JP2016065180A - Ink, electrochromic device using the ink, and apparatus for fabricating electrochromic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink to be used for printing an electrochromic device in which inkjet printing for characters and patterns can be performed with high safeness.SOLUTION: An inkjet ink of an electrochromic iron complex is provided for an inkjet printer to discharge droplets and to print. The ink is prepared by adding propylene glycol and ethanol to an iron-iron complex aqueous solution, or the ink is prepared by adding propylene glycol and ethanol to a nickel-iron complex aqueous solution so as to control the viscosity of the obtained ink to a predetermined value for stable discharge of droplets. The composition ratios of the iron complex aqueous solution, the propylene glycol and the ethanol are adjusted so as to obtain a viscosity of 3 to 5 mPa S of the above ink.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an ink-jet ink used for printing an electrochromic device, an electrochromic device using the ink-jet ink, and an apparatus for producing the electrochromic device.

  An electrochromic device is a device in which different metal complexes are formed on a pair of conductive transparent substrates as a structure, and the electrolyte is sandwiched between them. The color of the device can be changed by an oxidation-reduction reaction by applying a voltage. As a different metal complex, the color change of an electrochromic device using an iron (Fe) -iron complex and a nickel (Ni) -iron complex becomes light yellow when a voltage is applied from blue. By adding methanol and glycerin to the solvent of the aqueous solution, these iron complexes become aqueous solutions that can be ejected from an inkjet head without causing aggregation and precipitation.

  An example of the composition ratio of this aqueous solution is: iron complex aqueous solution (3 wt%) = 1: methanol = 1: glycerin = 1. Conventionally, a method for manufacturing an electrochromic display element with improved durability has been provided (see Patent Document 1). This display device manufacturing method is a method for manufacturing a display element having an electrochromic dye and a porous layer containing a metal oxide supporting the electrochromic dye between opposing electrodes, And a step of applying a plurality of types of ink having a function of uniformizing the amount of the electrochromic dye supported on the porous layer containing the metal oxide in one pixel of the display device by an inkjet device. Features.

Republished Patent WO2008 / 146573

  With an aqueous solution that can eject droplets from an inkjet head, inkjet printing of characters and patterns is insufficient. For inkjet printing, stable and repeated ejection of droplets, flight, landing, and reproduction of ejection positions There is a need for an aqueous solution, i.e., a water-based ink, that has the property of being capable of. Further, the water-based ink needs to be able to be repeatedly printed in an actual ink jet printer. If the viscosity of the ink is not appropriate, the nozzles of the ink jet printer are clogged, and the ink discharge is not stable, resulting in a problem that the printing result is deteriorated. Moreover, even if it is a printable aqueous solution (aqueous ink), when a deleterious methanol is contained in a solvent, it is not preferable as an inkjet ink from the viewpoint of safety.

  The present invention is an electrochromic metal complex, particularly an iron-iron complex, a nickel-iron complex, which can be stably ejected by an inkjet printer using a highly safe solvent that is also used in commercially available water-based inks. An object of the present invention is to provide an ink-jet ink for film formation of a cobalt-iron complex.

In order to achieve the above object, the present invention provides an inkjet ink containing an electrochromic metal complex for ejecting and printing droplets with an inkjet printer, and the ink is used for ejecting droplets with stable ink viscosity. This is characterized in that propylene glycol and ethanol are added to an aqueous metal complex solution so as to have a value within the predetermined range.
Further, the invention is characterized in that the metal complex aqueous solution is an iron complex aqueous solution.
In the invention, the iron complex aqueous solution is one of an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex.
In the present invention, the iron complex aqueous solution is a combination of two or more of an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex.
In the invention, it is preferable that the predetermined viscosity value of the ink is 3 to 5 mPa · S.
The present invention is also characterized in that the composition ratio of the iron-iron complex aqueous solution, the nickel-iron complex aqueous solution, or the cobalt-iron complex aqueous solution, propylene glycol, and ethanol is 8-12: 2-4: 1-2. To do.
The present invention is characterized in that a glycol other than the propylene glycol is substituted for the propylene glycol.
The present invention also relates to an electrochromic device in which a metal complex is formed on a pair of conductive transparent substrates and bonded with an electrolyte interposed therebetween, and the metal complex film is added to a metal complex aqueous solution by adding propylene glycol and ethanol. It is formed by printing using an ink jet metal complex ink.
The present invention also relates to an electrochromic device in which an iron complex is formed on a pair of conductive transparent substrates and bonded together with an electrolyte sandwiched between the iron complex film and propylene glycol and ethanol added to an iron complex aqueous solution. It is formed by printing using an iron complex ink for inkjet.
Further, the present invention is an electrochromic device in which different metal complexes are formed on a pair of conductive transparent substrates, and the electrolytes are sandwiched, and the different metal complexes are composed of an iron-iron complex and a nickel-iron complex. An iron-iron complex film is formed by printing using an iron-iron complex ink for ink jet, in which propylene glycol and ethanol are added to an iron-iron complex aqueous solution, and the nickel-iron complex film is formed by nickel-iron It is formed by printing using an ink-jet nickel-iron complex ink obtained by adding propylene glycol and ethanol to an aqueous complex solution.
In the present invention, the different metal complex comprises an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex, and a film of the selected iron complex is added to the aqueous solution of iron complex by adding propylene glycol and ethanol. It is formed by printing using an iron complex ink for inkjet.
In the invention, it is preferable that the ink has a viscosity value of 3 to 5 mPa · s.
Moreover, this invention is characterized by the composition ratio of the said iron-iron complex aqueous solution, propylene glycol, and ethanol being 8-12: 2-4: 1-2.
In the present invention, the composition ratio of the nickel-iron complex aqueous solution, propylene glycol, and ethanol is 8-12: 2-4: 1-2.
The present invention is characterized in that a glycol other than the propylene glycol is substituted for the propylene glycol.
The present invention is also an apparatus for creating an electrochromic device, comprising a plurality of ink supply units, storing different metal complex inks in the plurality of ink supply units, and selecting from the plurality of ink supply units The ink thus formed is ejected from an ink jet head onto a part of an electrochromic device and printed to form a metal complex layer used in the electrochromic device.

  According to the present invention, by using this water-based ink, ink jet printing of characters and patterns can be performed with high safety. In addition, since stable ejection and printing results can be obtained with an ink jet printer, it is possible to create an electrochromic device that enables a variety of printing that matches the resolution of the printer. In addition, by providing a plurality of inks in an ink jet printer and printing, it is possible to create parts such as necessary colors without replacing the inks.

It is explanatory drawing of an electrochromic device. It is explanatory drawing of an inkjet printer. It is explanatory drawing of an inkjet printer. It is a table | surface which shows experimental data.

Hereinafter, the ink-jet ink used for printing the electrochromic device of the present invention, the electrochromic device using the ink-jet ink, and the configuration of an apparatus for producing the electrochromic device will be described in detail.
In this embodiment, the electrochromic device 2 is composed of five layers, and the first layer is a transparent and conductive glass such as ITO glass provided with a transparent and conductive film such as indium tin oxide (ITO). The electrode 4 is configured. The second layer is composed of an iron-iron complex layer 6 made of iron (Fe) -iron complex.

The third layer is composed of a transparent electrolyte layer 8 made of a transparent electrolyte such as KTFSI (potassium trifluoromethanesulfonylimide). The fourth layer is composed of a nickel-iron complex layer 10 made of a nickel (Ni) -iron complex. The fifth layer is composed of a transparent electrode 12 such as ITO glass.
When a voltage is applied from the power source V between the transparent electrodes of the electrochromic device having the above five-layer structure, the chemical formula of the color change of the second layer by the voltage application is as follows.

電圧印加による４層目の色変化の化学式は次の通りである。

The chemical formula of the color change of the fourth layer by voltage application is as follows.

The second and fourth iron complex layers 6 and 10 are printed and formed by the ink jet printer shown in FIGS. The ink used in the ink jet printer is composed of an iron complex aqueous solution, a propylene glycol and an ethanol solvent, and the ink component ratio is an appropriate value that enables ink droplets to be stably ejected by the ink jet head. To be experimentally selected.
Based on this, the present inventor conducted various experiments regarding the composition and composition ratio of the ink, and as a result, the experimental data shown in the table of FIG. 4 could be obtained. Based on these experimental data, in this embodiment, the composition and composition ratio of the ink are set as follows.

[Ink solvent and composition ratio]
Iron-iron complex aqueous solution (3-4 wt%) = 8-12: Propylene glycol = 2-4: Ethanol = 1-2
Viscosity 3-5mPa · S
Nickel-iron complex aqueous solution (3-4 wt%) = 8-12: Propylene glycol = 2-4: Ethanol = 1-2
Viscosity 3-5mPa · S
Cobalt-iron complex aqueous solution (3-4 wt%) = 8-12: Propylene glycol = 2-4: Ethanol = 1-2
Viscosity 3-5mPa · S

  In the above embodiment, the solvent is high in safety, does not contain a deleterious substance such as methanol, and ink jet printing drawing is possible. Electrolysis that can be printed by an actual ink jet printer without causing aggregation and precipitation. Ink-jet ink of chromic iron complex is realized. The viscosity for stable droplet discharge is desirably 3 to 5 mPa · S. In this embodiment, the composition ratio of the iron complex aqueous solution, propylene glycol, and ethanol was determined so that a viscosity of 3 to 5 mPa · S was obtained.

The propylene glycol can be replaced with an organic compound such as glycols other than propylene glycol.
FIG. 2 shows an ink jet printer used to create an electrochromic. This printer 14 is composed of a main body 16 and a computer 18 such as a personal computer connected to a controller of the main body 16 via an input / output interface. Is done.

Transparent components (parts) such as an electrode plate of an electrochromic device on which a metal complex is formed by printing are printed with the printing surface up and held by the conveyance auxiliary member 22 on the platen 20, It is conveyed by the media drive mechanism. The ink jet head 24 ejects metal complex ink, that is, iron complex aqueous solution containing propylene glycol and ethanol, from the nozzle in the main scanning direction perpendicular to the transport direction to the device constituent material on the platen 20. The print data that moves while being transferred from the computer 18 to the controller of the inkjet printer 14 is printed on the device component under the control of software stored in the controller. In each ink tank 26 (ink supply unit) connected to the ink jet head 24, inks of iron-iron complex, nickel-iron complex, cobalt-iron complex and inks having different composition ratios of these solvents are used. The stored and selected ink is supplied to the inkjet head 24.
The iron-iron complex, nickel-iron complex, and cobalt-iron complex can express cyan, yellow, and magenta in the case of non-luminous display, and therefore other colors can be created by combining them. In addition, you may use the combination with another metal which can be used besides an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex.
Various transparent components such as an electrode plate of a chromic device on which a metal complex is formed by printing can be used depending on the application.

The controller of the computer 18 or the printer main body 16 is provided with an ink discharge waveform combination table for combining ink discharge waveforms for each print resolution in order to correspond to the print resolution. The ink jet printer 14 sets an appropriate ink ejection waveform based on this table, selects an appropriate ink tank 26 from a plurality of ink tanks 26 filled with different metal complex inks or inks of different composition ratios, Printing is performed according to the printing resolution using the selected ink.

2 Electrochromic device 4 Transparent electrode 6 Iron-iron complex layer 8 Transparent electrolyte layer 10 Nickel-iron complex layer 12 Transparent electrode 14 Inkjet printer 16 Main body 18 Computer 20 Platen 22 Transport auxiliary member 24 Inkjet head 26 Ink tank

Claims (16)

An inkjet ink containing an electrochromic metal complex for ejecting and printing droplets with an inkjet printer so that the ink has a viscosity within a predetermined range for droplet ejection with a stable viscosity. An ink-jet ink used for producing an electrochromic device, characterized in that propylene glycol and ethanol are added to an aqueous metal complex solution. The ink used for making an electrochromic device according to claim 1, wherein the metal complex aqueous solution is an iron complex aqueous solution. The inkjet ink used for producing an electrochromic device according to claim 2, wherein the iron complex aqueous solution is one of an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex. . The said iron complex aqueous solution is a combination of two or more of an iron-iron complex, a nickel-iron complex, and a cobalt-iron complex, The inkjet use used for preparation of the electrochromic device of Claim 2 characterized by the above-mentioned. ink. The ink-jet ink used for producing an electrochromic device according to any one of claims 1 to 4, wherein the predetermined viscosity value of the ink is 3 to 5 mPa · S. . The composition ratio of said iron-iron complex aqueous solution, nickel-iron complex aqueous solution, or cobalt-iron complex aqueous solution, propylene glycol, and ethanol is 8-12: 2-4: 1-2. Ink-jet ink used to make the electrochromic device described. The inkjet ink used for producing an electrochromic device according to any one of claims 1 to 6, wherein a glycol other than the propylene glycol is substituted for the propylene glycol. . An electrochromic device in which a metal complex is formed on a pair of conductive transparent substrates and bonded together with an electrolyte interposed therebetween, and the metal complex film is formed by adding propylene glycol and ethanol to a metal complex aqueous solution. An electrochromic device formed by printing using a complex ink. An electrochromic device in which an iron complex is formed on a pair of conductive transparent substrates and bonded together with an electrolyte interposed therebetween, and the iron complex film is formed by adding propylene glycol and ethanol to an iron complex aqueous solution. An electrochromic device formed by printing using a complex ink. An electrochromic device in which different metal complexes are formed on a pair of conductive transparent substrates and bonded together with an electrolyte interposed therebetween, wherein the different metal complexes are composed of an iron-iron complex and a nickel-iron complex. A complex film is formed by printing using an iron-iron complex ink for inkjet, which is obtained by adding propylene glycol and ethanol to an iron-iron complex aqueous solution, and a nickel-iron complex film is formed on the nickel-iron complex aqueous solution by propylene glycol. An electrochromic device formed by printing using an ink-jet nickel-iron complex ink comprising ethanol and ethanol. The different metal complexes include iron-iron complexes, nickel-iron complexes, and cobalt-iron complexes, and a film of selected iron complexes is added to the iron for inkjet by adding propylene glycol and ethanol to an iron complex aqueous solution. The electrochromic device according to claim 10, wherein the electrochromic device is formed by printing using a complex ink. 12. The electrochromic device according to claim 8, wherein the ink has a viscosity value of 3 to 5 mPa · S. The electrochromic device according to claim 11, wherein the composition ratio of the iron-iron complex aqueous solution, propylene glycol, and ethanol is 8-12: 2-4: 1-2. The electrochromic device according to claim 11, wherein the composition ratio of the nickel-iron complex aqueous solution, propylene glycol, and ethanol is 8 to 12: 2 to 4: 1 to 2. The electrochromic device according to any one of claims 8 to 14, wherein a glycol other than the propylene glycol is substituted for the propylene glycol. An apparatus for creating an electrochromic device, comprising a plurality of ink supply units, storing inks of different metal complexes in the plurality of ink supply units, and selecting an ink selected from the plurality of ink supply units by an inkjet head An apparatus for producing an electrochromic device, characterized in that a metal complex layer used in an electrochromic device is formed on the component by discharging and printing on the component of the electrochromic device.

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