JP2010047716A - Electroconductive ink composition for screen printing and electroconductive coated film - Google Patents
Electroconductive ink composition for screen printing and electroconductive coated film Download PDFInfo
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本発明は、微細パターンを形成することが可能なスクリーン印刷用導電性インキ組成物に関するものである。 The present invention relates to a conductive ink composition for screen printing capable of forming a fine pattern.
電子部品あるいは電磁波シールド用の薄膜形成あるいは導電回路のパターニングは、一般的に、熱硬化型、熱可塑型の導電性インキなどによる回路あるいは回路パターンを印刷し、熱処理による焼結する方法、または銅張り基材からのエッチング法が知られている。 Thin film formation for electronic parts or electromagnetic shielding or patterning of conductive circuits is generally performed by printing a circuit or circuit pattern using a thermosetting or thermoplastic conductive ink, and sintering by heat treatment or copper. Etching from a stretched substrate is known.
焼結法の例としては、特開２０００−３０５２６０号公報には、感光性導電性ペーストとして、アルカリ可溶性ネガ型感光性樹脂組成物、光重合開始剤、金属粉末および金属超微粒子からなる感光性ペーストが開示されている。該公報では、感光性樹脂組成物をパターニングした後、電気炉やベルト炉等の焼成炉で有機成分を揮発させ、無機粉末を焼成させることにより導電性パターン膜を形成しており、その際の焼成の雰囲気は、大気中または窒素雰囲気あるいは水素雰囲気で、５００℃以上であり、大型の設備が必要となる。 As an example of the sintering method, Japanese Patent Application Laid-Open No. 2000-305260 discloses a photosensitive conductive paste composed of an alkali-soluble negative photosensitive resin composition, a photopolymerization initiator, a metal powder, and metal ultrafine particles. A paste is disclosed. In this publication, after patterning a photosensitive resin composition, an organic component is volatilized in a firing furnace such as an electric furnace or a belt furnace, and an inorganic powder is fired to form a conductive pattern film. The firing atmosphere is 500 ° C. or higher in the air, a nitrogen atmosphere, or a hydrogen atmosphere, and a large facility is required.
エッチング法については、金属の表面や形状を、化学的あるいは電気化学的に溶解除去し、それを表面処理を含めた広義の加工技術とすることである。エッチングはすなわち化学加工の一種であり、主に金属表面に希望のパターン形状を得るために行われるが、一般的に工程が煩雑であり、また後工程で廃液処理が必要であるため、問題が多い。また、エッチング法によって形成された導電回路は、アルミニウムや銅など金属のみで形成されたものであるため、折り曲げ等の物理的衝撃に対して弱いという問題がある。 As for the etching method, the surface or shape of a metal is dissolved or removed chemically or electrochemically, and this is used as a processing technique in a broad sense including surface treatment. Etching is a kind of chemical processing, and is mainly performed to obtain a desired pattern shape on the metal surface. However, since the process is generally complicated and waste liquid treatment is necessary in the subsequent process, there is a problem. Many. Moreover, since the conductive circuit formed by the etching method is formed only of a metal such as aluminum or copper, there is a problem that it is weak against physical impact such as bending.
導電性インキは、電子部品の小型軽量化あるいは生産性の向上、低コスト化が期待でき、また基材に印刷あるいは塗工し、乾燥させることによって容易に導電性を付与できる。この乾燥、硬化工程では、基材や電子部品に高温を加えることなく、低温にて行うことが出来ることから、近年急速に需要が高まっている。 The conductive ink can be expected to reduce the size and weight of electronic parts, improve productivity, and reduce costs, and can easily impart conductivity by printing or coating on a substrate and drying. In this drying and curing process, demand can be rapidly increased in recent years because it can be performed at a low temperature without applying a high temperature to the substrate or the electronic component.
熱硬化型導電性インキの内、バインダー成分としてガラスフリットなどの無機物質を用いている物は、基材に塗布または印刷後に高温で過熱する必要がある。加熱による硬化には、多大なエネルギー、時間、装置設置のための床の面積を必要とし、不経済であるばかりでなく、次に示すような大きな制約がある。 Among thermosetting conductive inks, those using an inorganic substance such as glass frit as a binder component must be heated at a high temperature after being applied or printed on a substrate. Curing by heating requires a great deal of energy, time, and floor space for equipment installation, which is not only uneconomical, but also has the following major limitations.
すなわち、ガラスフリット等の無機物質をバインダーとする導電性インキは、通常８００℃以上での焼成を必要とするため、合成樹脂系の基材には適用できない。一方、熱硬化性樹脂をバインダーとする導電性インキは、合成樹脂系の基材に対して適用可能であるが、導電性インキを硬化させる際の過熱によって基材が変形し、得られたプリント配線回路を用いた後工程の部品搭載に支障を来たすなどの大きな障害があった。 That is, a conductive ink using an inorganic substance such as glass frit as a binder usually requires baking at 800 ° C. or higher, and thus cannot be applied to a synthetic resin base material. On the other hand, the conductive ink using a thermosetting resin as a binder can be applied to a synthetic resin-based substrate, but the substrate is deformed by overheating when the conductive ink is cured, and the resulting print is obtained. There were major obstacles such as hindering the mounting of components in the post-process using the wiring circuit.
また従来より、例えばプリント配線板におけるメッキレジストパターンやエッチングレジストパターンあるいはＰＤＰ用の隔壁等を形成する方法としてスクリーン印刷法が多様用されている。 Conventionally, for example, a screen printing method has been widely used as a method for forming a plating resist pattern, an etching resist pattern, a PDP partition, or the like on a printed wiring board.
このようなスクリーン印刷法自体はよく知られているように、スクリーン上にスクリーン印刷インキを盛り、スキージー等で押圧しながら、スクリーンの網目を通して印刷材を印刷するものである（特表平０５−５０６８７６）。 As is well known, such a screen printing method is one in which a printing material is printed through a mesh of a screen while screen printing ink is put on the screen and pressed with a squeegee or the like (Japanese Patent Laid-Open No. 05- 506676).
しかしながら、スクリーン印刷法においては、スキージー等で押圧することで、スクリーンが撓んだ状態で印刷される等の種々の要因から、高精細な印刷を行った場合に印刷精度が得られ難いという問題点があった。 However, in the screen printing method, it is difficult to obtain printing accuracy when high-definition printing is performed due to various factors such as printing with the screen being bent by pressing with a squeegee or the like. There was a point.
特に、高精細なパターンを形成するためのスクリーン印刷に用いられるスクリーン用印刷用インキとしては粘度が高すぎるとスキージー等で押圧した際にインキをスクリーン版に十分に落とし込むことが出来ず、このため精度の高い印刷をすることが出来ず、一方スクリーン印刷用インキの粘度が低い場合は、転写時にインキが印刷版の裏側に回ってしまうといった不具合が生じ、この場合も精度の高い印刷を行うことが出来ないといった問題点があった。 In particular, if the viscosity of the screen printing ink used for screen printing to form a high-definition pattern is too high, the ink cannot be sufficiently dropped onto the screen plate when pressed with a squeegee, etc. If printing with high accuracy is not possible, and the viscosity of the screen printing ink is low, the ink may turn to the back side of the printing plate during transfer. There was a problem that it was not possible.
高精細なパターンを形成することが可能なスクリーン印刷用インキ組成物については特開２００３−２３８８７６に開示されているが、カラーフィルター用インキについて書かれているものであり、導電性について、触れておらず、本用途とは異なる。 A screen printing ink composition capable of forming a high-definition pattern is disclosed in Japanese Patent Application Laid-Open No. 2003-238876, but it is written for a color filter ink. It is different from this application.
またＴＩ値に関する導電性インキについては特開２００１−２３４１０６に開示されているが、平版オフセット印刷法について書かれているものであり、印刷法が異なり、本方式とは異なる。
本発明は、上記問題点に鑑みてなされたものであり、高精細なパターンを形成することが可能なスクリーン印刷用導電性インキ組成物を提供することを主目的とするものである。 The present invention has been made in view of the above problems, and has as its main object to provide a conductive ink composition for screen printing capable of forming a high-definition pattern.
本発明は、導電性物質とバインダー成分を含有する導電性インキにおいて、粘度測定法としてＥ型回転粘度計測定法を用いて、測定部の形状が円錐で円板型の試料容器を用い、測定温度２５℃で測定した粘度（５ｒｐｍ）が、１０Ｐａ・Ｓ〜２００Ｐａ・Ｓであり、粘度が２ｒｐｍと２０ｒｐｍとの比率（ＴＩ値）が４．０〜１０．０であることを特徴とするスクリーン印刷用導電性インキ組成物に関するものである。 In the conductive ink containing a conductive substance and a binder component, the present invention uses an E-type rotational viscometer measurement method as a viscosity measurement method, and uses a disk-shaped sample container with a conical shape in the measurement part. Viscosity (5 rpm) measured at a temperature of 25 ° C. is 10 Pa · S to 200 Pa · S, and the ratio of viscosity (TI value) between 2 rpm and 20 rpm is 4.0 to 10.0. The present invention relates to a conductive ink composition for printing.
なお、ここで、ＴＩ値とはＥ型回転粘度計測定法を用いて、２ｒｐｍの粘度Ｖ2rpmと２０ｒｐｍとの粘度Ｖ20rpmの比率であり、ＴＩ値＝Ｖ2rpm／Ｖ20rpmで表される。 Note that, the TI value using an E-type rotary viscometer measuring method, is the ratio of the viscosity V 20 rpm and the viscosity of 2 rpm V 2 rpm and 20 rpm, represented by TI value = V 2rpm / V 20rpm.
さらに、本発明は、全固形分が７０重量％〜９７重量％であることを特徴とする上記のスクリーン印刷用導電性インキ組成物に関するものである。 Furthermore, the present invention relates to the above-described conductive ink composition for screen printing, wherein the total solid content is 70% by weight to 97% by weight.
また、本発明は、導電性物質と樹脂との固形分の重量比率が９０：１０〜９９：１である事を特徴とする上記のスクリーン印刷用導電性インキ組成物に関するものである。 The present invention also relates to the above-mentioned conductive ink composition for screen printing, wherein the weight ratio of the solid content of the conductive substance and the resin is 90:10 to 99: 1.
さらに、本発明は、導電性物質が、タップ密度１．５〜５ｇ／cm3であり、平均粒径０．５〜５μｍであることを特徴とする上記のスクリーン印刷用導電性インキ組成物に関するものである。 Furthermore, the present invention relates to the above conductive ink composition for screen printing, wherein the conductive material has a tap density of 1.5 to 5 g / cm 3 and an average particle size of 0.5 to 5 μm. Is.
また、本発明は、上記のスクリーン印刷用導電性インキ組成物を基材上に印刷後、硬化させてなることを特徴とする導電性塗膜に関するものである。 Moreover, this invention relates to the electroconductive coating film characterized by making it harden | cure after printing said conductive ink composition for screen printing on a base material.
本発明の導電性インキは高速状態では低粘度になり、スクリーン印刷用版内に正確にインキを落とし込むことが可能となり、またスクリーン印刷用版から被印刷物へとインキが転写される状態、すなわち低速状態では高粘度になり、転写時にインキがスクリーン版印刷用版の裏側に回る等の不具合が無く、正確な転写を行なうことが可能となった。したがって、高精細なパターンをスクリーン印刷により形成する際のスクリーン印刷用インキ組成物として好適に用いることが可能となる。 The conductive ink of the present invention has a low viscosity in a high speed state, and can accurately drop the ink into the screen printing plate. In addition, the ink is transferred from the screen printing plate to the printing material, that is, the low speed. In this state, the viscosity became high, and there was no problem such as the ink rotating to the back side of the screen printing plate during transfer, and accurate transfer was possible. Therefore, it can be suitably used as an ink composition for screen printing when a high-definition pattern is formed by screen printing.
以下、本発明について、実施の形態に基づいてさら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。 Hereinafter, the present invention will be described in more detail based on embodiments, but the present invention is not limited to these embodiments unless departing from the technical idea of the present invention.
本発明者は、上述したように、スクリーン印刷法において、スキージーによりインキを落とし込む際には、インキの粘度が低いほうが好ましく、且つスクリーン印刷版に落とし込まれた後は、インキ粘度が高いほうが好ましい点に着目し、スクリーン印刷用インキ組成物のレオロジー特性を重視した印刷要因を鋭意検討した結果、本発明を見出すに至ったものである。 As described above, when the ink is dropped by a squeegee in the screen printing method, the inventor preferably has a low ink viscosity, and after being dropped on the screen printing plate, the ink viscosity is preferably high. The present invention has been found as a result of diligent investigation of printing factors focusing on the point and emphasizing the rheological properties of the ink composition for screen printing.
本発明のスクリーン印刷用導電性インキ組成物は、少なくとも導電性物質とバインダー成分とを含有するスクリーン印刷用導電性インキ組成物であって、粘度測定法として、Ｅ型回転粘度計を使用し、測定部の形状が円錐で、円盤型の試料容器を用い、温度条件２５℃で測定した粘度が５ｒｐｍ及び粘度が２ｒｐｍと２０ｒｐｍの比率（ＴＩ値）での測定値を所定の範囲として決定した点に特徴を有するものである。 The conductive ink composition for screen printing of the present invention is a conductive ink composition for screen printing containing at least a conductive substance and a binder component, and uses an E-type viscometer as a viscosity measurement method. The shape of the measuring part is a cone, a disk-shaped sample container is used, and the viscosity measured at a temperature condition of 25 ° C. is 5 rpm, and the measured value at a ratio (TI value) between 2 rpm and 20 rpm is determined as a predetermined range. It has the characteristics.
すなわち、粘度（５ｒｐｍ）が、１０Ｐａ・Ｓ〜２００Ｐａ・Ｓであり、粘度が２ｒｐｍと２０ｒｐｍとの比率（ＴＩ値）が４．０〜１０．０であることを特徴とするスクリーン印刷用導電性インキ組成物に関するものである。 That is, the conductivity for screen printing is characterized in that the viscosity (5 rpm) is 10 Pa · S to 200 Pa · S, and the ratio (TI value) between 2 rpm and 20 rpm is 4.0 to 10.0. The present invention relates to an ink composition.
なお、ここで、ＴＩ値とはＥ型回転粘度計測定法を用いて、２ｒｐｍの粘度Ｖ2rpmと２０ｒｐｍの粘度Ｖ20rpmの比率であり、ＴＩ値＝Ｖ2rpm／Ｖ20rpmで表される。 Note that, the TI value using an E-type rotary viscometer measuring method, is the ratio of the viscosity V 20rpm viscosity V 2 rpm and 20rpm of 2 rpm, represented by TI value = V 2rpm / V 20rpm.
ＴＩ値が４以上の場合、スキージーによりインキを落とし込む状態、すなわち高速状態では低粘度になり、スクリーン印刷用版内に正確にインキを落とし込むことが可能となる。またスクリーン印刷用版から被印刷物へとインキが転写される状態、すなわち低速状態では高粘度になり、転写時にインキがスクリーン版印刷用版の裏側に回る等の不具合が無く、正確な転写を行なうことが可能となる。したがって、高精細なパターンをスクリーン印刷により形成する際のスクリーン印刷用インキ組成物として好適に用いることが可能となる。 When the TI value is 4 or more, the ink is dropped by the squeegee, that is, the viscosity becomes low in the high speed state, and the ink can be accurately dropped into the screen printing plate. In addition, the ink is transferred from the screen printing plate to the printing material, that is, the viscosity becomes high at a low speed, and there is no trouble such as the ink rotating to the back side of the screen printing plate at the time of transfer. It becomes possible. Therefore, it can be suitably used as an ink composition for screen printing when a high-definition pattern is formed by screen printing.
また、本発明において、スクリーン印刷用導電性インキ組成物は、全固形分が７０％〜９７％、好ましくは８０％〜９３％の範囲内であることが好ましい。 In the present invention, the conductive ink composition for screen printing has a total solid content of 70% to 97%, preferably 80% to 93%.
さらに、本発明において、スクリーン印刷用導電性インキ組成物は、導電性物質と樹脂比率が９０：１０〜９９：１、好ましくは９４：６〜９８：２の範囲内であることが好ましい。このような範囲内で含有させることにより、チクソトロピー性が付与され、高精細な印刷が可能となる。 Furthermore, in the present invention, the conductive ink composition for screen printing has a conductive material to resin ratio of 90:10 to 99: 1, preferably 94: 6 to 98: 2. By containing within such a range, thixotropy is imparted and high-definition printing becomes possible.
次に本発明に用いる導電性インキについて説明する。 Next, the conductive ink used in the present invention will be described.
導電性物質としては、例えば、金、銀、銅、銀メッキ銅粉、銀−銅複合粉、銀−銅合金、アモルファス銅、ニッケル、クロム、パラジウム、ロジウム、ルテニウム、インジウム、ケイ素、アルミニウム、タングステン、モリブデン、白金などの金属粉、これらの金属で被覆した無機物粉末、酸化銀、酸化インジウム、酸化スズ、酸化亜鉛、酸化ルテニウムなどの金属酸化物の粉末、これらの金属酸化物で被覆した無機物粉末、およびカーボンブラック、グラファイト等を用いることができる。これらの導電性物質は、２種類以上組み合わせて用いても良い。これらの導電性物質のなかでも、高導電性で酸化による抵抗値の上昇の少ないことから銀が好ましい。 Examples of the conductive material include gold, silver, copper, silver-plated copper powder, silver-copper composite powder, silver-copper alloy, amorphous copper, nickel, chromium, palladium, rhodium, ruthenium, indium, silicon, aluminum, and tungsten. Metal powders such as molybdenum and platinum, inorganic powders coated with these metals, powders of metal oxides such as silver oxide, indium oxide, tin oxide, zinc oxide and ruthenium oxide, inorganic powders coated with these metal oxides , And carbon black, graphite and the like can be used. Two or more kinds of these conductive materials may be used in combination. Among these conductive materials, silver is preferable because of its high conductivity and little increase in resistance due to oxidation.
この導電性物質の形状は不定形、鱗片状、塊状、微結晶状、球状、フレーク状等の種々の形状であっても良い。このような導電性粉体は、上記のようにタップ密度が１．５〜５ｇ／cm3の銀粉を用いることで、基材への密着性、屈曲性が良好である。また、平均粒径が０．５〜５μｍの範囲内の銀粉を用いることで、凝集し難く、版からの転移が良好なものが得られる。 The shape of the conductive substance may be various shapes such as an indeterminate shape, a scale shape, a lump shape, a microcrystalline shape, a spherical shape, and a flake shape. Such a conductive powder uses the silver powder having a tap density of 1.5 to 5 g / cm 3 as described above, so that the adhesion to the substrate and the flexibility are good. In addition, by using silver powder having an average particle size in the range of 0.5 to 5 μm, it is possible to obtain a material that hardly aggregates and has good transfer from the plate.
バインダーは有機樹脂を単独或いは併用することができる。有機樹脂としては、ポリエステル樹脂、ウレタン変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂、アクリル変性ポリエステルなどの各種変性ポリエステル樹脂、塩化ビニル、酢酸ビニル共重合樹脂、ブチラール樹脂、ポリエーテルウレタン樹脂、ポリエステルウレタン樹脂、ポリカーボネートウレタン樹脂、エポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリアミド、ポリアミドイミド、ポリオレフィン樹脂、塩素化ポリオレフィン、塩化ゴム、メラミン樹脂、尿素樹脂、ニトロセルロース、セルロース・アセテート・ブチレート（ＣＡＢ）、セルロース・アセテート・プロピオネート（ＣＡＰ）などの変性セルロース類、ロジン、マレイン酸樹脂、天然樹脂、アルキッド樹脂などが挙げられる。 As the binder, an organic resin can be used alone or in combination. Examples of organic resins include polyester resins, urethane-modified polyester resins, epoxy-modified polyester resins, various modified polyester resins such as acrylic-modified polyester, vinyl chloride, vinyl acetate copolymer resins, butyral resins, polyether urethane resins, polyester urethane resins, and polycarbonates. Urethane resin, epoxy resin, phenol resin, acrylic resin, polyamide, polyamideimide, polyolefin resin, chlorinated polyolefin, chlorinated rubber, melamine resin, urea resin, nitrocellulose, cellulose acetate butyrate (CAB), cellulose acetate propionate Modified celluloses such as (CAP), rosin, maleic resin, natural resin, alkyd resin and the like.
本発明に係わる導電性インキは、樹脂の種類、分子量、溶解性に応じて、エステル系溶剤、ケトン系溶剤、グリコールエーテル系溶剤、脂肪族系溶剤、芳香族系溶剤、アルコール系溶剤、水等を使用することができ、２種類以上を混合して使用することもできる。 The conductive ink according to the present invention is an ester solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, water, etc., depending on the type, molecular weight, and solubility of the resin. It is also possible to use a mixture of two or more.
エステル系溶剤としては、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ｎ−ブチル、酢酸イソブチル、酢酸（イソ）アミル、酢酸シクロヘキシル、乳酸エチル、酢酸３−メトキシブチル等が挙げられ、ケトン系溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、メチルアミルケトン、イソホロン、シクロヘキサノン等が挙げられる。また、グリコールエーテル系溶剤としては、エチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノｎ−ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、プロピレングリコールモノｎ−ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノｎ−プロピルエーテル、及びこれらモノエーテル類の酢酸エステル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル等のジアルキルエーテル類が挙げられる。 Examples of ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, (iso) amyl acetate, cyclohexyl acetate, ethyl lactate, and 3-methoxybutyl acetate. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, isophorone, cyclohexanone and the like. The glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol. Mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono n-propyl ether, and acetates of these monoethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, etc. Zia Kill ethers and the like.
脂肪族系溶剤としては、ｎ−ヘプタン、ｎ−ヘキサン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサンが挙げられ、芳香族系溶剤としては、トルエン、キシレンが挙げられる。アルコール系溶剤としては、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、シクロヘキサノール、３−メトキシブタノール、ジアセトンアルコール等が挙げられる。 Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, and examples of the aromatic solvent include toluene and xylene. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol, 3-methoxybutanol, diacetone alcohol and the like.
また、その他の液状媒体として、ジメチルカーボネート、エチルメチルカーボネート、ジ−ｎ−ブチルカーボネートが挙げられる。 Other liquid media include dimethyl carbonate, ethyl methyl carbonate, and di-n-butyl carbonate.
その他に、本発明のインキは必要に応じて、分散剤、耐摩擦向上剤、赤外線吸収剤、紫外線吸収剤、芳香剤、酸化防止剤、消泡剤、シランカップリング剤、可塑剤、難燃剤、保湿剤、などを含むことが出来る。 In addition, the ink of the present invention is optionally dispersed, friction-resistant, infrared absorber, ultraviolet absorber, fragrance, antioxidant, antifoaming agent, silane coupling agent, plasticizer, flame retardant , Moisturizers, and the like.
本発明のスクリーン印刷用導電性インキは、使用用途に応じて紙、プラスチック等の基材の片面または両面上に印刷される。 The conductive ink for screen printing of the present invention is printed on one side or both sides of a substrate such as paper or plastic depending on the intended use.
紙基材としては、コート紙、非コート紙、その他、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が、安定した印刷物を得るためには、コート紙、加工紙が好ましい。コート紙の場合は、平滑度の高いものほど好ましい。 As the paper substrate, various processed papers such as coated paper, non-coated paper, synthetic paper, polyethylene coated paper, impregnated paper, water-resistant processed paper, insulating processed paper, and stretch processed paper can be used. In order to obtain, coated paper and processed paper are preferable. In the case of coated paper, the higher the smoothness, the better.
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、ビニルアルコール、エチレン−ビニルアルコール、ナイロン、ポリイミド、ポリカーボネート等が挙げられる。 Examples of the plastic substrate include polyester, polyethylene, polypropylene, cellophane, vinyl chloride, vinylidene chloride, polystyrene, vinyl alcohol, ethylene-vinyl alcohol, nylon, polyimide, polycarbonate, and the like.
また、表面を改質して、印刷効果を上げる手段として、アンカー処理が挙げられる。アンカー処理剤としてはポリエステル樹脂、ウレタン変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂、アクリル変性ポリエステルなどの各種変性ポリエステル樹脂、塩化ビニル、酢酸ビニル共重合樹脂、ブチラール樹脂、ポリエーテルウレタン樹脂、ポリエステルウレタン樹脂、ポリカーボネートウレタン樹脂、エポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリアミド、ポリアミドイミド、ポリオレフィン樹脂、塩素化ポリオレフィン、塩化ゴム、メラミン樹脂、尿素樹脂、ニトロセルロース、セルロース・アセテート・ブチレート（ＣＡＢ）、セルロース・アセテート・プロピオネート（ＣＡＰ）などの変性セルロース類、ロジン、マレイン酸樹脂、天然樹脂、アルキッド樹脂などが挙げられる。
塗布方法としては、フレキソ印刷、グラビア印刷、グラビアオフセット印刷、オフセット印刷、スクリーン印刷、ロータリースクリーン印刷等、従来公知の印刷方法を用いて印刷することができる。
Further, as a means for improving the printing effect by modifying the surface, anchor treatment can be mentioned. Anchor treatment agents include polyester resin, urethane-modified polyester resin, epoxy-modified polyester resin, various modified polyester resins such as acrylic-modified polyester, vinyl chloride, vinyl acetate copolymer resin, butyral resin, polyether urethane resin, polyester urethane resin, polycarbonate Urethane resin, epoxy resin, phenol resin, acrylic resin, polyamide, polyamideimide, polyolefin resin, chlorinated polyolefin, chlorinated rubber, melamine resin, urea resin, nitrocellulose, cellulose acetate butyrate (CAB), cellulose acetate propionate Modified celluloses such as (CAP), rosin, maleic resin, natural resin, alkyd resin and the like.
As a coating method, it can print using conventionally well-known printing methods, such as flexographic printing, gravure printing, gravure offset printing, offset printing, screen printing, and rotary screen printing.
本発明のスクリーン印刷用導電性インキ組成物の用途としては、種々の微細パターンを必要とする機能性素子の形成に用いることが出来る。具体的にはプリント配線板におけるメッキレジストパターンやエッチングレジストパターンあるいはＰＤＰ用の隔壁、ＥＭＩシールド材等を挙げることが出来る。 As an application of the conductive ink composition for screen printing of the present invention, it can be used for forming functional elements that require various fine patterns. Specifically, a plating resist pattern, an etching resist pattern, a PDP partition, an EMI shield material, and the like on a printed wiring board can be used.
以下に、実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。なお、本発明において、「部」は「重量部」を、「％」は「重量％」を表す。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the present invention, “part” represents “part by weight” and “%” represents “% by weight”.
［銀粉Ａ］
ＭＥＴＡＬＯＲ社製銀粉Ｃ−１２８４Ｐ（タップ密度２．８ｇ／cm3、平均粒径１．２μｍ）を銀粉Ａとした。
[Silver powder A]
Silver powder C-1284P (tap density 2.8 g / cm 3 , average particle size 1.2 μm) manufactured by METALOR was used as silver powder A.
［銀粉Ｂ］
福田金属箔工業製銀粉シルコートＡｇＣ−Ａ（タップ密度３．４ｇ／cm3、平均粒径３．１μｍ）を銀粉Ｂとした。
[Silver powder B]
Silver powder sill coat AgC-A (tap density: 3.4 g / cm 3 , average particle size: 3.1 μm) manufactured by Fukuda Metal Foil Industry was used as silver powder B.
［銀粉Ｃ］
ＳＩＮＯ−ＰＬＡＴＩＵＭ製銀粉（タップ密度２．９ｇ／cm3、平均粒径５．６μｍ）を銀粉Ｃとした。
[Silver powder C]
Silver powder C was made of SINO-PLATIUM silver powder (tap density 2.9 g / cm 3 , average particle size 5.6 μm).
［ワニスＡ］
日信化学工業社製塩ビ酢ビ共重合樹脂ソルバインＴＡ−３を４０部、イソホロンを６０部、丸底フラスコに投入し、６０℃、２時間攪拌、溶解しワニスＡ（固形分４０％）とした。
[Varnish A]
Nissin Chemical Industry Co., Ltd., vinyl acetate / vinyl chloride copolymer resin Solvein TA-3, 40 parts, isophorone 60 parts, charged into a round bottom flask, stirred at 60 ° C. for 2 hours, dissolved and varnish A (solid content 40%) did.
［ワニスＢ］
東洋紡社製ポリエステル樹脂バイロン６３０を４０部、イソホロンを６０部、丸底フラスコに投入し、６０℃、２時間攪拌、溶解しワニスＢ（固形分４０％）とした。
[Varnish B]
40 parts of polyester resin Byron 630 manufactured by Toyobo Co., Ltd. and 60 parts of isophorone were placed in a round bottom flask, stirred and dissolved at 60 ° C. for 2 hours to obtain varnish B (solid content 40%).
［ワニスＣ］
ジャパンエポキシレジン社製エポキシ樹脂エピコート１２５６を４０部、イソホロンを６０部、丸底フラスコに投入し８０℃、２時間攪拌、溶解しワニスＣ（固形分４０％）とした。
[Varnish C]
40 parts of epoxy resin Epicoat 1256 manufactured by Japan Epoxy Resin Co., Ltd. and 60 parts of isophorone were charged into a round bottom flask, and stirred and dissolved at 80 ° C. for 2 hours to obtain Varnish C (solid content 40%).
表１に記載した配合比率にて銀粉、ワニス、溶剤をディスパー、３本ロールにより混練し、導電性インキを調整した。得られた導電性インキの流動性は下記の方法で測定した。 Silver powder, varnish, and solvent were kneaded with a disperser and three rolls at the blending ratio shown in Table 1 to prepare a conductive ink. The fluidity of the obtained conductive ink was measured by the following method.
この導電性インキを４００メッシュスクリーン版を用いて長さ７０ｍｍ、線巾１００μｍ、２００μｍ、３００μｍ、５００μｍ、１ｍｍ、２ｍｍ、３ｍｍ、５ｍｍ、ピッチ幅１０ｍｍの格子状テストパターンを５０μｍＰＥＴフィルム上に印刷し、１５０℃オーブン中で１０分間乾燥させた。得られた印刷物外観評価用とした。 The conductive ink was printed on a 50 μm PET film using a 400 mesh screen plate with a length of 70 mm, a line width of 100 μm, 200 μm, 300 μm, 500 μm, 1 mm, 2 mm, 3 mm, 5 mm, and a pitch width of 10 mm. Dry in a 150 ° C. oven for 10 minutes. The obtained printed matter was used for appearance evaluation.
（銀粉末のタップ密度及び平均粒径の測定）
１）タップ密度
ＪＩＳ Ｚ ２５１２：２００６法に基づいて測定した。
２）平均粒径
島津製作所製レーザー回折粒度分布測定装置「ＳＡＬＡＤ−３０００」を用いて測 定した体積粒度分布の累積粒度５０の粒子径（Ｄ５０）を平均粒径と定義し記載し た。
(Measurement of tap density and average particle diameter of silver powder)
1) Tap density It measured based on JIS Z 2512: 2006 method.
2) Average particle size The particle size (D50) of the cumulative particle size 50 of the volume particle size distribution measured using a Shimadzu laser diffraction particle size distribution measuring device “SALAD-3000” was defined and described as the average particle size.
（インキの粘度及びＴＩ値の測定）
導電性インキを所定量秤り取り、Ｅ型回転粘度計（東機産業社製「ＲＥ８０Ｈ」）を使用して、測定部の形状が円錐で、円盤型の試料容器を用い、２５℃環境下で、インキ粘度測定の場合は５ｒｐｍで、ＴＩ値（チキソトロピーインデックス値）測定の場合は２ｒｐｍ及び２０ｒｐｍにて測定し、インキ粘度、ＴＩ値を求めた。
ここで、ＴＩ値とは、２ｒｐｍの粘度Ｖ2rpmと２０ｒｐｍとの粘度Ｖ20rpmの比率であり、ＴＩ値＝Ｖ2rpm／Ｖ20rpmのことである。
(Measurement of ink viscosity and TI value)
Weigh out a specified amount of conductive ink, and use an E-type rotational viscometer ("RE80H" manufactured by Toki Sangyo Co., Ltd.). The ink viscosity was measured at 5 rpm, and the TI value (thixotropic index value) was measured at 2 rpm and 20 rpm to determine the ink viscosity and TI value.
Here, the TI value is a ratio of the viscosity V 2 rpm of 2 rpm to the viscosity V 20 rpm of 20 rpm , and TI value = V 2 rpm / V 20 rpm .
（印刷物外観評価）
印刷物の外観を光学顕微鏡（ＫＥＹＥＮＣＥ社製「ＶＨ−Ｚ４５０」、倍率：×１００倍）にて観察し評価した。
○：断線、インキの滲み、欠け等が無く良好。
×：断線、或いはインキの滲み、欠け等が見られる。
(Appearance evaluation of printed matter)
The appearance of the printed matter was observed and evaluated with an optical microscope (“VH-Z450” manufactured by KEYENCE, magnification: × 100 times).
○: Good with no disconnection, ink bleeding or chipping.
X: Wire breakage or ink bleeding or chipping is observed.
（印刷適性）
印刷物外観測定用以外に４００メッシュシルクスクリーン版を用いて、５０μｍＰＥＴフィルム上に５０ｍｍ×８０ｍｍのテストパターンを印刷し、１５０℃オーブン中で１０分乾燥させた。印刷適性は版からインキの転移性を目視評価した。
○：異常なく良好なもの
×：版から転移しない。または印刷表面が不良のもの。
(Printability)
A test pattern of 50 mm × 80 mm was printed on a 50 μm PET film using a 400 mesh silk screen plate in addition to the printed matter appearance measurement, and dried in an oven at 150 ° C. for 10 minutes. For printability, the transferability of the ink from the plate was visually evaluated.
○: Good without abnormality ×: No transfer from the plate. Or the printed surface is defective.
（比抵抗の測定）
上記印刷物と同じ印刷物の表面抵抗率をダイアインスツルメント社製抵抗率計ロレスタＧＰにて測定し、株式会社仙台ニコン社製ＭＨ−１５Ｍ型測定器を用いて測定した膜厚を乗じて比抵抗を求めた。
(Measurement of resistivity)
The surface resistivity of the same printed material as the above printed material was measured with a resistivity meter Loresta GP manufactured by Dia Instruments, and multiplied by the film thickness measured using a MH-15M type measuring instrument manufactured by Sendai Nikon Co., Ltd. Asked.
（接着の測定）
上記印刷物と同じ印刷物を用い、セロハンテープ（１２ｍｍ巾）を印刷物表面に貼り付け、急激に剥離し、印刷物の接着性を評価した。
○：剥離せず、異常なし。
×：剥離あり。
(Measurement of adhesion)
Using the same printed material as the above-mentioned printed material, a cellophane tape (12 mm width) was attached to the surface of the printed material, peeled off rapidly, and the adhesive property of the printed material was evaluated.
○: No peeling and no abnormality.
X: There is peeling.
表１に示すように、実施例１〜３に関しては良好な印刷効果を有し、低抵抗な印刷物を得られるが、比較例１〜３においては粘度、ＴＩ値が本発明範囲を逸脱しており、細線印刷に問題を発生する。 As shown in Table 1, Examples 1 to 3 have good printing effects and low resistance printed matter can be obtained, but in Comparative Examples 1 to 3, the viscosity and TI value deviated from the scope of the present invention. This causes problems in fine line printing.
Claims (5)
A conductive coating film, wherein the conductive ink composition for screen printing according to claim 1 is printed on a substrate and then cured.
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