JPH10203004A - Recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To heighten jetting stability when two liquids are to be mixedly jetted and correctly present gradation. SOLUTION: A jet medium 4 and a quantitative medium 6 having a relationship q-p>=0, wherein the surface tension of the jet medium 4 is q(dyn/cm) and the surface tension of the quantitative medium 6 is p(dyn/cm), are used. These media are mixed at a predetermined mixing ratio immediately before jetting. A mixed liquid 10 is jetted on a recording medium for coating it. When the viscosity of the quantitative medium 6 is α(cp) and the viscosity of the jet medium 4 is β(cp), establishment of a relationship of β-α>=0 is preferable. Further, it is preferable that a time period from the mixing of the jet medium 4 and the quantitative medium 6 until the recording medium is coated with the mixed liquid 10 is set to 1(msec) or shorter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a recording method,
In particular, the present invention relates to a recording method that achieves high ejection stability and enables accurate gradation expression by optimizing the correlation between physical values of the ejection medium and the quantitative medium.

[0002]

2. Description of the Related Art In recent years, with the spread of personal computers and the like, it has been required to display images displayed on the personal computers on photographic paper in the same manner as silver halide photographs.

As a means for printing a display image or the like of a personal computer on photographic paper, for example, an ink jet recording technique or the like is used.

In this ink jet recording technique,
Printing is performed by discharging liquid ink from a nozzle onto a printing paper using electrolysis, heat, pressure, or the like as a driving source, and forming an image with the ink.

On the other hand, especially in offices and the like, document creation by a computer called desktop publishing has become popular, and recently there has been an increasing demand for printing not only characters and figures but also color natural images such as photographs with characters and figures. doing.

[0006] In personal use, for example, the production of New Year's cards, greeting cards, and the like has been actively performed, and the above-mentioned demands have been increasing.

[0007] With such an increase in demand, it is required to print a high-quality natural image, and gradation expression by halftone display becomes important.

By the way, conventionally, according to a control signal corresponding to a recording signal, ink droplets are ejected from nozzles only when necessary at the time of printing and adhered onto a recording medium such as paper or film to perform recording. An on-demand type ink jet recording system is known. This on-demand type ink jet recording method has a possibility of miniaturization and cost reduction, and is rapidly spreading in recent years.

In such an on-demand type ink jet recording system, various methods have been proposed as a method of discharging the ink droplets from nozzles.
A method using a piezo element or a method using a heating element is generally used. The former method using a piezo element is a method in which pressure is applied to ink by deformation of the piezo element to discharge ink, and the latter method using a heating element generates bubbles generated by heating and evaporating ink in a nozzle by the heating element. Is a method of ejecting ink at a pressure of.

The following method has been proposed as a method for simulating the gradation expression by halftone display in such an on-demand type ink jet recording system.

The first method is a method of modulating a voltage or a pulse width applied to a piezo element or a heating element to control the size of a droplet to be ejected, and expressing the gradation by changing the diameter of a print dot.

In the second method, one pixel is constituted by a matrix composed of, for example, 4 × 4 dots while the diameter of the print dot is kept constant, and the matrix unit is obtained by image processing such as the so-called dither method or error diffusion method. It is a way to express the key. In this case, in addition to this, an image processing technique such as an outline emphasis process or a smoothing process may be combined.

However, the first method has a limitation on the minimum droplet diameter because the ink is not ejected if the voltage or pulse width applied to the piezo element or the heating element is too low. There is a disadvantage that gradation expression is very difficult. Therefore, it is not suitable for printing out a natural image.

In the second method, for example, when one pixel is composed of a 4.times.4 matrix, the density of 17 gradations can be expressed. Resolution is 1/4 when printed with
And the roughness is conspicuous, which is also unsatisfactory for printing out a natural image.

If the image processing is strictly performed to solve this inconvenience, the circuit becomes complicated and the calculation processing speed is reduced, that is, the printout time is lengthened.

As a solution to the problem of such a conventional on-demand type ink jet recording system,
For example, as disclosed in Japanese Unexamined Patent Publication No. Hei 5-201024, the ink and a diluent, which is a transparent solvent, are mixed at a predetermined mixing ratio immediately before ejection to produce diluted ink, and this diluted ink is immediately ejected from a nozzle. A recording method in which recording is performed by attaching the recording medium to a recording medium (hereinafter, among such methods, the ink is used as a quantifying medium, the diluent is used as a discharge medium, and the quantifying medium is used as a discharge medium as a diluent. A method of performing recording by discharging a discharge medium by mixing into a diluted ink is referred to as a carrier jet method. However, in the above recording method, there is no problem even if the diluent is used as a quantitative medium and the ink is used as a discharge medium. .) Has been proposed by the present applicant.

According to the carrier jet method, the density can be controlled for each of the discharged diluted ink droplets, and the gradation can be freely expressed for each dot printed on the recording medium. Therefore, it is possible to print out a natural image with abundant halftones without deteriorating the resolution.

[0018]

As described above, the carrier jet method is a method in which the ink and the diluent are mixed at an arbitrary mixing ratio immediately before ejection. In addition, the degree of freedom of physical properties and the like increases dramatically.

Further, in the case of the conventional ink jet recording system, only the ink is ejected, so that the only consideration is to make the physical properties of the ink suitable for the ejection operation. In the carrier jet method in which the ink and the diluent are mixed and discharged immediately before the discharge,
Since the operation that the ink is measured and mixed with the diluting liquid is added, it is necessary to make the physical properties of each liquid suitable not only for the discharging operation but also for the mixing operation. Mutual relationships also become important.

Therefore, the present invention has been proposed in view of such a situation, and the ejection in the case of mixing and ejecting two liquids by optimizing the correlation between the physical properties of the ink and the diluting liquid. An object of the present invention is to provide an ink jet recording method which has high stability and enables accurate gradation expression.

[0021]

In order to achieve the above object, according to the present invention, a fixed amount medium is mixed with a discharge medium at a predetermined mixing ratio immediately before discharge, and the mixed liquid is discharged to cover a recording medium. In the recording method, the surface tension of
(Dyn / cm), and the surface tension of the ejection medium is q (dy).
n / cm), the relationship that qp ≧ 0 holds.

Further, in the recording method of the present invention,
Let the viscosity of the quantification medium be α (cp) and the viscosity of the ejection medium be β
When (cp) is satisfied, it is preferable that the relationship of β−α ≧ 0 holds.

In the recording method of the present invention, it is preferable that the time from mixing of the ejection medium and the quantitative medium to the application of the mixed liquid on the recording medium is 1 (msec) or less.

In the recording method of the present invention, the time factor greatly affects the mixing operation of the quantitative medium and the ejection medium. Here, the temporal element represents the time from the quantitative mixing of the quantitative medium and the discharge medium to the deposition on the recording medium. Can be easily guessed.

As a method of extending the time from the quantitative mixing of the above-mentioned quantitative medium and the discharge medium to the deposition on the recording medium, the time from the quantitative mixing to the discharge is increased.
Further, the distance from the ejection nozzle to the recording medium may be increased, and the speed of the ejection liquid may be decreased.

However, each of these methods has a problem. That is, if the time from the quantitative mixing to the ejection is lengthened, the ejection frequency is lowered, so that it is not possible to cope with the demands of the era of high-speed printing and cannot be adopted as a practical problem. In addition, increasing the distance from the ejection nozzle to the recording medium or decreasing the ejection liquid speed affects the ejection properties and significantly affects the deposition position accuracy and the like, so there is a limit.

Therefore, when the ejection frequency, the distance from the ejection nozzle to the recording medium, and the like are set to a practical level, the upper limit of the time from quantitative mixing to application to the recording medium is 1 ms, preferably It is preferable to set it to 500 μs or less.

In the recording method of the present invention, the quantitative medium may be one of the ink and the diluent, and the ejection medium may be the other.

When the measurement medium is ink and the ejection medium is diluent, the surface tension of the measurement medium is 25 to 60 (dyn / cm) and the surface tension of the ejection medium is 3
The viscosity is preferably 0 to 70 (dyn / cm), and when the viscosity is also specified, the viscosity of the measurement medium is 1 to 1 (dyn / cm).
5 (cp), and the viscosity of the ejection medium is preferably 1 to 15 (cp).

When the quantifying medium is a diluting liquid and the ejection medium is ink, the surface tension of the quantifying medium is 25 to 60 (dyn / cm) and the surface tension of the ejection medium is 3
It is preferably 0 to 60 (dyn / cm), and when the viscosity is also specified, the viscosity of the measurement medium is 1 to 1 (dyn / cm).
5 (cp), and the viscosity of the ejection medium is preferably 1 to 15 (cp).

In any of these cases, the solvent of the ink and the diluent is preferably composed of water and a water-soluble organic solvent, and preferably contains a surfactant.

Examples of the water-soluble organic solvent used as a solvent for such inks or diluents include aliphatic monohydric alcohols, polyhydric alcohols and derivatives thereof.

More specifically, examples of the aliphatic monohydric alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, s-butyl alcohol and t-butyl alcohol.
Lower alcohols such as -butyl alcohol;
In particular, ethyl alcohol, n-propyl alcohol, i-
Propyl alcohol and the like are preferred.

When this monohydric alcohol is used as a solvent for the ink, the surface tension of the ink is adjusted, and the mixed liquid droplet obtained by mixing the ink and the diluent penetrates into a recording medium such as plain paper or special paper. The effect of improving the properties, dot shape, and drying property of a printed image is high, and good characteristics are obtained.

On the other hand, when this monohydric alcohol is used as a solvent for the diluting liquid, the mixed droplets obtained by mixing the ink and the diluting liquid can penetrate into a recording material such as plain paper or special paper, and form dots. And the effect of improving the drying property of the printed image is high, which is preferable.

Examples of the polyhydric alcohol include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, and glycerol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; and thiodiglycol. .

The polyhydric alcohol derivatives include lower alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and propylene glycol monomethyl ether. And lower carboxylic acid esters such as ethylene glycol diacetate.

When this polyhydric alcohol and its derivative are used as a solvent for the ink, it has the effect of preventing clogging of the nozzles of the printer device and also lowers the freezing point of the ink, which is an auxiliary agent for dissolving the dye. To improve the storage stability of the ink.

On the other hand, even when the polyhydric alcohol and its derivative are used as a solvent for the diluting liquid, the polyhydric alcohol and the derivative have the effect of preventing clogging of the nozzles of the printer device.
There are effects such as lowering the freezing point of the diluent to enhance the storage stability of the diluent.

In addition, alcohol amines such as mono, di, and triethanolamine, amides such as dimethylformamide and dimethylacetamide, ketones such as acetone and methyl ethyl ketone, and ethers such as dioxane can be appropriately used. is there.

As the above-mentioned surfactant, any conventionally known surfactant can be arbitrarily used. Examples of the surfactant include nonionic, anionic, and cationic surfactants, and nonionic surfactants are preferred.

Specific examples include polyoxyethylene ethers, polyethylene glycol fatty acid esters, glycerin ester, sucrose ester, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and the like.

Needless to say, the ink contains a dye and / or a pigment in addition to the solvent described above. Examples of the dye include a water-soluble dye.

Examples of the water-soluble dye include a water-soluble anionic dye (a water-soluble direct dye and a water-soluble acid dye) and a water-soluble cationic dye.

The water-soluble anionic dye has a monoazo group, an anthraquinone skeleton, a triphenylmethane skeleton or the like as a chromophore, and further has one to three anionic groups such as a sulfonic acid group or a carboxyl group in the molecule. Those having a water-soluble group can be used.

Specifically, as a yellow direct dye,
C. I. Direct Yellow 1, 8, 11, and 1
2, 24, 26, 27, 28, 33, 3
9, 44, 50, 58, 85, 86, 8
7, 88, 89, 98, 100, 110, and magenta direct dyes such as C.I. I. Direct Red 1, Same 2, Same 4, Same 9, Same 11, Same 13, Same 17, Same 2
0, 23, 24, 28, 31, 33, 3
7, 39, 44, 46, 62, 63, 7
5, 79, 80, 81, 83, 84, 8
9, 95, 99, 113, 197, 201,
218, 220, 224, 225, 226,
227, 228, 229, 230, 321
As a cyan direct dye, C.I. I. Direct Blue 1, 2, 8, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 9
0, 98, 106, 108, 120, 15
8, 160, 163, 165, 168, 19
2, 193, 194, 195, 196, 19
9, 200, 201, 202, 203, 20
7, 225, 226, 236, 237, 24
6, 248, 249, and black direct dyes such as C.I. I. Direct Black 17, 19, 2
2, 32, 38, 51, 56, 62, 7
1, 74, 75, 77, 94, 105, 1
06, 107, 108, 112, 113, 1
17, 118, 132, 133, and 146 are preferably exemplified.

As a yellow acid dye, C.I.
I. Acid Yellow 1, 3, 7, 11, 11
7, 19, 23, 25, 29, 36, 3
8, 40, 42, 44, 49, 59, 6
1, 70, 72, 75, 76, 78, 7
9, 98, 99, 110, 111, 112,
114, 116, 118, 119, 127,
128, 131, 135, 141, 142,
161, 162, 163, 164, 165,
As magenta acid dyes, C.I. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 18, 2
6, 27, 32, 35, 37, 42, 5
1, 52, 57, 75, 77, 80, 8
2, 83, 85, 87, 88, 89, 9
2, 94, 97, 106, 111, 114,
115, 117, 118, 119, 129,
130, 131, 133, 134, 138,
143, 145, 154, 155, 158,
168, 180, 183, 184, 186,
194, 198, 199, 209, 211,
215, 216, 217, 219, 249,
252, 254, 256, 257, 262,
265, 266, 274, 276, 282,
283, 303, 317, 318, 320,
Nos. 321, 322, and C.I.
I. Acid Blue 1, 7, 7, 9, 15, 22,
23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 7
2, 74, 78, 80, 82, 83, 9
0, 92, 93, 100, 102, 103,
104, 112, 113, 117, 120,
126, 127, 129, 130, 131,
138, 140, 142, 143, 151,
154, 158, 161, 166, 167,
168, 170, 171, 175, 182,
183, 184, 187, 192, 199,
203, 204, 205, 229, 234,
236, C.I. I. Acid Black 1, 2, 7, 24, 26, 2
9, same 31, same 44, same 48, same 50, same 51, same 5
2, 58, 60, 62, 63, 64, 6
7, 72, 76, 77, 94, 107, 1
08, 109, 110, 112, 115, 1
18, 119, 121, 122, 131, 1
32, 139, 140, 155, 156, 1
57, 158, 159, and 191 can be preferably exemplified.

The water-soluble cationic dyes include:
An azo dye having an amine salt or a quaternary ammonium group, a triphenylmethane dye, an azine dye, an oxazine dye, a thiazine dye, or the like can be used.

Specifically, C.I. I.
Basic Yellow 1, 2, 11, 11, 13, 1
4, 19, 21, 25, 28, 32, 3
3, 34, 35, 36, magenta, C.I.
I. Basic Red 1, 2, 9, 9, 12, 1
3, 14, 14, 17, 17, 18, 22, 2
3, 24, 27, 29, 32, 38, 3
9, 40, C.I. I. Basic Violet 7, 1
0, 15, 15, 21, 25, 26, 27, 2
8, C.I. I. Basic Blue 1, 3, 5, 7, 7, 9, 19, 21, 22, 22
4, 25, 26, 28, 29, 40, 4
1, 44, 47, 54, 58, 59, 6
0, 64, 65, 66, 67, 68, 7
5. As a black type, C.I. I. Basic Black 2, 8 and the like.

In addition, additives such as an antifoaming agent, a pH adjusting agent and a fungicide may be optionally added to the components of the ink or the diluting liquid, if necessary.

In the recording method of the present invention, when the surface tension of the ejection medium is q (dyn / cm) and the surface tension of the quantitative medium is p (dyn / cm), the relationship of qp ≧ 0 is satisfied. Using a discharge medium and a quantitative medium that are established, they are mixed at a predetermined mixing ratio immediately before discharge, and the mixed liquid is discharged and adhered onto a recording medium. Thus, a mixture having good mixing properties and good mixing properties is discharged.

In the recording method of the present invention, the viscosity of the quantitation medium is α (cp) and the viscosity of the ejection medium is β
In the case of (cp), if the relationship of β−α ≧ 0 is established, the ejection after mixing these is performed stably.

Further, in the recording method of the present invention, if the time from mixing of the discharge medium and the fixed amount medium to the application of the mixed liquid on the recording medium is set to 1 (msec) or less, a practical printing speed and discharge rate can be improved. The mixing property between the quantitative medium and the ejection medium is further improved while ensuring the positional accuracy.

[0054]

Embodiments of the present invention will be described below in detail with reference to the drawings.

First, the configuration of a printer to which the recording method of the present invention can be applied will be described. What is shown here is a so-called on-demand type printer device, which is a so-called carrier in which ink is provided on a fixed amount side, diluent is provided on a discharge side, and a mixed liquid obtained by mixing these is discharged onto a recording medium such as recording paper. This is a jet printer.

It should be noted that, in this printer, there is no problem if the diluent is introduced into the quantitative side and the ink is introduced into the discharge side.

Further, in this printer apparatus, the nozzle on the discharge side and the nozzle on the fixed amount side are independently provided, and the ink and the diluting liquid are mixed outside the nozzle on the discharge side ( Hereinafter, such a printer device is referred to as an external mixed type printer device.)
In addition, the discharge side nozzle and the discharge port of the fixed amount side nozzle are provided on the same surface, and the fixed amount side nozzle is inclined with respect to the discharge side nozzle.

As shown in FIGS. 1 and 2, such a printer device has an orifice plate 3 provided with a nozzle 1 on the discharge side and a nozzle 2 on the metering side independently. The orifice plate 3 is formed from a metal plate such as nickel or stainless steel, a ceramic plate such as glass or silicon, or a plastic film such as polyimide or polyethylene terephthalate.

The nozzle 1 on the discharge side formed in the orifice plate 3 is formed as a straight through hole penetrating in the thickness direction of the orifice plate 3. One opening of the nozzle 1 on the discharge side is a discharge port 1a serving as a diluent orifice, and the other opening is a supply port 1b. In this supply port 1b,
For example, the transparent solvent 4 as a diluent is supplied to the transparent solvent supply flow path 5.
Is supplied via the Internet.

On the other hand, the nozzle 2 on the metering side is formed as a through hole inclined toward the nozzle 1 on the ejection side for the purpose of facilitating quantitative mixing of the ink. That is,
The nozzle 2 on the fixed amount side is formed so as to be inclined such that the discharge port 2a serving as an ink orifice gradually approaches the discharge port 1a of the nozzle 1 on the discharge side. In order to form the nozzle 2 on the fixed amount side as an oblique hole, for example, laser processing is used.

In the present embodiment, the nozzle 2 on the metering side is formed on a polyimide film having a thickness of 50 μm by an excimer laser at an inclination of 43 degrees with respect to the normal direction of the orifice plate 3. The inclination angle of the nozzle 2 on the fixed amount side is not particularly limited.

One opening of the nozzle 2 on the metering side is a discharge port 2a serving as an ink orifice, and the other opening is a supply port 2b. In this supply port 2b,
For example, the ink 6 is supplied via an ink supply channel 7.

It is desirable that the discharge port 1a of the nozzle 1 on the discharge side has a point-symmetrical shape in terms of the function of discharging droplets. Further, a circular shape or a square shape is preferable from the viewpoint of ease of design and manufacture. In the present embodiment, the shape is circular.

On the other hand, the discharge port 2a of the nozzle 2 on the quantitative side has a high degree of freedom and is not limited to a circular shape, but may be, for example, an elliptical shape, a triangular shape, or a crescent shape as shown in FIG. . In this example, it is circular. The shape of the discharge port 2 can be easily formed by changing the shape of a mask used during laser processing. For example, in order to obtain a circular shape, the shape of the mask may be an elliptical shape.

Next, the recording operation of the printer will be described with reference to FIG.

First, at the time of waiting for the discharge of the ink 6 and the transparent solvent 4, a transparent solvent meniscus 8 is formed at the discharge port 1 a of the nozzle 1 on the discharge side by the surface tension as shown in FIG. An ink meniscus 9 is formed at the discharge port 2a of the nozzle 2 on the fixed amount side.

At the time of the discharge standby, the nozzle 2 on the fixed amount side and the nozzle 1 on the discharge side are provided independently, so that the ink and the diluent do not come into contact with each other and natural mixing is reliably avoided.

Next, the ink 6 is quantified and mixed with the transparent solvent 4. That is, the pressure in the nozzle 2 on the metering side is increased by a pressure applying means such as a piezo element or a heating element (not shown), and the ink 6 is metered as shown in FIG. The mixing amount of the ink 6 can be adjusted by controlling the voltage value or the pulse width of the voltage pulse applied to the pressure applying means.

Then, since the fixed amount nozzle 2 is inclined toward the discharge side nozzle 1, the ink 6 is discharged in the direction of the discharge port 1a of the discharge side nozzle 1 and mixed with the transparent solvent 4 by surface tension. Mix slowly.

Next, when the voltage applied to the pressure applying means provided on the metering side is turned off and a drive pulse is applied to the pressure applying means provided on the discharging side, the pressure in the nozzle 2 on the metering side becomes negative pressure, The pressure in the nozzle 1 increases. As a result, as shown in FIG. 2C, a mixture 10 formed by mixing the ink 6 and the transparent solvent 4 and the ink 6 returning to the nozzle 2 on the quantification side are separated, and the ink meniscus 9 is formed on the quantification side. The nozzle 2 is drawn into the inside. In addition, the mixed solution 10
Protrudes from the discharge port 1a of the nozzle 1 on the discharge side.

Subsequently, the drive pulse to the pressure applying means on the ejection side is cut off. Then, the pressure in the nozzle 1 on the discharge side becomes negative pressure, and as shown in FIG.
And the mixed liquid 10 is torn off and discharged as droplets having a predetermined ink concentration.

Thereafter, as shown in FIG. 7E, the fixed amount nozzle 2 is refilled with the ink 6, and the discharge side nozzle 1 is also refilled with the transparent solvent 4, so that the first standby state is achieved. Return to.

The discharge operation of one cycle has been described above. This cycle is sequentially repeated to form an image or the like on the recording medium. In the case of a color image, yellow (hereinafter referred to as Y
), Magenta (hereinafter referred to as M), cyan (hereinafter referred to as C)
For example, four nozzles on the fixed amount side are set as one set corresponding to black (hereinafter referred to as B) and the like, and ink of each color is supplied to each nozzle. If they are arranged in parallel, a color image can be formed.

Here, in the recording method of the present embodiment, the surface tension of the diluent as the ejection medium is set to q (dyn / cm),
P (dyn / cm)
In this case, the relationship of qp ≧ 0 is established, and when these are mixed at a predetermined mixing ratio immediately before ejection, they are mixed with good mixing properties, and a mixed liquid with good mixing properties is obtained. Is discharged, and accurate gradation expression is enabled.

In the recording method of the present embodiment, when the viscosity of the ink as the quantifying medium is α (cp) and the viscosity of the diluting liquid as the ejection medium is β (cp), β-cp
The relationship of α ≧ 0 is established, the ejection after mixing these is performed stably, and the ejection stability is high.

Further, in the recording method of this embodiment, the time from mixing of the discharge medium and the quantitative medium to the application of the mixed liquid on the recording medium is set to 1 (msec) or less. The mixing property between the quantitative medium and the ejection medium is further improved while ensuring the positional accuracy, and more accurate gradation expression is enabled.

[0077]

Next, in order to confirm the effect of the present invention, the following experiment was conducted. That is, printing was performed using a printer having the above-described configuration while changing the physical properties of the ejection medium and the quantitative medium, and the characteristics were investigated. In addition, printing was performed while changing the time from the mixing of the ejection medium and the fixed amount medium to the application of the mixed liquid on the recording medium, and the characteristics thereof were investigated.

<Experimental Example 1> In this experimental example, a diluent was used as a discharge medium and ink was used as a quantitative medium. Diluent samples and ink samples having different surface tensions were prepared, and these samples were prepared as described above. The evaluation of the two-liquid mixing property was carried out by using it as a discharge medium and a quantitative medium of a suitable printer device.

[Experimental example 1-1] First, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were appropriately added thereto to obtain the surface tension and viscosity shown in Table 1 below (both values at a temperature of 20 ° C were shown). .) Were prepared. In the ink sample 1-1, C.I. I. Direct Yellow 50 was used, and C.I. I. Direct Yellow 87 was used, and C.I.
I. Ink sample 1 using Direct Red 83
-4, C.I. I. Direct Red 2
27 and the dye concentration was 3% by weight.

The surface tension was measured using a surface tension meter CBVP-Z (model name) manufactured by Kyowa Interface Chemical Co., Ltd.
The viscosity was measured by a viscometer DV-I manufactured by BROOK FIELD.
It measured using I + (model name).

[0081]

[Table 1]

Next, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were added as appropriate to obtain the viscosity and surface tension shown in Table 2 below (both at a temperature of 20).
The value at ° C is shown. Sample 1-1 having
~ 1-3 were prepared.

[0083]

[Table 2]

Subsequently, these ink samples 1-1 to 1-1
Using -4 and the diluent samples 1-1 to 1-3, the two liquids were quantitatively mixed and discharged, and the two-liquid mixing property was evaluated.

That is, the above ink samples 1-1 to 1-4
And the diluent samples 1-1 to 1-3 are combined to change the mixing ratio (ink density) of the two, and printing is carried out. The dots when they are deposited on the recording medium are observed with a microscope, and the dots in the dots are observed. Whether the concentration was uniform or not was evaluated and evaluated in the following three grades. That is, as shown in FIG. 5 (a), those in which the inside of the dots 11 are uniformly dyed are represented by "O"
As shown in FIG. 5 (b), a high density portion 12 can be confirmed in the dot 11, but there is no problem in practical use as △. As shown in FIG. The sample was not dyed, had a dark portion 12 formed only in a part thereof, and was evaluated as unacceptable.

The mixing ratio of the ink and the diluting liquid can be adjusted by the voltage, pulse width, and waveform of the printer head drive unit.
0% range.

In the evaluation, the discharge conditions were as follows. The voltage on the ejection side is 20 (V), and the pulse width is 80 (μs).
ec), and the voltage on the quantitative side is set to 20 (V) as the maximum value, and is changed as needed in accordance with the ratio.
0 (μsec). The ejection frequency is 5 (kHz), and the time from quantitative mixing to application to the recording medium is about 1
(Msec). The diameter of the discharge nozzle is 35 (μ
m), the diameter of the fixed quantity nozzle was set to 20 (μm), and the size of the dot diameter on the recording medium was set to 120 (μm).

The results are shown in Table 3 below together with the combination of the ink sample and the diluent sample and the ink concentration. Here, a in Table 3 shows the case where the ink: diluent is 50:50, b in Table 3 shows the case where the ink: diluent is 10:90, and c in Table 3 shows the case where the ink: diluent is 1:50. 99 is shown.

[0089]

[Table 3]

As can be seen from the results in Table 3, the surface tension q (dyn / cm) of the diluent sample as the discharge medium was obtained.
And the surface tension p (dyn of the ink sample as the quantification medium)
/ Cm) in a combination of a diluent sample and an ink sample having a relationship of qp ≧ 0, a good two-liquid mixing property is obtained, and when these are mixed at a predetermined mixing ratio immediately before ejection, Were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, and it was confirmed that accurate gradation expression was possible.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than that of the diluent sample as the discharge medium.

[Experimental Example 1-2] Next, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents, and these solvents were appropriately added.
In addition, non-ionic surfactants (Kao,
(Emulgen 985) was added to prepare ink samples 1-5 to 1-7 having the surface tension and viscosity shown in Table 4 below (all values at a temperature of 20 ° C.). In the ink sample 1-5, C.I. I. Direct Blue 6 was used, and C.I. I. Direct Blue 86 was used, and C.I. I. Direct Black 38 was used and the dye concentration was 5% by weight.

[0093]

[Table 4]

On the other hand, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents,
These solvents are appropriately added, and a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) is further added as a surfactant to obtain a surface tension and a viscosity shown in Table 5 below (both values at a temperature of 20 ° C.). Are shown.) To prepare diluent samples 1-4 to 1-6.

[0095]

[Table 5]

The ink samples 1-5 to 1-5
Using -7 and the diluent samples 1-4 to 1-6, quantitative mixing and discharging of the two liquids was performed in the same manner as in Experimental Example 1-1.
The mixability of the liquid was evaluated in the same manner as described above. The results are shown in Table 6 below. Table 6 also shows the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 3.

[0097]

[Table 6]

As can be seen from the results in Table 6, the surface tension q (dyn / cm) of the diluent sample as the discharge medium was obtained.
And the surface tension p (dyn of the ink sample as the quantification medium)
/ Cm) in a combination of a diluent sample and an ink sample having a relationship of qp ≧ 0, a good two-liquid mixing property is obtained, and when these are mixed at a predetermined mixing ratio immediately before ejection, Were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, and it was confirmed that accurate gradation expression was possible.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a better result was obtained when the ratio of the ink sample as the quantitative medium was smaller than that of the diluent sample as the discharge medium.

[Experimental Example 1-3] Next, water was used as a solvent.
-(2-butoxyethoxy) ethanol, triethanolamine and glycerin were used, and these solvents were appropriately added thereto to obtain an ink sample having the surface tension and viscosity (all values at a temperature of 20 ° C.) shown in Table 7 below. 1
-8 to 1-10 were prepared. Ink sample 1-
8 is C.I. I. Acid Yellow 23
Is used as the dye in the ink sample 1-9. I. Acid Red 27 was used, and C.I. I. Acid Blue 9 was used and the dye concentration was 3% by weight.

[0101]

[Table 7]

On the other hand, water, 2- (2-butoxyethoxy) ethanol, triethanolamine and glycerin were used as solvents, and these solvents were added as appropriate and the surface tension and viscosity (all at a temperature of 20 ° C.) shown in Table 8 below. The diluent samples 1-7 to 1-9 having the following values were prepared.

[0103]

[Table 8]

Further, a mixture of water and a small amount of glycerin was used as a solvent, and these solvents were appropriately added to adjust the surface tension to 70 (dyn / cm) and the viscosity to 1.5 (cp). This was designated as diluent sample 1-10.

Then, these ink samples 1-8 to 1
Using -10 and the diluent samples 1-7 to 1-10, two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 1-1, and the two-liquid mixing property was evaluated. The results are shown in Table 9 below. Table 9 also shows the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 3.

[0106]

[Table 9]

As can be seen from the results in Table 9, the surface tension q (dyn / cm) of the diluent sample as the discharge medium was obtained.
And the surface tension p (dyn of the ink sample as the quantification medium)
/ Cm) in a combination of a diluent sample and an ink sample having a relationship of qp ≧ 0, a good two-liquid mixing property is obtained, and when these are mixed at a predetermined mixing ratio immediately before ejection, Were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, and it was confirmed that accurate gradation expression was possible.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than that of the diluent sample as the discharge medium.

[Experiment 1-4] In the above Experiment 1-1, the time from the quantitative mixing to the attachment to the recording medium was set to about 1 (msec), but about 500 (μsec)
In the other manner, the two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 1-1, and the two-liquid mixing property was evaluated. The results are shown in Tables 10 to 12 below. Tables 10 to 12 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 3.

[0110]

[Table 10]

[0111]

[Table 11]

[0112]

[Table 12]

As can be seen from the results shown in Tables 10 to 12, the surface tension q (dy) of the diluent sample as the discharge medium was measured.
n / cm) and a combination of a diluent sample and an ink sample having a relationship of q-p ≧ 0 with respect to the surface tension p (dyn / cm) of the ink sample serving as the quantification medium, a good two-liquid mixing property is obtained. Was.

However, since the time from the quantitative mixing of the quantitation medium and the ejection medium to the attachment to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than that of the diluent sample as the discharge medium.

[Experimental Example 1-5] Further, the combination of each ink sample and the diluent sample used so far was changed, and quantitative mixing and discharging of the two liquids was performed in the same manner as in Experimental Example 1-4. The miscibility was evaluated. The results are shown in Tables 13 to 15 below. In Tables 13 to 15, similarly to Table 3, the mixing ratio of the ink and the diluent (ink concentration)
Is shown.

[0117]

[Table 13]

[0118]

[Table 14]

[0119]

[Table 15]

As can be seen from the results shown in Tables 13 to 15, the surface tension q (dy) of the diluent sample as the discharge medium was measured.
n / cm) and a combination of a diluent sample and an ink sample having a relationship of q-p ≧ 0 with respect to the surface tension p (dyn / cm) of the ink sample serving as the quantification medium, a good two-liquid mixing property is obtained It was confirmed that when these were mixed at a predetermined mixing ratio immediately before ejection, they were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, and accurate gradation expression was possible.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the ink sample as the quantifying medium than the diluent sample as the ejection medium showed a better result.

[Experimental Example 1-6] In the experimental example 1-5, the time from quantitative mixing to adhering to the recording medium was set to about 500 (msec), but about 100 (μsec)
The procedure of c) was repeated, and the other two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 1-5 to evaluate the mixing properties of the two liquids. The results are shown in Tables 16 to 18 below. Table 16
Also in Tables 1 to 18, the mixing ratio (ink concentration) between the ink and the diluent is shown in the same manner as in Table 3.

[0123]

[Table 16]

[0124]

[Table 17]

[0125]

[Table 18]

As can be seen from the results shown in Tables 16 to 18, the surface tension q (dy) of the diluent sample as the discharge medium was obtained.
n / cm) and a combination of a diluent sample and an ink sample having a relationship of q-p ≧ 0 with respect to the surface tension p (dyn / cm) of the ink sample serving as the quantification medium, a good two-liquid mixing property is obtained. Was.

However, the time from the quantitative mixing of the quantitation medium and the ejection medium to the deposition on the recording medium was the same as in Experimental Example 1-5
Since the mixing time is shorter than the above, the two-liquid mixing property is reduced, and it was confirmed that the time from the quantitative mixing to the application to the recording medium affects the two-liquid mixing property.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than the diluent sample as the discharge medium.

From the results of Experimental Example 1 described above, as in the recording method of the present invention, a fixed amount medium, which is an ink, is mixed with a discharge medium, which is a diluting liquid, at a predetermined mixing ratio immediately before discharging. When the diluted ink is applied on a recording medium, the surface tension of the ejection medium is q (dyn / cm), and the surface tension of the measurement medium is p (dyn / cm). When the ejection medium and the quantifying medium satisfying the relationship of qp ≧ 0 is used, the surface tension values of the quantifying medium and the ejection medium and the relationship between them are suitable for the mixing operation. It was confirmed that accurate gradation expression was possible.

<Experimental Example 2> In this experimental example, the ink was used as a discharge medium, the diluent was used as a quantification medium, diluent samples and ink samples having different surface tensions were prepared, and these samples were prepared as described above. The evaluation of the two-liquid mixing property was carried out by using it as a discharge medium and a quantitative medium of a suitable printer device.

[Experimental Example 2-1] First, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were appropriately added thereto to obtain the surface tension and viscosity shown in Table 19 below (both values at a temperature of 20 ° C. are shown). .) Were prepared. In the ink sample 2-1, C.I. I. Direct Yellow 50 was used, and C.I. I. Direct Yellow 87 was used, and C.I.
I. Direct Red 83 was used, and the dye concentration was 3% by weight.

The surface tension was measured using a surface tension meter CBVP-Z (model name) manufactured by Kyowa Interface Chemical Co., Ltd.
The viscosity was measured by a viscometer DV-I manufactured by BROOK FIELD.
It measured using I + (model name).

[0133]

[Table 19]

Next, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were added as appropriate to obtain the surface tension and viscosity shown in Table 20 below (both at a temperature of 2).
The value at 0 ° C. is shown. Diluent sample 2-) having
1-2 were prepared.

[0135]

[Table 20]

Subsequently, these ink samples 2-1 to 2
-3 and diluent samples 2-1 to 2-4, diluent samples 2-1 to 2-4 were used as quantification media, and ink samples 2-1 to 2-3 were used as ejection media. In the same manner as in Experimental Example 1-1, the two liquids were mixed and discharged in a fixed amount, and the two-liquid mixing property was evaluated.

The results are shown in Table 21 below together with the combination of the ink sample and the diluent sample and the ink concentration. However, a in Table 21 is 50: 5 for diluent: ink.
0 indicates the case of “0”, and “b” in Table 21 indicates that the dilution liquid: ink is 10:
90 is shown, and in Table 21 c, diluent: ink is 1:
99 is shown.

[0138]

[Table 21]

As can be seen from the results shown in Table 21, the surface tension q (dyn / c) of the ink sample serving as the ejection medium was obtained.
m) and the surface tension p (d
yn / cm) has a good 2 in the combination of the diluent sample and the ink sample having a relationship of qp ≧ 0.
Liquid mixing properties are obtained, and when they are mixed at a predetermined mixing ratio immediately before discharge, they are mixed with good mixing properties, and a mixed liquid with good mixing properties is discharged, and accurate gradation expression is possible. It was confirmed that.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantification medium than the ink sample as the ejection medium gave better results.

Experimental Example 2-2 Next, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents, and these solvents were added as appropriate.
In addition, non-ionic surfactants (Kao,
(Emulgen 985) was added to prepare ink samples 2-4 to 2-6 having the surface tension and viscosity shown in Table 22 below (all values at a temperature of 20 ° C.). In the ink sample 2-4, C.I. I. Direct Red 227 was used, and C.I. I. Direct Blue 6 was used, and C.I. I. Direct Blue 86 was used and the dye concentration was 5% by weight.

[0142]

[Table 22]

On the other hand, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents,
These solvents are appropriately added, and a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) is further added as a surfactant to obtain the surface tension and viscosity shown in Table 23 below (all values at a temperature of 20 ° C.). Are shown.) To prepare diluent samples 2-5 to 2-7.

[0144]

[Table 23]

Then, these diluent samples 2-5 to 2-5
-7 and the ink samples 2-4 to 2-6, the two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 2-1.
The mixability of the liquid was evaluated. The results are shown in Table 24 below.
Table 24 also shows the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 21.

[0146]

[Table 24]

As can be seen from the results shown in Table 24, the surface tension q (dyn / c) of the ink sample as the ejection medium was obtained.
m) and the surface tension p (d
yn / cm) has a good 2 in the combination of the diluent sample and the ink sample having a relationship of qp ≧ 0.
It was confirmed that a liquid mixture was obtained, a mixed liquid having a good mixture was discharged, and accurate gradation expression was possible.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantitative medium than the ink sample as the ejection medium showed better results.

[Experimental example 2-3] Next, water was used as the solvent.
-(2-butoxyethoxy) ethanol, triethanolamine, and glycerin were used, and these solvents were added as appropriate to obtain an ink sample having the surface tension and viscosity (all values at a temperature of 20 ° C.) shown in Table 25 below. 2-7 to 2-9 were prepared. Ink sample 2-
7, C.I. I. Acid Yellow 23
Is used as the dye in the ink sample 2-8. I. Acid Red 27, and C.I. I. Acid Blue 9
And the dye concentration was 3% by weight.

[0150]

[Table 25]

On the other hand, water, 2- (2-butoxyethoxy) ethanol, triethanolamine and glycerin were used as solvents.
Diluent samples 2-8 to 2-10 having the surface tension and viscosity shown in Table 2 (all values at a temperature of 20 ° C.).
Was prepared.

[0152]

[Table 26]

Then, these diluent samples 2-8 to 2
Using -10 and ink samples 2-7 to 2-9, two liquids were mixed and discharged in the same manner as in Experimental Example 2-1.
The two-liquid mixing property was evaluated. The results are shown in Table 27 below.
Table 27 also shows the mixture ratio (ink concentration) between the ink and the diluent in the same manner as in Table 21.

[0154]

[Table 27]

As can be seen from the results in Table 27, the surface tension q (dyn / c) of the ink sample serving as the ejection medium was obtained.
m) and the surface tension p (d
yn / cm) has a good 2 in the combination of the diluent sample and the ink sample having a relationship of qp ≧ 0.
It was confirmed that a liquid mixture was obtained, a mixed liquid having a good mixture was discharged, and accurate gradation expression was possible.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantitative medium than the ink sample as the ejection medium showed better results.

[Experimental example 2-4] The above experimental examples 2-1 to 2-
In 3, the time from the quantitative mixing to the attachment to the recording medium was set to about 1 (msec),
sec), and in the same manner as in Experimental Example 2-1 above, two-liquid quantitative mixing and discharge were performed, and the two-liquid mixing property was evaluated.
The results are shown in Tables 28 to 30 below. Tables 28-30
Also in Table 2, the mixing ratio (ink concentration) between the ink and the diluent is shown in the same manner as in Table 21.

[0158]

[Table 28]

[0159]

[Table 29]

[0160]

[Table 30]

As can be seen from the results of Tables 28 to 30, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm) and the diluent sample and the ink sample in which the surface tension p (dyn / cm) of the diluent sample as the quantification medium has a relationship of qp ≧ 0, a good two-liquid mixing property is obtained. Was done.

However, since the time from the quantitative mixing of the quantitative medium and the discharge medium to the application to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantitative medium than the ink sample as the ejection medium showed better results.

[Experimental Example 2-5] Further, the combination of each ink sample and the diluent sample used so far was changed, and two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 2-4. The miscibility was evaluated. The results are shown in Tables 31 to 33 below. Tables 31 to 33 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 21.

[0165]

[Table 31]

[0166]

[Table 32]

[0167]

[Table 33]

As can be seen from the results in Tables 31 to 33, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm) and the diluent sample and the ink sample in which the surface tension p (dyn / cm) of the diluent sample as the quantification medium has a relationship of qp ≧ 0, a good two-liquid mixing property is obtained. Was done.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantification medium than the ink sample as the ejection medium showed better results.

[Experimental Example 2-6] In the experimental example 2-5, the time from the quantitative mixing to the attachment to the recording medium was set to about 500 (μsec), but the time was changed to about 100 (μsec).
The procedure of c) was repeated, and the other two liquids were mixed and discharged in the same manner as in Experimental Example 2-5 to evaluate the mixing property of the two liquids. The results are shown in Tables 34 and 36 below. Tables 34 to 36 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Table 21.

[0171]

[Table 34]

[0172]

[Table 35]

[0173]

[Table 36]

As can be seen from the results shown in Tables 34 to 36, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm) and the diluent sample and the ink sample in which the surface tension p (dyn / cm) of the diluent sample as the quantification medium has a relationship of qp ≧ 0, a good two-liquid mixing property is obtained. Was done.

However, the time from the quantitative mixing of the quantitation medium and the ejection medium to the deposition on the recording medium was not described in Experimental Example 2-5.
Since the mixing time is shorter than the above, the two-liquid mixing property is reduced, and it was confirmed that the time from the quantitative mixing to the application to the recording medium affects the two-liquid mixing property.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantitative medium than the ink sample as the ejection medium showed a better result.

From the results of Experimental Example 2 described above, as in the recording method of the present invention, a fixed amount medium as a diluting liquid was mixed with a discharging medium as an ink at a predetermined mixing ratio immediately before discharging, and a diluted liquid as a mixed liquid was obtained. When the diluted ink is applied on a recording medium, the surface tension of the ejection medium is q (dyn / cm), and the surface tension of the measurement medium is p (dyn / cm). When the ejection medium and the quantifying medium satisfying the relationship of qp ≧ 0 is used, the surface tension values of the quantifying medium and the ejection medium and the relationship between them are suitable for the mixing operation. It was confirmed that accurate gradation expression was possible.

<Experimental Example 3> In this experimental example, diluent was used as a discharge medium and ink was used as a quantification medium. Diluent samples and ink samples having different surface tensions and viscosities were prepared, and these samples were used as described above. Using as a discharge medium and a quantitative medium of the printer device
The liquid mixing property and the discharge stability were evaluated.

[Experimental Example 3-1] First, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were appropriately added to obtain the surface tension and viscosity shown in Table 37 below (both values at a temperature of 20 ° C.). .) Were prepared. In the ink sample 3-1, C.I. I. Direct Yellow 50 was used, and C.I. I. Direct Yellow 87 was used, and C.I.
I. Using Direct Red 83, ink sample 3
-4, C.I. I. Direct Red 2
27, and C.I. I. Direct Blue 6 was used, and C.I. I. Direct Blue 86 was used, and C.I. I. Direct Black 38 was used, and C.I. I. Direct Black 154 was used and the dye concentration was 3% by weight.

The surface tension was measured using a surface tension meter CBVP-Z (model name) manufactured by Kyowa Interface Chemical Co., Ltd.
The viscosity was measured by a viscometer DV-I manufactured by BROOK FIELD.
It measured using I + (model name).

[0181]

[Table 37]

Next, water, isopropyl alcohol and glycerin were used, and these solvents were appropriately added.
Diluent sample 3-1 to 3-6 having the surface tension and viscosity shown in Fig. 8 (all values at a temperature of 20 ° C).
Was prepared.

[0183]

[Table 38]

Subsequently, these ink samples 3-1 to 3-3
Using -8 and diluent samples 3-1 to 3-6, quantitative mixing and discharging of the two liquids were performed in the same manner as in Experimental Example 1-1, and the two-liquid mixing properties and the discharge stability were evaluated.

Evaluation of the two-liquid mixing property was performed in the same manner as in the above-mentioned Experimental Example 1-1. On the other hand, the evaluation of the ejection stability was performed by the ink sample 3-1 to 3-8 and the diluent sample 3-1 to 3-
6, printing is performed by changing the ink density.
The degree of deviation of the print pattern formation position from the print pattern formation position when only the diluent sample was ejected was examined, and evaluated in the following three grades. That is, the case where the size of the shift was smaller than 30 μm was evaluated as ○, the case where the size of the shift was in the range of 30 μm to 60 μm was evaluated as Δ, and the case where the size of the shift was larger than 60 μm was evaluated as ×.

The printing pattern at this time is, as shown in FIG. 6, two adjacent circular patterns 41 and 42 each having a diameter of 120 μm indicated by D in FIG. Here, the circular patterns 41 and 42 will be described as patterns formed using only a diluent. That is,
A circular pattern 4 of circular patterns 43 and 44 in which a circular pattern similar to the above circular pattern is formed by mixed droplets.
5, the deviation from the formation position, that is, d in FIG.
_1, to measure the magnitude of the displacement indicated by d _2.

The results are shown in Tables 39 and 40 below together with the combinations of the ink samples and the diluent samples and the ink concentrations. However, in Tables 39 and 40, a is the ink:
In Tables 39 and 40, b indicates the case where the ink: diluent was 10:90, and Tables 39 and 4 indicate the case where the diluent was 50:50.
In 0, c indicates the case where the ink: diluent is 1:99. Then, in Tables 39 and 40, the results of the two-liquid mixing properties were mixed,
The result of ejection stability is indicated as ejection, and the same applies hereafter.

[0188]

[Table 39]

[0189]

[Table 40]

As can be seen from the results of Tables 39 and 40, the surface tension q (d
yn / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller result of the ratio of the ink sample as the quantitative medium than the diluent sample as the ejection medium showed a better result.

Experimental Example 3-2 Next, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents, and these solvents were added as appropriate.
In addition, non-ionic surfactants (Kao,
Ink samples 3-9 to 3-14 having the surface tension and viscosity shown in Table 41 below (both values at a temperature of 20 ° C.) were prepared by adding trade name: Emulgen 985). In the ink sample 3-9, C.I. I. Acid Yellow 23 and C.I. I. Acid Yellow 42 and C.I. I. Using Acid Red 27,
In the ink sample 3-12, C.I. I.
Using Acid Red 52, ink sample 3-13
Has C.I. I. Acid Blue 9 and C.I.
I. Use Acid Blue 15 and dye concentration of 3% by weight
And

[0193]

[Table 41]

On the other hand, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents,
These solvents are appropriately added, and a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) is further added as a surfactant to obtain the surface tension and viscosity shown in Table 42 below (both values at a temperature of 20 ° C.). The diluted solution samples 3-7 to 3-12 having the following formulas were prepared.

[0195]

[Table 42]

Then, these diluted solution samples 3-7 to 3
Using -12 and Ink Samples 3-9 to 3-14, quantitative mixing and discharging of two liquids were performed in the same manner as in Experimental Example 3-1 to evaluate two-liquid mixing properties and discharging stability. The results are shown in Tables 43 and 44 below. Tables 43 and 44 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 39 and 40.

[0197]

[Table 43]

[0198]

[Table 44]

As can be seen from the results of Tables 43 and 44, the surface tension q (d
yn / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the ink sample as the quantification medium than the diluent sample as the ejection medium showed better results.

[Experimental Example 3-3] Next, water as a solvent, 2
-Using (2-butoxyethoxy) ethanol, triethanolamine and glycerin, adding these solvents as appropriate, and further adding a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) as a surfactant. The surface tension and viscosity shown in Table 45 below (both at a temperature of 2
The value at 0 ° C. is shown. Ink sample 3-)
15-3-17 were prepared. Note that the ink sample 3-
In No. 15, C.I. I. Acid Black 2
4 was used, and C.I. I. Acid Black 72 and C.I. I. Acid Black 94 was used and the dye concentration was 3% by weight.

[0202]

[Table 45]

On the other hand, water, 2- (2-butoxyethoxy) ethanol, triethanolamine and glycerin were used as solvents, and these solvents were appropriately added.
In addition, non-ionic surfactants (Kao,
(Product name: Emulgen 985) was added to prepare diluent samples 3-13 to 3-15 having the surface tension and viscosity shown in Table 46 below (both values at a temperature of 20 ° C.).

[0204]

[Table 46]

Further, a mixture of water and a small amount of glycerin was used as a solvent, and these solvents were appropriately added to adjust the surface tension to 70 dyn / cm and the viscosity to 1.5 cp. 3-16.

Then, these diluent samples 3-13 to
Using 3-16 and Ink Samples 3-15 to 3-17, quantitative mixing and discharging of two liquids were performed in the same manner as in Experimental Example 3-1 to evaluate two-liquid mixing properties and discharging stability. The results are shown in Table 47 below. Table 47 also shows Table 39,
Similarly to 40, the mixing ratio (ink concentration) between the ink and the diluent is shown.

[0207]

[Table 47]

As can be seen from the results shown in Table 47, the surface tension q (dyn / c) of the diluent sample as the discharge medium was obtained.
m), the viscosity β (cp), the surface tension p (dyn / cm), and the viscosity α (cp)
In a combination of a diluent sample and an ink sample having a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property is obtained, and when these are mixed at a predetermined mixing ratio immediately before ejection. In addition, it was confirmed that these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than that of the diluent sample as the discharge medium.

[Experimental example 3-4] The above experimental examples 3-1 to 3-
In 3, the time from the quantitative mixing to the attachment to the recording medium was set to about 1 (msec),
sec), the other two liquids were mixed and discharged in the same manner as in Experimental Example 3-1 above, and the two-liquid mixing property and discharge stability were evaluated. The results are shown in Tables 48 to 51 below.
Tables 48 to 51 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 39 and 40.

[0211]

[Table 48]

[0212]

[Table 49]

[0213]

[Table 50]

[0214]

[Table 51]

As can be seen from the results of Tables 48 to 51, the surface tension q (dy) of the diluent sample as the discharge medium was obtained.
n / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In the combination of the diluent sample and the ink sample, in which p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property and ejection stability were obtained.

However, since the time from the quantitative mixing of the quantitation medium and the ejection medium to the application to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than the diluent sample as the discharge medium.

[Experimental Example 3-5] Further, the combination of each ink sample and the diluent sample used so far was changed, and two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 3-4. The miscibility was evaluated. The results are shown in Tables 52 to 55 below. Tables 52 to 55 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 39 and 40.

[0219]

[Table 52]

[0220]

[Table 53]

[0221]

[Table 54]

[0222]

[Table 55]

As can be seen from the results of Tables 52 to 55, the surface tension q (dy) of the diluent sample as the discharge medium was obtained.
n / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than the diluent sample as the discharge medium.

[Experimental Example 3-6] In the above Experimental Example 3-5, the time from the quantitative mixing to the attachment to the recording medium was set to about 500 (μsec), but the time was changed to about 100 (μsec).
The procedure of Example 3-5 was repeated, except that the two liquids were mixed and discharged in the same manner as in Experimental Example 3-5. The results are shown in Tables 56 to 59 below. Tables 56 to 59 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 39 and 40.

[0226]

[Table 56]

[0227]

[Table 57]

[0228]

[Table 58]

[0229]

[Table 59]

As can be seen from the results in Tables 56 to 59, the surface tension q (dy) of the diluent sample as the ejection medium was obtained.
n / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In the combination of the diluent sample and the ink sample, in which p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property and ejection stability were obtained.

However, since the time from the quantitative mixing of the quantitation medium and the ejection medium to the attachment to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the ink sample as the quantitative medium was smaller than the diluent sample as the discharge medium.

From the results of Experimental Example 3 described above, as in the recording method of the present invention, a fixed amount medium as an ink was mixed with a discharge medium as a diluent at a predetermined mixing ratio immediately before discharging, and a dilution liquid as a mixed liquid was obtained. When the diluted ink is applied on a recording medium, the surface tension of the ejection medium is q (dyn / cm), the viscosity is β (cp), and the viscosity is β (cp).
The surface tension of the measurement medium is p (dyn / cm), and the viscosity is α
When the ejection medium and the quantification medium satisfy the relationship of qp ≧ 0 and β−α ≧ 0 when (cp) is used, the values of the surface tension of the quantification medium and the ejection medium and the relationship thereof are obtained. It is made suitable for mixing operation and discharge operation,
It was confirmed that the ejection stability was ensured regardless of the material, and that accurate gradation expression was possible.

<Experimental Example 4> In this experimental example, the ink was used as a discharge medium, the diluent was used as a quantification medium, diluent samples and ink samples having different surface tensions and viscosities were prepared, and these samples were used as described above. Using as a discharge medium and a quantitative medium of the printer device
The liquid mixing property and the discharge stability were evaluated.

[Experimental Example 4-1] First, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were appropriately added thereto to obtain the surface tension and viscosity shown in Table 60 below (both values at a temperature of 20 ° C. are shown). .) Were prepared. In the ink sample 4-1, C.I. I. Direct Yellow 50 was used, and C.I. I. Direct Yellow 87 was used, and C.I.
I. Ink sample 4 using Direct Red 83
-4, C.I. I. Direct Red 2
27, and C.I. I. Direct Blue 6 was used, and C.I. I. Direct Blue 86 was used and the dye concentration was 3% by weight.

The surface tension was measured using a surface tension meter CBVP-Z (model name) manufactured by Kyowa Interface Chemical Co., Ltd.
The viscosity was measured by a viscometer DV-I manufactured by BROOK FIELD.
It measured using I + (model name).

[0237]

[Table 60]

Next, water, isopropyl alcohol and glycerin were used as solvents, and these solvents were added as appropriate to obtain the surface tension and viscosity shown in Table 61 below (both at a temperature of 2).
The value at 0 ° C. is shown. Diluent sample 4-)
1-4 were prepared.

[0239]

[Table 61]

Subsequently, these ink samples 4-1 to 4
Using -6 and the diluent samples 4-1 to 4-8, quantitative mixing and discharging of two liquids were performed in the same manner as in Experimental Example 1-1, and the two-liquid mixing properties and discharge stability were evaluated. The evaluation of the two-liquid mixing property was performed in the same manner as in Experimental Example 1-1, and the evaluation of ejection stability was performed in the same manner as in Experimental Example 3-1.

The results are shown in the following Table 62 and Table 63 together with the combination of the ink sample and the diluent sample and the ink concentration. However, in Tables 62 and 63, a is a diluent:
In Tables 62 and 63, “b” in Tables 62 and 63 indicates the case where the ratio of diluent: ink was 10:90.
C in 3 shows the case where the ratio of the diluent: ink is 1:99. Then, in Tables 39 and 40, the results of the two-liquid mixing properties were mixed,
The result of ejection stability is indicated as ejection, and the same applies hereafter.

[0242]

[Table 62]

[0243]

[Table 63]

As can be seen from the results of Tables 62 and 63, the surface tension q (d
yn / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the diluent sample as the quantitative medium was smaller than that of the ink sample as the ejection medium.

Experimental Example 4-2 Next, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents, and these solvents were added as appropriate.
In addition, non-ionic surfactants (Kao,
(Emulgen 985) was added to prepare ink samples 4-7 to 4-12 having the surface tension and viscosity shown in Table 64 below (all values at a temperature of 20 ° C.). In the ink sample 4-7, C.I. I. Acid Yellow 23, and C.I. I. Acid Yellow 42 and C.I. I. Acid Red 27 was used, and C.I. I. Acid Red 52 was used, and C.I. I. Using Acid Blue 9,
In the ink sample 4-12, C.I. I.
Acid Blue 15 was used and the dye concentration was 3% by weight.

[0247]

[Table 64]

On the other hand, water, ethylene glycol monomethyl ether and diethylene glycol were used as solvents,
These solvents are appropriately added, and a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) is further added as a surfactant to obtain a surface tension and a viscosity shown in Table 65 below (both values at a temperature of 20 ° C.). The diluent samples 4-9 to 4-14 having the following formulas were prepared.

[0249]

[Table 65]

Then, these diluent samples 4-9 to 4-4
Using -14 and ink samples 4-7 to 4-12, quantitative mixing and discharging of two liquids were performed in the same manner as in Experimental Example 4-1 to evaluate two-liquid mixing properties and discharging stability. The results are shown in Tables 66 and 67 below. Tables 66 and 67 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 62 and 63.

[0251]

[Table 66]

[0252]

[Table 67]

As can be seen from the results in Tables 66 and 67, the surface tension q (d
yn / cm), viscosity β (cp), surface tension p (dyn / cm), viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the diluent sample as the quantitative medium was smaller than that of the ink sample as the ejection medium.

[Experimental Example 4-3] Next, water as a solvent, 2
-Using (2-butoxyethoxy) ethanol, triethanolamine and glycerin, adding these solvents appropriately, and further adding a nonionic surfactant (trade name: Emulgen 985, manufactured by Kao) as a surfactant. The surface tension and viscosity shown in Table 68 below (both at a temperature of 2
The value at 0 ° C. is shown. Ink sample 4-)
13-4-15 were prepared. Ink sample 4-
In C.13, C.I. I. Acid Black 2
No. 4 was used, and C.I. I. Acid Black 72, and C.I. I. Acid Black 94 was used and the dye concentration was 3% by weight.

[0256]

[Table 68]

On the other hand, water, 2- (2-butoxyethoxy) ethanol, triethanolamine and glycerin were used as solvents, and these solvents were appropriately added.
In addition, non-ionic surfactants (Kao,
A trade name: Emulgen 985) was added to prepare diluent samples 4-15 to 4-17 having the surface tension and viscosity shown in Table 69 below (both values at a temperature of 20 ° C.).

[0258]

[Table 69]

Then, these diluent samples 4-15 to
Using 4-17 and Ink Samples 4-13 to 4-15, quantitative mixing and ejection of two liquids were performed in the same manner as in Experimental Example 4-1 to evaluate two-liquid mixing properties and ejection stability. The results are shown in Table 70 below. Also in Table 70, Tables 62 and 6
Mixing ratio of ink and diluent (ink concentration) in the same manner as in 3.
Is shown.

[0260]

[Table 70]

As can be seen from the results shown in Table 70, the surface tension q (dyn / c) of the ink sample as the ejection medium was obtained.
m), viscosity β (cp), surface tension p (dyn / cm), and viscosity α (cp)
In a combination of a diluent sample and an ink sample having a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property is obtained, and when these are mixed at a predetermined mixing ratio immediately before ejection. It was confirmed that these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the diluent sample as the quantitative medium was smaller than that of the ink sample as the discharge medium.

[Experimental Example 4-4] Experimental Examples 4-1 to 4-
In Example 2, the time from the quantitative mixing to the attachment to the recording medium was set to about 1 (msec) by about 500 (μm).
sec), the other two liquids were mixed and discharged in the same manner as in Experimental Example 4-1 to evaluate the two-liquid mixing property and discharge stability. The results are shown in Tables 71 to 74 below.
Also in Tables 71 to 74, the mixing ratio (ink concentration) between the ink and the diluent is shown in the same manner as in Tables 62 and 63.

[0264]

[Table 71]

[0265]

[Table 72]

[0266]

[Table 73]

[0267]

[Table 74]

As can be seen from the results shown in Tables 71 to 74, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm), the viscosity β (cp), the surface tension p (dyn / cm), and the viscosity α (c
In the combination of the diluent sample and the ink sample, in which p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property and ejection stability were obtained.

However, since the time from the quantitative mixing of the quantitation medium and the ejection medium to the application to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

In addition, when the combination of the diluent sample and the ink sample was the same, it was found that a smaller ratio of the diluent sample as the quantitative medium than the ink sample as the ejection medium showed better results.

[Experimental Example 4-5] Furthermore, the combination of each ink sample and the diluent sample used so far was changed, and two liquids were quantitatively mixed and discharged in the same manner as in Experimental Example 4-4. The miscibility was evaluated. The results are shown in Tables 75 to 78 below. Tables 75 to 78 also show the mixing ratio (ink concentration) between the ink and the diluting liquid in the same manner as in Tables 62 and 63.

[0272]

[Table 75]

[0273]

[Table 76]

[0274]

[Table 77]

[0275]

[Table 78]

As can be seen from the results in Tables 75 to 78, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm), the viscosity β (cp), the surface tension p (dyn / cm), and the viscosity α (c
In a combination of a diluent sample and an ink sample, where p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing properties are obtained, and these are mixed immediately before ejection at a predetermined mixing ratio. It was confirmed that when these were mixed, these were mixed with good mixing properties, a mixed liquid with good mixing properties was discharged, accurate gradation expression was possible, and discharge stability was good.

Further, when the combination of the diluent sample and the ink sample was the same, it was found that better results were obtained when the ratio of the diluent sample as the quantitative medium was smaller than that of the ink sample as the discharge medium.

[Experimental Example 4-6] In the above Experimental Example 4-5, the time from the quantitative mixing to the attachment to the recording medium was set to about 500 (μsec), but the time was changed to about 100 (μsec).
The procedure of Example 4-5 was repeated, except that the two liquids were mixed and discharged in the same manner as in Experimental Example 4-5, and the two-liquid mixing properties and discharge stability were evaluated. The results are shown in Tables 79 to 82 below. Tables 79 to 82 also show the mixing ratio (ink concentration) between the ink and the diluent in the same manner as in Tables 62 and 63.

[0279]

[Table 79]

[0280]

[Table 80]

[0281]

[Table 81]

[0282]

[Table 82]

As can be seen from the results shown in Tables 79 to 82, the surface tension q (dy) of the ink sample serving as the ejection medium was obtained.
n / cm), the viscosity β (cp), the surface tension p (dyn / cm), and the viscosity α (c
In the combination of the diluent sample and the ink sample, in which p) has a relationship of qp ≧ 0 and β−α ≧ 0, good two-liquid mixing property and ejection stability were obtained.

However, since the time from the quantitative mixing of the quantitation medium and the ejection medium to the application to the recording medium was shorter than in the previous experiments, the two-liquid mixing property was reduced. It was confirmed that the time from mixing to application to the recording medium affects the two-liquid mixing properties.

Further, it was found that, when the combination of the diluent sample and the ink sample was the same, a better result was obtained when the ratio of the diluent sample as the quantitative medium was smaller than that of the ink sample as the ejection medium.

From the results of Experimental Example 4 described above, as in the recording method of the present invention, a diluting ink was prepared by mixing a discharge medium, which is an ink, with a quantitative medium, which is a diluent, at a predetermined mixing ratio immediately before discharging. When depositing the diluted ink on the recording medium,
As the ejection medium and the quantification medium, the surface tension of the ejection medium is q
(Dyn / cm), the viscosity is β (cp), the surface tension of the quantification medium is p (dyn / cm), and the viscosity is α (cp), qp ≧ 0 and β−α ≧ 0 If a discharge medium and a quantitation medium are used such that the relationship holds, the surface tension values of the quantification medium and the discharge medium and the relationship between them are suitable for the mixing operation and the discharge operation. It was confirmed that ejection stability was ensured and accurate gradation expression was possible.

[0287]

As is clear from the above description, in the recording method of the present invention, the surface tension of the ejection medium is set to q (d
yn / cm) and the surface tension of the quantification medium is p (dyn / cm
cm), a discharge medium and a quantitative medium satisfying the relationship of qp ≧ 0 are used, and these are mixed at a predetermined mixing ratio immediately before discharge, and the mixed liquid is discharged to cover the recording medium. Since the surface tension of the discharge medium and the quantitative medium has the above-described relationship, their mixing properties are good,
A mixed liquid with good mixing properties is discharged, and accurate gradation expression is possible.

In the recording method of the present invention, the viscosity of the quantitation medium is α (cp) and the viscosity of the ejection medium is β
In the case of (cp), if the relationship of β−α ≧ 0 is established, the ejection after mixing these is performed stably, and the ejection stability is improved.

Further, in the recording method of the present invention, if the time from mixing of the ejection medium and the fixed amount medium to the application of the mixed liquid on the recording medium is set to 1 (msec) or less, a practical printing speed and ejection can be achieved. The mixing property between the quantitative medium and the ejection medium is further improved while ensuring the positional accuracy, and more accurate gradation expression is possible.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a main part showing a printer device.

FIG. 2 is a schematic plan view of an essential part showing an enlarged orifice plate of the printer device.

FIG. 3 is an enlarged schematic plan view of a main part of a modified example of a nozzle of an orifice plate of the printer device.

FIG. 4 is a sectional view illustrating a recording operation of the printer in order.

FIG. 5 is a schematic diagram showing a stage of a dot density.

FIG. 6 is a schematic diagram showing a print pattern.

[Explanation of symbols]

1 Nozzle on the discharge side, 2 nozzle on the fixed amount side, 3 orifice plate, 4 transparent solvent, 5 transparent solvent supply channel,
6 ink, 7 ink supply channel, 8 transparent solvent meniscus, 9 ink meniscus, 10 mixed liquid

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

[0001] The present invention relates to a recording method,
Particularly, the present invention relates to a recording method in which the density in dots is made uniform by making the correlation between the physical values of the ejection medium and the quantification medium appropriate, accurate gradation expression is possible, and the ejection stability is good.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

Further, in the case of the conventional ink jet recording system, only the ink is ejected, so that the only consideration is to make the physical properties of the ink suitable for the ejection operation. However, in the method of mixing two liquids such as the carrier jet method in which the ink and the diluting liquid are mixed and discharged immediately before the discharging as described above, an operation that the ink is measured and mixed with the diluting liquid is added. ,
It is necessary to make the physical properties of each liquid suitable not only for the discharging operation but also for the mixing operation. That is, in the two-liquid mixing method, it is important how quickly these two liquids are mixed during the mixing operation of the two types of liquids, that is, the ejection medium and the quantitative medium. If the two liquids are mixed poorly, there will be inconveniences such as the dot not becoming a predetermined size and the shading of density within the dot, making accurate gradation expression impossible. In consideration of the above, the mutual relationship between the physical properties of the ink and the diluent becomes important.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Therefore, the present invention has been proposed in view of such circumstances. By optimizing the correlation between the physical properties of the ink and the diluting liquid, the density in the dots becomes uniform and accurate. It is an object of the present invention to provide a recording method which enables gradation expression and has good ejection stability.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

[0021]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made the following studies. The present inventors have focused on the surface tension among the physical properties of the liquids, and studied to make the two liquids suitable for the mixing operation. The surface tension is a measure of the wetting of an object, and a liquid having a low surface tension makes a partner easily wet. On the other hand, a liquid having a high surface tension is unlikely to be wet with the other party, and the action of itself to be united becomes very strong. Then, it was examined whether or not these properties can be used in a two-liquid mixing system. Then, when the surface tension of the ejection medium is increased to improve the unity of the ejection medium, and at the same time, the surface tension of the measurement medium is decreased by quantifying the measurement medium to the ejection medium, the measurement medium wets the surface of the ejection medium. It has been found that such behavior is exhibited. That is, it has been found that by setting the surface tension of the ejection medium to be equal to or higher than the surface tension of the quantitative medium, these mixing operations are performed smoothly, and the density in the dots becomes uniform.
Therefore, the present invention provides a recording method in which a quantitative medium is mixed with a discharge medium at a predetermined mixing ratio immediately before ejection, and the mixed liquid is ejected and deposited on a recording medium.
(Dyn / cm), and the surface tension of the ejection medium is q (dy).
n / cm), the relationship that qp ≧ 0 holds. When the relationship between the surface tension of the quantitation medium and the surface tension of the ejection medium is reversed, the ejection medium passes through the surface of the quantification medium, so that the quantification medium suddenly penetrates into the ejection medium, and the density in the dots tends to become uneven.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

In the recording method of the present invention, when the surface tension of the ejection medium is q (dyn / cm) and the surface tension of the quantitative medium is p (dyn / cm), the relationship of qp ≧ 0 is satisfied. Using a discharge medium and a quantitative medium that are established, they are mixed at a predetermined mixing ratio immediately before discharge, and the mixed liquid is discharged and adhered onto a recording medium. Therefore, when the quantification medium is quantified into the ejection medium, the quantitation medium wets the surface of the ejection medium, the mixing operation is performed smoothly, and the mixture having good mixing properties is ejected.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Here, in the recording method of the present embodiment, the surface tension of the diluent as the ejection medium is set to q (dyn / cm),
P (dyn / cm)
In this case, the relationship of qp ≧ 0 is established, and when these are mixed at a predetermined mixing ratio immediately before discharge, the quantitative medium wets the surface of the discharge medium, and the mixing operation of these is performed. Smoothly, a mixed liquid with good mixing properties is discharged, and accurate gradation expression is enabled.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0287

[Correction method] Change

[Correction contents]

[0287]

As is clear from the above description, in the recording method of the present invention, the surface tension of the ejection medium is set to q (d
yn / cm) and the surface tension of the quantification medium is p (dyn / cm
cm), a discharge medium and a quantitative medium satisfying the relationship of qp ≧ 0 are used, and these are mixed at a predetermined mixing ratio immediately before discharge, and the mixed liquid is discharged to cover the recording medium. Since the surface tension of the discharge medium and the quantitation medium has the above-mentioned relationship, when the quantification medium is quantified into the discharge medium, the quantitation medium wets the surface of the discharge medium, and the mixing operation of these is smooth. The mixture is discharged with good mixing properties, and accurate gradation expression is possible.

Claims (30)

[Claims] 1. A recording method in which a quantitation medium is mixed with a discharge medium at a predetermined mixing ratio immediately before ejection, and the mixed liquid is ejected and deposited on a recording medium, wherein the surface tension of the quantitation medium is p (dyn / cm) and the surface tension of the ejection medium is q (dyn / cm), q-p
A recording method, wherein a relationship of ≧ 0 is established. 2. The recording method according to claim 1, wherein the time from mixing of the ejection medium and the fixed amount medium to the application of the mixed liquid on the recording medium is 1 (msec) or less. 3. The recording method according to claim 1, wherein the quantifying medium is an ink, and the ejection medium is a diluting liquid. 4. The measurement medium has a surface tension of 25 to 60 (dy).
n / cm) and the surface tension of the ejection medium is 30 to 70 (dyn).
/ Cm). 5. The recording method according to claim 3, wherein the solvent of the quantification medium comprises water and a water-soluble organic solvent. 6. The recording method according to claim 5, wherein the quantification medium contains a surfactant. 7. The recording method according to claim 3, wherein the solvent of the ejection medium comprises water and a water-soluble organic solvent. 8. The recording method according to claim 7, wherein the ejection medium contains a surfactant. 9. The recording method according to claim 1, wherein the quantification medium is a diluting liquid, and the ejection medium is an ink. 10. The measuring medium has a surface tension of 25 to 60 (d).
yn / cm), and the surface tension of the ejection medium is 30 to 60 (dy).
10. The recording method according to claim 9, wherein n / cm). 11. The recording method according to claim 9, wherein the solvent of the quantification medium comprises water and a water-soluble organic solvent. 12. The recording method according to claim 11, wherein the quantification medium contains a surfactant. 13. The recording method according to claim 9, wherein the solvent of the ejection medium comprises water and a water-soluble organic solvent. 14. The recording method according to claim 13, wherein the ejection medium contains a surfactant. 15. The recording according to claim 1, wherein when the viscosity of the quantification medium is α (cp) and the viscosity of the ejection medium is β (cp), a relationship of β−α ≧ 0 is established. Method. 16. The recording method according to claim 15, wherein the time from mixing of the ejection medium and the fixed amount medium to the application of the liquid mixture on the recording medium is 1 (msec) or less. 17. The recording method according to claim 15, wherein the quantification medium is ink and the ejection medium is a diluting liquid. 18. The surface tension of the measurement medium is 25 to 60 (d
yn / cm) and the surface tension of the ejection medium is 30 to 70 (dy).
18. The recording method according to claim 17, wherein the value is n / cm). 19. The viscosity of the measurement medium is 1 to 15 (cp),
18. The recording method according to claim 17, wherein the viscosity of the ejection medium is 1 to 15 (cp). 20. The recording method according to claim 17, wherein the solvent of the quantification medium comprises water and a water-soluble organic solvent. 21. The recording method according to claim 20, wherein the quantification medium contains a surfactant. 22. The recording method according to claim 17, wherein the solvent of the ejection medium comprises water and a water-soluble organic solvent. 23. The recording method according to claim 22, wherein the ejection medium contains a surfactant. 24. The recording method according to claim 15, wherein the quantification medium is a diluting liquid, and the ejection medium is an ink. 25. The measurement medium has a surface tension of 25 to 60 (d)
yn / cm), and the surface tension of the ejection medium is 30 to 60 (dy).
25. The recording method according to claim 24, wherein n / cm). 26. The measuring medium has a viscosity of 1 to 15 (cp),
The recording method according to claim 24, wherein the viscosity of the ejection medium is 1 to 15 (cp). 27. The recording method according to claim 24, wherein the solvent of the quantification medium comprises water and a water-soluble organic solvent. 28. The recording method according to claim 27, wherein the quantification medium contains a surfactant. 29. The recording method according to claim 24, wherein the solvent of the ejection medium comprises water and a water-soluble organic solvent. 30. The recording method according to claim 29, wherein the ejection medium contains a surfactant.