CN102149540B - 覆金属酚醛树脂层叠板 - Google Patents
覆金属酚醛树脂层叠板 Download PDFInfo
- Publication number
- CN102149540B CN102149540B CN200980135736.7A CN200980135736A CN102149540B CN 102149540 B CN102149540 B CN 102149540B CN 200980135736 A CN200980135736 A CN 200980135736A CN 102149540 B CN102149540 B CN 102149540B
- Authority
- CN
- China
- Prior art keywords
- phenolic resins
- resin composition
- base material
- weight
- type phenolic
- 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.)
- Expired - Fee Related
Links
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 130
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 92
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 59
- 239000011120 plywood Substances 0.000 claims description 47
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 39
- 239000011152 fibreglass Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002966 varnish Substances 0.000 claims description 27
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000007767 bonding agent Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- 239000002759 woven fabric Substances 0.000 claims description 7
- 230000007774 longterm Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 claims 6
- 238000003825 pressing Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- 229920003987 resole Polymers 0.000 abstract 2
- 239000012792 core layer Substances 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 239000003365 glass fiber Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 description 27
- 229920000647 polyepoxide Polymers 0.000 description 27
- 150000001896 cresols Chemical class 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012530 fluid Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000004080 punching Methods 0.000 description 9
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 phosphorus compound Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 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 4
- 238000012360 testing method Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- FJKVRVFGUXMMAO-UHFFFAOYSA-N (3-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 FJKVRVFGUXMMAO-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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Abstract
本发明的目的在于，提供兼具机械特性、电特性、耐漏电性的覆金属酚醛树脂层叠板。本发明的覆金属酚醛树脂层叠板的特征在于，使含有甲酚型树脂的第一酚醛树脂组合物浸渍到纸基材中而得到纸基材半固化片，仅使用一片该纸基材半固化片作为中心层状部，或重叠规定片数的该纸基材半固化片作为中心层状部，在该中心层状部的上面和下面，仅重叠一片或重叠规定片数的使含有甲酚型树脂的第二酚醛树脂组合物浸渍到玻璃纤维基材而得到的玻璃纤维基材半固化片，从而层叠外侧层状部，进而，在上述上面侧和下面侧的外侧层状部中的至少一个单面上层叠金属箔而得到层叠体，并对该层叠体加热加压而得到。
Description
技术领域
本发明涉及覆金属酚醛树脂层叠板。
背景技术
作为电子设备等所搭载的印刷电路用基板，多使用纸基材酚醛树脂层叠板。但是，此类纸基材酚醛树脂层叠板，或者使用纸基材酚醛树脂作为芯材，并由浸渍了环氧树脂的玻璃纤维基材来夹住该芯材两面而形成复合结构的层叠板(专利文献3)，在吸水率、机械强度上存在问题。
作为其替代材料，有纸基材环氧树脂层叠板，或者使用纸基材环氧树脂半固化片作为芯材，并由浸渍了环氧树脂的玻璃纤维基材来夹住该芯材两面而形成复合结构的层叠板，但是电特性，特别是作为印刷电路基板所必要的长期耐湿性和电绝缘性并不充分(专利文献1及2)。又，有时也会在高电压下使用印刷电路基板，必须防止因漏电(Tracking)所造成的火灾。但是，纸基材环氧树脂层叠板，或使用纸基材环氧树脂半固化片作为芯材，并由浸渍了环氧树脂的玻璃纤维基材来夹住该芯材两面而形成复合结构的层叠板，在实际的印刷电路基板中的耐漏电性低，存在着在电路设计上受到约束的问题，期望开发出兼具电特性、机械强度、耐漏电性(Tracking resistance)等要求的酚醛树脂层叠板。
专利文献1：日本特开昭61-255850号公报
专利文献2：日本特开昭62-56137号公报
专利文献3：日本特开昭63-39332号公报
发明内容
发明要解决的课题
本发明是鉴于上述问题而完成的，其目的在于，提供兼具电特性、机械强度、耐漏电性的酚醛树脂层叠板。
解决课题的方法
本发明通过下述(1)～(5)而达成。
(1)一种覆金属酚醛树脂层叠板，其特征在于，使含有甲酚型树脂的第一酚醛树脂组合物浸渍到纸基材中而得到纸基材半固化片，仅使用一片该纸基材半固化片作为中心层状部，或重叠规定片数的该纸基材半固化片作为中心层状部，在该中心层状部的上面和下面，仅重叠一片使含有甲酚型树脂的第二酚醛树脂组合物浸渍到玻璃纤维基材而得到的玻璃纤维基材半固化片或重叠规定片数的使含有甲酚型树脂的第二酚醛树脂组合物浸渍到玻璃纤维基材而得到的玻璃纤维基材半固化片，从而层叠外侧层状部，进而，在上述上面侧和下面侧的外侧层状部中的至少一个单面上层叠金属箔而得到层叠体，并对该层叠体加热加压而得到。
(2)如上述(1)记载的覆金属酚醛树脂层叠板，其中，上述层叠体的金属箔为附有粘接剂的金属箔，并以上述粘接剂面与上述玻璃纤维基材半固化片面相互对置的方式加以配置。
(3)如上述(1)或(2)记载的覆金属酚醛树脂层叠板，其中，上述玻璃纤维基材为玻璃织布。
(4)如上述(1)至(3)中任一项记载的覆金属酚醛树脂层叠板，其中，构成上述第一酚醛树脂涂布液的树脂组合物与构成上述第二酚醛树脂涂布液的树脂组合物为相同的树脂组合物。
(5)如上述(1)至(4)中任一项记载的覆金属酚醛树脂层叠板，其中，在60℃、相对湿度90％的环境下放置1000小时后的长期吸湿率为2重量％以下。
发明效果
根据本发明，可提供兼具机械特性、电特性、耐漏电性的覆金属酚醛树脂层叠板。
具体实施方式
以下，详细说明本发明的覆金属酚醛树脂层叠板。
本发明的覆金属酚醛树脂层叠板，是通过下述方法而形成：使调制成液状的第一酚醛树脂组合物(称为“酚醛树脂液”)浸渍到纸基材中并加以干燥而得到纸基材半固化片，仅使用一片该纸基材半固化片作为芯材(称为“中心层状部”)，或重叠规定片数的该纸基材半固化片作为芯材(称为“中心层状部”)，在该芯材(称为“中心层状部”)的上面和下面，仅重叠一片使第二酚醛树脂液浸渍到玻璃纤维基材并加以干燥而得到的玻璃纤维基材半固化片或重叠规定片数的使第二酚醛树脂液浸渍到玻璃纤维基材并加以干燥而得到的玻璃纤维基材半固化片，从而设置外侧部分(称为“外侧层状部”)，进而，在至少单面侧层叠金属箔而得到层叠体，并对该层叠体加热加压而形成。
通过在芯材(使用将酚醛树脂组合物浸渍到纸基材而成的纸基材半固化片)的上面和下面，重叠一片或规定片数的将浸酚醛树脂组合物浸渍到玻璃纤维基材而成的玻璃纤维基材半固化片，能够改善在纸基材酚醛树脂层叠板中不充分的强度、吸水性，而且能够改善在纸基材环氧树脂层叠板、或者在将纸基材环氧树脂半固化片作为芯材且从其两面用环氧树脂浸渍玻璃纤维基材夹住而成的层叠板中不充分的长期耐湿性、电绝缘性、耐漏电性。
通过在使用纸基材半固化片的芯材的上面和下面采用玻璃纤维基材，可在纸基材酚醛树脂层叠板中不充分的强度及吸水率方面得到改善效果。
更且，通过使用酚醛树脂，可在长期耐湿性及电绝缘性方面取得改善效果。虽然纸基材是吸水性比玻璃纤维基材更高的原材料，但通过将树脂浸渍到纸纤维中，可抑制其吸水特性，并且可作为层叠板使用。从吸水性优良的方面看纸基材也是亲水性，浸渍到其纸纤维内的树脂液，也优选为更具有亲水性的树脂液。若比较树脂本身的吸水特性时，则环氧树脂比酚醛树脂更优良。但是，环氧树脂液的疏水性强，即使将纸基材浸渍在其中，树脂也几乎不会浸渍到纸纤维内，但当使用酚醛树脂液时，则树脂可浸渍至纸纤维中。
其耐湿效果，在使用JIS-C6481所示的层叠板的短期间的浸水试验中，水的渗透速度慢，不明显，但在作为最终产品形态的印刷布线板所必要的长期耐湿性、和加压引起的饱和吸湿量方面，则使用酚醛树脂液时为优良，作为印刷板的电绝缘性也优良。具体而言，关于长期耐湿性，可采用印刷板的绝缘性试验中实施的通常的条件，即温度：60℃、相对湿度90％下1000小时、或温度：40℃、相对湿度90％下1000小时的条件，但在温度：60℃、相对湿度90％下1000小时的处理更为严格，可观察到更显著的差别，因而优选。当以温度：60℃、相对湿度90％下1000小时的处理中，若吸湿率为2重量％以上，则作为印刷板的绝缘性降低。优选吸湿率在1.5重量％以下。
又，漏电(Tracking)现象是指因碳化物引起短路和因发热引起起火的现象，通过将不会碳化的玻璃纤维基材重叠于由纸基材半固化片所构成的芯材的上面和下面，由此可提高耐漏电性。
层叠板的耐漏电性试验方法，一般采用UL-1410所示的方法。以本方法试验时，酚醛树脂与环氧树脂中并无明确差别，但若作成实际的印刷板，并以根据UL-1410的方法进行铜电路间的耐漏电性试验时，则使用酚醛树脂时为优良。
对用于层叠板的酚醛树脂组合物的详细组成则在后面叙述，但为了发挥冲孔性(punching quality)，使用油改性甲酚型酚醛树脂。因此，与环氧树脂相比，在较低温度下不分解而碳化的苯环浓度低且难以发生漏电。
以下，详细说明各构成。
本发明的酚醛树脂层叠板，使用将第一酚醛树脂组合物浸渍到纸基材中者作为芯材。此处所说的芯材，形成被浸渍了第二酚醛树脂组合物的玻璃纤维基材半固化片夹住的中间层。
本发明所用的第一酚醛树脂组合物和第二酚醛树脂组合物，均含有甲酚型树脂。第一酚醛树脂组合物和第二酚醛树脂组合物可为相同的树脂组合物，也可为不同的树脂组合物。此处，所谓相同的树脂组合物，意指树脂组合物的固体成分组成为相同。特别优选第一酚醛树脂组合物和第二酚醛树脂组合物不仅固体成分组成相同，且使用相同的溶剂。
第一酚醛树脂组合物和第二酚醛树脂组合物也可含有甲酚型酚醛树脂和酚醛清漆型酚醛树脂。通过含有甲酚型酚醛树脂，可提高对纸基材的浸渍性。又，可使纸基材酚醛树脂层叠板低成本化。对甲酚型酚醛树脂并无特别限定，可使用通常所使用的甲酚型酚醛树脂。
对甲酚型酚醛树脂的含量并无特别限定，但优先为酚醛树脂组合物总量(以固体成分为基准)的20重量％以上，更优选为20重量％～80重量％，特别优选为30～60重量％。当甲酚型酚醛树脂的含量在上述范围内时，后述的酚醛清漆型酚醛树脂的固化充分且可提高耐热性、耐药品性等。又，具有减低臭味等效果。
对本发明的甲酚型酚醛树脂并无特别限定，但优先含有油改性甲酚型酚醛树脂。由此，可提高由酚醛树脂层叠板的印刷板的冲孔性。作为油改性甲酚型酚醛树脂，可列举例如桐油、亚麻仁油、核桃油等的干性油改性甲酚型酚醛树脂；大豆油、绵籽油、红花油等的半干性油改性甲酚型酚醛树脂等。其中，优选桐油改性甲酚型酚醛树脂。由此，可更加提高冲孔性。又，对上述油改性甲酚型酚醛树脂的含量并无特别限定，但优选为酚醛树脂组合物总量(以固体成分为基准)的5～50重量％，特别优选为10～40重量％为佳。由此，可更加提高酚醛树脂层叠板的冲孔性。
通过含有酚醛清漆型酚醛树脂，可减低未反应的酚和甲醛。酚醛清漆型酚醛树脂与甲酚型酚醛树脂相比，合成时残存的未反应酚和甲醛少，因此，通过使将甲酚型酚醛树脂和酚醛清漆型酚醛树脂加以混合的酚醛树脂组合物浸渍到纸基材中，可取得未反应的酚和甲醛少的半固化片。作为除去甲酚型酚醛树脂的未反应酚的方法，已知有对酚醛树脂进行水蒸气蒸馏的方法，但由于导致加工工序的增加，因而不优选。另一方面，在本发明中，由于通过通常实施的酚醛树脂组合物的配合来削减未反应物，因此，在不会增加工序的情况下，可减低未反应的酚和甲醛。
又，通过与上述甲酚型酚醛树脂的并用，可在不使用酚醛树脂以外的交联剂的情况下进行固化。进而，通过上述甲酚型酚醛树脂与酚醛清漆型酚醛树脂的组合，可减低对印刷板冲孔时所产生的粉。从由以往的树脂组合物所构成的纸基材酚醛树脂层叠板打穿印刷板时，由冲孔的剖面产生树脂组合物等的粉。此类粉对焊锡的涂敷性和连接可靠性造成影响。
上述酚醛清漆型酚醛树脂，例如，可列举苯酚酚醛清漆型树脂、双酚A酚醛清漆型酚醛树脂、双酚F酚醛清漆型酚醛树脂、甲酚酚醛清漆型酚醛树脂、烷基苯酚酚醛清漆型酚醛树脂等。其中，优选苯酚酚醛清漆型树脂、双酚F酚醛清漆型酚醛树脂、甲酚酚醛清漆型酚醛树脂。由此，可更加减低对印刷板冲孔时产生的粉。
对上述酚醛清漆型酚醛树脂的含量并无特别限定，但优选为酚醛树脂组合物总量(以固体成分为基准)的3～30重量％，特别优选为5～20重量％。若酚醛清漆型酚醛树脂的含量在上述范围内，则可减低臭味等的同时，可进一步减低对印刷板冲孔时产生的粉。
又，在不违反本发明目的的范围下，可配合卤素化合物、磷化合物、氨基树脂等的阻燃性化合物。对上述阻燃性化合物的含量并无特别限定，但优选为酚醛树脂组合物总量(以固体成分为基准)的5～30重量％，特别优选为10～20重量％。由此，在不会损害纸基材酚醛树脂层叠板的特性的情况下，可提高阻燃性。卤素化合物可列举四溴双酚A(TBBA)、TBBA-环氧低聚物等。
作为磷化合物，可列举例如磷酸酯、缩合磷酸酯、氧化膦等。例如，作为磷酸酯，可列举磷酸三乙酯、磷酸三丁酯、磷酸三苯酯、磷酸三甲酚酯、磷酸甲酚基二苯酯、磷酸间苯二酚基二苯酯、磷酸三异丙基苯酯等，它们可使用一种或两种以上的混合系。其中，就取得的容易性方面而言，优选由磷酸三苯酯、磷酸三甲酚酯、磷酸甲酚基二苯酯中选出的一种以上的磷化合物，。
氨基树脂例如为三聚氰胺树脂、胍胺树脂等，但为了提高阻燃化效果，优选为三聚氰胺树脂。氨基树脂为三聚氰胺、胍胺等的氨基化合物与甲醛等醛类的初期反应物，也包含将它们的羟甲基的一部分或全部用甲醇、丁醇等的低级醇予以醚化者。
上述金属箔为附有粘接剂的金属箔，也可配置成上述粘接剂面与上述玻璃纤维基材半固化片面相互对置。通过使用附有粘接剂的金属箔，可取得耐漏电性的强化和稳定的铜箔密合性。作为粘接剂，并无特别限定，但优选与耐漏电性对应的粘接剂。
其次，说明半固化片。本发明的酚醛树脂层叠板的纸基材和玻璃纤维基材半固化片，是将上述酚醛树脂组合物浸渍到基材而成者。由此，可取得未反应的酚和甲醛少的酚醛树脂层叠板。作为纸基材，可列举例如牛皮纸、棉绒纸等。又，用水溶性酚醛树脂、羟甲基三聚氰胺树脂等进行预处理的纸基材也包含在本发明中。
作为玻璃纤维基材，并无特别限定，可使用玻璃织布、玻璃无纺布等。玻璃织布因可取得比玻璃无纺布更高的强度，因而优选。
将酚醛树脂组合物浸渍到基材的方法，可使用通常所使用的方法。例如，可列举将基材浸渍于树脂清漆的方法、以各种涂敷器予以涂布的方法、以喷雾器进行的吹附法等。
半固化片的树脂浸渍率并无特别限定，通常，为35～70重量％。半固化片的树脂浸渍率可根据下式计算。
半固化片树脂浸渍率＝[(半固化片重量-基材重量)/半固化片重量]×100
关于芯部分所用的半固化片的片数、及重叠于芯部分的上面与下面的半固化片的片数，适当决定即可，可在芯部分仅使用一片半固化片，也可在芯部分的上面与下面仅重叠一片半固化片。
当要求层叠板强度时，在芯部分或芯的外侧部分(上面部分与下面部分)中，或者在它们的两者中，层叠两片以上的半固化片。当层叠半固化片时，在各个部分，优选为2～10片的范围，更优选为4～8片的范围。
作为本发明的酚醛树脂层叠板的层叠条件，加热温度并无特别限定，但优选为130～240℃，特别优选为140～200℃。
又，对上述加压的压力并无特别限定，但优选为4～15MPa，特别优选为7～12MPa。
对加压时间并无特别限定，通常为60分钟～80分钟。
[实施例]
以下，根据实施例及比较例详细说明本发明，但本发明并不限定于此。说明中，「％」表示「重量％」。
(实施例1)
[未改性甲酚型酚醛树脂的制造]
使由苯酚1000克、37％甲醛水溶液980克、三乙胺20克所构成的混合物，在60℃下反应2小时，接着在减压下浓缩，并将其用甲醇稀释，从而得到树脂成分50％的未改性甲酚型酚醛树脂清漆。
[酚醛清漆型酚醛树脂的制造]
装入苯酚1000克和草酸10克，升温至100℃，并花60分钟逐次添加37％甲醛水溶液450克，一边以100℃回流一边反应1小时。其后，进行常压蒸馏，升温至130℃，并于500Pa的减压下进行减压蒸馏，升温至190℃，将其用甲醇稀释，从而得到树脂成分50％的酚醛清漆型酚醛树脂。
[油改性甲酚型酚醛树脂的制造]
在对甲苯磺酸存在下，将苯酚1600克和桐油1000克以95℃反应2小时，再加入对甲醛650克、六亚甲基四胺30克、甲苯2000克并以90℃下反应2小时后，在减压下浓缩，将其用甲苯与甲醇的混合溶剂稀释，从而得到树脂成分50％的油改性酚醛树脂清漆(油改性量30％)。
(纸基材和玻璃纤维基材浸渍用的树脂涂布液的制备)
配合上述未改性甲酚型酚醛树脂清漆100重量份(以固体成分基准为25.6％)、油改性甲酚型酚醛树脂清漆100重量份(25.6％)、酚醛清漆型酚醛树脂清漆50重量份(12.8％)、溴化环氧(GX-153、大日本油墨化学工业公司制)30重量份(15.4％)、磷酸三苯酯(TPP、大八化学公司制)20重量份(10.3％)、和羟甲基化三聚氰胺树脂(Phenolite TD-2538、大日本油墨化学工业公司制)20重量份(10.3％)，得到浸渍用的树脂涂布液。
(层叠板的制造)
其次，使上述浸渍用树脂涂布液浸渍到纸基材和玻璃织布中，以使树脂浸渍率达到55％(相对于半固化片整体的比例)，从而得到半固化片。将纸基材半固化片重叠6片，在该芯材的上面和下面各重叠一片玻璃织布半固化片，再于其两外面重叠附有粘接剂的铜箔(FGM日本电解公司制)，在150℃、10MPa、120分钟的条件进行加热加压成型，得到厚度1.6mm的层叠板。
(实施例2)
除了使浸渍到玻璃织布的第二酚醛树脂涂布液的配合量改变为如下以外，其它与实施例1相同地处理。
配合上述未改性甲酚型酚醛树脂清漆75重量份(以固体成分基准为18.1％)、油改性甲酚型酚醛树脂清漆150重量份(36.1％)、酚醛清漆型酚醛树脂清漆50重量份(12.0％)、溴化环氧(GX-153大日本油墨化学工业公司制)30重量份(14.5％)、磷酸三苯酯(TPP、大八化学公司制)20重量份(9.6％)、和羟甲基化三聚氰胺树脂(Phenolite TD-2538、大日本油墨化学工业公司制)20重量份(9.6％)，得到第二酚醛树脂涂布液。
(实施例3)
除了使用玻璃无纺布作为玻璃纤维基材以外，其它与实施例1相同地处理。
(比较例1)
除了使用如下制备的环氧树脂涂布液来代替浸渍到基材中的第一酚醛树脂涂布液和第二酚醛树脂涂布液，并且使用不含有粘接剂的铜箔以外，其它与实施例1相同地处理。
配合上述酚醛清漆型酚醛树脂清漆20重量份以(固体成分基准为15.9％)、溴化环氧(GX-153大日本油墨化学工业公司制)100重量份(79.4％)、磷酸三苯酯(TPP、大八化学公司制)5重量份(4.0％)、和咪唑(2P4MZ、四国化成公司制)1重量份(0.8％)，并再配合50重量份氢氧化铝，得到第一环氧树脂涂布液及第二环氧树脂涂布液。
(比较例2)
除了使用如下制备的环氧树脂涂布液来代替浸渍到基材中的第一酚醛树脂涂布液及第二酚醛树脂涂布液，重叠4片纸基材半固化片作为芯材，并在其上面和下面各重叠两片玻璃纤维基材半固化片，且使用不含有粘接剂的铜箔以外，其它与实施例1相同地处理。
配合上述酚醛清漆型酚醛树脂清漆20重量份(15.9％)、溴化环氧(GX-153大日本油墨化学工业公司制)100重量份(79.4％)、磷酸三苯酯(TPP、大八化学公司制)5重量份(4.0％)、和咪唑(2P4MZ、四国化成公司制)1重量份(0.8％)，并再配合50重量份氢氧化铝，得到第一环氧树脂涂布液及第二环氧树脂涂布液。
(比较例3)
除了使用如下制备的环氧树脂涂布液来代替浸渍到基材中的第一酚醛树脂涂布液及第二酚醛树脂涂布液以外，其它与实施例1相同地处理。
配合上述酚醛清漆型酚醛树脂清漆20重量份(15.9％)、溴化环氧(GX-153大日本油墨化学工业公司制)100重量份(79.4％)、磷酸三苯酯(TPP、大八化学公司制)5重量份(4.0％)、和咪唑(2P4MZ、四国化成公司制)1重量份(0.8％)，并再配合50重量份氢氧化铝，得到第一环氧树脂涂布液及第二环氧树脂涂布液。
(比较例4)
除了使用如下制备的环氧树脂涂布液来代替浸渍到玻璃纤维基材中的第二酚醛树脂涂布液，并且使用不含有粘接剂的铜箔以外，其它与实施例1相同地处理。
配合上述酚醛清漆型酚醛树脂清漆20重量份(15.9％)、溴化环氧(GX-153大日本油墨化学工业公司制)100重量份(79.4％)、磷酸三苯酯(TPP、大八化学公司制)5重量份(4.0％)、和咪唑(2P4MZ、四国化成公司制)1重量份(0.8％)，并再配合50重量份氢氧化铝，得到第二环氧树脂涂布液。
(比较例5)
除了使用如下制备的环氧树脂涂布液来代替浸渍到纸基材中的第一酚醛树脂涂布液，并且使用不含有粘接剂的铜箔以外，其它与实施例1相同地处理。
配合上述酚醛清漆型酚醛树脂清漆20重量份(15.9％)、溴化环氧(GX-153大日本油墨化学工业公司制)100重量份(79.4％)、磷酸三苯酯(TPP、大八化学公司制)5重量份(4.0％)、和咪唑(2P4MZ、四国化成公司制)1重量份(0.8％)，并再配合50重量份氢氧化铝，得到第一环氧树脂涂布液。
(比较例6)
除了全部使用纸基材以外，其它与实施例1相同地处理。
(比较例7)
除了全部使用纸基材，并且使用不含有粘接剂的铜箔以外，其它与比较例3相同地处理。
评价根据上述实施例及比较例所得到的层叠板的各特性。各特性是以下列方法评价。所得结果示于表1。
(1)弯曲强度
弯曲强度是根据JIS C6481评价。
(2)吸水率
吸水率是根据JIS C6481评价。
(3)长期吸湿性
将样品的形状调整为根据JIS C6481的吸水率测定的形状。切出50×50mm见方的样品，除去全部铜箔。作为预处理，在50℃下处理24小时者视为初期重量。于60℃/90％的恒温恒湿槽中放置1000小时，取出样品后于20℃/65％的环境下放置30分钟，然后在30分钟以内测定重量，并由重量变化算出吸湿率。
(4)银浆料通孔间绝缘性
设定铜箔刃径φ0.75mm，使用φ0.5mm的钻孔机，以通孔间距为1.5mm的方式进行钻孔加工。通孔中印刷银浆料，使之固化而进行上下面的导通，作成银浆料通孔间的绝缘性试验印刷板。
对此基板加以50V的电压，并于40℃/90％的恒温恒湿槽中放置1000小时后，取出后加以100V电压，测定通孔间的绝缘电阻值。
(5)耐漏电性
耐漏电性是依据UL-1410评价。
(6)铜箔电路间的耐漏电性
制作电路宽1mm、电路长30mm、电路间隙1mm的铜箔电路，并依据UL-1410评价。
从表明确可知，实施例1～3的弯曲强度、吸水率、长期吸湿率、电绝缘性、及铜箔电路间的耐漏电性优良。
由实施例1～3与比较例6、7的对比可知，弯曲强度、吸水率是通过在使用纸基材半固化片的芯材的两面，将使用玻璃纤维基材半固化片的外侧部分加以重叠而体现。
由实施例1～3与比较例1～3、5、7的对比可知，长期耐湿性、电绝缘性是通过将酚醛树脂液浸渍到纸基材中而体现。
又，由实施例1～3与比较例1～4、7的对比可知，铜箔电路间的耐漏电性是通过使酚醛树脂液浸渍到外侧部分的玻璃纤维基材中以及使用附有粘接剂的铜箔而体现。
由上述可知，兼具弯曲强度、吸水率、长期吸湿率、电绝缘性、及铜箔电路间的耐漏电性的印刷电路用层叠板，是通过在芯材(使用将酚醛树脂涂布液浸渍到纸基材中的纸基材半固化片)的上面和下面，重叠将酚醛树脂涂布液浸渍到玻璃纤维基材中而成的玻璃纤维基材半固化片，而且，在至少单面上层叠金属箔而得到层叠体，并对该层叠体予以加热加压而形成，而且，优选使用附有粘接剂的金属箔，并以其粘接剂面与上述玻璃纤维基材半固化片面相互对置的方式加以配置，从而得到覆金属酚醛树脂层叠板。
Claims (5)
1.一种覆金属酚醛树脂层叠板，其特征在于，
使第一酚醛树脂组合物浸渍到纸基材中而得到纸基材半固化片，仅使用一片该纸基材半固化片作为中心层状部，或重叠规定片数的该纸基材半固化片作为中心层状部，在该中心层状部的上面和下面，仅重叠一片使第二酚醛树脂组合物浸渍到玻璃纤维基材而得到的玻璃纤维基材半固化片或重叠规定片数的使第二酚醛树脂组合物浸渍到玻璃纤维基材而得到的玻璃纤维基材半固化片，从而层叠外侧层状部，进而，在上述上面侧和下面侧的外侧层状部中的至少一个单面上层叠金属箔而得到层叠体，并对该层叠体加热加压而得到，
所述第一酚醛树脂组合物和所述第二酚醛树脂组合物均含有未改性甲酚型酚醛树脂、酚醛清漆型酚醛树脂以及油改性甲酚型酚醛树脂，
以固体成分为基准，包括所述未改性甲酚型酚醛树脂和油改性甲酚型酚醛树脂的甲酚型酚醛树脂的合计含量是酚醛树脂组合物总量的20重量%～80重量%，
以固体成分为基准，所述酚醛清漆型酚醛树脂的含量是酚醛树脂组合物总量的3重量%～30重量%，
以固体成分为基准，所述油改性甲酚型酚醛树脂的含量是酚醛树脂组合物总量的5重量%～50重量%。
2.如权利要求1所述的覆金属酚醛树脂层叠板，其中，上述层叠体的金属箔为附有粘接剂的金属箔，并以上述粘接剂面与上述玻璃纤维基材半固化片面相互对置的方式加以配置。
3.如权利要求1所述的覆金属酚醛树脂层叠板，其中，上述玻璃纤维基材为玻璃织布。
4.如权利要求1所述的覆金属酚醛树脂层叠板，其中，构成上述第一酚醛树脂涂布液的树脂组合物与构成上述第二酚醛树脂涂布液的树脂组合物为相同的树脂组合物。
5.如权利要求1～4中任一项所述的覆金属酚醛树脂层叠板，其中，在60℃、相对湿度90%的环境下放置1000小时后的长期吸湿率为2重量%以下。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-258830 | 2008-10-03 | ||
| JP2008258830 | 2008-10-03 | ||
| JP2008-279052 | 2008-10-30 | ||
| JP2008279052 | 2008-10-30 | ||
| PCT/JP2009/066797 WO2010038703A1 (ja) | 2008-10-03 | 2009-09-28 | 金属張フェノール樹脂積層板 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102149540A CN102149540A (zh) | 2011-08-10 |
| CN102149540B true CN102149540B (zh) | 2014-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200980135736.7A Expired - Fee Related CN102149540B (zh) | 2008-10-03 | 2009-09-28 | 覆金属酚醛树脂层叠板 |
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| Country | Link |
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| US (1) | US8999510B2 (zh) |
| JP (1) | JPWO2010038703A1 (zh) |
| KR (1) | KR20110063445A (zh) |
| CN (1) | CN102149540B (zh) |
| TW (1) | TWI458627B (zh) |
| WO (1) | WO2010038703A1 (zh) |
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| JP5941847B2 (ja) * | 2013-01-17 | 2016-06-29 | 信越化学工業株式会社 | シリコーン・有機樹脂複合積層板及びその製造方法、並びにこれを使用した発光半導体装置 |
| CN104476902A (zh) * | 2014-12-30 | 2015-04-01 | 烟台柳鑫新材料科技有限公司 | 一种pcb背钻的盖板及其制造方法 |
| US20220134710A1 (en) * | 2019-02-13 | 2022-05-05 | Sekisui Chemical Co., Ltd. | Layered sheet |
| CN110421904A (zh) * | 2019-07-31 | 2019-11-08 | 东莞市汇驰纸业有限公司 | 一种再生瓦楞纸板的加工方法 |
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| CN87214958U (zh) * | 1987-11-09 | 1988-10-05 | 刘俊泉 | 印制电路用新型覆铜箔层压板 |
| CN1780528A (zh) * | 2004-11-16 | 2006-05-31 | 日立化成工业株式会社 | 预浸料及使用该预浸料的层积板和印刷电路板 |
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| JPS6256137A (ja) * | 1985-09-05 | 1987-03-11 | 松下電工株式会社 | 片面金属箔張積層板 |
| US4803115A (en) * | 1985-09-27 | 1989-02-07 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Glass fiber-reinforced electrical laminates and a continuous production method therefor |
| JPS6339332A (ja) | 1986-08-04 | 1988-02-19 | 松下電工株式会社 | 電気用積層板 |
| JPH04364941A (ja) * | 1991-06-11 | 1992-12-17 | Sumitomo Bakelite Co Ltd | フェノール樹脂積層板 |
| JPH10279645A (ja) * | 1997-03-31 | 1998-10-20 | Hitachi Chem Co Ltd | レゾール型フェノール樹脂の製造方法、フェノール樹脂積層板の製造方法及び銅張積層板の製造方法 |
| JPH10279715A (ja) * | 1997-04-08 | 1998-10-20 | Sumitomo Bakelite Co Ltd | 難燃性フェノール樹脂積層板 |
| JP4141578B2 (ja) * | 1999-03-30 | 2008-08-27 | 住友ベークライト株式会社 | フェノール樹脂積層板 |
| JP4259031B2 (ja) * | 2002-03-28 | 2009-04-30 | 住友ベークライト株式会社 | 樹脂組成物、プリプレグおよび紙基材フェノール樹脂積層板 |
| JP2005290144A (ja) * | 2004-03-31 | 2005-10-20 | Sumitomo Bakelite Co Ltd | 樹脂組成物、プリプレグおよびフェノール樹脂積層板 |
| US20080036097A1 (en) * | 2006-08-10 | 2008-02-14 | Teppei Ito | Semiconductor package, method of production thereof and encapsulation resin |
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2009
- 2009-09-28 US US13/121,867 patent/US8999510B2/en not_active Expired - Fee Related
- 2009-09-28 CN CN200980135736.7A patent/CN102149540B/zh not_active Expired - Fee Related
- 2009-09-28 WO PCT/JP2009/066797 patent/WO2010038703A1/ja active Application Filing
- 2009-09-28 KR KR1020117005329A patent/KR20110063445A/ko not_active Application Discontinuation
- 2009-09-28 JP JP2010531845A patent/JPWO2010038703A1/ja active Pending
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| CN87214958U (zh) * | 1987-11-09 | 1988-10-05 | 刘俊泉 | 印制电路用新型覆铜箔层压板 |
| CN1780528A (zh) * | 2004-11-16 | 2006-05-31 | 日立化成工业株式会社 | 预浸料及使用该预浸料的层积板和印刷电路板 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010038703A1 (ja) | 2010-04-08 |
| US8999510B2 (en) | 2015-04-07 |
| KR20110063445A (ko) | 2011-06-10 |
| JPWO2010038703A1 (ja) | 2012-03-01 |
| US20110183564A1 (en) | 2011-07-28 |
| TWI458627B (zh) | 2014-11-01 |
| TW201026494A (en) | 2010-07-16 |
| CN102149540A (zh) | 2011-08-10 |
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