed water produced by imidization was distilled off azeotropically with xylene while stirring vigorously on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain a polyimide resin.
[0049]
(Varnish formulation)
A polyimide varnish was prepared by blending 500 parts by weight of DMAc (dimethylacetamide) and 200 parts by weight of TCG-1 (filler) with respect to 100 parts by weight of the obtained polyimide resin. 5 parts by weight of the obtained phenol derivative represented by the formula (1a ′) was blended.
[0050]
(Creation of adhesive film)
The above varnish is applied on a polypropylene film substrate to a thickness of 30-50 μm, dried at 80 ° C. for 10 minutes, then at 150 ° C. for 30 minutes, cooled at room temperature, and then the dried product is peeled off from the substrate. To obtain an adhesive film.
[0051]
<Comparative Example 1>
An adhesive film was obtained in the same manner as in Example 5 except that the phenol derivative represented by the formula (1a ′) was not added.
[0052]
(Evaluation of adhesive film)
For the adhesive films of Example 5 and Comparative Example 1, peel strength (peeling strength) was measured. That is, the adhesive film is cut into a size of 5 mm × 5 mm, sandwiched between a 5 mm × 5 mm silicon chip and a copper lead frame, applied with a weight of 1 kg, and pressed at 180 ° C. or 250 ° C. The adhesive film was cured by heating at 180 ° C. for 1 hour. And the peeling strength at the time of 245 degreeC or 275 degreeC and 20 second heating was measured with the push pull gauge. The measurement results are shown in Table 1.
[Table 1]
[Application to sealing materials]
<Example 6>
(Example 6-1)
The cresol novolac epoxy resin (epoxy equivalent 215) was 19% by weight, the novolac type phenolic resin (phenol equivalent 107) was 9% by weight, and the phenol derivative represented by the formula (1a ′) obtained in Example 3 was 0.2%. These were mixed at room temperature so that the content was 71.2% by weight, the fused silica powder was 71.2% by weight, the curing accelerator was 0.3% by weight, and the ester wax was 0.3% by weight. After being kneaded in the above, the mixture was cooled and pulverized to produce a molding material.
[0054]
(Example 6-2)
The cresol novolac epoxy resin (epoxy equivalent 215) was 19% by weight, the novolac type phenolic resin (phenol equivalent 107) was 9% by weight, and the phenol derivative represented by the formula (1a ″) obtained in Example 4 was 0. Mixing in the same manner as in Example 6-1 so that 2% by weight, fused silica powder was 71.2% by weight, the curing accelerator was 0.3% by weight, and the ester wax was 0.3% by weight. Thereafter, kneading and pulverization were performed to produce a molding material.
[0055]
(Comparative Example 2)
A molding material was produced in the same manner as in Example 6-1 except that the phenol derivative represented by the formula (1a ′) was not used (the ratio of materials other than the phenol derivative was the same as in Example 6-1). .
[0056]
(Evaluation of adhesive strength)
The molding materials of Examples 6-1 and 6-2 and Comparative Example 2 were transfer-injected into a mold heated to 170 ° C., and a molded article having an adhesion area of 4 mm 2 was Pd or Pd-Au pre-plated base material After molding on top and leaving at 175 ° C. for 8 hours, the shear bond strength was determined.
[0057]
(Evaluation of moisture resistance)
Using the molding materials of Examples 6-1 and 6-2 and Comparative Example 2, a silicon chip (test element) having two or more aluminum wirings was adhered to a Pd preplating frame and 175 ° C. for 2 minutes. A molded product was produced by transfer molding, and post-curing was performed at 175 ° C. for 8 hours. The obtained molded article was subjected to moisture absorption treatment at 40 ° C. and 90% RH for 100 hours, and passed through an IR reflow furnace having a maximum temperature of 240 ° C. four times. Thereafter, a PCT test was performed in saturated steam at 127 ° C. and 2.5 atm, and disconnection due to corrosion of aluminum was regarded as defective. The PCT test was performed with 20 molded products, and the number of defective products after 100 hours, 300 hours, and 500 hours was examined.
[0058]
The above results are summarized in Table 2. The numerical values in the column of moisture resistance in Table 2 indicate the number of defective products / number of molded products.
[Table 2]
【The invention's effect】
As described above, according to the present invention, it can be used as an additive to a resin such as a thermosetting resin or a photosensitive resin, and the resin after the addition is gold, silver, copper, palladium, a gold-palladium alloy, It is possible to provide a compound capable of imparting a high adhesive force to a substrate coated with silicon nitride or the like and improving the moisture resistance of the bonded product after bonding. Such a compound can be used as an additive useful for semiconductor packaging technology.
Claims (10)
下記一般式（２１）又は一般式（２２）で表されるフェノール化合物と、下記一般式（３１）で表されるジチオールと、を反応させることを特徴とする方法。
A method comprising reacting a phenol compound represented by the following general formula (21) or general formula (22) with a dithiol represented by the following general formula (31).
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