JPWO2015005220A1 - 導電性硬化物の製造方法及び導電性硬化物並びにパルス光硬化性組成物の硬化方法及びパルス光硬化性組成物 - Google Patents
導電性硬化物の製造方法及び導電性硬化物並びにパルス光硬化性組成物の硬化方法及びパルス光硬化性組成物 Download PDFInfo
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- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- GHBKQPVRPCGRAQ-UHFFFAOYSA-N octylsilicon Chemical compound CCCCCCCC[Si] GHBKQPVRPCGRAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- RQZVTOHLJOBKCW-UHFFFAOYSA-M silver;7,7-dimethyloctanoate Chemical compound [Ag+].CC(C)(C)CCCCCC([O-])=O RQZVTOHLJOBKCW-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- QEEPNARXASYKDD-UHFFFAOYSA-J tris(7,7-dimethyloctanoyloxy)stannyl 7,7-dimethyloctanoate Chemical compound [Sn+4].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O QEEPNARXASYKDD-UHFFFAOYSA-J 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2312/00—Crosslinking
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0215—Metallic fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
パルス化された光を照射することにより、導電性硬化物を形成することを特徴とする。本願明細書において、パルス光照射により硬化する組成物をパルス光硬化性組成物と称する。
上記R1の具体例としては、たとえばメチル基、エチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、ベンジル基等のアラルキル基や、R1 3SiO−で示されるトリオルガノシロキシ基等があげられる。これらの中ではメチル基が好ましい。
架橋性珪素基を形成する珪素原子は1個以上であるが、シロキサン結合などにより連結された珪素原子の場合には、20個以下であることが好ましい。
−R2−O− ・・・(4)
前記一般式(4)中、R2は炭素原子数1〜14の直鎖状もしくは分岐アルキレン基であり、炭素原子数1〜14、好ましくは2〜4の、直鎖状もしくは分岐アルキレン基が好適である。
−CH2O−、−CH2CH2O−、−CH2CH(CH3)O−、−CH2CH(C2H5)O−、−CH2C(CH3)2O−、−CH2CH2CH2CH2O−
等が挙げられる。
前記ポリオキシアルキレン系重合体の主鎖骨格は、1種類だけの繰り返し単位からなってもよいし、2種類以上の繰り返し単位からなってもよい。
主鎖骨格が飽和炭化水素系重合体であるものは、耐熱性、耐候性、耐久性、及び、湿気遮断性に優れる特徴を有する。
−CH2−C(R3)(COOR4)−(5)
−CH2−C(R3)(COOR5)−(6)
また式(5)の単量体単位と式(6)の単量体単位の存在比は、質量比で95:5〜40:60が好ましく、90:10〜60:40がさらに好ましい。
また、上記導電性フィラーの他、ネオデカン酸銀や、オレイン酸銀等のカルボン酸銀塩;銀アセチルアセトナート錯体や、銀アミン錯体等の銀錯体等を更に添加することができる。これらを添加することにより、前記パルス光硬化性組成物の硬化物をより低抵抗化することができる。
a工程;プリント配線板やフレキシブルプリント基板の上に本発明に係るパルス光硬化性組成物を塗布又は印刷してパルス光照射して回路や電極を形成する工程、
b工程;多層基板のスルーホールに本発明に係るパルス光硬化性組成物を充填しパルス光照射して層間の電気的導通を得る工程、
c工程;プリント基板上にディスペンス、スクリーン印刷ないしステンシル印刷で本発明に係るパルス光硬化性組成物を塗布又は印刷した上に、半導体素子やチップ部品を搭載しパルス光照射して接合する工程。
また、無機系基材としては、例えば、メタル・ベース、メタル・コア、ホーロー等の金属系基板;アルミナ基板、窒化アルミニウム基板(AlN)、炭化ケイ素基板(SiC)、低温焼成基板等のセラミック系基板;ガラス基板等が挙げられるが、これらに限定されない。
窒素雰囲気下、250L反応機にCuBr(1.09kg)、アセトニトリル(11.4kg)、アクリル酸ブチル(26.0kg)及び2,5−ジブロモアジピン酸ジエチル(2.28kg)を加え、70〜80℃で30分程度撹拌した。これにペンタメチルジエチレントリアミンを加え、反応を開始した。反応開始30分後から2時間かけて、アクリル酸ブチル(104kg)を連続的に追加した。反応途中ペンタメチルジエチレントリアミンを適宜添加し、内温70℃〜90℃となるようにした。ここまでで使用したペンタメチルジエチレントリアミン総量は220gであった。反応開始から4時間後、80℃で減圧下、加熱攪拌することにより揮発分を除去した。これにアセトニトリル(45.7kg)、1,7−オクタジエン(14.0kg)、ペンタメチルジエチレントリアミン(439g)を添加して8時間撹拌を続けた。混合物を80℃で減圧下、加熱攪拌して揮発分を除去した。この濃縮物にトルエンを加え、重合体を溶解させた後、ろ過助剤として珪藻土、吸着剤として珪酸アルミ、ハイドロタルサイトを加え、酸素窒素混合ガス雰囲気下(酸素濃度6%)、内温100℃で加熱攪拌した。混合液中の固形分をろ過で除去し、ろ液を内温100℃で減圧下、加熱攪拌して揮発分を除去した。
更に吸着剤として珪酸アルミ、ハイドロタルサイトを追加し、酸化防止剤を加え、酸素窒素混合ガス雰囲気下(酸素濃度6%)、内温150℃で加熱攪拌した。この濃縮物にトルエンを加え、重合体を溶解させた後、混合液中の固形分をろ過で除去し、ろ液を減圧下加熱攪拌して揮発分を除去し、アルケニル基を有する重合体を得た。このアルケニル基を有する重合体、ジメトキシメチルシラン(アルケニル基に対して2.0モル当量)、オルトギ酸メチル(アルケニル基に対して1.0モル当量)、白金触媒[ビス(1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン)白金錯体触媒のキシレン溶液白金として重合体1kgに対して10mg)を混合し、窒素雰囲気下、100℃で加熱攪拌した。アルケニル基が消失したことを確認し、反応混合物を濃縮して末端にジメトキシシリル基を有するポリ(アクリル酸−n−ブチル)重合体A1を得た。得られた重合体A1の数平均分子量は約26000、Mw/Mnが1.3であり、Tgは−56.0℃であった。重合体1分子当たりに導入された平均のシリル基の数を1H NMR分析により求めたところ、約1.8個であった。
フラスコに溶剤である酢酸エチル40質量部、メチルメタクリレート59質量部、2−エチルヘキシルメタクリレート25質量部、γ−メタクリロキシプロピルメチルジメトキシシラン21質量部、及び金属触媒としてルテノセンジクロライド0.1質量部を仕込み窒素ガスを導入しながら80℃に加熱した。ついで、3−メルカプトプロピルメチルジメトキシシラン7.5質量部をフラスコ内に添加し80℃で6時間反応を行った。室温に冷却後、ベンゾキノン溶液(95%THF溶液)を20質量部添加して重合を停止した。溶剤および未反応物を留去し、ポリスチレン換算の質量平均分子量が約6000であり、Mw/Mnが1.6であり、Tgが61.2℃であるジメトキシシリル基を有するアクリル酸エステル系重合体A2を得た。
フラスコに溶剤である酢酸エチル40質量部、メチルメタクリレート59質量部、2−エチルヘキシルメタクリレート25質量部、γ−メタクリロキシプロピルトリメトキシシラン22質量部、及び金属触媒としてルテノセンジクロライド0.1質量部を仕込み、窒素ガスを導入しながら80℃に加熱した。ついで、3−メルカプトプロピルトリメトキシシラン8質量部をフラスコ内に添加し80℃で6時間反応を行った。室温に冷却後、ベンゾキノン溶液(95%THF溶液)を20質量部添加して重合を停止した。溶剤および未反応物を留去し、ポリスチレン換算の質量平均分子量が約6000であり、Mw/Mnが1.6であり、Tgが61.2℃であるトリメトキシシリル基を有するアクリル酸エステル系重合体A3を得た。
攪拌装置、窒素ガス導入管、温度計、滴下装置および環流冷却器を備えたフラスコに、3−アミノプロピルトリメトキシシラン(商品名:Z−6610、東レ・ダウコーニング・シリコーン(株)製)100g、3−グリシドキシプロピルトリメトキシシラン(商品名:Z−6040、東レ・ダウコーニング・シリコーン(株)製)276gを加え、50℃にて72時間撹拌し、カルバシラトランを得た。得られたカルバシラトランについて、FT−IRにて910cm−1付近のエポキシ基に起因するピークの消失を確認し、1140cm−1付近の2級アミンのピークを確認し、また、29Si−NMRより−60ppmから−70ppmに新たなピークの出現が確認できた。
攪拌装置、窒素ガス導入管、温度計、滴下装置および環流冷却器を備えたフラスコに、合成例4で得たカルバシラトランを100g入れ、続いてオルガチックス TC−750[マツモトファインケミカル(株)製の商品名、チタニウムジイソプロポキシビス(エチルアセトアセテート)]を63.1g入れ、70℃にて144時間加熱撹拌することにより熟成し、合成チタン触媒を得た。得られた合成チタン触媒について、29Si−NMRよりピークの変化を確認した。
表1に示した如く、合成例1の樹脂80質量部、合成例2の樹脂20質量部に、アエロジルR972〔日本アエロジル(株)製の商品名、ジメチルジクロロシラン処理された疎水性シリカ〕5質量部を攪拌混合機にて攪拌・脱泡した後、100℃にて1時間加熱脱水して50℃以下まで冷却した。その後、残りの配合物質を加え、撹拌・脱泡してペースト状のパルス光硬化性組成物を得た。
*1)MA440:(株)カネカ製、商品名サイリルMA440、主鎖がポリオキシプロピレンで分子末端にジメトキシシリル基を有するポリマーと、主鎖がポリメタクリル酸エステルの共重合体で分子中にジメトキシシリル基を有するポリマーとの混合物。
*2)EP−505S:(株)カネカ製、商品名:エピオンEP−505S、プロセスオイルを33重量%含有する、主鎖がポリイソブチレンで分子末端にメチルジメトキシシリル基を有するポリマー。
*3)アエロジルR972:日本アエロジル(株)製の商品名、ジメチルジクロロシラン処理された疎水性シリカ。
*4)AO−60:(株)ADEKA製、フェノール系酸化防止剤。
*5)ノクラックCD: 大内新興化学(株)製の商品名、4,4'−ビス(α,α−ジメチルベンジル)ジフェニルアミン。
*6)LA−63P:(株)ADEKA製の商品名、ヒンダードアミン系老化防止剤。
*7)シルコートAgC−B:福田金属箔粉工業(株)製の商品名、比表面積1.35m2/g、タップ密度4.6g/cm3、50%平均粒径4μm、フレーク状銀粉。
*8)シルコートAgC−G:福田金属箔粉工業(株)製の商品名、比表面積2.5m2/g、タップ密度1.4g/cm3、粒状銀粉(還元粉))。
*9)ACAX−3:三井金属鉱業(株)製の商品名、樹枝状銅粉に重量比20%で銀メッキした銀メッキ銅粉。
*10)1400YP(10%):三井金属鉱業(株)製、1400YP(銅粉)に重量比10%で銀メッキした銀メッキ銅粉。
*11)N−11:JX日鉱日石エネルギー(株)製、商品名カクタスノルマルパラフィンN−11、パラフィン系希釈剤。
*12)KBM−1003:信越化学工業(株)製の商品名、ビニルトリメトキシシラン。
*13)KBM−903:信越化学工業(株)製の商品名、3−アミノプロピルトリメトキシシラン。
*14)アルミキレートD:川研ファインケミカル(株)製の商品名、アルミニウムモノアセチルアセトネートビス(エチルアセトアセテート)。
*15)U−800P:ジオクチル錫オキサイド、商品名:ネオスタンU−800P、日東化成(株)製。
1)パルス光照射による硬化性試験
パルス光硬化性組成物を用いて、厚さ75μmのメタルマスクを用いて、PETフィルム(厚さ100μm、ルミラー100S、東レ(株)社製)に導体幅1.0mm、導体間隔1mm、長さ70.0mmで回路パターンを孔版印刷し、印刷後直ちに米国Xenon Corporation製キセノンパルス照射装置RC−802を用い下記照射条件によりパルス光を照射した。
・パルス幅:168μsec
・照射時間:10秒
・照射距離:25mm
・積算照射エネルギー量:55J/cm2
・ランプの種類:LH−810(パルスエネルギー 207J/パルス)
照射後、パルス光硬化性組成物が硬化したことを下記評価基準で評価した。結果を表2に示す。
・評価基準 ○:硬化、△:一部未硬化、×:未硬化。
上述したパルス光照射による硬化性試験後、PETフィルムの歪み具合を下記評価基準で評価した。結果を表2に示す。
・評価基準 ○:歪みなし、△:一部歪み有り、×:歪み有り。
上述したパルス光照射による硬化性試験後、日置電機株式会社製抵抗計RM3548にて両端間の抵抗値を測定した。測定上限である1.0MΩを超えた場合はN.D.とした。結果を表2に示した。
上述したパルス光照射による硬化性試験後、パルス光硬化性組成物で作成した導体に粘着テープを貼った後勢いよく引きはがし、はく離状態を観察した。結果を表2に示す。
・評価基準 〇:はく離なし、△:はく離した面積が50%以下、×:PETフィルムから全てはく離。
表1に示した如く、配合物を変更した以外は実施例1と同様にパルス光硬化性組成物を得た。得られたパルス光硬化性組成物に対して、実施例1と同様に測定1)〜4)を行った。結果を表2に示した。
実施例1に示したパルス光硬化性組成物を用いて、厚さ75μmのメタルマスクを用いて、PETフィルム(厚さ100μm、ルミラー100S、東レ(株)社製)に導体幅1.0mm、導体間隔1mm、長さ70.0mmで回路パターンを孔版印刷し、印刷後直ちに米国Xenon Corporation製キセノンパルス照射装置SINTERON2000を用い下記照射条件によりパルス光を照射した。
・パルス幅:500μsec
・電圧:3800V
・照射時間:10秒
・照射距離:25mm
・照射エネルギー量:55J/cm2
・パルス幅:2000μsec
・電圧:2000V
・照射時間:10秒
・照射距離:25mm
・照射エネルギー量:29J/cm2
セメダイン(株)製脱オキシム型シリコーンシーラント100質量部に福田金属箔粉工業(株)製シルコートAgC−Bを300質量部、シルコートシルコートAgC−Gを200質量部、JX日鉱日石エネルギー(株)製カクタスノルマルパラフィンN−11を30質量部加え、撹拌・脱泡してペースト状のパルス光硬化性組成物を得た。
得られたパルス光硬化性組成物を用いて、実施例10と同様の条件により試験を行った。結果を表3に示す。
表4に示した如く、配合物を変更した以外は実施例1と同様にペースト組成物を得た。得られたペースト組成物に対して、実施例1と同様に測定1)〜4)を行った。結果を表5に示した。
*16)ハイジライトH32:昭和電工(株)製、水酸化アルミニウム(平均粒径8μm)。
*17)ホワイトンSB:白石カルシウム(株)製の商品名、重質炭酸カルシウム。(平均粒径2.2μm)
*18)カルファイン200:丸尾カルシウム(株)製の商品名、脂肪酸表面処理炭酸カルシウム、一次粒子径(電子顕微鏡)0.07μm。
Claims (6)
- (A)架橋性珪素基含有有機重合体及び湿気硬化型ウレタン系有機重合体からなる群から選択される1種以上の湿気硬化性樹脂、
(B)導電性フィラー、及び
(C)縮合触媒、
を含む組成物に対し、パルス化された光を照射することにより、導電性硬化物を形成することを特徴とする導電性硬化物の製造方法。 - 前記導電性硬化物を、基材上に形成させることを特徴とする請求項1記載の導電性硬化物の製造方法。
- (A)架橋性珪素基含有有機重合体及び湿気硬化型ウレタン系有機重合体からなる群から選択される1種以上の湿気硬化性樹脂、
(B)導電性フィラー、及び
(C)縮合触媒、
を含む組成物に対し、パルス化された光を照射することにより、硬化せしめることを特徴とするパルス光硬化性組成物の硬化方法。 - (A)架橋性珪素基含有有機重合体及び湿気硬化型ウレタン系有機重合体からなる群から選択される1種以上の湿気硬化性樹脂、
(B)導電性フィラー、及び
(C)縮合触媒、
を含むことを特徴とするパルス光硬化性組成物。 - 請求項1又は2記載の方法により製造されてなることを特徴とする導電性硬化物。
- 請求項5記載の導電性硬化物を用いてなることを特徴とする電子回路。
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US20160174385A1 (en) | 2016-06-16 |
EP3020767A4 (en) | 2017-03-15 |
KR20160058743A (ko) | 2016-05-25 |
KR102175447B1 (ko) | 2020-11-06 |
JP6489441B2 (ja) | 2019-03-27 |
EP3020767A1 (en) | 2016-05-18 |
WO2015005220A1 (ja) | 2015-01-15 |
CN105377993A (zh) | 2016-03-02 |
CN105377993B (zh) | 2019-03-22 |
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