JP5831762B2 - Thermosetting conductive paste - Google Patents
Thermosetting conductive paste Download PDFInfo
- Publication number
- JP5831762B2 JP5831762B2 JP2012194666A JP2012194666A JP5831762B2 JP 5831762 B2 JP5831762 B2 JP 5831762B2 JP 2012194666 A JP2012194666 A JP 2012194666A JP 2012194666 A JP2012194666 A JP 2012194666A JP 5831762 B2 JP5831762 B2 JP 5831762B2
- Authority
- JP
- Japan
- Prior art keywords
- resin component
- curable resin
- resin
- conductive paste
- crosslinking
- 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.)
- Active
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 26
- 229920005989 resin Polymers 0.000 claims description 106
- 239000011347 resin Substances 0.000 claims description 106
- 238000001723 curing Methods 0.000 claims description 42
- 239000012948 isocyanate Substances 0.000 claims description 39
- 150000002513 isocyanates Chemical class 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 36
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 238000004132 cross linking Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000002981 blocking agent Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000013007 heat curing Methods 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 17
- 239000010410 layer Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000004020 conductor Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000001856 Ethyl cellulose Substances 0.000 description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 10
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
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- 230000015572 biosynthetic process Effects 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
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- BZUILZIKDIMXBK-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1OC1 BZUILZIKDIMXBK-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 150000001735 carboxylic acids Chemical class 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
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- 229910000679 solder Inorganic materials 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IUIRWOGXLQFRHG-UHFFFAOYSA-N 2-aminoethanol;trifluoroborane Chemical compound NCCO.FB(F)F IUIRWOGXLQFRHG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
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- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
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- 239000002923 metal particle Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- DBIWHDFLQHGOCS-UHFFFAOYSA-N piperidine;trifluoroborane Chemical compound FB(F)F.C1CCNCC1 DBIWHDFLQHGOCS-UHFFFAOYSA-N 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Non-Insulated Conductors (AREA)
- Paints Or Removers (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
Description
本発明は電子デバイスや太陽電池の電極、配線などに使用可能な熱硬化型導電性ペーストに関するものである。また、この熱硬化型導電性ペーストを用いて形成された電極や配線を有する電子デバイス及び太陽電池に関するものである。 The present invention relates to a thermosetting conductive paste that can be used for electrodes and wiring of electronic devices and solar cells. The present invention also relates to an electronic device and a solar cell having electrodes and wirings formed using this thermosetting conductive paste.
熱硬化型導電性ペーストは銀や銅などの金属粉末を樹脂および必要により溶剤やその他の添加成分に分散したものであり、コンデンサ、インダクタやアクチュエータ等の電子部品の電極、太陽電池パネルの集電極、プリント基板、タッチパネル、表示素子等の電子回路の導体配線や電磁波遮断材、或いは導電性接着剤として使用されている。このような熱硬化型導電性ペーストは一般的にスクリーン印刷、ディップ法、ディスペンス法、インクジェット法等様々な塗布法で基板上に所望の形状・厚みでパターン形成した後、比較的低温、例えば１００〜３００℃で熱処理することにより乾燥及び／又は樹脂が加熱硬化され、樹脂マトリックス中に金属粒子が分散された構造を持った導電層が形成される。
樹脂としては一般に、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アルキッド樹脂、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ポリイミド樹脂などが使用されるが、特に導電性、接着性、耐熱性が要求される用途には主にエポキシ樹脂、フェノール樹脂などの熱硬化性樹脂が使用されている。
Thermosetting conductive paste is a dispersion of metal powders such as silver and copper in resin and, if necessary, solvent and other additive components. Electrodes for electronic parts such as capacitors, inductors and actuators, and collectors for solar cell panels It is used as a conductor wiring, electromagnetic wave shielding material, or conductive adhesive for electronic circuits such as printed circuit boards, touch panels, and display elements. Such a thermosetting conductive paste is generally formed on a substrate with a desired shape and thickness by various coating methods such as screen printing, dipping, dispensing, and inkjet, and then at a relatively low temperature, for example, 100 By heat treatment at ˜300 ° C., drying and / or resin is heat-cured to form a conductive layer having a structure in which metal particles are dispersed in a resin matrix.
Generally, epoxy resin, phenol resin, melamine resin, alkyd resin, polyester resin, urethane resin, acrylic resin, polyimide resin, etc. are used as the resin, especially for applications that require electrical conductivity, adhesion, and heat resistance. In general, thermosetting resins such as epoxy resins and phenol resins are used.
特に、結晶性シリコンにアモルファスシリコンを積層したヘテロ接合型シリコン太陽電池は優れた変換効率を持つことから注目されており、このようなアモルファスシリコン層を有する太陽電池の集電極として低温硬化型の導電性ペーストが使用されている。太陽電池用導電性ペーストへの要求特性としては、優れたスクリーン印刷性と硬化後の導電性、密着性に加え、該導電性ペーストで形成された導電層上にセル接続のための半田リボンを接合させるために、優れた耐熱性と半田濡れ性が必要となる。
これを実現するために、例えば特許文献１には、フレーク状の銀粉末と球状銀粉末を組み合わせ、加熱硬化性成分としてエポキシ樹脂と、特定の硬化剤と、ブロック化ポリイソシアネートを用いた導電性、密着性の優れた導電性ペーストが開示されている。
また、特許文献２には、フレーク状銀粉末と球状銀粉末を用い、樹脂として特定のエポキシ当量のビスフェノールＡ系エポキシ樹脂と特定のエポキシ当量、特定粘度のエポキシ樹脂を使用したペーストが開示されている。
特許文献３には特定のフタル酸系グリシジルエステル型エポキシ樹脂を用いた熱硬化型導電性ペーストが開示されている。
特許文献４には繊維素誘導体高分子とその他の樹脂を併用し、硬化剤としてイソシアネートを用いて、２種類の高分子をイソシアネートで架橋することにより屈曲性、導電性を両立させた導電性ペーストが開示されている。
In particular, heterojunction silicon solar cells in which amorphous silicon is laminated on crystalline silicon are attracting attention because of their excellent conversion efficiency, and low temperature curing type conductive materials are used as collector electrodes for solar cells having such an amorphous silicon layer. Sex paste is used. In addition to excellent screen printability, conductivity after curing, and adhesion, the required characteristics of conductive paste for solar cells include a solder ribbon for cell connection on the conductive layer formed of the conductive paste. In order to join, excellent heat resistance and solder wettability are required.
In order to achieve this, for example, Patent Document 1 discloses a combination of flaky silver powder and spherical silver powder, and an electrically conductive material using an epoxy resin, a specific curing agent, and a blocked polyisocyanate as a heat-curable component. A conductive paste having excellent adhesion is disclosed.
Patent Document 2 discloses a paste using flaky silver powder and spherical silver powder, and using a specific epoxy equivalent bisphenol A type epoxy resin, a specific epoxy equivalent, and an epoxy resin having a specific viscosity as a resin. Yes.
Patent Document 3 discloses a thermosetting conductive paste using a specific phthalic acid glycidyl ester type epoxy resin.
Patent Document 4 discloses a conductive paste that combines flexibility and conductivity by using a fibrous derivative polymer in combination with other resins, using isocyanate as a curing agent, and crosslinking two types of polymers with isocyanate. Is disclosed.
一方、高分子材料の物性改善の手段として相互侵入型高分子網目（Ｉｎｔｅｒ Ｐｅｎｅｔｒａｔｉｎｇ Ｐｏｌｙｍｅｒ−Ｎｅｔｗｏｒｋｓ、以下「ＩＰＮ」という）構造体の利用が知られている。ＩＰＮ構造体とは、個別に架橋された２以上の高分子鎖が分子レベルで互いに絡み合った状態のものを指すが、性質の違った高分子鎖を絡み合った状態にすることにより、特異な、優れた物性が得られることが知られている。例えば特許文献５には、エポキシ樹脂にアクリル樹脂を組み合わせてＩＰＮ構造とすることにより柔軟性、応力緩和性を改善した非導電性のＩＰＮ型接着剤が開示されている。また特許文献６には、ラジカル重合性モノマーと高分子量バインダーポリマーを組み合わせた光重合性導電ペーストが開示されている。なお後者は塗布後光照射により部分的にＩＰＮ構造を形成してゲル化させ、現像後焼成されるものであり、形成された導電層中に樹脂は残存しない。 On the other hand, the use of interpenetrating polymer-networks (hereinafter referred to as “IPN”) structures is known as means for improving the physical properties of polymer materials. An IPN structure refers to a state in which two or more individually crosslinked polymer chains are entangled with each other at the molecular level, but by making polymer chains with different properties entangled, a unique, It is known that excellent physical properties can be obtained. For example, Patent Document 5 discloses a non-conductive IPN adhesive that has improved flexibility and stress relaxation by combining an epoxy resin with an acrylic resin to form an IPN structure. Patent Document 6 discloses a photopolymerizable conductive paste in which a radical polymerizable monomer and a high molecular weight binder polymer are combined. In the latter, an IPN structure is partially formed by light irradiation after coating, gelled, and baked after development. No resin remains in the formed conductive layer.
前記特許文献１〜３のペーストは導電性、接着性が共に優れ、スクリーン印刷も可能であるため、太陽電池の電極をはじめ各種回路、電極の形成に適している。しかし近年要求特性がますます厳しくなる中で、耐熱性、接着性、信頼性が十分満足いくものとはいえない。とりわけ太陽電池の電極用途にはこれら諸特性をさらに改善すること、特に高い導電性と耐熱性、接着性等を両立させることが要求されている。
特許文献４は、少なくとも２種類の高分子をイソシアネートで架橋した非ＩＰＮ型網目構造体であり、屈曲性と機械強度を改善するものであるが、導電性や耐熱性は十分なものではない。
本発明の目的は、前述の問題を解決し、高い導電性と優れた印刷性、接着性、さらには耐熱性を両立し得る導電性ペーストを提供することにある。
Since the pastes of Patent Documents 1 to 3 are both excellent in conductivity and adhesiveness and can be screen-printed, they are suitable for forming various circuits and electrodes including electrodes for solar cells. However, in recent years, the required characteristics have become more severe, and it cannot be said that the heat resistance, adhesiveness and reliability are sufficiently satisfactory. In particular, it is required for solar cell electrodes to further improve these characteristics, particularly to achieve both high conductivity, heat resistance, adhesion, and the like.
Patent Document 4 is a non-IPN type network structure in which at least two kinds of polymers are crosslinked with isocyanate and improves flexibility and mechanical strength, but is not sufficient in conductivity and heat resistance.
An object of the present invention is to solve the above-described problems and provide a conductive paste that can achieve both high conductivity and excellent printability, adhesion, and heat resistance.
上記問題を解決する本発明は、以下より構成される。
（１）第１の硬化性樹脂成分と、前記第１の硬化性樹脂成分の架橋温度より１０℃以上高い架橋温度で架橋反応する第２の硬化性樹脂成分と、導電性粉末とを含み、前記第１の硬化性樹脂成分と前記第２の硬化性樹脂成分との合計の樹脂固形分量と導電性粉末との重量比は１：１００〜２０：１００であって、前記第１の硬化性樹脂成分と前記第２の硬化性樹脂成分は加熱硬化によりそれぞれの架橋温度で個別に架橋されて高分子鎖を形成し、かつ各高分子鎖同士が架橋することなく互いに絡み合った相互侵入型高分子網目（ＩＰＮ）構造を形成し、前記導電性粉末と共にＩＰＮ構造を有する導電層を形成することを特徴とする熱硬化型導電性ペースト。
（２）前記第１の硬化性樹脂成分がエポキシ樹脂とその硬化剤とを含むことを特徴とする、上記（１）に記載の熱硬化型導電性ペースト。
（３）前記第２の硬化性樹脂成分がイソシアネートと架橋可能な官能基を有する熱可塑性高分子と、ブロックイソシアネートとを含むことを特徴とする上記（１）又は（２）に記載の熱硬化型導電性ペースト。
（４）前記導電性粉末が銀、銅、ニッケル、アルミニウム、金、白金から選択される金属の少なくとも１種を含むことを特徴とする、上記（１）乃至（３）のいずれか一項に記載の熱硬化型導電性ペースト。
（５） 前記ブロックイソシアネートが、前記第１の硬化性樹脂成分の架橋温度より高い温度でブロック剤を解離するブロックイソシアネートであることを特徴とする上記（３）に記載の熱硬化型導電性ペースト。
（６）上記（１）乃至（５）のいずれか一項に記載の熱硬化型導電性ペーストを基板上に塗布し、加熱硬化を行うことによって得られた前記相互侵入型高分子網目（ＩＰＮ）構造を有する導電層を有することを特徴とする電気デバイス。
（７）上記（１）乃至（５）のいずれか一項に記載の熱硬化型導電性ペーストを基板上に塗布し、加熱硬化を行うことによって得られた前記相互侵入型高分子網目（ＩＰＮ）構造を有する電極を有することを特徴とする太陽電池。
The present invention for solving the above-described problems is composed of the following.
(1) including a first curable resin component, a second curable resin component that undergoes a crosslinking reaction at a crosslinking temperature that is 10 ° C. or higher than the crosslinking temperature of the first curable resin component, and a conductive powder. the weight ratio of the sum of resin solids weight and conductive powder of the first curable resin component and the second curable resin component is 1: 100 to 20: a 100, the first curing The interstitial resin component and the second curable resin component are individually crosslinked at each crosslinking temperature by heat curing to form polymer chains, and the polymer chains are entangled with each other without crosslinking. A thermosetting conductive paste that forms a polymer network (IPN) structure and forms a conductive layer having an IPN structure together with the conductive powder .
(2) The thermosetting conductive paste according to (1) above, wherein the first curable resin component contains an epoxy resin and a curing agent thereof.
( 3 ) The thermosetting according to (1) or (2) above, wherein the second curable resin component comprises a thermoplastic polymer having a functional group capable of crosslinking with isocyanate and a blocked isocyanate. Type conductive paste.
( 4 ) The conductive powder according to any one of (1) to ( 3 ), wherein the conductive powder contains at least one metal selected from silver, copper, nickel, aluminum, gold, and platinum. The thermosetting conductive paste described.
( 5 ) The thermosetting conductive paste according to ( 3 ), wherein the blocked isocyanate is a blocked isocyanate that dissociates the blocking agent at a temperature higher than the crosslinking temperature of the first curable resin component. .
( 6 ) The interpenetrating polymer network (IPN) obtained by applying the thermosetting conductive paste according to any one of (1) to ( 5 ) above onto a substrate and performing heat curing. An electrical device comprising a conductive layer having a structure.
( 7 ) The interpenetrating polymer network (IPN) obtained by applying the thermosetting conductive paste according to any one of (1) to ( 5) on a substrate and performing heat curing. A solar cell having an electrode having a structure.
本発明の導電性ペーストは、熱硬化によって架橋された２種以上の高分子がＩＰＮ構造を形成することで、機械強度、高温時の粘弾性特性等が改善され、単独の高分子架橋体のみ、或いはそれらの単なる混合物では得られない優れた耐熱性、密着性、耐衝撃性といった特性を得ることができ、これにより、導電性を損なうことなく、信頼性の優れた電極や導体配線を形成することが可能になる。 In the conductive paste of the present invention, two or more kinds of polymers cross-linked by thermosetting form an IPN structure, so that mechanical strength, viscoelastic properties at high temperature, etc. are improved. Or, it is possible to obtain excellent heat resistance, adhesion, and impact resistance characteristics that cannot be obtained by a simple mixture of them, thereby forming highly reliable electrodes and conductor wiring without impairing conductivity. It becomes possible to do.
本発明において、ＩＰＮ構造とは、導電性ペーストに含有される少なくとも２種の樹脂成分が、熱硬化によりそれぞれ個別に架橋されて高分子鎖を形成し、かつ各高分子鎖同士が架橋することなく互いに絡み合っている状態の構造を言い、一方の樹脂成分のみが架橋して高分子鎖を形成し、そこに他方の成分が架橋しないまま侵入したいわゆるｓｅｍｉ−ＩＰＮ構造は含まない。また例えば特許文献４のように、該２種以上の高分子がＩＰＮ構造とならず、架橋してブロック共重合体のような複合体になる場合は、本発明の効果は得られない。これは、必ずしも明確ではないが、ＩＰＮ構造においては該２種以上の高分子鎖が絡んだ部分である程度の可動性を有しているのに対し、異種高分子鎖の間に化学結合が生じると自由な運動性が束縛されて、例えば応力破壊が起こりやすくなるものと考えられる。
なお、本発明においては、前記少なくとも２種の樹脂成分のそれぞれがほぼすべて架橋してＩＰＮ構造に寄与し、未架橋の樹脂成分がほとんど残らないことが好ましいが、硬化物の特性に悪影響のない範囲で、それぞれの樹脂の１０重量％以下の未架橋物が残留していても差支えない。
In the present invention, the IPN structure means that at least two kinds of resin components contained in the conductive paste are individually crosslinked by thermosetting to form polymer chains, and the polymer chains are crosslinked with each other. In other words, the structure is intertwined with each other, and does not include a so-called semi-IPN structure in which only one resin component is crosslinked to form a polymer chain and the other component enters without being crosslinked. Further, for example, as in Patent Document 4, when the two or more kinds of polymers do not have an IPN structure and are crosslinked to form a composite such as a block copolymer, the effect of the present invention cannot be obtained. Although this is not necessarily clear, the IPN structure has a certain degree of mobility in the portion where the two or more polymer chains are entangled, whereas a chemical bond is formed between different polymer chains. It is considered that free mobility is constrained, and stress fracture is likely to occur, for example.
In the present invention, it is preferable that each of the at least two kinds of resin components is almost all crosslinked to contribute to the IPN structure, and there is almost no uncrosslinked resin component, but there is no adverse effect on the properties of the cured product. In the range, 10% by weight or less uncrosslinked product of each resin may remain.
本発明において、ＩＰＮ構造を形成する第１の硬化性樹脂成分としては制限はなく、熱硬化性樹脂や架橋可能な熱可塑性樹脂、例えばエポキシ樹脂、フェノール樹脂、アクリル樹脂、メタクリル樹脂、スチレン系樹脂、ブチラール樹脂、メラミン樹脂、ユリア樹脂、アルキッド樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、ポリイミド樹脂、ポリエステル樹脂、セルロース誘導体などが挙げられる。特にエポキシ樹脂、レゾール型フェノール樹脂、アクリル樹脂などは設計の自由度が高く、また優れた導電性、接着性、耐熱性、安定性を得やすいため好ましく、中でもエポキシ樹脂が好ましく使用される。第１の硬化性樹脂成分には、通常樹脂に使用される硬化剤、架橋剤、硬化促進剤、硬化触媒等が含有されていてもよい。これら第１の硬化性樹脂成分は、単独あるいは複数種の樹脂を組み合わせて使用してもよい。 In the present invention, the first curable resin component forming the IPN structure is not limited, and is a thermosetting resin or a crosslinkable thermoplastic resin such as an epoxy resin, a phenol resin, an acrylic resin, a methacrylic resin, or a styrene resin. , Butyral resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyester resin, cellulose derivative and the like. In particular, an epoxy resin, a resol type phenol resin, an acrylic resin, and the like are preferable because they have a high degree of design freedom and easily obtain excellent conductivity, adhesiveness, heat resistance, and stability. Among them, an epoxy resin is preferably used. The first curable resin component may contain a curing agent, a crosslinking agent, a curing accelerator, a curing catalyst, and the like that are usually used for the resin. You may use these 1st curable resin components individually or in combination of multiple types of resin.
エポキシ樹脂としては従来公知の様々なものが使用可能である。その代表例としては、ビスフェノールＡ型グリシジルエーテル系、ビスフェノールＦ型グリシジルエーテル系、オリゴエチレングリコール型グリシジルエーテル系、オリゴプロピレングリコール型グリシジルエーテル系、ビフェニル型グリシジルエーテル系、フタル酸グリシジルエステル系、水添フタル酸グリシジルエステル系、直鎖アルキルグリシジルエーテル系などの２官能性エポキシ化合物、ノボラックフェノールグリシジルエーテル系、ジグリセロールグリシジルエーテル系、ソルビトールグリシジルエーテル系、ペンタエリスリトールグリシジルエーテル系、トリメチロールプロパングリシジルエーテル系などの３官能性以上のエポキシ化合物が挙げられる。これらの化合物は単独でも複数種類を混合して使用してもよい。また、特に常温での粘度の低いものが良好な導電性を得る上で有用であり、特に２５℃での粘度が５Ｐａ・ｓ 以下のものが好ましい。これらの観点から特に好ましいものとしては、フタル酸グリシジルエステル系、水添フタル酸グリシジルエステル系、オリゴエチレングリコール型グリシジルエーテル系、オリゴプロピレングリコール型グリシジルエーテル系が使用できる。 Various conventionally known epoxy resins can be used. Typical examples are bisphenol A glycidyl ether, bisphenol F glycidyl ether, oligoethylene glycol glycidyl ether, oligopropylene glycol glycidyl ether, biphenyl glycidyl ether, glycidyl phthalate, hydrogenated Bifunctional epoxy compounds such as phthalic acid glycidyl ester and linear alkyl glycidyl ether, novolac phenol glycidyl ether, diglycerol glycidyl ether, sorbitol glycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane glycidyl ether The epoxy compound more than trifunctional of these is mentioned. These compounds may be used alone or in combination of two or more. In particular, those having a low viscosity at room temperature are useful for obtaining good conductivity, and those having a viscosity at 25 ° C. of 5 Pa · s or less are particularly preferable. Particularly preferable from these viewpoints are glycidyl phthalate ester, hydrogenated glycidyl phthalate ester, oligoethylene glycol glycidyl ether, and oligopropylene glycol glycidyl ether.
第１の硬化性樹脂成分に配合される硬化剤、架橋剤は、第１の硬化性樹脂成分の架橋硬化時に第２の硬化性樹脂成分との間に実質的に架橋を生じないようなものであれば特に限定はなく、例えばエポキシ樹脂の場合はフッ化ホウ素などのルイス酸類、アミン類、イミダゾール類等のアニオン系硬化剤や、酸無水物などの重付加性硬化剤等が使用可能であり、また、これらの硬化剤に公知の硬化促進剤を併用してもよい。これらの硬化剤の中でもポットライフの視点から潜在硬化剤が有用であり、例えば三フッ化ホウ素エチルエーテル、三フッ化ホウ素フェノール、三フッ化ホウ素ピペリジン、酢酸三フッ化ホウ素、三フッ化ホウ素トリエタノールアミン、三フッ化ホウ素モノエチルアミン、三フッ化ホウ素モノエタノールアミンなどのフッ化ホウ素系、ジアミノフェニルメタン、ｍ−フェニレンジアミン、ジアミノジフェニルスルフォンなどの芳香族アミン潜在硬化剤を挙げることができる。これらの中で、三フッ化ホウ素モノエチルアミン、三フッ化ホウ素モノエタノールアミン、芳香族アミンを好ましく使用することができる。フッ化ホウ素系潜在硬化剤を使用する場合、その望ましい添加量はエポキシ樹脂に対して１重量％から２０重量％の範囲である。１重量％よりも少ない場合、硬化反応が不十分となり、また２０重量％よりも多い場合、過剰な硬化剤によって、いずれも膜物性が低下する恐れがある。第１の硬化性樹脂成分においてエポキシ樹脂以外の樹脂、フッ化ホウ素系潜在硬化剤以外の硬化剤を使用する場合についても、樹脂に対する硬化剤の添加量は上記と同様であることが好ましい。 The curing agent and the crosslinking agent blended in the first curable resin component are such that substantially no crosslinking occurs between the first curable resin component and the second curable resin component when the first curable resin component is crosslinked and cured. For example, in the case of an epoxy resin, an anionic curing agent such as a Lewis acid such as boron fluoride, an amine or an imidazole, or a polyaddition curing agent such as an acid anhydride can be used. In addition, a known curing accelerator may be used in combination with these curing agents. Among these curing agents, latent curing agents are useful from the viewpoint of pot life, such as boron trifluoride ethyl ether, boron trifluoride phenol, boron trifluoride piperidine, boron acetate trifluoride, boron trifluoride trioxide. Examples include boron fluorides such as ethanolamine, boron trifluoride monoethylamine, and boron trifluoride monoethanolamine, and aromatic amine latent curing agents such as diaminophenylmethane, m-phenylenediamine, and diaminodiphenylsulfone. Among these, boron trifluoride monoethylamine, boron trifluoride monoethanolamine, and aromatic amine can be preferably used. When a boron fluoride-based latent curing agent is used, its desirable addition amount is in the range of 1 to 20% by weight with respect to the epoxy resin. When the amount is less than 1% by weight, the curing reaction becomes insufficient. When the amount is more than 20% by weight, the physical properties of the film may be lowered due to an excessive curing agent. Also in the case of using a resin other than an epoxy resin and a curing agent other than a boron fluoride latent curing agent in the first curable resin component, the addition amount of the curing agent to the resin is preferably the same as described above.
前記第１の硬化性樹脂成分と共にＩＰＮ構造を形成する他の硬化性樹脂成分（以下第２の硬化性樹脂成分という）としては、第１の硬化性樹脂成分とは独立に架橋して第１の硬化性樹脂成分の硬化物とＩＰＮ構造体を形成し得るものであれば制限はない。例えばエポキシ樹脂、フェノール樹脂、アクリル樹脂、メタクリル樹脂、スチレン系樹脂、ブチラール樹脂、メラミン樹脂、ユリア樹脂、アルキッド樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、ポリイミド樹脂、ポリエステル樹脂、セルロース誘導体など第１の硬化性樹脂成分として例示された熱硬化性樹脂や、架橋可能な熱可塑性樹脂が挙げられ、これらの中から導電性ペーストの硬化条件でその架橋体と第１の硬化性樹脂成分の架橋体との間に実質的に架橋を生じないようなものが選択される。また第１の硬化性樹脂成分について述べたように、通常樹脂に使用される硬化剤、架橋剤、硬化促進剤、硬化触媒等が含有されていてもよい。なお、第１の硬化性樹脂と異なる種類の樹脂を組み合わせることがＩＰＮ構造体の形成や得られる物性の観点で望ましい。これら第２の硬化性樹脂成分としては、複数種の樹脂を併用してもよい。 As the other curable resin component that forms an IPN structure together with the first curable resin component (hereinafter referred to as the second curable resin component), the first curable resin component is cross-linked independently of the first curable resin component. If it can form the hardened | cured material of this curable resin component and an IPN structure, there will be no restriction | limiting. For example, epoxy resin, phenol resin, acrylic resin, methacrylic resin, styrene resin, butyral resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyester resin, cellulose derivative, etc. The thermosetting resin exemplified as the curable resin component and the crosslinkable thermoplastic resin can be mentioned. Among these, the crosslinked body and the crosslinked body of the first curable resin component can be used under the curing conditions of the conductive paste. Those that do not substantially cause cross-linking between them are selected. Moreover, as described about the 1st curable resin component, the hardening | curing agent normally used for resin, a crosslinking agent, a hardening accelerator, a hardening catalyst, etc. may contain. In addition, it is desirable to combine a different kind of resin with the first curable resin from the viewpoint of formation of the IPN structure and obtained physical properties. As these 2nd curable resin components, you may use multiple types of resin together.
２種以上の高分子鎖同士が互いに架橋することなく絡み合ったＩＰＮ構造体を形成するためには、第２の硬化性樹脂成分の架橋剤として、第１の硬化性樹脂成分との間に架橋を生じさせないようなものを選択して配合し、同じ温度域でそれぞれを同時に架橋させてＩＰＮ構造体を得ることも可能であるが、好ましくは、第２の硬化性樹脂成分として、第１の硬化性樹脂成分と異なる温度で架橋するものを使用する。後者の方法では、例えば初めに第１の硬化性樹脂成分を架橋させた後、それより高い温度で第２の硬化性樹脂成分が架橋するように樹脂、架橋剤（硬化剤）が選択される。その場合、初めに架橋した樹脂成分の硬化物中に、他の硬化性樹脂成分と架橋し得る反応基が実質的に残留していないことが好ましい。これにより、第１の硬化性樹脂成分の架橋体と第２の硬化性樹脂成分の架橋体との間に実質的に架橋のない硬化物を得ることができる。この手法の場合、異種高分子同士が架橋反応を起こさず良好なＩＰＮ構造を形成するためには各架橋反応温度の差は１０℃以上あることがより好ましい。さらには２０℃以上であればより良好なＩＰＮ構造を形成することが可能であるため好ましい。 In order to form an IPN structure in which two or more polymer chains are entangled with each other without cross-linking each other, a cross-linking agent for the second curable resin component is used as a cross-linking agent for the first curable resin component. It is possible to obtain an IPN structure by selecting and blending those that do not cause the occurrence of the above, and simultaneously cross-linking each in the same temperature range, but preferably, as the second curable resin component, A material that crosslinks at a temperature different from that of the curable resin component is used. In the latter method, for example, after the first curable resin component is first crosslinked, the resin and the crosslinking agent (curing agent) are selected so that the second curable resin component is crosslinked at a higher temperature. . In that case, it is preferable that the reactive group which can be bridge | crosslinked with another curable resin component does not remain substantially in the hardened | cured material of the resin component bridge | crosslinked initially. Thereby, the hardened | cured material with substantially no bridge | crosslinking can be obtained between the crosslinked body of the 1st curable resin component, and the crosslinked body of the 2nd curable resin component. In the case of this method, in order to form a good IPN structure without causing a cross-linking reaction between different kinds of polymers, it is more preferable that the difference in cross-linking reaction temperature is 10 ° C. or more. Furthermore, if it is 20 degreeC or more, since a more favorable IPN structure can be formed, it is preferable.
第２の硬化性樹脂成分としては、特に分子内にイソシアネート基と反応可能な官能基を持った熱可塑性高分子と、架橋剤としての多官能性イソシアネートの組合せが、導電性を損なうことなくより耐熱性、接着性の優れた導電層を形成し得るので好ましい。
イソシアネート基と反応可能な官能基を持った熱可塑性高分子としては、水酸基、カルボキシル基やアミド基などを分子内に有した高分子でありポリビニルブチラール、酢酸ビニル−ビニルアルコール共重合体、メチルセルロース、エチルセルロースやヒドロキシエチルセルロースなどの変性セルロース、（メタ）アクリル酸と種々の（メタ）アクリル酸アルキルエステルとの共重合体、２−ヒドロキシエチル（メタ）アクリレートと種々の（メタ）アクリル酸アルキルエステルとの共重合体、（メタ）アクリルアミドと種々の（メタ）アクリル酸アルキルエステル、ノボラック型フェノール樹脂などが挙げられる。これらの高分子は単独であっても複数種を混合して用いても構わない。中でもエチルセルロースやポリビニルブチラール等が、成膜性や導電性の観点で好ましい。
As the second curable resin component, a combination of a thermoplastic polymer having a functional group capable of reacting with an isocyanate group in the molecule and a polyfunctional isocyanate as a cross-linking agent is preferable without impairing conductivity. This is preferable because a conductive layer having excellent heat resistance and adhesiveness can be formed.
The thermoplastic polymer having a functional group capable of reacting with an isocyanate group is a polymer having a hydroxyl group, a carboxyl group or an amide group in the molecule, such as polyvinyl butyral, vinyl acetate-vinyl alcohol copolymer, methylcellulose, Modified cellulose such as ethyl cellulose and hydroxyethyl cellulose, copolymers of (meth) acrylic acid and various (meth) acrylic acid alkyl esters, 2-hydroxyethyl (meth) acrylate and various (meth) acrylic acid alkyl esters Examples thereof include copolymers, (meth) acrylamide and various (meth) acrylic acid alkyl esters, novolac type phenol resins, and the like. These polymers may be used alone or as a mixture of plural kinds. Of these, ethyl cellulose, polyvinyl butyral, and the like are preferable from the viewpoint of film formability and conductivity.
イソシアネートとしては分子内に二つ以上のイソシアネート基を有するものが使用され、脂肪族系や芳香族系の様々なものが使用可能であるが、より高い耐熱性を与えるという観点で芳香族系が好ましい。具体的にはトリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）などが代表的なものである。またイソシアネートとしては、ブロック剤によって特定温度までの反応性が抑制されたいわゆるブロックイソシアネートを用いることが好ましい。ブロックイソシアネートを用いると、ブロック剤が解離する温度を選択することにより第２の硬化性樹脂成分の架橋温度を制御することができる。例えば前述のとおり最適なＩＰＮ構造を形成するためには、第１の硬化性樹脂成分として使用された樹脂の架橋温度より高い温度で反応活性を示すブロックイソシアネートが好ましく使用される。 As the isocyanate, those having two or more isocyanate groups in the molecule are used, and various aliphatic and aromatic ones can be used, but aromatics are preferred from the viewpoint of providing higher heat resistance. preferable. Specific examples include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). As the isocyanate, it is preferable to use a so-called blocked isocyanate in which the reactivity up to a specific temperature is suppressed by a blocking agent. When the blocked isocyanate is used, the crosslinking temperature of the second curable resin component can be controlled by selecting the temperature at which the blocking agent is dissociated. For example, in order to form an optimal IPN structure as described above, a blocked isocyanate exhibiting a reaction activity at a temperature higher than the crosslinking temperature of the resin used as the first curable resin component is preferably used.
また、後述する理由から、本発明において優れた導電性を得るためには、最終的な硬化温度は１５０℃以上であることが好ましく、この観点から、第１の硬化性樹脂成分として低温で架橋する樹脂を使用する場合には、好ましくは１５０℃以上の温度でブロック剤が解離する高温タイプのブロックイソシアネートが、第２の硬化性樹脂成分での架橋剤として使用される。より好ましくは１７０℃以上の温度でブロック剤が解離する高温タイプのブロックイソシアネートが使用される。具体的にはアルコール類、フェノール類、ラクタム類、オキシム類などをブロック剤として使用したものが好ましい。 In addition, for the reason described later, in order to obtain excellent conductivity in the present invention, the final curing temperature is preferably 150 ° C. or higher. From this viewpoint, the first curable resin component is crosslinked at a low temperature. When the resin to be used is used, a high-temperature type blocked isocyanate in which the blocking agent dissociates preferably at a temperature of 150 ° C. or higher is used as a crosslinking agent in the second curable resin component. More preferably, a high-temperature type blocked isocyanate in which the blocking agent dissociates at a temperature of 170 ° C. or higher is used. Specifically, those using alcohols, phenols, lactams, oximes and the like as blocking agents are preferred.
イソシアネートの好ましい添加量は、前記イソシアネートと該イソシアネート基と架橋可能な官能基を有する熱可塑性高分子に対して１重量％〜５０重量％の範囲である。１重量％よりも少ないと架橋密度が低く目的の物性が得られない可能性があり、５０重量％よりも多いと未反応のイソシアネートが物性を低下させる恐れが生じる。 A preferable addition amount of the isocyanate is in the range of 1% by weight to 50% by weight with respect to the thermoplastic polymer having a functional group capable of crosslinking with the isocyanate and the isocyanate group. If the amount is less than 1% by weight, the crosslink density is low and the desired physical properties may not be obtained. If the amount is more than 50% by weight, unreacted isocyanate may reduce the physical properties.
ＩＰＮ構造を形成する前記第１の硬化性樹脂成分と第２の硬化性樹脂成分の好ましい混合比は、硬化物としての重量比で１：５０〜５０：１の範囲から選択される。この範囲外ではＩＰＮ構造が形成されても目的の物性が得られなくなる恐れが生じる。また、これらの樹脂成分に加えて様々な目的で他の樹脂を配合することも可能である。 A preferable mixing ratio of the first curable resin component and the second curable resin component forming the IPN structure is selected from a range of 1:50 to 50: 1 as a weight ratio as a cured product. Outside this range, there is a fear that even if the IPN structure is formed, the desired physical properties cannot be obtained. In addition to these resin components, other resins can be blended for various purposes.
ここで一例として、エポキシ樹脂と、イソシアネートとポリビニルブチラール（ＰＶＢ）を使ってＩＰＮ構造を形成するための手法を示す。第１の硬化性樹脂成分として一分子中に２以上のエポキシ基を有する多官能性エポキシ化合物と、１２０℃で活性を示す潜在硬化剤として三フッ化ホウ素モノエチルアミンを、さらに第二の硬化性樹脂成分としてＰＶＢと、１５０℃より高い温度で反応活性を与えるブロックイソシアネート（架橋剤）とを混合した樹脂組成物を調製する。この組成物を基板に塗布して１８０〜２００℃程度の温度で加熱硬化処理を行うと、昇温過程で以下のように反応が進行する。１２０℃の加熱によって潜在硬化剤が活性化し、重合、架橋によるエポキシ樹脂の硬化反応が進行し、１５０℃ではほぼ反応が終了する。一方でＰＶＢはエポキシ樹脂やその硬化剤とは反応しないために、１５０℃では未架橋状態であり、そのため一方の高分子（エポキシ樹脂）のみが架橋したいわゆるｓｅｍｉ−ＩＰＮ構造をとっている。さらに加熱を続けて１５０℃を超える温度になるとブロックイソシアネートのブロック剤が解離し、遊離したイソシアネートとＰＶＢの水酸基とが反応し、ＰＶＢが架橋されると共にエポキシ樹脂架橋体とＰＶＢ架橋体が相互に絡み合ったＩＰＮ構造体が形成される。これらの反応過程は示差走査熱量測定（ＤＳＣ）等における発熱・吸熱の挙動として把握することができる。また、前記ｓｅｍｉ−ＩＰＮ構造とＩＰＮ構造の違いは、ＴＭＡ（熱機械分析）測定でのＴｇ（ガラス転移点）の変化や加熱時の粘弾性特性の違い、また硬化後の樹脂の溶媒抽出試験等から把握することができる。例えば、上記の例においてはｓｅｍｉ−ＩＰＮ状態からＩＰＮ構造の形成に伴ってＴｇが上昇することと、硬化物を未架橋のＰＶＢに対する良溶媒、例えばテトラヒドロフラン（ＴＨＦ）に浸漬することにより抽出される物質を定量、定性分析すると、ｓｅｍｉ−ＩＰＮ構造では架橋していないＰＶＢが抽出されるのに対してＩＰＮ構造では架橋していないＰＶＢが殆ど抽出されないことによってＩＰＮ構造体の形成が確認できる。 Here, as an example, a method for forming an IPN structure using an epoxy resin, isocyanate, and polyvinyl butyral (PVB) is shown. A polyfunctional epoxy compound having two or more epoxy groups in one molecule as a first curable resin component, boron trifluoride monoethylamine as a latent curing agent showing activity at 120 ° C., and a second curable property A resin composition is prepared by mixing PVB as a resin component and a blocked isocyanate (crosslinking agent) that gives reaction activity at a temperature higher than 150 ° C. When this composition is applied to a substrate and heat-cured at a temperature of about 180 to 200 ° C., the reaction proceeds as follows in the temperature rising process. The latent curing agent is activated by heating at 120 ° C., and the curing reaction of the epoxy resin by polymerization and crosslinking proceeds, and the reaction is almost completed at 150 ° C. On the other hand, since PVB does not react with an epoxy resin or its curing agent, it is in an uncrosslinked state at 150 ° C., and therefore has a so-called semi-IPN structure in which only one polymer (epoxy resin) is crosslinked. Further, when the heating is continued and the temperature exceeds 150 ° C., the blocking agent of the blocked isocyanate is dissociated, the liberated isocyanate reacts with the hydroxyl group of PVB, PVB is crosslinked, and the crosslinked epoxy resin and crosslinked PVB are mutually An intertwined IPN structure is formed. These reaction processes can be grasped as exothermic / endothermic behavior in differential scanning calorimetry (DSC) or the like. Moreover, the difference between the semi-IPN structure and the IPN structure is the difference in Tg (glass transition point) in TMA (thermomechanical analysis) measurement, the difference in viscoelastic properties during heating, and the solvent extraction test of the resin after curing. Etc. For example, in the above example, the Tg increases with the formation of the IPN structure from the semi-IPN state, and the cured product is extracted by dipping in a good solvent for uncrosslinked PVB, such as tetrahydrofuran (THF). When the substance is quantitatively and qualitatively analyzed, PVB that is not crosslinked is extracted in the semi-IPN structure, whereas PVB that is not crosslinked in the IPN structure is hardly extracted, so that formation of an IPN structure can be confirmed.
本発明の導電性ペーストにおいて、導電性粉末としては通常熱硬化型導電性ペーストに使用されるものであれば制限はないが、高い導電性を持つ銀、銅、ニッケル、アルミニウム、金、白金等の金属粉末やこれらの金属の少なくとも１種を含む混合粉末、合金粉末、複合粉末などの１種又は複数種組み合わせて使用可能である。特に導電性とコストの観点から銀粉末、銀被覆銅粉末、銅粉末が好ましく使用される。またこれらに加えて、基板や被接着物との接続性の向上のためにスズ、ビスマス、インジウム、鉛、半田などの低融点金属の粉末や、これらの金属を含む合金粉末、複合粉末を添加してもよい。
導電性粉末の形状は球状、多面形状、フレーク状、樹枝状、繊維状などの種々が使用可能であり、異なった形状や粒子径のものを混合して使用しても構わない。中でも球状粉末は高い充填性を持つために導電性が良いこと、また細線印刷性が優れることから好ましく使用される。また、導電性粉末の大きさは、球状粉末ではＳＥＭ分析の数平均粒径が０．０１μｍ〜５μｍの範囲のものが好ましく、導電性特性からはより好ましくは０．１μｍ〜２μｍのものである。導電性を改善するためにこれらの粉末に前記したものと同様の導電性金属の超微粒子、例えば金属ナノ粒子を配合してもよい。
In the conductive paste of the present invention, the conductive powder is not limited as long as it is normally used for thermosetting conductive paste, but silver, copper, nickel, aluminum, gold, platinum, etc. having high conductivity These metal powders, mixed powders containing at least one of these metals, alloy powders, composite powders, and the like can be used alone or in combination. In particular, silver powder, silver-coated copper powder, and copper powder are preferably used from the viewpoint of conductivity and cost. In addition to these, low melting point metal powders such as tin, bismuth, indium, lead and solder, alloy powders containing these metals, and composite powders are added to improve connectivity with substrates and adherends. May be.
Various shapes such as a spherical shape, a polyhedral shape, a flake shape, a dendritic shape, and a fibrous shape can be used as the conductive powder, and those having different shapes and particle sizes may be mixed and used. Among these, spherical powders are preferably used because they have high filling properties and good electrical conductivity and excellent fine line printability. The size of the conductive powder is preferably a spherical powder having a SEM analysis number average particle size in the range of 0.01 μm to 5 μm, and more preferably 0.1 μm to 2 μm in terms of conductive properties. . In order to improve conductivity, ultrafine particles of conductive metal similar to those described above, for example, metal nanoparticles, may be added to these powders.
導電性粉末の表面には、ペースト中での分散性を改善するために従来から公知の吸着層や保護層が形成されていてもよい。このような分散性改善剤としては、例えば、有機カルボン酸類やその塩、有機アミン類やその塩、アミノアルコール類やその塩、親水基と疎水基を分子内に持ったいわゆる界面活性剤などが、単独であるいは混合して使用される。また、これらの材料は導電性粉末に対して０．０１重量％〜２重量％の範囲で含まれることが分散性と導電性の観点から望ましい。 A conventionally known adsorption layer or protective layer may be formed on the surface of the conductive powder in order to improve dispersibility in the paste. Examples of such a dispersibility improving agent include organic carboxylic acids and salts thereof, organic amines and salts thereof, amino alcohols and salts thereof, and so-called surfactants having a hydrophilic group and a hydrophobic group in the molecule. , Used alone or in combination. Moreover, it is desirable from the viewpoint of dispersibility and conductivity that these materials are contained in the range of 0.01% by weight to 2% by weight with respect to the conductive powder.
本発明の導電性ペーストにおいて、樹脂成分の量は、樹脂固形分と導電性粉末の重量比で、１：１００〜２０：１００の範囲が好ましい。もし１：１００の比よりも樹脂成分が少なくなると、硬化後の導電層の密着性や耐久性が低下する、一方で２０：１００の比より樹脂成分が多くなると導電性が低下する恐れがある。 In the conductive paste of the present invention, the amount of the resin component is preferably in the range of 1: 100 to 20: 100 in terms of the weight ratio of the resin solid content to the conductive powder. If the resin component is less than the ratio of 1: 100, the adhesion and durability of the conductive layer after curing will be reduced, while if the resin component is more than the ratio of 20: 100, the conductivity may be reduced. .
なお優れた導電性を得るためには、導電性粉末の種類や物性に合わせて最適な樹脂設計を行うこと、特に架橋温度を選択することも重要である。本発明者等の検討によれば、導電性粉末として樹脂の硬化温度付近の低温で焼結を始めるようなものを用いた場合は、焼結を開始する温度領域で樹脂に分子運動がある程度許容されることが、導電性粉末の焼結促進、導電性の向上には有効である。従って本発明においては、前記２以上の硬化性樹脂成分のうち高温で架橋する方の架橋温度が導電性粉末の焼結開始温度以上であること、例えば銀粉末を用いた場合には１５０℃以上であることが好ましい。このようにして導電性粉末の焼結を阻害しないような温度プロファイルで架橋反応を段階的に進めることで、優れた導電性を得ることができる。 In order to obtain excellent conductivity, it is also important to design an optimum resin in accordance with the type and physical properties of the conductive powder, particularly to select a crosslinking temperature. According to the study by the present inventors, when a powder that starts sintering at a low temperature near the curing temperature of the resin is used as the conductive powder, molecular motion is allowed to some extent in the temperature range where the sintering starts. It is effective for promoting the sintering of the conductive powder and improving the conductivity. Therefore, in the present invention, among the two or more curable resin components, the crosslinking temperature of the one that is crosslinked at a high temperature is equal to or higher than the sintering start temperature of the conductive powder, for example, 150 ° C. or higher when silver powder is used. It is preferable that Thus, the outstanding electroconductivity can be acquired by advancing a crosslinking reaction in steps by the temperature profile which does not inhibit sintering of electroconductive powder.
本発明の導電性ペーストには、塗布性や粘度調整等のために必要に応じて有機溶剤を含有させてもよい。この場合有機溶剤は、樹脂固形分と導電性粉末との総計に対して１重量％〜１００重量％の範囲で添加される。有機溶剤としては制限はなく、例えばアルコール系溶剤、エステル系溶剤、エーテル系溶剤、ケトン系溶剤、炭化水素系溶剤、脂肪酸系溶剤、反応性希釈剤等が適宜選択される。特に沸点が１００℃以上のものが好ましく使用され、例えばトルエン、ヘキサノン、メチルイソブチルケトン、エチルカルビトールアセテート、ブチルカルビトールアセテート、ブチルカルビトール、ブチルセロソルブ、ブチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノブチルエーテル、イソホロン、テルピネオール等様々な公知の有機溶剤が使用できる。 The conductive paste of the present invention may contain an organic solvent as needed for coating properties and viscosity adjustment. In this case, the organic solvent is added in the range of 1% by weight to 100% by weight with respect to the total of the resin solid content and the conductive powder. There is no restriction | limiting as an organic solvent, For example, alcohol solvent, ester solvent, ether solvent, ketone solvent, hydrocarbon solvent, fatty acid solvent, a reactive diluent, etc. are selected suitably. Particularly those having a boiling point of 100 ° C. or more are preferably used. For example, toluene, hexanone, methyl isobutyl ketone, ethyl carbitol acetate, butyl carbitol acetate, butyl carbitol, butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, triethylene glycol Various known organic solvents such as monobutyl ether, isophorone, and terpineol can be used.
さらに、本発明の導電性ペーストには、印刷性、電気特性、安定性や耐候性等の改善のために様々の添加剤を配合してもよい。例えば印刷性改善のためには、チクソ剤、界面活性剤や種々の熱可塑性高分子類などが、安定性と耐候性改善のためには酸化防止剤、紫外線吸収剤などが使用される。その他にも金属の酸化膜を除去するためのロジンやその誘導体に代表されるフラックス剤や多価カルボン酸を含めた有機カルボン酸、種々の色素、さらにはシリカ、酸化チタンなどの金属酸化物、カーボンブラック、グラファイト、カーボンナノチューブ、フラーレン、グラフェンなどの炭素類等の無機粒子も適宜添加可能である。
さらには酸化銀、炭酸銀などの無機の銀化合物や炭素数１〜３０の脂肪酸銀のような有機銀化合物を添加してもよい。これらの銀化合物が添加される場合、さらにこれらの銀化合物を還元するアルコール類、アミン類等の還元剤を添加してもよい。これらの銀化合物は加熱過程において銀粒子に還元転換され、導電性粉末との相乗効果によって導電性を改善し、また導電性の基板や電極上に塗布、硬化された場合や太陽電池の集電極等に適用された場合には接触抵抗を改善する効果がある。銀化合物の好ましい添加量は導電性粉末に対して０．１重量％〜１０重量％の範囲、より好ましくは１重量％〜８重量％の範囲である。
Furthermore, you may mix | blend various additives with the electrically conductive paste of this invention in order to improve printability, an electrical property, stability, a weather resistance, etc. For example, thixotropic agents, surfactants and various thermoplastic polymers are used for improving printability, and antioxidants, ultraviolet absorbers and the like are used for improving stability and weather resistance. In addition, rosin for removing metal oxide films and flux agents represented by derivatives thereof, organic carboxylic acids including polyvalent carboxylic acids, various dyes, and metal oxides such as silica and titanium oxide, Inorganic particles such as carbons such as carbon black, graphite, carbon nanotubes, fullerene and graphene can be added as appropriate.
Furthermore, you may add inorganic silver compounds, such as silver oxide and silver carbonate, and organic silver compounds, such as C1-C30 fatty acid silver. When these silver compounds are added, reducing agents such as alcohols and amines that reduce these silver compounds may be further added. These silver compounds are reduced and converted to silver particles during the heating process, improving the conductivity by a synergistic effect with the conductive powder, and when applied and cured on a conductive substrate or electrode, or the collector electrode of a solar cell When applied to the above, there is an effect of improving the contact resistance. A preferable addition amount of the silver compound is in the range of 0.1% by weight to 10% by weight, more preferably in the range of 1% by weight to 8% by weight with respect to the conductive powder.
次に本発明の導電性ペーストの作製方法を一例として示す。第１の硬化性樹脂成分と、第２の硬化性樹脂成分、導電性粉末、及び必要に応じて有機溶剤や添加剤を配合し、これをロールミル、ボールミル、サンドミル、ペブルミル、トロンミル、サンドグラインダー、セグバリアトライター、高速インペラー分散機、高速ストーンミル、高速度衝撃ミル、ニーダー、ホモジナイザー、超音波分散機等の公知の分散装置にて均一に混合することでペーストを作製する。ペーストの粘度やレオロジー特性は、従来と同様に用途、塗布方法等目的に応じて適宜設定される。 Next, a method for producing a conductive paste according to the present invention will be described as an example. A first curable resin component, a second curable resin component, a conductive powder, and an organic solvent and additives as necessary are blended, and this is mixed with a roll mill, a ball mill, a sand mill, a pebble mill, a tron mill, a sand grinder, A paste is prepared by uniformly mixing with a known dispersion apparatus such as a seg barrier triter, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, and an ultrasonic disperser. The viscosity and rheological properties of the paste are appropriately set according to the purpose such as use, coating method and the like as in the past.
本発明の導電性ペーストはディップ法、ディスペンス法、スクリーン印刷法、オフセット印刷法、グラビア印刷法、インクジェット法、刷毛塗り、スピンコートなどの各種方法によって所望の基板上に必要なパターン形状で塗布され、その後、加熱硬化処理することで導電層が形成される。基板としてはアモルファスシリコン基板や結晶シリコン基板、樹脂、セラミック、ガラス、ガラスエポキシ、紙、化合物半導体などの種々のものが使用できる。 The conductive paste of the present invention is applied in a desired pattern shape on a desired substrate by various methods such as a dipping method, a dispensing method, a screen printing method, an offset printing method, a gravure printing method, an ink jet method, brush coating, and spin coating. Then, a conductive layer is formed by heat curing treatment. Various substrates such as an amorphous silicon substrate, a crystalline silicon substrate, resin, ceramic, glass, glass epoxy, paper, and compound semiconductor can be used as the substrate.
本発明の導電性ペーストは、例えば太陽電池用には、半導体性アモルファスシリコン基板や結晶シリコン基板上に電極配線として形成される。この他、プリント基板の回路配線、ジャンパー回路、スルーホール導体、電極、コンデンサやアクチュエータ等各種電子部品の電極等、様々な電気デバイスに応用することが可能な有用なものである。 The conductive paste of the present invention is formed as an electrode wiring on a semiconductor amorphous silicon substrate or a crystalline silicon substrate, for example, for solar cells. In addition, it is useful that can be applied to various electrical devices such as printed circuit board wiring, jumper circuits, through-hole conductors, electrodes, electrodes of various electronic components such as capacitors and actuators.
以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this.
実施例、比較例で使用したペースト材料は以下のとおりである。
エポキシ樹脂ａ：プリンテック社製ＥＰＯＸ−ＭＫ Ｒ５０８（フタル酸ジグリシジルエステル系、２５℃粘度４．４Ｐａ．ｓ）
エポキシ樹脂ｂ：プリンテック社製ＥＰＯＸ−ＭＫ Ｒ５４０（水素置換フタル酸ジグリシジルエステル系、２５℃粘度０．４Ｐａ．ｓ）
エポキシ樹脂ｃ：ナガセケムテックス社製デナコールＥＸ−２１２（ヘキサンジオールジグリシジルエーテル系、２５℃粘度０．０２Ｐａ．ｓ）
エポキシ樹脂ｄ：三菱化学社製ＪＥＲ−８２８（ビスフェノールＡジグリシジルエーテル系、２５℃粘度１３．５Ｐａ．ｓ）
エチルセルロース：ダウケミカル社製エトセルの２０ｗｔ％ブチルカルビトール溶液
ポリビニルブチラール：積水化学工業社製エスレックＢ ＢＸ−５
ノボラックフェノール樹脂：明和化成社製ＭＥＨＣ−７８００Ｈ
レゾール型フェノール樹脂：群栄化学社製ＰＬ４２２２
多官能アクリレートモノマ：東亜合成社製Ｍ−３０９（トリメチロールトリアクリレート）
ブロックイソシアネートａ：日本ポリウレタン社製ミリオネートＭＳ５０（ＭＤＩ系、ブロック剤解離温度１７０℃）
ブロックイソシアネートｂ：日本ポリウレタン社製コロネートＡＰ（ＴＤＩ系、ブロック剤解離温度１７０℃）
ブロックイソシアネートｃ：日本ポリウレタン社製コロネート２５１２（ＭＤＩ系、ブロック剤解離温度１４０℃）
エポキシ硬化剤：東京化成社製三フッ化ホウ素モノエチルアミン
アゾ系ラジカル重合開始剤：和光純薬製ＶＡｍ−１１０（１０時間半減期１１０℃）
球状銀粉末：ＳＥＭ観察による数平均粒径が０．４μｍの球状銀粒子
フレーク状銀粉末：ＳＥＭ観察による数平均粒子径（長軸と短軸の和の１／２の平均値）が２μｍのフレーク状銀粉末
酸化銀：和光純薬工業社製酸化銀（Ｉ）
各実施例、比較例のペースト特性の評価は次のようにして行った。
The paste materials used in the examples and comparative examples are as follows.
Epoxy resin a: Epox-MK R508 manufactured by Printec Co., Ltd. (diglycidyl phthalate ester system, viscosity at 25 ° C., 4.4 Pa.s)
Epoxy resin b: Epox-MK R540 manufactured by Printec Co., Ltd. (hydrogen-substituted phthalic acid diglycidyl ester system, 25 ° C., viscosity 0.4 Pa.s)
Epoxy resin c: Denacol EX-212 manufactured by Nagase ChemteX Corporation (hexanediol diglycidyl ether system, 25 ° C. viscosity 0.02 Pa.s)
Epoxy resin d: JER-828 (bisphenol A diglycidyl ether type, 25 ° C. viscosity 13.5 Pa.s) manufactured by Mitsubishi Chemical Corporation
Ethylcellulose: 20 wt% butyl carbitol solution of Etocel manufactured by Dow Chemical Company Polyvinyl butyral: S-REC B BX-5 manufactured by Sekisui Chemical Co., Ltd.
Novolac phenol resin: MEHC-7800H manufactured by Meiwa Kasei Co., Ltd.
Resol type phenol resin: PL4222 by Gunei Chemical Co., Ltd.
Multifunctional acrylate monomer: M-309 (trimethylol triacrylate) manufactured by Toa Gosei Co., Ltd.
Block isocyanate a: Nippon Polyurethane Millionate MS50 (MDI system, blocking agent dissociation temperature 170 ° C.)
Block isocyanate b: Coronate AP manufactured by Nippon Polyurethane Co., Ltd. (TDI system, blocking agent dissociation temperature 170 ° C.)
Block isocyanate c: Coronate 2512 manufactured by Nippon Polyurethane Co., Ltd. (MDI type, blocking agent dissociation temperature 140 ° C.)
Epoxy curing agent: Boron trifluoride monoethylamine manufactured by Tokyo Chemical Industry Co., Ltd. Azo radical polymerization initiator: VAm-110 manufactured by Wako Pure Chemical Industries (10-hour half-life 110 ° C.)
Spherical silver powder: Spherical silver particles having a number average particle diameter of 0.4 μm observed by SEM Flaky silver powder: number average particle diameter (an average value of 1/2 of the sum of the major axis and the minor axis) of 2 μm Flaky silver powder Silver oxide: Silver oxide (I) manufactured by Wako Pure Chemical Industries, Ltd.
The paste characteristics of each example and comparative example were evaluated as follows.
［導電性の評価］
導電性ペーストをガラス基板上に 厚み１５μｍ、０．６ｍｍ×６０ｍｍの長方形パターンにスクリーン印刷し、２００℃で３０分硬化処理を行って導体層を形成し、４端子法によって電気抵抗値を測定し、比抵抗を算出した。
［耐熱性（密着性）の評価］
導電性ペーストをガラス基板上に厚み１０μｍ、２ｍｍ×２ｍｍの正方形パターンにスクリーン印刷し、２００℃で３０分硬化処理を行った。得られた導体層を有する基板を２００℃のホットプレート上に置き、導体層表面にナイフの刃を３０°の角度であて、５Ｎの力で横方向に押して剥離の有無を調べた。パターンごと剥離したものを×、剥離しないものを○とした。
［ＩＰＮ構造形成の有無の確認（溶媒抽出試験）］
導電性粉末を含まないペーストをフッ素樹脂フイルム上に塗布して２００℃で３０分硬化処理した。硬化後の試料を剥離し、その２．０ｇを粉砕し、テトラヒドロフラン（ＴＨＦ）５０ｍｌに２４時間浸漬後、ろ過し、ろ液中のＴＨＦをエバポレータで除去して残留物（抽出物）の量を測定した。抽出物があった場合は赤外吸収分光法（ＩＲ）で成分を分析した。抽出物が全く無いもの、或いは未架橋の樹脂成分が配合量の１０重量％以下しか抽出されなかった場合はＩＰＮ構造を形成したと判断し、○とした。一方で未架橋の樹脂成分が１０重量％を超えて抽出されたものは×とした。
[Evaluation of conductivity]
Conductive paste is screen-printed on a glass substrate in a rectangular pattern with a thickness of 15 μm and 0.6 mm × 60 mm, cured at 200 ° C. for 30 minutes to form a conductor layer, and measured for electrical resistance by a four-terminal method. The specific resistance was calculated.
[Evaluation of heat resistance (adhesion)]
The conductive paste was screen-printed on a glass substrate in a square pattern having a thickness of 10 μm and 2 mm × 2 mm, and cured at 200 ° C. for 30 minutes. The obtained substrate having the conductor layer was placed on a hot plate at 200 ° C., and the presence or absence of peeling was examined by pressing a knife blade on the surface of the conductor layer at an angle of 30 ° and laterally with a force of 5N. What peeled with the pattern was set as x, and what did not peel off was set as (circle).
[Confirmation of IPN structure formation (solvent extraction test)]
A paste containing no conductive powder was applied onto a fluororesin film and cured at 200 ° C. for 30 minutes. The cured sample was peeled off, and 2.0 g of the sample was pulverized, immersed in 50 ml of tetrahydrofuran (THF) for 24 hours, filtered, and the THF in the filtrate was removed by an evaporator to reduce the amount of residue (extract). It was measured. When there was an extract, the component was analyzed by infrared absorption spectroscopy (IR). When there was no extract at all, or when an uncrosslinked resin component was extracted only at 10% by weight or less of the blending amount, it was judged that an IPN structure was formed, and it was rated as “◯”. On the other hand, the case where the uncrosslinked resin component was extracted in excess of 10% by weight was marked as x.
実施例１
球状銀粉末１００重量部、エポキシ樹脂ａ ３．７重量部、エポキシ硬化剤０．２重量部、エチルセルロース（熱可塑性高分子）０．７重量部、ブロックイソシアネートａ ０．１５重量部及び粘度調整用溶媒としてブチルカルビトールアセテート（ＢＣＡ）５．５重量部を３本ロールミルによって混合、分散させて導電性ペーストを作製した。導電性ペーストのブルックフィールド粘度計での剪断速度４．０／ｓの粘度は２５℃で２００Ｐａ・ｓであった。
このペーストをガラス基板上にスクリーン印刷し、２００℃に設定した乾燥機中で３０分間熱処理して加熱硬化を行い、導体パターンを形成した。熱処理中の樹脂の硬化過程をＤＳＣによって評価したところ、エポキシ硬化剤とエポキシ樹脂の反応が１４０〜１５０℃に発熱ピークとなって現れ、その後に１８０℃〜１９０℃の範囲にブロックイソシアネートとエチルセルロースとの架橋反応による発熱ピークが観察された。この結果から、エポキシ樹脂の硬化・架橋反応とエチルセルロースのブロックイソシアネートによる架橋反応は３０℃以上の温度の差異があることがわかった。また、溶媒抽出試験では抽出物が１重量％以下であり、ＩＰＮ構造を形成しているものと判断される。
硬化後導体パターンの断面をＳＥＭ観察したところ、銀粒子が焼結して連続相を形成していた。導電性と耐熱性の評価を行ったところ比抵抗は４．５μΩ・ｃｍであり、また優れた耐熱性を示した。
Example 1
100 parts by weight of spherical silver powder, 3.7 parts by weight of epoxy resin a, 0.2 parts by weight of epoxy curing agent, 0.7 parts by weight of ethyl cellulose (thermoplastic polymer), 0.15 parts by weight of blocked isocyanate a and for viscosity adjustment A conductive paste was prepared by mixing and dispersing 5.5 parts by weight of butyl carbitol acetate (BCA) as a solvent with a three-roll mill. The viscosity of the conductive paste at a shear rate of 4.0 / s on a Brookfield viscometer was 200 Pa · s at 25 ° C.
This paste was screen-printed on a glass substrate, and heat-cured for 30 minutes in a dryer set at 200 ° C. to form a conductor pattern. When the curing process of the resin during the heat treatment was evaluated by DSC, the reaction between the epoxy curing agent and the epoxy resin appeared as an exothermic peak at 140 to 150 ° C., and then blocked isocyanate and ethyl cellulose in the range of 180 ° C. to 190 ° C. An exothermic peak due to the crosslinking reaction was observed. From this result, it was found that there is a temperature difference of 30 ° C. or higher between the curing / crosslinking reaction of epoxy resin and the crosslinking reaction of ethyl cellulose with blocked isocyanate. In the solvent extraction test, the extract is 1% by weight or less, and it is determined that an IPN structure is formed.
When the cross section of the conductor pattern after curing was observed with an SEM, the silver particles were sintered to form a continuous phase. When the electrical conductivity and heat resistance were evaluated, the specific resistance was 4.5 μΩ · cm, and excellent heat resistance was exhibited.
実施例２〜２１
実施例１と同様な手法によって、表１−１、表１−２に示した組成の導電性ペーストを作製して評価し、同表に結果を示した。表１−１、表１−２から明らかなように、実施例で得られた導体層はいずれもＩＰＮ構造を形成しており、また優れた導電性と耐熱性を併せ持っている。
なお、実施例１９は１４０℃でブロック剤が解離して反応するタイプのブロックイソシアネートを使用したものである。使用したエポキシ樹脂ｂはイソシアネートと反応しないのでＩＰＮ構造は形成されるが、エポキシ樹脂の硬化反応とほぼ同じ温度範囲でエチルセルロースの架橋反応が進行するために、反応系の粘度が上昇し、相対的に導電性が低下する結果を示した。
実施例２０はエポキシ樹脂に代えて自己架橋型のレゾール型フェノール樹脂を用いたものである。ＤＳＣ分析からはレゾール型フェノール樹脂は１００℃で自己架橋しており、またブロックイソシアネートとエチルセルロースの反応は１７０℃以上で進行していることが観察された。溶媒抽出試験からＩＰＮ構造体の形成を確認した。
実施例２１は第１の硬化性樹脂成分としてラジカル重合性の多官能アクリルレートモノマとアゾ系ラジカル重合開始剤を、また第２の硬化性樹脂成分としてポリビニルブチラールを用いた構成であり、ＤＳＣ分析からは１００℃でラジカル重合が起り、ブロックイソシアネートとポリビニルブチラールの反応は１７０℃以上で進行していることが観察された。溶媒抽出評価からＩＰＮ構造体の形成を確認した。
Examples 2 to 21
Using the same method as in Example 1, conductive pastes having the compositions shown in Table 1-1 and Table 1-2 were prepared and evaluated, and the results are shown in the same table. As is clear from Table 1-1 and Table 1-2, the conductor layers obtained in the examples all have an IPN structure and have both excellent conductivity and heat resistance.
Note that Example 19 uses a blocked isocyanate of a type in which the blocking agent dissociates and reacts at 140 ° C. Since the used epoxy resin b does not react with isocyanate, an IPN structure is formed. However, since the crosslinking reaction of ethyl cellulose proceeds in almost the same temperature range as the curing reaction of the epoxy resin, the viscosity of the reaction system increases, Shows the results of the decrease in conductivity.
In Example 20, a self-crosslinking resol type phenol resin was used instead of the epoxy resin. From the DSC analysis, it was observed that the resol type phenol resin was self-crosslinked at 100 ° C., and the reaction between the blocked isocyanate and ethyl cellulose proceeded at 170 ° C. or higher. Formation of the IPN structure was confirmed from the solvent extraction test.
In Example 21, a radical polymerizable polyfunctional acrylate monomer and an azo radical polymerization initiator were used as the first curable resin component, and polyvinyl butyral was used as the second curable resin component. DSC analysis It was observed that radical polymerization occurred at 100 ° C. and the reaction between the blocked isocyanate and polyvinyl butyral proceeded at 170 ° C. or higher. Formation of the IPN structure was confirmed from the solvent extraction evaluation.
比較例１〜８
実施例１と同様な手法によって、表２に示した組成の導電性ペーストを作製して評価し、表２に結果を示した。
比較例１は実施例１のペーストからエチルセルロースとその架橋剤（ブロックイソシアネート）を除いた組成であるが、耐熱性が不十分であった。比較例１と実施例１について銀粒子を含まない組成で熱機械分析（ＴＭＡ）を行ったところ、Ｔｇ（ガラス転移温度）はいずれも９０℃で差異はなかったが、２００℃における粘弾性を測定すると、弾性率は実施例１の方が約２０％低い値を示し、この弾性率の違いが加熱時の密着性（耐熱性）に寄与しているものと推定される。
比較例２、比較例６はそれぞれ実施例１および実施例５のペーストからエポキシ硬化剤を除いた組成であるが、エポキシ樹脂の硬化が起らず、耐熱性が悪かった。また、溶媒抽出試験においても未反応のエポキシ樹脂が添加量とほぼ同量で抽出され、ＩＰＮ構造体を形成していなかった。
比較例３は実施例１のペーストからブロックイソシアネートを除いた組成であるが、やはり耐熱性が不十分であった。同様にＴＭＡで熱物性を評価した結果、比較例３ではＴｇが６０℃で、実施例１より低く、また、２００℃における粘弾性を測定すると、弾性率が約２０％低かった。ＴＨＦによる溶媒抽出試験では未架橋のエチルセルロースが添加量の６０重量％抽出されたことから、ＩＰＮ構造ではなくｓｅｍｉ−ＩＰＮ構造であることが推定される。
同様に比較例４、５、７、８はそれぞれ実施例１４、５、１１、１８からブロックイソシアネートを除いた組成であるが、いずれもＩＰＮ構造を形成せず耐熱性が劣っている。
Comparative Examples 1-8
A conductive paste having the composition shown in Table 2 was prepared and evaluated by the same method as in Example 1, and the results are shown in Table 2.
Comparative Example 1 was a composition obtained by removing ethyl cellulose and its crosslinking agent (block isocyanate) from the paste of Example 1, but the heat resistance was insufficient. When Comparative Example 1 and Example 1 were subjected to thermomechanical analysis (TMA) with a composition not containing silver particles, Tg (glass transition temperature) was 90 ° C., but there was no difference, but viscoelasticity at 200 ° C. was observed. When measured, the elastic modulus of Example 1 is about 20% lower, and it is estimated that this difference in elastic modulus contributes to adhesion (heat resistance) during heating.
Comparative Examples 2 and 6 were compositions obtained by removing the epoxy curing agent from the pastes of Example 1 and Example 5, respectively, but the epoxy resin did not cure and the heat resistance was poor. Also in the solvent extraction test, the unreacted epoxy resin was extracted in almost the same amount as the amount added, and no IPN structure was formed.
Comparative Example 3 had a composition obtained by removing the blocked isocyanate from the paste of Example 1, but the heat resistance was still insufficient. Similarly, as a result of evaluating thermophysical properties with TMA, in Comparative Example 3, Tg was 60 ° C., which was lower than Example 1, and when measuring viscoelasticity at 200 ° C., the elastic modulus was about 20% lower. In the solvent extraction test with THF, 60% by weight of the uncrosslinked ethylcellulose was extracted, so that it was presumed to be a semi-IPN structure rather than an IPN structure.
Similarly, Comparative Examples 4, 5, 7, and 8 have compositions obtained by removing the blocked isocyanate from Examples 14, 5, 11, and 18, respectively, but all do not form an IPN structure and have poor heat resistance.
以上の実施例、比較例から本発明が良好な導電性と耐熱性の両立において高い効果を示すことが明らかである。 From the above examples and comparative examples, it is clear that the present invention exhibits a high effect in achieving both good conductivity and heat resistance.
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| US9972740B2 (en) | 2015-06-07 | 2018-05-15 | Tesla, Inc. | Chemical vapor deposition tool and process for fabrication of photovoltaic structures |
| TWI770013B (en) * | 2016-03-29 | 2022-07-11 | 日商拓自達電線股份有限公司 | Conductive paint and manufacturing method of shielding package using the same |
| US9748434B1 (en) | 2016-05-24 | 2017-08-29 | Tesla, Inc. | Systems, method and apparatus for curing conductive paste |
| US9954136B2 (en) | 2016-08-03 | 2018-04-24 | Tesla, Inc. | Cassette optimized for an inline annealing system |
| TWI778976B (en) * | 2016-09-15 | 2022-10-01 | 德商漢高股份有限及兩合公司 | Graphene-containing materials for coating and gap filling applications |
| US10115856B2 (en) | 2016-10-31 | 2018-10-30 | Tesla, Inc. | System and method for curing conductive paste using induction heating |
| WO2019058727A1 (en) * | 2017-09-20 | 2019-03-28 | 矢崎総業株式会社 | Conductive composition and wiring board using same |
| JP7156831B2 (en) * | 2017-09-20 | 2022-10-19 | 矢崎総業株式会社 | Conductive composition and wiring board using the same |
| JP6877750B2 (en) * | 2017-12-06 | 2021-05-26 | ナミックス株式会社 | Conductive paste |
| JP7395979B2 (en) * | 2019-11-15 | 2023-12-12 | 住友ベークライト株式会社 | Conductive paste and semiconductor devices |
| CN114189983B (en) * | 2020-09-15 | 2024-03-26 | 北京梦之墨科技有限公司 | Flexible conductive paste and flexible circuit board |
| CN117457253A (en) * | 2021-10-14 | 2024-01-26 | 武宇涛 | Conductive paste for photovoltaic cells |
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| CN116779211A (en) * | 2022-03-11 | 2023-09-19 | 四川东树新材料有限公司 | Heterojunction low-temperature silver paste doped with graphene microemulsion and preparation method thereof |
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