WO2022039179A1 - Resin ink and electronic device - Google Patents

Resin ink and electronic device Download PDF

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Publication number
WO2022039179A1
WO2022039179A1 PCT/JP2021/030115 JP2021030115W WO2022039179A1 WO 2022039179 A1 WO2022039179 A1 WO 2022039179A1 JP 2021030115 W JP2021030115 W JP 2021030115W WO 2022039179 A1 WO2022039179 A1 WO 2022039179A1
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compound
ink
solvent
viscosity
resin
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PCT/JP2021/030115
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French (fr)
Japanese (ja)
Inventor
綾子 吉田
大介 熊木
敏成 千葉
静士 時任
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国立大学法人山形大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins

Definitions

  • the present invention relates to a resin ink obtained by mixing a resin with a solvent to form an ink, and an electronic device on which the resin ink is printed.
  • Print electronics the manufacturing technology of electronic devices using printing technology is called "Printed electronics” and is attracting attention as a resource-saving, low-power, low-environmental-load electronic device manufacturing technology.
  • a semiconductor material, a conductive material, an insulating material or another functional material mixed with a solvent and made into an ink (ink composition) is printed on a substrate such as a film.
  • a substrate such as a film.
  • printing methods such as screen printing, gravure offset printing, flexographic printing, and inkjet printing are used.
  • an ink composition capable of forming an optimum film formation is possible.
  • the range of viscosity of an object is fixed. Therefore, the viscosity of the ink composition is adjusted to have an appropriate range for the printing method to be used. Therefore, if the viscosity of the ink composition changes significantly, the shape of the print pattern is disturbed, the smoothness of the printed resin layer is lowered, and the like, and circuits, elements, devices, and the like cannot be formed in a desired printing state. ..
  • the inventors have found that the viscosity of the ink composition changes significantly by absorbing moisture in a specific solvent constituting the ink composition.
  • the inventors have found that in a high-viscosity ink composition (resin ink) in which a resin is dissolved in a solvent, the viscosity significantly fluctuates due to the influence of moisture absorption when a specific polar organic solvent is used, resulting in a printing state. It was found that the quality of the ink was impaired.
  • the present invention has been proposed in order to avoid deterioration of the printing state in electronic circuit manufacturing in the process in which the resin ink is used. That is, it is an object of the present invention to provide a resin ink capable of ensuring quality maintenance in a printed state even when printing in the atmosphere, and an electronic device on which the resin ink is printed.
  • the present invention has the following configurations.
  • the resin ink of the present invention is a resin ink obtained by mixing a resin material with a solvent to form an ink, and the solvent has a thickening rate when 30 parts by mass of water is added to 100 parts by mass of the solvent. It is characterized in that it is a polar organic solvent having a value of 50% or less.
  • the solvent is characterized in that the solubility of water is 500 g / L or less.
  • the solvent is a saturated cyclic compound having a carbonyl group (including one having an oxygen atom as a hetero atom in the ring skeleton) or a chain skeleton having a carbonyl group and having 5 or more carbon atoms. It is characterized by being a polar organic solvent which is a saturated chain compound (including a compound having an oxygen atom as a hetero atom in the chain skeleton).
  • the resin material is a fluororesin.
  • the electronic device of the present invention is printed with the resin ink of the present invention.
  • the present invention it is possible to provide a resin ink capable of ensuring quality maintenance in a printed state even when printing in the atmosphere, and an electronic device on which the resin ink is printed.
  • the resin ink of the present embodiment is a paste-like composition (ink composition) in which a resin material is mixed (dissolved or dispersed) in a solvent to form an ink, and is mainly used in the manufacture of electronic circuits using a printing device. , Used as an ink for printing various patterns such as desired circuit patterns on a substrate.
  • Some such resin inks include a resin material having a polar group and a polar organic solvent having excellent compatibility (or miscibility) with the resin material.
  • the polar organic solvent is, for example, a cyclic or chain type (linear or chain type) having one or more polar groups such as a carbonyl group, an ester group, a hydroxy group, a phosphoric acid group, a sulfinyl group, an amino group and an amide group. Branched chain) compound.
  • Examples of polar organic solvents are saturated cyclic compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the ring skeleton) (compounds 1 to 5 below) and saturated cyclic compounds having a nitrogen atom (compounds below). 6-8), unsaturated cyclic compounds having a carbonyl group (compounds 9 to 24 below), saturated chain compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the chain skeleton) (compounds below). 25 to 51), chain compounds having a nitrogen atom (compound 52 below), chain compounds having a phosphate group (compound 53 below), chain compounds having a sulfinyl group (compound 54 below) and the like can be mentioned.
  • the polar organic solvent in the resin ink of the present embodiment is thickened even if it absorbs moisture in order to prevent the viscosity from changing significantly due to moisture absorption in the printing process. It is a polar organic solvent that does not absorb moisture or does not easily absorb moisture. Since the degree of moisture absorption is affected by the environment and the amount of exposure to the atmosphere (printing work time), it is necessary to select a solvent having a low thickening rate even when mixed with an excessive amount of water. Specifically, a polar organic solvent having a thickening ratio of 50% or less when 30 parts by mass of water is added to 100 parts by mass of the polar organic solvent is used.
  • the "viscosity thickening rate” means the ratio of the viscosity change due to moisture absorption to the viscosity of the solvent. For example, when the viscosity of the solvent alone is Da and the viscosity after the solvent absorbs (moisture absorbs) water is Db, the thickening rate due to the absorption of the solvent is Db ⁇ Da ⁇ 100-100 (%). be.
  • the polar organic solvent used as the solvent for the resin ink includes saturated cyclic compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the ring skeleton) (for example, compounds 1 to 5). Saturated chain compounds having a carbonyl group and having 5 or more carbon atoms in the chain skeleton (including those having an oxygen atom as a hetero atom in the chain skeleton) (for example, compounds 26 to 51), chains having a phosphate group.
  • Formula compounds (eg, compound 53) and the like can be mentioned.
  • resin material examples include fluororesins (polyvinylidene fluoride trifluoride (PVDF-TrFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc.) and polyvinylphenol (PVP).
  • fluororesins polyvinylidene fluoride trifluoride (PVDF-TrFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc.
  • PVDF-TrFE polyvinylidene fluoride trifluoride
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVP polyvinylphenol
  • resin materials having a polar group such as an insulating resin such as a resin.
  • the weight ratio of the resin material in the resin ink varies depending on the required viscosity and the target film thickness, so there is no particular optimum value. It is preferable to select a solvent having a smaller viscosity when water is added, because it is more likely to occur.
  • Other materials to be mixed with polar organic solvents include, for example, conductive particles (eg, copper, zinc, chromium, platinum, gold, silver, aluminum, palladium, iron, cobalt, nickel, or their metal oxides, carbon.
  • conductive particles eg, copper, zinc, chromium, platinum, gold, silver, aluminum, palladium, iron, cobalt, nickel, or their metal oxides, carbon.
  • additives eg, wetting agents, dispersants, defoaming agents, adhesion promoters, corrosion inhibitors, stabilizers, surfactants, etc.
  • additives particles consisting of one or more materials such as materials
  • substrate examples of the substrate (base material) of the object to be printed on which various patterns such as circuit patterns are printed by the resin ink include flexible substrates made of resin such as polyimide, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN). Examples include ceramics (alumina, aluminum nitride, etc.), glass, paper, and the like.
  • the resin ink of this embodiment is used when printing various patterns such as a desired circuit pattern on a substrate (base material).
  • Examples of electronic devices on which such resin ink (pattern) is printed include semiconductors, electronic displays, electronic circuits (print circuits, etc.), sensors, and the like.
  • Printing of this pattern is, for example, screen printing method, inkjet printing method, letterpress reversal printing method, gravure offset printing method, offset printing method, spin coating method, spray coating method, bar coating method, die coating method, slit coating method, roll coating method. It is performed by a method such as a method or a dip coat method.
  • polar organic solvents Nos. [1] to [15] shown in [Table 1] and [Table 2] Fifteen types of polar organic solvents were selected as solvent candidates for the resin ink (polar organic solvents Nos. [1] to [15] shown in [Table 1] and [Table 2]).
  • the viscosity of only the polar organic solvent is D 1
  • 30 parts by mass of ultrapure water is mixed with 100 parts by mass of the polar organic solvent.
  • the viscosity of the polar organic solvent was D 2
  • the thickening rate (D 2 ⁇ D 1 ⁇ 100-100) (%) of the polar organic solvent calculated from D 1 and D 2 was calculated.
  • Viscosity D 1 and viscosity D 2 were measured using a rotary viscometer (DV-3T: LV) manufactured by Brookfield.
  • the spindle used was a cone plate type spindle (CPA-40). Viscosity D 1 and viscosity D 2 were measured when the spindle was rotated at 50 rpm while the temperature was maintained at 25 ° C.
  • the numbers [4] (Compound 6), No. [8] (Compound 8), and No. [10] (Compound 52) are structures containing nitrogen atoms such as an amino group and an amine group, and have such a structure. It was found that the thickening rate of this compound was large.
  • Example 2 Viscosity change in the printing process of fluororesin ink
  • the two types of polar organic solvents confirmed in Experiment 1 No. [2] (Compound 3) and No. [4] (Compound 6) were each subjected to polyvinylidene fluoride trifluoride (PVDF-TrFE), which is a fluororesin.
  • PVDF-TrF ink was prepared as a fluororesin ink by mixing with a copolymer, and it was confirmed whether the viscosity of PVDF-TrF ink changed before and after printing using the adjusted PVDF-TrF ink.
  • PVDF-TrFE polyvinylidene fluoride copolymer
  • polar organic solvents No. [2] (Compound 3) and No. [4] (Compound 6).
  • two types of PVDF-TrFE ink having a resin concentration of 18 wt% were adjusted.
  • a screen printing device As a printing device, a screen printing device SSA-PC250E-IP manufactured by Ceria Co., Ltd. was used. In this printing apparatus, a mask (plate) having a printing area of 100 mm ⁇ 100 mm and a plate frame size of 320 mm ⁇ 320 mm was used, and screen printing was performed with a squeegee moving speed of 10 mm / s.
  • each of the two prepared PVDF-TrFE inks is filled in the screen printing device, and screen printing is continuously performed on the PEN substrate which is the 10 sheets to be printed (that is, 10 times of printing), and then the mask is performed.
  • the PVDF-TrFE ink remaining on the (plate) was collected and its viscosity was measured. Since the time required for printing is about 3 minutes for one printed matter, it takes about 30 to 40 minutes for 10 printed matter, during which the PVDF-TrFE ink has a working atmosphere in this printing process. It was exposed (hygroscopic) to the atmosphere inside. The temperature and humidity of this working atmosphere were 25 ° C. and 50% humidity (relative humidity) RH.
  • FIG. 1 shows the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) of the rotor.
  • the broken line a1 indicates the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) before printing (initial state) in the PVDF-TrFE ink using the polar organic solvent of No. [2] (Compound 3).
  • the solid line a2 is the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) in the state after printing 10 times in the PVDF-TrFE ink using the polar organic solvent of No. [ 2 ] (Compound 3). Is shown.
  • the broken line b1 indicates the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) before printing (initial state) in the PVDF-TrFE ink using the polar organic solvent of No. [ 4 ] (Compound 6).
  • Solid line b 2 shows the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) in the state after printing 10 times in the PVDF-TrFE ink using the polar organic solvent of No. [4] (Compound 6). There is.
  • PVDF-TrFE ink had a greater thickening in the printing process. From this, it can be seen that the PVDF-TrFE ink absorbs moisture and thickens due to the atmosphere in the working atmosphere in the printing process.
  • Example 3 Viscosity change due to moisture absorption of polyvinylphenol ink
  • the two types of polar organic solvents confirmed in Experiment 1 No. [2] (Compound 3) and No. [4] (Compound 6)) were mixed with polyvinylphenol (PVP), which is an insulating resin, respectively.
  • PVP ink was adjusted as the insulating resin ink, and it was confirmed whether or not the viscosity of the insulating resin ink changed due to moisture absorption.
  • PVP ink which is an insulating resin
  • each polar organic solvent of No. [2] (Compound 3) and No. [4] (Compound 6) is mixed with each polar organic solvent of No. [2] (Compound 3) and No. [4] (Compound 6), and the resin concentration is 10 wt%. Two types of (insulating resin ink) were adjusted.
  • the viscosities of the two adjusted PVP inks were measured before adding ultrapure water.
  • FIG. 2 the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) of the rotor is shown.
  • the broken line c 1 indicates the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) before water addition in the PVP ink using the polar organic solvent of No. [2] (Compound 3), and is a solid line.
  • c 2 indicates the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) after the addition of water in the PVP ink using the polar organic solvent of No. [2] (Compound 3).
  • the broken line d 1 indicates the viscosity (mPa ⁇ s) with respect to the rotation speed (rpm) before water addition in the PVP ink using the polar organic solvent of No. [4] (Compound 6), and the solid line d 2 is. , No. [4] (Compound 6) shows the viscosity (mPa ⁇ s) with respect to the number of revolutions (rpm) in the state after water addition in the PVP ink using the polar organic solvent.
  • the PVP ink using the hygroscopic polar organic solvent (No. [4] (Compound 6)) is more than the PVP ink using the non-hygroscopic polar organic solvent (No. [2] (Compound 3)).
  • the thickening was greater in. From this, it was found that the PVP ink also thickened by moisture absorption.

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Abstract

The present invention provides: a resin ink which is capable of ensuring quality maintenance of the print state even if printing is carried out in the atmosphere; and an electronic device on which this resin ink is printed.　A resin ink according to the present invention is obtained by mixing a resin material into a solvent to form an ink; and the solvent is a polar organic solvent, the thickening ratio of which is 50% or less as determined by adding 30 parts by mass of water to 100 parts by mass of the solvent.

Description

樹脂インク及び電子デバイスResin inks and electronic devices
　本発明は、樹脂を溶媒に混合してインク化した樹脂インク、及びその樹脂インクが印刷された電子デバイスに関するものである。 The present invention relates to a resin ink obtained by mixing a resin with a solvent to form an ink, and an electronic device on which the resin ink is printed.
　近年、印刷技術を用いた電子デバイスの製造技術は、「プリンテッドエレクトロニクス（Printed electronics）」等と称され、省資源、低電力で環境負荷の少ない電子デバイス製造技術であるとして注目されている。 In recent years, the manufacturing technology of electronic devices using printing technology is called "Printed electronics" and is attracting attention as a resource-saving, low-power, low-environmental-load electronic device manufacturing technology.
　このような電子デバイスの製造技術は、半導体材料、導電性材料、絶縁性材料或いは他の機能性材料を溶媒に混合してインク化したもの（インク組成物）をフィルム等の基板に印刷して、回路・素子やデバイスを形成する（例えば、下記特許文献１参照）。 In the manufacturing technology of such an electronic device, a semiconductor material, a conductive material, an insulating material or another functional material mixed with a solvent and made into an ink (ink composition) is printed on a substrate such as a film. , Forming circuits / elements and devices (see, for example, Patent Document 1 below).
特開２０１７－１９７７６５号公報Japanese Unexamined Patent Publication No. 2017-197765
　印刷法を用いて電子回路を形成する場合、スクリーン印刷やグラビアオフセット印刷、フレキソ印刷、インクジェット印刷等の印刷法が用いられるが、各印刷法において、最適な成膜を行うことが可能なインク組成物の粘度の範囲が決まっている。そのため、インク組成物の粘度は、使用したい印刷法に対して適正な範囲を持つよう調整されている。従って、インク組成物の粘度が大きく変化すると、印刷パターン形状の乱れや印刷された樹脂層の平滑度の低下等が生じ、所望の印刷状態で回路、素子、デバイス等を形成することができなくなる。 When forming an electronic circuit by using a printing method, printing methods such as screen printing, gravure offset printing, flexographic printing, and inkjet printing are used. In each printing method, an ink composition capable of forming an optimum film formation is possible. The range of viscosity of an object is fixed. Therefore, the viscosity of the ink composition is adjusted to have an appropriate range for the printing method to be used. Therefore, if the viscosity of the ink composition changes significantly, the shape of the print pattern is disturbed, the smoothness of the printed resin layer is lowered, and the like, and circuits, elements, devices, and the like cannot be formed in a desired printing state. ..
　電子回路製造において、印刷状態の品質維持は、回路の短絡や電気特性の低下等の不具合を生じさせないために不可欠であり、印刷状態の品質が維持できない場合には、電子デバイスの製造において著しく歩留まりの低下を引き起こすことになる。 In the manufacture of electronic circuits, maintaining the quality of the printed state is indispensable in order not to cause problems such as short circuit of the circuit and deterioration of electrical characteristics. Will cause a decrease in.
　発明者らは、インク組成物を構成する特定の溶媒において、吸湿することでインク組成物の粘度が大きく変動することを見出した。特に、発明者らは、樹脂を溶媒に溶解させた高粘度のインク組成物（樹脂インク）において、特定の極性有機溶媒を用いた場合に吸湿の影響により粘度が著しく変動してしまい、印刷状態の品質が損なわれることを見出した。 The inventors have found that the viscosity of the ink composition changes significantly by absorbing moisture in a specific solvent constituting the ink composition. In particular, the inventors have found that in a high-viscosity ink composition (resin ink) in which a resin is dissolved in a solvent, the viscosity significantly fluctuates due to the influence of moisture absorption when a specific polar organic solvent is used, resulting in a printing state. It was found that the quality of the ink was impaired.
　本発明では、樹脂インクが用いられる工程において、電子回路製造における印刷状態の品質低下を回避するために提案されたものである。すなわち、大気中での印刷であっても、印刷状態の品質維持を確保することが可能な樹脂インク、及びその樹脂インクが印刷された電子デバイスを提供することが、本発明の課題である。 The present invention has been proposed in order to avoid deterioration of the printing state in electronic circuit manufacturing in the process in which the resin ink is used. That is, it is an object of the present invention to provide a resin ink capable of ensuring quality maintenance in a printed state even when printing in the atmosphere, and an electronic device on which the resin ink is printed.
　このような課題を解決するために、本発明は、以下の構成を具備するものである。 In order to solve such a problem, the present invention has the following configurations.
　すなわち、本発明の樹脂インクは、樹脂材料を溶媒に混合してインク化した樹脂インクであって、前記溶媒は、前記溶媒１００質量部に対して水を３０質量部加えたときの増粘率が５０％以下である極性有機溶媒であることを特徴とする。 That is, the resin ink of the present invention is a resin ink obtained by mixing a resin material with a solvent to form an ink, and the solvent has a thickening rate when 30 parts by mass of water is added to 100 parts by mass of the solvent. It is characterized in that it is a polar organic solvent having a value of 50% or less.
　好適には、前記溶媒は、水の溶解度が５００ｇ／Ｌ以下であることを特徴とする。 Preferably, the solvent is characterized in that the solubility of water is 500 g / L or less.
　好適には、前記溶媒は、カルボニル基を有する飽和環式化合物（環骨格中にヘテロ原子として酸素原子を有するものも含む）、又は、カルボニル基を有し鎖状骨格の炭素数が５以上の飽和鎖式化合物（鎖状骨格中にヘテロ原子として酸素原子を有するものを含む）である極性有機溶媒であることを特徴とする。 Preferably, the solvent is a saturated cyclic compound having a carbonyl group (including one having an oxygen atom as a hetero atom in the ring skeleton) or a chain skeleton having a carbonyl group and having 5 or more carbon atoms. It is characterized by being a polar organic solvent which is a saturated chain compound (including a compound having an oxygen atom as a hetero atom in the chain skeleton).
　好適には、前記樹脂材料がフッ素系樹脂であることを特徴とする。 Preferably, the resin material is a fluororesin.
　本発明の電子デバイスは、本発明の樹脂インクが印刷されてなる。 The electronic device of the present invention is printed with the resin ink of the present invention.
　本発明によれば、大気中での印刷であっても、印刷状態の品質維持を確保することが可能な樹脂インク及びその樹脂インクが印刷された電子デバイスを提供することができる。 According to the present invention, it is possible to provide a resin ink capable of ensuring quality maintenance in a printed state even when printing in the atmosphere, and an electronic device on which the resin ink is printed.
実験２の結果（フッ素樹脂インクの印刷工程での粘度変化）を示す図である。It is a figure which shows the result of Experiment 2 (viscosity change in a printing process of a fluororesin ink). 実験３の結果（ポリビニルフェノールインクの吸湿による粘度変化）を示す図である。It is a figure which shows the result of Experiment 3 (viscosity change by moisture absorption of polyvinyl phenol ink).
　以下、図面を参照して本発明の実施形態を説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
　（樹脂インク）
　本実施形態の樹脂インクは、樹脂材料を溶媒に混合（溶解又は分散）してインク化したペースト状の組成物（インク組成物）であり、主に、印刷装置を用いた電子回路の製造において、基板に所望の回路パターン等の各種のパターンを印刷するためのインクとして用いられる。このような樹脂インクには、極性基を有する樹脂材料と、その樹脂材料との相溶性（又は混和性）に優れた極性有機溶媒とが含まれるものがある。 (Resin ink)
The resin ink of the present embodiment is a paste-like composition (ink composition) in which a resin material is mixed (dissolved or dispersed) in a solvent to form an ink, and is mainly used in the manufacture of electronic circuits using a printing device. , Used as an ink for printing various patterns such as desired circuit patterns on a substrate. Some such resin inks include a resin material having a polar group and a polar organic solvent having excellent compatibility (or miscibility) with the resin material.
　（極性有機溶媒）
　極性有機溶媒は、例えば、カルボニル基、エステル基、ヒドロキシ基、リン酸基、スルフィニル基、アミノ基、アミド基等の極性基の１種又は２種以上を有する環式又は鎖式（直鎖又は分岐鎖）の化合物をいう。 (Polar organic solvent)
The polar organic solvent is, for example, a cyclic or chain type (linear or chain type) having one or more polar groups such as a carbonyl group, an ester group, a hydroxy group, a phosphoric acid group, a sulfinyl group, an amino group and an amide group. Branched chain) compound.
　極性有機溶媒の例として、カルボニル基を有する飽和環式化合物（環骨格中にヘテロ原子として酸素原子を有するものも含む）（下記化合物１～５）、窒素原子を有する飽和環式化合物（下記化合物６～８）、カルボニル基を有する不飽和環式化合物（下記化合物９～２４）、カルボニル基を有する飽和鎖式化合物（鎖状骨格中にヘテロ原子として酸素原子を有するものを含む）（下記化合物２５～５１）、窒素原子を有する鎖式化合物（下記化合物５２）、リン酸基を有する鎖式化合物（下記化合物５３）、スルフィニル基を有する鎖式化合物（下記化合物５４）等が挙げられる。 Examples of polar organic solvents are saturated cyclic compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the ring skeleton) (compounds 1 to 5 below) and saturated cyclic compounds having a nitrogen atom (compounds below). 6-8), unsaturated cyclic compounds having a carbonyl group (compounds 9 to 24 below), saturated chain compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the chain skeleton) (compounds below). 25 to 51), chain compounds having a nitrogen atom (compound 52 below), chain compounds having a phosphate group (compound 53 below), chain compounds having a sulfinyl group (compound 54 below) and the like can be mentioned.
　このような極性有機溶媒の内、本実施形態の樹脂インク中の極性有機溶媒としては、印刷工程での吸湿によりその粘度が大きく変化してしまうことを抑制するために、吸湿しても増粘しない、又は、吸湿し難い極性有機溶媒である。吸湿の度合いは、環境や大気への暴露量（印刷作業時間）等に影響されるため、過剰量の水分と混合しても増粘率が低い溶媒を選定する必要がある。具体的には、極性有機溶媒１００質量部に対して水を３０質量部加えたときの増粘率が５０％以下である極性有機溶媒を用いるようにする。なお、本実施形態において「増粘率」とは、溶媒の粘度に対する吸湿による粘度変化の割合をいう。例えば、溶媒のみの粘度をＤａとし、その溶媒が水を吸収（吸湿）した後の粘度をＤｂとしたとき、その溶媒の吸湿による増粘率は、Ｄｂ÷Ｄａ×１００－１００（％）である。 Among such polar organic solvents, the polar organic solvent in the resin ink of the present embodiment is thickened even if it absorbs moisture in order to prevent the viscosity from changing significantly due to moisture absorption in the printing process. It is a polar organic solvent that does not absorb moisture or does not easily absorb moisture. Since the degree of moisture absorption is affected by the environment and the amount of exposure to the atmosphere (printing work time), it is necessary to select a solvent having a low thickening rate even when mixed with an excessive amount of water. Specifically, a polar organic solvent having a thickening ratio of 50% or less when 30 parts by mass of water is added to 100 parts by mass of the polar organic solvent is used. In the present embodiment, the "viscosity thickening rate" means the ratio of the viscosity change due to moisture absorption to the viscosity of the solvent. For example, when the viscosity of the solvent alone is Da and the viscosity after the solvent absorbs (moisture absorbs) water is Db, the thickening rate due to the absorption of the solvent is Db ÷ Da × 100-100 (%). be.
　本実施形態において、樹脂インクの溶媒として用いられる極性有機溶媒としては、カルボニル基を有する飽和環式化合物（環骨格中にヘテロ原子として酸素原子を有するものも含む）（例えば化合物１～５）、カルボニル基を有し鎖状骨格の炭素数が５以上の飽和鎖式化合物（鎖状骨格中にヘテロ原子として酸素原子を有するものを含む）（例えば化合物２６～５１）、リン酸基を有する鎖式化合物（例えば化合物５３）等が挙げられる。 In the present embodiment, the polar organic solvent used as the solvent for the resin ink includes saturated cyclic compounds having a carbonyl group (including those having an oxygen atom as a hetero atom in the ring skeleton) (for example, compounds 1 to 5). Saturated chain compounds having a carbonyl group and having 5 or more carbon atoms in the chain skeleton (including those having an oxygen atom as a hetero atom in the chain skeleton) (for example, compounds 26 to 51), chains having a phosphate group. Formula compounds (eg, compound 53) and the like can be mentioned.
　［化合物１］シクロヘキサノン
　［化合物２］シクロヘプタノン
　［化合物３］3,3,5-トリメチルシクロヘキサノン
　［化合物４］γ-ブチロラクトン
　［化合物５］プロピレンカルボナート
　［化合物６］ＮＭＰ(1-メチル-2-ピロリドン)
　［化合物７］1,3-ジメチル-2-イミダゾリジノン
　［化合物８］Ｎ,Ｎ-ジメチルシクロヘキシルアミン
　［化合物９］イソホロン [Compound 1] Cyclohexanone [Compound 2] Cycloheptanone [Compound 3] 3,3,5-trimethylcyclohexanone [Compound 4] γ-Butyrolactone [Compound 5] Propylene Carbonate [Compound 6] NMP (1-Methyl-2-) Pyrrolidone)
[Compound 7] 1,3-dimethyl-2-imidazolidinone [Compound 8] N, N-dimethylcyclohexylamine [Compound 9] Isophorone
　［化合物１０］2-メトキシ-4-メチルフェノール
　［化合物１１］サリチル酸メチル（メチルサリチレート）
　［化合物１２］2'-ヒドロキシアセトフェノン
　［化合物１３］ベンズアルデヒド
　［化合物１４］p-トルアルデヒド
　［化合物１５］アセトフェノン
　［化合物１６］4'-メチルアセトフェノン
　［化合物１７］4-エチルベンズアルデヒド
　［化合物１８］4'-エチルアセトフェノン
　［化合物１９］安息香酸メチル（メチルベンゾエート） [Compound 10] 2-Methoxy-4-methylphenol [Compound 11] Methyl salicylate (methyl salicylate)
[Compound 12] 2'-Hydroxyacetophenone [Compound 13] Benzaldehyde [Compound 14] p-tolualdehyde [Compound 15] Acetphenone [Compound 16] 4'-Methylacetophenone [Compound 17] 4-Ethylbenzaldehyde [Compound 18] 4' -Ethylacetophenone [Compound 19] Methyl benzoate (Methylbenzoate)
　［化合物２０］安息香酸エチル（エチルベンゾエート）
　［化合物２１］メチルｐ-トルエート
　［化合物２２］プロピルベンゾエート
　［化合物２３］エチルｐ-トルエート
　［化合物２４］ブチルベンゾエート
　［化合物２５］ＭＥＫ（2-ブタノン）
　［化合物２６］2-ペンタノン
　［化合物２７］2-ヘキサノン
　［化合物２８］2-ヘプタノン
　［化合物２９］2-オクタノン [Compound 20] Ethyl benzoate (ethylbenzoate)
[Compound 21] Methyl p-toluate [Compound 22] Propylbenzoate [Compound 23] Ethyl p-toluate [Compound 24] Butylbenzoate [Compound 25] MEK (2-butanone)
[Compound 26] 2-Pentanone [Compound 27] 2-Hexanone [Compound 28] 2-Heptanone [Compound 29] 2-Octanone
　［化合物３０］2-ノナノン
　［化合物３１］2-デカノン
　［化合物３２］ノナナール
　［化合物３３］酢酸2-エトキシエチル
　［化合物３４］エチレングリコールモノブチルエーテルアセテート
　［化合物３５］ジエチレングリコールモノエチルエーテルアセテート
　［化合物３６］ジエチレングリコールモノブチルエーテルアセタート
　［化合物３７］プロピルヘキサノエート
　［化合物３８］プロピルｎ-オクタノエート
　［化合物３９］エチルｎ-オクタノエート [Compound 30] 2-Nonanone [Compound 31] 2-Decanone [Compound 32] Nonanal [Compound 33] 2-ethoxyethyl acetate [Compound 34] Ethylene glycol monobutyl ether acetate [Compound 35] Diethylene glycol monoethyl ether acetate [Compound 36] Diethylene glycol monobutyl ether acetate [Compound 37] propylhexanoate [Compound 38] propyl n-octanoate [Compound 39] ethyl n-octanoate
　［化合物４０］メチルデカノエート
　［化合物４１］2-エチルヘキシルアセテート
　［化合物４２］3,4-ヘキサンジオン
　［化合物４３］ジエチルオキサレート
　［化合物４４］ジブチルオキサレート
　［化合物４５］アセチルアセトン
　［化合物４６］メチルアセトアセテート
　［化合物４７］ジエチルマロネート
　［化合物４８］アセトニルアセトン
　［化合物４９］エチレングリコールジアセタート [Compound 40] Methyldecanoate [Compound 41] 2-Ethylhexyl acetate [Compound 42] 3,4-Hexanedione [Compound 43] diethyl oxalate [Compound 44] Dibutyl oxalate [Compound 45] Acetylacetone [Compound 46] Methyl Acetoacetate [Compound 47] Diethylmalonate [Compound 48] Acetonylacetone [Compound 49] Ethylene glycol diacetate
　［化合物５０］1,2-ジアセトキシプロパン
　［化合物５１］2,6-ジメチル-4-ヘプタノン
　［化合物５２］テトラメチル尿素
　［化合物５３］リン酸トリメチル
　［化合物５４］ＤＭＳＯ（ジメチルスルホキシド） [Compound 50] 1,2-Diacetoxypropane [Compound 51] 2,6-dimethyl-4-heptanone [Compound 52] Tetramethylurea [Compound 53] Trimethyl phosphate [Compound 54] DMSO (dimethyl sulfoxide)
　樹脂濃度が高く粘度の高いインクでは、吸湿による粘度変化が起こり易くなるため、水を加えた際の増粘率がより小さい溶媒を選択することが好ましい。 For inks with a high resin concentration and high viscosity, the viscosity changes easily due to moisture absorption, so it is preferable to select a solvent with a smaller viscosity increase rate when water is added.
（樹脂材料）
　樹脂インク中に含まれる樹脂材料としては、例えば、フッ素系樹脂（ポリフッ化ビニリデントリフルオライド（ＰＶＤＦ‐ＴｒＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等）、ポリビニルフェノール（ＰＶＰ）樹脂等の絶縁性樹脂等の極性基を有する樹脂材料を１種又は２種以上含むものが挙げられる。 (Resin material)
Examples of the resin material contained in the resin ink include fluororesins (polyvinylidene fluoride trifluoride (PVDF-TrFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc.) and polyvinylphenol (PVP). Examples thereof include one or more resin materials having a polar group such as an insulating resin such as a resin.
　樹脂インク（インク組成物）における樹脂材料の重量比率は、要求される粘度や目標膜厚により変わるため、特に最適な値はないが、樹脂濃度が高く粘度の高いインクでは、吸湿による粘度変化が起こり易くなるため、水を加えた際の増粘率がより小さい溶媒を選択することが好ましい。 The weight ratio of the resin material in the resin ink (ink composition) varies depending on the required viscosity and the target film thickness, so there is no particular optimum value. It is preferable to select a solvent having a smaller viscosity when water is added, because it is more likely to occur.
（その他の材料）
　極性有機溶媒に混合させるその他の材料としては、例えば、導電性粒子（例えば、銅、亜鉛、クロム、白金、金、銀、アルミニウム、パラジウム、鉄、コバルト、ニッケル、或いはこれらの金属酸化物、カーボン材料等の１種又は２種以上の材料からなる粒子）、添加剤（例えば、湿潤剤、分散剤、消泡剤、接着促進剤、腐食防止剤、安定剤、界面活性剤等の１種又は２種以上からなるもの）等が更に含まれるようにしてもよい。 (Other materials)
Other materials to be mixed with polar organic solvents include, for example, conductive particles (eg, copper, zinc, chromium, platinum, gold, silver, aluminum, palladium, iron, cobalt, nickel, or their metal oxides, carbon. One or more of additives (eg, wetting agents, dispersants, defoaming agents, adhesion promoters, corrosion inhibitors, stabilizers, surfactants, etc.), additives (particles consisting of one or more materials such as materials) (Those consisting of two or more types) and the like may be further included.
（基板）
　樹脂インクにより、回路パターン等の各種のパターンが印刷される被印刷物の基板（基材）としては、例えば、ポリイミド、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等の樹脂からなるフレキシブル基板、セラミックス（アルミナ、窒化アルミニウム等）、ガラス、紙等が挙げられる。 (substrate)
Examples of the substrate (base material) of the object to be printed on which various patterns such as circuit patterns are printed by the resin ink include flexible substrates made of resin such as polyimide, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN). Examples include ceramics (alumina, aluminum nitride, etc.), glass, paper, and the like.
（電子デバイス）
　本実施形態の樹脂インクは、基板（基材）上に所望の回路パターン等の各種のパターンを印刷する際に用いられる。このような樹脂インク（パターン）が印刷された電子デバイスとしては、例えば半導体、電子ディスプレイ、電子回路（プリント回路等）、センサ等が挙げられる。このパターンの印刷は、例えばスクリーン印刷法、インクジェット印刷法、凸版反転印刷法、グラビアオフセット印刷法、オフセット印刷法、スピンコート法、スプレーコート法、バーコート法、ダイコート法、スリットコート法、ロールコート法、ディップコート法等の方法で行われる。 (Electronic device)
The resin ink of this embodiment is used when printing various patterns such as a desired circuit pattern on a substrate (base material). Examples of electronic devices on which such resin ink (pattern) is printed include semiconductors, electronic displays, electronic circuits (print circuits, etc.), sensors, and the like. Printing of this pattern is, for example, screen printing method, inkjet printing method, letterpress reversal printing method, gravure offset printing method, offset printing method, spin coating method, spray coating method, bar coating method, die coating method, slit coating method, roll coating method. It is performed by a method such as a method or a dip coat method.
　以下に、実施例を挙げて本発明を詳細に説明する。但し、本発明は、この実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this embodiment.
（実験１：溶媒に対する含水による粘度変化）
　構造が異なる極性基を有する極性有機溶媒について、その溶媒に対する含水による粘度変化の影響を調査した。 (Experiment 1: Viscosity change due to water content with respect to solvent)
For polar organic solvents having polar groups with different structures, the effect of changes in viscosity due to water content on the solvent was investigated.
　樹脂インクの溶媒の候補として、１５種類の極性有機溶媒を選定した（［表１］及び［表２］に示す番号［１］～［１５]の極性有機溶媒）。番号［１］～［１５]の各極性有機溶媒について、極性有機溶媒のみの粘度をＤ１、極性有機溶媒１００質量部に対し、３０質量部の超純水をその極性有機溶媒に混合した後の粘度をＤ２とし、Ｄ１とＤ２とから計算されるその極性有機溶媒の増粘率（Ｄ２÷Ｄ１×１００－１００）（％）を算出した。 Fifteen types of polar organic solvents were selected as solvent candidates for the resin ink (polar organic solvents Nos. [1] to [15] shown in [Table 1] and [Table 2]). For each of the polar organic solvents Nos. [1] to [15], the viscosity of only the polar organic solvent is D 1 , and 30 parts by mass of ultrapure water is mixed with 100 parts by mass of the polar organic solvent. The viscosity of the polar organic solvent was D 2 , and the thickening rate (D 2 ÷ D 1 × 100-100) (%) of the polar organic solvent calculated from D 1 and D 2 was calculated.
　粘度Ｄ１、粘度Ｄ２は、ブルックフィールド社製の回転式粘度計（DV-3T：LV）を用いて測定した。スピンドルは、コーンプレート型スピンドル（CPA-40）を使用した。温度を２５℃に保ち、スピンドルを５０ｒｐｍで回転させたときの粘度Ｄ１、粘度Ｄ２を測定した。 Viscosity D 1 and viscosity D 2 were measured using a rotary viscometer (DV-3T: LV) manufactured by Brookfield. The spindle used was a cone plate type spindle (CPA-40). Viscosity D 1 and viscosity D 2 were measured when the spindle was rotated at 50 rpm while the temperature was maintained at 25 ° C.
　また、参考として、溶媒便覧等の文献に記載されている、水に対する溶解度を併せて示した。この実験１の結果を［表１］及び［表２］に示す。 In addition, as a reference, the solubility in water described in the literature such as the solvent handbook is also shown. The results of this experiment 1 are shown in [Table 1] and [Table 2].
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　［表１］及び［表２］に示すように、番号［４］（化合物６）、番号［８］（化合物８）、番号［９］（化合物２５）、番号［１０］（化合物５２）の極性有機溶媒では、増粘率が５０％を超えたことから、極性有機溶媒１００質量部に対して３０質量部の水を混合することによる状態変化が大きいことが確認された。 As shown in [Table 1] and [Table 2], of No. [4] (Compound 6), No. [8] (Compound 8), No. [9] (Compound 25), No. [10] (Compound 52). Since the thickening rate of the polar organic solvent exceeded 50%, it was confirmed that the state change was large by mixing 30 parts by mass of water with 100 parts by mass of the polar organic solvent.
　また、番号［４］（化合物６）、番号［８］（化合物８）、番号［１０］（化合物５２）は、アミノ基、アミン基等の窒素原子を含有する構造であり、このような構造の化合物で増粘率が大きいことがわかった。 Further, the numbers [4] (Compound 6), No. [8] (Compound 8), and No. [10] (Compound 52) are structures containing nitrogen atoms such as an amino group and an amine group, and have such a structure. It was found that the thickening rate of this compound was large.
　番号［３］（化合物４）、番号［１４］（化合物３５）、番号［１５］（化合物５３）の極性有機溶媒は、水との親和性（水に対する溶解度（ｇ／Ｌ））が高いにもかかわらず、増粘率が５０％以下であり、樹脂インクの溶媒として適用可能であることがわかった。 The polar organic solvents of No. [3] (Compound 4), No. [14] (Compound 35), and No. [15] (Compound 53) have high affinity with water (solubility in water (g / L)). Nevertheless, the thickening rate was 50% or less, and it was found that it could be applied as a solvent for resin ink.
　番号［５］（化合物９）、番号［６］（化合物１９）、番号［７］（化合物１１）の極性有機溶媒は、水を混合したときに極性有機溶媒の層と、水の層とに分離してしまい、正確に粘度Ｄ２、増粘率を測定することができなかったが、粘度Ｄ２は粘度Ｄ１とほぼ同等の値であり、粘度の大きな増加は観測されなかった。 The polar organic solvents of Nos. [5] (Compound 9), No. [6] (Compound 19), and No. [7] (Compound 11) were added to the layer of the polar organic solvent and the layer of water when water was mixed. Although they were separated and the viscosity D 2 and the thickening rate could not be measured accurately, the viscosity D 2 was almost the same value as the viscosity D 1 , and no large increase in the viscosity was observed.
　以上の実験１の結果から、番号［１］（化合物１）、番号［２］（化合物３）、及び、番号［３］（化合物４）（カルボニル基を有する飽和環式化合物（環骨格中にヘテロ原子として酸素原子を有するものも含む））の極性有機溶媒と、番号［１１］（化合物３３）、番号［１２］（化合物４６）、番号［１３］（化合物４７）、番号［１４］（化合物３５）（カルボニル基を有し鎖状骨格の炭素数が５以上の鎖飽和鎖式化合物（鎖状骨格中にヘテロ原子として酸素原子を有するもの））の極性有機溶媒と、番号［１５］（化合物５３）（リン酸基を有する鎖式化合物）の極性有機溶媒とが、樹脂インクの溶媒として好適であることがわかる。 From the results of Experiment 1 above, No. [1] (Compound 1), No. [2] (Compound 3), and No. [3] (Compound 4) (saturated cyclic compound having a carbonyl group (in the ring skeleton). (Including those having an oxygen atom as a hetero atom)) and the polar organic solvent of No. [11] (Compound 33), No. [12] (Compound 46), No. [13] (Compound 47), No. [14] ( Compound 35) (a chain saturated chain compound having a carbonyl group and having 5 or more carbon atoms in the chain skeleton (having an oxygen atom as a hetero atom in the chain skeleton)) and the number [15]. It can be seen that the polar organic compound of (Compound 53) (chain compound having a phosphoric acid group) is suitable as a solvent for the resin ink.
（実験２：フッ素樹脂インクの印刷工程での粘度変化）
　実験１で確認した２種類の極性有機溶媒（番号［２］（化合物３）、及び、番号［４］（化合物６））を、それぞれ、フッ素樹脂であるポリフッ化ビニリデントリフルオライド（PVDF-TrFE）共重合体と混合し、フッ素樹脂インクとしてPVDF-TrFインクを調整し、その調整したPVDF-TrFインクを用いた印刷前後で、PVDF-TrFインクの粘度変化が生じるかどうかを確認した。 (Experiment 2: Viscosity change in the printing process of fluororesin ink)
The two types of polar organic solvents confirmed in Experiment 1 (No. [2] (Compound 3) and No. [4] (Compound 6)) were each subjected to polyvinylidene fluoride trifluoride (PVDF-TrFE), which is a fluororesin. PVDF-TrF ink was prepared as a fluororesin ink by mixing with a copolymer, and it was confirmed whether the viscosity of PVDF-TrF ink changed before and after printing using the adjusted PVDF-TrF ink.
　具体的には、フッ素樹脂であるポリフッ化ビニリデントリフルオライド（PVDF-TrFE）共重合体の粉末を、番号［２］（化合物３）、番号［４］（化合物６）の各極性有機溶媒と混合し、樹脂濃度が１８ｗｔ％であるPVDF-TrFEインク（フッ素樹脂インク）を２種類調整した。 Specifically, the powder of the polyvinylidene fluoride (PVDF-TrFE) copolymer, which is a fluororesin, is mixed with the polar organic solvents of No. [2] (Compound 3) and No. [4] (Compound 6). Then, two types of PVDF-TrFE ink (fluororesin ink) having a resin concentration of 18 wt% were adjusted.
　印刷装置として、セリア社製のスクリーン印刷装置SSA-PC250E-IPを用いた。この印刷装置において、印刷エリアが１００ｍｍ×１００ｍｍであり版枠サイズが３２０ｍｍ×３２０ｍｍであるマスク（版）を用い、スキージの移動速度を１０ｍｍ／ｓとしてスクリーン印刷を行った。 As a printing device, a screen printing device SSA-PC250E-IP manufactured by Ceria Co., Ltd. was used. In this printing apparatus, a mask (plate) having a printing area of 100 mm × 100 mm and a plate frame size of 320 mm × 320 mm was used, and screen printing was performed with a squeegee moving speed of 10 mm / s.
　調整した２種類のPVDF-TrFEインクについて、スクリーン印刷を行う前の初期状態の粘度をそれぞれ測定した。 The viscosities of the two adjusted PVDF-TrFE inks in the initial state before screen printing were measured.
　次に、調整した２種類のPVDF-TrFEインクをそれぞれスクリーン印刷装置に充填し、１０枚の被印刷物であるＰＥＮ基板に対してスクリーン印刷を連続で行い（すなわち１０回の印刷）、その後、マスク（版）に残ったPVDF-TrFEインクを回収し、その粘度を測定した。印刷に要した時間は、１枚の被印刷物につき３分程度要することから、１０枚の被印刷物で３０分～４０分程度要し、その間、PVDF-TrFEインクは、この印刷工程での作業雰囲気中の大気に暴露された（吸湿可能な）状態にあった。なお、この作業雰囲気の温度及び湿度は、温度２５℃、湿度（相対湿度）５０％ＲＨであった。 Next, each of the two prepared PVDF-TrFE inks is filled in the screen printing device, and screen printing is continuously performed on the PEN substrate which is the 10 sheets to be printed (that is, 10 times of printing), and then the mask is performed. The PVDF-TrFE ink remaining on the (plate) was collected and its viscosity was measured. Since the time required for printing is about 3 minutes for one printed matter, it takes about 30 to 40 minutes for 10 printed matter, during which the PVDF-TrFE ink has a working atmosphere in this printing process. It was exposed (hygroscopic) to the atmosphere inside. The temperature and humidity of this working atmosphere were 25 ° C. and 50% humidity (relative humidity) RH.
　このように、２種類のPVDF-TrFEインクの粘度について、初期状態の粘度と、１０回の印刷後の粘度とを測定することで、１０回の印刷動作中における大気中の水分を吸湿したことによるPVDF-TrFEインクの粘度の変化を調査した。粘度の測定では、ブルックフィールド社製の回転式粘度計（DV-2T：HV）を用いた。この実験２の結果を図１に示す。 In this way, regarding the viscosities of the two types of PVDF-TrFE inks, by measuring the viscosities in the initial state and the viscosities after 10 printings, the moisture in the atmosphere during the 10th printing operation was absorbed. The change in viscosity of PVDF-TrFE ink was investigated. A rotary viscometer (DV-2T: HV) manufactured by Brookfield Co., Ltd. was used for measuring the viscosity. The result of this experiment 2 is shown in FIG.
　この図１は、ロータの回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。この図１において、破線ａ１は、番号［２］（化合物３）の極性有機溶媒を用いたPVDF-TrFEインクにおける、印刷前（初期状態）での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示し、実線ａ２は、番号［２］（化合物３）の極性有機溶媒を用いたPVDF-TrFEインクにおける、１０回印刷後の状態での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。 FIG. 1 shows the viscosity (mPa · s) with respect to the rotation speed (rpm) of the rotor. In FIG. 1 , the broken line a1 indicates the viscosity (mPa · s) with respect to the rotation speed (rpm) before printing (initial state) in the PVDF-TrFE ink using the polar organic solvent of No. [2] (Compound 3). ), The solid line a2 is the viscosity (mPa · s) with respect to the rotation speed (rpm) in the state after printing 10 times in the PVDF-TrFE ink using the polar organic solvent of No. [ 2 ] (Compound 3). Is shown.
　また、破線ｂ１は、番号［４］（化合物６）の極性有機溶媒を用いたPVDF-TrFEインクにおける、印刷前（初期状態）での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示し、実線ｂ２は、番号［４］（化合物６）の極性有機溶媒を用いたPVDF-TrFEインクにおける、１０回印刷後の状態での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。 Further, the broken line b1 indicates the viscosity (mPa · s) with respect to the rotation speed (rpm) before printing (initial state) in the PVDF-TrFE ink using the polar organic solvent of No. [ 4 ] (Compound 6). , Solid line b 2 shows the viscosity (mPa · s) with respect to the rotation speed (rpm) in the state after printing 10 times in the PVDF-TrFE ink using the polar organic solvent of No. [4] (Compound 6). There is.
　図１の破線ａ１及び実線ａ２に示すように、実験１の水との混合において増粘の変化が小さい番号［２］（化合物３）の極性有機溶媒を用いたPVDF-TrFEインクでは、初期状態の粘度（破線ａ１）に比較して、１０回の印刷後の粘度（実線ａ２）は、ほとんど変化しなかった。 As shown by the broken line a1 and the solid line a2 in FIG. 1 , the PVDF-TrFE ink using the polar organic solvent of No. [2] (Compound 3) having a small change in viscosity when mixed with water in Experiment 1 Compared with the viscosity in the initial state (dashed line a1), the viscosity after 10 printings (solid line a2 ) hardly changed.
　一方、図１の破線ｂ１及び実線ｂ２に示すように、実験１の水との混合において増粘の変化が大きい番号［４］（化合物６）の極性有機溶媒を用いたPVDF-TrFEインクでは、初期状態の粘度（破線ｂ１）に比較して、１０回の印刷後の粘度（実線ｂ２）は、２倍以上に変化した。 On the other hand, as shown by the broken line b1 and the solid line b2 in FIG . 1 , the PVDF-TrFE ink using the polar organic solvent of No. [4] (Compound 6) having a large change in viscosity when mixed with water in Experiment 1 Then, the viscosity after 10 printings (solid line b 2 ) changed more than twice as much as the viscosity in the initial state (dashed line b 1 ).
　このように、非吸湿性の極性有機溶媒（番号［２］（化合物３））を用いたPVDF-TrFEインクよりも、吸湿性の極性有機溶媒（番号［４］（化合物６））を用いたPVDF-TrFEインクの方が、印刷工程での増粘が大きかった。これにより、印刷工程での作業雰囲気中の大気により、PVDF-TrFEインクが吸湿して増粘したことがわかる。 As described above, a hygroscopic polar organic solvent (No. [4] (Compound 6)) was used rather than a PVDF-TrFE ink using a non-moisture-absorbing polar organic solvent (No. [2] (Compound 3)). PVDF-TrFE ink had a greater thickening in the printing process. From this, it can be seen that the PVDF-TrFE ink absorbs moisture and thickens due to the atmosphere in the working atmosphere in the printing process.
（実験３：ポリビニルフェノールインクの吸湿による粘度変化）
　実験１で確認した２種類の極性有機溶媒（番号［２］（化合物３）、及び、番号［４］（化合物６））を、それぞれ、絶縁性樹脂であるポリビニルフェノール（ＰＶＰ）に混合し、絶縁性樹脂インクとしてＰＶＰインクを調整し、吸湿による絶縁性樹脂インクの粘度変化が生じるかどうかを確認した。 (Experiment 3: Viscosity change due to moisture absorption of polyvinylphenol ink)
The two types of polar organic solvents confirmed in Experiment 1 (No. [2] (Compound 3) and No. [4] (Compound 6)) were mixed with polyvinylphenol (PVP), which is an insulating resin, respectively. PVP ink was adjusted as the insulating resin ink, and it was confirmed whether or not the viscosity of the insulating resin ink changed due to moisture absorption.
　具体的には、絶縁性樹脂であるＰＶＰの粉末を、番号［２］（化合物３）、番号［４］（化合物６）の各極性有機溶媒に混合し、樹脂濃度が１０ｗｔ％であるＰＶＰインク（絶縁性樹脂インク）を２種類調整した。 Specifically, PVP ink, which is an insulating resin, is mixed with each polar organic solvent of No. [2] (Compound 3) and No. [4] (Compound 6), and the resin concentration is 10 wt%. Two types of (insulating resin ink) were adjusted.
　調整した２種類のＰＶＰインクについて、それぞれ超純水を加える前の粘度を測定した。 The viscosities of the two adjusted PVP inks were measured before adding ultrapure water.
　次に、調整した２種類のＰＶＰインクについて、それぞれＰＶＰインク１００質量部に対して５質量部の超純水を加えた状態とし、その状態の粘度を測定した。 Next, for each of the two prepared PVP inks, 5 parts by mass of ultrapure water was added to 100 parts by mass of the PVP ink, and the viscosity in that state was measured.
　このように、２種類のＰＶＰインクの粘度について、水（超純水）添加前の粘度と、水（超純水）添加後の粘度とを測定することで、印刷動作中における吸湿によるＰＶＰインクの粘度の変化を調査した。この実験３の結果を図２に示す。 In this way, regarding the viscosity of the two types of PVP ink, by measuring the viscosity before the addition of water (ultrapure water) and the viscosity after the addition of water (ultrapure water), the PVP ink due to moisture absorption during the printing operation. The change in the viscosity of the ink was investigated. The result of this experiment 3 is shown in FIG.
　この図２においても、ロータの回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。この図２において、破線ｃ１は、番号［２］（化合物３）の極性有機溶媒を用いたＰＶＰインクにおける、水添加前での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示し、実線ｃ２は、番号［２］（化合物３）の極性有機溶媒を用いたＰＶＰインクにおける、水添加後での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。 Also in FIG. 2, the viscosity (mPa · s) with respect to the rotation speed (rpm) of the rotor is shown. In FIG. 2, the broken line c 1 indicates the viscosity (mPa · s) with respect to the rotation speed (rpm) before water addition in the PVP ink using the polar organic solvent of No. [2] (Compound 3), and is a solid line. c 2 indicates the viscosity (mPa · s) with respect to the rotation speed (rpm) after the addition of water in the PVP ink using the polar organic solvent of No. [2] (Compound 3).
　また、破線ｄ１は、番号［４］（化合物６）の極性有機溶媒を用いたＰＶＰインクにおける、水添加前での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示し、実線ｄ２は、番号［４］（化合物６）の極性有機溶媒を用いたＰＶＰインクにおける、水添加後の状態での回転数（ｒｐｍ）に対する粘度（ｍＰａ・ｓ）を示している。 Further, the broken line d 1 indicates the viscosity (mPa · s) with respect to the rotation speed (rpm) before water addition in the PVP ink using the polar organic solvent of No. [4] (Compound 6), and the solid line d 2 is. , No. [4] (Compound 6) shows the viscosity (mPa · s) with respect to the number of revolutions (rpm) in the state after water addition in the PVP ink using the polar organic solvent.
　図２の破線ｃ１及び実線ｃ２に示すように、番号［２］（化合物３）の極性有機溶媒を用いたＰＶＰインクでは、水を添加する前（破線ｃ１）と、水を添加した後（実線ｃ２）とで粘度の変化はほとんど見られなかった。 As shown by the broken line c 1 and the solid line c 2 in FIG. 2, in the PVP ink using the polar organic solvent of No. [2] (Compound 3), water was added before water was added (broken line c 1 ). Almost no change in viscosity was observed after (solid line c 2 ).
　一方、図２の破線ｄ１及び実線ｄ２に示すように、番号［４］（化合物６）の極性有機溶媒を用いたＰＶＰインクでは、水を添加する前（破線ｄ１）と比較して、水を添加した後（実線ｄ２）には大きく増粘し、インクの状態が変化することが確認された。 On the other hand, as shown by the broken line d1 and the solid line d2 in FIG . 2 , the PVP ink using the polar organic solvent of No. [4] (Compound 6 ) is compared with that before water is added (broken line d1). After adding water (solid line d 2 ), it was confirmed that the ink was greatly thickened and the state of the ink changed.
　このように、非吸湿性の極性有機溶媒（番号［２］（化合物３））を用いたＰＶＰインクよりも、吸湿性の極性有機溶媒（番号［４］（化合物６））を用いたＰＶＰインクの方が、増粘が大きかった。これにより、ＰＶＰインクにおいても、吸湿により増粘することがわかった。 As described above, the PVP ink using the hygroscopic polar organic solvent (No. [4] (Compound 6)) is more than the PVP ink using the non-hygroscopic polar organic solvent (No. [2] (Compound 3)). The thickening was greater in. From this, it was found that the PVP ink also thickened by moisture absorption.

Claims (5)

  1. 　樹脂材料を溶媒に混合してインク化した樹脂インクであって、
    　前記溶媒は、前記溶媒１００質量部に対して水を３０質量部加えたときの増粘率が５０％以下である極性有機溶媒であることを特徴とする樹脂インク。     A resin ink made by mixing a resin material with a solvent to make ink.
    The solvent is a resin ink characterized by being a polar organic solvent having a thickening rate of 50% or less when 30 parts by mass of water is added to 100 parts by mass of the solvent.
  2. 　前記溶媒は、水の溶解度が５００ｇ／Ｌ以下であることを特徴とする請求項１に記載の樹脂インク。 The resin ink according to claim 1, wherein the solvent has a solubility of water of 500 g / L or less.
  3. 　前記溶媒は、カルボニル基を有する飽和環式化合物（環骨格中にヘテロ原子として酸素原子を有するものも含む）、又は、カルボニル基を有し鎖状骨格の炭素数が５以上の飽和鎖式化合物（鎖状骨格中にヘテロ原子として酸素原子を有するものを含む）である極性有機溶媒であることを特徴とする請求項１又は２に記載の樹脂インク。 The solvent is a saturated cyclic compound having a carbonyl group (including one having an oxygen atom as a hetero atom in the ring skeleton), or a saturated chain compound having a carbonyl group and having a chain skeleton having 5 or more carbon atoms. The resin ink according to claim 1 or 2, which is a polar organic solvent (including one having an oxygen atom as a hetero atom in a chain skeleton).
  4. 　前記樹脂材料がフッ素系樹脂であることを特徴とする請求項１～３のいずれか１項に記載の樹脂インク。 The resin ink according to any one of claims 1 to 3, wherein the resin material is a fluororesin.
  5. 　請求項１～４のいずれか１項に記載の樹脂インクが印刷された電子デバイス。 An electronic device on which the resin ink according to any one of claims 1 to 4 is printed.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001514A (en) * 2009-06-22 2011-01-06 Teijin Chem Ltd Electric-electronic device component obtained by performing injection molding of glass fiber-reinforced resin composition
JP2011178832A (en) * 2010-02-26 2011-09-15 Dic Corp Ultraviolet-curable ink for inkjet recording, insulation film obtained therefrom, electronic element and process for production thereof
JP2011231170A (en) * 2010-04-26 2011-11-17 Hitachi Chem Co Ltd Insulator ink, and insulating layer, composite layer, circuit board and semiconductor package using the same
CN102863845A (en) * 2012-10-11 2013-01-09 复旦大学 Silver-organic conductive ink for printed electronics
JP2015159169A (en) * 2014-02-24 2015-09-03 出光興産株式会社 Composition for electrode modification, method for electrode modification, and organic thin film transistor
WO2017080307A1 (en) * 2015-11-12 2017-05-18 广州华睿光电材料有限公司 Composition for printing electronic devices and application thereof in electronic devices
WO2018190347A1 (en) * 2017-04-13 2018-10-18 Jnc株式会社 Heat curable resin composition, cured film, substrate with cured film, electronic component, and inkjet ink
WO2019020906A1 (en) * 2017-07-28 2019-01-31 Arkema France Method for preparing a cross-linked fluorinated polymer film
JP2019109348A (en) * 2017-12-18 2019-07-04 東洋インキＳｃホールディングス株式会社 Quantum dot, quantum dot-containing composition and ink jet ink
WO2020070420A1 (en) * 2018-10-02 2020-04-09 Arkema France Fluoropolymer ink with the rheological behavior of a yield stress fluid

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001514A (en) * 2009-06-22 2011-01-06 Teijin Chem Ltd Electric-electronic device component obtained by performing injection molding of glass fiber-reinforced resin composition
JP2011178832A (en) * 2010-02-26 2011-09-15 Dic Corp Ultraviolet-curable ink for inkjet recording, insulation film obtained therefrom, electronic element and process for production thereof
JP2011231170A (en) * 2010-04-26 2011-11-17 Hitachi Chem Co Ltd Insulator ink, and insulating layer, composite layer, circuit board and semiconductor package using the same
CN102863845A (en) * 2012-10-11 2013-01-09 复旦大学 Silver-organic conductive ink for printed electronics
JP2015159169A (en) * 2014-02-24 2015-09-03 出光興産株式会社 Composition for electrode modification, method for electrode modification, and organic thin film transistor
WO2017080307A1 (en) * 2015-11-12 2017-05-18 广州华睿光电材料有限公司 Composition for printing electronic devices and application thereof in electronic devices
WO2018190347A1 (en) * 2017-04-13 2018-10-18 Jnc株式会社 Heat curable resin composition, cured film, substrate with cured film, electronic component, and inkjet ink
WO2019020906A1 (en) * 2017-07-28 2019-01-31 Arkema France Method for preparing a cross-linked fluorinated polymer film
JP2019109348A (en) * 2017-12-18 2019-07-04 東洋インキＳｃホールディングス株式会社 Quantum dot, quantum dot-containing composition and ink jet ink
WO2020070420A1 (en) * 2018-10-02 2020-04-09 Arkema France Fluoropolymer ink with the rheological behavior of a yield stress fluid

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