JP6972536B2 - Coating agent and discharge - Google Patents

Description

The present invention relates to a coating agent and a discharge product , and more particularly to a coating agent and a discharge product used in a technical field in which a line pattern or a stripe pattern having a precise and uniform film thickness and a pattern having a three-dimensional structure are required.

Conventionally, in the field of printable electronics technology, attempts have been made to form wiring patterns of conductive materials and insulating materials by gravure printing, screen printing, flexographic printing, offset printing, inkjet printing, and the like.
However, as shown in FIG. 8, these printing methods often result in printing in which the cross-sectional shape of the printed matter 101 is a semicircular shape and the aspect ratio is low. Therefore, as a future trend, printing with a rectangular cross-sectional shape and a high aspect ratio is desired. If the cross-sectional shape of the printed matter is rectangular and the aspect ratio is high, for example, in the case of a conductive material, by making it closer to a rectangle, the cross-sectional area can be obtained simply by multiplying the base dimension by the height dimension, and the wiring resistance value etc. can be obtained. It can be easily obtained. Further, when the aspect ratio of the cross-sectional shape of the printed matter is high (the base is narrow and the height is high), dense wiring such as an electronic circuit can be concentrated in a narrow area, and a larger amount of current flows through the wiring. It becomes possible.

The fact that the cross-sectional shape of the printed matter 101 is a semicircular shape has a large unstable factor in circuit formation in which the electrical characteristic value based on the cross-sectional area is emphasized. For example, the calculation of the cross-sectional area of a semicircular shape requires a destructive test such as directly measuring the cut surface, which causes problems in various fields. For example, it is superior in the electronics field, which requires a continuity inspection in the final process without breaking in the manufacturing process because it fluctuates in each printed matter, and soft correction for each shipped product, as well as rectangles and other shapes. There is an application production field that issues. Further, when a wiring pattern made of a conductive material is printed on an elastic material, there is a problem that the resistance value of the wiring changes due to the expansion and contraction of the elastic material.

Here, as shown in FIG. 9A, the shape of the discharge port 11 of the coater head 10 for strip coating, which is generally used, is rectangular or round, and has a number of several μm to several hundred μm. It is formed with a discharge port diameter such as mm. In particular, when a coater head 10 having a discharge port 11 having a diameter of several μm to several hundred μm and a diameter of several mm is used, it is caused by friction between the coater head 10 and the coating agent 101 in the vicinity of the discharge flow path 12 and the discharge port 11. Due to the shear stress, a difference occurs between the flow velocity (shear velocity) v1 at the center of the discharge flow path 12 and the flow velocity (shear velocity) v2 on the wall surface of the discharge flow path 12.

In particular, in the case of the coating agent 101 having a high viscosity of several thousand cp to several million cp, the shear stress due to friction with the coater head 10 having the discharge port 11 having a diameter of several μm to several hundred μm and several mm becomes high. , The phenomenon that discharge was not possible sometimes occurred.

The commonly used countermeasure for such a situation is that the SP value (solubility parameter value at 25 ° C.) is close in order to further increase the discharge pressure to the coater head or reduce the viscosity of the coating agent 101. The solvent is added. This coping method is not limited to the coater head, but is the same for printing methods such as gravure printing, screen printing, flexographic printing, offset printing, and inkjet printing.

Japanese Patent No. 3213983 Japanese Unexamined Patent Publication No. 11-207237

However, even if the above countermeasures are taken, the problem that the coating agent 101 spreads and is discharged due to the shear stress due to the friction between the coater head near the discharge flow path 12 and the discharge port 11 and the coating agent 101 can be solved. Was difficult. Specifically, as shown in FIG. 9B, there is a difference between the flow velocity (shear velocity) v1 at the center of the discharge flow path 12 and the flow velocity (shear velocity) v2 on the wall surface of the discharge flow path 12, and the discharge occurs. It is not discharged in the shape of the outlet 11, but is discharged in a rounded shape bulging outward.

Therefore, the present invention has been made in view of such circumstances, and an object of the present invention is to provide a coating agent and a discharged product that are discharged while maintaining the shape of the discharge port of the coater head.

As a result of diligent studies by the present inventor in order to solve the above problems, it is necessary to specify a solvent to be added to the coating agent used for ejection by a coater head for stripe coating or a dispenser using a syringe to improve the ejection accuracy. It was found that it is suitable in terms of

The present invention is based on the above findings by the present inventor, and the coating agent according to one aspect of the present invention is a coating agent for a coater head and a dispenser.
With a binder in which the filler is dispersed,
It has a water-insoluble or water-soluble additive solvent that contradicts the dispersion medium of the binder and the main solvent of the additive.

Further, the discharged material according to one aspect of the present invention has a corner portion having an arc shape having a cross-sectional shape of 10 μm or less discharged onto the base material from the coater head and the dispenser. This discharge has a binder in which a filler is dispersed and a water-insoluble or water-soluble additive solvent that contradicts the dispersion medium of the binder and the main solvent of the additive.

Further, the coating apparatus according to one aspect of the present invention is a coater head and a dispenser having a binder in which a filler is dispersed and a water-insoluble or water-soluble additive solvent contradictory to the dispersion medium of the binder and the main solvent of the additive. It has a discharge port for discharging the coating agent for use, and a discharge flow path that communicates with and supplies the discharge port.

According to one aspect of the present invention, it is possible to provide a coating agent and a discharged product that are discharged while maintaining the shape of the discharge port of the coater head.

It is a figure which shows the ejection state of the coating agent which concerns on one Embodiment of this invention, (a) is the front view of the coater head, (b) is the sectional view of the coater head. It is a side view which shows the state which discharged the coating agent which concerns on one Embodiment of this invention on a substrate. It is a figure which shows the discharge which concerns on one Embodiment of this invention. It is a figure which shows the discharge which concerns on one Embodiment of this invention. It is a figure which shows the state which discharged the coating agent of Example 1 onto a substrate, (a) is the sectional image, (b) is the enlarged sectional view explaining the main part. It is a figure which shows the state which discharged the coating agent of the comparative example 1 on a substrate, (a) is the sectional image, (b) is the enlarged sectional view explaining the main part. (A) is a front view of the coater head used in Example 3, and (b) is a sectional view of the structure obtained in Example 3. It is an image which shows the cross-sectional structure of the conventional printed matter. It is a figure which shows the discharge state of the conventional coating agent, (a) is a front view of a coater head, (b) is a sectional view of a coater head.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, in each of the figures described below, the parts corresponding to each other are designated by the same reference numerals, and the description below will be omitted as appropriate in the overlapping parts. Further, the embodiment of the present invention exemplifies a configuration for embodying the technical idea of the present invention, and specifies the material, shape, structure, arrangement, dimensions, etc. of each part to the following. Not. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims described in the claims.

(Coating agent)
The coating agent of the present embodiment uses a conductive material, an insulating material, etc., which have been conventionally used in gravure printing, screen printing, flexographic printing, offset printing, inkjet, etc., through a discharge port formed on a coater head. Stretchable conductive inks, carbon elastomer materials, electrostatic elastomers, developed with one or more coating agents, such as conductive pastes composed of silver, carbon, copper powder, insulating pastes, urethane-based materials, etc. A coating agent such as a sticking agent or a non-sticking agent is discharged to apply a line pattern, a three-dimensional structural pattern, or a discontinuous pattern on the surface of the base material in a striped manner.

<Structure>
The coating agent (coating composition) of the present embodiment has a binder in which a filler is dispersed and an additive solvent, and the additive may be added if necessary.
Here, the additive solvent exhibits water-insoluble or water-soluble properties that are contrary to the dispersion medium of the binder and the main solvent of the additive. That is, the coating agent of the present embodiment is a water-soluble solvent if the binder (polymer) in which the inorganic filler or the organic filler (pigment) is dispersed, the solvent (organic solvent), and the main solvent of the additive are water-insoluble. If it is sex, it is a mixture of a water-insoluble solvent.
Specifically, the physical characteristics of the coating agent are dependent on the water-insoluble or water-soluble content of the dispersion medium of the binder (polymer) constituting the main agent having a filler content of 50 to 99.9% and the main solvent of the additive. Has an additive solvent with a different polarity that does not destroy. Examples of the filler include fillers, silver pastes developed for printing applications, copper pastes, insulating inks, and the like. The coating agent of this embodiment is a coating agent for a coater head and a dispenser.

The solvent composition of an ink generally used in fillers, printing methods and the like is a solvent composition containing a solvent and a compound represented by the following formula (1) (excluding monohydroxystearic acid). In the following formula (1), R ¹ represents a monohydroxyalkyl group, and R ² represents a carboxyl group (C (= O) OH) or an amide group (C (= O) NH ₂ ).
R ^1- CH _2- R ² ... (1)

[Purpose of composition]
As described above, the components constituting the coating agent of the present embodiment include binders (polymers), pigments (coloring, rust prevention, constitution, other functionality, etc.), solvents (organic solvents, water, etc.), additives, and the like. , And the above-mentioned additive solvent. The concept of the solubility parameter (hereinafter sometimes referred to as SP value) that is generally used is that the intramolecular force assuming that the force acting between the solvent and the solute is the intramolecular force is used as a measure of the cohesive force. It is generally accepted that two components having a small difference in SP value are easily mixed (high solubility), and two components having a large difference in SP value are difficult to mix (small solubility). That is, the coating agent used for general printing is commercialized and used by mixing a binder (polymer) having a small difference in SP value, a solvent (organic solvent, water, etc.) and an additive. The components of the invention are defined in a completely different way of thinking. That is, in the present invention, instead of examining the solubility parameter, emphasis is placed on whether the main solvent and main solvent of the coating agent used are a water-insoluble solvent or a water-soluble solvent. And define the constituents.

<Additional solvent>
Examples of the additive solvent include n-heptane (SP value: 7.3), n-propanol (SP value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (SP value: 11.3), and the like. Diethylene glycol ethyl ether (SP value: 10.9), 3-methoxybutanol (SP value: 10.9), triacetin (SP value: 10.2), propylene glycol monomethyl ether (SP value: 10.2), cyclopenta Non (SP value: 10.0), γ-butyrolactone (SP value: 9.9), cyclohexanone (SP value: 9.9), propylene glycol-n-propyl ether (SP value: 9.8), propylene glycol -N-butyl ether (SP value: 9.7), dipropylene glycol methyl ether (SP value: 9.7), 1,4-butanediol diacetate (SP value: 9.6), 3-methoxybutyl acetate (SP value: 9.6) SP value: 8.7), propylene glycol diacetate (SP value: 9.6), ethyl lactate acetate (SP value: 9.6), ε-caprolactone (SP value: 9.6), 1,3-butylene Glycoldiacetate (SP value: 9.5), dipropylene glycol-n-propyl ether (SP value: 9.5), 1,6-hexanediol diacetate (SP value: 9.5), dipropylene glycol- n-butyl ether (SP value: 9.4), tripropylene glycol methyl ether (SP value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), cyclohexanol acetate (SP value: 9) .2), Diethylene glycol monoethyl ether acetate (SP value: 9.0), ethylene glycol methyl ether acetate (SP value: 9.0), diethylene glycol monobutyl ether acetate (SP value: 8.9), ethylene glycol monobutyl ether acetate (SP value: 8.9), methyl acetate (SP value: 8.8), ethyl acetate (SP value: 8.7), propylene glycol monomethyl ether acetate (SP value: 8.7), n-propyl acetate (SP value: 8.7) SP value: 8.7), dipropylene glycol methyl ether acetate (SP value: 8.7), 3-methoxybutanol acetate (SP value: 8.7), butyl acetate (SP value: 8.7), isopropyl acetate (SP value: 8.5), tetrahydrofuran (SP value: 8.3), dipropylene glycol methyl-n- Butyl ether (SP value: 8.0), dipropylene glycol methyl-n-propyl ether (SP value: 8.0), dipropylene glycol dimethyl ether (SP value: 7.9), propylene glycol methyl-n-butyl ether (SP) Values: 7.8), propylene glycol methyl-n-propyl ether (SP value: 7.8) and the like can be mentioned.

The solubility parameter (SP value: Fedors calculated value) of the added solvent mentioned here at 25 ° C. is about 7.3 to 11.8, but in this embodiment, the SP value is positioned as a reference for the selected solvent. There is only. What is important is to determine whether the dispersion medium of the binder (polymer) and the main solvent of the additive are water-insoluble or water-soluble, and add a solvent that is the exact opposite of the dispersion medium and the main solvent as the additive solvent.

[Water-insoluble and water-soluble]
Regarding the definitions of water-insoluble and water-soluble, the definitions of water-soluble liquids of Class 4 dangerous goods are shown. Class 4 dangerous goods are flammable liquids. Further, it is divided into (1) water-soluble (water-soluble) and (2) water-insoluble (water-insoluble). It is defined as follows in the Cabinet Order.

The water-soluble liquid is a mixture of pure water and pure water of the same volume at 1 atm and 20 ° C. to maintain a uniform appearance. The water-insoluble liquid is other than the water-soluble liquid, and the water-insoluble liquid is water. When mixed, it splits into two layers. If the specific density of the liquid is smaller than that of water, a water-insoluble layer is formed above the layer of water, and if the specific gravity is higher than that of water, a water-insoluble layer is formed below the layer of water. In the case of water-soluble liquids, when mixed, the layers become uniform without separation. Some are slightly soluble in water, such as the special flammable diethyl ether and the first petroleum ethyl acetate, but by definition they are classified as water-insoluble.

Therefore, the additive solvent can be classified as follows based on the definitions of water-insoluble and water-soluble.
[Water-soluble additive solvent]
The water-soluble additive solvent is n-propanol (SP value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (SP value: 11.3), diethylene glycol ethyl ether (SP value: 10.9). , 3-methoxybutanol (SP value: 10.9), propylene glycol monomethyl ether (SP value: 10.2), γ-butyrolactone (SP value: 9.9), propylene glycol-n-propyl ether (SP value:) 9.8), dipropylene glycol methyl ether (SP value: 9.7), ethylldebrand ethyl acetate (SP value: 9.6), ε-caprolactone (SP value: 9.6), tripropylene glycol methyl ether (SP) Value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), diethylene glycol monoethyl ether acetate (SP value: 9.0), ethylene glycol methyl ether acetate (SP value: 9.0) , Tetrahydrofuran (SP value: 8.3), dipropylene glycol methyl-n-butyl ether (SP value: 8.0), dipropylene glycol methyl-n-propyl ether (SP value: 8.0), dipropylene glycol dimethyl ether (SP value: 7.9), propylene glycol methyl-n-propyl ether (SP value: 7.8) and the like can be mentioned.

[Water-insoluble additive solvent]
The water-insoluble additive solvent is triacetin (SP value: 10.2), cyclopentanone (SP value: 10.0), cyclohexanone (SP value: 9.9), propylene glycol-n-butyl ether (SP value:). 9.7), 1,4-butanediol diacetate (SP value: 9.6), 3-methoxybutyl acetate (SP value: 8.7), propylene glycol diacetate (SP value: 9.6), 1 , 3-Buylene glycol diacetate (SP value: 9.5), Dipropylene glycol-n-propyl ether (SP value: 9.5), 1,6-hexanediol diacetate (SP value: 9.5), Dipropylene glycol-n-butyl ether (SP value: 9.4), cyclohexanol acetate (SP value: 9.2), diethylene glycol monobutyl ether acetate (SP value: 8.9), ethylene glycol monobutyl ether acetate (SP value:) 8.9), methyl acetate (SP value: 8.8), ethyl acetate (SP value: 8.7), propylene glycol monomethyl ether acetate (SP value: 8.7), n-propyl acetate (SP value: 8) .7), Dipropylene glycol methyl ether acetate (SP value: 8.7), 3-methoxybutanol acetate (SP value: 8.7), butyl acetate (SP value: 8.7), isopropyl acetate (SP value: 8.5), propylene glycol methyl-n-butyl ether (SP value: 7.8) and the like can be mentioned.

[Amount of added solvent added]
The amount of the additive solvent added is preferably the same as long as the content of the target solvent of the dispersion medium and the additive is 0.1 wt% to 50 wt% with respect to the main agent. Specifically, if the main solvent of the dispersion medium and the additive is a water-soluble solvent and the content is 0.1 wt% to 50 wt%, one of the same amount of the water-insoluble solvent group is added as the additive solvent. Add as. On the contrary, if the main solvent of the dispersion medium and the additive is a water-insoluble solvent and the content is 0.1 wt% to 50 wt%, one of the same amount of the water-soluble solvent group is added. It may be added as a solvent.

As described above, in the composition of the coating agent of the present embodiment, it is confirmed whether the main solvent of the coating agent to be applied and the organic solvent which is the main solvent are water-insoluble or water-soluble, and if the water-insoluble is the main solvent. , It is a composition of a coating agent used and dispersed by adding a water-soluble organic solvent. As an example of the idea, a mixture of rubber (polymer) and oil (solvent) is taken as an example, but when rubber (polymer) and oil (solvent) are mixed, the rubber swells. This is a phenomenon in which oil enters between the molecules of rubber, and if the oil is easily mixed with the rubber, it will swell, and if it is difficult to mix, it will be difficult to swell. In other words, when the main solvent of the coating agent is water-insoluble, by adding a water-soluble additive solvent, substances having different polarities, in this case, the water-insoluble solvent and the water-soluble solvent are difficult to mix with each other. A state in which the water-soluble solvent floats is formed on the surface of the coating agent in which the main solvent is a water-insoluble solvent.

The coating agent of the present embodiment is used, for example, in a state where the water-soluble solvent floats on the surface and is used for ejection by a coater head (or a dispenser with a syringe) 10 for stripe coating. That is, as shown in FIG. 1, when the coating agent 1 is discharged from the coater head 10 having a discharge port 11 opened in the front surface and having a discharge flow path 12 communicating with the discharge port 11, the coater head (or dispenser nozzle) , Needle) 10 and an appropriate oil film 13 are formed at the interface between the coating agent 1. The generation of the oil film 13 reduces the friction between the coater head 10 and the coating agent 1, and thus the shear stress causes the central flow velocity (shear velocity) v3 of the discharge flow path 12 and the flow velocity (shear velocity) v3 on the side surface of the discharge flow path 12. Shear velocity) There is almost no difference from v4.
Then, even if the diameter of the discharge port 11 is equal to or equal to the size of the diameter of the discharge port 11 or the diameter of the discharge port 11 is reduced or expanded to the outside (the diameter of the discharge port 11 is expanded) by adjusting the discharge amount and the coating speed, the rectangle or the shape is formed. The degree to which the coating agent 1 is discharged while maintaining the cross-sectional shape of the discharge port 11 such as a round shape, a triangular shape, a convex shape, a trapezoidal shape, a diamond shape, and an M shape, and the line is discharged in a rounded shape bulging outward. Can be mitigated.

In this way, since the cross-sectional shape of the ejected matter (printed matter) from which the coating agent 1 is ejected can form a rectangular pattern, the cross-sectional area can be calculated from the vertical × horizontal dimensions when formed with conductive ink. It will be possible. That is, it is possible to form a pattern showing a non-destructive and stable electric resistance value.
Further, since the coating agent 1 can be discharged in a shape close to the cross-sectional shape of the discharge port 11, it is possible to form a pattern having a visual effect (including an optical effect) depending on the shape.

For example, as shown in FIG. 2, the cross-sectional shape of the plurality of ejected matter (printed matter) 30 from which the coating agent 1 is ejected can be rectangular, so that the surface 30a is vertically steep with respect to the base material 20. Can be formed. As a result, when the discharged material 30 is formed by line discharge, for example, a structure 40 can be formed in which the gap S of the rectangular line (discharged material 30) is filled to the utmost limit.
Further, as shown in FIG. 2, a rectangular pattern 30 having an aspect ratio (height L1 / base L2) of 1 or more can be formed, and more lines can be formed due to a narrow width.

Further, by mounting the coater head and the dispenser using the coating agent of the present embodiment on the XYZ robot, it is possible to form a three-dimensional rectangular line structure.
For example, as shown in FIG. 3, the coating agent 1 of the present embodiment having elastic conductivity is applied to the elastic base material (elastomer) 21 in the Z direction in the process of applying to the elastic base material 21. Repeat the operation of the coater head and dispenser with variable speed. By doing so, it is possible to continuously form the arch-shaped or loop-shaped rectangular conductive wiring 41 in the Z direction with respect to the upper surface of the elastic base material 21.
As described above, since the wiring in the Z direction can be formed in a loop shape upward with respect to the base material, the resistance value is less likely to change as compared with the wiring in which all the wiring crawls on the base material. On the other hand, by making the cross-sectional shape of the printed matter rectangular, the ejection shape can always be maintained, and the risk when the cross-sectional shape becomes round or the ejection shape collapses can be reduced. Here, when ejected with a normal syringe or the like, the cross-sectional shape may be rounded or the ejected shape may be distorted. The risk is that, for example, when the cross-sectional shape is round, the ground contact area is small and it is easy to peel off. Further, if the discharge shape is broken, the wiring height becomes thin, it is easy to tear, and the resistance may increase.
Further, since the cross-sectional shape of the conductive wiring 41 (coating agent 1) is rectangular, as shown in FIG. 4, the ground contact area at the bottom is wide, and even if the elastic base material 21 is expanded and contracted, the arch or loop-shaped conductive wiring is formed. It responds flexibly without stretching. Therefore, it is possible to form circuits, sensors, etc. with almost the same wiring resistance.

As described above, the composition of the coating agent of the present embodiment used for the coater and the dispenser confirms whether the main solvent of the coating agent to be applied and the organic solvent as the main solvent are water-insoluble or water-soluble, and is water-insoluble. If the main solvent is a water-soluble organic solvent, a water-soluble organic solvent is added and used to disperse the coating agent. By using such a coating agent, it is suitable for the discharge flow path, the coater head or dispenser nozzle near the discharge outlet, and the interface between the needle and the coating agent in the discharge application by the coater head for stripe coating or the dispenser by the syringe. A flexible oil film can be formed and friction can be eliminated. Therefore, the shear stress almost eliminates the difference between the flow velocity at the center of the discharge flow path (shear velocity) and the flow velocity at the side surface of the discharge flow path (shear velocity). That is, it is the same as the size of the discharge port, or even if the discharge diameter is reduced or expanded to the outside (expansion of the discharge diameter) by adjusting the discharge amount and coating speed, it is discharged in a form that maintains the shape of the discharge port. The rounded shape that swells outward can reduce the degree of line ejection.

(Example 1)
Silicone-based dielectric elastomer film "ELASTOSIL 2030, manufactured by Asahi Kasei Wacker", silicone-based two-component mixed type thermosetting carbon elastomer "ERASTOSILL R3162A, manufactured by Asahi Kasei Wacker" and "Asahi Kasei Wacker" A conductive coating agent prepared by mixing "ElastomerILLR3162B, manufactured by Asahi Kasei Wacker Co., Ltd." in a 1: 1 ratio.

Next, diethylene glycol monoethyl ether acetate (SP value 9.0), which is a water-soluble solvent contradictory to the water-insoluble main agent of the present invention, is selected, and the amount of diethylene glycol is 0.1 wt% to 50 wt% with respect to the main agent. A line in which seven rectangular discharge ports of 500 μm in length × 500 μm in width mounted on a dispensing controller and a desktop robot are formed at a pitch of 1000 μm using the coating agent of Example 1 mixed with monoethyl ether acetate (SP value 9.0). A 6 mm long stripe pattern was discharged from the coater head onto the dielectric elastomer film with a discharge port of 0.3 mm away from the film surface at a discharge pressure of 360 kPa and a head speed of 10 mm / sec. For the line ejection of the coating agent onto the dielectric elastomer film, a dispense controller (manufactured by Musashi Engineering Co., Ltd.) capable of controlling a high-viscosity liquid and a desktop robot capable of controlling the XYZ axes were used.

As a result, as shown in FIGS. 5 (a) and 5 (b), a rectangle (aspect ratio 1) having approximately one-to-one vertical and horizontal dimensions is sharp and flat on all sides perpendicular to the base and the base material. An acute-angled line-shaped discharge 30 having an arc with a radius of 10 μm or less having four corners (indicated by a broken line in the figure) 30e was formed.
From this result, the coater head near the discharge flow path and the discharge outlet is discharged by discharging the mixed coating agent of the water-insoluble and water-soluble solvent which is the configuration of the coating agent of Example 1 from the rectangular discharge port of 500 μm in length × 500 μm in width. The friction between the and the coating agent is relaxed, the difference between the flow velocity (shear velocity) at the center of the discharge channel and the flow velocity (shear velocity) at the side of the discharge channel due to shear stress disappears, and the flow velocity does not spread to the outside of the discharge port. It can be seen that the shape of the outlet was discharged as it was.

Therefore, the coating agent of Example 1 discharged from the smaller rectangular discharge port of 50 μm in length × 50 μm in width is compared with the coating agent of Comparative Example 1 described later when focusing on the corners of the cross-sectional shape shown in FIG. 5 (a). It can be seen that the ejection can be performed while maintaining the rectangular shape with an acute angle having an arc having a radius of at least 10 μm or less. Incidentally, in the case of a general coating agent, since it has an arc having a radius of 50 μm or less, it can be seen that it is not possible to discharge with a straight cross section on the vertical and horizontal sides of the rectangular cross section.

(Comparative Example 1)
As the composition of the coating agent of Comparative Example 1 , since the silicone (SP value 7.3 to 7.6) which is the main solvent of the "ERSTOSILLR" AB mixture is water-insoluble, it is water-insoluble and the SP value is relatively close. A polar n-heptane (SP value 7.5) was selected as the additive solvent, and the coating agent of Comparative Example 1 was prepared by mixing n-heptane in an amount of 0.1 wt% to 50 wt% with respect to the main agent. Then, diethylene glycol monoethyl ether acetate (SP value 9.0), which is a water-soluble solvent contradictory to water-insoluble, is selected, and the amount of diethylene glycol monoethyl ether acetate (SP value 9) is 0.1 wt% to 50 wt% with respect to the main agent. It was compared with the coating agent of Example 1 in which 0.0) was mixed.

Next, using a mixed coating agent having a small SP value difference, which is a general coating agent configuration, seven rectangular discharge ports of 500 μm in length × 500 μm in width mounted on the dispense controller and the desktop robot were formed at a pitch of 1000 μm. A 6 mm long stripe pattern was ejected from the line coater head onto the dielectric elastomer film with a discharge port of 0.3 mm away from the film surface at a discharge pressure of 360 kPa and a head speed of 10 mm / sec.

As a result, as shown in FIGS. 7 (a) to 7 (c), a rounded line having an arc having a radius of 50 μm or more at the four corners (indicated by a broken line in the figure) 130e of the stripe pattern (discharge) 130. It became a formation. From this result, when a mixed coating agent of the same polar solvent, which is a general coating agent composition, is discharged from a rectangular discharge port of 500 μm in length × 500 μm in width, shearing due to friction between the coater head near the discharge flow path and the discharge outlet and the coating agent. It was found that the stress causes a difference between the flow velocity in the center of the discharge flow path (shear velocity) and the flow velocity on the side surface of the discharge flow path (shear velocity), so that the flow velocity spreads outward from the size of the discharge port diameter and is discharged. ..
Therefore, as shown in FIGS. 7 (a) to 7 (c), the coating agent of Comparative Example 1 discharged from the smaller rectangular discharge port of 50 μm in length × 50 μm in width is already rounded when focusing on the corners of the cross-sectional shape. Since it is tinged, it was found that the possibility of discharging while maintaining the rectangular shape is extremely low.

(Example 2)
By repeating the operation of the coater head and the dispenser at variable speeds in the Z direction in the process of applying to the base material using the coating agent of Example 1, an arch shape or a loop in the Z direction with respect to the upper surface of the stretchable base material. A rectangular conductive wiring having a shape was continuously formed. For example, the coater head is fed 10 mm while discharging the coating agent of the present invention in the Y-axis direction, the head is moved 2 mm in the Z-axis direction and 1 mm in the Y-axis minus direction without stopping the discharge, and then the Z-axis remains as it is. Keeping the coordinates, move 3 mm to the plus side in the Y-axis direction, then land the discharge port on the upper surface of the elastic base material while moving the head 1 mm in the minus direction of the Y-axis, and repeat the operation of sending 1 mm in the plus direction of the Y-axis. As a result, it was possible to form a line in which loop-shaped wirings were continuously connected in the Y-axis direction. As a result, because it is rectangular, the ground contact area at the bottom is wide, and even if the elastic base material is expanded and contracted, the arch or loop-shaped conductive wiring does not stretch and flexibly responds, forming circuits, sensors, etc. with almost no change in wiring resistance. Is now possible.

(Example 3)
As shown in FIG. 7A, a head 14 having 13 discharge ports 15 having a pitch of 1000 μm, a width of 500 μm, and a height of 500 μm was produced. The discharge ports 15 were configured with seven discharge ports 15A at equal intervals on the bottom and six discharge ports 15B on the top with a pitch shift of 500 μm in a staggered manner.
In the same manner as in Example 1, the coating agent of Example 1 was simultaneously discharged from the discharge ports 15A and 15B to form a line. As a result of discharging under the optimum conditions by changing the upper and lower coating conditions, as shown in FIG. 7 (b), the bottom and the base material 20 are rectangular and have approximately 1: 1 vertical and horizontal dimensions (aspect ratio 1). A total of 13 structures 42 could be formed in a horizontal row without gaps, with lines that were sharp and flat on all sides orthogonal to and with sharp corners at the four corners.
In the third embodiment, the coating agents of the same material are used, but by implementing the coating agents of different materials, for example, the positive electrode active material layer and the conductive material layer, which are the constituents of a lithium ion battery, are separately discharged. By doing so, it was found that it is possible to develop applications such as increasing the speed at which distant ions reach.

As described above, according to one aspect of the present invention, the following effects are obtained.
(A) Since a rectangular pattern can be formed, when formed with conductive ink, the cross-sectional area can be calculated only by the vertical and horizontal dimensions, and a conducting wire showing a non-destructive and stable electric resistance value can be formed. ..
(B) Since the coating agent can be discharged in a shape close to the shape of the discharge port, it is possible to form a pattern having a visual effect (including an optical effect) depending on the shape.
(C) Since a steep surface can be formed perpendicular to the base material, in the case of line ejection, for example, it is possible to create a structure in which the gaps between rectangular lines are closed to the utmost limit.
(D) A rectangular pattern having an aspect ratio (height / base) of 1 or more can be formed, and more lines can be formed due to a narrow width.
(E) By mounting a coater head and a dispenser using a coating agent on an XYZ robot, a three-dimensional rectangular line structure can be formed. For example, the coater head and the dispenser are repeatedly operated by varying the speed in the Z direction in the process of applying the coating agent of the present invention having elastic conductivity to the elastic base material (epolymer). This makes it possible to continuously form an arch-shaped or loop-shaped rectangular conductive wiring with respect to the upper surface of the stretchable base material, and because of the rectangular shape, the ground contact area at the bottom is wide and the stretchable base material can be expanded and contracted. It is possible to form circuits, sensors, etc. with almost the same wiring resistance by flexibly responding to the fact that the arch or loop-shaped conductive wiring does not extend even if it is made to do so.
That is, it may be used in the fields of electronics, high-performance films, security, etc., and may be able to form structures that cannot be formed by photolithography or nanoimprint.

The present invention relates to a field where a line pattern, a stripe pattern, or a three-dimensional structure pattern having a precise and uniform film thickness is required, for example, a color for a small electronic component such as a resistor or a capacitor, or a liquid crystal display element (LCD). Structures such as filters, fuel cell electrodes, lithium ion battery electrodes, stretchable electrodes, and sensors can be easily manufactured with good quality and at low cost. A conductive paste, an insulating paste, or a urethane-based material composed of one or more types of coating agents such as silver, carbon, and copper powder via a discharge port formed on the surface of the base material in a coater head. Discharge coating agents such as stretchable conductive inks, carbon elastomer materials, dielectric elastomers, adhesives and non-adhesives developed in the above, and apply them in line patterns, three-dimensional structural patterns, and stripes on the surface of the base material. It can be used as a coating device for coating agents.

1 ... Coating agent 10 ... Coater head 11 ... Discharge port 12 ... Discharge flow path 13 ... Oil film 14 ... Coater head 15 ... Discharge port 20 ... Base material 21 ... Elastic base material 30 ... Discharge 40 ... Structure 41 ... Structure 42 ... Structure

Claims (4)

A conductive coating agent for coater heads and dispensers.
It has a binder in which a filler is dispersed and an additive solvent.
The dispersion medium of the binder is water-insoluble, and the additive solvent is water-soluble.
A coating agent, wherein the binder is a silicone polymer, the dispersion medium is silicone, and the additive solvent is diethylene glycol monoethyl ether acetate. The coating agent according to claim 1, wherein the binder is an elastomer having rubber elasticity containing siloxane as a main component. The coating agent according to claim 1 or 2, wherein the cross-sectional shape discharged onto the base material from the coater head and the dispenser has a corner portion having an arc shape having a radius of 10 μm or less. A discharge having a cross-sectional shape of the coating agent according to claim 1 or 2 discharged onto a base material from a coater head and a dispenser having an arcuate corner portion having a radius of 10 μm or less.

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