JP2013189548A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP2013189548A JP2013189548A JP2012056624A JP2012056624A JP2013189548A JP 2013189548 A JP2013189548 A JP 2013189548A JP 2012056624 A JP2012056624 A JP 2012056624A JP 2012056624 A JP2012056624 A JP 2012056624A JP 2013189548 A JP2013189548 A JP 2013189548A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- component
- parts
- mass
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 83
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 10
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 10
- 239000011029 spinel Substances 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000002216 antistatic agent Substances 0.000 claims abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 239000004065 semiconductor Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000005022 packaging material Substances 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 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 15
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000049 pigment Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- -1 black Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 2
- 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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- DRPJWBIHQOHLND-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]oxybutyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)OCCCCOC(=O)C(C)=C DRPJWBIHQOHLND-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- GOYGTBXFJBGGLI-UHFFFAOYSA-N 7a-but-1-enyl-3a-methyl-4,5-dihydro-2-benzofuran-1,3-dione Chemical compound C1=CCCC2(C)C(=O)OC(=O)C21C=CCC GOYGTBXFJBGGLI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 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
- 238000013007 heat curing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、樹脂組成物に関し、詳しくは、電子部品用絶縁材料に適した樹脂組成物、特に、チップ抵抗器用保護膜等の受動部品用外装材や半導体用封止剤に適した樹脂組成物に関する。 The present invention relates to a resin composition, and in particular, a resin composition suitable for an insulating material for electronic parts, particularly a resin composition suitable for a packaging material for passive parts such as a protective film for chip resistors and a sealing agent for semiconductors. About.
チップ抵抗器用保護膜等の受動部品用外装材や半導体用封止剤に使用される電子部品用絶縁材料には、樹脂組成物が使用される場合が多い。しかし、使用される用途によっては、樹脂組成物の帯電が問題となる場合がある。 Resin compositions are often used for insulating materials for electronic components used for packaging materials for passive components such as protective films for chip resistors and sealants for semiconductors. However, depending on the application used, charging of the resin composition may be a problem.
ここで、受動部品用外装材や半導体用封止剤に使用される電子部品用絶縁材料としての特性を保持しながら、樹脂組成物に導電性を付与し、帯電性を低減させる方法として、カーボンブラックや金属繊維または金属粉等の導電性物質を配合する方法が知られている（特許文献１）。 Here, carbon is used as a method for imparting conductivity to the resin composition and reducing the chargeability while maintaining the characteristics as an insulating material for electronic components used for exterior materials for passive components and sealants for semiconductors. A method of blending a conductive material such as black, metal fiber, or metal powder is known (Patent Document 1).
しかしながら、カーボンブラックを用いて、樹脂組成物に導電性を付与し、樹脂組成物の帯電性を低減させるためには、樹脂組成物に多量のカーボンブラックを添加しなければならず、樹脂組成物の流動性が損なわれるため、印刷作業性や塗装作業性が悪くなる。また、金属繊維または金属粉を用いて樹脂組成物の帯電性を低減させようとすると、少量の配合で十分な効果が得られる反面、配合割合の少量の変化により絶縁抵抗率が大きく変化するため、配合する際の計量に厳しい管理が必要となる。また、配合量が少ないため、均一分散することが難しい。さらに、一般的に他の方法に比べて高コストになってしまう。また、絶縁材料にこのような導電物を配合することは、局部的に塗膜の絶縁性を損ねることとなり、電子部品用絶縁材料としての機能を損なうことになる。 However, in order to impart conductivity to the resin composition using carbon black and reduce the chargeability of the resin composition, a large amount of carbon black must be added to the resin composition. Therefore, the printing workability and the painting workability are deteriorated. In addition, when trying to reduce the chargeability of the resin composition using metal fibers or metal powder, a sufficient effect can be obtained with a small amount of blending, but the insulation resistivity changes greatly due to a small amount of blending proportion. Strict management is required for weighing when blending. Moreover, since there are few compounding quantities, it is difficult to carry out uniform dispersion. In addition, it is generally more expensive than other methods. Further, when such a conductive material is blended in the insulating material, the insulating properties of the coating film are locally impaired, and the function as an insulating material for electronic parts is impaired.
一方、受動部品用外装材や半導体用封止剤に使用される電子部品用絶縁材料には、美観の向上や内部構造の隠蔽や電子部品への紫外線照射の抑制などのために、着色剤を添加する場合があるが、着色剤を添加した樹脂組成物で、帯電性について言及した文献は報告されていない。 On the other hand, in insulating materials for electronic parts used for packaging materials for passive parts and encapsulants for semiconductors, coloring agents are used to improve aesthetics, conceal internal structures, and suppress ultraviolet irradiation on electronic parts. There is a case where it is added, but there is no report on a resin composition to which a coloring agent is added and mentions charging property.
本発明は、電子部品用絶縁材料に使用可能な樹脂組成物を、印刷作業性や塗装作業性を維持しつつ、帯電性を抑制することを目的とする。本発明者らは、樹脂組成物に、特定の着色顔料を添加して、絶縁性を調整することにより、帯電しにくい樹脂組成物が得られることを見出した。 An object of the present invention is to suppress chargeability of a resin composition that can be used for an insulating material for electronic parts while maintaining printing workability and painting workability. The present inventors have found that a resin composition that is difficult to be charged can be obtained by adding a specific color pigment to the resin composition to adjust the insulation.
本発明は、以下の構成を有することによって上記問題を解決した樹脂組成物に関する。
〔１〕（Ａ）エポキシ樹脂、（Ｂ）硬化剤、および（Ｃ）化学式：Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４で表され、スピネル構造である帯電防止剤を含むことを特徴とする、樹脂組成物。
〔２〕さらに、（Ｄ）溶剤を含む、上記〔１〕記載の樹脂組成物。
〔３〕さらに、（Ｅ）フィラーを含む、上記〔１〕または〔２〕記載の樹脂組成物
〔４〕（Ｄ）成分が、高沸点溶剤である、上記〔１〕〜〔３〕のいずれか記載の樹脂組成物。
〔５〕さらに、（Ｆ）カップリング剤を含む、上記〔１〕〜〔４〕のいずれか記載の樹脂組成物。
〔６〕さらに、（Ｇ）ゴム添加物を含む、上記〔１〕〜〔５〕のいずれか記載の樹脂組成物。
〔７〕（Ｂ）成分が、アミン系硬化剤またはイミダゾール系硬化剤を含む、上記〔１〕〜〔６〕のいずれか記載の樹脂組成物。
〔８〕さらに、（Ｂ）成分が、フェノール樹脂系硬化剤を含む、上記〔１〕〜〔７〕のいずれか記載の樹脂組成物。
〔９〕（Ｃ）成分を、樹脂組成物１００質量部に対して、３〜４０質量部含有する、上記〔１〕〜〔８〕のいずれか記載の樹脂組成物。
〔１０〕上記〔１〕〜〔９〕のいずれか記載の樹脂組成物を用いる、受動部品用外装材または半導体用封止剤。
〔１１〕上記〔１０〕の受動部品用外装材または半導体用封止剤の硬化物を有する、電子部品。
This invention relates to the resin composition which solved the said problem by having the following structures.
[1] A resin comprising an antistatic agent represented by (A) an epoxy resin, (B) a curing agent, and (C) a chemical formula: Cu (Cr, Mn) 2 O 4 and having a spinel structure Composition.
[2] The resin composition according to [1], further including (D) a solvent.
[3] In addition, any of the above [1] to [3], wherein the resin composition [4] or (D) component described in [1] or [2] above containing (E) filler is a high boiling point solvent A resin composition as described above.
[5] The resin composition according to any one of [1] to [4], further including (F) a coupling agent.
[6] The resin composition according to any one of [1] to [5], further including (G) a rubber additive.
[7] The resin composition according to any one of [1] to [6], wherein the component (B) includes an amine curing agent or an imidazole curing agent.
[8] The resin composition according to any one of [1] to [7], wherein the component (B) further comprises a phenol resin curing agent.
[9] The resin composition according to any one of [1] to [8], wherein the component (C) is contained in an amount of 3 to 40 parts by mass with respect to 100 parts by mass of the resin composition.
[10] A packaging material for passive parts or a sealing agent for semiconductors using the resin composition according to any one of [1] to [9].
[11] An electronic component having a cured product of the packaging material for passive components or the semiconductor sealant according to [10] above.
本発明〔１〕によれば、印刷作業性や塗装作業性を維持しつつ、帯電性を抑制した樹脂組成物を提供することができる。 According to the present invention [1], it is possible to provide a resin composition in which charging performance is suppressed while maintaining printing workability and painting workability.
本発明〔１０〕によれば、帯電性が抑制された受動部品用外装材または半導体用封止剤を提供することができる。 According to the present invention [10], it is possible to provide a packaging material for passive parts or a sealing agent for semiconductors in which chargeability is suppressed.
本発明の樹脂組成物は、（Ａ）エポキシ樹脂、（Ｂ）硬化剤、および（Ｃ）化学式：Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４で表され、スピネル構造である帯電防止剤含むことを特徴とする。この樹脂組成物は、印刷作業性や塗装作業性の観点から、液状であると好ましい。 The resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, and (C) a chemical formula: Cu (Cr, Mn) 2 O 4 and an antistatic agent having a spinel structure. And This resin composition is preferably in a liquid form from the viewpoint of printing workability and coating workability.
（Ａ）成分としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、アミノフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂、アルコールエーテル型エポキシ樹脂、環状脂肪族型エポキシ樹脂、フルオレン型エポキシ樹脂、シロキサン系エポキシ樹脂等が挙げられ、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、アミノフェノール型エポキシ樹脂、シロキサン系エポキシ樹脂が、硬化性、耐熱性、接着性、耐久性の観点から好ましい。市販品としては、三菱化学製ビスフェノールＡ型エポキシ樹脂（品名：ＪＥＲ８２８、エピコート１００１、エピコート１００４）、旭化成イーマテリアルズ製ビスフェノールＡ型エポキシ樹脂（品名：ＡＥＲ２６０、６００４）、ＤＩＣ製ビスフェノールＡ型エポキシ樹脂（品名：ＥＰＩＣＬＯＮ８５０、１０５０、４０５０）、新日鐵化学製ビスフェノールＡ型エポキシ樹脂（品名：ＹＤＦ８１７０）、新日鐵化学製ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８７０ＧＳ）、三菱化学製アミノフェノール型エポキシ樹脂（グレード：ＪＥＲ６３０、ＪＥＲ６３０ＬＳＤ）、ＤＩＣ製ナフタレン型エポキシ樹脂（品名：ＨＰ４０３２Ｄ）、信越化学製シロキサン系エポキシ樹脂（品名：ＴＳＬ９９０６）等が挙げられ、これら品名に限定されるものではない。（Ａ）成分は、単独でも２種以上を併用してもよい。 As the component (A), bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, aminophenol type epoxy resin, hydrogenated bisphenol type epoxy resin, fat Cyclic epoxy resin, alcohol ether type epoxy resin, cycloaliphatic type epoxy resin, fluorene type epoxy resin, siloxane type epoxy resin, and the like. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin, Siloxane-based epoxy resins are preferred from the viewpoints of curability, heat resistance, adhesion, and durability. Commercially available products include bisphenol A type epoxy resin (product name: JER828, Epicoat 1001, Epicoat 1004) manufactured by Mitsubishi Chemical, bisphenol A type epoxy resin manufactured by Asahi Kasei E-Materials (product name: AER260, 6004), and bisphenol A type epoxy resin manufactured by DIC. (Product name: EPICLON 850, 1050, 4050), Nippon Steel Chemical's bisphenol A type epoxy resin (Product name: YDF8170), Nippon Steel Chemical's bisphenol F type epoxy resin (Product name: YDF870GS), Mitsubishi Chemical's aminophenol type epoxy resin (Grade: JER630, JER630LSD), DIC naphthalene type epoxy resin (product name: HP4032D), Shin-Etsu Chemical siloxane-based epoxy resin (product name: TSL9906), etc. Not intended to be constant. (A) A component may be individual or may use 2 or more types together.
（Ｂ）成分は、アミン系硬化剤、イミダゾール系硬化剤、フェノール樹脂系硬化剤、酸無水物が挙げられ、スクリーン印刷用途については、吸湿により変質する酸無水物系硬化剤は、好ましくない。アミン系硬化剤としては、鎖状脂肪族アミン、環状脂肪族アミン、脂肪芳香族アミン、芳香族アミンが挙げられ、芳香族アミン、ジシアンジアミド、が好ましい。ここで、フェノール樹脂系硬化剤とは、１分子中に上記（Ａ）成分のエポキシ基と反応し得るフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般をいう。フェノール樹脂系硬化剤としては、例えば、レゾール型フェノール樹脂、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡ型ノボッラク樹脂、トリアジン変性フェノールノボラック樹脂等が挙げられ、硬化性の観点から、レゾール型フェノール樹脂が好ましい。酸無水物としては、メチルテトラヒドロフタル酸無水物、メチルブテニルテトラヒドロフタル酸無水物等が挙げられる。イミダゾール系硬化剤としては、ビスマレイミドトリアジン樹脂（ＢＴレジン）が挙げられる。市販品としては、四国化成工業製アミン系硬化剤（品名：キュアゾール２Ｅ４ＭＺ）、日本化薬製アミン硬化剤（品名：カヤハードＡ−Ａ）、群栄化学製フェノール樹脂（品名：レヂトップＰＬ２２０５）、三菱ガス化学製フェノール樹脂（品名：ニカノールＰＲ１４４０Ｍ）、三菱化学製酸無水物（グレード：ＹＨ３０６、ＹＨ３０７）、三菱ガス化学製ＢＴレジン（品名：ＢＴ２１００Ｂ、ＢＴ２１７０）、等が挙げられ、これら品名に限定されるものではない。（Ｂ）成分は、単独でも２種以上を併用してもよい。 Examples of the component (B) include amine-based curing agents, imidazole-based curing agents, phenol resin-based curing agents, and acid anhydrides. For screen printing applications, acid anhydride-based curing agents that are altered by moisture absorption are not preferable. Examples of amine-based curing agents include chain aliphatic amines, cycloaliphatic amines, aliphatic aromatic amines, and aromatic amines, with aromatic amines and dicyandiamide being preferred. Here, the phenol resin-based curing agent refers to all monomers, oligomers, and polymers having two or more phenolic hydroxyl groups capable of reacting with the epoxy group of the component (A) in one molecule. Examples of the phenol resin-based curing agent include a resol type phenol resin, a phenol novolak resin, a cresol novolak resin, a bisphenol A type novolak resin, a triazine-modified phenol novolak resin, and the like. preferable. Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, and the like. Examples of the imidazole curing agent include bismaleimide triazine resin (BT resin). Commercially available products include amine curing agents (product name: Curesol 2E4MZ) manufactured by Shikoku Kasei Kogyo Co., Ltd., amine curing agents manufactured by Nippon Kayaku (product name: Kayahard A-A), phenol resins manufactured by Gunei Chemicals (product name: Resitop PL2205), Mitsubishi. Gas chemical phenol resins (product name: Nikanol PR1440M), Mitsubishi Chemical acid anhydrides (grade: YH306, YH307), Mitsubishi Gas Chemical BT resin (product names: BT2100B, BT2170), etc. It is not something. (B) A component may be individual or may use 2 or more types together.
（Ｃ）成分は、化学式：Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４で表され、スピネル構造である帯電防止剤であり、樹脂組成物を着色し、かつ絶縁抵抗を低減し、帯電性を抑制する。スピネル構造は、一般に、式：ＡＢ２Ｏ４で表され、（Ｃ）成分は、ＡサイトにＣｕが、ＢサイトにＣｒまたはＭｎが一定の割合で入っている、と考えられる。図１に、化学式：Ｃｕ（Ｃｒ，Ｍｎ）２Ｏ４のスピネル構造の模式図を示す。ここで、スピネル構造であることの確認は、Ｘ線回折で行う。また、Ｃｕ、Ｃｒ、Ｍｎ、Ｏの定量分析は、エネルギー分散型Ｘ線分析装置で行う。なお、（Ｃ）成分は、Ｃｕ、Ｃｒ、Ｍｎ、Ｏが、正確に「１：１：１：４」の比でなくても、スピネル構造を保持できる比であれば、よい。また、（Ｃ）成分は、Ｃ．Ｉ． ＧＮ．がＢｌａｃｋ２８で表される顔料であり、市販品としては、東罐マテリアル・テクノロジー製顔料（品名：４２−３０２Ａ、４２−３０３Ａ、４２−３０３Ｂ、４２−３０７Ａ）、アサヒ化成工業製顔料、（品名：ブラック ３０３１）等が挙げられ、これら品名に限定されるものではない。（Ｃ）成分は、吸油量が１５±２ｃｍ３／１００ｇ、見掛け比容が２．２±０．４ｃｍ３／ｇ、ｐＨが５．０±１．０、平均粒子径が０．５〜３．０μｍであると、好ましい。ここで、（Ｃ）成分の平均粒径は、動的光散乱式ナノトラック粒度分析計により測定する。（Ｃ）成分は、単独でも２種以上を併用してもよい。 The component (C) is an antistatic agent represented by the chemical formula: Cu (Cr, Mn) 2 O 4 and having a spinel structure, coloring the resin composition, reducing the insulation resistance, and suppressing the charging property. . The spinel structure is generally represented by the formula: AB 2 O 4 , and the component (C) is considered to contain Cu at the A site and Cr or Mn at the B site at a certain ratio. FIG. 1 shows a schematic diagram of a spinel structure of the chemical formula: Cu (Cr, Mn) 2 O 4 . Here, confirmation of the spinel structure is performed by X-ray diffraction. The quantitative analysis of Cu, Cr, Mn, and O is performed with an energy dispersive X-ray analyzer. The component (C) may be any ratio as long as the ratio of Cu, Cr, Mn, and O can maintain the spinel structure even if the ratio is not exactly 1: 1: 1: 4. The component (C) is C.I. I. GN. Is a pigment represented by Black 28, and commercially available pigments (product names: 42-302A, 42-303A, 42-303B, 42-307A), Asahi Kasei Kogyo pigments (product names) : Black 3031), and the like, and are not limited to these product names. Component (C), oil absorption 15 ± 2cm 3 / 100g, apparent specific volume is 2.2 ± 0.4cm 3 / g, pH is 5.0 ± 1.0, an average particle diameter of 0.5 to 3 .Mu.m is preferable. Here, the average particle diameter of the component (C) is measured by a dynamic light scattering nanotrack particle size analyzer. (C) A component may be individual or may use 2 or more types together.
樹脂組成物は、良好な反応性、信頼性の観点から、（Ａ）成分のエポキシ樹脂１００質量部に対して、（Ｂ）成分のアミン系硬化剤、フェノール樹脂等質量部が、好ましくは０．１〜２００であり、より好ましくは０．１〜１５０である。 From the viewpoint of good reactivity and reliability, the resin composition preferably has 0 parts by mass of the amine curing agent, phenolic resin, etc. of the (B) component with respect to 100 parts by mass of the epoxy resin of the (A) component. 0.1 to 200, and more preferably 0.1 to 150.
（Ｃ）成分は、着色性、帯電性抑制の観点から、樹脂組成物：１００質量部に対して、３〜５０質量部含有すると好ましく、３〜４０質量部であると、より好ましい。 The component (C) is preferably contained in an amount of 3 to 50 parts by mass and more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of colorability and chargeability suppression.
また、（Ｃ）成分は、着色性、帯電性抑制の観点から、樹脂組成物の硬化物：１００質量部に対して、３〜６０質量部含有すると好ましく、５〜５０質量部であると、より好ましい。 In addition, the component (C) is preferably contained in an amount of 3 to 60 parts by mass, and 5 to 50 parts by mass with respect to 100 parts by mass of the cured product of the resin composition, from the viewpoint of colorability and chargeability suppression. More preferred.
樹脂組成物は、さらに、（Ｄ）溶剤を含有すると、樹脂組成物をスクリーン印刷等での塗布に適した粘度に調整できるため好ましく、沸点が１５０℃以上の高沸点溶剤であると、印刷中に樹脂組成物から揮発しにくいため、より好ましく、カルビトール（沸点：２００℃）、ブチルカルビトール（沸点：２３０℃）、ブチルカルビトールアセテート（沸点：２４７℃）、トリエチレングリコール（沸点：２８７℃）が、さらに好ましい。また、（Ｄ）成分は、これら品名に限定されるものではない。（Ｄ）成分は、単独でも２種以上を併用してもよい。 When the resin composition further contains (D) a solvent, the resin composition can be adjusted to a viscosity suitable for application in screen printing or the like, and is preferably a high boiling solvent having a boiling point of 150 ° C. or higher. It is more preferable that carbitol (boiling point: 200 ° C.), butyl carbitol (boiling point: 230 ° C.), butyl carbitol acetate (boiling point: 247 ° C.), triethylene glycol (boiling point: 287). Is more preferred. Moreover, (D) component is not limited to these product names. (D) A component may be individual or may use 2 or more types together.
樹脂組成物は、さらに、（Ｅ）成分であるフィラーを含有すると、ヒートサイクル時等の応力緩和、密着性の観点から、好ましい。（Ｅ）成分としては、コロイダルシリカ、疎水性シリカ、球状シリカ等のシリカ、タルク等が挙げられ、球状シリカが、塗布時の流動性の観点から、より好ましい。（Ｅ）成分は、平均粒径：０．０１〜２０μｍのシリカが、より好ましく、平均粒径：０．０２〜１０μｍのシリカがさらに好ましい。市販品としては、アドマテックス製球状シリカ（品名：ＳＯ−Ｅ２）が挙げられるが、この品名に限定されるものではない。ここで、（Ｅ）成分の平均粒径は、動的光散乱式ナノトラック粒度分析計により測定する。（Ｅ）成分は、単独でも２種以上を併用してもよい。 If the resin composition further contains a filler as the component (E), it is preferable from the viewpoints of stress relaxation during heat cycle and adhesion. Examples of the component (E) include colloidal silica, hydrophobic silica, silica such as spherical silica, talc, and the like, and spherical silica is more preferable from the viewpoint of fluidity during coating. Component (E) is more preferably silica having an average particle size of 0.01 to 20 μm, and further preferably silica having an average particle size of 0.02 to 10 μm. Commercially available products include Admatex spherical silica (product name: SO-E2), but are not limited to this product name. Here, the average particle diameter of the component (E) is measured by a dynamic light scattering nanotrack particle size analyzer. (E) A component may be individual or may use 2 or more types together.
樹脂組成物は、さらに、（Ｆ）成分であるカップリング剤を含有すると、密着性の観点から好ましく、（Ｆ）成分としては、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３−イソシアネートプロピルトリエトキシシラン等が挙げられ、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシランが、密着性の観点から好ましい。市販品としては、信越化学工業製ＫＢＭ４０３、ＫＢＥ９０３、ＫＢＥ９１０３等が挙げられるが、これらの品名に限定されるものではない。（Ｆ）成分は、単独でも２種以上を併用してもよい。 When the resin composition further contains a coupling agent as component (F), it is preferable from the viewpoint of adhesion, and as component (F), 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxy are preferable. Silane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like can be mentioned, and 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane are preferable from the viewpoint of adhesion. Examples of commercially available products include KBM403, KBE903, and KBE9103 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these product names. (F) A component may be individual or may use 2 or more types together.
樹脂組成物は、さらに、（Ｇ）成分であるゴム添加物を含有すると、樹脂組成物の応力緩和の観点から好ましく、（Ｇ）成分としては、アクリルゴム、ウレタンゴム、シリコーンゴム、ブタジエンゴムが挙げられる。（Ｇ）成分は、固体のものを使用することができる。形態は特に限定されず、例えば粒子状、粉末状、ペレット状のものを使用することができ、粒子状の場合は、例えば、平均粒径が、０．０１〜２０μｍ、好ましくは０．０２〜１０μｍ、より好ましくは、０．０３〜５μｍである。（Ｇ）成分は、常温で液状のものも使用することもでき、例えば、平均分子量が比較的低いポリブタジエン、ブタジエン・アクリロニトリルコポリマー、ポリイソプレン、ポリプロピレンオキシド、ポリジオルガノシロキサンが挙げられる。また、（Ｇ）成分は、末端にエポキシ基と反応する基を有するものを使用することができ、これらは固体、液状いずれの形態であってもよい。市販品としては、宇部興産製ＣＴＢＮ１３００、ＡＴＢＮ１３００−１６、ＣＴＢＮ１００８−ＳＰ、東レ・ダウコーニング製シリコーンゴムパウダー（品名：ＡＹ）等が挙げられる。また、（Ｇ）成分は、これら品名に限定されるものではない。（Ｇ）成分は、単独でも２種以上を併用してもよい。 When the resin composition further contains a rubber additive as the component (G), it is preferable from the viewpoint of stress relaxation of the resin composition. As the component (G), acrylic rubber, urethane rubber, silicone rubber, and butadiene rubber are preferable. Can be mentioned. (G) A solid thing can be used for a component. The form is not particularly limited, and for example, particles, powders, and pellets can be used. In the case of particles, for example, the average particle diameter is 0.01 to 20 μm, preferably 0.02 to 0.02 μm. The thickness is 10 μm, more preferably 0.03 to 5 μm. The component (G) can also be used at room temperature, and examples thereof include polybutadiene, butadiene / acrylonitrile copolymer, polyisoprene, polypropylene oxide, and polydiorganosiloxane having a relatively low average molecular weight. Moreover, what has a group which reacts with an epoxy group at the terminal can be used for (G) component, These may be a solid or liquid form. Commercially available products include Ube Industries' CTBN1300, ATBN1300-16, CTBN1008-SP, Toray Dow Corning silicone rubber powder (product name: AY), and the like. Moreover, (G) component is not limited to these product names. (G) A component may be individual or may use 2 or more types together.
（Ｄ）成分は、樹脂組成物にスクリーン印刷等に適した粘性を付与する観点から、樹脂組成物１００質量部に対して、１〜５０質量部含有すると好ましく、１〜４０質量部であるとより好ましい。 (D) It is preferable to contain 1-50 mass parts with respect to 100 mass parts of resin compositions from a viewpoint of providing the viscosity suitable for screen printing etc. to a resin composition, and it is 1-40 mass parts. More preferred.
（Ｅ）成分は、樹脂組成物：１００質量部に対して、好ましくは０．１〜９０質量部、より好ましくは０．５〜４０質量部、さらに好ましくは１〜３０質量部含有される。１〜３０質量部であると、線膨張係数の上昇を抑制しながら注入性の悪化をさけることができる。 The component (E) is preferably 0.1 to 90 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin composition. When the content is 1 to 30 parts by mass, deterioration of injectability can be avoided while suppressing an increase in linear expansion coefficient.
（Ｆ）成分は、樹脂組成物：１００質量部に対して、好ましくは０．０５〜１５質量部、より好ましくは０．１〜１０質量部含有される。０．０５質量部以上であると、密着性が向上し、ＰＣＴ試験での耐湿信頼性がより良好になり、１５質量部以下であると、樹脂組成物の発泡が抑制される。 The component (F) is preferably contained in an amount of 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition. Adhesiveness improves that it is 0.05 mass part or more, moisture resistance reliability in a PCT test becomes more favorable, and foaming of a resin composition is suppressed as it is 15 mass parts or less.
（Ｇ）成分は、樹脂組成物：１００質量部に対して、好ましくは０．１〜３０質量部、より好ましくは０．５〜２５質量部、さらに好ましくは１〜２０質量部含有される。０．１質量部以上であると、樹脂組成物の応力を緩和し、３０質量部以下であると耐湿信頼性が低下しない。 The component (G) is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and further preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin composition. When it is 0.1 part by mass or more, the stress of the resin composition is relieved, and when it is 30 parts by mass or less, moisture resistance reliability is not lowered.
樹脂組成物は、さらに、硬化促進剤を含有すると、適切な硬化性が得られるので好ましく、硬化促進剤は、エポキシ樹脂の硬化促進剤であれば、特に限定されず、公知のものを使用することができる。例えば、アミン系硬化促進剤等が挙げられる。 When the resin composition further contains a curing accelerator, it is preferable because appropriate curability can be obtained. The curing accelerator is not particularly limited as long as it is an epoxy resin curing accelerator, and a known one is used. be able to. For example, an amine hardening accelerator etc. are mentioned.
アミン系硬化促進剤としては、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール等のイミダゾール化合物、２，４−ジアミノ−６−〔２’―メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジン等のトリアジン化合物、１，８−ジアザビシクロ［５，４，０］ウンデセン−７（ＤＢＵ）、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン等の第三級アミン化合物が挙げられる。中でも、２，４−ジアミノ−６−〔２’―メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジン、２−フェニル−４−メチルイミダゾールが好ましい。硬化促進剤は、単独でも２種以上を併用してもよい。なお、（Ｂ）成分に酸無水物系硬化剤を使用する場合には、硬化性、保存安定性の点から、アミン系硬化促進剤を使用することが好ましい。 Examples of amine-based curing accelerators include imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Compounds, triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) And tertiary amine compounds such as triethylenediamine, benzyldimethylamine, and triethanolamine. Of these, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine and 2-phenyl-4-methylimidazole are preferable. A hardening accelerator may be individual or may use 2 or more types together. In addition, when using an acid anhydride type hardening | curing agent for (B) component, it is preferable to use an amine hardening accelerator from the point of sclerosis | hardenability and storage stability.
また、硬化促進剤は、エポキシ樹脂等でアダクトされたアダクト型であっても、マイクロカプセル型であってもよい。 Further, the curing accelerator may be an adduct type adducted with an epoxy resin or the like, or may be a microcapsule type.
硬化促進剤は、樹脂組成物：１００質量部に対して、好ましくは０．０１質量部より多く５質量部未満、より好ましくは０．０５〜４質量部、さらに好ましくは０．１〜３．０質量部含有される。０．０１質量部以上であると、反応性が良好であり、５質量部以下であると、耐湿信頼性が良好あり、更に保存安定性が良好である。 The curing accelerator is preferably more than 0.01 parts by weight and less than 5 parts by weight, more preferably 0.05 to 4 parts by weight, and still more preferably 0.1 to 3. parts by weight with respect to 100 parts by weight of the resin composition. 0 parts by mass is contained. When it is 0.01 part by mass or more, the reactivity is good, and when it is 5 parts by mass or less, the moisture resistance reliability is good and the storage stability is also good.
本発明の樹脂組成物には、本発明の目的を損なわない範囲で、更に必要に応じ、染料、消泡剤、酸化防止剤、応力緩和剤、揺変剤、その他の添加剤等を配合することができる。 In the resin composition of the present invention, a dye, an antifoaming agent, an antioxidant, a stress relaxation agent, a thixotropic agent, other additives, and the like are further blended as necessary without departing from the object of the present invention. be able to.
本発明の樹脂組成物は、例えば、（Ａ）成分〜（Ｃ）成分およびその他添加剤等を同時にまたは別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、デゾルバー、ライカイ機、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 The resin composition of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (C) and other additives simultaneously or separately, with heat treatment as necessary. Can do. The apparatus for mixing, stirring, dispersing, etc. is not particularly limited, but a dissolver, a reiki machine, a three roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. Moreover, you may use combining these apparatuses suitably.
本発明の樹脂組成物は、温度：２５℃での粘度が２０〜１４０Ｐａ・ｓであると、印刷性の観点から好ましい。ここで、粘度は、ブルックフィールド社製ＨＢＴ型粘度計（型番：ＤＶ−１）で測定する。 The resin composition of this invention is preferable from a printable viewpoint that the viscosity in temperature: 25 degreeC is 20-140 Pa.s. Here, the viscosity is measured with a Brookfield HBT viscometer (model number: DV-1).
本発明の樹脂組成物は、スクリーン印刷やロール転写やディッピングやディスペンス等により被着体へ塗布することができる。 The resin composition of the present invention can be applied to an adherend by screen printing, roll transfer, dipping, dispensing, or the like.
本発明の樹脂組成物は、加熱硬化により、チップ抵抗器用保護膜等の受動部品用外装材や半導体封止剤として形成することができる。硬化条件は、硬化剤により必要に応じて調整ができる。また、硬化または乾燥により溶剤を揮発させ、タックフリーにすることで、樹脂組成物や他の樹脂組成物等を重ねて塗布、形成することも可能である。なお、樹脂組成物の硬化は、８０〜２６０℃、好ましくは１２０〜２４０℃で、１０〜１２０分間、好ましくは２０〜４０分間行うことが、硬化物の物性の安定性の観点から好ましい。 The resin composition of the present invention can be formed as a packaging material for passive components such as a protective film for chip resistors or a semiconductor encapsulant by heat curing. The curing conditions can be adjusted as necessary by the curing agent. Moreover, it is also possible to apply | coat and form a resin composition, another resin composition, etc. by making a solvent volatilize by hardening or drying and making it tack-free. The curing of the resin composition is preferably performed at 80 to 260 ° C., preferably 120 to 240 ° C., for 10 to 120 minutes, preferably 20 to 40 minutes, from the viewpoint of the stability of the physical properties of the cured product.
このように、本発明の樹脂組成物は、受動部品用外装材または半導体用封止剤に適しており、この受動部品用外装材または半導体用封止剤を使用した電子部品は、帯電防止抑制に優れており、高信頼性である。 Thus, the resin composition of the present invention is suitable for a passive component exterior material or a semiconductor sealant, and an electronic component using the passive component exterior material or semiconductor sealant has antistatic suppression. It is excellent in reliability.
本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。 The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.
〔実施例１〜７、比較例１〕
表１に示す配合で、樹脂組成物を作製した。（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、（Ｃ）成分のブラック３０３１を、３〜１００質量部、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、実施例１〜７、比較例１の樹脂組成物を作製した。
[Examples 1 to 7, Comparative Example 1]
A resin composition was prepared with the formulation shown in Table 1. (A) The epoxy resin of component is heated and dissolved together with the solvent of component (D) to be resin-cleared, and (A) component: 100 parts by mass of (C) component black 3031, 100 parts by mass, 6 parts by mass of imidazole as a curing agent for component (B), 65 parts by mass of silica as a filler for component (E), and 5 parts by mass of a coupling agent for component (F) were blended. These were knead | mixed with the 3 roll mill, and the resin composition of Examples 1-7 and the comparative example 1 was produced.
〔比較例２〕
（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、比較例２の樹脂組成物を作製した。
[Comparative Example 2]
The component (A) epoxy resin is dissolved by heating together with the component (D) solvent to form a resin clear. The component (A): 100 parts by mass, imidazole as the curing agent for the component (B) 6 65 parts by mass of silica and 5 parts by mass of the coupling agent of component (F) were blended as part by mass of the filler of component (E). These were knead | mixed with the 3 roll mill, and the resin composition of the comparative example 2 was produced.
〔比較例３〕
（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、着色顔料としてカーボンブラックを３質量部、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、比較例３の樹脂組成物を作製した。
[Comparative Example 3]
(A) The epoxy resin of component is heated and dissolved together with the solvent of component (D) to be resin-cleared, and (A) component: 3 parts by mass of carbon black as a coloring pigment with respect to 100 parts by mass, 6 parts by mass of imidazole as a curing agent for component B), 65 parts by mass of silica as filler for component (E), and 5 parts by mass of coupling agent for component (F) were blended. These were knead | mixed with the 3 roll mill, and the resin composition of the comparative example 3 was produced.
〔比較例４〕
（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、着色顔料としてカーボンブラックを６０質量部、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、比較例４の樹脂組成物を作製した。
[Comparative Example 4]
(A) The epoxy resin of component is heated and dissolved together with the solvent of component (D) to be resin-cleared, and (A) component: 60 parts by mass of carbon black as a coloring pigment with respect to 100 parts by mass, ( 6 parts by mass of imidazole as a curing agent for component B), 65 parts by mass of silica as filler for component (E), and 5 parts by mass of coupling agent for component (F) were blended. These were knead | mixed with the 3 roll mill, and the resin composition of the comparative example 4 was produced.
〔比較例５〕
（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、着色顔料として有機顔料を５０質量部、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、比較例５の樹脂組成物を作製した。
[Comparative Example 5]
(A) The epoxy resin of component is heated and dissolved together with the solvent of component (D) to be resin-cleared, and (A) component: 50 parts by mass of an organic pigment as a coloring pigment with respect to 100 parts by mass, ( 6 parts by mass of imidazole as a curing agent for component B), 65 parts by mass of silica as filler for component (E), and 5 parts by mass of coupling agent for component (F) were blended. These were knead | mixed with the 3 roll mill, and the resin composition of the comparative example 5 was produced.
〔比較例６〕
（Ａ）成分のエポキシ樹脂を、（Ｄ）成分の溶剤とともに加熱溶解し、樹脂クリヤー化したものに、（Ａ）成分：１００質量部に対して、着色顔料として無機顔料を５０質量部、（Ｂ）成分の硬化剤としてイミダゾールを６質量部、（Ｅ）成分のフィラーとしてシリカを６５質量部、（Ｆ）成分のカップリング剤を５質量部配合した。これらを、３本ロールミルで混練し、比較例６の樹脂組成物を作製した。
[Comparative Example 6]
(A) The epoxy resin of the component is heated and dissolved together with the solvent of the (D) component to be resin-cleared, and the component (A): 50 parts by mass of an inorganic pigment as a coloring pigment with respect to 100 parts by mass 6 parts by mass of imidazole as a curing agent for component B), 65 parts by mass of silica as filler for component (E), and 5 parts by mass of coupling agent for component (F) were blended. These were knead | mixed with the 3 roll mill, and the resin composition of the comparative example 6 was produced.
〔実施例８〜１３〕
表３に示す配合で、実施例１〜７と同様にして、樹脂組成物を作製した。
[Examples 8 to 13]
Resin compositions were prepared in the same manner as in Examples 1 to 7 with the formulation shown in Table 3.
〔評価〕
上述の実施例１〜１３、比較例１〜５により得られた樹脂組成物について、以下の評価を行った。
[Evaluation]
The following evaluation was performed about the resin composition obtained by the above-mentioned Examples 1-13 and Comparative Examples 1-5.
《体積抵抗率》
ステンレス板上に、作製した直後の樹脂組成物を、スクリーン印刷により塗布し、２００℃×３０分間加熱硬化したものを試験片とした。東亜電波工業製極超絶縁計（型番：ＳＭ−８２２０）を用いて、試験片の初期体積抵抗率を測定した。初期体積抵抗率は、１×１０１３Ω・ｃｍ以上１×１０１５Ω・ｃｍ未満であると、帯電性を抑制でき、好ましい。表１〜３に、結果を示す。なお、表中の「１．０Ｅ＋１５」は、１．０×１０１５を表す。
《Volume resistivity》
On the stainless steel plate, the resin composition immediately after the production was applied by screen printing and heat cured at 200 ° C. for 30 minutes to obtain a test piece. The initial volume resistivity of the test piece was measured using a super-insulation meter (model number: SM-8220) manufactured by Toa Denpa Kogyo. The initial volume resistivity is preferably 1 × 10 13 Ω · cm or more and less than 1 × 10 15 Ω · cm, since the chargeability can be suppressed. Tables 1 to 3 show the results. In the table, “1.0E + 15” represents 1.0 × 10 15 .
《ＰＣＴ試験後の体積抵抗率》
上述の体積抵抗率の測定で使用した試験片を、プレッシャークッカー試験器（１２１℃、２気圧、水蒸気飽和状態）へ２０時間投入した。試験片を取り出してから、直ちに、上述の極超絶縁計を用いて、体積抵抗率を測定した。表１〜３に、結果を示す。
<< Volume resistivity after PCT test >>
The test piece used in the above-described volume resistivity measurement was put into a pressure cooker tester (121 ° C., 2 atm, steam saturated state) for 20 hours. Immediately after taking out the test piece, the volume resistivity was measured using the above ultra-insulation meter. Tables 1 to 3 show the results.
《印刷作業性》
ステンレス板上に、樹脂組成物をスクリーン印刷により塗布し、印刷性を確認した。肉眼で観察し、かすれがない場合を「○」、かすれがある場合を「×」とした。表１〜３に、結果を示す。
《Printability》
On the stainless steel plate, the resin composition was applied by screen printing to confirm the printability. When observed with the naked eye, the case where there was no fading was indicated as “◯”, and the case where there was faint was indicated as “X”. Tables 1 to 3 show the results.
表１、表３からわかるように、実施例１〜１３の全てで、初期体積抵抗率が１．０×１０１３〜１．０×１０１４と良好であり、また、ＰＣＴ試験後の体積抵抗率も１．０×１０１０〜１．０×１０１４と良好であり、かつ印刷作業性も良好であった。これに対して、（Ｃ）成分が少ない比較例１、（Ｃ）成分を含有しない比較例２では、初期体積抵抗率が１．０×１０１５と高かった。（Ｃ）成分の代わりのカーボンブラックが少量の比較例３でも、初期体積抵抗率が１．０×１０１５と高かった。カーボンブラックが多量の比較例４では、かすれが発生し、印刷作業性が悪かった。（Ｃ）成分の代わりに有機顔料を用いた比較例５では、初期体積抵抗率が１．０×１０１５と高かった。 As can be seen from Tables 1 and 3, in all of Examples 1 to 13, the initial volume resistivity is good as 1.0 × 10 13 to 1.0 × 10 14, and the volume resistance after the PCT test The rate was also as good as 1.0 × 10 10 to 1.0 × 10 14 and the printing workability was also good. On the other hand, in the comparative example 1 with few (C) component and the comparative example 2 which does not contain the (C) component, initial volume resistivity was as high as 1.0 * 10 < 15 >. Even in Comparative Example 3 with a small amount of carbon black instead of the component (C), the initial volume resistivity was as high as 1.0 × 10 15 . In Comparative Example 4 with a large amount of carbon black, blurring occurred and printing workability was poor. In Comparative Example 5 using an organic pigment instead of the component (C), the initial volume resistivity was as high as 1.0 × 10 15 .
上記のように、本発明の樹脂組成物は、印刷特性が良好で、体積抵抗率が低く、帯電性を抑制することができ、チップ抵抗器用保護膜等の受動部品用外装材や半導体用封止剤に適している。 As described above, the resin composition of the present invention has good printing characteristics, low volume resistivity, can suppress chargeability, and is used as a packaging material for passive components such as a protective film for chip resistors, and a sealing for semiconductors. Suitable for stopping agent.
Claims (11)
The electronic component which has the hardened | cured material of the exterior material for passive components of Claim 10, or the sealing agent for semiconductors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012056624A JP5937855B2 (en) | 2012-03-14 | 2012-03-14 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012056624A JP5937855B2 (en) | 2012-03-14 | 2012-03-14 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013189548A true JP2013189548A (en) | 2013-09-26 |
| JP5937855B2 JP5937855B2 (en) | 2016-06-22 |
Family
ID=49390150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012056624A Active JP5937855B2 (en) | 2012-03-14 | 2012-03-14 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5937855B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018053111A (en) * | 2016-09-29 | 2018-04-05 | 株式会社ノリタケカンパニーリミテド | Thermosetting insulating composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5734150A (en) * | 1980-08-08 | 1982-02-24 | Toray Silicone Co Ltd | Organopolysiloxane resin composition |
| JPS63162730A (en) * | 1986-12-26 | 1988-07-06 | Sumitomo Bakelite Co Ltd | Production of black thermosetting resin laminate |
| JPH11181345A (en) * | 1997-12-22 | 1999-07-06 | Dainippon Toryo Co Ltd | Composition for ink jet printing |
| JP2009035728A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | Prepreg and laminate |
| JP2010229410A (en) * | 2009-03-27 | 2010-10-14 | Lanxess Deutschland Gmbh | Glow wire resistant polyester |
-
2012
- 2012-03-14 JP JP2012056624A patent/JP5937855B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5734150A (en) * | 1980-08-08 | 1982-02-24 | Toray Silicone Co Ltd | Organopolysiloxane resin composition |
| JPS63162730A (en) * | 1986-12-26 | 1988-07-06 | Sumitomo Bakelite Co Ltd | Production of black thermosetting resin laminate |
| JPH11181345A (en) * | 1997-12-22 | 1999-07-06 | Dainippon Toryo Co Ltd | Composition for ink jet printing |
| JP2009035728A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | Prepreg and laminate |
| JP2010229410A (en) * | 2009-03-27 | 2010-10-14 | Lanxess Deutschland Gmbh | Glow wire resistant polyester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018053111A (en) * | 2016-09-29 | 2018-04-05 | 株式会社ノリタケカンパニーリミテド | Thermosetting insulating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5937855B2 (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6534189B2 (en) | Resin composition | |
| TWI547520B (en) | Epoxy resin composition and semiconductor-sealing material using the same | |
| EP3279261B1 (en) | Resin composition, electroconductive resin composition, adhesive, electroconductive adhesive, paste for forming electrodes, and semiconductor device | |
| EP3184588A1 (en) | Liquid epoxy resin composition | |
| TW201531515A (en) | Flexible epoxy resin composition | |
| JP6742027B2 (en) | Resin composition | |
| JP5736122B2 (en) | Structural adhesive | |
| JP6013906B2 (en) | Liquid epoxy resin composition | |
| JP2023078194A (en) | Resin composition and cured material thereof, adhesive agent for electronic component, semiconductor device, as well as electronic component | |
| JP6420626B2 (en) | Conductive resin composition for bonding electronic components | |
| JP5937855B2 (en) | Resin composition | |
| JP2012193284A (en) | Liquid epoxy resin composition | |
| KR101373035B1 (en) | Ultrahigh heat resistant epoxy resin composition | |
| JP2012087192A (en) | Thermosetting epoxy resin composition | |
| JP5159684B2 (en) | Thermosetting resin composition | |
| JP2008248099A (en) | Liquid semiconductor encapsulating material, and semiconductor device encapsulated with the same | |
| JP5886051B2 (en) | Resin composition | |
| JP2012056979A (en) | Epoxy resin composition | |
| KR101927567B1 (en) | Resin composition | |
| JP5415334B2 (en) | Pre-feed type liquid semiconductor encapsulating resin composition | |
| JPWO2018159564A1 (en) | Resin composition | |
| JP6758051B2 (en) | Liquid epoxy resin compositions, semiconductor encapsulants, and semiconductor devices | |
| WO2012124180A1 (en) | Liquid resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150120 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151221 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160119 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160318 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160510 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160513 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5937855 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |