JP2001088306A - Method for adhering liquid having specific electric conductivity by electric field jetting method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for ejecting capable of stabilizing an ejection quantity or direction by an electric field jetting method. SOLUTION: There is disclosed a method for adhering a liquid in such a manner that the liquid is ejected from an ejection nozzle and is adhered to a base body provided opposite to the ejection nozzle. The liquid has an electric conductivity of 1×10-10-1×10-4 Θ-1.cm-1. An electrode is provided to a portion in the vicinity of the outlet of the ejection nozzle. The liquid is ejected to adhere the liquid by applying a voltage to a portion between the electrode and base body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric field jet, that is, a novel method of applying a voltage between an electrode in the vicinity of a liquid discharge port and a substrate to discharge and deposit the liquid by applying a voltage to the substrate. To a method and a liquid thereof.

[0002]

2. Description of the Related Art A recording method in which a liquid substance is discharged from a nozzle-shaped or slit-shaped opening and adhered onto a medium is widely used for graphics and various markings. Examples of these methods include the inkjet method,
Dispenser methods and the like can be mentioned, but these methods have advantages such as simpler apparatus and lower material cost as compared with the conventional printing method and photolithography method. Recently, many attempts have been made to apply such techniques to manufacture members requiring fine patterning such as liquid crystal color filters.

[0003] The ink jet recording method is a recording method in which a small droplet of ink is ejected from a fine nozzle, flies, and is directly attached to a recording member such as paper to form an image. The principle of the ejection is a piezo method in which the ink flow is deformed by the vibration of the piezoelectric element to eject the ink, bubbles are generated in the ink by the heat from the heating element in the ink passage, and the ink is ejected by the pressure. A thermal method and an electrostatic method of ejecting ink by applying an electrostatic attraction force to the ink have been proposed. In particular, the electrostatic method has a simple structure of a recording head, which facilitates multi-nozzle operation, and a pulse width modulation. Is different from the other methods in that gradation expression is possible.

However, a major problem with these ink jet systems is that they can only discharge very low-viscosity inks having a viscosity of 20 cps or less. For this reason, it has been difficult to perform ejection recording on a substrate such as a film that does not absorb ink or to form a thick pattern using a high-viscosity ink.
In addition, regardless of the viscosity, when discharging ink in which particles having a particle size of several hundred nm or more were dispersed, clogging due to drying or the like was likely to occur near the outlet, and stable discharge was not possible. Since the optical or magnetic properties of phosphors, pearl pigments, magnetic materials, etc. are greatly impaired when the particle size is reduced, it is not preferable from the functional aspect to produce a fine particle dispersion type ink that can be ejected by inkjet. As a result, patterning by the inkjet method was extremely difficult.

[0005] On the other hand, the dispenser system can discharge and adhere a high-viscosity substance in a linear or dot form. The smaller the inner diameter of the nozzle, the finer the line or dot can be ejected and recorded.
If it is less than μm, clogging of the holes frequently occurs, which is not practically preferable. Further, since the line width or dot diameter of the ejection-recorded line is larger than the nozzle inner diameter, it has been difficult to use it for fine patterning with a line width or dot diameter of 300 μm or less.

[0006] Screen printing and photolithography are common techniques for performing fine patterning requiring a film thickness of several μm or more. Examples of such patterning are the formation of phosphors, ribs, and electrodes of a plasma display panel (PDP). When the phosphor is patterned by the screen printing method, an RGB paste obtained by dispersing the phosphor powder in a dispersion medium in which a binder is dissolved with a three-roll or the like is used, and three screen plates for each color are used. In general, printing is performed three times in accordance with the cell position, and the phosphor paste of each color is applied in the cell for each color. Screen printing is suitable for mass production because the manufacturing equipment is relatively inexpensive and the number of manufacturing steps is small. However, there is a problem that it is difficult to obtain sufficient pattern accuracy due to deformation of the screen plate or change over time. PDPs are expected to have larger areas and higher resolution in the future.
It is expected that forming a phosphor layer by such a screen printing method will become more difficult technically and costly.

On the other hand, in the photolithography method,
A photosensitive phosphor paste is pressed into the cells between the ribs, and is baked after exposure and development to burn off organic substances in the pressed-in photosensitive composition, thereby forming a phosphor layer on the cell surface. In this case, since the paste to be used contains the phosphor powder, transmission of the ultraviolet rays is inhibited, and it becomes difficult for the ultraviolet rays to reach the bottom. That is, the sensitivity of the phosphor paste is extremely low. Therefore, it is difficult to make the thickness of the phosphor layer after patterning and baking 10 μm or more, and there is a problem that the luminance of the obtained phosphor screen is not sufficient. Therefore, it is conceivable to increase the amount of the photosensitive resin in order to increase the sensitivity of the phosphor paste. However, when a phosphor paste having a relatively large amount of resin is used, the shrinkage rate during firing becomes large, so that the phosphor layer is easily peeled and cracked during firing, and in a severe case, the phosphor screen is curled. Problems arise. In addition, exposure and development steps are indispensable for forming a phosphor pattern for each color. For this reason, there is a restriction that a developable resin must be used as the photosensitive resin, particularly a photosensitive resin which can be alkali-developed. For this reason, it was difficult to select a photosensitive resin having excellent burnout properties. Further, the layer to be developed and removed also contains expensive phosphor at a high concentration, and it is difficult to recover the developed and removed phosphor. Therefore, the effective utilization rate of the phosphor is less than 30% by weight. However, this was a major disadvantage in terms of cost.

The present inventors have conducted various studies on a method capable of forming an ink containing high viscosity or coarse particles by discharging as a fine pattern, and have arrived at the invention of the electric field jet method. The electric field jet method typically supplies ink to a discharge head having a nozzle-shaped or slit-shaped opening in which an electrode is arranged near a discharge port, and then applies an AC or DC voltage to the electrode. This is a pattern forming method for continuously or intermittently discharging the ink from the opening.

According to the electric field jet method, not only can a high-viscosity ink of several tens of thousands cps be discharged like a dispenser, but also a low-viscosity ink of several cps or less can be discharged in the same manner. The greatest feature of the electric field jet method is that the diameter of the tip of the ejected ink can be made smaller than the diameter of the opening due to the effect of the electric field. Depending on the combination of ink and head, the size of the line or dot to be patterned can be reduced to 1/10 or less of the opening. At the same time, since the opening can be made relatively large with respect to the target recording size, the ink containing coarse particles can be stably discharged at high resolution without clogging.

[0010] However, even with the electric field jet method, there is a case where a sufficient effect cannot be obtained depending on the type of ink.
In some cases, whether or not the ink can be ejected cannot be predicted only by evaluating the viscosity or the particle diameter in advance. Therefore, when converting a material to be patterned into an ink, the composition to be used depends on the experience so far, and it takes a lot of time to determine the ink composition that can be actually ejected. was there.

[0011]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a discharge method for stabilizing a discharge amount and a discharge direction by an electric field jet method. It is to be. Still another object of the present invention is to provide a liquid which can be stably ejected by an electric field jet method.

[0012]

Means for Solving the Problems The present inventors have found that the above object can be achieved by using a liquid having a specific electric conductivity when discharging a liquid by the electric field jet method, and completed the present invention. Was.

Therefore, according to the method of depositing a liquid having a specific electric conductivity by an electric field jet according to the present invention, a liquid is discharged from a discharge port and the liquid is deposited on a substrate provided opposite to the discharge port. a deposition method of a liquid, the electrical conductivity of the liquid is ^{10 - 10 ~1} × ^{10 -4} ohms
⁻¹ · cm ⁻¹ , an electrode is arranged near the outlet of the discharge port, and the liquid is discharged while applying a voltage between the electrode and the base to adhere the liquid. It is a feature.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Electric Field Jet The electric field jet method of the present invention is a method in which an electrode is provided at or near a liquid discharge port, and a voltage is applied between the electrode and a substrate to which the liquid is attached, thereby discharging the liquid. Meaning can include various aspects.

FIG. 1 is a conceptual view of a liquid deposition apparatus using an electric field jet method, in which a liquid in a head 2 having a discharge port 1 is pressurized by a pump 3 while a waveform generated by an arbitrary waveform generator is converted to a high pressure. The liquid 6 is applied to the head 2 via the power supply 5 to cause the liquid 6 to adhere to the base 7.

Liquid to be Attached (Electric Conductivity of Liquid) In the present invention, the liquid to be ejected to be attached by an electric field jet has an electric conductivity of 1 × 10 5
^There is no particular limitation as long as it is between ^{−10 and} 1 × 10 ⁻⁴ ohm− ¹ · cm ⁻¹ . Within this range, as an effect of the voltage application, the liquid is sucked in the direction of the base material, and the liquid discharged from the discharge port can be thinly stretched near the base and stably adhere the liquid in a thin line shape. That is, when the electric conductivity of the liquid is low, pulsation increases, the ejection amount is not stable, large droplets are intermittently ejected, and the landing position is not stable. on the other hand,
When the electric conductivity of the liquid is high, it is easy to be sucked by the already ejected substance or electrode, and the ejection direction is not stable.
Intermittent ejection is likely to occur, and the problem that the ejection amount is not stable tends to occur.

The electric conductivity may vary depending on the frequency of the applied voltage at the time of measurement or at the time of carrying out the present invention. In the present invention, the electric conductivity at the frequency of the applied voltage at the time of ejection is shown.

(Method of Determining Electric Conductivity of Liquid) In the present invention, the electric conductivity of a liquid can be measured, for example, by the following method. In this method, since the liquid of the present invention includes a non-uniform liquid such as a paste-like liquid, the electric conductivity is obtained using a model that takes into account a capacitor component in addition to a resistance component.

FIG. 2 shows a parallel circuit model of C and R for obtaining the electric conductivity. When a sine wave is used as an applied voltage to measure the simplification of the measurement and analysis, the applied voltage V is expressed as follows.

[0020] _{V = V o · sin ωt V} o: the amplitude of the voltage omega: angular frequency t: the time this current ir flowing through the resistor R flows into _{ir = V / R = (V} o / R) sinωt capacitor C current ic is expressed as ic = C (dV / dt) = V o · ω · C · cosωt, the current I flowing _{I = ir + ic = V o} {(1 / R) sinωt + ω ·
C · cosωt｝.

Here, the current I is I / V _o = (1 / R) sin ωt + ω · C · cos ω
From t, I / V _o = {1 / R ² ) + (ωC) ² } · si
n (ωt + α ′) α ′ = tan ⁻¹ (ωC / (1 / R)) = tan
^-1 (ωCR) tan α = ωC / (1 / R) = ωCR α ′: phase difference between voltage V and current I can be rewritten as shown in FIG.

Here, r is r ² = Imax / V _o = 1 / R ² + (ωC) ² Imax: maximum current value. As a result, the resistance R and the capacitor C are given by: 1 / R = r · cos α ′ R = (1 / r) cos α ′ = (V _o / Imax) co
s2παf ωC = r′sinα ′ C = (r / ω) sinα ′ = (Imax / V _o · 2π
f) cos2παf α: phase difference between voltage V and current I (measured value [s]) f: frequency of applied voltage V _o and f are known because they are measurement conditions,
The resistance R and the capacitor C are obtained by measuring Imax and α.

Accordingly, from the obtained resistance R, the electric conductivity σ can be obtained by σ = l / (R · a) l: length of the measured object a: area of the specific measured object

FIG. 4 shows the shape of the measuring electrode, and FIG. 5 shows the measuring device.

As the measuring electrode, two sheets of glass 42 obtained by patterning ITO 41 as shown in FIG. 4 are used.

As shown in FIG. 5, the ITO portions of the two electrodes face each other, and a spacer 51 (thickness: 3 mm) is inserted between them and fixed to form a measurement electrode 52. And I
The 10 mm square portion of TO is put in the sample, and one of the 5 mm square portions is connected to the amplifier 53 and the other is connected to the measuring resistor 54. When the measurement electrode 52 is inserted into the sample 55, the
It is desirable that the O10 mm square portion is just immersed.
Not only that the whole is not completely immersed, but also that it is immersed too deeply causes a measurement error.

The measurement is performed using the function generator 56.
Creates a waveform (sine wave) of the applied voltage, and adjusts the amplitude and frequency. One of the pulses (voltage) generated by the function generator 56 is monitored by an oscilloscope 57, and the other is sent to an amplifier 53. The pulse sent to the amplifier is amplified here by 100 times (1000 times), output, and applied to the liquid as the sample 55 via the measurement electrode.

The current flowing between the measuring electrodes is
Through the oscilloscope 57. The resistance used at this time is selected depending on the liquid that is the sample 55.
(Use resistance: 1Ω ・ 10Ω ・ 100Ω ・ 1kΩ ・ 10k
(Ω · 100 kΩ · 1 MΩ) The protection resistor 58 of the device when a large current flows has a resistance value that is five times the measured resistance.

The applied voltage waveform and the current waveform obtained on the oscilloscope are analyzed by the computer 59, and the applied voltage,
The maximum current value and phase difference are obtained, and the electric conductivity is obtained.

In this method, the structure of the measuring electrode is simple, so that it is easy to clean, the electric conductivity at an arbitrary frequency can be measured, the electric conductivity can be measured at the same time as the electric conductivity, and the measuring resistance can be selected. This is advantageous in that a wide range of electric conductivity can be measured.

(Liquid to be Discharged) The liquid to be discharged (for example, ink) to be adhered according to the present invention is not limited to a single-phase liquid, but may be a liquid composed of a plurality of phases called a suspension, a dispersion, or an emulsion. It may be. For example, the liquid to be ejected needs to be liquid (has fluidity) at the ejection temperature, and therefore, a liquid in which a component (target substance) to be patterned according to the intended use is dissolved or dispersed, which contains an organic or inorganic liquid as a main component. Can be used. Usually, the liquid to be ejected is composed of a liquid, a binder, and a target substance, but if the electric conductivity is within the above range, a dispersant, an antifoaming agent, a thixotropic agent, etc. Can be freely mixed.

In many cases, the electric conductivity of the liquid to be discharged is determined by the composition of the organic or inorganic liquid as the main component. If the liquid to be ejected is designed with a liquid having a desired electric conductivity as a main component, the electric conductivity of the obtained liquid to be ejected is almost the same as that of the liquid, depending on the composition.

The electric conductivity used in the present invention is 10
^-10Ω^-1・ Cm^-1From 10^-4Ω^-1・ Cm^-1
As an example of the liquid in the range, as the inorganic liquid,
Water, COCl₂, HBr, HNO₃, H₃PO₃, H₂
SO₄, SOCl₂, SO₂Cl ₂, FSO₃H etc.
No.

As the organic liquid, methanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-propanol, tert-butanol, 4-
Methyl-2-pentanol, benzyl alcohol, α-
Alcohols such as terpineol, ethylene glycol, glycerin, diethylene glycol, triethylene glycol; phenols such as phenol, o-cresol, m-cresol, p-cresol; dioxane, furfural, ethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve; Ethers such as butyl cellosolve, ethyl carbitol, butyl carbitol, butyl carbitol acetate, epichlorohydrin; ketones such as acetone, methyl ethyl ketone, 2-methyl-4-pentanone, acetophenone; formic acid, acetic acid, dichloroacetic acid, and trichloroacetic acid Fatty acids such as acetic acid; methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid-3
-Methoxybutyl, -n-pentyl acetate, ethyl propionate, ethyl lactate, methyl benzoate, diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate, ethylene carbonate, propylene carbonate, cellosolve acetate, butyl carbitol acetate, Esters such as ethyl acetoacetate, methyl cyanoacetate, ethyl cyanoacetate; nitromethane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, valeronitrile, benzonitrile, ethylamine, diethylamine, ethylenediamine, aniline, N-methylaniline, N , N-dimethylaniline, o-toluidine, p-
Toluidine, piperidine, pyridine, α-picoline,
2,6-lutidine, quinoline, propylenediamine, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N-methylpropionamide, N, N, N ', N'-tetramethylurea,
Nitrogen-containing compounds such as N-methylpyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; hydrocarbons such as benzene, p-cymene, naphthalene, cyclohexylbenzene and cyclohexene; 1,1-dichloroethane, 1,2- Dichloroethane, 1,1,1-trichloroethane, 1,1,1,2-tetrachloroethane,
1,1,2,2-tetrachloroethane, pentachloroethane, 1,2-dichloroethylene (cis-), tetrachloroethylene, 2-chlorobutane, 1-chloro-2-
Halogenated hydrocarbons such as methylpropane, 2-chloro-2-methylpropane, bromomethane, tribromomethane, and 1-bromopropane;

When there is no liquid having the desired electric conductivity by itself, two or more liquids may be mixed and used. For example, butyl carbitol having an electric conductivity of 9.6 × 10 ⁻⁷ Ω− ¹ · cm ⁻¹ and 3.8 × 10 ⁻⁹ Ω− ¹ · cm ^−1.
When butyl carbitol acetate is mixed, the electric conductivity changes as shown in FIG. 6 depending on the mixing ratio. If it is desired to make the electric conductivity of the mixed solvent be around 1 × 10 ⁻⁷ Ω ⁻¹ · cm ⁻¹ , it is understood from FIG. 6 that the mixing ratio of butyl carbitol and butyl carbitol acetate should be 41:59. If a powder or resin to be patterned is dispersed and dissolved in the mixed solvent, a mixture having an electric conductivity of about 1 × 10 ⁻⁷ Ω− ¹ · cm ⁻¹ can be obtained in many cases.

As another means for obtaining a desired electric conductivity, there is a method in which a liquid to be ejected is prepared by using a liquid having a low electric conductivity as a main component, and a small amount of a substance having high conductivity is added later. Examples of the substance having high conductivity include a metal substance such as an aluminum powder and a substance obtained by dissolving an electrolyte in water. In the latter case, since they are incompatible with many organic liquids, they are often added in emulsion form together with a surfactant. According to these techniques, it is possible to increase only the electric conductivity without largely changing the solvent composition.

When a substance (silver powder or the like) having a higher electric conductivity than the liquid component is contained as in the case of the conductive paste, it is difficult to adjust the electric conductivity by the composition of the liquid. Therefore, it is preferable to design the composition of the liquid to be discharged after knowing the correlation between the solid content concentration and the electric conductivity in advance by preliminary measurement or the like.

Of the substances mentioned above, those which are solid at room temperature can be discharged by heating them to a temperature higher than their melting point and then supplying them to the head. Such a method is generally used in, for example, a hot-melt type ink jet recording method.However, there is a problem in that a heater unit must be provided in the recording apparatus and a disadvantage that it takes time to warm up, but a quick drying property is required. It is useful for such applications.

The boiling point of the liquid is important because it affects the degree of clogging at the opening. The preferred boiling point range is 150
C. to 300 C., more preferably 180 C. to 250 C.
° C. If the temperature is lower than 150 ° C., clogging due to drying is likely to occur. If the temperature is higher than 300 ° C., drying after recording takes a long time, which is not preferable. Such a high-boiling liquid preferably accounts for 50% by weight or more of the total liquid in the liquid to be discharged, and more preferably 70% by weight or more.

(Substance that can be dissolved or dispersed in liquid) The substance that can be dissolved or dispersed in liquid is
There is no particular limitation except for coarse particles that cause clogging at the nozzle.

For example, a known organic pigment or inorganic pigment is usually used as the coloring material.

Examples of the black colorant include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black; copper, iron (CI Pigment Black 11); Examples thereof include metals such as titanium oxide and organic pigments such as aniline black (CI pigment black 1).

As the yellow pigment, inorganic yellow lead,
Cadmium yellow, yellow iron oxide, titanium yellow, ocher and the like. Examples of the acetoacetic acid arylide monoazo pigments of poorly soluble metal salts (Azo Lake) include C.I. I.
Pigment Yellow 1, 3, 65, 74, 97, 98,
133, 169 and allylic disazo acetoacetate pigments include C.I. I. Pigment Yellow 12, 13, 1
4, 17, 55, 81, and 83. Examples of the condensed azo pigment include C.I. I. Pigment Yellow 93, 94,
95. Further, benzimidazolone monoazo pigments include C.I. I. Pigment Yellow 120,
151, 154, 156, and 175. Also,
Isoindolinone pigments include C.I. I. Pigment Yellow 109, 110, 137, and 173. In addition, C.I. I. Pigment Yellow 24, 99, 108, 123, C.I. I. Pigment Green 10, C.I. I. Pigment Yellow 117 and 153, and quinophthalone pigments such as C.I. I. Pigment Yellow 138 and the like.
In addition, examples of the magenta pigment include inorganic cadmium red, redwood, silver vermilion, lead red, and antimony vermilion. Examples of the azo lake-based azo pigments include C.I.
I. Pigment Red 48, 49, 51, 53: 1, 5
4, 57: 1, 60: 1, 63, 64: 1, C.I. I. Pigment Orange 17, 18, 19, and
Examples of the insoluble azo type (monoazo, disazo type, condensed azo type) include C.I. I. Pigment Red 1, 2, 3, 5,
9, 38, 112, 114, 146, 150, 170,
185, 187, C.I. I. Pigment Orange 5, 1
3, 16, 36, 38, C.I. I. Pigment Brown 2
5 as a condensation azo pigment. I. Pigment red 144, 166, C.I. I. Pigment Orange 31 and the like.

As anthraquinone pigments which are condensed polycyclic pigments, C.I. I. Pigment Red 177, C.I.
I. Pigment Orange 40 and 168, and thioindigo pigments such as C.I. I. Pigment Red 88,
C. I. Pigment Violet 36 and 38, and C.I. I. Pigment Orange 43; and perylene pigments such as C.I. I.
Pigment Red 123, 149, 178, 179, 1
And quinacridone pigments such as C.I. I. Pigment Red 122, 206, 207, C.I. I. Pigment Violet 19; and, as condensed polycyclic pigments, pyrocholine pigments, red fluoropine pigments, and basic dye lake pigments such as C.I. I. Pigment Red 81 and the like.

Examples of the cyan pigment include inorganic ultramarine blue, navy blue, cobalt blue, cerulean blue and the like.
As phthalocyanine-based compounds, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 1
5: 6, 16, 17, C.I. I. Pigment Green 7,
36, C.I. I. Pigment Violet 23, and C.I. I. Pigment Blue 21, 22, 60, 64, and C.I. I. Pigment Violet 3 and the like.

Further, a coloring agent which is a so-called processed pigment obtained by coating a resin on the surface of the above coloring agent can also be used.

As the dyes, water-insoluble oil-soluble dyes and disperse dyes, and water-soluble direct dyes, acid dyes, basic dyes, food dyes, and reactive dyes dispersed or dissolved in an aqueous solvent can be used. it can.

The water-insoluble dyes include, for example, diarylmethane, triarylmethane, thiazole,
Methine, azomethine, xanthine, oxazine, azo and azo derivatives, anthraquinone derivatives,
A quinophthalone derivative, a spirodipyran-based dye, an isodorinospiropyran-based dye, a fluoran-based dye, or a rhodamine lactam-based dye are preferably used. For example, C.I. I. Disperse Yellow 51, 3, 54, 7
9, 60, 23, 7, 141, C.I. I. Disperse Blue 24, 56, 14, 301, 334, 165, 1
9, 72, 87, 287, 154, 26, 359, C.I.
I. Disperse threads 135, 146, 59, 1, 7
3, 60, 167, C.I. I. Disperse Violet 4, 13, 26, 36, 56, 31, C.I. I. Solvent Violet 13, C.I. I, Solvent Black 3,
C. I. Solvent Green 3, C.I. I. Solvent Yellow 56, 14, 16, 29, 105, C.I. I. Solvent Blue 70, 35, 63, 36, 50, 49, 1
11, 105, 97, 11, C.I. I. Solvent Red 135, 81, 18, 25, 19, 23, 24, 14
3, 146, 182 and the like.

As the water-soluble dye, for example, the following dyes represented by a color index are used. C. I. Acid Yellow 17, 23, 42, 44, 79, 142,
C. I. Acid Red 1, 8, 13, 14, 18, 2
6, 27, 35, 37, 42, 52, 82, 87, 8
9, 92, 97, 106, 111, 114, 115, 1
34, 186, 249, 254, 289, C.I. I. Acid Blue 9, 29, 45, 92, 249, C.I. I. Acid Black 1, 2, 7, 24, 26, 94, C.I.
I. Food yellow 3, 4, C.I. I. Food red 7,
9, 14, C.I. I. Food black 2, C.I. I. Direct Yellow 1, 12, 24, 26, 33, 44, 5
0, 142, 144, 86, C.I. I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 8
0, 81, 83, 89, 225, 227, C.I. I. Direct Orange 26, 29, 62, 102, C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 71,
76, 79, 86, 87, 90, 98, 163, 16
5, 199, 202, C.I. I. Direct Black 1
9, 22, 32, 38, 51, 56, 71, 74, 7
5, 77, 154, 168, C.I. I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 21, 2
3, 24, 25, 28, 29, 32, 36, 40, 4
1, 45, 49, 51, 53, 63, 65, 67, 7
0, 73, 77, 87, 91, C.I. I. Basic Red 1, 2, 12, 13, 14, 15, 18, 22, 2
3, 24, 27, 29, 35, 36, 38, 39, 4
6, 49, 51, 52, 54, 59, 68, 69, 7
0, 73, 78, 82, 102, 14, 109, 11
2, C.I. I. Basic Blue 1, 3, 5, 7, 9, 2
1, 22, 26, 35, 41, 45, 47, 54, 6
2, 65, 66, 67, 69, 75, 77, 78, 8
9, 92, 93, 105, 117, 120, 122, 1
24, 129, 137, 141, 147, 155, C.I.
I. Basic Black 2,8.

In addition to the coloring material, various functional materials such as magnetic substances, brilliant pigments, matte pigments, fluorescent substances, conductive substances, ceramics and precursors thereof can be mixed and used according to the purpose.

As the magnetic material, Fe, Co, Ni, etc.
Metal magnetic material, Fe₃O₄, Γ-Fe ₂O₃Oxides such as
Magnetic materials, various ferrites, rare earth strong magnetism such as Sm and Eu
Or a Prussian blue-type metal complex
Organic magnetic material.

Examples of the brilliant pigments include (1) pigments called pearl pigments, more specifically, scales obtained by baking titanium oxide or iron oxide on the inner part of shells, crushed pearls, or mica fine particles. (2) metal powder, more specifically, powder of aluminum, brass, bronze, gold, silver, etc., preferably 1-1.
20 μm fine particles or scaly foil pieces;
(3) A piece of a plastic film that has been deposited, more specifically, a silver powder obtained by depositing and crushing the above metal, usually aluminum, on a polyethylene terephthalate film, and then painting a transparent yellow color after the deposition. (4) Two or more resin layers having different refractive indices, for example, a polyester resin layer and an acrylic resin layer, each of which has a thickness of several μm or less, are laminated. Examples thereof include foil powder obtained by finely cutting a composite film that produces iris color due to interference.

As matte pigments, kaolinite,
Examples include clay minerals such as halosite, muscovite, and talc, and synthetic achromatic pigments such as anhydrous silica, anhydrous alumina, calcium carbonate, magnesium carbonate, and barium carbonate.

As the phosphor, a conventionally known phosphor can be used without any particular limitation. For example, as a red phosphor, (Y, Gd) BO ₃ : Eu, YO ₃ : Eu
For example, Zn ₂ SiO ₄ : Mn, Ba as a green phosphor
Al ₁₂ O ₁₉ : Mn, (Ba, Sr, Mg) O · α-
As a blue phosphor such as Al ₂ O ₃ : Mn, BaMgA
l ₁₄ O ₂₃ : Eu, BaMgAl ₁₀ O ₁₇ : Eu and the like.

In order to firmly adhere the above-mentioned target substance, it is preferable to add various binders. As the binder used, for example, ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate,
Cellulose such as hydroxyethyl cellulose and derivatives thereof; alkyd resin; polymethacrylic acid, polymethyl methacrylate, 2-ethylhexyl methacrylate / methacrylic acid copolymer, lauryl methacrylate.2
(Meth) acrylic resins such as -hydroxyethyl methacrylate copolymers and metal salts thereof; poly (meth) acrylamide resins such as poly N-isopropylacrylamide and poly N, N-dithymeracrylamide; polystyrene, acrylonitrile / styrene copolymer Styrene resins such as styrene / maleic acid copolymers and styrene / isoprene copolymers; styrene / acrylic resins such as styrene / n-butyl methacrylate copolymers;
Various unsaturated polyester resins; Polyolefin resins such as polypropylene; Halogenated polymers such as polyvinyl chloride and polyvinylidene chloride; Vinyl resins such as polyvinyl acetate, vinyl chloride / vinyl acetate copolymer; Polycarbonate resins; Resin; polyurethane resin;
Polyacetal resins such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal; polyethylene resins such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer resin; amide resins such as benzoguanamine; urea resins; melamine resins; Modified anionic cations; polyvinylpyrrolidone and its copolymers; alkylene oxide homopolymers, copolymers and crosslinked products such as polyethylene oxide and carboxylated polyethylene oxide; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyether polyols;
SBR, NBR latex; textulin: sodium alginate; gelatin and its derivatives, casein, trollooi, tragacanth gum, pullulan, gum arabic,
Natural or semi-synthetic resins such as locust bean gum, guar gum, pectin, carrageenan, glue, albumin, various starches, corn starch, konjac, seaweed, agar, soy protein; terpene resins; ketone resins; rosin and rosin esters; polyvinyl methyl ether , Polyethyleneimine, polystyrenesulfonic acid, polyvinylsulfonic acid, and the like. These resins may be used not only as a homopolymer but also as a blend within a compatible range.

Electrodes (Form of Electrodes) Various forms of electrodes can be used. For example, the nozzles and the slits themselves are made of an electrode material, the electrodes are arranged on the inner wall of the slits. Nozzles in which electrodes are arranged inside, electrodes are arranged outside slits, and electrodes are arranged inside the walls of nozzles and slits. In the cases described above, the distance from the tip of the discharge port to the electrode is related to the required voltage, but can be freely arranged within a very wide range. The present inventors have already found that if a sufficiently large voltage is applied, ejection can be performed even when the electrode is separated from the nozzle tip by 10 cm or more, depending on the ejection speed. From the viewpoint of the required applied voltage strength, the distance from the tip of the discharge port to the electrode is preferably within 100 mm,
More preferably, it is within 30 mm. Such freedom of electrode arrangement can be a great advantage in the design of the ejection head.

When the conductivity of the recording medium is high, or when a plurality of nozzles are arranged in an array and different signals are given to adjacent nozzles, the discharge ports are controlled to suppress discharge or crosstalk. The distance from the electrode to the electrode is preferably 0.5 mm or more, more preferably 1 m
m to 100 mm, more preferably 1 mm to 30 mm
It is good to arrange in the range.

When the electrode is arranged outside the nozzle and the slit, the thickness of the nozzle wall or the slit wall is 1 to 100.
It is preferably 0 μm.

(Material of Electrode) The material of the electrode is not particularly limited. For example, metals such as Au, Ag, Cu and Al, alloys such as stainless steel and brass, and conductive ceramics such as ITO are preferably used. When an electrode is disposed inside the flow path, a hard coat may be applied to the electrode surface for the purpose of preventing deterioration and wear of the electrode.

[0060] In the voltage application present invention, a voltage is applied between the electrode and the substrate. In this case, either AC or DC may be used,
Basically, AC is preferred. Further, although the electrodes are directly electrically connected, the base may be electrically connected or not. If the liquid to be deposited is likely to cause electrodeposition, alternating current is particularly preferred for the purpose of preventing electrodeposition.

FIG. 7 is a diagram schematically showing the effect of voltage application in the electric field jet method. FIG. 7A shows a case in which a small amount of liquid is ejected by the conventional method without voltage application, and even if an attempt is made to eject continuously, only droplets of irregular size are ejected discontinuously. FIG. 7B shows a case where the discharge amount is increased, and continuous discharge is performed, but the liquid is discharged as a liquid column thicker than the opening of the discharge port. FIG. 7C shows a case where a voltage is applied by a small amount of discharge, and the discharge is continuously performed with a thin line. FIG. 7D shows a case where a voltage is applied in a large amount of discharge, and the discharge is continuously performed with a slightly thicker line as the discharge amount increases.

The case of continuous ejection and intermittent ejection (ON / OFF
The preferred method of applying a voltage differs in the case of (discharge) discharge, which will be described below.

(In the case of continuous discharge) In the case of continuous discharge, AC or DC discharge is possible. Preferably, the alternating current is as shown in FIG. As the voltage intensity, Vp-p = 100
It is preferably from V to 10 kV, and more preferably from 1 to 7 kV from the viewpoint of voltage control and ejection stability. Preferably, the waveform is a rectangular wave.

Depending on the viscosity and material composition of the liquid, if the electric conductivity differs, the optimum applied voltage frequency also changes. In many cases, the optimum applied voltage frequency increases as the electrical conductivity increases. If the frequency is low, deposition on the electrode or the like is likely to occur, which is not preferable. Further, when the frequency is high, there is a problem that control becomes difficult due to the performance of the power supply. A preferred frequency range is 1 Hz to 10 kHz. From the viewpoints of ejection continuity and voltage control, the frequency is more preferably 100 Hz to 4 kHz. ± 100V to 10kV for DC
(The polarity is the same in both cases).

(In the case of intermittent ejection) Intermittent ejection (ON / OF)
For F discharge), the absolute value of the applied voltage is utilized that the discharge in V ₁ or more occurs. (In FIG. 9, pulses a and b are ejected but c is not ejected.) The ejection amount can be controlled by the voltage intensity. The magnitude of the threshold value V1 depends on the liquid and electrode arrangement, but is preferably in the range of 100 V to ₃ kV. The discharge voltage is 100 V to 10 k as in the case of continuous discharge.
V, more preferably in the range of 1 to 7 kV.

Substrate In the present invention, the term “substrate” means an object to which a liquid is to be adhered. The material is not particularly limited as long as the liquid to be ejected is adhered thereto. Can be ejected. Discharge to a low-viscosity liquid surface or the like is difficult because the liquid may be sucked to the recording electrode side. In addition, continuous ejection to an object having irregularities of several hundred μm or more is not preferable because the ejection amount is not stable due to a gap variation.

The conductivity of the surface has only a small effect on the suction force of the liquid adhering to the substrate to the substrate, and has no significant effect. However, in the case of a highly conductive substrate such as a metal, a discharge may occur between the electrodes and an excessive current may flow through the liquid to be discharged. preferable.

Discharge port In the present invention, the discharge port may be any discharge port from which the liquid to be discharged can be discharged. Specific examples of such a material include a nozzle and a slit.

FIG. 10 shows a head 10 having a liquid discharge port.
FIG. 2 is a diagram illustrating a structural example of a first example. FIG. 10A is a cross-sectional view of the whole. A liquid to be discharged 103 is filled in a liquid to be discharged 102 in a head 101 and a back pressure 104 is applied. FIG. 10b is an enlarged view of the head ejection port portion,
An electrode 105 provided inside the head, a tapered portion 106, a nozzle portion 107, and an opening 108 are provided. FIG.
c is a diagram viewed from the direction of the ejection port of the head 101, and in this case, seven openings 108 are provided.

(Material for Forming Discharge Port) The material for forming the discharge port is not particularly limited. Examples of the conductive material include stainless steel, brass, Al, Cu, Fe, and the like. Semiconductor materials include ceramic materials such as glass, mica, zirconium oxide, alumina, and silicon nitride, and plastic materials such as PEEK, fluororesin, and polyamide.

The tip end face of the discharge port is preferably covered with a material having a low surface free energy such as a fluororesin so that the liquid to be discharged does not spread. If the liquid to be ejected spreads wet, the formation of the meniscus at the ejection port becomes unstable, and it remains as a stain when the ejection is stopped, adversely affecting the subsequent recording.

(Shape of Discharge Port) When the discharge port is a nozzle, its opening shape may be either a circle or a polygon. The opening diameter is preferably in the range of 50 to 2000 μm, and from the viewpoint of stability of the meniscus and prevention of clogging, 1
More preferably, the thickness is from 00 to 1000 μm.

When the discharge port is a slit, as in the case of the nozzle, the opening gap is preferably in the range of 50 to 2000 μm, and from the viewpoint of meniscus stability and prevention of clogging, it is preferably 100 to 1000 μm. More preferred.

(Recording gap) The distance from the discharge port to the substrate can be set as appropriate, but is preferably 0.1 mm to 10 m.
m, more preferably in the range of 0.2 to 2 mm. If the distance is smaller than 0.1 mm, a stable meniscus cannot be formed, and furthermore, it is not possible to follow delicate irregularities of the recording medium. On the other hand, if it is wider than 10 mm, the linearity of the ejection is impaired, which is not preferable.

Discharge In discharging the liquid in the method of the present invention, the liquid can be pressurized or depressurized. When the pressure of the liquid is reduced or the pressure is reduced, not only the discharge amount of the liquid is reduced but also a fine pattern can be easily formed. Further, when the liquid is pressurized, not only the liquid discharge amount can be easily increased, but also a thick pattern can be formed.

The ejection of the liquid may be intermittent or continuous. ON / OFF of discharge
Can be performed, for example, by pressurizing and depressurizing the liquid and / or changing the applied voltage.

FIG. 11 is a diagram showing an example of ejection from an ejection head having multi-row nozzles. A liquid 112 to be discharged from a head 111 connected to a pump
As the head 111 advances to the left in the figure.
Liquid streaks of the book adhere to the base 113.

Applications Examples of applications to which the method for applying an electric field jet according to the present invention can be applied include the following. Display applications include PDP phosphors, ribs, electrodes, CRT phosphors, color filters for liquid crystal displays (RGB color layer, black matrix), and microlenses. For memory and semiconductor applications, magnetic materials, ferroelectrics,
Conductive base (wiring, antenna), etc. For graphic applications, normal printing, printing on special media (film, cloth, steel plate, etc.), curved printing, various printing plates, etc. For processing applications, such as adhesives and sealing materials. Examples of bio and medical applications include pharmaceuticals (such as mixing a plurality of trace components) and samples for genetic diagnosis.

[0079]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Continuous discharge (line coating) using the apparatus of FIG.
Recording test. The substrate to be discharged was a glass plate having a thickness of 3 mm disposed on a horizontal stone plate. A liquid ejection head having the same shape as that of FIG. 10 was used. The specifications such as the hole diameter were as follows.

Hole diameter: 300 μm Hole depth: 1000 μm Number of holes: 1 Nozzle material: macerite The conditions of the apparatus such as voltage application were as follows.

・ Applied voltage: 5 kV, rectangular wave, frequency 500 Hz ・ Discharge amount: 25 cm ³ / min (adjusted by pump pressure) ・ Head scanning speed: 50 mm / min ・ Head-substrate distance: 0.5 mm The difference in the electrical conductivity of the liquid to be discharged was evaluated.
Further, in order to see the influence of the viscosity, ejection experiments were performed on a low-viscosity substance having a viscosity of several cps or less and a high-viscosity substance having a viscosity of several tens of thousands cps.

The measurement of the electric conductivity followed the method described above.
The liquid to be ejected is filled between two electrode plates having an electrode area of 1 cm × 1 cm and an electrode interval of 3 cm, and a voltage of 200 V, 500 is applied between both electrodes.
The electrical conductivity was calculated from the current value when an AC voltage of Hz was applied. The reason why the frequency is set to 500 Hz is based on the assumption of an actual ejection condition.

The discharge characteristics were evaluated according to the following criteria.

[0084]

[Table 1] (Discharge Characteristics of Low Viscosity Substance) Each of the liquids to be discharged was a single liquid. However, for substances having an electric conductivity of 10 ⁻⁴ Ω ⁻¹ · cm ⁻¹ or more, a suitable amount of electrolyte ( KC
prepared by dissolving 1). The following table shows the electrical conductivity and discharge characteristics of each liquid to be discharged.

[0085]

[Table 2] From Table 2, it was confirmed that the liquid to be discharged having a constant electric conductivity was discharged stably.

When the electric conductivity was reduced to about 10 ⁻⁹ Ω ⁻¹ · cm ⁻¹ , pulsation of the liquid to be ejected was observed during continuous ejection, and the line width was not constant. However, the lower the applied voltage frequency was, the more the quantity stability tended to be improved, and good quantity stability was recognized under the optimal frequency conditions. Isopar G, an isoparaffinic hydrocarbon solvent, has a diameter of several meters even when the frequency is reduced.
Only about m droplets were ejected intermittently, and continuous linear ejection was impossible.

On the other hand, the electric conductivity is 10 ⁻⁴ Ω ⁻¹ · cm.
^If it is larger than ^{-1, the} droplets will be in the form of droplets even if the conditions such as the frequency are changed, so that continuous ejection cannot be performed. The result was flying.

(Discharge Characteristics of High Viscosity Substance) (Preparation of Liquid to be Discharged) 70 parts by weight of a solvent and 30 parts by weight of a resin were placed in a closed container and heated and dissolved at 120 ° C. while stirring. After cooling this to room temperature, it was confirmed that no resin was precipitated, and the viscosity was measured by a B-type viscometer to 200 poise.
Solvent was added until. The stirring after the addition of the solvent was performed by a stirring and defoaming machine (MX-2001 manufactured by Sinky).

Subsequently, a pigment was added to the above resin solution, pre-dispersed by a kneader, and then dispersed with three rolls until coarse particles having a particle diameter of 5 μm or more disappeared. The viscosity of the obtained paste was measured with a B-type viscometer, a solvent was added until the viscosity became 300 poise, and the paste subjected to stirring and defoaming with a stirring and defoaming machine was used as a liquid to be discharged.

The content of the pigment in each composition was as shown in Table 3. For a substance having an electric conductivity of 10 ⁻⁴ Ω ⁻¹ · cm ⁻¹ or more, 10 ⁻⁶ Ω ⁻¹ · cm ⁻¹
It was prepared by adding a small amount of an aqueous solution of copper nitrate to a paste of a degree.

(Ejection Experiment) The ejection characteristics of each liquid to be ejected are shown in Table 3.

[0092]

[Table 3] As shown in Table 3, it was confirmed that the discharge of the high-viscosity substance had almost the same dependence on the electric conductivity as that of the low-viscosity substance. From this, it was confirmed that the influence of the difference in the viscosity on the optimum range of the electric conductivity was small, and the discharge characteristics could be similarly controlled by the electric conductivity in a wide viscosity range.
However, the linearity of ejection tends to be slightly stabilized in a high-viscosity substance as compared to a low-viscosity substance, and the linearity is not impaired even at a low electric conductivity.

The electric conductivity is 10 ^-11 Ω ^-1 · cm
^{When the value is} reduced to about ^-1 , the linearity is not largely reduced as described above, but basically, droplet-like ejection is performed similarly to the low-viscosity substance, resulting in poor quantity stability. This could not be sufficiently improved even by lowering the applied voltage frequency.

On the other hand, when the electric conductivity was high, the phenomenon that the liquid to be ejected was wound on the head wall surface was observed, and both the linearity and the quantity stability were largely reduced. When the applied voltage was increased, the ejection tended to be slightly stabilized, but this was not sufficient. Further, when the voltage exceeded 7 kV, discharge or excessive current frequently caused scorching of the liquid to be ejected with the base material. It was judged that it was not practically preferable.

(PDP Phosphor Application Test) In Table 3, no. The second phosphor paste was discharged and filled.

The head for liquid ejection uses the one described above.
The ejection conditions were as follows.

Head scanning speed: 80 mm / sec Applied voltage: 6 kV, 1 kHz, rectangular wave Head-substrate distance: 1 mm Back pressure: 3.2 kg / cm ² Removes one cell between barriers
It was adjusted to fill up to 00%. The filling amount was confirmed by observing the shape of the substrate with a laser microscope immediately after coating.

The coated substrate is placed in an oven at 120 ° C. for 30 minutes.
After drying for a minute, microscopic observation was performed from above and from the cross section.
As in the case of the above-mentioned glass plate, the discharge characteristics were good, and there was no unevenness in the discharge amount and no “jump” to adjacent cells. Further, the phosphor paste after drying was firmly adhered to above the barrier.

[0099]

According to the present invention, it is possible to provide a discharge method for stabilizing a discharge amount and a discharge direction by the electric field jet method. Still another object of the present invention is to provide a liquid that can be stably ejected by an electric field jet method.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a liquid deposition apparatus using an electric field jet method.

FIG. 2 is a parallel circuit model of C and R for obtaining the electric conductivity of a liquid.

FIG. 3 is a graph showing a current value when calculating the electric conductivity of a liquid.

FIG. 4 is a schematic explanatory view of the shape of a measurement electrode when determining the electric conductivity of a liquid.

FIG. 5 is a schematic explanatory view of a shape of a measuring device when obtaining electric conductivity of a liquid.

FIG. 6 is a diagram showing a change in electric conductivity of a liquid depending on a mixing ratio of butyl carbitol and butyl carbitol acetate.

FIG. 7 is a diagram schematically showing the effect of voltage application in the electric field jet method.

FIG. 8 is a graph showing an example of an alternating current waveform that can be applied in the method of the present invention.

FIG. 9 is a graph showing an example of a pulse current waveform that can be applied in the method of the present invention.

FIG. 10 is a diagram illustrating a structural example of a head having a discharge port.

FIG. 11 is a diagram illustrating an example of ejection from an ejection head having multi-row nozzles.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Discharge port 2 Head 3 Pump 4 Arbitrary waveform generator 5 High voltage power supply 6 Liquid 7 Substrate 41 ITO 42 Glass 51 Spacer 52 Measurement electrode 53 Amplifier 54 Measurement resistance 55 Sample 56 Function generator 57 Oscilloscope 58 Protection resistance 59 Computer 101 Head 102 Discharge Liquid tank 103 Liquid 104 Back pressure 105 Electrode 106 Tapered part 107 Nozzle part 108 Opening 111 Head 112 Liquid 113 Base

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41J 2/01 B41J 3/04 103G 5C058 2/07 101Y H04N 5/66 101 104Z F-term (Reference) 2C056 EA04 EC42 FA02 FA05 FA07 FB01 FC01 2C057 AF71 AG12 AG22 AH01 AH05 AJ01 AM16 BD05 DB01 DB02 DC08 DC15 4D075 AC02 AC06 AC86 AC88 AC99 BB81X CA22 CA47 DA06 DB14 DC22 EA14 4F034 AA10 BA05 BA33 CA23 4A04 ABA35 BA01 BA01A01 BA01A01 AB01

Claims (17)

[Claims] 1. A method for depositing a liquid by ejecting a liquid from an ejection port and attaching the liquid to a substrate provided opposite to the ejection port, wherein the liquid has an electric conductivity of 1 × 10 ^{− 10} to 1 × 10 ^-4
Ohm- ¹ cm ^-1 , wherein an electrode is disposed near the outlet of the discharge port, and the liquid is discharged by applying a voltage between the electrode and the base to adhere the liquid. A method for adhering a liquid using an electric field jet. 2. The method according to claim 1, wherein the discharge port is a nozzle or a slit. 3. The method according to claim 2, wherein the nozzle or the slit itself is an electrode. 4. The method for attaching a liquid according to claim 1, wherein the liquid is discharged while pressurizing or depressurizing the liquid. 5. The method according to claim 1, wherein the liquid is intermittently ejected. 6. The method according to claim 5, wherein the intermittent ejection of the liquid is performed by changing the applied voltage and / or changing the pressurization of the liquid. . 7. The method for applying a liquid according to claim 1, wherein the discharge of the liquid is continuous. 8. The method according to claim 1, wherein the substrate is a plasma display panel. 9. The method for applying a liquid according to claim 1, wherein the applying of the liquid is to coat at least a part of the substrate. 10. The method according to claim 1, wherein a voltage applied between the electrode and the base is 50 V to 10 kV. 11. The method according to claim 1, wherein the voltage applied between the electrode and the base is an AC voltage. 12. An electric conductivity of 1 × 10 ⁻¹⁰ to 1 × 10.
^The liquid used in the method according to claim 1, wherein the liquid is ^-4 ohm- ¹ cm- ¹ . 13. The liquid according to claim 12, wherein said liquid is a mixture of two or more liquids. 14. The liquid according to claim 12, wherein said liquid is a suspension. 15. The liquid according to claim 12, wherein said liquid is ink. 16. The liquid according to claim 12, wherein said liquid is a phosphor paste. 17. The liquid of claim 1, wherein 50 to 100 weight percent of the liquid portion of the liquid is a liquid having a boiling point of 150 ° C. or higher.
3. The liquid according to 2.