JPS639018B2 - - Google Patents
Info
- Publication number
- JPS639018B2 JPS639018B2 JP13780580A JP13780580A JPS639018B2 JP S639018 B2 JPS639018 B2 JP S639018B2 JP 13780580 A JP13780580 A JP 13780580A JP 13780580 A JP13780580 A JP 13780580A JP S639018 B2 JPS639018 B2 JP S639018B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- transparent conductive
- acid
- conductive film
- boiling point
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 25
- 238000009835 boiling Methods 0.000 claims description 19
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 150000003606 tin compounds Chemical class 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- BUPPDJMCERLPJD-UHFFFAOYSA-L [dimethyl(octanoyloxy)stannyl] octanoate Chemical compound C[Sn+2]C.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BUPPDJMCERLPJD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 150000001991 dicarboxylic acids Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 6
- 229940018557 citraconic acid Drugs 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- -1 ketone ethers Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- MSDSZLDEVZYENE-UHFFFAOYSA-N ethoxy(diethyl)indigane Chemical compound CCO[In](CC)CC MSDSZLDEVZYENE-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- IVECIWLVOYDMRU-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O.COC(C)=O IVECIWLVOYDMRU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
- Chemically Coating (AREA)
Description
本発明は、ガラスまたはセラミツク基板表面に
組成物を塗布し、ついで焼成することによつて透
明導電膜を形成しようとする際に必要な組成物に
関するものである。
液晶表示素子、プラズマ表示素子、エレクトロ
ルミネツセンス素子などの表示素子類、光電池、
撮像管などの感光素子類、飛行機、自動車、家庭
等の防曇用窓ガラスなどに用いられる抵抗発熱体
などにおいては、光に対して透明性を有する導電
膜が使用されている。
この透明導電膜に使用される材料としては、酸
化スズにアンチモンをドーピングした系と酸化イ
ンジウムにスズをドーピングした系があるが、電
気伝導性の高い酸化インジウム系が広く使用され
ている。従来、塗布、焼成することによつて透明
導電膜を形成するのに使用される組成液には次の
2つがある。
(1) インジウムのアルコキシドまたはカルボン酸
塩の有機溶液。
(2) ナフテン酸インジウムまたはジエチルモノエ
トキシインジウムにオクチル酸スズまたはカプ
リル酸スズを添加したシンナーまたはアルコー
ル溶液。
しかし、これらは、ガラス基板上ではじき易
く、均一な被膜を得ることが困難であり、電気抵
抗も大きいなどの問題があつた。
本発明の目的は、上記した組成物の欠点をなく
し、均一で電気抵抗も低い透明導電膜の得られる
組成物を提供することにある。
この目的を達成するための本発明の組成物は硝
酸インジウムと、ジカルボン酸と、沸点30゜〜100
℃の一価アルコール、エステル、ケトンエーテル
のうち少なくとも1種の有機溶剤と、沸点130゜〜
250℃のセロソルブ類、カルビトール類、グリコ
ール類のうちから選ばれた少なくとも1種の有機
溶剤と、2−エチルヘキサン酸スズ、カプロン酸
スズ、ジメチルジアセテート、ジメチルチンオク
タネートのうちから選ばれた1種のスズ化合物と
からなる。
このような組成の溶液を用いると、(1)硝酸イン
ジウムはジカルボン酸と反応して、硝酸イオンが
ジカルボン酸に一部置換されたような形のインジ
ウム錯体を形成し、(2)この錯体は、溶剤を取り除
いて行くとガラス状になる性質を持つている為、
結晶として析出することなく、(3)加熱することに
より、完全に酸化分解されるため、均一な酸化イ
ンジウム被膜を形成することができる。また、(4)
沸点100℃以下の有機溶剤を含んでいるため、塗
布した後溶剤が急速に揮発し、塗膜の粘度が高く
なるため、はじくことがなく、かつ、(5)沸点130
℃以上の有機溶剤も含んでいるため、乾燥が早す
ぎることで誘発される塗膜の白濁現象を起こしに
くく、したがつてピンホールや白濁のない均質な
透明導電膜を得ることができる。
次に、本発明に用いる材料について説明する。
(1) ジカルボン酸;炭素数3〜10のものが好まし
く、これよりも炭素数が少ないものでは、これ
と硝酸インジウムとの反応物の有機溶剤に対す
る溶解性に乏しく、炭素数が多い場合には、得
られる透明導電膜の抵抗値が大きくなる。ま
た、二重結合や、側鎖を有するジカルボン酸で
も差支えない。具体的には、マロン酸、コハク
酸、メチルマロン酸、グルタル酸、メチルコハ
ク酸、アジピン酸、ピメリン酸、スベリン酸、
アゼライン酸、セバシン酸、マレイン酸、シト
ラコン酸、イタコン酸、フタル酸、テトラヒド
ロフタル酸、ヘキサヒドロフタル酸、などが挙
げられる。これらのうちで、メチルコハク酸、
シトラコン酸が最も好適である。また、これら
のジカルボン酸の無水物は、有機溶剤中硝酸イ
ンジウムとともに撹拌することにより加水分解
され、ジカルボン酸と同様に挙動し、さらにそ
のエステル化物、特にモノエステル類は、加水
分解して、ジカルボン酸と同じように挙動する
と考えられ、ジカルボン酸も有機溶剤にアルコ
ール類を用いたときエステル化される可能性が
ある。このような、ジカルボン酸は硝酸インジ
ウムに対して0.3〜2.0モル比添加されるのが好
ましく、これよりも少ないと、硝酸インジウム
の溶解性が乏しく透明導電膜が白濁し、多いと
透明導電膜の導電性が悪くなる。
(2) 有機溶剤;沸点が30゜〜100℃のアルコール
類、ケトン類、エステル類、エーテル類のうち
少なくとも1種と、沸点が130゜〜250℃のセロ
ソルブ類、カルビトール類、グリコール類のう
ちから選ばれた少なくとも1種との混合系を用
いる。これらの有機溶剤は極性を有しているた
め、硝酸インジウムやジカルボン酸、あるい
は、これらの反応物の良溶媒となり、かなり高
い濃度範囲まで溶解することが可能である。沸
点30゜〜100℃の有機溶剤として具体的には、メ
チルアルコール、エチルアルコール、プロピル
アルコール、イソプロピルアルコール、アセト
ン、メチルエチルケトン、ギ酸エチル、ギ酸プ
ロピル、酢酸メチル、酢酸エチル、ジエチルエ
ーテル、ジプロピルエーテル、ジイソプロピル
エーテル、テトラヒドロフランなどがある。ま
た、沸点130゜〜250℃の有機溶剤としては、エ
チルセロソルブ、ブチルセロソルブ、エチルカ
ルビトール、ブチルカルビトール、エチレング
リコール、プロビレングリコール、ジエチレン
グリコール、トリメチレングリコール、などが
挙げられる。このように、低沸点溶剤と高沸点
溶剤との混合系とすることにより、急速な溶剤
蒸発を適度に押え塗膜に白濁を生じることがな
く、しかも、高沸点溶剤にだけを用いた場合に
生じ易い塗膜の膜厚むらをも同時になくすこと
ができる。また、低沸点溶剤の蒸発に伴つて塗
膜の粘度が高くなるため、はじくことが少ない
が、さらに基板に対する濡れ性を改善するため
には界面活性剤を添加することが有効である。
この界面活性剤としては、ノニオン系が好まし
く特に上記有機溶剤の表面張力を少量の添加で
著しく低下させることができるフツ素系界面活
性剤が有効である。
これらの低沸点溶剤に対する高沸点溶剤の混
合比は、30wt%以下が適当であり、特に3〜
20wt%の範囲にあるのが好ましい。これより
も多いと塗布したときに膜厚むらを生じやすく
なる。また、これらの溶剤の添加量は、低沸点
溶剤と高沸点溶剤との合計100重量部に対し、
硝酸インジウムが2〜50重量部となるように添
加されるのが好ましい。
(3) スズ化合物;透明導電膜の導電性を高めるた
めに加えられる。このようなスズ化合物とし
て、ハロゲン化スズ、有機酸スズ、アルコキシ
ド等があるが、ハロゲン化スズ、たとえば、塩
化第二スズを用いた場合には、透明導電膜とし
たときに、塩化スズが蒸発したり、塩素が膜中
に残つて膜の導電性が悪くなり好ましくない。
またアルコキシドでは、溶解性に乏しく均一な
組成物を得ることが困難である。有機酸スズを
用いると、蒸発することがなく、350〜400℃に
加熱することにより酸化分解して酸化スズとな
るため、透光性にすぐれ、高い導電性を有する
透明導電膜を得ることができる。また有機酸ス
ズのうち、炭素数が少ない、たとえば酢酸スズ
では溶解性に乏しく、逆に炭素数が大きすぎる
と、透明導電膜の導電性が悪くなる傾向にあ
る。具体的には2−エチルヘキサン酸スズ、カ
プロン酸スズが好ましい。また、Sn−C結合
を有する有機スズ化合物の有機酸塩も有機酸ス
ズと同様な傾向を示す。このようなスズ化合物
としてジメチルチンジアセテート、ジメチルチ
ンジオクタネートが挙げられる。これらのスズ
化合物は、Sn/(In+Sn)比で5〜20wt%添
加されるのが好ましく、これより多くても少な
くても透明導電膜の導電性が悪くなる。
以上の材料を用いて透明導電膜形成用組成物を
得るには、硝酸インジウム、ジカルボン酸、有機
溶剤を室温または加熱下、混合撹拌することによ
り完全に溶解し、これに、スズ化合物を添加する
方法で調製される。
次に、透明導電膜を形成するに際し、本発明の
組成物を基板に塗布するには、浸漬引き上げ法、
回転塗布法、吹付法、印毛塗り法など通常の塗布
技術が適用できる。また、本発明の組成物の塗膜
の焼成は、大気などの酸素存在雰囲気中で200〜
400℃に加熱した状態で紫外線を1分〜5分照射
し、ついで、450〜700℃に5分〜1時間加熱保持
することで行なうのが好ましい。
次に実施例を上げて本発明を説明する。
実施例 1
硝酸インジウムと、第1表(a)〜(d)に示すジカル
ボン酸を等モル量組み合わせてエチルアルコール
とエチレングリコールの9:1混液に溶解し、こ
れに(e)〜(f)に示すスズ化合物を添加して、第1表
No.1〜No.7の組成物を調製した。
これらの組成物を十分に洗浄した石英ガラス基
板に浸漬引き上げ法で塗布(引き上げ速度;20
cm/min)したのち、約350℃に加熱するととも
に、紫外線に5分間暴露し、さらに空気中で500
℃、1時間焼成して透明導電膜を作成した。得ら
れた透明導電膜は、いずれも膜厚500Å以下でシ
ート抵抗は20KΩ/ロであつた。また、透光性、
膜強度も十分満足できるものであつた。
The present invention relates to a composition necessary for forming a transparent conductive film by applying the composition to the surface of a glass or ceramic substrate and then baking the composition. Display elements such as liquid crystal display elements, plasma display elements, electroluminescence elements, photovoltaic cells,
2. Description of the Related Art Conductive films that are transparent to light are used in photosensitive elements such as image pickup tubes, resistive heating elements used in anti-fog window glasses for airplanes, automobiles, homes, etc., and the like. Materials used for this transparent conductive film include a system in which tin oxide is doped with antimony and a system in which indium oxide is doped with tin, but indium oxide, which has high electrical conductivity, is widely used. Conventionally, there are the following two composition liquids used to form a transparent conductive film by coating and baking. (1) Organic solutions of alkoxides or carboxylates of indium. (2) Thinner or alcohol solution containing tin octylate or tin caprylate added to indium naphthenate or diethylmonoethoxyindium. However, these have problems such as being easily repelled on glass substrates, making it difficult to obtain a uniform coating, and having high electrical resistance. An object of the present invention is to eliminate the drawbacks of the above-mentioned compositions and to provide a composition from which a uniform transparent conductive film with low electrical resistance can be obtained. To achieve this objective, the composition of the present invention comprises indium nitrate, dicarboxylic acid, and
At least one organic solvent among monohydric alcohols, esters, and ketone ethers with a boiling point of 130°~
At least one organic solvent selected from cellosolves, carbitols, and glycols at 250°C, and tin 2-ethylhexanoate, tin caproate, dimethyl diacetate, and dimethyltin octanate. and one type of tin compound. When a solution with such a composition is used, (1) indium nitrate reacts with dicarboxylic acid to form an indium complex in which nitrate ions are partially substituted with dicarboxylic acid, and (2) this complex , because it has the property of becoming glassy when the solvent is removed,
(3) It is completely oxidized and decomposed by heating without precipitating as crystals, so a uniform indium oxide film can be formed. Also, (4)
Contains an organic solvent with a boiling point of 100°C or less, so the solvent evaporates rapidly after application, increasing the viscosity of the coating, so it does not repel, and (5) has a boiling point of 130°C.
Since it also contains an organic solvent with a temperature of ℃ or higher, it is difficult to cause clouding of the coating film caused by premature drying, and therefore a homogeneous transparent conductive film without pinholes or clouding can be obtained. Next, materials used in the present invention will be explained. (1) Dicarboxylic acids; those with 3 to 10 carbon atoms are preferred; dicarboxylic acids with fewer carbon atoms have poor solubility in organic solvents of the reaction product of dicarboxylic acids with indium nitrate; , the resistance value of the resulting transparent conductive film increases. Further, a dicarboxylic acid having a double bond or a side chain may also be used. Specifically, malonic acid, succinic acid, methylmalonic acid, glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, maleic acid, citraconic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and the like. Among these, methylsuccinic acid,
Citraconic acid is most preferred. In addition, anhydrides of these dicarboxylic acids are hydrolyzed by stirring with indium nitrate in an organic solvent and behave similarly to dicarboxylic acids, and their esters, especially monoesters, are hydrolyzed to form dicarboxylic acids. It is thought that dicarboxylic acids behave in the same way as acids, and dicarboxylic acids may also be esterified when alcohols are used as organic solvents. Such dicarboxylic acid is preferably added in a molar ratio of 0.3 to 2.0 with respect to indium nitrate.If it is less than this, the solubility of indium nitrate will be poor and the transparent conductive film will become cloudy, and if it is more than this, the transparent conductive film will become cloudy. Conductivity deteriorates. (2) Organic solvent: At least one of alcohols, ketones, esters, and ethers with a boiling point of 30° to 100°C, and cellosolves, carbitols, and glycols with a boiling point of 130° to 250°C. A mixed system with at least one selected from these is used. Since these organic solvents have polarity, they serve as good solvents for indium nitrate, dicarboxylic acids, or their reactants, and can dissolve them up to a fairly high concentration range. Specifically, organic solvents with a boiling point of 30° to 100°C include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl formate, propyl formate, methyl acetate, ethyl acetate, diethyl ether, dipropyl ether, Examples include diisopropyl ether and tetrahydrofuran. Further, examples of organic solvents having a boiling point of 130° to 250°C include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, and the like. In this way, by creating a mixed system of a low-boiling point solvent and a high-boiling point solvent, rapid solvent evaporation can be moderately suppressed, preventing clouding of the coating film, and moreover, when only a high-boiling point solvent is used, At the same time, it is possible to eliminate unevenness in the thickness of the coating film, which tends to occur. Furthermore, since the viscosity of the coating film increases with the evaporation of the low boiling point solvent, it is less likely to be repelled, but it is effective to add a surfactant to further improve the wettability to the substrate.
The surfactant is preferably a nonionic surfactant, and a fluorine-based surfactant is particularly effective since it can significantly lower the surface tension of the organic solvent by adding a small amount. The appropriate mixing ratio of the high boiling point solvent to these low boiling point solvents is 30wt% or less, especially 3 to 30% by weight.
Preferably it is in the range of 20wt%. If the amount is more than this, unevenness in film thickness tends to occur when coating. In addition, the amount of these solvents added is 100 parts by weight in total of low boiling point solvent and high boiling point solvent.
Indium nitrate is preferably added in an amount of 2 to 50 parts by weight. (3) Tin compound; added to improve the conductivity of the transparent conductive film. Examples of such tin compounds include tin halides, organic tin acids, and alkoxides. However, when tin halides such as stannic chloride are used, the tin chloride evaporates when formed into a transparent conductive film. Otherwise, chlorine may remain in the film, resulting in poor conductivity of the film, which is undesirable.
Furthermore, alkoxides have poor solubility and it is difficult to obtain a uniform composition. When organic acid tin is used, it does not evaporate and is oxidized and decomposed into tin oxide when heated to 350 to 400°C, making it possible to obtain a transparent conductive film with excellent light transmission and high conductivity. can. Among organic tin acids, those with a small number of carbon atoms, such as tin acetate, have poor solubility, and conversely, if the number of carbon atoms is too large, the conductivity of the transparent conductive film tends to deteriorate. Specifically, tin 2-ethylhexanoate and tin caproate are preferred. Furthermore, organic acid salts of organotin compounds having Sn--C bonds also exhibit the same tendency as organic tin acids. Examples of such tin compounds include dimethyltin diacetate and dimethyltin dioctanate. These tin compounds are preferably added in an Sn/(In+Sn) ratio of 5 to 20 wt%, and if the amount is greater or less than this, the conductivity of the transparent conductive film will deteriorate. To obtain a composition for forming a transparent conductive film using the above materials, indium nitrate, dicarboxylic acid, and an organic solvent are completely dissolved by mixing and stirring at room temperature or under heating, and a tin compound is added to this. Prepared by method. Next, when forming a transparent conductive film, in order to apply the composition of the present invention to a substrate, a dipping and pulling method,
Usual coating techniques such as spin coating, spraying, and brush coating can be applied. In addition, the coating film of the composition of the present invention is baked in an oxygen-containing atmosphere such as the atmosphere for a temperature of 200 to
It is preferable to carry out this by irradiating ultraviolet rays for 1 minute to 5 minutes while heated to 400°C, and then holding the temperature at 450 to 700°C for 5 minutes to 1 hour. Next, the present invention will be explained with reference to Examples. Example 1 Indium nitrate and the dicarboxylic acids shown in Table 1 (a) to (d) were combined in equimolar amounts and dissolved in a 9:1 mixture of ethyl alcohol and ethylene glycol, and (e) to (f) were added to the mixture. By adding the tin compounds shown in Table 1,
Compositions No. 1 to No. 7 were prepared. These compositions were applied to a thoroughly cleaned quartz glass substrate using a dipping and pulling method (pulling speed: 20
cm/min), then heated to approximately 350°C, exposed to ultraviolet light for 5 minutes, and further exposed to 500°C in air.
℃ for 1 hour to create a transparent conductive film. The resulting transparent conductive films all had a film thickness of 500 Å or less and a sheet resistance of 20 KΩ/2. In addition, translucency,
The film strength was also sufficiently satisfactory.
【表】【table】
【表】
注)( )内はモル比
実施例 2
第1表のうち、No.3の成分物質を用い、それぞ
れの成分の配合比を種々変えた組成物を調製し
て、実施例1と同様に透明導電膜を形成した。
第2表No.8〜No.12は、硝酸インジウムに対する
シトラコン酸の配合比を変えた場合である。シト
ラコン酸を加えないときには、硝酸インジウムを
完全に溶解することができず、硝酸インジウム1
モルに対して、シトラコン酸を約0.5モル加えた
とき最も低いシート抵抗値を示し、さらにシトラ
コン酸の配合比を多くするとシート抵抗値は高く
なる。第2表No.13〜No.17は2−エチルヘキサン酸
スズの添加量を変えた場合である。Sn/(In+
Sn)で、10〜15wt%のとき最も低いシート抵抗
値が得られるが、5〜20wt%でも実用レベルの
シート抵抗値が得られる。5〜20wt%より多い
場合や少ない場合には、シート抵抗値が大きくな
る。
第2表No.18〜No.19は溶剤量を変えた場合であ
る。溶剤量の多少によつて得られる透明導電膜の
膜厚が変化し、膜厚800Åでシート抵抗0.5KΩ/
ロの透明導電膜を一回塗布で形成することが可能
である。[Table] Note: ( ) indicates molar ratio Example 2 Using the component material No. 3 in Table 1, compositions were prepared with various blending ratios of each component, and the results were as shown in Example 1. A transparent conductive film was formed in the same manner. Table 2 Nos. 8 to 12 show cases where the blending ratio of citraconic acid to indium nitrate was changed. When citraconic acid is not added, indium nitrate cannot be completely dissolved, and indium nitrate 1
When about 0.5 mol of citraconic acid is added, the lowest sheet resistance value is obtained, and as the blending ratio of citraconic acid is further increased, the sheet resistance value becomes higher. Table 2 No. 13 to No. 17 are cases where the amount of tin 2-ethylhexanoate added was changed. Sn/(In+
With Sn), the lowest sheet resistance value is obtained at 10 to 15 wt%, but a practical level sheet resistance value can be obtained even at 5 to 20 wt%. When the amount is more than or less than 5 to 20 wt%, the sheet resistance value increases. Table 2 No. 18 to No. 19 are cases where the amount of solvent was changed. The thickness of the transparent conductive film obtained changes depending on the amount of solvent, and the sheet resistance is 0.5KΩ/0 at a film thickness of 800Å.
It is possible to form the transparent conductive film (B) in one application.
【表】【table】
【表】
注) No.8は硝酸インジウム不溶、表中( )内
はモル比
実施例 3
本実施例では、実施例2の溶剤の種類を変えて
組成物を調製し、実施例1、2と同様に透明導電
膜を形成した。結果を第3表に示す。
沸点30〜100℃の溶剤、アセトン、酢酸メチル、
ジエチルエーテルとエチルアルコールおよびエチ
レングリコールとの混合系では、ほぼ、エチルア
ルコールとエチレングリコールの混合系のときと
同様である。これに対して、沸点130゜〜250℃の
溶剤、としてエチレングリコールの代りにエチル
セロソルブ、エチルカルビトールを用い、これと
エチルアルコールとの混合系とした場合にも、膜
厚500Åでも白濁することがなく、均一で、しか
もシート抵抗値の低い透明導電膜が得られた。ま
た、エチレングリコールの量を多くした場合には
膜厚むらが生じた。しかし、エチレングリコール
の量を少なくして溶剤に対する硝酸インジウムの
比の上げることにより、膜厚むらがなく、均一で
しかもかなり厚い膜厚の透明導電膜を得ることが
できる。[Table] Note) No. 8 is insoluble in indium nitrate. The values in parentheses in the table are molar ratio Example 3. In this example, compositions were prepared by changing the type of solvent in Example 2, and the compositions of Examples 1 and 2 were A transparent conductive film was formed in the same manner. The results are shown in Table 3. Solvents with a boiling point of 30-100℃, acetone, methyl acetate,
The mixed system of diethyl ether, ethyl alcohol and ethylene glycol is almost the same as the mixed system of ethyl alcohol and ethylene glycol. On the other hand, when ethyl cellosolve or ethyl carbitol is used instead of ethylene glycol as a solvent with a boiling point of 130° to 250°C, and a mixture of this and ethyl alcohol is used, the film becomes cloudy even at a film thickness of 500 Å. A transparent conductive film was obtained that was free of porosity, was uniform, and had a low sheet resistance value. Furthermore, when the amount of ethylene glycol was increased, unevenness in film thickness occurred. However, by decreasing the amount of ethylene glycol and increasing the ratio of indium nitrate to the solvent, it is possible to obtain a transparent conductive film that is uniform, fairly thick, and has no uneven thickness.
【表】
比較例
比較例として、ジカルボン酸の代りに、モノカ
ルボン酸を用いた場合、無添加の場合、有機酸ス
ズの代りに塩化第二スズを用いた場合、及び溶媒
としてエチルアルコール単独の場合についてそれ
ぞれの組成物を調製し、透明導電膜を形成した。
結果を表4に示す。
ジカルボン酸無添加、及びモノカルボン酸を用
いた場合には、膜に白濁を生じた。また、塩化第
二スズを用いた場合には、得られる透明導電膜の
シート抵抗値が高い。また、エチルアルコール単
独の場合には、同一塗布条件で膜厚を約500Åと
するため、硝酸インジウムに対するエチルアルコ
ールの量を少なくしなければならない。このよう
にして、膜厚を約500Åにすると膜が白濁してし
まう。[Table] Comparative Examples As comparative examples, monocarboxylic acid was used instead of dicarboxylic acid, no additive was used, stannic chloride was used instead of organic acid tin, and ethyl alcohol alone was used as the solvent. Each composition was prepared for each case, and a transparent conductive film was formed.
The results are shown in Table 4. When no dicarboxylic acid was added and when a monocarboxylic acid was used, the film became cloudy. Furthermore, when stannic chloride is used, the sheet resistance value of the resulting transparent conductive film is high. Furthermore, in the case of using ethyl alcohol alone, the amount of ethyl alcohol relative to indium nitrate must be reduced in order to obtain a film thickness of approximately 500 Å under the same coating conditions. In this way, when the film thickness is reduced to approximately 500 Å, the film becomes cloudy.
【表】
本発明の組成物を用いることにより、1回塗布
で高い導電性を有し、しかも透光性にすぐれ膜強
度も蒸着膜に匹敵する程の透明導電膜を、空気中
焼成することで得ることができる。また、本発明
の組成物を浸漬引き上げ塗布法に適用することに
より大面積基板への応用が可能となり、安価で、
すぐれた特性の透明導電膜を大量に生産すること
ができ、工業上極めて有利である。[Table] By using the composition of the present invention, a transparent conductive film that has high conductivity after one application, has excellent light transmittance, and has a film strength comparable to that of a vapor-deposited film can be baked in air. You can get it at Furthermore, by applying the composition of the present invention to a dip-and-pull coating method, it is possible to apply it to large-area substrates, and it is inexpensive.
Transparent conductive films with excellent properties can be produced in large quantities, which is extremely advantageous industrially.
Claims (1)
ル、ケトン、エーテルのうち少なくとも1種の有
機溶剤97〜80wt%と、沸点130℃〜250℃のセロ
ソルブ類、カルビトール類、グリコール類のうち
から選ばれた少なくとも1種の有機溶剤3〜
20wt%との混合物100重量部と、硝酸インジウム
が2〜50重量部と、硝酸インジウムに対するモル
比が0.3〜2.0モルのジカルボン酸と、2−エチル
ヘキサン酸スズ、カブロン酸スズ、ジメチルチン
ジアセテート、ジメチルチンジオクタネートのう
ちから選ばれた少なくとも1種のスズ化合物を
Sn/(In+Sn)比で5〜20wt%有することを特
徴とする透明導電膜形成用組成物。1 97 to 80 wt% of at least one organic solvent among monohydric alcohols, esters, ketones, and ethers with a boiling point of 30°C to 100°C, and cellosolves, carbitols, and glycols with a boiling point of 130°C to 250°C At least one selected organic solvent 3~
100 parts by weight of a mixture of 20 wt%, 2 to 50 parts by weight of indium nitrate, dicarboxylic acid with a molar ratio of 0.3 to 2.0 moles to indium nitrate, tin 2-ethylhexanoate, tin cabroate, dimethyltin diacetate, at least one tin compound selected from dimethyltin dioctanate;
A composition for forming a transparent conductive film, characterized by having a Sn/(In+Sn) ratio of 5 to 20 wt%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13780580A JPS5767048A (en) | 1980-10-03 | 1980-10-03 | Composition for forming electrically conductive transparent film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13780580A JPS5767048A (en) | 1980-10-03 | 1980-10-03 | Composition for forming electrically conductive transparent film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5767048A JPS5767048A (en) | 1982-04-23 |
JPS639018B2 true JPS639018B2 (en) | 1988-02-25 |
Family
ID=15207256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13780580A Granted JPS5767048A (en) | 1980-10-03 | 1980-10-03 | Composition for forming electrically conductive transparent film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5767048A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60130002A (en) * | 1983-12-15 | 1985-07-11 | 松下電器産業株式会社 | Ink for forming transparent electrode |
JP2561680B2 (en) * | 1987-11-20 | 1996-12-11 | 触媒化成工業株式会社 | Method for producing transparent oxide thin film-coated glass |
US5145602A (en) * | 1989-02-01 | 1992-09-08 | Union Oil Company Of California | Sol/gels containing nonionic surfactants and preparation methods |
JP3817749B2 (en) * | 1994-03-17 | 2006-09-06 | 日産化学工業株式会社 | Coating agent for pattern formation of silica-containing inorganic oxide film by ultraviolet irradiation and pattern formation method |
GB0222360D0 (en) * | 2002-09-26 | 2002-11-06 | Printable Field Emitters Ltd | Creating layers in thin-film structures |
JP4655472B2 (en) * | 2003-11-27 | 2011-03-23 | 日油株式会社 | Coating liquid for forming indium-tin oxide thin film |
JP4500915B1 (en) * | 2009-09-17 | 2010-07-14 | 有限会社ケイ・ビー・エル営繕センター | Photocatalytic coating for shielding heat rays |
JP6250481B2 (en) * | 2014-06-02 | 2017-12-20 | 富士フイルム株式会社 | Metal oxide film, metal oxide film manufacturing method, thin film transistor, and electronic device |
-
1980
- 1980-10-03 JP JP13780580A patent/JPS5767048A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5767048A (en) | 1982-04-23 |
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