JP2012066999A - Method for producing silver oxide composition - Google Patents
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- JP2012066999A JP2012066999A JP2011183663A JP2011183663A JP2012066999A JP 2012066999 A JP2012066999 A JP 2012066999A JP 2011183663 A JP2011183663 A JP 2011183663A JP 2011183663 A JP2011183663 A JP 2011183663A JP 2012066999 A JP2012066999 A JP 2012066999A
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000003223 protective agent Substances 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000007514 bases Chemical class 0.000 claims abstract description 16
- 239000011164 primary particle Substances 0.000 claims abstract description 15
- 239000011324 bead Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000010947 wet-dispersion method Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 12
- 229910052709 silver Inorganic materials 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 8
- 238000007796 conventional method Methods 0.000 abstract 2
- 239000010408 film Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000000123 paper Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
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- 239000010419 fine particle Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 241000282320 Panthera leo Species 0.000 description 4
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- 239000011521 glass Substances 0.000 description 4
- -1 is mentioned Chemical compound 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 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
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、還元・分解し、導電性被膜を形成し得る酸化銀含有導電性組成物に好適である酸化銀組成物の製造方法に関する。 The present invention relates to a method for producing a silver oxide composition suitable for a silver oxide-containing conductive composition that can be reduced and decomposed to form a conductive film.
従来から、プリント配線板等の基材上に電極や導電回路パターンを形成するため、導電性ペーストが広く用いられてきた。これは、導電性粉末や金属粒子を樹脂成分や有機溶媒等に分散したものである。
しかし、近年、導電性ペーストを塗布する基材として、耐熱性に乏しい、高分子フィルムが用いられるようになり、これまでのように高温での熱処理が出来なくなってきている。それに伴い、より低温での加熱処理で、導電回路を形成することができる導電性ペーストが要求されている。このような導電性ペーストの開発は多岐に渡るが、酸化銀は、貴金属の中で最も低温で熱還元し、銀を生成することから、研究も盛んに行われてきた。
酸化銀は、銀塩とアルカリを反応させることで生成する。生成時に、保護剤を共存させることで、粒子径のより小さな酸化銀微粒子を作製することが可能ではある。
しかし、より低温での導電性発現や、より低抵抗値化といったさらなる要求には十分応えるものではなかった。
Conventionally, conductive paste has been widely used to form electrodes and conductive circuit patterns on a substrate such as a printed wiring board. This is obtained by dispersing conductive powder and metal particles in a resin component, an organic solvent, or the like.
However, in recent years, a polymer film having poor heat resistance has been used as a base material on which a conductive paste is applied, and heat treatment at a high temperature cannot be performed as in the past. Accordingly, there is a demand for a conductive paste that can form a conductive circuit by heat treatment at a lower temperature. Although development of such a conductive paste is diverse, silver oxide is thermally reduced at the lowest temperature among noble metals to produce silver, and research has been actively conducted.
Silver oxide is produced by reacting a silver salt with an alkali. By making a protective agent coexist at the time of production, it is possible to produce silver oxide fine particles having a smaller particle diameter.
However, it did not sufficiently meet further demands such as the development of conductivity at lower temperatures and lower resistance values.
例えば、特許文献１には、銀化合物と塩基性物質を分散剤の存在下に反応させて、酸化銀微粒子の表面が分散剤で被覆されなる平均粒径が０．０１〜１０μｍの酸化銀微粒子の製造方法が開示されている。
そして、前記酸化銀微粒子を含有する導電性組成物のうち、前記酸化銀微粒子の粒子径が１μｍ以下の場合、還元剤を用いなくても、１８０℃程度の加熱で導電性被膜を形成できる旨記載されている。さらに、還元剤を利用することによって、より低い温度、例えば１５０℃程度で還元でき、導電性被膜を形成できる旨記載されている。また、粒子径が小さいほど、低温で還元反応が生じ得る点も開示されている。
また、還元剤が導電性被膜中に残存すると抵抗値が高くなる原因になるので、還元剤としては、揮発性に富むものが好適であるが、揮発性に富むものは還元性にも富む。従って、還元剤を含有する導電性組成物は、貯蔵安定性の点で難があり、対象物に塗布・印刷する直前に、還元剤を添加すべき旨記載されている。
なお、特許文献１には、還元剤を用いずに１８０℃程度の加熱でどの程度の導電性被膜を形成できるかは検証されていない。
For example, Patent Document 1 discloses silver oxide fine particles having an average particle diameter of 0.01 to 10 μm, in which a silver compound and a basic substance are reacted in the presence of a dispersant, and the surface of the silver oxide fine particles is coated with the dispersant. A manufacturing method is disclosed.
In the conductive composition containing the silver oxide fine particles, when the particle diameter of the silver oxide fine particles is 1 μm or less, a conductive film can be formed by heating at about 180 ° C. without using a reducing agent. Are listed. Furthermore, it is described that by using a reducing agent, it can be reduced at a lower temperature, for example, about 150 ° C., and a conductive film can be formed. It is also disclosed that a reduction reaction can occur at a lower temperature as the particle size is smaller.
In addition, if the reducing agent remains in the conductive film, the resistance value becomes high, so that the reducing agent is preferably volatile, but the volatile material is also highly reducible. Therefore, the conductive composition containing a reducing agent is difficult in terms of storage stability, and it is described that the reducing agent should be added immediately before coating / printing on an object.
Patent Document 1 does not verify how much conductive film can be formed by heating at about 180 ° C. without using a reducing agent.
また、特許文献２には、一次粒子の小さな酸化銀微粒子を析出させた後、高分子有機物により被覆処理した酸化銀粉末が開示されている。そして、前記酸化銀粉末を大気中で８０℃〜１５０℃に加熱すると、前記温度域で高分子有機化合物が燃焼し、その際の発熱エネルギーを利用することによって、還元剤を共存させない場合でも、低温での酸化銀の還元が可能になった旨、特許文献２は開示する。しかし、特許文献２には、得られた酸化銀粉末を用いて導電性被膜とした場合の性能については検証されていないが、高分子量有機物を被覆剤として用いると、燃焼後に導電性塗膜中に、有機物が残存し、抵抗値の悪化を引き起こす問題が存在する。また、燃焼時の発熱の影響が基材にまで及び、熱に弱い基材には結局適用できなかった。しかも、この特許で、酸化銀から銀への変化が確認されているのは、実施例においては、１４６℃、１４３℃であり、より低温での還元・導電性発現は確認されていない。 Patent Document 2 discloses a silver oxide powder that is formed by depositing silver oxide fine particles having small primary particles and then coating the polymer organic material. And, when the silver oxide powder is heated to 80 ° C. to 150 ° C. in the atmosphere, the polymer organic compound burns in the temperature range, and even when the reducing agent is not coexisting by utilizing the heat generation energy at that time, Patent Document 2 discloses that reduction of silver oxide at low temperature has become possible. However, Patent Document 2 does not verify the performance when the obtained silver oxide powder is used as a conductive coating, but when a high molecular weight organic substance is used as a coating agent, In addition, there is a problem that organic substances remain and cause deterioration of the resistance value. Further, the influence of heat generation during combustion extends to the base material, and it could not be applied to a base material that is vulnerable to heat. In addition, in this example, the change from silver oxide to silver is confirmed in this patent at 146 ° C. and 143 ° C., and reduction / conductivity expression at lower temperatures has not been confirmed.
本発明の１つの課題は、還元剤を共存させない場合でも、大気中にて従来よりも低い温度で還元し銀を生成し得る酸化銀を提供することであり、本発明の他の課題は、還元剤を共存させない場合でも、大気中にて還元し銀を生成し得る酸化銀であって、従来より抵抗値の低い導電性被膜を形成し得る導電性組成物に好適な酸化銀を提供することである。 One object of the present invention is to provide a silver oxide that can be reduced in the atmosphere at a lower temperature than before to produce silver even in the absence of a reducing agent, and the other object of the present invention is to provide Provided is a silver oxide that can be reduced in the atmosphere to produce silver even in the absence of a reducing agent, and that is suitable for a conductive composition that can form a conductive film having a lower resistance than conventional ones. That is.
本発明は、有機系保護剤を含有する水溶液と銀塩含有水溶液と塩基性化合物との混合液を、分散することを特徴とする、Ａｇ2Ｏを含有する酸化銀組成物（１）と有機系保護剤とを含有する、一次粒子径が１０〜１５０ｎｍの酸化銀組成物（２）の製造方法に関する。
前記分散は、ビーズを用いた湿式分散であることが好ましい。
In the present invention, a silver oxide composition (1) containing Ag 2 O and an organic compound, characterized by dispersing a mixed solution of an aqueous solution containing an organic protective agent, a silver salt-containing aqueous solution and a basic compound. The present invention relates to a method for producing a silver oxide composition (2) containing a system protective agent and having a primary particle size of 10 to 150 nm.
The dispersion is preferably wet dispersion using beads.
本発明により、貯蔵安定性を悪化させる還元剤を共存させなくても、大気中にて従来よりも低い温度で還元し銀を生成し得る酸化銀、もしくはより抵抗値の低い導電性被膜の形成が可能な高純度な酸化銀を提供することができるようになった。
前者の酸化銀は、従来よりも低い温度で導電性を発現し得るので、熱に弱い基材上に、導電回路を形成する用途には好適に用いられる。一方、後者の酸化銀はより低抵抗を目指す用途に好適に用いることができる。
According to the present invention, without the presence of a reducing agent that deteriorates storage stability, the formation of silver oxide or a conductive film having a lower resistance value that can be reduced in the atmosphere at a lower temperature than conventional to produce silver. Can provide high-purity silver oxide that can be used.
Since the former silver oxide can exhibit electrical conductivity at a lower temperature than before, it is suitably used for the purpose of forming a conductive circuit on a heat-sensitive substrate. On the other hand, the latter silver oxide can be suitably used for applications aiming at lower resistance.
以下、本発明について、実施の形態について更に詳しく説明するが、本発明の技術的思想を逸脱しない限り、本発明はこれらの実施の形態に限定されるものではない。
本発明の酸化銀組成物（２）の作製方法に関して説明する。
従来の塩基性化合物と銀塩とを有機系保護剤存在下で反応させる製造方法を基本とし、そこに、分散工程を加え、さらに塩基性化合物と銀塩との反応バランス等を適宜変更することにより得ることができる。
例えば、有機系保護剤含有水溶液と銀塩含有水溶液と塩基性化合物との混合物を分散処理し、過量の有機系保護剤、銀塩を構成していたアニオン成分、塩基性化合物を構成していたカチオン成分等を除去することにより、一次粒子径が１０〜１５０ｎｍの酸化銀組成物（２）を得ることができる。本発明の酸化銀組成物（２）を作製する際、有機系保護剤含有水溶液、銀塩含有水溶液、塩基性化合物の添加順は影響しない。しかし、有機系保護剤含有水溶液と銀塩含有水溶液とを混合した後、塩基性化合物を添加することがより好ましい。
Hereinafter, the present invention will be described in more detail with reference to embodiments. However, the present invention is not limited to these embodiments without departing from the technical idea of the present invention.
The method for producing the silver oxide composition (2) of the present invention will be described.
Based on a conventional production method in which a basic compound and a silver salt are reacted in the presence of an organic protective agent, a dispersion step is added thereto, and the reaction balance between the basic compound and the silver salt is appropriately changed. Can be obtained.
For example, a mixture of an organic protective agent-containing aqueous solution, a silver salt-containing aqueous solution, and a basic compound was dispersed to form an excessive amount of an organic protective agent, an anionic component constituting the silver salt, and a basic compound. By removing the cation component and the like, a silver oxide composition (2) having a primary particle size of 10 to 150 nm can be obtained. When producing the silver oxide composition (2) of the present invention, the order of addition of the organic protective agent-containing aqueous solution, the silver salt-containing aqueous solution and the basic compound is not affected. However, it is more preferable to add the basic compound after mixing the organic protective agent-containing aqueous solution and the silver salt-containing aqueous solution.
酸化銀組成物（２）の製造に用いられる銀塩含有水溶液としては、特に限定されないが、硝酸銀、過塩素酸銀、炭酸銀、酢酸銀などの銀塩の水溶液が挙げられ、硝酸銀水溶液が好ましい。 Although it does not specifically limit as silver salt containing aqueous solution used for manufacture of a silver oxide composition (2), Silver salt aqueous solution, such as silver nitrate, silver perchlorate, silver carbonate, silver acetate, is mentioned, Silver nitrate aqueous solution is preferable. .
酸化銀組成物（２）の製造に用いられる塩基性化合物としては、特に限定されないが、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどが挙げられる。 Although it does not specifically limit as a basic compound used for manufacture of a silver oxide composition (2), Sodium hydroxide, potassium hydroxide, sodium carbonate, etc. are mentioned.
酸化銀組成物（２）の製造に用いられる有機系保護剤の役割は、合成時に酸化銀組成物（１）の粒子径が大きくなるのを防ぐことにある。
有機系保護剤のうちアミノ基を有するものが、Ａｇ2Ｏ、ＡｇＯ、Ａｇ2Ｏ3、Ａｇ等への吸着力が強く、より好ましい。また、有機系保護剤は分子量の小さいものが好ましく、ポリスチレン換算ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定におけるＭｗが１０００以下であることがより好ましい。
The role of the organic protective agent used in the production of the silver oxide composition (2) is to prevent the particle diameter of the silver oxide composition (1) from increasing during synthesis.
Of the organic protective agents, those having an amino group are more preferred because of their strong adsorptive power to Ag 2 O, AgO, Ag 2 O 3 , Ag and the like. The organic protective agent preferably has a low molecular weight, and more preferably has an Mw of 1000 or less in polystyrene conversion gel permeation chromatography (GPC) measurement.
有機系保護剤としては、特に限定されず、一般に、界面活性剤や顔料分散剤として市販されているものを使用することができる。
例えば、ライオン株式会社製のアーカードシリーズ、エソカードシリーズ、エソデュオミンシリーズ、エナジコールシリーズ、エソマイドシリーズ、サンノールシリーズ、日本ルーブリゾール株式会社製のソルスパース３０００、ソルスパース９０００、ソルスパース１７０００、ソルスパース２４０００、ソルスパース２８０００、ソルスパース３２０００、ソルスパース３５１００、ソルスパース３６０００、ソルスパース４１０００、エフカアディティブズ社製のＥＦＫＡ４００９、ＥＦＫＡ４０４６、ＥＦＫＡ４０４７、ＥＦＫＡ４０８０、ＥＦＫＡ４０１０、ＥＦＫＡ４０１５、ＥＦＫＡ４０５０、ＥＦＫＡ４０５５、ＥＦＫＡ４０６０、ＥＦＫＡ４３３０、ＥＦＫＡ４３００、ＥＦＫＡ７４６２、味の素ファインテクノ株式会社製のアジスパーＰＢ８２１、アジスパーＰＢ７１１、アジスパーＰＢ８２２、アジスパーＰＮ４１１、アジスパーＰＡ１１１、コグニスジャパン株式会社製のＴＥＸＡＰＨＯＲＵＶ２０、ＴＥＸＡＰＨＯＲＵＶ２１、ＴＥＸＡＰＨＯＲＰ６１、ビッグケミー・ジャパン株式会社製のＤｉｓｐｅｒｂｙｋ−１０１、Ｄｉｓｐｅｒｂｙｋ−１０３、Ｄｉｓｐｅｒｂｙｋ−１０６、Ｄｉｓｐｅｒｂｙｋ−１１０、Ｄｉｓｐｅｒｂｙｋ−１１１、Ｄｉｓｐｅｒｂｙｋ−１６１、Ｄｉｓｐｅｒｂｙｋ−１６２、Ｄｉｓｐｅｒｂｙｋ−１６３、Ｄｉｓｐｅｒｂｙｋ−１６４、Ｄｉｓｐｅｒｂｙｋ−１６６、Ｄｉｓｐｅｒｂｙｋ−１６７、Ｄｉｓｐｅｒｂｙｋ−１６８、Ｄｉｓｐｅｒｂｙｋ−１７０、Ｄｉｓｐｅｒｂｙｋ−１７１、Ｄｉｓｐｅｒｂｙｋ−１７４、Ｄｉｓｐｅｒｂｙｋ−１８０、Ｄｉｓｐｅｒｂｙｋ−１８２、Ｄｉｓｐｅｒｂｙｋ−１８７、Ｄｉｓｐｅｒｂｙｋ−１９０等が挙げられるがこれらに限定されるものではない。これらの有機系保護剤は、1種類を単独で使用しても、２種類以上を組み合わせて使用してもよい。
It does not specifically limit as an organic type protective agent, Generally, what is marketed as surfactant or a pigment dispersant can be used.
For example, Lion Corporation's Arcade Series, Esocard Series, Esoduomine Series, Enajol Series, Esomeide Series, Sannor Series, Nippon Lubrizol Corporation Sol Sparse 3000, Sol Sparse 9000, Sol Sparse 17000, Sol Sparse 24000, Sol Sparse 28000, Sol Sparse 32000, Sol Sparse 35100, Sol Sparse 36000, Sol Sparse 41000, EFKA4009, EFKA4046, EFKA4047, EFKA4080, EFKA4010, EFKA4050, EFKA4055, EFKA4055, EFKA4055, EFKA4055, EFKA4055, EFKA4055 Ajisper PB821, Azisper PB711, Azisper PB822, Azisper PN411, Azisper PA111, TEXAPHORUV20, TEXAPHORUV21, TEXAPHORP61 from Cognis Japan, Disperbyk-101, DisperDkby-bykp-103, Disperbyk-byp-106 Disperbyk-111, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, Disperbik-170, Disperk-1170 4, Disperbyk-180, Disperbyk-182, Disperbyk-187, but Disperbyk-190 and the like are not limited thereto. These organic protective agents may be used alone or in combination of two or more.
このような有機系保護剤は、大気中での熱分解試験による熱分解開始温度が２００℃以上であるものが多い。しかし、それ自体の熱分解開始温度に依らず、粒子の生成と分散とを一体として行って得た本発明の酸化銀組成物（２）は、加熱により酸化銀組成物（１）が銀へ還元される際、その熱で酸化銀組成物（１）を被覆していた有機系保護剤のほとんどが分解・除去され、導電性被膜中には残らないものと考えられる。 Many of these organic protective agents have a thermal decomposition starting temperature of 200 ° C. or higher by a thermal decomposition test in the atmosphere. However, the silver oxide composition (2) of the present invention obtained by integrating the generation and dispersion of particles independently of the thermal decomposition initiation temperature of the silver oxide composition (1) is converted into silver by heating. When reduced, it is considered that most of the organic protective agent that has coated the silver oxide composition (1) is decomposed and removed by the heat and does not remain in the conductive film.
酸化銀組成物（２）を得る際、銀塩1モルに対して、塩基性化合物は０．１〜５モル使用することが好ましい。より低温還元可能なＡｇ2Ｏの含有量が少ない酸化銀組成物の生成を目指す場合には、銀塩1モルに対して、塩基性化合物は1モル以上であることが好ましく、１〜５モル使用することがより好ましく、１〜３モル使用することがさらに好ましい。一方、より低抵抗値を発現可能なＡｇ2Ｏの含有量が多い酸化銀組成物の生成を目指す場合には、銀塩1モルに対して、塩基性化合物は1モル未満使用することが好ましく、０．１〜０．９モル使用することがより好ましく、０．３〜０．７モル使用することがさらに好ましい。 When obtaining a silver oxide composition (2), it is preferable to use 0.1-5 mol of basic compounds with respect to 1 mol of silver salts. When aiming at the production of a silver oxide composition having a lower content of Ag 2 O that can be reduced at a lower temperature, the basic compound is preferably 1 mol or more with respect to 1 mol of the silver salt. It is more preferable to use it, and it is more preferable to use 1-3 mol. On the other hand, when aiming to produce a silver oxide composition having a high Ag 2 O content capable of expressing a lower resistance value, it is preferable to use less than 1 mol of basic compound per 1 mol of silver salt. 0.1-0.9 mol is more preferable, and 0.3-0.7 mol is more preferable.
また、有機系保護剤は、銀塩に含まれる銀１００重量部に対して、有効成分で０．１〜１００重量部使用することが好ましく、０．５〜５０重量部使用することがより好ましく、３０〜５０重量部使用することがさらに好ましい。 The organic protective agent is preferably used in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of silver contained in the silver salt. More preferably, 30 to 50 parts by weight are used.
酸化銀組成物（２）を製造する際の分散工程は、有機系保護剤含有水溶液、銀塩含有水溶液、塩基性化合物の混合液を得た直後に行うことが重要である。このようにすることによって、一次粒子径が１０〜１５０ｎｍの酸化銀組成物（２）を製造することができる。
例えば、有機系保護剤含有水溶液、銀塩含有水溶液、塩基性化合物の混合液を得た後、銀塩と塩基性化合物とを十分反応させ、銀塩の大部分から酸化銀粒子を生成し、固液分離した後、得られた酸化銀粒子に分散剤を添加し、その後、単に粒子を物理的・機械的に分散処理した場合、本発明の製造方法で得られる酸化銀組成物（２）とは、一次粒子径の点で異なるものとなる。
It is important to carry out the dispersing step when producing the silver oxide composition (2) immediately after obtaining the organic protective agent-containing aqueous solution, the silver salt-containing aqueous solution, and the basic compound mixture. By doing in this way, the silver oxide composition (2) whose primary particle diameter is 10-150 nm can be manufactured.
For example, after obtaining a mixed solution of an organic protective agent-containing aqueous solution, a silver salt-containing aqueous solution, and a basic compound, the silver salt and the basic compound are sufficiently reacted to produce silver oxide particles from most of the silver salt, After the solid-liquid separation, a silver oxide composition (2) obtained by the production method of the present invention when a dispersing agent is added to the obtained silver oxide particles and then the particles are simply physically and mechanically dispersed. Is different in terms of the primary particle diameter.
本発明で用いられる分散方法としては、ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノーミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル、ホモミキサー、ホモジナイザー（エム・テクニック社製「クレアミックス」等）、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、ナノマイザー社製「ナノマイザー」）、微小ビーズミル（寿工業社製「スーパーアペックミル」、「ウルトラアペックミル」）等の分散機が使用できる。分散機にメディアを使う場合には、ガラスビーズ、ジルコニアビーズ、アルミナビーズ、磁性ビーズ、スチレンビーズ等を用いることが好ましい。分散に関しては、二種類以上の分散機、または大きさの異なる二種類以上のメディアをそれぞれ用い、段階的に使用しても差し支えない。 As a dispersion method used in the present invention, a paint conditioner (manufactured by Red Devil), a ball mill, a sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), an attritor, a pearl mill (such as “DCP mill” manufactured by Eirich), Coball mill, homomixer, homogenizer ("Claremix" manufactured by M Technique), wet jet mill ("Genus PY" manufactured by Genus, "Nanomizer" manufactured by Nanomizer), micro-bead mill ("Super Apeck Mill manufactured by Kotobuki Kogyo Co., Ltd.) "," Ultra Apeck Mill ") or the like can be used. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.
そのビーズの直径としては、０．０３ｍｍ以上３．００ｍｍ以下が好ましく、それより小さいと分散時にエネルギーが得られず、活性面が十分に現れず、また、それより大きいと、生成する酸化銀の粒子径が大きくなる。 The diameter of the beads is preferably 0.03 mm or more and 3.00 mm or less. If the diameter is smaller than that, no energy is obtained during dispersion, and the active surface does not appear sufficiently. The particle size increases.
本発明の製造方法で得られた酸化銀組成物（２）は、酸化銀組成物（１）と有機系保護剤とを含有する。
有機系保護剤は、酸化銀組成物（２）１００重量％中、０．１重量〜２０重量％含まれることが好ましく、一次粒子を小さい状態で維持することができる範囲でできるだけ少ないことが好ましい。
The silver oxide composition (2) obtained by the production method of the present invention contains a silver oxide composition (1) and an organic protective agent.
The organic protective agent is preferably contained in an amount of 0.1 to 20% by weight in 100% by weight of the silver oxide composition (2), and is preferably as small as possible within a range in which the primary particles can be maintained in a small state. .
酸化銀組成物（１）は、Ａｇ2Ｏを必須とし、ＡｇＯ、Ａｇ、Ａｇ2Ｏ3のうち少なくとも１種以上を含有するものであり、酸化銀組成物（２）を低温で還元し得るように、ＡｇＯを含むことが好ましい。一次粒子径が上記範囲にあることによって、Ａｇ2Ｏ、ＡｇＯ、Ａｇ2Ｏ3等を含む粒子の表面エネルギーが増大し、低温還元が可能となり、低温還元時に生成しつつあるＡｇ粒子同士の融着が生じ、導電性を効果的に発現すると考察される。
低温還元の点からは、酸化銀組成物（２）に含まれるＡｇ2Ｏは、７０重量％未満であることが好ましく、４０重量％以上７０重量％未満であることがより好ましい。
一方、Ａｇ2Ｏの含有量が７０％以上の場合、低温では還元しにくいので、１３０℃程度の加熱では７×１０-5〜１×１０-4Ω・ｃｍレベルの抵抗値しか発現できない。しかし、より高温、例えば１８０℃で加熱すれば、８×１０-6Ω・ｃｍレベルの低抵抗を発現できる。
つまり、本発明の製造方法は、低温還元に好適な酸化銀組成物（２）を提供することも、低抵抗な導電性被膜形成に好適な酸化銀組成物（２）を提供することもできる。
Silver oxide composition (1) is an essential and Ag 2 O, AgO, Ag, and those containing at least one or more of Ag 2 O 3, can reduce silver oxide composition (2) at low temperatures Thus, it is preferable to contain AgO. When the primary particle diameter is in the above range, the surface energy of particles containing Ag 2 O, AgO, Ag 2 O 3 and the like is increased, enabling low-temperature reduction, and the fusion of Ag particles being generated during low-temperature reduction. It is considered that adhesion occurs and the conductivity is effectively expressed.
From the viewpoint of low temperature reduction, Ag 2 O contained in the silver oxide composition (2) is preferably less than 70% by weight, and more preferably 40% by weight or more and less than 70% by weight.
On the other hand, when the content of Ag 2 O is 70% or more, it is difficult to reduce at a low temperature. Therefore, only a resistance value of 7 × 10 −5 to 1 × 10 −4 Ω · cm level can be expressed by heating at about 130 ° C. However, if it is heated at a higher temperature, for example, 180 ° C., a low resistance of 8 × 10 −6 Ω · cm level can be developed.
That is, the production method of the present invention can provide a silver oxide composition (2) suitable for low-temperature reduction or a silver oxide composition (2) suitable for forming a low-resistance conductive film. .
なお、本発明において、Ａｇ2Ｏの含有率は、例えば、酸化銀組成物（２）をＸ線回折装置（ＰＡＮａｌｙｔｉｃａｌ社製 Ｘ線回折装置 Ｘ'ｐｅｒｔ ＰＲＯ−ＭＰＤ）を用い測定し、得られたＸ線回折パターンにおいて、ピーク強度を元にした準定量法により求められる。 In the present invention, the content of Ag 2 O, for example, silver oxide composition (2) was measured using an X-ray diffractometer (PANalytical, Inc. X-ray diffraction apparatus X'pert PRO-MPD), obtained The X-ray diffraction pattern is obtained by a semi-quantitative method based on the peak intensity.
次に、酸化銀含有導電性組成物、導電性被膜を具備する積層体とその製造方法について説明する。
酸化銀含有導電性組成物は、樹脂もしくは有機溶剤の少なくとも一方と、前記の酸化銀組成物（２）とを含有する。
樹脂種、溶剤種は特に限定されない。
後述する導電性被膜は、酸化銀組成物（２）以外の成分はできるだけ含まない方が好ましいが、支障のない範囲で、酸化銀含有導電性組成物には、一般的なインキに用いられるような添加剤も添加できる。
Next, the laminated body provided with a silver oxide containing electroconductive composition and an electroconductive film, and its manufacturing method are demonstrated.
The silver oxide-containing conductive composition contains at least one of a resin or an organic solvent and the silver oxide composition (2).
Resin species and solvent species are not particularly limited.
Although it is preferable that the conductive film described later does not contain components other than the silver oxide composition (2) as much as possible, the silver oxide-containing conductive composition may be used for general inks as long as there is no hindrance. Additives can also be added.
本発明の酸化銀含有導電性組成物を、基材上に塗工し、加熱し、酸化銀組成物（１）中の酸化銀を還元し、銀を生成し、導電性被膜を形成し、導電性被膜を具備する積層体を製造することができる。加熱処理は、耐熱性に乏しい基材を用いる場合には、１５０℃未満であることが好ましく、１１０℃以上、１４０℃以下であることが、より好ましい。一方、耐熱性に優れる基材を用いる場合には、１５０℃以上であることが好ましく、２００℃以下であることがより好ましい。 The silver oxide-containing conductive composition of the present invention is coated on a substrate, heated, and the silver oxide in the silver oxide composition (1) is reduced to produce silver, to form a conductive film, A laminate having a conductive coating can be produced. In the case of using a substrate having poor heat resistance, the heat treatment is preferably less than 150 ° C., more preferably 110 ° C. or more and 140 ° C. or less. On the other hand, when using a base material excellent in heat resistance, it is preferably 150 ° C. or higher, and more preferably 200 ° C. or lower.
上記導電性被膜の形態については、特に限定されないが、通常の印刷法で形成可能なパターンなどを挙げることができる。例えば、細線状、膜状、格子状、回路状などの形態が挙げられる。これらの用途として、微細導電回路、電磁波シールド、電極、アンテナ回路、めっき代替、印刷エレクトロニクス用導電材料、フレキシブル基板回路等が挙げられるがこれらに限定されるものではない。 Although the form of the said conductive film is not specifically limited, The pattern etc. which can be formed with a normal printing method can be mentioned. For example, forms such as a thin line shape, a film shape, a lattice shape, and a circuit shape are exemplified. Examples of these applications include, but are not limited to, fine conductive circuits, electromagnetic wave shields, electrodes, antenna circuits, plating substitutes, conductive materials for printed electronics, and flexible circuit boards.
本発明の導電性被膜は、使用用途に応じて紙、プラスチック、ガラス等の基材の片面または両面上に、フレキソ印刷、グラビア印刷、グラビアオフセット印刷、インキジェット印刷、オフセット印刷、ロータリースクリーン印刷、シルクスクリーン印刷、レタープレス、スプレーコート、スピンコート、ダイコート、リップコート、ナイフコート、ディップコート、カーテンコート、ロールコート、バーコート等、従来公知の方法を用いて本発明の導電性インキを印刷・塗布することで形成することができる。
紙基材としては、コート紙、非コート紙の他、合成紙、ポリエチレンコート紙、含浸紙、耐水加工紙、絶縁加工紙、伸縮加工紙等の各種加工紙が使用できる。
プラスチック基材としては、ポリエステル、ポリエチレン、ポリプロピレン、セロハン、塩化ビニル、塩化ビニリデン、ポリスチレン、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ナイロン、ポリイミド、ポリカーボネート等の通常のプラスチック基材を使用することができる。プラスチックフィルムやガラス基材の表面には、密着性を高める目的で、必要に応じて、コロナ放電処理やプラズマ処理を施したり、またはポリウレタン、ポリイソシアネート、有機チタネート、ポリエチレンイミン、ポリブタジエン等のアンカーコート剤を塗布したりすることができる。
The conductive coating of the present invention is flexographic printing, gravure printing, gravure offset printing, ink jet printing, offset printing, rotary screen printing, on one or both sides of a substrate such as paper, plastic, glass, etc., depending on the intended use. Print the conductive ink of the present invention using conventionally known methods such as silk screen printing, letter press, spray coating, spin coating, die coating, lip coating, knife coating, dip coating, curtain coating, roll coating, and bar coating. It can be formed by coating.
As the paper substrate, various processed papers such as synthetic paper, polyethylene coated paper, impregnated paper, water-resistant processed paper, insulating processed paper, and stretch-processed paper can be used in addition to coated paper and uncoated paper.
As the plastic substrate, it is possible to use ordinary plastic substrates such as polyester, polyethylene, polypropylene, cellophane, vinyl chloride, vinylidene chloride, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon, polyimide, polycarbonate and the like. it can. The surface of a plastic film or glass substrate is subjected to corona discharge treatment or plasma treatment as necessary for the purpose of improving adhesion, or an anchor coat such as polyurethane, polyisocyanate, organic titanate, polyethyleneimine, polybutadiene, etc. An agent can be applied.
本発明において、加熱処理は、その方法を特に限定するものではなく、例えば、熱風乾燥オーブン、熱ロールまたは熱プレスロール等を使用することが出来る。 In the present invention, the method for the heat treatment is not particularly limited, and for example, a hot air drying oven, a hot roll or a hot press roll can be used.
以下、実施例、比較例に基づき本発明をさらに詳しく説明する。実施例、比較例中、部および％は、重量部および重量％をそれぞれ表す。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples. In the examples and comparative examples, parts and% represent parts by weight and% by weight, respectively.
（実施例１）
２０％エソデュオミンＴ／１３（ライオン（株）製、アミノ基を有する分子量４５８の有機系保護剤、熱分解開始温度：２３９℃）水溶液２４．０部に、３０％硝酸銀水溶液５０部を攪拌しながら滴下し、さらに１２％水酸化ナトリウム水溶液２９．５部を加え、これらを１０分間攪拌後、ペイントシェーカーにて１時間分散処理し、酸化銀組成物の懸濁液を得た。前記の分散には、直径１ｍｍのガラスビーズを用いた。
この懸濁液に、この懸濁液と同量のアセトンを加え、析出する沈殿物をろ過し、酸化銀組成物を回収した。さらにこの酸化銀組成物をアセトンで洗浄し、不純物を除去した。再分散性向上のため、溶媒は完全には除去しなかった。こうして、本発明の酸化銀組成物（２）を得た。この酸化銀組成物を電界放出走査電子顕微鏡（日立Ｓ−４３００）で観察したところ、その一次粒子径は５０ｎｍから１００ｎｍの範囲であった。
次いで、この酸化銀組成物５．０部に、ジヒドロターピネオール（日本テンペル化学（株）製）２．５部、テルソルブＭＴＰＨ（日本テンペル化学（株）製）２．５部を加え、マーラーで混練することで、酸化銀含有導電性組成物を得た。
この酸化銀含有導電性組成物を用い、７５μｍ厚のコロナ処理ＰＥＴフィルム（ユニチカ（株）製エリーテル）に、スクリーン印刷法により、塗工し、１３０℃で３０分間加熱し、膜厚１．５μｍの導電性被膜（Ａ）を形成した。
上記ＰＥＴフィルムの代わりに５０μｍ厚ポリイミドフィルム（藤森工業（株）製カプトン）を用い、１５０℃で３０分間、又は１８０℃で３０分間で加熱し、導電性被膜（Ａ）を形成した。
Example 1
While stirring 20.0 parts of an aqueous solution of 20% Esoduomine T / 13 (manufactured by Lion Corporation, an organic protective agent having a molecular weight of 458 having an amino group, thermal decomposition start temperature: 239 ° C.) with 50 parts of an aqueous 30% silver nitrate solution Then, 29.5 parts of a 12% aqueous sodium hydroxide solution was added, and these were stirred for 10 minutes and then dispersed for 1 hour in a paint shaker to obtain a suspension of a silver oxide composition. For the dispersion, glass beads having a diameter of 1 mm were used.
To this suspension, the same amount of acetone as this suspension was added, and the deposited precipitate was filtered to recover the silver oxide composition. Further, this silver oxide composition was washed with acetone to remove impurities. In order to improve redispersibility, the solvent was not completely removed. Thus, a silver oxide composition (2) of the present invention was obtained. When this silver oxide composition was observed with a field emission scanning electron microscope (Hitachi S-4300), the primary particle diameter was in the range of 50 nm to 100 nm.
Next, 2.5 parts of dihydroterpineol (Nippon Tempel Chemical Co., Ltd.) and 2.5 parts of Tersolve MTPH (Nihon Tempel Chemical Co., Ltd.) are added to 5.0 parts of this silver oxide composition, and kneaded with a Mahler. Thus, a silver oxide-containing conductive composition was obtained.
Using this silver oxide-containing conductive composition, a 75 μm-thick corona-treated PET film (Elitel manufactured by Unitika Co., Ltd.) was applied by screen printing, heated at 130 ° C. for 30 minutes, and a film thickness of 1.5 μm. The conductive film (A) was formed.
A 50 μm-thick polyimide film (Kapton manufactured by Fujimori Kogyo Co., Ltd.) was used in place of the PET film and heated at 150 ° C. for 30 minutes or 180 ° C. for 30 minutes to form a conductive film (A).
（実施例２）
２９．５部であった１２％水酸化ナトリウム水溶液を３２．４部とした以外は実施例１と同様にして、一次粒子径が５０ｎｍから１００ｎｍの酸化銀組成物を得、酸化銀含有導電性組成物を得、同様にして導電性被膜（Ｂ）を形成した。
(Example 2)
A silver oxide composition having a primary particle diameter of 50 nm to 100 nm was obtained in the same manner as in Example 1 except that 32.4 parts of 12% sodium hydroxide aqueous solution, which was 29.5 parts, were obtained. A composition was obtained, and a conductive film (B) was formed in the same manner.
（実施例３）
２０％エソデュオミンＴ／１３（ライオン（株）製）水溶液９．５部に、３０％硝酸銀水溶液５０部を攪拌しながら滴下し、さらに６％水酸化ナトリウム水溶液２９．５部を加えた以外は実施例１と同様にして、一次粒子径が５０ｎｍから１００ｎｍの酸化銀組成物を得、酸化銀含有導電性組成物を得、同様にして導電性被膜（Ｃ）を形成した。
(Example 3)
Implemented except that 50 parts of a 30% silver nitrate aqueous solution was added dropwise to 9.5 parts of a 20% aqueous solution of Esoduomine T / 13 (manufactured by Lion Corporation) with stirring, and 29.5 parts of a 6% aqueous sodium hydroxide solution were further added. In the same manner as in Example 1, a silver oxide composition having a primary particle size of 50 nm to 100 nm was obtained to obtain a silver oxide-containing conductive composition, and a conductive film (C) was formed in the same manner.
（実施例４）
２０％エソデュオミンＴ／１３の代わりに、２０％ＢＹＫ−１９０（ビックケミー（株）製、アミノ基を有さない分子量約２５００の有機系保護剤、熱分解開始温度：２８０℃））水溶液を２４．０部用いた以外は実施例１と同様にして、一次粒子径が５０ｎｍから１００ｎｍの酸化銀組成物を得、酸化銀含有導電性組成物を得、同様にして導電性被膜（Ｄ）を形成した。
Example 4
24. A 20% BYK-190 (manufactured by Big Chemie Co., Ltd., organic protective agent having a molecular weight of about 2500 having no amino group, thermal decomposition starting temperature: 280 ° C.) in place of 20% esododumine T / 13. A silver oxide composition having a primary particle size of 50 nm to 100 nm is obtained in the same manner as in Example 1 except that 0 part is used, and a silver oxide-containing conductive composition is obtained. Similarly, a conductive film (D) is formed. did.
（比較例１）
２０％エソデュオミンＴ／１３（ライオン（株）製）水溶液９．５部に、３０％硝酸銀水溶液５０部を攪拌しながら滴下し、さらに６％水酸化ナトリウム水溶液２９．５部を加え、これらを４時間攪拌することで、酸化銀組成物の懸濁液を調整した。
この懸濁液に、この懸濁液と同量のアセトンを加え、析出する沈殿物をろ過し、酸化銀組成物を回収した。さらにこの酸化銀組成物をアセトンで洗浄し、不純物を除去した。再分散性向上のため、溶媒は完全には除去しなかった。こうして、酸化銀組成物を得た。この酸化銀組成物を電界放出走査電子顕微鏡（日立Ｓ−４３００）で観察したところ、その一次粒子径１００ｎｍから１５０ｎｍであった。
以下実施例１と同様にして、酸化銀含有導電性組成物を得、導電性被膜（Ｅ）を形成した。
(Comparative Example 1)
To 9.5 parts of a 20% aqueous solution of Esoduomine T / 13 (manufactured by Lion Corporation), 50 parts of a 30% aqueous silver nitrate solution was added dropwise with stirring, and 29.5 parts of a 6% aqueous sodium hydroxide solution were added. The suspension of the silver oxide composition was prepared by stirring for a period of time.
To this suspension, the same amount of acetone as this suspension was added, and the deposited precipitate was filtered to recover the silver oxide composition. Further, this silver oxide composition was washed with acetone to remove impurities. In order to improve redispersibility, the solvent was not completely removed. Thus, a silver oxide composition was obtained. When this silver oxide composition was observed with a field emission scanning electron microscope (Hitachi S-4300), the primary particle diameter was 100 nm to 150 nm.
Hereinafter, it carried out similarly to Example 1, the silver oxide containing electroconductive composition was obtained, and the electroconductive film (E) was formed.
（比較例２）
２０％ＢＹＫ−１９０水溶液（ビックケミー（株）製）９．５部に、３０％硝酸銀水溶液５０部を攪拌しながら滴下し、さらに６％水酸化ナトリウム水溶液２９．５部を加え、これらを４時間攪拌することで、酸化銀組成物の懸濁液を調整した。
以下比較例１と同様にして一次粒子径が５０ｎｍから１００ｎｍの酸化銀組成物（ｆ）を得、導電性被膜（Ｆ）を形成した。
(Comparative Example 2)
To 9.5 parts of 20% BYK-190 aqueous solution (manufactured by Big Chemie Co., Ltd.), 50 parts of 30% aqueous silver nitrate solution was added dropwise with stirring, and 29.5 parts of 6% aqueous sodium hydroxide solution were added, and these were added for 4 hours. A suspension of the silver oxide composition was prepared by stirring.
Thereafter, in the same manner as in Comparative Example 1, a silver oxide composition (f) having a primary particle diameter of 50 nm to 100 nm was obtained, and a conductive film (F) was formed.
［酸化銀組成物、導電性被膜の評価］
上記で作製した酸化銀組成物について、熱分解開始温度、１５０℃までの無機物由来の重量減少量、Ａｇ2Ｏ含有率、加熱処理後の有機系保護剤残存量を、導電性被膜について、体積抵抗値を、下記の方法で評価した。その結果を表１に示す。
[Evaluation of silver oxide composition and conductive film]
About the silver oxide composition produced above, thermal decomposition start temperature, weight loss amount derived from inorganic materials up to 150 ° C., Ag 2 O content, residual amount of organic protective agent after heat treatment, volume of conductive coating, The resistance value was evaluated by the following method. The results are shown in Table 1.
（評価方法）
（１）熱分解開始温度
酸化銀組成物を、示差熱分析測定装置（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ Ｉｎｃ．社製ＥＸＳＴＡＲ６０００ ＴＧ／ＤＴＡ６３００）を用いて、大気中６００℃まで、毎分５℃の昇温速度で測定したときの、酸化銀からの酸素の解離による重量減少開始温度とする。
(Evaluation methods)
(1) Thermal decomposition onset temperature The silver oxide composition was measured at a rate of temperature increase of 5 ° C. per minute up to 600 ° C. in the atmosphere using a differential thermal analysis measuring device (EXSTAR TG TG / DTA6300 manufactured by Seiko Instruments Inc.). The starting temperature of weight reduction due to the dissociation of oxygen from silver oxide.
（２）１５０℃までの無機物由来の重量減少量
酸化銀組成物を、示差熱分析測定装置（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ Ｉｎｃ．社製ＥＸＳＴＡＲ６０００ ＴＧ／ＤＴＡ６３００）を用いて、大気中６００℃まで、毎分５℃の昇温速度で測定したときの、１５０℃までの重量減少量から、該酸化銀組成物中の炭素量を、例えば、ＣＨＮ元素分析装置（（株）パーキンエルマー社製 ２４００ＣＨＮ Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｚｅｒ）を用い求めた値を差し引いた値とする。
(2) Weight-reducing amount derived from inorganic materials up to 150 ° C. The silver oxide composition was subjected to 5 ° C. per minute up to 600 ° C. in the atmosphere using a differential thermal analysis measuring apparatus (EXSTAR TG TG / DTA6300 manufactured by Seiko Instruments Inc.). From the weight loss amount up to 150 ° C. when measured at a rate of temperature increase, the amount of carbon in the silver oxide composition is determined using, for example, a CHN element analyzer (2400CHN Elemental Analyzer, manufactured by PerkinElmer Co., Ltd.). The value obtained by subtracting the obtained value.
（３）Ａｇ2Ｏ含有率
酸化銀組成物を、Ｘ線回折装置（ＰＡＮａｌｙｔｉｃａｌ社製 Ｘ線回折装置 Ｘ'ｐｅｒｔ ＰＲＯ−ＭＰＤ）を用い測定し、得られたＸ線回折パターンにおいて、ピーク強度を元にした準定量法により求められる。
(3) Ag 2 O content rate The silver oxide composition was measured using an X-ray diffractometer (X-ray diffractometer X'pert PRO-MPD manufactured by PANalytical). In the obtained X-ray diffraction pattern, the peak intensity was measured. Obtained by the original semi-quantitative method.
（４）酸化銀組成物中の有機系保護剤量
酸化銀組成物中の炭素量を、ＣＨＮ元素分析装置（（株）パーキンエルマー社製 ２４００ＣＨＮ Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｚｅｒ）を用い求め、その結果と有機系保護剤の分子量とから、有機系保護剤の含有量を算出する。
（５）加熱処理後の有機系保護剤残存量
酸化銀組成物を、熱分解試験にて１５０℃まで加熱し、冷却した後の試料中の炭素量を、上記と同様にして求め、有機系保護剤の残存量を算出する。
(4) Amount of organic protective agent in silver oxide composition The amount of carbon in the silver oxide composition was determined using a CHN elemental analyzer (2400CHN Elemental Analyzer manufactured by PerkinElmer Co., Ltd.), and the results and organic protection. The content of the organic protective agent is calculated from the molecular weight of the agent.
(5) Residual amount of organic protective agent after heat treatment The amount of carbon in the sample after the silver oxide composition was heated to 150 ° C. in the thermal decomposition test and cooled was determined in the same manner as described above, and the organic system The remaining amount of protective agent is calculated.
（６）体積抵抗値
導電性被膜の抵抗値を、四探針抵抗値測定器（三和電気計器（株）製 ＤＲ−１０００ＣＵ）で測定した。又、膜厚を膜厚計（（株）ニコン製 ＭＨ−１５Ｍ）で測定し、得られた抵抗値と膜厚から体積抵抗値を算出した。
(6) Volume resistance value The resistance value of the conductive film was measured with a four-probe resistance value measuring instrument (DR-1000CU, manufactured by Sanwa Denki Keiki Co., Ltd.). The film thickness was measured with a film thickness meter (MH-15M manufactured by Nikon Corporation), and the volume resistance value was calculated from the obtained resistance value and film thickness.
表１の結果より、実施例の通り、本発明の製造方法では、低温で銀へと還元し、また加熱処理後の有機系保護剤の残存量も少ない酸化銀含有導電性組成物を得ることができ、該酸化銀含有導電性組成物を用いた導電性被膜は、低温の加熱条件下でも、良好な導電性を有しているか、または１８０度の加熱条件下で、従来よりも低い抵抗値を示す。 From the results of Table 1, as in the Examples, the production method of the present invention obtains a silver oxide-containing conductive composition that is reduced to silver at a low temperature and that has a small residual amount of organic protective agent after heat treatment. The conductive film using the silver oxide-containing conductive composition has good conductivity even under low-temperature heating conditions, or has a lower resistance than conventional under heating conditions of 180 degrees. Indicates the value.
Claims (2)
Ａｇ2Ｏを含有する酸化銀組成物（１）と有機系保護剤とを含有する、一次粒子径が１０〜１５０ｎｍの酸化銀組成物（２）の製造方法。 Dispersing an aqueous solution containing an organic protective agent, a silver salt-containing aqueous solution, and a basic compound,
A method for producing a silver oxide composition (2) having a primary particle diameter of 10 to 150 nm, comprising a silver oxide composition (1) containing Ag 2 O and an organic protective agent.
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