JPH09255907A - Diluent and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diluent which can yield recorded images having improved waterproofness by incorporating a water-insoluble resin into a diluent which is mixed in a given amt. with an ink and ejected and deposited as mixed droplets onto a recording material. SOLUTION: This diluent, which is mixed in a given amt. with an ink and ejected and deposited as mixed droplets onto a recording material, comprises at least a water-insoluble resin. Pref., the water-insoluble resin is contained in an amt. of 1 to 50wt.% in the diluent. The resin may be contained as an emulsion or one soluble in a solvent contg. an aliph. monohydric alcohol or polyhydric alcohol (deriv.). The diluent may further comprise 0.1 to 20wt.% compd. selected among cyanoacrylate compds. of formula I (wherein R1 represents CN; and R2 represents an alkyl), benzophenone compds. of formula II, and benzotriazole compds. of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diluting liquid which is fixedly mixed with ink, discharged as mixed droplets, and deposited on a recording material, and a recording method using the same. More specifically, the present invention relates to a diluting liquid that contains a water-insoluble resin to improve the water resistance of a recorded image, and a recording method using the same.

[0002]

2. Description of the Related Art In recent years, especially in offices and the like, document creation using a computer called desktop publishing has become popular, and recently, not only characters and figures but also colors such as photographs are displayed. There is an increasing demand for outputting natural images together with characters and figures. Furthermore, in the field of personal use, the production of New Year's cards, greeting cards, and the like has been actively performed, and the above-mentioned demands have been increasing. Along with this, it is required to print a high-quality natural image, and gradation expression by halftone display is important.

A so-called on-demand type in which ink droplets are ejected from nozzles only when necessary during printing in accordance with a control signal in accordance with a recording signal and are adhered to a recording material such as paper or film to perform recording. In recent years, the printer device has been rapidly spreading because of the possibility of miniaturization and cost reduction.

As described above, various methods have been proposed for discharging ink droplets from nozzles.
A method using a piezo element or a method using a heating element is generally used. The former is a method in which pressure is applied to ink to discharge it by deformation of a piezo element. The latter is a method in which the ink in the nozzle is heated and vaporized by the heating element, and the ink is ejected at the pressure of bubbles generated.

Various methods have been proposed as methods for simulating the above-described gray scale display by halftone display with an on-demand type printer apparatus which discharges the above-described ink droplets. That is, the first method is to control the size of a droplet to be ejected by changing the voltage or the pulse width of the voltage pulse applied to the piezo element or the heating element, and to express the gradation by changing the diameter of the print dot. To be

However, in the first method, if the voltage or pulse width applied to the piezo element or the heating element is too low, the ink will not be ejected, so that the minimum droplet diameter is limited. It has the disadvantage of being very difficult to express, especially at low concentrations. Therefore,
It is unsatisfactory to print out natural images.

As a second method, one pixel is constituted by a matrix of, for example, 4 × 4 dots without changing the dot diameter, and image processing such as a so-called dither method or an error diffusion method is performed in units of the matrix. There is a method for performing gradation expression. 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, also in the second method, when one pixel is constituted by a 4 × 4 matrix, a density of 17 gradations can be expressed. For example, the dot density is the same as that of the first method. When printed, the resolution is reduced to 1/4, and the roughness is conspicuous, which is also unsatisfactory for printing out a natural image.

If the image processing is strict in order to solve this inconvenience, it is not preferable because the circuit becomes complicated and the arithmetic processing speed is reduced, that is, the printout time is lengthened.

In order to solve the problem of the conventional on-demand type printer device in principle, the inventors of the present invention used ink and a transparent solvent as disclosed in Japanese Patent Application Laid-Open No. Hei 5-201024. A printer device has been proposed in which a certain diluting liquid is mixed at a predetermined mixing ratio immediately before ejection to form a diluted ink, and the diluted ink is immediately ejected from a nozzle and applied to a recording material to perform recording. Hereinafter, among such methods, a method using ink as a quantifying medium and using a diluting liquid as a discharge medium is referred to as a carrier jet method. There is no problem at all. .

In such a printer of the carrier jet system, it is possible to control the density of the diluted ink droplets to be discharged and to change the density for each dot to be printed, thereby causing a deterioration in resolution. It is possible to print out a natural image rich in intermediate gradations without any problem.

Further, in the printer apparatus to which the carrier jet method is applied, the degree of freedom of the constituent materials of the ink and the diluting liquid is considerably large.

[0013]

By the way, in such a carrier jet type printer, a water-soluble direct dye is used as ink similarly to a conventional printer (hereinafter referred to as an ink jet type printer). And acid dyes are mainly used. On the other hand, as the recording material, plain paper or special paper having a dye receiving layer formed on a support is used. The dye-receiving layer of this special paper contains a water-soluble polymer with excellent affinity for dyes, an organic or inorganic filler material, and other auxiliary materials. Is controlling.

After the direct dye in the ink is transferred to the dye receiving layer as represented by the theory of dyeing of the direct dye, the direct dye interacts with the components of the dye receiving layer such as van der Waals force and hydrogen bonding. It is held in the receiving layer by the action force. On the other hand, acidic dyes are generally said to have a low molecular weight and a high water solubility.

Therefore, from these facts, if water adheres to the surface of the dedicated paper on which a recording image formed by the ink containing the above-mentioned dye is formed, the dye may flow out, and the durability is not good. Absent. When plain paper is used as the recording material, such a problem is more remarkable.

Further, when the dye forming the recorded image is exposed to light such as ultraviolet rays, the dye molecules themselves are destroyed, and the image may be discolored, discolored or reduced in density. Therefore, a recorded image formed with an ink containing such a dye has low light fading resistance, and its durability is not good.

Various measures have been taken to resolve these inconveniences. That is, a cover film provided with an adhesive layer made of a known adhesive on one main surface side of an organic polymer film made of transparent polyester having light transparency is adhered to the recording image forming surface of a recording material. The water resistance and scratch resistance of the recorded image are imparted, and the cover film is made to contain, for example, an organic ultraviolet absorber to reduce the photobleaching of the recorded image.

However, in order to dispose such a cover film on a recorded image of a recording material, a step of attaching the cover film is newly required, and equipment such as a laminator for performing this step is required. This necessitates an increase in the size of the printer device and an increase in the processing time, leading to a decrease in productivity.

In the recorded image formed as described above, water resistance is a particularly important characteristic, and it is an important subject to ensure this.

Accordingly, the present invention has been proposed in view of the conventional circumstances, and has as its object to provide a diluent and a recording method capable of improving the durability, particularly the water resistance, of an image. .

[0021]

As a result of diligent studies by the present inventors in order to solve the above-mentioned problems, as a result, they are quantitatively mixed with ink, ejected as mixed droplets, and diluted on a recording material. It has been found that the inclusion of a water-insoluble polymer in the liquid can improve the water resistance of a recorded image formed by adhering mixed droplets of an ink and a diluting liquid to a recording material. .

That is, the present invention is characterized in that at least a water-insoluble resin is contained in the diluting liquid which is quantitatively mixed with the ink and is ejected as mixed droplets to be deposited on the recording material. is there.

The above water-insoluble resin is added to the diluting solution at 1%.
It is preferably contained in a proportion of 50% by weight to 50% by weight. When the content of the water-insoluble resin is less than 1% by weight,
The effect of improving the water resistance is weak, and the effect of improving the water resistance does not change even if the amount is more than 50% by weight. Further, the drying property of the diluting liquid is impaired, and the nozzle is easily clogged. Furthermore, considering the stability of the diluted solution, 3
It is preferably contained in a proportion of 30% by weight to 30% by weight.

In the diluting solution of the present invention, a water-insoluble resin may be contained as an emulsion, and a urethane resin, a styrene resin, an acrylic resin, a vinyl acetate resin, a vinylidene chloride resin or the like may be prepared as an emulsion using water as a solvent. It is preferably contained. In addition, an emulsifier, a stabilizer, and other additives may be added to the emulsion as needed.

Further, in the diluting solution of the present invention, the water-insoluble resin may be soluble in a solvent containing at least one of an aliphatic monohydric alcohol, a polyhydric alcohol and a polyhydric alcohol derivative. .

Examples of the above water-insoluble resins include resins soluble in at least one of aliphatic monohydric alcohols, polyhydric alcohols and polyhydric alcohol derivatives. Polyamide resins, polyvinyl butyral resins Butyral resin and the like are exemplified.

Further, examples of the water-insoluble resin as described above include resins soluble in a mixed solvent of at least one kind of an aliphatic monohydric alcohol, a polyhydric alcohol and a polyhydric alcohol derivative and water. Examples include modified polyvinyl acetal resin, hydroxypropylmethyl cellulose acetate succinate, cellulose derivatives such as cellulose acetate, ethylene-vinyl alcohol copolymer and the like.

When the water-insoluble resin is soluble in a solvent containing at least one of an aliphatic monohydric alcohol, a polyhydric alcohol and a polyhydric alcohol derivative,
These solvents are preferably contained in the diluting liquid, and the content thereof is preferably 1% by weight or more based on the total amount of the diluting liquid, from the viewpoint of the solubility of the resin. The upper limit of the content of these solvents is not particularly limited, but the total of these solvents may be the balance of the diluent. Needless to say, the diluent of the present invention may contain various additives such as stabilizers.

Examples of the above aliphatic monohydric alcohols include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, s-butyl alcohol and t-butyl alcohol. Among these monohydric alcohols, ethyl alcohol, isopropyl alcohol and n-butyl alcohol are preferably used. This monohydric alcohol improves the penetrability of the diluted ink, which is a mixed solution of the diluting liquid and the ink, into a recording material such as plain paper or special paper, the dot forming property, and the drying property of the printed recorded image.

On the other hand, as the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol,
Examples thereof include alkylene glycols such as glycerol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and thioglycol.

Further, as the polyhydric alcohol derivative,
Examples include lower alkyl ethers of the above polyhydric alcohols such as ethylene glycol dimethyl ether, cellosolve and diethylene glycol monomethyl ether, and lower carboxylic acid esters of the above polyhydric alcohols such as ethylene glycol diacetate. These polyhydric alcohols and their derivatives prevent clogging of the nozzles of the printer and, when water is contained in the diluting liquid, lower the freezing point and improve the storage stability.

When the diluent contains at least one of the above solvents and water, alcohol amines such as mono-, di-, triethanolamine, amides such as dimethylformamide and dimethylacetamide, Ketones such as acetone and methyl ethyl ketone, and ethers such as dioxane may be added.

By the way, also in a recorded image formed by a carrier jet type printer device, the photofading resistance is an important characteristic as described above, and the improvement of the photofading resistance is also desired.

Then, as a result of diligent study by the present inventors,
In the diluting solution of the present invention containing a water-insoluble resin as described above, a cyanoacrylate compound having a predetermined structure,
It has been found that it is possible to improve the light fading resistance of a recorded image by including either a benzophenone compound having a predetermined structure or a benzotriazole compound having a predetermined structure.

That is, the diluting solution of the present invention may contain a cyanoacrylate compound having a structure represented by the following chemical formula 4 together with the water-insoluble resin.

[0036]

Embedded image

The cyanoacrylate compound is preferably contained in a proportion of 0.1% by weight to 20% by weight, and the content of the cyanoacrylate compound is less than 0.1% by weight. However, the effect of improving the photo-fading resistance of the image is weak, and if it is more than 20% by weight, the dispersibility of the cyanoacrylate compound in the diluting solution is lowered, which is not preferable.

A specific example of the cyanoacrylate compound is BA having a structure shown in Chemical formula 5.
Examples thereof include Uvinul N35 (trade name) manufactured by SF Co., Ltd., Uvinul N539 (trade name) manufactured by BASF Co., Ltd., which has a structure shown in Chemical formula 6.

[0039]

Embedded image

[0040]

[Chemical 6]

Further, the diluting solution of the present invention may contain a benzophenone compound having a structure represented by the following chemical formula 7 together with the water-insoluble resin.

[0042]

Embedded image

The benzophenone compound is
It is preferably contained in a proportion of 0.1% by weight to 20% by weight. Content of benzophenone compound is 0.1
If it is less than 20% by weight, the effect of improving the photofading resistance of the image is weak, and if it is more than 20% by weight, the dispersibility of the benzophenone compound in the diluting solution is lowered, which is not preferable.

Specific examples of the above-mentioned benzophenone compounds include SEESORB 100 (trade name) manufactured by Cypro Kasei Co., Ltd., which has a structure shown in Chemical formula 8, and a cipro having a structure shown in Chemical formula 9. SEESORB 101 (trade name) manufactured by Kasei Co., Ltd., SEES manufactured by Cipro Kasei Co., Ltd., having a structure shown in Chemical formula 10
ORB 101S (trade name), SEESORB manufactured by Cypro Kasei Co., Ltd., having a structure shown in Chemical formula 11
102 (trade name) and SEESORB 103 (trade name) manufactured by Cypro Kasei Co., Ltd. having a structure shown in Chemical formula 12 are listed.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

In addition, Uvinul D49 manufactured by BASF Corp. having the structure shown in Chemical formula 13
(Trade name), BA having a structure as shown in Chemical formula 14
Uvinul D50 (trade name) manufactured by SF Co., Ltd., Uvinul DS49 (trade name) manufactured by BASF Co., Ltd., or a structure having a structure shown in chemical formula 16 Vi made by Yakuhin Co., Ltd.
osorb 112 (trade name), SEESORB manufactured by Cipro Kasei Co., Ltd. having a structure shown in Chemical formula 17
105 (trade name) and the like.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

Furthermore, in the diluting solution of the present invention,
A benzotriazole compound having a structure represented by the following chemical formula 18 may be contained together with the water-insoluble resin.

[0057]

Embedded image

The benzotriazole compound is preferably contained in a proportion of 0.1% by weight to 20% by weight. If the content of the benzotriazole-based compound is less than 0.1% by weight, the effect of improving the photobleaching resistance of the image is weak, and if it is more than 20% by weight, the dispersibility of the benzotriazole-based compound in the diluent is Is decreased, which is not preferable.

Specific examples of the above-mentioned benzotriazole compounds include SEESORB 701 (trade name) manufactured by Cypro Kasei Co., Ltd., which has a structure shown in Chemical formula 19, and a structure shown in Chemical formula 20. SEESORB702 (trade name) manufactured by Cipro Kasei Co., Ltd.
SEESORB 703 (trade name) manufactured by Cipro Kasei Co., Ltd., which has a structure shown in, and SEESO manufactured by Cipro Kasei Co., Ltd., which has a structure shown in Chemical formula 22
RB 704 (trade name), SEESORB 70 manufactured by Cypro Kasei Co., Ltd. having a structure shown in Chemical formula 23
5 (trade name), SEESORB 706 manufactured by Cipro Kasei Co., Ltd. having a structure shown in Chemical formula 24, SEESORB 708 manufactured by Cipro Kasei Co., Ltd. having a structure shown in Chemical formula 25 (Product name)
SEESORB 709 (trade name) manufactured by Cypro Kasei Co., Ltd. having a structure as shown in FIG.

[0060]

Embedded image

[0061]

Embedded image

[0062]

[Chemical 21]

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

In addition, TINUVIN 2 manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical formula 27
34 (trade name), TINUVIN 571 (trade name) manufactured by Ciba-Geigy Co., Ltd. and having the structure shown in Chemical formula 28.

[0069]

Embedded image

[0070]

Embedded image

Further, various kinds of surfactants, antifoaming agents, pH adjusters, fungicides and the like may be added to the diluting solution of the present invention.

Further, as a result of further intensive studies by the present inventors, in the diluted solution, a hindered phenol compound, a cyanoacrylate compound, a benzophenone compound, and a benzotriazole compound,
It has also been found that the inclusion of at least one of a thioether compound and a hindered amine compound further improves the photobleaching resistance of a recorded image.

That is, in the diluting solution of the present invention, in addition to one of cyanoacrylate compounds, benzophenone compounds and benzotriazole compounds, hindered phenol compounds, thioether compounds and hindered amine compounds are used. You may make it contain at least 1 sort (s) of a compound.

Illustrative examples of the above hindered phenol compounds are IRGANOX 245 (trade name) manufactured by Ciba-Geigy Co., Ltd., which has a structure shown in Chemical formula 29, and Ciba-Geigy (structure shown in Chemical formula 30). IRGANOX 259 (trade name) manufactured by K.K.
IRGANOX 565 (trade name) manufactured by Ciba-Geigy Co., Ltd. having the structure shown in FIG. 1, IRGANO manufactured by Ciba-Geigy Co., Ltd. having the structure shown in Chemical formula 32
X 1010 (trade name), IRGANOX 103 manufactured by Ciba-Geigy Co., Ltd., having a structure shown in Chemical formula 33
5 (trade name), IRGANOX 1076 (trade name) manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical formula 34, IRGANOX 1098 (trade name) manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical formula 35 ), S manufactured by Sumitomo Chemical Co., Ltd. having a structure shown in Chemical formula 36
Umilizer GA80 (trade name) and the like.

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

When the above thioether compounds are specifically exemplified, the structure as shown in Chemical Formula 38 and Adekastab A0-23 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. having the structure as shown in Chemical formula 37 ADEKA STAB A0-412S (trade name) manufactured by Asahi Denka Kogyo Co., Ltd., ADEKA STAB A0-503A (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. having the structure as shown in chemical formula 39 SEENOX B. manufactured by Cipro Kasei Co., Ltd. having a structure as shown. C. S (brand name) etc. are mentioned.

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

Furthermore, when the above hindered amine compounds are specifically exemplified, TINUVIN 622L manufactured by Ciba-Geigy Co., Ltd. and having a structure shown in Chemical formula 41.
D, TINUVIN 944LD manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical Formula 42, and TIN manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical Formula 43
UVIN 119FL, TINUVIN 770D manufactured by Ciba-Geigy Co., Ltd. and having a structure shown in Chemical formula 44.
F, TINUVIN 144 manufactured by Ciba-Geigy Co., Ltd. having a structure shown in Chemical Formula 45, and the like.

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

In the present invention, the diluting liquid contains at least a water-insoluble resin. After the ink and the diluting liquid are quantitatively mixed, these mixed droplets are ejected to be deposited on the recording material. In the formed recorded image, a film of a water-insoluble resin is formed on the recorded image, the dye does not flow out even if water adheres to the recorded image, and the water resistance is improved.

If the diluting solution of the present invention contains one of a cyanoacrylate compound, a benzophenone compound, and a benzotriazole compound, in addition to the above water-insoluble resin, the light resistance of a recorded image is improved. The fading property is also improved.

[0096]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments to which the present invention is applied will be described based on experimental results. First, an example of a printer device using a diluent to which the present invention is applied will be described.

Here, the printer device of this example is a so-called on-demand type printer device, in which the ink is provided on the fixed amount side and the diluting liquid is provided on the ejection side, and a mixed liquid obtained by mixing these is recorded on a recording paper or the like. This is a so-called carrier jet type printer device that discharges onto a material. Then, in this example, an example using a pressure element such as a piezo element as a quantitative means of the ink or the diluent will be described. Note that the diluting liquid may be on the quantitative side and the ink may be on the discharging side.

As shown in FIG. 1, the printer device of this embodiment is provided with an orifice plate 1 having nozzles, a first liquid container 4 connected to the orifice plate 1 and filled with a first liquid 2, and a first liquid container 4 inside. The second liquid storage container 5 is filled with the two liquids 3.

The orifice plate 1 includes a first plate 11 and a second plate 12 as shown in FIG.
And a third plate 13. The third plate 13 is formed as a so-called laminated plate in which the third plate 13 is sandwiched and laminated by the first plate 11 and the second plate 12 in the thickness direction.

The first and second supply ports 21 and 22 are provided on the first plate 11, in other words, one surface 1a of the laminated plate, and the second plate 12, in other words, the other of the laminated plates. The surface 1b is provided with a nozzle 23 for ejecting a mixed liquid obtained by mixing two kinds of liquids supplied from the first and second supply ports 21 and 22.

Further, the third plate 13 is provided between the first plate 11 and the second plate 12.
The third plate 13 is made of a dry film resist and has a channel 24 in the direction of the inner surface of the plate.
The channel 24 is connected to the first and second supply ports 21 and 22 and also to the nozzle 23.

The first and second supply ports 21 and 22
FIG. 3 shows the first and second supply ports 2 of the orifice plate.
As shown in a plan view from the surface 1b opposite to the surface 1a on which the first and second 22 are provided, the first plate 11 is formed as a circular through hole. Note that the first and second supply ports 21 and 22 do not necessarily have to be circular through holes, and may have, for example, an elliptical shape or a rectangular shape.

Further, the nozzle 23 is provided at a position facing the first supply port 21, and is formed as a circular through hole having an opening diameter larger than the opening diameter of the first supply port 21. It is preferable that the nozzle 23 has an opening diameter larger than the opening diameter of the first supply port 21 as described above, but the nozzle 23 has the same diameter as the opening diameter of the first supply port 21 or a smaller diameter. There may be. Further, the nozzle 23 does not have to be a circular through hole like the first and second supply ports 21 and 22, and may have, for example, an elliptical shape or a rectangular shape.

Further, the flow path 24 is, as shown in FIG.
Nozzle 2 from second supply port 22 not facing nozzle 23
The taper shape is such that the width gradually decreases toward 3. The flow path 24 may have a straight shape or a tapered shape whose width gradually increases. The front end of the flow path 24 is connected to the side wall of the nozzle 23 and forms a part of the nozzle 23.

Next, the first and second liquid storage containers 4 and 5 connected to the orifice plate 1 will be described.

As shown in FIG. 1, the first liquid container 4 is a container having a substantially box-shaped hollow portion 6 inside,
The opening 6 a corresponding to the upper surface of the cavity 6 is connected to the first supply port 21 of the orifice plate 1. Also the second
Is also a container having a substantially box-shaped cavity 7 inside, and an opening 7 a on the upper surface of the cavity 7 is connected to the second supply port 22.

Further, a through hole 8 connected to the cavity 6 and to the outside is provided on the bottom surface 6b side of the cavity 6 of the first liquid container 4 facing the opening 6a.
A through hole 9 connected to the cavity 7 and also to the outside is provided on the bottom surface 7b of the liquid container 5 opposite to the opening 7a of the cavity 7.

Therefore, in the printer apparatus of this example,
The through-hole 8, the cavity 6, and the first supply port 21 are connected to form the first
A through hole filled with the diluent as the solution 2 is formed. On the other hand, the through hole 9, the cavity 7, the second supply port 22, and the flow path 24 are also connected to form a through hole in which ink is filled as the second solution 3.

Then, the first and second liquid container 4,
5, piezoelectric elements 31 and 3 such as piezo elements
2 are provided respectively. Such piezoelectric elements 31, 32
Are deformed by a signal supplied to the piezoelectric elements 31 and 32, and the pressure at the time of the deformation causes the liquid container 4,
5 is to change each pressure.

In the printer device of this example using the piezoelectric elements 31 and 32, the second pulse contained in the mixed liquid is adjusted by adjusting the voltage pulse applied to the piezoelectric elements 31 and 32.
It is possible to adjust the mixing ratio of the liquid 3, that is, the ink concentration.

Therefore, when printing is performed by the printer device, first, as shown in FIG. 1, the second solution 3 which is the ink supplied from the second supply port 22 is flowed by the capillary phenomenon. 24 is filled with 24 and the tip portion 24a of the channel 24 is filled.
A second meniscus M ₂ is formed on the first meniscus M ₁ by the first solution 2 which is a diluting liquid supplied from the first supply port 21 and the tip portion of the first supply port 21 is formed by a capillary phenomenon. 21a.

Next, a voltage pulse is applied to the piezo element 32 provided in the second liquid container 5 filled with the second liquid 3 to apply pressure to the second liquid container 5, and the cavity 7 is formed. And the pressure P2 in the flow path 24 is increased. As a result, as shown in FIG. 4, the second meniscus M ₂ of the second liquid 3 moves toward the nozzle 23 serving as a mixing chamber, and the second liquid 3 is pushed into the nozzle 23. At this time, the amount of the second liquid 3 pushed out is controlled by the magnitude of the pressure applied to the second liquid container 5 by the piezo element 32, and the piezo element 32
Is controlled by the voltage value or the pulse width of the voltage pulse supplied to.

Then, the second meniscus M ₂ is adjusted to the first meniscus M ₁ of the first liquid 2 and the inside of the nozzle 23 by adjusting the rising amount and the rising time of the pressure P2, as shown in FIG. Will be contacted at. As a result, the second liquid droplet 33 is left in the nozzle 23.

Next, the voltage pulse supplied to the piezo element 32 provided in the second liquid container 5 is returned to the original value. Then, when the pressure rise of the second liquid 3 in the channel 24 is not present, the second meniscus M ₂ of the second liquid 3 is in contact first with the meniscus M ₁ of the first liquid 2 Since it is stable to be present at a position where the first liquid 2 is not present, as shown in FIG. You. Then, as shown in FIG. 7, a mixed liquid 10 having an intermediate concentration is formed inside the nozzle 23.

The droplet 33 of the second liquid in the above description is
This is illustrated to explain the transitional state, and the time during which the second liquid droplet 33 exists alone is extremely short. That is, the mixed liquid 10 is immediately mixed with the first liquid 2 to form the mixed liquid 10.

It should be noted that, here, by increasing the amount of rise of the pressure P2 of the second liquid 3 and the rising time, that is, the voltage value or pulse width of the voltage pulse applied to the piezo element 32, the liquid P is contained in the mixed liquid 10. The mixing ratio of the second liquid 3 thus generated, that is, the ink concentration can be increased. That is, the mixing ratio (ink concentration) of the generated mixed liquid 10 is adjusted by the rising amount and rising time of the pressure P2, that is, the voltage value or the pulse width of the voltage pulse applied to the piezo element 32. Therefore, at this stage, a mixed liquid that is a diluted ink capable of expressing a halftone density is adjusted.

Next, a voltage pulse is applied to the piezo element 31 provided in the first liquid container 4 filled with the first liquid 2 to apply a pressure to the first liquid container 4, and the cavity 6 is formed.
And the pressure P1 in the first supply port 21 is increased. Then, the mixed liquid 10 moves toward the nozzle 23 side. Here, the first supply port 21
When the internal pressure P1, in other words, the pressure of the first liquid 2, is increased, as shown in FIG.
The ink is further discharged into the atmosphere and adheres to a recording paper (not shown), which is a recording material provided to face the nozzle 23. On the other hand, a new first meniscus M ₁ is generated at the first supply port 21 to which the first liquid 2 is supplied. At this time, in the above-described printer device, one of the voltage pulses serving as a pressure pulse for applying pressure is applied.
One droplet of the mixed liquid is ejected for each pulse. By repeating this operation, a recorded image expressing halftones is formed.

When a color image is to be formed, for example, the above-described printer device corresponding to each color such as yellow, magenta, cyan, and black is prepared, and one set of these (four in this case) is prepared. A plurality of printer devices may be used as a head assembly, and a large number of the head assemblies may be arranged on a line to form a recorded image.

The above-described series of operations in the printer device is an example, and the timing and state of each operation, such as the shape of the mixed liquid and the filling operation, are structural elements such as the size of the supply port and the nozzle, the ink and the diluent. It changes according to physical factors such as viscosity and surface tension, and operating conditions such as ejection frequency. Also,
In the above-described printer device, it is also possible to change the shape of the orifice plate and each liquid storage container.

In the above-mentioned printer device, the mixed liquid is adjusted by adjusting the rising amount and the rising time of the pressure P2 of the second liquid 3 made into ink, that is, the voltage value or the pulse width of the voltage pulse applied to the piezo element 32. It is possible to adjust the mixing ratio of the second liquid 3 contained in the ink 10, that is, the ink density, and it is possible to change the density for each dot. Tones can be expressed, and a natural image can be formed by accurate gradation expression.

Further, in the above-mentioned printer device, the example in which the so-called d ₃₃ mode laminated piezo element which extends in the longitudinal direction by the voltage application is used as the piezo elements 31 and 32 has been described. It goes without saying that a so-called d ₃₁ mode laminated piezo element that shrinks in the direction may be used.

Here, the example of the printer device using the piezo element for the quantitative determination of the ink or the diluent has been described, but the present invention can be applied to the printer device using the heating element for the quantitative determination of the ink or the diluent. Needless to say. Also, instead of a piezo element, an actuator using an electromagnetic conversion element or an electrostrictive element may be adopted,
Depending on the type of these driving devices, they may be provided inside the first liquid container 4 or the second liquid container 5.

Further, here, the ink is on the fixed amount side,
Although the example in which the diluting liquid is used as the discharge side has been described, the diluting liquid may be used as the quantitative side and the ink may be used as the discharging side.

Next, various diluting liquids were used and an image was recorded by using the printer having the above-mentioned constitution, and the characteristics of the recorded image were investigated.

Experimental Example 1 In this Experimental Example, a diluting liquid containing a water-insoluble resin was prepared as a diluting liquid, and the characteristics of a recorded image formed by using this diluting liquid were investigated. First, each diluted liquid sample was manufactured. That is, the diluted solutions having the formulations shown below were prepared as practical samples 1 to 5. However, the emulsions used in the practical samples 1 and 2 may be diluted with water as needed.

Water-insoluble resin (polyurethane emulsion) blended with Example 1 sample Superflex 300 100.0% by weight (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content: 30% by weight) Water-insoluble resin blended with Example 2 (polystyrene) Emulsion) Nipol LX430 100.0% by weight (trade name, manufactured by Nippon Zeon Co., Ltd., solid content 50% by weight) Implementation sample 3 blended isopropyl alcohol 48.5% by weight ethylene glycol monoethyl ether 38.5% by weight ethylene glycol 10 0.0% by weight Water-insoluble resin (polyamide) Versamide 725 (trade name, manufactured by Henkel Hakusui Co., Ltd.) 3.0% by weight Practical sample 4 blended isopropyl alcohol 57.0% by weight Ethylene glycol monoethyl ether 36.9% by weight Diethylene glycol 0.0 wt% Water-insoluble resin (polyvinyl butyral) # 2000-L (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 wt% nonionic surfactant Emulgen 985 (trade name, manufactured by Kao Co., Ltd.) 0.1% by weight Implementation sample 5 blended water 47.8% by weight Isopropyl alcohol 39.2% by weight Polyethylene glycol PEG 400 (trade name, manufactured by Lion Corporation) 3.0% by weight Water-insoluble resin (modified polyvinyl) Acetal) S-REC KX-5 10.0 wt% (trade name, manufactured by Sekisui Chemical Co., Ltd., solid content 10 wt%) The modified polyvinyl acetal has a property of being soluble only in a mixed solvent of water and alcohol. Is.

Next, for comparison, diluted solutions having the following formulations were prepared as comparative samples 1 to 4.

Comparative sample 1 formulated water 100.0% by weight Comparative sample 2 formulated isopropyl alcohol 50.0% by weight Ethylene glycol 50.0% by weight Comparative sample 3 formulated isopropyl alcohol 56.9% by weight Diethylene glycol 43.0% by weight Nonionic Emulgen 985 (trade name, manufactured by Kao Co., Ltd.) 0.1% by weight Comparative sample 4 water 53.3% by weight isopropyl alcohol 43.7% by weight Polyethylene glycol PEG 400 (trade name, Lion (stock) ) Made by company) 3.0 wt% Next, an ink was prepared. That is, two conventional printers that eject only commercially available ink (hereinafter referred to as inkjet printers) are provided with yellow, magenta, and cyan colors, respectively, and one inkjet printer is used. The ink of each color corresponding to the apparatus was used as an ink sample 1, and the ink of each color corresponding to the other inkjet type printer apparatus was used as an ink sample 2. Also, inks of yellow, magenta, and cyan were prepared with the following composition, and prepared as an ink sample 3.

Ink sample 3 Compounded dye 3% by weight Diethylene glycol 14% by weight Isopropyl alcohol 3% by weight Water 80% by weight As the dye, C.I. I. Acid Yellow 23,
C. I. Acid Red 52, C.I. I. Acid Blue 9 was used, and inks of yellow, magenta, and cyan were prepared.

Subsequently, a color pattern of each color is recorded by the printer device as described above by using the diluted liquids of the above-mentioned working samples 1 to 5 and the comparative samples 1 to 4 and the inks of each color of the ink samples 1 to 3 in combination. Formed as an image. Note that a commercially available plain paper was used as the recording material.

Subsequently, the water resistance of the recorded image formed as described above was investigated as follows. That is,
The recording material on which the recorded image was formed was immersed in distilled water for 3 hours so that the surface on which the recorded image was formed was contacted, and bleeding and elution of the dye were visually examined. In addition, the results are represented by a three-stage evaluation. ○: No leaching in water and no bleeding in the image were observed. ○: No leaching of dye in water, but bleeding in the image was observed. The case where the dye was eluted into water was represented by x. The results are shown in Table 1 together with the combination of diluent and ink.

[0132]

[Table 1]

As is clear from the results shown in Table 1, Example Sample 1 which is a diluent containing at least a water-insoluble resin.
The recorded images using Nos. 5 to 5 had good water resistance regardless of the type of ink. On the other hand, in the recorded images using Comparative Samples 1 to 4, which are diluting solutions containing no water-insoluble resin, the water resistance was low regardless of the type of ink. In particular, in the recorded images using Comparative Samples 1 and 4, the image was eluted and the prototype was hardly retained.

From this, a diluting liquid containing at least a water-insoluble resin is used as the diluting liquid, the diluting liquid and ink are quantitatively mixed, and then these mixed droplets are ejected to be deposited on the recording material. It was confirmed that the water resistance of the recorded image formed in this way was significantly improved.

In addition, the recorded images using the practical samples 1 to 5 all have good water resistance. Therefore, as in the practical samples 1 and 2, the water-insoluble resin is added as an emulsion. In any of the methods of using a resin soluble in a solvent containing at least one of an aliphatic monohydric alcohol, a polyhydric alcohol and a polyhydric alcohol derivative as the water-insoluble resin, It was confirmed that the effect could be brought out.

Experimental Example 2 In this Experimental Example, a diluting liquid containing a water-insoluble resin and a cyanoacrylate compound having a specific structure as described above was prepared as a diluting liquid, and the diluting liquid was used to form the liquid. The characteristics of the recorded images were investigated. First, each diluted liquid sample was manufactured. That is, the diluted solutions having the formulations shown below were prepared as the practical samples 6 to 11. However, the emulsion used in Working Sample 6 may be diluted with water as needed.

Example 6 Blended water-insoluble resin (polystyrene emulsion) Nipol LX430 99.9% by weight (trade name, manufactured by Nippon Zeon Co., Ltd., solid content 50% by weight) Cyanoacrylate compound (2-ethylhexyl-2-cyano) -3,3'-diphenyl acrylate) Viosorb 930 (trade name, manufactured by Kyodo Pharmaceutical Co., Ltd.) 0.1% by weight Implementation sample 7 blended isopropyl alcohol 48.3% by weight Ethylene glycol monoethyl ether 38.2% by weight Ethylene Glycol 10.0% by weight Water insoluble resin (polyamide) Versamide 725 (trade name, manufactured by Henkel Hakusui Co., Ltd.) 3.0% by weight Cyanoacrylate compound (ethyl-2-cyano-3,3'-diphenylacrylate) Uvinul N35 (trade name, BASF ( ) Co., Ltd.) 0.5 wt% inventive sample 8 formulated isopropyl alcohol 56.9% by weight of ethylene glycol monoethyl ether 36.7 wt% Diethylene glycol 5.0 wt% water-insoluble resin (polyvinyl butyral) # 2000-L (trade name , Denki Kagaku Kogyo Co., Ltd.) 1.0 wt% cyanoacrylate compound (2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate) Viosorb 930 (trade name, Kyodo Yakuhin Co., Ltd.) 0.1 wt% Hindered phenolic compound IRGANOX 1010 0.1 wt% (trade name, manufactured by Ciba-Geigy Co., Ltd.) Hindered amine-based compound TINUVIN 622LD 0.1 wt% (trade name, manufactured by Ciba-Geigy Co., Ltd.) ) Nonionic surfactant Emulgen 985 (trade name, Kao Co.) Ltd.) 0.1 wt% inventive sample 9 formula water 47.25 wt% isopropyl alcohol 38.65% by weight of polyethylene glycol PEG 400 (trade name, Lion Co., Ltd.) 3.0 wt% water-insoluble resin (Modified polyvinyl acetal) S-REC KX-5 10.0 wt% (trade name, Sekisui Chemical Co., Ltd., solid content 10 wt%) Cyanoacrylate compound (ethyl-2-cyano-3,3'-diphenylacrylate) Uvinul N35 (trade name, manufactured by BASF Co., Ltd.) 0.5% by weight Hindered phenol-based compound Sumilizer GA80 0.5% by weight (trade name, manufactured by Sumitomo Chemical Co., Ltd.) Hindered amine-based compound TINUVIN 944LD 0 .1% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) Incidentally, the above modified polyvinyl Acetal has the property of being soluble only in a mixed solvent of water and alcohol.

Further, for comparison, the cyanoacrylate compound was removed from the execution sample 9, the execution sample 10 having a composition in which the water content was increased by the weight thereof, and the cyanoacrylate compound was removed from the execution sample 8, and An execution sample 11 having a composition in which the content of isopropyl alcohol was increased by weight was prepared.

Then, the color patterns of the respective colors were formed as recording images in the same manner as in the experimental example 1 by using the inks of the respective colors of the above-mentioned practical samples 6 to 11 and the ink samples 1 to 3 used in the experimental example 1 in combination. . Note that a commercially available plain paper was used as the recording material.

Subsequently, the photobleaching resistance of the recorded image formed as described above was investigated. That is, first, the density of each recorded image formed by combining each diluting liquid and ink is measured by a densitometer (model name: TR-92, manufactured by Macbeth Co., Ltd.).
4) was measured.

Next, each recorded image was irradiated with energy of 30,000 kJ / m ² as a cumulative amount for 24 hours by a xenon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.).

Subsequently, the density of each recorded image after energy irradiation was measured again as described above. Then, the density residual ratio of each color in each recorded image after the energy irradiation was calculated by Equation 1. The results are shown in Table 2 together with the combination of diluent and ink. For comparison, the photobleaching resistance of the recorded images using the practical samples 1, 3, 4, 5, 10, and 11 shown in Experimental Example 1 was similarly examined, and the results are also shown in Table 2.

[0143]

[Equation 1]

[0144]

[Table 2]

From the results shown in Table 2, recorded images using the diluted solutions of the working samples 6 to 9 containing the cyanoacrylate compound having the above-mentioned predetermined structure and the working sample 1 containing no cyanoacrylate compound 1, Three
Comparing the results of the recorded images using the diluted liquids of Nos. 4 and 5, the density of the recorded images using the sample Nos. 6 to 9 remains higher regardless of which of the ink samples 1 to 3 was used as the ink. You can see that the rate is high. That is,
The cyanoacrylate compounds having a predetermined structure contained in the practical samples 6 to 9 suppress the photobleaching of the dye,
It was confirmed that the light-fading resistance of the recorded image was improved.

Further, comparing the results of Examples 6 and 7 in Table 2, it was found that the density residual ratio of the recorded image was improved in proportion to the content of the cyanoacrylate compound. It was confirmed that the light fastness and color fastness of the image were improved, and comparing the results of the execution samples 6 and 8 and the execution samples 7 and 9, in addition to the cyanoacrylate compound, the hindered phenol compound, the hindered compound It was found that the inclusion of the amine compound further improved the residual density ratio of the recorded image, and it was confirmed that the photobleaching resistance of the recorded image was further improved. further,
From the results of the practical samples 10 and 11, it was confirmed that the light fastness and color fastness of the recorded image was not improved even when the hindered phenol type compound and the hindered amine type compound were not contained and the cyanoacrylate compound was not contained.

From these results, it was confirmed that the inclusion of a cyanoacrylate compound in addition to the water-insoluble resin in the diluent improves not only the water resistance of the recorded image but also the light fading resistance. .

Experimental Example 3 In this Experimental Example, a diluting solution containing a water-insoluble resin and a benzophenone compound having a specific structure as described above was prepared as a diluting solution, and this diluting solution was used for the formation. The characteristics of the recorded images were investigated. First, each diluted liquid sample was manufactured. That is, the diluted solutions having the formulations shown below were prepared as the working samples 12 to 15. However, the emulsion used in Working Sample 12 may be diluted with water as needed.

Example 12 Blended water-insoluble resin (polystyrene emulsion) Nipol LX430 99.9% by weight (trade name, manufactured by Nippon Zeon Co., Ltd., solid content 50% by weight) Benzophenone compound Viosorb 112 (trade name, joint drug ( Co., Ltd.) 0.1 wt% Example 13 blended isopropyl alcohol 48.0 wt% ethylene glycol monoethyl ether 38.0 wt% ethylene glycol 10.0 wt% water-insoluble resin (polyamide) Versamide 725 (trade name, Henkel Hakusui Co., Ltd.) 3.0 wt% Benzophenone compound Uvinul D50 (trade name, manufactured by BASF Ltd.) 1.0 wt% Implementation sample 14 blended isopropyl alcohol 56.9 wt% Ethylene glycol monoethyl ether 36.7 weight % Diethylene glycol 5.0 wt% Water-insoluble resin (polyvinyl butyral) # 2000-L (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 wt% Benzophenone-based compound Viosorb 112 (trade name, Kyodo Pharmaceutical Co., Ltd.) 0.1 wt% hindered phenolic compound IRGANOX 1010 0.1 wt% (trade name, manufactured by Ciba-Geigy Co., Ltd.) Hindered amine-based compound TINUVIN 622LD 0.1 wt% (trade name, Ciba-Geigy Co., Ltd.) Nonionic surfactant Emulgen 985 (trade name, manufactured by Kao Co., Ltd.) 0.1% by weight Implementation sample 15 blended water 46.6% by weight Isopropyl alcohol 38.2% by weight Polyethylene glycol PEG 400 ( Product name, manufactured by Lion Corporation 3.0 wt% Water-insoluble resin (modified po Vinyl acetal) S-REC KX-5 10.0 wt% (trade name, Sekisui Chemical Co., Ltd. solid content 10 wt%) Benzophenone compound Uvinul D50 (trade name, BASF Co., Ltd.) 1.0 wt% Hindered phenol type compound IRGANOX 245 0.5% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) Sumilizer GA80 0.5% by weight (trade name, manufactured by Sumitomo Chemical Co., Ltd.) Hindered amine type compound TINUVIN 944LD 0 0.2% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) The modified polyvinyl acetal has a property of being dissolved only in a mixed solvent of water and alcohol.

For comparison, a working sample 16 was prepared in which the benzophenone compound was removed from the working sample 15 and the amount of water was increased by the weight.

Then, the color patterns of the respective colors were formed as recording images in the same manner as in the experimental example 1 by using the inks of the respective colors of the above-mentioned practical samples 12 to 16 and the ink samples 1 to 3 used in the experimental example 1 in combination. . Note that a commercially available plain paper was used as the recording material.

Subsequently, the water resistance and photofading resistance of these recorded images were investigated and evaluated by the methods described in Experimental Examples 1 and 2. The results of water resistance are shown in Table 3 together with the combination of the diluent and the ink, and the results of light fade resistance are shown in Table 4 together with the combination of the diluent and the ink.

[0153]

[Table 3]

[0154]

[Table 4]

From the results shown in Table 3, it was confirmed that the recorded images using the water-insoluble resin and the benzophenone compound-containing working samples 12 to 16 had good water resistance regardless of the type of ink.

Further, comparing the results of Table 4 with the results of the practical samples 1, 3, 4, 5, 16 shown in Table 2 above,
No matter which of the ink samples 1 to 3 was used as the ink, the practical samples 12 to 15 containing the benzophenone-based compound having the predetermined structure as described above.
It can be seen that the residual density of the recorded image is higher than that of the recorded image using the diluted liquid. That is, it was confirmed that the benzophenone-based compound having a predetermined structure contained in each of the practical samples 12 to 15 suppressed the photobleaching of the dye and improved the photobleaching resistance of the recorded image.

Further, comparing the results of the practical samples 12 and 13 in Table 4, it was found that the density residual ratio of the recorded image was improved in proportion to the content of the benzophenone compound, and It was confirmed that the light fastness and color fastness were improved, and the execution samples 12 and 14 and the execution samples 13 and 15
Comparing the results of 1., it was found that the density residual ratio of the recorded image was further improved by adding a hindered phenol compound and a hindered amine compound in addition to the benzophenone compound. It was confirmed that the photobleaching resistance of the recorded image was further improved. further,
From the results of the execution sample 16, it was confirmed that the light fastness and color fastness of the recorded image was not improved even when the hindered phenol type compound and the hindered amine type compound were not contained and the benzophenone type compound was not contained.

From these results, it was confirmed that the inclusion of a benzophenone compound in addition to the water-insoluble resin in the diluent improves not only the water resistance of the recorded image but also the light fading resistance.

Experimental Example 4 In this Experimental Example, a diluting solution containing a water-insoluble resin and a benzotriazole compound having a specific structure as described above was prepared, and the diluting solution was used to form The characteristics of the recorded images were investigated. First, each diluted liquid sample was manufactured. That is, the diluted solutions having the formulations shown below were prepared as the working samples 17 to 20. However, the emulsion used in the practical sample 17 may be diluted with water as needed.

Example 17 Blended water-insoluble resin (polystyrene emulsion) Nipol LX430 99.9% by weight (trade name, manufactured by Nippon Zeon Co., Ltd., solid content: 50% by weight) Benzotriazole compound SEESORB 701 (trade name, Cypro Kasei) Co., Ltd.) 0.1 wt% inventive sample 18 mixing isopropyl alcohol 48.0% by weight of ethylene glycol 48.0 wt% water-insoluble resin (polyamide) VERSAMID 725 (trade name, Henkel Hakusui Co., Ltd.) 3 0.0% by weight benzotriazole compound SEESORB 702 (trade name, manufactured by Cypro Kasei Co., Ltd.) 1.0% by weight Implementation sample 19 blended isopropyl alcohol 56.9% by weight diethylene glycol 41.7% by weight Water-insoluble resin (polyvinyl butyral) ) # 2000-L (Brand name, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 wt% benzotriazole-based compound SEESORB 701 (Brand name, manufactured by Cypro Kasei Co., Ltd.) 0.1 wt% Hindered phenol-based compound IRGANOX 1010 0. 1% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) Hindered amine compound TINUVIN 622LD 0.1% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) Nonionic surfactant Emulgen 985 (trade name, Kao) Co., Ltd. 0.1% by weight Water containing 20 samples 46.4% by weight Isopropyl alcohol 38.2% by weight Polyethylene glycol PEG 400 (trade name, manufactured by Lion Corporation) 3.0% by weight Water insoluble Resin (modified polyvinyl acetal) S-REC KX-5 10.0 wt% (trade name, Sekisui Chemical Co., Ltd. Solid content 10% by weight) Benzotriazole-based compound SEESORB 702 (trade name, manufactured by Cypro Kasei Co., Ltd.) 1.0% by weight Hindered phenol-based compound IRGANOX 245 0.5% by weight (trade name, Ciba Geigy Co., Ltd.) Sumilizer GA80 0.5% by weight (trade name, manufactured by Sumitomo Chemical Co., Ltd.) Hindered amine compound TINUVIN 944LD 0.2% by weight (trade name, manufactured by Ciba-Geigy Co., Ltd.) The above-mentioned modified polyvinyl acetal Has the property of being soluble only in a mixed solvent of water and alcohol.

Then, the color patterns of the respective colors were formed in the same manner as the recorded image and the experimental example 1 by using the inks of the respective colors of the working samples 17 to 20 and the ink samples 1 to 3 used in the experimental example 1 in combination. . Note that a commercially available plain paper was used as the recording material.

Subsequently, the water resistance and photofading resistance of these recorded images were investigated and evaluated by the methods described in Experimental Examples 1 and 2. The results of the water resistance are shown in Table 5 together with the combination of the diluting liquid and the ink, and the results of the light fading resistance are shown in Table 6 together with the combination of the diluting liquid and the ink.

[0163]

[Table 5]

[0164]

[Table 6]

From the results of Table 5, practical samples 17 to 20 containing the water-insoluble resin and the benzotriazole-based compound.
It was confirmed that the water resistance of the recorded image using No. 3 was good regardless of the type of ink.

In addition, comparing the results of Table 6 with the results of the practical samples 1, 3, 4, and 5 shown in Table 2 above, it was found that, in the case of using any of the ink samples 1 to 3 as the ink, It can be seen that the recorded images using the diluted solutions of the working samples 17 to 20 containing the benzotriazole-based compound having the predetermined structure as described above have a higher density residual ratio. That is, it was confirmed that the benzotriazole-based compound having a predetermined structure contained in each of the practical samples 17 to 20 suppressed the photobleaching of the dye and improved the photobleaching resistance of the recorded image.

Further, comparing the results of the practical samples 17 and 18 in Table 6, it was found that the density residual ratio of the recorded image was improved in proportion to the content of the benzotriazole type compound. It was confirmed that the color fastness to light was improved, and comparing the results of the execution samples 17 and 19, and the execution samples 18 and 20, in addition to the benzotriazole compound, the hindered phenol compound, the hindered amine It was found that the inclusion of the system compound further improved the residual density ratio of the recorded image, and it was confirmed that the photobleaching resistance of the recorded image was further improved.

From these results, it was confirmed that the inclusion of a benzotriazole compound in addition to the water-insoluble resin in the diluent improves not only the water resistance of the recorded image but also the light fading resistance. .

[0169]

As is apparent from the above description, in the present invention, the diluting liquid contains at least a water-insoluble resin, and after the ink and the diluting liquid are quantitatively mixed, these mixed droplets are mixed. In a recorded image formed by discharging and depositing on a recording material, a film of a water-insoluble resin is formed on the recorded image, and the dye does not flow out even if water adheres to the recorded image. Water resistance is improved.

If the diluting solution of the present invention contains one of a cyanoacrylate compound, a benzophenone compound, and a benzotriazole compound in addition to the above water-insoluble resin, the light resistance of the recorded image can be improved. The fading property is also improved.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a main part showing an example of a printer device.

FIG. 2 is a schematic cross-sectional view of a main part of an enlarged example of an orifice plate of the printer device.

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

FIG. 4 is a cross-sectional view schematically showing an operation of an example of the printer device, in which a meniscus is formed on an orifice plate.

FIG. 5 is a cross-sectional view schematically showing an operation of an example of the printer device, in which a second meniscus is in contact with a first meniscus.

FIG. 6 is a cross-sectional view showing the operation of an example of the printer device in order and schematically showing a state in which the second meniscus retracts and is separated from the first liquid.

FIG. 7 is a cross-sectional view that sequentially shows an operation of an example of a printer apparatus and schematically shows a state in which a mixed liquid is formed inside a nozzle.

FIG. 8 is a cross-sectional view that sequentially shows an operation of an example of a printer device and schematically shows a state in which a mixed liquid is discharged.

[Description of Signs] 1 orifice plate, 2 first liquid, 3 second liquid, 4 first liquid storage container, 5 second liquid storage container, 10 mixed liquid, 21 first supply hole, 22nd liquid 2 supply holes, 23 nozzles, 24 channels, 31, 32 piezo elements

Claims (13)

[Claims] 1. A diluting liquid which is quantitatively mixed with an ink, is discharged as a mixed droplet, and is deposited on a recording material, wherein the diluting liquid contains at least a water-insoluble resin. 2. The diluting solution according to claim 1, wherein the water-insoluble resin is contained in a proportion of 1% by weight to 50% by weight. 3. The diluting solution according to claim 1, wherein the water-insoluble resin is contained as an emulsion. 4. The water-insoluble resin is an aliphatic monohydric alcohol,
The diluent according to claim 1, which is soluble in a solvent containing at least one of a polyhydric alcohol and a polyhydric alcohol derivative. 5. The diluent according to claim 1, containing a cyanoacrylate compound having a structure represented by the following chemical formula 1. Embedded image 6. The cyanoacrylate compound is 0.1
The diluent according to claim 5, wherein the diluent is contained in a proportion of 20% by weight to 20% by weight. 7. A benzophenone-based compound having a structure represented by the following chemical formula 2 is contained.
Diluted solution described. Embedded image 8. The diluent according to claim 7, wherein the benzophenone compound is contained in a proportion of 0.1% by weight to 20% by weight. 9. The diluent according to claim 1, containing a benzotriazole compound having a structure represented by the following chemical formula 3. Embedded image 10. The benzotriazole-based compound is
The diluting liquid according to claim 9, wherein the diluting liquid is contained in a proportion of 1% by weight to 20% by weight. 11. The diluent according to claim 1, which contains a surfactant. 12. The diluent according to claim 1, which contains at least one of a viscosity adjusting agent, an antiseptic fungicide, and a pH adjusting agent. 13. A recording method in which an ink and a diluent are quantitatively mixed, and then a mixed droplet of these is ejected to adhere onto a recording material, wherein the diluent contains at least a water-insoluble resin. How to record.