JPH1088056A - Recording fluid and method for recording image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording fluid having excellent delivery stability and being capable of giving an image having a high density, not undergoing blotting or penetration on or into recording paper and having excellent water resistance by mixing a colorant with water and at least tree types of resin microparticles. SOLUTION: This fluid comprises a colorant, water and at least three type of resin microparticles. It is desirable that the content of the colorant be 1-50wt.% based on the fluid when the colorant is a pigment, and it is 0.2-40wt.% when the colorant is a dye. It is desirable that the resin microparticles of each of at least three types have a mean particle diameter of 0.01-5μm, and the resin microparticles of at least one of these types are ones of a non-crosslinkable fluorocarbon having fluoroolefin units. It is desirable that the total content of the resin miroparticles be 10-95wt.% based on the entire fluid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a recording liquid and an image recording method, and more particularly to a recording liquid containing a colorant, water and resin fine particles, and an image recording method using the same.

[0002]

2. Description of the Related Art Recently, as an output device of an information device such as a computer, a system in which droplets of a recording liquid are ejected from a recording head to perform recording on a recording medium has been used as a system which has a low running cost and is easy to colorize. Attention has been paid to the inkjet method, which is a method. As a recording liquid for an ink jet printer, a dye aqueous solution containing water and a dye as a main component has been used.However, when the recording liquid ejected from a nozzle adheres to the recording paper, the recording liquid is applied to the recording paper. There are problems such as bleeding, which results in dots that are significantly larger than the recording droplets formed during flight, and that the density of the recorded image is low and the image quality is low. Further, since the recorded image has low water resistance, there has been a problem that the image easily bleeds or flows due to water. Furthermore, there is a problem that the light resistance is low and the image is easily discolored by irradiation with light such as sunlight.

Conventionally, in order to solve these problems of a dye aqueous solution for a recording liquid for an ink jet printer, a technique of adding film-forming resin fine particles to the recording liquid has been proposed. For example, JP-B-60-32663 discloses a recording liquid containing latex as resin fine particles, and JP-A-5-239392 discloses a recording liquid containing a water-dispersible resin having a carboxyl group and a nonionic hydrophilic group. A recording liquid to which a non-crosslinked vinyl polymer is added is disclosed in
Japanese Patent Application Laid-Open No. 6-34083 discloses a recording liquid containing polyester particles having an ionic group.
No. 5, each of which is disclosed. Japanese Patent Publication No. 7-47355 discloses a technique of crosslinking a resin of a recording liquid containing resin fine particles such as polyester and a crosslinking agent on a recording medium.
No. 6,086,045.

[0004]

However, in any of the recording liquids disclosed in the above publications, resin fine particles are generated at the discharge port of the recording head due to evaporation of moisture in the recording liquid due to contact with air. Since film formation was started and clogging occurred, it was impossible to stably discharge the recording liquid. In addition, these recording liquids cannot completely prevent the bleeding of the recording liquid due to the capillary phenomenon on the recording paper textile,
It was impossible to provide high quality images. further,
These recording liquids cannot completely prevent permeation into the recording paper, and there is a limit to high density image formation and high image quality.
Also, there was a similar limitation in water resistance. further,
When the recording liquid of the conventional disclosure is diluted with water in order to avoid clogging at the discharge port, the content of the resin fine particles contained in the liquid droplets of the same volume as before the dilution, that is, image formation The content of resin solids that contributes to the reduction in image density decreases, the image density significantly decreases, and it is impossible to provide high-quality images. That is, in the recording liquid disclosed in the related art, it is possible to provide a high-quality image with a high image density by increasing the content of resin fine particles (increase in the content of resin solids) and to avoid clogging at the discharge port. Balancing was impossible.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a high image density,
An object of the present invention is to provide a recording liquid capable of providing an image having excellent water resistance without bleeding or penetration on a recording paper and having excellent ejection stability. Another object of the present invention is to provide an image recording method using the recording liquid.

[0006]

The recording liquid of the present invention, which can achieve the above object, is characterized by containing a colorant, water and three or more kinds of resin fine particles.

Further, the present invention is characterized in that the above-mentioned recording liquid is used in an image recording method for recording on a recording medium by discharging droplets of the recording liquid from a recording head.

The above-described recording liquid makes it possible to achieve both high image density by increasing the content of resin fine particles (increase in the content of resin solids) and avoiding clogging at the ejection openings of the recording head. The reason is not always clear, but it is inferred as follows.

When three or more kinds of different resin fine particles are contained in the recording liquid, there is a probability that the same kind of resin fine particles as this resin fine particle exist around a certain resin fine particle (closest coordinate position) in the recording liquid. It is reduced to less than one third. This reduces the probability of similar resin particles approaching and colliding with each other, and prevents a series of processes from approaching similar resin particles through collision and fusion to film formation (coordination effect), thereby preventing clogging. You.

[0010] Further, in the case where different kinds of resin fine particles are present in the recording liquid, the attractive force between the particles is less likely to be exerted than in the case where only the same kind of resin fine particles is present (the repulsive force is more likely to be exerted).
Therefore, the approach of the resin fine particles is hindered from each other, and the probability of collision between the resin fine particles is reduced (the effect of interparticle repulsion). A series of processes is inhibited (coordination effect) and clogging is prevented.

Further, with respect to the prevention of clogging, it is considered that the difference in particle size and shape between different kinds of fine particles is larger than the difference in particle size and shape between fine particles of the same kind. By the presence of different types of resin fine particles having a particle size, shape, etc., significantly different from the particle size, shape, etc. of the resin fine particles, compared to the case where only fine particles having a similar particle size, shape, etc. are present, the same type, It is considered that the approach between different kinds of resin fine particles is hindered (geometric structure effect), and clogging is prevented in the same manner as described above.

In the present invention, the approach of the resin fine particles to each other is remarkably suppressed by the above-described overall effect, so that the total content of the resin fine particles contained in the recording liquid can be increased, and, consequently, the ratio of one droplet in one droplet can be increased. The content of the resin fine particles can be increased, and an image having a high image density can be formed.

The film formation of these three or more types of resin fine particles proceeds in parallel, preventing bleeding or permeation of a recording liquid on a recording medium such as paper, and forming a resin and a colorant confined therein. Thus, an image having high image density and high water resistance can be formed on a recording medium.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The recording liquid of the present invention contains water, a colorant, and three or more types of fine resin particles. As the resin fine particles used in the present invention, non-crosslinkable resin fine particles, self-crosslinkable resin fine particles, and resin fine particles that can be crosslinked by the action of a crosslinking agent can be used.
Polyester resin fine particles, vinyl acetate resin fine particles,
Vinyl chloride resin fine particles, styrene-butadiene polymer resin fine particles, polyurethane resin resin fine particles, polystyrene resin fine particles, vinyl acetate-acryl copolymer resin fine particles, vinyl acetate-acrylamide copolymer resin fine particles, ethylene-vinyl acetate Copolymer resin, epoxy resin-based resin fine particles, polyamide resin-based resin fine particles,
Resin fine particles such as silicone resin fine particles, acrylic resin fine particles, and acrylic silicone resin fine particles can be used. In the present invention, the self-crosslinkable resin is
It refers to a resin that crosslinks not by the action of a crosslinking agent but by the reactivity of a functional group incorporated in the main chain and / or side chain of the resin.

According to the present invention, a time difference is caused in a film forming process by each resin, and it is difficult to form a film due to a difference in composition, thereby causing clogging, that is, film formation at a recording head discharge port. From the perspective of preventing
It is preferable that at least one of the three or more types of resin fine particles contained in the recording liquid is a non-crosslinkable resin fine particle. In addition, among the non-crosslinkable resin fine particles listed above, they have excellent film forming properties (image forming properties), and have high water repellency, high water resistance, and high weather resistance, and have high water resistance and high image density. Fluorine-based resin fine particles are preferred because they are useful for image formation. As the fluorine-based resin fine particles, fluorine-based resin fine particles having a fluoroolefin unit are preferable, and among them, fluorine-containing vinyl ether-based resin fine particles composed of a fluoroolefin unit and a vinyl ether unit are particularly preferable.

Here, an example of the fluoroolefin unit is-
_{CF 2 CF 2 -, - CF} 2 CF (CF 3) -, - CF 2
CFCl- and the like. On the other hand, examples of the vinyl ether unit include the following.

[0018]

Embedded image

As the fluorine-containing vinyl ether resin fine particles composed of a fluoroolefin unit and a vinyl ether unit, an alternating copolymer in which the above-mentioned fluoroolefin unit and vinyl ether unit are alternately combined is preferable.

The recording liquid of the present invention only needs to contain three or more types of resin fine particles, thereby sufficiently achieving high image density by increasing the resin solid content, and simultaneously achieving high image quality and avoiding clogging. However, by containing four or more types of resin fine particles, the probability of the presence of the same type of resin fine particles at the closest coordination position described above is further reduced (promoting the coordination effect),
Further, since the attraction between particles becomes more difficult, clogging can be prevented more effectively. Although there is no particular upper limit for the type of resin fine particles contained in the recording liquid, the shape and size of each resin fine particle are constant, and assuming that the shape is spherical, the closest particles when the particles are closest packed are used. The number (coordination number), that is, the number of particles existing in contact with a certain particle is 12. Therefore, the optimum value of the upper limit of the type of the resin fine particles is considered to be 12, and the upper limit of the type of the resin fine particles is 18 types (12 types + 6) in consideration of the stochastic fluctuation width.
Type). From the above, the types of the resin fine particles contained in the recording liquid in the present invention are preferably 3 or more and 18 or less from the viewpoint of approaching the same type of resin fine particles and reducing the collision probability due to the coordination effect.
More preferably, the number is 4 or more and 12 or less. In addition,
In the present invention, even if the monomers constituting the resin are the same, the characteristics of the resin fine particles or a dispersion thereof, that is, the minimum film forming temperature, the glass transition point, the ionicity, the pH, the weight average, depend on the method of modification and the like. If at least one of the molecular weight and the average particle diameter is different, it is considered to be another type of resin fine particles.

The average particle diameter of each fat fine particle used in the present invention is preferably 0.01 μm or more and 5 μm or less, more preferably 0.05 μm or more and 3 μm or less. If the average particle diameter of the resin fine particles is less than 0.01 μm, the film-forming property is poor, and if it exceeds 5 μm, the optical density (image density) decreases.

In the present invention, the total content of the resin fine particles (the total content of solid resin fine particles) is preferably 10 to 95% by weight based on the total amount of the recording liquid.
More preferably, it is in the range of 15 to 90% by weight.
More preferably, it is in the range of 0 to 80% by weight. If the total content of the resin fine particles is less than 10% by weight, the optical density of the image will be low, and if it exceeds 95% by weight, there is a concern that the ejection stability may be reduced. Further, the content ratio of each resin fine particle contained in the recording liquid is appropriately selected in order to realize desired characteristics to the maximum, but n kinds (n: a positive integer of 3 or more) of resin fine particles are mixed. In this case, assuming that the total amount of the solid content of the resin fine particles in the recording liquid is W parts by weight, the solid content of each resin fine particle in the recording liquid ranges from 2 W / n parts by weight to 0.1 W / n parts by weight. Preferably, there is. If the amount is more or less than this range, the effect of preventing clogging due to the coexistence of a plurality of different resin fine particles may be reduced. In addition, the content ratio of the non-crosslinkable resin fine particles in the resin fine particles contained in the recording liquid is in the range of 2 W / n parts by weight to 0.1 W / n parts by weight for one kind thereof in the same manner as described above. It is more preferred, but more preferably in the range from 2 W / n parts by weight to 0.3 W / n parts by weight. When the content is more than 2 W / n parts by weight, the effect of preventing clogging due to the coexistence of a plurality of different types of resin fine particles is reduced as described above. When the content is less than 0.3 W / n parts by weight, the effect of preventing clogging is reduced and water resistance is reduced. There is a concern that the properties will decrease.

In the present invention, as the coloring agent, those having good affinity for water as a main solvent and those having good uniform dispersibility can be used. Specifically, pigments, water-soluble dyes and disperse dyes can be used. Used.

Examples of the pigment which can be used in the present invention include organic pigments and inorganic pigments. For example, carbon blacks such as furnace black and channel black (C.I. And organic pigments such as aniline black (CI pigment black 1). Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 1
3, 14, 17, 24, 34, 35, 37, 42, 5,
3, 55, 81, 83, 95, 97, 98, 100, 1,
01, 104, 108, 109, 110, 117, 12
0, 138, 153, C.I. I. Pigment Violet 1, 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2,
There are pigments such as 15: 3, 15: 4, 15: 6, 16 and the like.
The content of the pigment contained in the recording liquid is preferably from 1 to 50% by weight, more preferably from 1.5 to 40% by weight. In order to disperse these pigments more evenly, dispersion treatment may be performed by a ball mill or the like in some cases.

Examples of the water-soluble dye that can be used in the present invention include direct dyes and acid dyes.
C. I. Direct Black 9, 17, 19, 22, 3
2, 51, 56, 62, 69, 77, 80, 91, 9
4, 97, 108, 112, 113, 114, 117,
118, 121, 122, 125, 132, 146, 1
54, 166, 168, 173, 199, C.I. I. Direct violet 7, 9, 47, 48, 51, 66,
90, 93, 94, 95, 98, 100, 101, C.I.
I. Direct Yellow 8, 9, 11, 12, 27, 2
8, 29, 33, 35, 39, 41, 44, 50, 5,
3, 58, 59, 68, 86, 87, 93, 95, 9
6, 98, 100, 106, 108, 109, 110,
130, 132, 144, 161, 163, C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 6
7, 68, 71, 76, 77, 78, 80, 84, 8
6, 87, 90, 98, 106, 201, 202, 24
4, 251, 280, C.I. I. Acid Black 7, 2
4, 29, 48, C.I. I. Acid Violet 5, 3
4, 43, 47, 48, 90, 103, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 4
4, 49, 50, 61, 110, 174, 218, C.I.
I. Acid Blue 9, 25, 40, 41, 62, 7
2, 76, 80, 106, 112, 120, 205, 2,
30, 271 and 280, but are not limited to these. The content of these dyes contained in the recording liquid is determined depending on the type of dye, the type of solvent component, the properties required for the recording liquid, and the like.
The range is from 0.2 to 40% by weight, preferably from 0.5 to 30% by weight.

As the water used in the present invention, it is preferable to use ion-exchanged water, ultrapure water, distilled water and ultrafiltration water.

In addition, if necessary, a pH adjuster such as potassium dihydrogen phosphate and sodium dihydrogen phosphate, and benzoic acid, diclofen, hexachlorophene, sorbic acid and the like for the purpose of fungicide, preservation, rust prevention and the like. It may be added to the recording liquid. If necessary, various general additives such as ethylene glycol and glycerin may be added to the recording liquid. The recording liquid of the present invention can be used for an image recording method in which droplets of the recording liquid are ejected from a head to perform recording on a recording medium such as paper.

The recording liquid of the present invention can be used not only for ink jet recording but also for electrostatic suction type image recording and writing implements.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. (Example 1) A recording liquid was prepared as follows. Water-based copper phthalocyanine pigment (Pigment Blue 15: 3)
A resin dispersion (solid content: 22 parts by weight of a dispersion (solid content = 35%)) and fluorine-containing vinyl ether-based resin fine particles (average particle size: 0.15 μm) produced by emulsion polymerization of water, a fluoroolefin, and vinyl ether = 50
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000), a resin dispersion liquid containing 21 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content =
45%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) 23 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2)
of resin dispersion (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G) was added, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles were filtered through a 0 μm membrane filter to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid {= pigment solid content × 100 / the total amount of the recording liquid (liquid)} was 8% by weight.
Pigment (colorant) concentration in solid content = pigment solid content x 100 /
(Pigment solid content + Resin fine particle solid content) = 20% by weight, total concentration of resin fine particle total solid content in the recording liquid == Total resin fine particle solid content × 100 / Total amount of recording liquid} = 31% by weight. .

The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.4.

When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.

On the other hand, the clogging property of the recording liquid at the discharge port of the recording head was evaluated as follows. A standard syringe needle (manufactured by Iwashita Engineering) having an inner diameter of 180 μm was set at the tip of a syringe having an inner diameter of 15 mm, and 10 μl of the recording liquid was placed in the syringe.
ml was inhaled. Next, the upper part of the syringe was closed, and dripping of the recording liquid from the injection needle was stopped, and the syringe was left.
After a lapse of a predetermined time, the upper portion was opened, and it was examined whether the recording liquid could be continuously dropped from the injection needle. This operation was repeated while gradually increasing the predetermined time of leaving, and the longest leaving time during which the recording liquid could be dropped from the injection needle was defined as a margin time until the occurrence of clogging. The margin time until the clogging of the recording liquid in this method measured in this way was as long as 50 seconds.

Next, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Further, water was spilled on the solid image by the bar coater and the print sample by the printer, and the water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 2) 22 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 20 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, Sumika ABS.
Latex Co., Ltd., trade name: SN-335) 20 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G, pH and glass transition point are A
(Different from -215G) was added and stirred to mix uniformly. Thereafter, the mixed solution was added with a pore size of 10 μm.
To remove dirt and coarse particles, the pigment (colorant) concentration in the recording liquid is 7% by weight,
A recording liquid having a pigment (colorant) concentration in the solid content of 20% by weight and a total solid content of the resin fine particles in the recording liquid of 29% by weight was obtained.

The recording liquid thus prepared was coated on plain paper for a copying machine using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.4.

When the longitudinal section of the solid image on the plain paper was observed by an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.

Next, the clogging of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 50 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 3) 23 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 16 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, trade name: G)
-45) 18 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle size:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and a resin dispersion liquid containing 27 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.%). 5%, 17 parts by weight of Sumika ABS Latex Co., Ltd., trade name: SN-335) were added thereto, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles were filtered through a 0 μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 8% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 32% by weight was obtained.

The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.6.

When the longitudinal section of the solid image on the plain paper was observed by an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 100 seconds.

Further, a printing test of this recording liquid on plain paper was carried out using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 4 20 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 14 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, Sumika ABS.
Latex Co., Ltd., product name: SN-335) 15 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 23 parts by weight of solid dispersion (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having carboxyl groups added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) 28 parts by weight were added, and the mixture was stirred and uniformly mixed. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid content of the resin fine particles in the recording liquid was 28% by weight.

The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.5.

When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 105 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 5 20 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 0.2 μm) ) (Solid content =
Resin dispersion liquid containing 15 parts by weight of 45% (manufactured by Sanyo Chemical Industries, Ltd., trade name: G-45), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), 14 parts by weight, and modified polyester resin fine particles having carboxyl groups added to water and side chains (average particle diameter: 0.1 to 0) .2 μm) (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-
215G) A resin dispersion (solid content = 23 parts by weight) containing modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) having carboxyl groups added to water and side chains.
25% by weight, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G) and mixed with stirring. afterwards,
The mixed solution was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 7% by weight, and the concentration of the pigment (colorant) in the solid content was 20% by weight. The total solid content of the resin fine particles in the recording liquid is 2
8% by weight of the recording liquid was obtained.

The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.4.

When a longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 90 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 6) 21 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., containing 12 parts by weight, water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm), trade name: G)
-45) 13 parts by weight and water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) and 19 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 23 parts by weight of a resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) (Solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
N-335), 12 parts by weight, and stirred to mix uniformly. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 29% by weight was obtained.

The recording liquid thus prepared was coated on plain paper for a copying machine using a bar coater, and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.6.

When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was recognized. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 135 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 7) 21 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 10 parts by weight, water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., trade name: G)
-45) 11 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter:
0.1-0.2 μm) (solid content = 30)
%, Manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) and 16 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 19 parts by weight of a resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G), and water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) (Solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
N-335) 10 parts by weight of acrylic silicon resin fine particles having water and a methoxysilyl group (average particle diameter = 0.
1 to 0.2 μm) (solid content = 35%,
14 parts by weight (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: SW-135) were added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 29% by weight was obtained.

The recording liquid thus prepared was coated on plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.6.

When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and almost no permeation of the recording liquid into the plain paper was observed. Was.

Next, the clogging of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 170 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 8 20 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) A resin dispersion containing 7 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, trade name: G-
45) 8 parts by weight and water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter: 0.
1 to 0.2 μm) (solid content = 30%,
Takamatsu Yushi Co., Ltd., trade name: A-215G) 12 parts by weight,
Resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-) containing water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm) 115G) A resin dispersion (solid content = 30%, Takamatsu Yushi Co., Ltd.) containing 14 parts by weight and water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm) Product name: A-515G,
12 parts by weight of A-215G and A-115G having different pH and glass transition point) and water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm)
m)) (solid content = 48.5%, manufactured by Sumika ABS Latex, trade name: SN-335) 7
Resin dispersion containing 3 parts by weight of water and acrylic acid ester-silicone copolymer resin fine particles (average particle diameter: 0.16 μm) (solid content = 38.8%, manufactured by Showa Polymer Co., Ltd., trade name: ROY-) 6312) A resin dispersion liquid containing 9 parts by weight of water and acrylsilicone resin fine particles having a methoxysilyl group (average particle diameter = 0.1 to 0.2 μm) (solid content =
35%, manufactured by Sanyo Chemical Industries, trade name: SW-135) 1
And 0 parts by weight, and stirred to mix uniformly. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, the concentration of the pigment (colorant) in the recording liquid was 7% by weight, and the pigment (colorant) in the solid content.
A recording liquid having a concentration of 20% by weight and a total solid content of resin fine particles in the recording liquid of 28% by weight was obtained.

The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater and dried at room temperature to obtain a solid image consisting of a coating and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.6.

When the longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 195 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 9 Fluorine-containing vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water, a fluoroolefin and vinyl ether in 48 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%) .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000), a resin dispersion containing 6 parts by weight of water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm) (solid content =
45%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) 7 parts by weight, water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m), 11 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) A resin dispersion containing 13 parts by weight of water and modified styrene-butadiene copolymer resin fine particles (average particle size: 0.19 μm) (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd.) Name: SN-335) A resin dispersion (solid content: 35%, Sanyo Chemical Industries, Ltd.) containing 7 parts by weight of water and acrylsilicone resin fine particles having a methoxysilyl group (average particle size = 0.1 to 0.2 μm) (Product name: SW-135) (9 parts by weight), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore diameter of 10 μm to remove dust and coarse particles, and the dye (colorant) concentration in the recording liquid was 5% by weight, and the dye (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 19% by weight was obtained.

The recording liquid thus prepared was applied to plain paper for copying machines using a bar coater, and dried at room temperature to obtain a solid image consisting of a coated and dried film on plain paper. Then, the optical density of the obtained image was measured from the image surface side. As a result, the optical density of a solid image applied with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was as high as 1.4.

When a longitudinal section of the solid image on the plain paper was observed with an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly penetrated into the plain paper. Was.

Next, the clogging property of the recording liquid at the recording head discharge port was evaluated in the same manner as in Example 1. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 180 seconds.

Further, a printing test of this recording liquid on plain paper was performed using a commercially available ink jet printer. As a result, it was possible to stably discharge the stock solution of the recording liquid that was not diluted with water. Observation of the printed dots of the sample printed in this manner with a magnifying loupe and an optical microscope revealed that the dots were clear with no bleeding around the dots.

Subsequently, water was spilled on the solid image by the bar coater and the print sample by the printer,
The water resistance was evaluated. As a result, no bleeding of the image and no spreading of the coloring agent due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Comparative Example 1 26 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and fluorine-containing vinyl ether resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 74 parts by weight were added and stirred to mix uniformly.
Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 9% by weight, and the concentration of the pigment (colorant) in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 37% by weight was obtained.

With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time until clogging was as short as 8 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted four times with distilled water (recording liquid: water = 1: 3), the recording liquid could be ejected by a commercially available ink jet printer.
The optical density of a solid image coated with a small amount of recording liquid of 0.9 mg per ² was as low as 0.4. (Comparative Example 2) 24 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 0.2 µm) ) (Solid content =
76% by weight of 45% (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: G-45) was added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The concentration of the pigment (colorant) in the recording liquid was 9% by weight, and the concentration of the pigment (colorant) in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 34% by weight was obtained.

With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.3, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted four times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 3) 18 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1-0.2μ
82 parts by weight of a resin dispersion containing m) (solid content = 30%, manufactured by Takamatsu Oil & Fat Co., Ltd., trade name: A-215G) was added, and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 6% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 25% by weight was obtained.

With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of the solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of the} image area was 1.2, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted four times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 4) 26 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) ) Was added thereto (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 9% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 36% by weight was obtained.

With respect to the recording liquid thus prepared,
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time until clogging was as short as 8 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 5) 15 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1-0.2μ
m) was added (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G) (85 parts by weight), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 10
The particles were filtered through a μm membrane filter to remove dust and coarse particles. The pigment (colorant) concentration in the recording liquid was 5% by weight, the pigment (colorant) concentration in the solid content was 20% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 21% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of the solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of the} image area was 1.2, and the margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted four times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 6) 20 parts by weight of an aqueous copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and acrylic silicon resin fine particles having water and a methoxysilyl group (average particle size = 0.1) 80 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) was added thereto, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 20%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 28% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time before the occurrence of clogging was as short as 7 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.5
Was low. (Comparative Example 7) 21 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin, and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 30 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to the side chain (average particle diameter: 0.1%).
1 to 0.2 μm) (solid content = 30%,
49 parts by weight of Takamatsu Yushi Co., Ltd., trade name: A-215G), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 30% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time before the occurrence of clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 8) 19 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), and fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water, a fluoroolefin and vinyl ether (Average particle diameter: 0.15 μm) Resin dispersion liquid (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-300)
0) 30 parts by weight of water and a modified polyester resin fine particle having a carboxyl group added to the side chain (average particle diameter: 0.1%).
1 to 0.2 μm) (solid content = 25%,
54 parts by weight of Takamatsu Yushi Co., Ltd., trade name: A-115G), and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 7% by weight, and the pigment (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of fine resin particles in the recording liquid of 27% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time before the occurrence of clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 9) 21 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 µm) 30 parts by weight of a resin dispersion (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335), and modified polyester resin fine particles having a carboxyl group added to water and a side chain. (Average particle diameter: 0.1 to 0.2 μm) Resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-2)
15G) 49 parts by weight, and stirred to mix uniformly. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid content of the resin fine particles in the recording liquid was 29% by weight.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time before the occurrence of clogging was as short as 18 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected by a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.4
Was low. (Comparative Example 10) 19 parts by weight of a water-based copper phthalocyanine-based pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and modified polyester resin fine particles having a carboxyl group added to water and a side chain (average particle diameter) : 0.1-0.2μ
m), 30 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1 to 0.2 µm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-1)
15G) 54 parts by weight were added, and the mixture was stirred and uniformly mixed. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles,
A recording liquid was obtained in which the concentration of the pigment (colorant) in the recording liquid was 7% by weight, the concentration of the pigment (colorant) in the solid content was 20% by weight, and the total solid concentration of the resin fine particles in the recording liquid was 27% by weight.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image coated with a small amount of recording liquid of 0.9 mg per 1 cm ^{2 of} image area was 1.3, and the margin time until clogging was as short as 20 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted four times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.3
Was low. (Comparative Example 11) Fluorinated vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water and a fluoroolefin with vinyl ether were added to 56 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%). .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) (44 parts by weight) was added, and the mixture was stirred and uniformly mixed. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles. The dye (colorant) concentration in the recording liquid was 6% by weight, and the dye (colorant) concentration in the solid content was 2%.
A recording liquid having a concentration of 0% by weight and a total solid content of the resin fine particles in the recording liquid of 22% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time until the occurrence of clogging was as short as 10 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.3
Was low. (Comparative Example 12) Fluorinated vinyl ether-based resin fine particles (average particle diameter: 0) prepared by emulsion polymerization of water and a fluoroolefin with vinyl ether were added to 48 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%). .15 μm) (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) and 19 parts by weight of water and modified polyester resin fine particles having a carboxyl group added to a side chain (average particle diameter: 0.1 to 0.2 μm)
m)) and 32 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), and the mixture was stirred and uniformly mixed. Thereafter, the mixed solution was added with a pore size of 1
The particles are filtered through a 0 μm membrane filter to remove dust and coarse particles. The dye (colorant) concentration in the recording liquid is 5% by weight, the dye (colorant) concentration in the solid content is 20% by weight, and the resin in the recording liquid is A recording liquid having a total solid content of fine particles of 19% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 9, an optical density measurement, a measurement of a margin time until the occurrence of clogging, and a printing test on plain paper by a commercially available inkjet printer were performed. as a result,
The optical density of a solid image applied with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was 1.4,
The margin time before the occurrence of clogging was as short as 22 seconds. In addition, as a result of performing a printing test using a commercially available ink jet printer, clogging occurred, and it was not possible to stably discharge a stock solution of a recording liquid that was not diluted with water.

When this recording liquid was diluted 4 times with distilled water, it could be ejected with a commercially available ink jet printer. However, a solid image coated with a small recording liquid amount of 0.9 mg per 1 cm ^{2 of} image area was obtained. Has an optical density of 0.3
Was low. (Comparative Examples 13 to 17) The resin dispersions used in Comparative Examples 2 to 6, respectively, were used instead of the resin dispersions containing the fluorine-containing vinyl ether-based resin fine particles produced by emulsion polymerization of water and a fluoroolefin and vinyl ether. A recording liquid was prepared and tested in the same manner as in Comparative Example 11, except that the combination using only one type of resin fine particles was compatible with both high optical density and prevention of clogging. Was impossible. (Comparative Example 18) Instead of a resin dispersion liquid (manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) containing water and a modified polyester resin fine particle having a carboxyl group added to a side chain, a carboxyl group was added to water and a side chain. Resin dispersion containing added modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A)
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that -115G) was used, and it was impossible to achieve both high optical density and prevention of clogging. (Comparative Example 19) Water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0) were used instead of a resin dispersion containing fine particles of a fluorinated vinyl ether resin prepared by emulsion polymerization of water and a fluoroolefin and vinyl ether. .19 μm) (solid content = 48.
5%, manufactured by Sumika ABS Latex, trade name: S
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that N-335) was used, and it was impossible to achieve both high optical density and prevention of clogging. (Comparative Example 20) Instead of a resin dispersion containing fine particles of a fluorine-containing vinyl ether resin produced by emulsion polymerization of water and a fluoroolefin and vinyl ether, fine particles of a modified polyester resin having a carboxyl group added to water and a side chain (average) Resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-
215G), instead of water and a resin dispersion containing modified polyester resin fine particles having a carboxyl group added to the side chain (manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), a carboxyl group is added to water and a side chain. Resin dispersion (solid content = 25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A)
A recording liquid was prepared and tested in the same manner as in Comparative Example 12 except that each of -115G) was used, and it was impossible to achieve both high optical density and prevention of clogging.

[0099]

According to the present invention, since it contains three or more kinds of resin fine particles, it is possible to provide an image having high image density and excellent in water resistance without bleeding or permeation on recording paper.
In addition, a recording liquid having excellent ejection stability can be provided.

Further, the present invention can provide an image recording method having the above advantages.

Continued on the front page (72) Inventor Yasushi Suwabe 430 Green Tech Nakai, Nakai-cho, Ashigarakami-gun, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.

Claims (15)

[Claims] 1. A recording liquid comprising a colorant, water and three or more kinds of resin fine particles. 2. The recording liquid according to claim 1, further comprising non-crosslinkable resin fine particles. 3. The recording liquid according to claim 2, wherein the non-crosslinkable resin fine particles are fluorine resin fine particles. 4. The recording liquid according to claim 3, wherein the fluororesin fine particles have a fluoroolefin unit. 5. The recording liquid according to claim 1, wherein the average particle diameter of each of the resin fine particles is 0.01 μm to 5 μm. 6. A total content of the fine resin particles is 10 to 9.
5. The composition according to claim 1, wherein the content is 5% by weight.
6. The recording liquid according to any one of claims 5 and 6. 7. The recording liquid according to claim 1, wherein the recording liquid contains four or more types of resin fine particles. 8. The recording liquid according to claim 1, wherein the colorant is a pigment. 9. The recording liquid according to claim 8, wherein the content of the pigment is 1 to 50% by weight. 10. The method according to claim 1, wherein the colorant is a dye.
The recording liquid according to the item. 11. The recording liquid according to claim 10, wherein the content of the dye is 0.2 to 40% by weight. 12. An image recording method in which a recording liquid is ejected from a recording head to record on a recording medium, wherein the recording liquid is used as the recording liquid. ,
12. An image recording method using the recording liquid according to any one of 9, 10, and 11. 13. An image recording method for discharging a droplet of a recording liquid from a recording head to perform recording on a recording medium, wherein the recording liquid contains water, a colorant, and four or more types of resin fine particles. An image recording method characterized by using: 14. The image recording method according to claim 12, wherein the recording medium is plain paper. 15. An image recording method in which droplets of a recording liquid are ejected from a recording head to record on a recording medium, wherein the recording liquid contains water, a colorant, and four or more types of resin fine particles. And using plain paper as the recording medium.