JP3011107B2 - Recording liquid and image recording method - Google Patents

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. 6,009,045.

[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, the recording liquid disclosed in the related art can provide both high density and high quality images by increasing the content of resin fine particles (increase in the content of resin solids) and avoiding clogging at the ejection openings. 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 capable of achieving the above object contains a colorant, water and two or more kinds of resin fine particles, and at least one of them is a self-crosslinkable resin fine particle. It is characterized by.

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.

If two or more types of different resin fine particles are contained in the recording liquid, there is a probability that the same type of resin fine particles as this resin fine particle exist around a certain resin fine particle (the closest coordinate position) in the recording liquid. Decrease. 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 hindered 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 is remarkably suppressed by the above-mentioned overall effect, so that the total content of the resin fine particles contained in the recording liquid can be increased, and as a result, the liquid value of one droplet can be reduced. The content of the resin fine particles can be increased, and an image having a high image density can be formed.

Then, an image is quickly formed on the recording paper by the high-speed film forming property of the self-crosslinkable resin fine particles contained in the recording liquid. That is, immediately after the droplet of the recording liquid flying from the recording head adheres to the recording paper, the cross-linking reaction of the self-crosslinkable resin fine particles is rapidly performed due to the evaporation of the water in the recording droplet and the penetration of the recording liquid into the paper. And a strong image film in which the colorant is confined in the resin is rapidly formed. Also, at this time, the film formation of other co-existing self-crosslinkable resin fine particles and non-self-crosslinkable resin fine particles also progressed, thereby preventing bleeding and penetration of the recording liquid and confining the resin and the resin. It is possible to form a high-image-density and high-water-resistance image composed of a colorant on a recording medium such as paper.

[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 a colorant, water, and two or more types of fine resin particles. At least one of the fine resin particles is a self-crosslinkable fine resin particle.

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. Examples of such self-crosslinkable resin fine particles include acrylic silicon-based resin fine particles and acrylamide-based resin fine particles. Among them, high-speed film forming properties suitable for rapid image formation and strength of the formed film are exemplified. In view of the above, alkoxysilyl group-containing acrylic silicon-based resin fine particles capable of rapidly forming a strong siloxane crosslinked film containing a colorant are preferable. The alkyl of the alkoxysilyl group of the alkoxysilyl group-containing acrylic silicone resin fine particles is preferably an alkyl having 1 to 3 carbon atoms, and more preferably an alkyl having 1 to 2 carbon atoms. As the acrylic skeleton, for example, styrene, vinyl toluene, methyl methacrylate, ethyl methacrylate,
N-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, acrylic acid, methacrylic acid 2 And polymers and copolymers containing -hydroxyethyl, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylolacrylamide, glycidyl methacrylate, and the like as monomers.

Examples of the resin fine particles usable together with the self-crosslinkable resin fine particles include non-crosslinkable resin fine particles and resin fine particles crosslinkable by the action of a cross-linking agent. Fine particles, acrylic resin fine particles, polyester resin fine particles, vinyl acetate resin fine particles, vinyl chloride resin fine particles, styrene-butadiene polymer fine particles, polyurethane resin fine particles, polystyrene resin fine particles, vinyl acetate-acryl copolymer System resin particles, vinyl acetate-acrylamide copolymer resin particles, ethylene-vinyl acetate copolymer resin, epoxy resin resin particles, polyamide resin resin particles, and silicone resin particles.

The resin fine particles contained in the recording liquid of the present invention are:
It may be composed of only self-crosslinkable resin fine particles, or may be composed of self-crosslinkable resin fine particles and non-crosslinkable resin fine particles and / or resin fine particles that are crosslinked by the action of a crosslinking agent. From the viewpoint of causing a time difference in the film forming process using a resin and making the film difficult to form due to a difference in composition, thereby preventing clogging, that is, preventing film formation at the recording head discharge port portion, It is preferable to be composed of crosslinkable resin fine particles and non-crosslinkable resin fine particles. 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.

[0020]

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 may contain two or more types of resin fine particles including self-crosslinkable resin fine particles, whereby high image density, high image quality and clogging due to high content of resin solids can be obtained. Although it is possible to achieve compatibility with avoidance sufficiently,
By containing three or more types of resin fine particles including self-crosslinkable 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 (promotion of the coordination effect), Because attraction becomes harder to work,
The occurrence of clogging is more effectively prevented. 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 resin fine particles is considered to be 12, and considering the range of stochastic fluctuation, the upper limit of the type of resin fine particles is preferably 18 (12 types + 6 types). As described above, the types of the resin fine particles contained in the recording liquid in the present invention are preferably two or more and eighteen or less from the viewpoint of approaching the same type of resin fine particles due to the coordination effect and reducing the collision probability. Preferably, the number is 3 or more and 12 or less.
In the present invention, even if the monomers constituting the resin are the same, the characteristics of the resin fine particles or the dispersion thereof, that is, the minimum film forming temperature, the glass transition point, the ionicity, the pH, depend on the method of modification and the like. If any one or more of the weight average molecular weight, the average particle diameter and the like are different, it is considered as another kind of resin fine particles.

The average particle size 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 resin fine particles (the total content of solid resin fine particles) is preferably from 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. When the total content of the resin fine particles is less than 10% by weight, the optical density of the image is reduced. Further, the content of the self-crosslinkable resin fine particles contained in the recording liquid is 0.9 W to 0.05 W parts by weight, when two resin fine particles are used and the total solid content of the resin fine particles is W parts by weight. A range is preferred. Further, when three or more resin fine particles are used, 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: 3 or more) When 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 is 2 W / n parts by weight. To 0.1 W / n parts by weight. 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. The content ratio of the self-crosslinking 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 0.4 W / n parts by weight. The ratio is 2W / n
If the amount is more than the weight part, the effect of preventing clogging due to the coexistence of a plurality of different kinds of resin fine particles is reduced as described above, and 0.4 W /
When the amount is less than n parts by weight, the image forming speed on paper becomes slow, and there is a concern that the image density is reduced.

In the present invention, as the colorant, those having a 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, writing instruments and the like.

[0031]

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 (solids = 35%, solids = 35%) containing 33 parts by weight of a dispersion (solids = 35%) and water and acrylsilicone resin particles having a methoxysilyl group (average particle diameter = 0.1 to 0.2 μm) Product name: SW-13, manufactured by Sanyo Chemical Industries, Ltd.
5) A resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd.) containing 39 parts by weight and fluorine-containing vinyl ether resin fine particles (average particle diameter: 0.15 μm) prepared by emulsion polymerization of water, a fluoroolefin and vinyl ether. ,Product name:
FE-3000) was added and mixed with stirring. Thereafter, this mixture was filtered through a membrane filter having a pore size of 10 μm to remove dust and coarse particles, and the concentration of the pigment (colorant) in the recording liquid ｛= the solid content of the pigment ×
100 / the total amount of the recording liquid (liquid) １２ is 12% by weight, the concentration of the pigment (colorant) in the solid content ｛= the pigment solid content × 100 / (the total of the solid content of the pigment and the solid content of the resin fine particles)｝ is 30% by weight, and the recording liquid is Medium resin fine particle total solid content concentration = total resin fine particle solid content x
100 / recording liquid total amount ２８ was 28% 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 1.7.

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.

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 extending 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 the present method measured in this manner was as long as 40 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 above 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) 28 parts by weight of an aqueous copper phthalocyanine 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) 33 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135), 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 liquid (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G)
39 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 11% by weight, and the pigment (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of fine resin particles in the recording liquid of 23% 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 by an optical microscope, the solid image was mainly formed on the plain paper, and the recording liquid hardly permeated 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 45 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 3) 32 parts by weight of a water-based 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) 38 parts by weight of a resin dispersion (solid content: 35%, manufactured by Sanyo Chemical Industries, trade name: SW-135) containing water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm). ~ 0.2μ
m) and 30 parts by weight of a resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., trade name: G-45) were 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 11% by weight, the pigment (colorant) concentration in the solid content was 30% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 27% 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 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 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 40 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 4) 34 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%) and acrylic silicon resin fine particles having water and methoxysilyl groups (average particle size = 0.1) 27 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) containing water and a fluoroolefin and vinyl ether prepared by emulsion polymerization of vinyl ether. Vinyl ether resin fine particles (average particle diameter: 0.1
19 parts by weight of a resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) containing water and silicon-modified acrylic resin fine particles (average particle size: 0.1 μm).
21% by weight of a resin dispersion (solid content = 45%, product name: G-45, manufactured by Sanyo Kasei Kogyo Co., Ltd.) containing the mixture and stirred to mix uniformly. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm,
After removing dust and coarse particles, the concentration of the pigment (colorant) in the recording liquid was 12% by weight, the concentration of the pigment (colorant) in the solid content was 30% by weight, and the total solid content of the resin fine particles in the recording liquid was 28% by weight. A recording liquid was obtained.

The recording liquid thus prepared was applied to 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 1.7.

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 ejection 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 55 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 5) 34 parts by weight of an aqueous copper phthalocyanine 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) 27 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) containing water and a fluoroolefin and vinyl ether prepared by emulsion polymerization of vinyl ether. Vinyl ether resin fine particles (average particle diameter: 0.1
19 parts by weight of a resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) containing water and a modified polyester resin fine particle having a carboxyl group added to a side chain (average particle diameter: 15 μm). 0.1 to 0.2 μm) (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A)
-215G) 31 parts by weight, 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 11% by weight, and the pigment (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 25% 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 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 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 60 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 6) 34 parts by weight of a water-based 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) 27 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) containing water and a fluoroolefin and vinyl ether prepared by emulsion polymerization of vinyl ether. Vinyl ether resin fine particles (average particle diameter: 0.1
19 parts by weight of a resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) containing water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0.19 μm) Resin dispersion (solid content = 4
8.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335) (19 parts by weight) was added, and the mixture was stirred and uniformly mixed. Thereafter, the mixture was filtered through a membrane filter having a pore diameter of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 13% by weight.
A recording liquid having a pigment (colorant) concentration in the solid content of 30% by weight and a resin particle total solid concentration in the recording liquid of 28% 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 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 1.7.

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 55 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 7 31 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) 24% by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: SW-135), and modified polyester resin fine particles having carboxyl groups added to water and side chains. (Average particle diameter: 0.1 to 0.2 μm) Resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G)
Resin dispersion containing 28 parts by weight, 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: SN-335) and 17 parts by weight, and stirred to mix uniformly. Thereafter, the mixture was filtered through a membrane filter having a pore size of 10 μm,
After removing dust and coarse particles, the concentration of the pigment (colorant) in the recording liquid was 11% by weight, the concentration of the pigment (colorant) in the solid content was 30% by weight, and the total solid content of the resin fine particles in the recording liquid was 25% by weight. A 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 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 60 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 8) 32 parts by weight of a water-based 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 diameter = 0.1) 19 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135), and fluorine-containing liquid produced by emulsion polymerization of water, fluoroolefin and vinyl ether. Vinyl ether resin fine particles (average particle diameter: 0.1
13 parts by weight of a resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) containing water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 μm).
15% by weight of a resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., trade name: G-45), and modified polyester resin fine particles having carboxyl groups added to water and side chains. 22 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) containing (average particle diameter: 0.1 to 0.2 μm) and stirring to make the mixture uniform Mixed. Thereafter, the 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 11% by weight.
A recording liquid having a pigment (colorant) concentration in the solid content of 30% by weight and a total solid content of the resin fine particles in the recording liquid of 26% 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 almost no permeation of the recording liquid into the plain paper was observed. Was.

Next, in the same manner as in Example 1, the clogging property of the recording liquid at the recording head discharge port was evaluated. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 80 seconds.

Further, a printing test of this recording liquid on plain paper was conducted 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 9 31 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) 12 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-135) containing water and a fluoroolefin and vinyl ether prepared by emulsion polymerization of vinyl ether. Vinyl ether resin fine particles (average particle diameter: 0.1
8 parts by weight of a resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) containing water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 10 μm).
9 parts by weight of a resin dispersion containing 0.2 μm) (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., trade name: G-45), and modified polyester resin fine particles having carboxyl groups added to water and side chains ( Resin dispersion (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 = 14 parts by weight) and modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) having carboxyl groups added to water and side chains.
25%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-115G, pH and glass transition point are different from A-215G) 17 parts by weight, water and modified styrene-butadiene copolymer resin fine particles (average particle diameter: 0. 9 parts by weight of a resin dispersion (solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335) was added thereto, followed by stirring and uniformly mixing. 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 11% by weight, the pigment (colorant) concentration in the solid content was 30% 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.

The recording solution 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, in the same manner as in Example 1, the clogging property of the recording liquid at the recording head discharge port was evaluated. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 110 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. (Example 10) Acrylic silicone resin fine particles having a methoxysilyl group (average particle diameter = 0.1 to 0.2 µm) were added to 64 parts by weight of an aqueous solution (solid content = 10%) of a phthalocyanine dye (acid blue 9). Containing resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-13)
5) A resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd.) containing 14 parts by weight and fluorine-containing vinyl ether-based resin fine particles (average particle size: 0.15 μm) prepared by emulsion polymerization of water, a fluoroolefin and vinyl ether. ,Product name:
FE-3000) 10 parts by weight, water and silicon-modified acrylic resin fine particles (average particle diameter: 0.1 to 0.2 μm)
And 11 parts by weight of a resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: G-45). Thereafter, the mixed solution was added with a pore size of 10 μm.
m, removing dirt and coarse particles, the dye (colorant) concentration in the recording liquid is 6% by weight, the dye (colorant) concentration in the solid content is 30% by weight, the resin in the recording liquid is A recording liquid having a total solid content of fine particles of 15% by weight was obtained.

The recording liquid thus prepared was applied to 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 1.8.

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 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 60 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 colorant due to water were observed, and it was found that the recording liquid according to the present example had high water resistance. Example 11 61 parts by weight of an aqueous solution (solid content = 10%) of a phthalocyanine-based dye (acid blue 9) was mixed with acrylic silicon resin fine particles (average particle size = 0.1 to 0.2 μm) having water and a methoxysilyl group. Containing resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-13)
5) A resin dispersion (solid content = 50%, manufactured by Asahi Glass Co., Ltd.) containing 7 parts by weight and fluorine-containing vinyl ether resin fine particles (average particle size: 0.15 μm) prepared by emulsion polymerization of water, a fluoroolefin and vinyl ether. , Product name: F
E-3000) 5 parts by weight, and a resin dispersion (solid content = 45%, manufactured by Sanyo Chemical Industries, Ltd., containing water and silicon-modified acrylic resin fine particles (average particle size: 0.1 to 0.2 μm), trade name: G-45) A resin dispersion liquid containing 5 parts by weight of water and modified polyester resin fine particles (average particle diameter: 0.1 to 0.2 μm) having a carboxyl group added to a side chain (solid content = 30%, Takamatsu 8 parts by weight, modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter: 0.1 to 0.2)
μm), 10 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), 5 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 dye (colorant) concentration in the recording liquid was 6% by weight, and the dye (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 14% 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 1.8.

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, in the same manner as in Example 1, the clogging of the recording liquid at the recording head discharge port was evaluated. As a result, the margin time until the clogging of the recording liquid occurred in this method was as long as 115 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 colorant 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) 30 parts by weight of a water-based 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) 70 parts by weight of a resin dispersion (solid content = 35%, manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: SW-135) 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, and the concentration of the pigment (colorant) in the recording liquid was 10% by weight, and the concentration of the pigment (colorant) in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 25% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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 amount of recording liquid of 0.9 mg per 1 cm ^{2 of} the image area was 1.6, but 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 with 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 0.6. (Comparative Example 2) 38 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) 62 parts by weight were added 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, and the pigment (colorant) concentration in the recording liquid was 13% by weight, and the pigment (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 31% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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 1.4, but the margin time until 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 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 3 27 parts by weight of an aqueous copper phthalocyanine pigment (Pigment Blue 15: 3) dispersion (solid content = 35%), modified polyester resin fine particles having a carboxyl group added to water and side chains (average particle diameter) : 0.1-0.2μ
73) by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G) containing m) 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 9% by weight, the pigment (colorant) concentration in the solid content was 30% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 22% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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 1.4, but the margin time until the occurrence of clogging was as short as 12 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 4) 35 parts by weight of an aqueous copper phthalocyanine-based 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 =
65% by weight of 45% (manufactured by Sanyo Chemical Industries, 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 diameter of 10 μm to remove dust and coarse particles, and the pigment (colorant) concentration in the recording liquid was 12% by weight, and the pigment (colorant) concentration in the solid content was 30%. % By weight, the total solids concentration of the resin fine particles in the recording liquid is 29.
% By weight of the recording liquid was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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 1.4, but the margin time until 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 0.6
Was low. (Comparative Example 5) 37 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) ) (Solid content = 48.5%, manufactured by Sumika ABS Latex Co., Ltd., trade name: SN-335) (63 parts by weight) 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 13% by weight, the pigment (colorant) concentration in the solid content was 30% by weight, and the resin in the recording liquid was A recording liquid having a total solid content of fine particles of 31% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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, but the margin time until 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 0.6
Was low. (Comparative Example 6) Acrylic silicone resin fine particles (average particle size = 0.1 to 0.2 µm) having water and a methoxysilyl group in 60 parts by weight of an aqueous solution of phthalocyanine dye (acid blue 9) (solid content = 10%). Containing resin dispersion (solid content = 35%, manufactured by Sanyo Chemical Industries, Ltd., trade name: SW-13)
5) 40 parts by weight 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 dye (colorant) concentration in the recording liquid was 6% by weight, and the dye (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 14% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the 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 amount of recording liquid of 0.9 mg per 1 cm ^{2 of} the image area was 1.6, but the margin time until 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 0.6
Was low. (Comparative Examples 7 to 10) Comparative Examples except that the resin dispersions used in Comparative Examples 2 to 5 were used instead of the resin dispersions containing water and acrylic silicone resin fine particles having a methoxysilyl group, respectively. A recording liquid was prepared in the same manner as in 6, and
As a result of the test, it was impossible to achieve both high optical density and prevention of clogging in any of the combinations using only one type of resin fine particles. (Comparative Example 11) 31 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), 43 parts by weight of a resin dispersion (solid content = 30%, manufactured by Takamatsu Yushi Co., Ltd., trade name: A-215G), 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) containing resin dispersion (solid content = 50)
%, Manufactured by Asahi Glass Co., Ltd., trade name: FE-3000) and mixed with stirring. 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 11% by weight, and the pigment (colorant) concentration in the solid content was 30%. By weight, a recording liquid having a total solid content of resin fine particles in the recording liquid of 26% by weight was obtained.

The recording liquid thus prepared was
In the same manner as in Examples 1 to 11, the measurement of the optical density, the measurement of the margin time until the occurrence of clogging, and the printing test on plain paper by a commercially available inkjet printer were performed. As a result, the margin time before clogging was 40 seconds, and a commercially available ink jet printer was able to stably discharge the stock solution of the recording liquid not diluted with water,
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 low as 1.3.

As described above, the recording liquids of Examples 1 to 11, unlike the comparative examples, were able to achieve both high optical density and prevention of clogging.

[0101]

Since the present invention contains two or more kinds of resin fine particles including at least one kind of self-crosslinkable resin fine particles, the present invention has a high image density and has no water bleeding or penetration on recording paper. This makes it possible to provide a recording liquid which can provide an image excellent in discharge stability and has excellent ejection stability.

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

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasufumi Suwabe 430 Green, Nakai-cho, Nakai-cho, Ashigara-gun, Kanagawa Inside Fuji Xerox Fuji Xerox Co., Ltd. (56) References JP-A-7-118583 (JP, A) JP-A-8- 60062 (JP, A) JP-A-3-160069 (JP, A) JP-A-10-88056 (JP, A) JP-A-10-88045 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (15)

(57) [Claims] 1. A recording liquid comprising a colorant, water and two or more types of resin fine particles, wherein at least one type is a self-crosslinkable resin fine particle. 2. The recording liquid according to claim 1, further comprising non-crosslinkable resin fine particles. 3. The self-crosslinking resin fine particles are acrylic silicon-based resin fine particles.
Or the recording liquid according to 2. 4. The acrylic silicon resin fine particles contain an alkoxysilyl group.
The recording liquid according to 1. 5. The recording liquid according to claim 2, wherein the non-crosslinkable resin fine particles are fluorine resin fine particles. 6. The recording liquid according to claim 5, wherein the fluororesin fine particles have a fluoroolefin unit. 7. 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. . 8. The 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.
The recording liquid according to any one of 4, 5, 6, and 7. 9. The method according to claim 1, wherein the composition contains three or more kinds of resin fine particles.
The recording liquid according to any one of the above. 10. The recording liquid according to claim 1, wherein the colorant is a pigment. 11. The recording liquid according to claim 10, wherein the content of the pigment is 1 to 50% by weight. 12. The recording liquid according to claim 1, wherein the colorant is a dye. 13. The recording liquid according to claim 12, wherein the content of the dye is 0.2 to 40% by weight. 14. An image recording method in which a recording liquid is ejected from a recording head to perform recording on a recording medium, wherein the recording liquid is used as the recording liquid. ,
An image recording method using the recording liquid according to any one of 9, 10, 11, 12, and 13. 15. The image recording method according to claim 14, wherein the recording medium is plain paper.