JP2002205457A - Method for measuring porous physical properties caused by liquid composition, liquid composition, ink set, method for forming colored part on medium to be recorded, and ink jet recorder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for measuring a physical property value caused by a liquid composition capable of obtaining an ink jet recorded matter of high quality particularly having excellent color developability, the liquid composition, an ink set, a method for forming a colored part on a medium to be recorded and an ink jet recorder. SOLUTION: The method for measuring the liquid composition comprises the steps of pretreating the composition containing at least fine particles by the steps of (1) drying the composition at 120 deg.C for 10 hours in an atmosphere to substantially evaporate a solvent content to dry the composition; (2) raising the dried matter to 120 to 700 deg.C in 1 hour, then baking the matter at 700 deg.C for 3 hours; and (3) gradually returning the baked matter to the ambient temperature after baking and then powdering the baked matter, and then a step of vacuum degassing at 120 deg.C for 8 hours and measuring pore physical properties of a fine particle aggregate formed of the composition by a nitrogen adsorbing and desorbing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for obtaining an image having excellent color developability and color uniformity in forming a color image, and more particularly to a liquid composition which can be optimally used for image formation using an ink jet recording system. TECHNICAL FIELD The present invention relates to a method for measuring physical properties of pores, a liquid composition, an ink set using the same, a method for forming a colored portion on a recording medium, and an ink jet recording apparatus.

[0002]

2. Description of the Related Art In an ink jet recording method, recording is performed by flying ink and attaching the ink to a recording medium such as paper. For example, Japanese Patent Publication No. 61-59911, Japanese Patent Publication No. 61-59912 and Japanese Patent Publication No. 61-5
According to an ink jet recording method disclosed in Japanese Patent No. 9914, in which an electric converter is used as a discharge energy supply unit and droplets are discharged by applying thermal energy to ink to generate bubbles, High-density multi-orifices can be easily realized, and high-resolution and high-quality images can be recorded at high speed.

[0003] The ink used in the conventional ink jet recording method is mainly composed of water, and a water-soluble high-boiling solvent such as glycol for the purpose of preventing drying of the ink in the nozzles and clogging of the nozzles. Is generally contained. Therefore, when recording is performed on a recording medium using such an ink, sufficient fixability cannot be obtained, or due to uneven distribution of fillers and sizing agents on the recording paper surface as the recording medium. In some cases, problems such as generation of an estimated non-uniform image may occur. On the other hand, in recent years, there has been a strong demand for ink-jet recorded matter to have the same high image quality as silver halide photographs, and to increase the image density of the ink-jet recorded image, expand the color reproduction area, and furthermore, Technical requirements for improving the color uniformity of recorded matter are very high.

[0004] Under such circumstances, various proposals have been made so far in order to stabilize the ink jet recording method and to improve the quality of recorded matter by the ink jet recording method. As one of the proposals regarding a recording medium, a method of applying a filler or a sizing agent on the surface of a base paper of the recording medium has been proposed. For example, a base material is coated with porous fine particles that adsorb a coloring material as a filler,
A technique for forming an ink receiving layer by using the porous fine particles is disclosed. As recording media using these technologies, inkjet coated paper and the like are on the market.

Some typical proposals made so far for stabilizing the ink jet recording method and improving the quality of recorded matter by the ink jet recording method will be described below. (1) a method of internally adding a volatile solvent or a penetrating solvent to the ink;
As a means for accelerating the fixability of the ink to the recording medium, Japanese Patent Application Laid-Open No. 55-65269 discloses a method of adding a compound such as a surfactant to the ink to enhance the permeability. Japanese Patent Application Laid-Open No. 55-66976 discloses the use of an ink mainly containing a volatile solvent. (2) a method of mixing a liquid composition that reacts with the ink with the ink on a recording medium; improvement in image density, improvement in water resistance,
Furthermore, for the purpose of suppressing bleeding, prior to or after the ejection of ink for forming a recorded image,
There has been proposed a method of applying a liquid composition for improving an image on a recording medium.

For example, Japanese Patent Application Laid-Open No. 63-60783 discloses a method in which a liquid composition containing a basic polymer is applied to a recording medium and then recorded with an ink containing an anionic dye. JP-A-63-226
No. 81 discloses a recording method in which a first liquid composition containing a reactive species and a second liquid composition containing a compound which reacts with the reactive species are mixed on a recording medium. Further, JP-A-63-2999971 discloses that
A method is disclosed in which a liquid composition containing an organic compound having two or more cationic groups per molecule is applied onto a recording medium, and then recording is performed with an ink containing an anionic dye. JP-A-64-9279 discloses a method in which an acidic liquid composition containing succinic acid or the like is applied onto a recording medium, and recording is performed with an ink containing an anionic dye.

Japanese Patent Application Laid-Open No. 63-63185 discloses a method in which a liquid composition for insolubilizing a dye is applied to paper prior to applying the ink. Further, Japanese Patent Application Laid-Open No. Hei 8-224595 discloses a method of using a liquid composition containing a cationic substance having a different molecular weight distribution region together with an ink containing an anionic compound. A method is disclosed in which a liquid composition containing a cationic substance and finely divided cellulose is used together with ink, and the image density is high for each of the methods.
It is described that print quality and water resistance are good, and good images can be obtained in color reproducibility and bleeding. Japanese Patent Application Laid-Open No. 55-150396 discloses a method in which after recording on a recording medium with a dye ink, a water-resistant agent for forming a lake with the dye is applied to impart water resistance to the recorded image. It has been proposed.

(3) A method of mixing the ink and the fine particle-containing liquid composition on a recording medium;
Japanese Patent Application Laid-Open No. 6-92010 discloses a method in which a colorless liquid containing colorless fine particles made of an inorganic substance is applied onto a recording medium, and then a non-aqueous recording liquid is attached thereto. A method of applying a solution containing a pigment, a water-soluble resin, a water-soluble solvent and water to a recording medium after applying a solution containing the solution or a solution containing fine particles and a binder polymer to a recording medium is disclosed. 34
No. 432 discloses a recording material containing a liquid composition comprising water-insoluble fine particles and an ink, and describes that an image having good print quality and color development can be obtained regardless of the type of paper. I have.

[0009]

The present inventors have conducted various studies on the above-described various types of ink jet recording techniques, and as a result, have been able to confirm excellent effects for each technical problem. It has been found that other ink jet recording characteristics may be deteriorated. For example, a recording medium (hereinafter referred to as coated paper) obtained by applying a filler or a sizing agent on the surface of a base paper of the recording medium described above has been recognized as a technology capable of forming a high-quality image. However, there are technical issues as described below.

In general, it is known that in order to obtain a high chroma image, it is necessary to leave the coloring material in a monomolecular state on the surface of the recording medium without agglomeration. The porous fine particles of the coated paper have such a function. However,
In order to obtain high image density and image saturation, it is indispensable to form a thick ink receiving layer that covers the base paper with a large amount of porous fine particles for the coloring material in the given ink. There is a problem that the texture of the base paper is lost. On the other hand, the present inventors need such an ink receiving layer to lose the texture of the base paper, because the coloring material is
It was presumed that this was caused by the ineffective adsorption to the porous fine particles.

[0011] This point will be described below, assuming a coated paper having one ink receiving layer. FIG. 9 schematically shows a cross section near the surface of the coated paper. In the figure, reference numeral 901 denotes a base paper, and 903 denotes an ink receiving layer. In general, the ink receiving layer 903 has porous fine particles 905 and an adhesive 907 for fixing them.
When the ink is applied, the ink penetrates the gap between the porous fine particles 905 by capillary action, and the ink penetrates 909.
To form As shown in FIG.
Since the density of the porous fine particles 905 differs locally, the way of permeation of the ink by the capillary phenomenon differs depending on the location. Therefore, during the ink permeation process, the coloring material cannot uniformly contact the surface of the porous fine particles, and the coloring material is not efficiently adsorbed on the porous fine particles.

Further, there are portions where ink penetration is inhibited by the adhesive 907 constituting the ink receiving layer, and there are portions in the ink receiving layer 903 where ink cannot penetrate, which contributes to color development. Some parts do not. That is, in the conventional coated paper, the coloring material cannot be efficiently adsorbed in a monomolecular state with respect to the amount of the porous fine particles for the above-described reason, and as a result, a high-quality image is obtained. For this reason, it is considered that a large amount of porous fine particles was required, which impaired the texture of the base paper.

Further, according to the study of the present inventors, by adopting the technology classified into the above (1), although the fixing property of the ink to the recording medium is improved, it is possible to reduce the image density and the like. It has been found that the color reproduction range, which is important for recording on plain paper or recording a color image, may be reduced. According to the study of the present inventors, the above (2)
According to the technology classified as, since the coloring material in the ink can be kept on the surface of the recording medium, a recorded matter having a high image density can be obtained, but the coloring material is aggregated on the surface of the recording medium. In some cases, the color reproduction range and saturation were not sufficiently obtained. Further, in the prior art described in the above (3), although the surface condition of the recording medium was modified by applying the solution containing the fine particles, a high-definition image at the same level as coated paper was not obtained. Was. In particular, non-aqueous recording liquids are limited by the selectivity of coloring materials and the recording method, and the degree of freedom remains a problem. As described above, since the conventional methods still have problems, the present inventors have developed a new ink jet recording technique for higher quality ink jet recordings required in recent years. Has come to the realization that development is necessary. The present invention has been made based on these recognitions.

On the basis of the above-described new findings, the present inventors have used fine particles having a function of adsorbing a coloring material, and in order to efficiently adsorb or bind the coloring material to the fine particles, By dispersing and using the ink in a liquid state together with the ink, it becomes possible to cause the colorant and the fine particles to react in a liquid-liquid state, and as a result, it was possible to improve the density and saturation of the image. Invented the invention.

Accordingly, an object of the present invention is to provide a method for measuring the physical properties of pores originating from a liquid composition which can specify a liquid composition capable of obtaining a higher quality ink jet recorded matter having particularly excellent coloring properties. Is to do. Also,
Another object of the present invention is to have a wider color reproduction range,
An object of the present invention is to provide a liquid composition used for obtaining a high-quality ink jet recorded matter having excellent color uniformity. Another object of the present invention is to provide an excellent ink jet recording having an even wider color reproduction range, excellent color uniformity, less solid streaks, and excellent scratch resistance. It is another object of the present invention to provide a method for forming a colored portion on a recording medium which can form an object on plain paper. Further, another object of the present invention is to provide an ink-jet recorded material having an even wider color reproduction range, excellent color uniformity, and excellent scratch resistance in which the occurrence of solid streaks is suppressed to a satisfactory state. It is an object of the present invention to provide a liquid composition capable of forming a liquid composition, an ink set combining the liquid composition, and an ink jet recording apparatus. It is still another object of the present invention to provide a liquid composition having excellent storage stability and excellent ink jet recording characteristics which are excellent in ejection stability from a recording head.

[0016]

DISCLOSURE OF THE INVENTION In view of the above objects, the inventors of the present invention have provided an ink jet method including a step of bringing a liquid composition containing fine particles having a function of adsorbing a coloring material and an ink into a liquid-liquid state. The study was repeated with the aim of further improving the record. In the process, the present inventors initially recognized that the larger the particle size of the fine particles in the liquid composition, the higher the color developability of the printed matter. However, when the experiment was further advanced, it was concluded that an image with good coloring properties could be obtained even when the particle diameter of the fine particles was small, and this recognition might not always be accurate.

Therefore, the present inventors have further studied and found that the fine particles dispersed in the liquid composition aggregated near the surface of the recording medium to form fine particles. Specifically, it was presumed that the pore radius and the pore volume had a close relationship with the color development of the printed matter. Therefore, based on the above estimation, the present inventors have conducted intensive studies in order to determine the exact pore physical properties of the fine particle aggregate formed from the liquid composition, and pretreated the liquid composition by a predetermined method. However, the inventors have found that the pore physical property values of the resulting fine particle aggregates have an extremely strong correlation with the color development of the printed matter, and have achieved the present invention having the following constitution. As described above, the present invention has been gradually made through the above-described examination process.

In one embodiment of the present invention, a liquid composition containing at least fine particles and a solvent is pretreated according to the following order (1) to (3), and then deaerated in vacuum at 120 ° C. for 8 hours. A step of measuring the pore properties of fine particle aggregates formed from the product by a nitrogen adsorption and desorption method, which provides a method for measuring pore properties caused by a liquid composition: (1) The liquid The composition is dried in an air atmosphere at 120 ° C. for 10 hours to evaporate almost the solvent, followed by drying. (2) The dried product is heated from 120 ° C. to 700 ° C. for 1 hour and then at 700 ° C. for 3 hours Firing; and (3) after firing, gradually return the fired product to room temperature to powder the fired product.

According to another embodiment of the present invention, there is provided a liquid composition which is applied to a recording medium together with an ink containing a coloring material to form a colored portion on the recording medium,
The liquid composition includes at least fine particles having reactivity with a solvent and the coloring material, and the pore physical properties of the fine particle aggregate formed from the liquid composition are measured by the above-described liquid composition. When measured by the method, the fine particle aggregate has a pore volume of 0.3 nm to 30 nm with a pore volume of 0.3 nm.
Provided is a liquid composition having a pore volume of 4 ml / g or more and a pore volume in a region having a pore radius of more than 30 nm of 0.1 ml / g or less.

Another embodiment of the present invention is an ink set independently comprising an ink containing a coloring material and a liquid composition containing fine particles reactive with the coloring material, Is an ink set, characterized in that the ink composition is the liquid composition described above.

According to another embodiment of the present invention, there are provided (i) a step of applying an ink containing a coloring material to a recording medium, and (ii) a step of applying a liquid composition having the above structure to the recording medium. The present invention provides a method for forming a colored portion on a recording medium, comprising:

According to another embodiment of the present invention, there is provided a first recording unit having an ink containing section containing an ink containing a color material, an ink jet head for discharging the ink, and the above-described configuration. Provided is an ink jet recording apparatus, comprising: a liquid composition storage section that stores a liquid composition; and a second recording unit including an ink jet head for discharging the liquid composition.

According to another embodiment of the present invention, there is provided an ink containing section containing an ink containing a coloring material, a liquid composition containing section having the above configuration, and an ink contained in the ink containing section. There is provided an ink jet recording apparatus comprising: an ink jet head for independently discharging the liquid composition contained in the liquid composition containing section, respectively.

A liquid composition according to another embodiment of the present invention is applied to a recording medium together with an anionic or cationic ink containing a coloring material, and forms a colored portion on the recording medium. The liquid composition having the above configuration used, wherein the formation of the colored portion is such that the liquid composition and the ink come into contact with each other in a liquid state, and the surface of the fine particles of the liquid composition has a color in the ink. Provided is a liquid composition characterized in that the material is adsorbed or bonded while maintaining the molecular state substantially equal to the molecular state of the ink. In this specification, the term "reaction between a coloring material and fine particles" means ionic bond, physical / chemical adsorption, absorption, adhesion, and other interaction between the two, in addition to the covalent bond between the two. Shall be.

[0025]

Next, the present invention will be described in more detail with reference to preferred embodiments. As a preferred embodiment of the method for forming a colored portion on a recording medium, (i) a step of applying an ink containing a coloring material to the recording medium, and (ii) applying the liquid composition of the present invention to the recording medium And a configuration in which the ink and the liquid composition are applied so as to be in contact with each other in a liquid state on the surface of the recording medium. By adopting such an embodiment, it has a wider color reproduction area,
Excellent color uniformity, less solid streaks,
An ink jet recorded matter having good scratch resistance can be stably obtained.

Further, as one embodiment of the ink set of the present invention which can achieve the above object, there is an ink set in which an ink containing a coloring material and the liquid composition of the present invention are combined. By using the ink set of such an embodiment, an ink jet recorded matter having a wider color reproduction area, excellent color uniformity, and also having good rubbing resistance with less solid streaks can be obtained. Obtained stably.
Further, as described above, since the ink and the liquid composition used for recording have a very simple configuration, both the ink and the liquid composition have excellent storability, and as a result, a high-quality inkjet The effect of stably performing image formation to obtain a recorded matter is also obtained.

The reason why the above-mentioned excellent effects are achieved by the present invention is not clear, but the present inventors believe that it is due to the following reasons. Heretofore, the present inventors have studied the mechanism by which fine particle aggregates are formed near the surface of the recording medium when the liquid composition and the ink are mixed on the recording medium. As a result of further study of the mechanism by the present inventors, a pore is formed inside the fine particle aggregate by the physical properties of the liquid composition, and when the pore has a certain size, the entrance of the pore is It has been found that the coloring material is further adsorbed on the inner wall in the vicinity or inside the pores, so that the coloring property can be further improved.

First, the recording mechanism of the present invention will be described with reference to FIGS. Here, an aqueous ink containing a water-soluble dye having an anionic group (anionic dye) is used as the ink, and fine particles whose surface is cationically charged are included in the liquid composition in a dispersed state. The case where an aqueous liquid composition is used will be described.

Hereinafter, a recorded image according to the present invention will be described with reference to FIG. First, prior to the explanation, words are defined. In the present invention, the “monomolecular state” means that a coloring material such as a dye or a pigment substantially maintains a state of being dissolved or dispersed in the ink. At this time, even if the coloring material causes some aggregation, the coloring material is included in the “monomolecular state” as long as the saturation is not reduced. For example, in the case of a dye, it is considered preferable that the dye is a single molecule, and for convenience, a coloring material other than the dye is also referred to as a “single molecular state”.

FIG. 13 is a diagram schematically showing a state in which a coloring portion I of a recorded image according to the present invention is composed of a main image portion IM and a peripheral portion IS thereof. In FIG. 13, reference numeral 1301 denotes a recording medium, and 1302 denotes a gap generated between fibers of the recording medium. Also, 1303 is the color material 13
Numeral 05 schematically shows fine particles which are chemically adsorbed. As shown in FIG. 13, in the ink jet recorded image of the present invention, the main image portion IM is such that the color material 1305 is uniformly formed on the surface in a single molecule or a state close to a single molecule (hereinafter abbreviated as “single molecule state”). It is composed of adsorbed fine particles 1303 and an aggregate 1307 of fine particles that keep the colorant in a monomolecular state. Reference numeral 1309 denotes an aggregate of fine particles existing near the recording medium fibers in the main image area IM. The main image portion IM is formed by a process in which the fine particles 1303 are physically or chemically adsorbed to the recording medium fibers, and a process in which the coloring material 1305 and the fine particles 1303 are adsorbed in a liquid-liquid state. Therefore, even in a recording medium such as plain paper in which the ink easily sinks, the image density and saturation are high, and an image having a wide color reproduction range similar to that of coated paper can be formed even when the coloring material of the coloring material itself is not impaired. It becomes possible.

On the other hand, it is not adsorbed on the fine particle surface 1303,
The coloring material 1305 remaining in the ink is a recording medium 1301.
Penetrates both in the lateral direction and in the depth direction with respect to the ink, the ink forms a slight blur in the peripheral portion IS. As described above, since the coloring material remains near the surface of the recording medium 1301 and a slight bleeding of the ink is formed in the peripheral portion, even in an image area where a large amount of ink is applied, such as a shadow portion or a solid portion, the white color is removed. Excellent color uniformity with little color unevenness. FIG.
In the case where the recording medium 1301 is permeable to the ink or the liquid composition as shown in the above, this embodiment does not necessarily prevent the penetration of the ink component or the liquid composition component into the recording medium. It is not something that allows some penetration.

Further, when the liquid composition of the present invention is used, when a fine particle aggregate 1309 existing near the surface of the recording medium is formed, pores of a certain size are formed inside the aggregate. It is formed. The coloring material 1305 which was present alone in the ink described above penetrates into the pores of the fine particle aggregates 1309 when penetrating into the recording medium,
The coloring material can be adsorbed to the vicinity of the entrance of the pores or to the inner wall in an ideal monomolecular state, so that more coloring material can be left near the surface of the recording medium. This makes it possible to obtain a recorded matter having even better coloring properties.

FIGS. 14 (1) to 14 (4) are schematic sectional views of a colored portion 1400 of one embodiment of a method for forming a colored portion on a recording medium according to the present invention, and schematic process diagrams for explaining the forming process. It is. In the figure, reference numeral 1401 denotes a portion mainly containing a reaction product of the ink and the liquid composition, for example, a reaction product of a coloring material and fine particles (hereinafter, abbreviated as “reaction portion”)
This is a portion corresponding to the main image portion IM in FIG. 1402
Is a portion formed by the ink that has not substantially participated in the reaction with the liquid composition flowing out to the periphery of the reaction portion 1401 (hereinafter referred to as “ink outflow portion”),
This corresponds to the peripheral part IS in FIG. Such a colored portion 1400
Is formed, for example, as follows. Incidentally, reference numeral 1405 shown in the figure schematically represents a gap generated between the fibers of the recording medium.

First, the coloring material 1404 and the liquid composition 1406 having reactivity are applied as droplets to the recording medium 1403 (FIG. 14A), and as a result, a liquid composition reservoir 1407 is formed. (FIG. 14 (2)). The pool 1
407, the fine particles 14 near the fiber surface of the recording medium.
09 is physically or chemically adsorbed on the fiber surface of the recording medium. At this time, it is considered that there is a case where the dispersion state becomes unstable and aggregates 1411 of the fine particles are formed. On the other hand, it is considered that the fine particles 1409 remain in the original dispersion state in the portion of the liquid reservoir 1407 farther from the fibers.

Next, the ink 1413 is applied as droplets to the recording medium 1403 (FIG. 14 (2)). As a result, first, at the interface between the ink 1413 and the liquid pool 1407, the coloring material 1404 is chemically adsorbed to the fine particles 1409. Since this reaction is a liquid-liquid reaction (liquid-liquid reaction), the coloring material 1404 is considered to be uniformly adsorbed on the surface of the fine particles 1409 in a monomolecular state (FIG. 14 (3)-).
2). That is, it is presumed that the coloring materials do not agglomerate on the surface of the fine particles, or even if the agglomeration is slight. As a result, the coloring material 14 is formed in a monomolecular state on the surface portion of the reaction portion 1401.
Since a large number of fine particles having adsorbed thereon 04 are formed, and the coloring material can remain in a monomolecular state on the surface layer that most affects color development, a recorded image with high image density and high saturation can be formed. Is done.

Next, the fine particles adsorbed by the coloring material 1404 are considered to be aggregated with each other because the dispersion state becomes unstable (FIG. 14 (3) -2). That is, the aggregate 1415 formed here also holds a monomolecular color material inside. The aggregate 1415 forms a recorded image with high image density and high chroma.

Further, a part of the unreacted coloring material 1404 diffuses in the liquid pool 1407 and is adsorbed on the surface of the unreacted fine particles 1409. As described above, since the reaction between the coloring material and the fine particles further proceeds inside the liquid reservoir 1407, an image having higher density and higher saturation is formed. The aggregate 1411 of fine particles formed on the fiber surface of the recording medium described above is considered to have a role of suppressing the liquid phase of the liquid pool 1407 from penetrating into the recording medium. Therefore, the sump 14
07, the fine particles 14 in the liquid composition whose permeation was suppressed
09 and the coloring material 1404 can be mixed more. As a result, the probability of contact between the coloring material 1404 and the fine particles 1409 is increased, the reaction proceeds relatively uniformly and sufficiently, and a more uniform image having excellent image density and saturation is formed.

The liquid composition 1406 is applied to the recording medium 1.
403 (FIG. 14 (1)) or the liquid pool 14
When the ink 1413 is applied to the ink cartridge 07 (see FIG.
(2)) Dispersion of the fine particles 1409 becomes unstable due to a change in the dispersion medium in which the fine particles 1409 are dispersed, and there are some substances that cause aggregation between the fine particles 1409 before the coloring material 1404 is adsorbed. The change of the dispersion medium as referred to herein is a change generally observed when two or more different kinds of liquids are mixed, such as a pH of a liquid phase, a solid content concentration, a solvent composition, and a dissolved ion concentration. It is thought that when the liquid composition comes into contact with the recording medium or ink, these changes occur rapidly and in a complex manner, destroying the dispersion stability of the fine particles, and generating aggregates. .

It is presumed that these aggregates have the effect of filling the voids between the fibers and the effect of leaving the fine particles adsorbing the coloring material more near the surface of the recording medium. Some of the aggregates formed in the liquid reservoir 1407 are adsorbed on the recording medium, and some are capable of moving in the liquid phase (having fluidity). Is similar to the above-described reaction process between the coloring material and the fine particles, in which the coloring material is adsorbed in a monomolecular state on the surface of the fine particle aggregates to form a larger aggregate, which contributes to the improvement of the coloring property. It is. When the liquid phase permeates along the fiber, it moves together with the liquid phase, filling the voids and smoothing the surface of the recording medium,
This is considered to contribute to the formation of a more uniform and high-density image.

It is clear from the results described below that a high color image can be obtained by the present invention. This is because, as described above, the coloring material is adsorbed to fine particles or fine particle aggregates in a monomolecular state. It is considered that this is because it remained near the surface of the recording medium in the state. The coloring material is adsorbed in a monomolecular state, and the fine particles remaining on the surface of the recording medium are fixed on the surface of the recording medium. This improves the fastness of the image such as scratch resistance.

Although the description has been given of the case where the liquid composition and the ink are applied to the recording medium in this order, if the liquid-liquid reaction between the ink and the liquid composition is achieved, the ink and the liquid are applied. The order of applying the composition to the recording medium is not limited to this, and the order of the ink and the liquid composition may be applied. Further, as shown in FIG. 14 (2), at least a part of the fine particles in the liquid composition applied to the recording medium penetrates into the recording medium as the liquid medium penetrates into the recording medium. it seems to do.

On the other hand, as clearly shown in FIG. 14 (4), it can be sufficiently assumed that the coloring material is adsorbed or bonded in a monomolecular state to the fine particles which have previously penetrated. Thus, it is considered that the fine particles in which the coloring material is adsorbed or bonded in a monomolecular state inside the recording medium also contributes to the improvement of the coloring property. Further, it is considered that the fixability is improved by the penetration of the liquid medium.

Further, by using the liquid composition of the present invention, when the fine particle aggregate 1411 existing near the surface of the recording medium is formed, pores of a certain size are formed inside the aggregate. Is formed. The coloring material 1404 that could not be completely absorbed by the fine particles 1409 in the liquid pool 1407 is
Some penetrate into the fine particle aggregate 1411 through the pores together with the solvent component when penetrating into the recording medium. At that time, the coloring material 1404 is adsorbed near the entrance of the pores in the fine particle aggregates or on the inner wall of the fine pores, and only the solvent component permeates into the recording medium. It can be efficiently adsorbed on the surface or inside of the recording medium 1411 and can be left near the surface of the recording medium. Further, when the coloring material 1404 is a dye, the fine particle aggregate 14
Since the pore diameter of No. 11 is about one to several times the molecular size of the coloring material 1404 existing in the ink, the coloring material 1404 adsorbed inside the pores is extremely unlikely to agglomerate between the coloring materials. Thus, an ideal monomolecular state can be formed. This greatly contributes to further improvement of the color developing property, and a recorded matter having a wider color reproduction range can be obtained.

Therefore, the fine particles 1 in the liquid composition
It has been found that the size of the pores inside the fine particle aggregates 1411 formed when the particles 409 aggregate on the recording medium is closely related to the further improvement of the color developing properties of the ink. As a result of repeated studies by the present inventors, the pore physical properties of the fine particle aggregates 1411 are not limited to the fine particles contained in the liquid composition,
It can be seen that it is also affected by the solvent composition, etc., and a fine particle aggregate is formed from the liquid composition, and the pore volume of the fine particle aggregate in a specific pore radius region is formed on the recording medium. It was found that the correlation with the forming ability was very high.

Further, in the present invention, when the coloring material is anionic, the coloring material is extremely efficiently applied to the surface of the cationic fine particles by reacting the fine particles and the coloring material in a liquid phase on the surface of the recording medium. Will be adsorbed. Here, in order to achieve the same level of colorant adsorption as in the present invention in ink-jet coated paper, a large amount of cationic porous fine particles is required, and the formation of a thick ink receiving layer that covers the base paper is indispensable. Becomes For this reason, the coated paper leads to the result of impairing the texture of the base paper, but since the amount of the fine particles constituting the liquid composition of the present invention can be reduced, the printed portion and the unprinted portion can be reduced without impairing the texture of the recording medium. Thus, it is possible to form an image without a sense of discomfort in texture.

Further, as in the prior art classified in (1), the amount of the color material itself remaining on the surface of the recording medium is not sufficient, or in the prior art classified in (2). Even if the amount of the coloring material remaining on the surface of the recording medium is sufficient, the coloring material does not agglomerate with each other. In this case, since the coloring material adsorbed on the surface of the fine particles remains on the surface of the recording medium together with the fine particles, and the coloring material maintains a single-molecule state, it is possible to obtain a highly colored image.

Further, the present invention relates to the above-mentioned prior art (3) in that an image is formed by applying a liquid composition containing fine particles and ink to the surface of a recording medium.
At first glance, it looks as if it is similar to the method of externally adding the liquid composition containing fine particles to the ink. However, in the present invention, as described above, the liquid composition and the coloring material are positively reacted with each other, and the fine particles in the liquid composition are used as a means for suppressing the aggregation (rake) of the coloring material. In the conventional technique described in (3), the purpose of applying the solution containing the fine particles is to modify the surface state of the recording medium, and the chemical between the fine particles having different polarities and the coloring material in the ink is changed. There is no disclosure of the idea of causing a natural reaction. The difference in quality between the recorded matter according to these recording techniques and the recorded matter obtained by the present invention, which is presumed to be based on the difference in the mechanism, was obvious.

Hereinafter, the method for measuring the physical properties of the pores resulting from the liquid composition which characterizes the present invention, and the constitutions of the ink and the liquid composition will be described in detail. First, the definition of the cationic ink or the anionic ink in this specification will be described. When talking about the ionic properties of ink,
It is well known in the art that the ink itself is uncharged and neutral in itself. The term “anionic ink or cationic ink” as used herein means a component in the ink, for example, a colorant has an anionic group or a cationic group, and in the ink, these groups are anionic or cationic. It refers to ink that has been adjusted to act as a base. The meaning of the anionic or cationic liquid composition is the same as described above.

[Method for Measuring Pore Properties Due to Liquid Composition] In the method for measuring pore properties due to the liquid composition according to the present invention, the aggregate of fine particles obtained from a liquid composition containing at least fine particles and a solvent is used. It is characterized in that the pore volume in a specific pore radius region is measured. First, in measuring these pore physical properties, a target liquid composition is pretreated according to the following procedure. (1) The liquid composition is dried at 120 ° C. for 10 hours in an air atmosphere, and the solvent is evaporated to dryness. (2) The dried product is heated from 120 ° C. to 700 ° C. for 1 hour, and then calcined at 700 ° C. for 3 hours. (3) After firing, the temperature of the fired product is gradually returned to room temperature, and the fired product is powdered. Here, the reason for performing the above pretreatment is to form fine particles aggregates from the liquid composition by drying, completely remove the solvent component by firing, and empty the pores inside the aggregates to form voids. It is.

As a method for measuring the pore radius and the pore volume used in the present invention, a nitrogen adsorption / desorption method can be suitably used. The size of the pores of the fine particle aggregate to be measured in the present invention is a pore volume in a region having a pore radius of 3 nm to 30 nm. It is not clear why the pore volume in this region is highly correlated to the image forming ability, but to speculate,
In the region smaller than the pore radius, the penetration of the coloring material and the solvent component into the inside of the fine particle aggregate is significantly reduced, the adsorption of the coloring material due to the pores is small, and it does not substantially contribute to the improvement of the coloring property. Conceivable. On the other hand, in the pores larger than this pore radius area, the coloring material and the solvent component easily penetrate, while the coloring material adsorbed near or inside the pores is affected by the light scattering of the pores themselves. It is considered that the material hardly participates in the absorption of light, and conversely, the coloring property is lowered.

Therefore, it is effective to measure the color development performance of the formed image by measuring the pore volume in the region where the pore radius is 3 nm to 30 nm and in the region exceeding 30 nm. As a method for measuring the physical properties of the pores in this region, a method by a nitrogen adsorption / desorption method is most suitable. The pore radius and the pore volume were determined by degassing the pretreated sample under vacuum at 120 ° C. for 8 hours, followed by the method of Barrett et al. (J. Am. Chem. Soc. Vol.
73, 373, 1951). As a more preferable measurement method, the pore radius is 3 nm to 20 nm.
It is to measure the pore volume in the region of nm and in the region exceeding 20 nm. In this range, when the coloring material is a dye, it is particularly preferable to measure a further improvement in color development.

<Liquid Composition> The liquid composition of the present invention will be described below. [Pore Radius and Pore Volume of Fine Particle Aggregate Obtained from Liquid Composition] In the present invention, as described above, when an image is formed, the coloring material quickly penetrates and is adsorbed near the pore entrance or on the inner wall. From the viewpoint of preventing aggregation of the coloring material inside the pores, the pore radius of the fine particle aggregate obtained from the liquid composition (hereinafter, simply referred to as pore radius) is preferably in the range of 3 nm to 30 nm. it is conceivable that. In addition, a certain amount of capacity is required at the same time in order to take in a color material that only contributes to the improvement of the color developing property. In addition, it is considered that the number of pores in the fine particle aggregate increases due to an increase in the pore volume. Conceivable.

From these viewpoints, the liquid composition suitably used in the present invention has a pore radius of 3 nm to 30 nm.
The pore volume in the range of nm is 0.4 ml / g or more,
The pore volume in the region where the pore radius exceeds 30 nm is 0.1%.
It is preferably at most ml / g. In the pores having a pore radius smaller than 3 nm, the coloring material and the solvent component hardly penetrate into the pores, and the pores of the fine particle aggregates cannot substantially contribute to the improvement of the coloring property. When the pore volume exceeds 0.1 ml / g in the region where the pore radius exceeds 30 nm, there are many pores with large light scattering. It is difficult to contribute. Further, when the pore volume in the region of the pore radius is less than this range, since the coloring material and the solvent component penetrate into the inside of the fine particle aggregate are small, the coloring material adsorbed near or at the entrance of the pore is small. It is not preferable because the amount is small, and the contribution to the improvement of the coloring property is low.

More preferably, the pore radius is 3n.
0.4 ml / g of pore volume in the range of m to 20 nm
As described above, the pore volume in the region where the pore radius exceeds 20 nm is preferably 0.1 ml / g or less. 3 nm pores
By virtue of being present in a large range of a radius of about 20 nm, especially when a dye is used as a coloring material, the color developability is further improved, and an image having a wider color reproduction range can be formed. The pore radius and pore volume of the fine particle aggregate formed from the liquid composition vary not only with the chemical species, shape, and size of the fine particles contained, but also with the solvent type, other additives, and their composition ratios. However, it is considered that the formation state of the fine particle aggregate can be controlled by controlling these conditions.

(Fine Particles) In the present invention, the desired action of the fine particles contained in the liquid composition is as follows: 1) When mixed with the ink, without impairing the original coloring property of the coloring material,
Adsorbing the coloring material; 2) when mixed with the ink or applied to the recording medium, the dispersion stability is reduced and remains on the surface of the recording medium. These functions may be achieved by one or more kinds of fine particles.

As a property for satisfying the function of 1), for example, the fine particles exhibit ionicity opposite to that of the coloring material. Thereby, the fine particles can electrostatically adsorb the coloring material. When the coloring material is anionic, cationic fine particles are used, and when the coloring material is cationic, anionic fine particles are used. Elements that adsorb the coloring material other than ionicity include the size and mass of the fine particles or the shape of the surface. For example, porous fine particles having a large number of pores on the surface exhibit unique adsorption characteristics, and can adsorb a coloring material by a plurality of factors such as the size and shape of the pores.

The operation 2) is caused by the interaction with the ink and the recording medium. For this reason, what is necessary is just to achieve by each structure, For example, as a property of a fine particle,
It has the opposite ionicity to the ink composition component and the recording medium component. Also, the coexistence of an electrolyte in the ink or liquid composition affects the dispersion stability of the fine particles. In the present invention, the above 1)
It is desirable that either one of the functions 2) and 3) be obtained instantaneously. Further, it is preferable that both the effects 1) and 2) be obtained instantaneously. Hereinafter, the liquid compositions containing the respective ionic fine particles will be specifically described.

[Cationic Liquid Composition] Examples of the cationic liquid composition include a liquid composition containing fine particles having a cationic group on the surface and an acid, and the fine particles are stably dispersed. In the present invention, as the cationic liquid composition, for example, an acid containing acid and having a pH of 2 to 7 is used.
The zeta potential is +5 to +90 m
V can be suitably used.

(Regarding pH and Zeta Potential) The zeta potential of the liquid composition will be described. The basic principle of the zeta potential will be described below. In general, in a system in which a solid is dispersed in a liquid, when there is free charge on the surface of a solid phase, a charged layer having an opposite charge appears in the liquid phase near the solid phase interface so as to maintain electrical neutrality. This is called an electric double layer, and the potential difference caused by the electric double layer is called zeta potential. When the zeta potential is positive, the surface of the fine particles is cationic, and when the zeta potential is negative, it is anionic.
In general, it is said that the higher the absolute value is, the stronger the electrostatic repulsion acting between the fine particles and the better the dispersibility. At the same time, it is considered that the ionicity of the fine particle surface is strong. That is, the higher the zeta potential of the cationic fine particles, the stronger the cationicity,
It can be said that the ability to attract the anionic compound in the ink is strong.

Furthermore, the present inventors have conducted intensive studies. As a result, when a liquid composition having a zeta potential in the range of +5 to +90 mV is used, the colored portion formed on the recording medium is particularly excellent in coloring. It has been found that it exhibits characteristics. The reason is not clear, but probably because the anionic compound (anionic colorant) does not agglomerate rapidly due to the moderate cationicity of the fine particles, the anionic compound is thinly and uniformly adsorbed on the surface of the fine particles. Therefore, it is considered that the coloring material hardly forms a huge lake, and as a result, the original coloring characteristics of the coloring material are expressed in a better state. Further, in the cationic liquid composition of the present invention, even after the anionic compound is adsorbed on the surface of the fine particles, the fine particles exhibit a weak cationic property and become in an unstable dispersion state, so that the fine particles are agglomerated while being agglomerated in the recording medium. It is considered that the ink is easily adsorbed on the surface of an anionic cellulose fiber or the like existing in the recording medium, and is likely to remain near the surface of the recording medium.

As a result, it is considered that the following excellent effects can be obtained. That is, in the image area where the amount of applied ink is large, such as a shadow portion and a solid portion, white haze and color unevenness are small, and the color uniformity is excellent. In addition, since the anionic compound is adsorbed to the fine particles more efficiently than the coated paper to form a color, the amount of the cationic fine particles to be applied can be reduced. And excellent scratch resistance of the printed portion. Still more preferably, the zeta potential of the liquid composition is +10 to +85 mV. Within this range, the boundary between dots becomes less noticeable when solid printing is performed, and a good image with less streaks due to head scanning can be obtained. Further, when a liquid composition containing cationic fine particles having a zeta potential in the range of +15 to +65 mV is used,
Regardless of the type of paper, it is possible to obtain an image having extremely excellent coloring properties.

The pH of the cationic liquid composition of the present invention
Is preferably in the range of 2 to 7 at around 25 ° C. from the viewpoints of storage stability and adsorptivity of the anionic compound.
Within this pH range, when mixed with an anionic ink, the stability of the anionic compound is not significantly reduced, so that strong aggregation of the anionic compounds does not occur, and the color of the recorded image does not increase. It is possible to effectively prevent the degree of the image from decreasing or becoming a dull image. Further, when the content is within the above range, the dispersion state of the cationic fine particles is good, so that the storage stability of the liquid composition and the stability of ejection from the recording head can be favorably maintained. Further, when mixed with the ink, the anionic substance is sufficiently adsorbed on the surface of the cationic fine particles, so that excessive penetration of the coloring material into the recording medium is suppressed, and an ink jet recorded matter having excellent coloring properties is obtained. can get. More preferred pH
Is in the range of pH 3 to 6, and in this range,
Corrosion of the recording head due to long-term storage can be extremely effectively prevented, and the scratch resistance of the printed portion is further improved.

(Cationic Fine Particles) Next, the components constituting the cationic liquid composition according to the present invention will be described. In order to achieve the above-mentioned effects, the cationic fine particles mentioned as the first component require that the surface of the fine particles themselves exhibit cationicity in a state of being dispersed in the liquid composition. By mixing the surface with cationic, when mixed with an anionic ink, the anionic coloring material is quickly adsorbed on the particle surface, and excessive penetration of the coloring material into the recording medium is suppressed, An ink jet recording having a sufficient image density can be obtained. On the other hand, when the surface of the fine particles is not cationic and is present separately from the water-soluble cationic compound in the liquid composition, the coloring material aggregates around the cationic compound. In this case, it is difficult to achieve a color developing property comparable to that of the coated paper for ink jet, since the coloring property of the coloring material itself is impaired. For this reason, the fine particles used in the liquid composition according to the present invention need to have a cationic surface, but not only fine particles that are essentially cationic but also electrostatically anionic or medium in nature. Even fine particles having a property can be suitably used as a constituent material of the liquid composition of the present invention as long as the fine particles have a surface cationized by the treatment.

As the cationic fine particles suitably used in the present invention, the object of the present invention can be sufficiently achieved as long as the fine particles formed on the recording medium have pores formed in the aggregate. There is no particular limitation on the material type of the fine particles. As specific examples, for example, cationized silica, alumina, alumina hydrate, titania, zirconia, boria, silica boria, ceria, magnesia, silica magnesia, calcium carbonate, magnesium carbonate, zinc oxide, hydro Examples thereof include talcite and the like, composite fine particles thereof, organic fine particles, and inorganic-organic composite fine particles. In the liquid composition of the present invention, these can be used alone or in combination of two or more.

Among the above, fine particles composed of alumina hydrate are particularly preferable because the particle surface has a positive charge. It is preferable in terms of excellent color developing property, color uniformity, storage stability and the like. Alumina hydrate is defined by the following general formula. Al ₂ O _3-n (OH) _2n · mH ₂ O (wherein, in the above formula, n represents one of integers from 0 to 3;
Has a value of 0-10, preferably 0-5. mH ₂ O
Expresses a detachable aqueous phase that is often not involved in the formation of a crystal lattice, so that m can take on non-integer values. However, m and n do not become 0 at the same time. )

Generally, the crystal of alumina hydrate having a boehmite structure is a layered compound whose (020) plane forms a giant plane, and shows a diffraction peak specific to an X-ray diffraction pattern. In addition to complete boehmite, it is called pseudo boehmite.
A structure in which excess water is contained between layers of the (020) plane can also be employed. The X-ray diffraction pattern of this pseudo-boehmite shows a broader diffraction peak than complete boehmite. Since boehmite and pseudo-boehmite cannot be clearly distinguished from each other, they are referred to as alumina hydrate having a boehmite structure (hereinafter simply referred to as alumina hydrate) including both, unless otherwise specified. The (020) plane is the plane spacing and (020)
Is measured by measuring a peak at a diffraction angle 2θ of 14 to 15 °. From the diffraction angle 2θ of the peak and the half width B, the interplanar spacing is represented by the Bragg equation, and the crystal thickness is determined by Scherrer. (Scherrer). The plane spacing of (020) is the hydrophilicity of alumina hydrate.
It can be used as a measure of hydrophobicity. The method for producing the alumina hydrate used in the present invention is not particularly limited, and any method capable of producing an alumina hydrate having a boehmite structure, for example, hydrolysis of aluminum alkoxide or hydrolysis of sodium aluminate And other known methods.

As disclosed in JP-A-56-120508, a boehmite structure is obtained by heat-treating amorphous alumina hydrate by X-ray diffraction at 50 ° C. or more in the presence of water. It can be changed and used. A method that can be particularly preferably used is a method of obtaining an alumina hydrate by adding an acid to a long-chain aluminum alkoxide and performing hydrolysis and peptization. Here, the long-chain aluminum alkoxide is, for example, an alkoxide having 5 or more carbon atoms, and further has 12 to 12 carbon atoms.
Use of the alkoxide of No. 22 is preferable because it facilitates removal of the alcohol component and control of the shape of the alumina hydrate during the production process as described later.

As the acid to be added, one or more of an organic acid and an inorganic acid can be freely selected and used. From the viewpoint of control and dispersibility, nitric acid is most preferred. After this step, it is also possible to control the particle size by performing hydrothermal synthesis or the like. When hydrothermal synthesis is performed using a dispersion of alumina hydrate containing nitric acid, nitric acid in the aqueous solution is incorporated as nitrate on the surface of the alumina hydrate, and the water dispersibility of the hydrate can be improved. it can.

The method of hydrolysis of the aluminum alkoxide has an advantage that impurities such as various ions are less likely to be mixed as compared with the method of producing alumina hydrogel or cationic alumina. Furthermore, long-chain aluminum alkoxides have a long-chain alcohol after hydrolysis. There is also the advantage of being able to do it. It is preferred to set the pH of the solution at the start of the hydrolysis to less than 6. When the pH is 8 or less, the alumina hydrate finally obtained can be effectively suppressed from being crystalline.

As the alumina hydrate used in the present invention, an alumina hydrate containing a metal oxide such as titanium dioxide can be used as long as it shows a boehmite structure by X-ray diffraction. . The content ratio of metal oxides such as titanium dioxide is 0.01 to 1.00 of alumina hydrate.
% Is preferable because the optical density is high, and more preferably 0.13 to 1.00% by mass. The adsorption speed of the coloring material is increased, and bleeding and beading are less likely to occur.
Further, the titanium dioxide needs to have a valence of +4. The content of titanium dioxide can be determined by dissolving in boric acid and by the ICP method. The distribution of titanium dioxide in alumina hydrate and the valence of titanium were determined by ESCA.
(Electron Spectroscopy for Chemical Analysis). ESCA is a surface analyzer that can examine the chemical bonding state of elements on the surface of an object at the nano-order level.

The surface of the alumina hydrate can be etched with argon ions for 100 seconds and 500 seconds to examine the change in the titanium content. When the valence of titanium is smaller than +4, the titanium dioxide acts as a catalyst to reduce the weather resistance of the printed matter,
In some cases, yellowing of the printed portion is likely to occur.

The titanium dioxide may be contained only in the vicinity of the surface of the alumina hydrate, or may be contained up to the inside. Further, the content may change from the surface to the inside. It is more preferable that titanium dioxide is contained only in the vicinity of the surface because the electrical characteristics of alumina hydrate are easily maintained.

As a method for producing alumina hydrate containing titanium dioxide, for example, an aluminum alkoxide described in “Surface Science”, p. 327 (ed. By Kenji Tamaru, 1985), published by Gakkai Shuppan Center. And a method in which a mixed solution of titanium alkoxide is hydrolyzed for production. As another method, it can be produced by adding alumina hydrate as a nucleus for crystal growth when hydrolyzing the mixed solution of aluminum alkoxide and titanium alkoxide.

Instead of titanium dioxide, silica, magnesium, calcium, strontium, barium, zinc,
An oxide such as boron, germanium, tin, lead, zirconium, indium, phosphorus, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, or the like can be used. For example, alumina hydrate containing silica is effective in improving the scratch resistance of a printed portion.

The spacing between the (020) planes of the alumina hydrate preferably used in the present invention is 0.614 to 0.626 nm.
The range is suitably used, and within this range, a liquid composition having good dispersion stability of alumina hydrate particles in the liquid composition and excellent storage stability and ejection stability can be obtained. The reason for this is not clear, but if the plane spacing of the (020) plane is within the above range, the amount ratio of hydrophobicity and hydrophilicity of the alumina hydrate is within an appropriate range, so that the particles in the liquid composition may not be mixed. It is presumed that the dispersion stability due to the appropriate repulsion and the appropriate balance of the wettability inside the ejection port improve the ejection stability of the liquid composition.

The crystal thickness of the (020) plane of the alumina hydrate is preferably in the range of 4.0 to 10.0 nm, and within this range, the transparency and the adsorbability of the coloring material are excellent. . According to the knowledge of the present inventors, the interplanar spacing of the (020) plane and the crystal thickness of the (020) plane have a correlation.
If the plane spacing of the (20) plane is within the above range, the crystal thickness of the (020) plane can be adjusted to a range of 4.0 to 10.0 nm.

Further, alumina (aluminum oxide) produced by heat-treating the above-mentioned alumina hydrate, metallic aluminum, aluminum salt or the like is preferably used because it also has a positive charge. As the alumina, α type, γ
There are also types that have crystalline states such as δ, χ, η, ρ, and β types, and any type that can be stably dispersed in water with the surface kept cationic is used. Can be. Among them, the γ-type has an active surface, has a high adsorptivity of a coloring material, and is easy to form a relatively finely dispersed stable fine particle dispersion. Can be used.

The above-mentioned cationic fine particles used in the present invention may have an average particle diameter measured by a dynamic light scattering method from the viewpoints of color development after printing, color uniformity and storage stability. Is in the range of 0.005 to 1 μm. Within this range, excessive penetration into the inside of the recording medium can be effectively prevented, and a decrease in color developability and color uniformity can be suppressed. In addition, sedimentation of the cationic fine particles in the liquid composition is suppressed, and a decrease in the storage stability of the liquid composition can be effectively prevented.
More preferably, the average particle diameter is in the range of 0.01 to 0.8 μm, and if such fine particles are used, the abrasion resistance of the image after printing on the recording medium and the texture of the recorded matter are particularly high. It will be preferable. More preferably, the average particle diameter is in the range of 0.03 to 0.3 μm. This is preferable because it can be effectively formed in a region.

(Physical Properties and Shape of Pore of Cationic Fine Particles) The above-mentioned cationic fine particles used in the present invention can efficiently form fine pores of fine particle aggregates formed on a recording medium. At the same time, in order to efficiently adsorb the coloring material on the surface of the fine particles themselves, the maximum fine pore radius of the fine particles in the above-mentioned nitrogen adsorption / desorption method is 2 to 12 nm, and the total fine pore volume is 0.3 ml / g or more. Are preferred.
More preferably, the maximum pore radius of the fine particles is 3 to 10 nm.
It is preferable that the total pore volume is 0.3 ml / g or more, since the fine pores of the fine particle aggregate formed on the recording medium are easily formed effectively in the target pore radius region. .

When the BET specific surface area of the fine particles used in the present invention is in the range of 70 to 300 m ² / g, the coloring material is in a monomolecular state due to sufficient adsorption of the coloring material on the surface of the fine particles. More effectively in the vicinity of the surface of the recording medium, which contributes to the improvement of the color developability.

The shape of the fine particles used in the present invention is as follows:
Fine particles can be dispersed in ion-exchanged water and dropped on a collodion film to prepare a measurement sample, which can be determined by observing with a transmission electron microscope. In the present invention, in forming fine particles in the aggregate when forming the fine particles on the recording medium, the primary particles having a needle shape, a flat plate shape, or a spherical shape have a certain direction. A non-spherical shape such as a rod shape or a necklace shape which forms secondary particles connected and held can be suitably used.

According to the findings of the present inventors, a flat plate shape has better dispersibility in water than a needle-like or hairy bundle (ciliform), and when a fine particle aggregate is formed, This is more preferable because the pore volume increases due to random orientation. Here, the hair bundle shape means a state in which needle-like fine particles are gathered like a bundle of hair with their side surfaces in contact with each other. In particular, among the alumina hydrates that can be preferably used in the present invention, pseudo-boehmite is described in the above literature (Rocek J., etal, Applie
d Catalysis, Vol. 74, pp. 29-36, 1991), it is generally known that there are cilia-like and other shapes.

The aspect ratio of the tabular grains can be determined by the method defined in Japanese Patent Publication No. Hei 5-16015. The aspect ratio is indicated by the ratio of the diameter to the thickness of the particle. Here, the diameter indicates the diameter of a circle having an area equal to the projected area of the particles when the alumina hydrate is observed with a microscope or an electron microscope. The aspect ratio is observed in the same manner as the aspect ratio, and is expressed by the ratio of the minimum value diameter to the maximum value diameter of the flat surface. In the case of the hair bundle shape, the method of obtaining the aspect ratio is to obtain the diameter and length of each of the upper and lower circles by using the individual acicular alumina hydrate particles forming the hair bundle as a cylinder. , And the ratio can be determined. The most preferred shape of the alumina hydrate is a flat plate having an average aspect ratio in the range of 3 to 10, and a hairy bundle having an average aspect ratio of 3 to 3.
A range from 10 to 10 is preferred. When the average aspect ratio is within the above range, a gap is easily formed between the particles when the fine particle aggregate is formed, so that the porous structure can be easily formed.

The content of the cationic fine particles as described above in the liquid composition of the present invention may be appropriately determined depending on the kind of the substance to be used. % Is a preferable range for achieving the object of the present invention, more preferably 1 to 30%.
%, More preferably 3 to 15%. Within such a range, an image having excellent color development can be stably obtained regardless of the type of paper, and the storage stability and ejection stability of the liquid composition are particularly excellent.

(Acid) As described above, the liquid composition of the present invention preferably contains an acid and has a pH adjusted to 2 to 7. Is to ionize the surface of the cationic fine particles to increase the surface potential, thereby improving the dispersion stability of the fine particles in the liquid, improving the adsorbability of the anionic compound (anionic color material) in the ink, and It plays a role in adjusting the viscosity of the composition.
The acid preferably used in the present invention is not particularly limited as long as the desired pH, zeta potential, or physical properties such as fine particle dispersibility can be obtained in combination with the cationic fine particles to be used. And organic acids and the like.

Specifically, the inorganic acids include, for example, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, boric acid, and carbonic acid. And sulfonic acids, amino acids and the like.

Examples of the carboxylic acid include formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, trimethylacetic acid, methoxyacetic acid, mercaptoacetic acid, glycolic acid, propionic acid, butyric acid, valeric acid, caproic acid and caprylic acid. Acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Linoleic acid, linolenic acid, cyclohexanecarboxylic acid,
Phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid , P-bromobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, maleic acid, fumaric acid, citric acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, p
-Hydroxybenzoic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid,
m-methoxybenzoic acid, p-methoxybenzoic acid and the like.

Examples of the sulfonic acid include benzenesulfonic acid, methylbenzenesulfonic acid, ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
4,6-trimethylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 5-sulfosalicylic acid, 1-
Sulfonaphthalene, 2-sulfonaphthalene, hexanesulfonic acid, octanesulfonic acid, dodecanesulfonic acid and the like can be mentioned.

The amino acids include glycine, alanine, valine, α-aminobutyric acid, γ-aminobutyric acid, and β-aminobutyric acid.
Alanine, taurine, serine, ε-amino-n-caproic acid, leucine, norleucine, phenylalanine and the like.

Then, in the liquid composition of the present invention,
These can be used alone or in combination of two or more. Among them, the primary dissociation constant pk of acid in water
Those having a of 5 or less can be suitably used because they are particularly excellent in the dispersion stability of the cationic fine particles and the adsorptivity of the anionic compound. Specific examples include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, lactic acid, citric acid, maleic acid, and malonic acid.

In the liquid composition of the present invention, the mixing ratio of the cationic fine particles (A) and the acid (B) in the liquid composition is A: B = 200: 1 to 5: 1 by mass, more preferably, It is preferable that the ratio be in the range of 150: 1 to 8: 1 in order to improve the dispersion stability of the cationic fine particles and the adsorbability of the anionic compound to the surface of the fine particles.

(Other components) Next, other components constituting the cationic liquid composition will be specifically described. The cationic liquid composition of the present invention contains the above-mentioned cationic fine particles as an essential component, preferably contains the above-mentioned acid, and, in addition, usually contains water as a liquid medium, and further contains a water-soluble organic solvent. And other additives such as a humectant.

Examples of the water-soluble organic solvent used in this case include amides such as dimethylformamide and dimethylacetamide, ketones such as acetone, ethers such as tetrahydrofuran and dioxane, and polyalkylenes such as polyethylene glycol and polypropylene glycol. Glycols, alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, trimethylolpropane, and 1,5-pentanediol Lower alkyls of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether Ether such as ethanol, isopropyl alcohol, n- butyl alcohol, other monohydric alcohols such as isobutyl alcohol, glycerin, N
-Methyl-2-pyrrolidone, 1,3-dimethyl-imidazolidinone, triethanolamine, sulfolane, dimethyl sulfoxide and the like. As a moisturizer,
Examples include nitrogen-containing compounds such as urea, thiourea, ethylene urea, alkyl urea, alkyl thiourea, dialkyl urea, and dialkyl thiourea, and sugars such as glucitol, mannitol, and inositol. The content of the water-soluble organic solvent and the humectant is not particularly limited, for example,
A suitable range is 5 to 60%, more preferably 5 to 40% of the total weight of the liquid composition.

The liquid composition of the present invention may further contain, if necessary, a viscosity adjuster, a pH adjuster, a preservative,
Additives such as various surfactants, antioxidants and evaporation promoters, water-soluble cationic compounds and binder resins may be appropriately blended. The selection of the surfactant is particularly important in adjusting the permeability of the liquid composition into the recording medium.

As the surfactant, primary, secondary and tertiary amine salt type compounds, specifically, hydrochlorides such as laurylamine, cocoamine, stearylamine and rosinamine;
Acetate and the like; quaternary ammonium salt type compounds, specifically, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl tributyl ammonium chloride, benzalkonium chloride and the like;
Pyridinium salt-type compounds, specifically, cetylpyridinium chloride, cetylpyridinium bromide, etc .; Imidazoline-type cationic compounds, specifically, 2-heptadecenyl-hydroxyethylimidazoline, etc .; ethylene oxide adducts of higher alkylamines, specifically Is
Cationic surfactants such as dihydroxyethylstearylamine and amphoteric surfactants exhibiting cationicity in a certain pH range can also be used. In particular,
For example, amino acid type amphoteric surfactant; R-NH-CH ₂
—CH ₂ —COOH type compounds; betaine type compounds,
Specific examples include carboxylate type amphoteric surfactants such as stearyl dimethyl betaine and lauryl dihydroxyethyl betaine, as well as sulfate ester type, sulfonic acid type and phosphate ester type amphoteric surfactants. Examples of the nonionic surfactant include, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohols, and acetylene glycols. In the present invention, one or more of these can be appropriately selected and used.

Among the above, particularly, acetylene alcohols and acetylene glycols have a high permeability to plain paper,
It can be suitably used for exhibiting an excellent effect on foam height. The amount used depends on the surfactant used, but is preferably 0.05 to 5% by mass with respect to the total amount of the liquid composition because sufficient permeability can be ensured. The water-soluble cationic compound can be freely selected and added within a range that does not impair the effects of the present invention, for the purpose of further imparting cationicity to the liquid composition.

The binder resin can be used together with the binder resin for the purpose of further improving the scratch resistance of the cationic fine particles as long as the texture of the recording medium and the storage stability and ejection stability of the liquid composition are not impaired. For example, emulsions of water-soluble polymers such as polyvinyl alcohol, gelatin, polyvinylpyrrolidone, polyethylene oxide, casein, starch, carboxymethylcellulose, and emulsions of polyacrylic acid, polyurethane, polyvinyl acetate and the like and copolymers thereof, and latexes such as SBR and NBR It can be freely selected and used from such as.

(Surface tension of liquid composition) The liquid composition of the present invention is more preferably colorless or white.
Toning may be performed according to the color of the recording medium. Further, as a suitable range of various physical properties of the liquid composition as described above,
The surface tension at 25 ° C. is 10 to 60 mN / m (dyn
/ Cm), more preferably 10 to 40 mN / m (dyn)
/ Cm) and the viscosity at 25 ° C. is 1 to 30 mPa ·
s (cP).

[Anionic liquid composition] The anionic liquid composition according to the present invention is characterized in that fine particles having an anionic group on the surface are essential components and the fine particles are stably dispersed. But also contain a base, pH
Is adjusted to 7 to 12, or the zeta potential is -5.
Those having a voltage of -90 mV are preferred.

(Regarding pH and Zeta Potential) As a result of intensive studies by the present inventors, the zeta potential of the liquid composition was -5.
Those having a range of from -90 mV find that the cationic compound (cationic coloring material) in the ink is particularly efficiently adsorbed on the surface of the anionic fine particles, and exhibits particularly excellent coloring properties on the recording medium. Was. The reason is not clear, but probably similar to the case of the cationic liquid composition described earlier, because of the moderate anionicity of the fine particles, the rapid aggregation of the cationic compound in the ink does not occur, It is considered that the coloring material does not form a huge lake by thinly and uniformly adsorbing on the surface of the fine particles, and the coloring characteristics inherent to the coloring material are more effectively exhibited. Furthermore, in the anionic liquid composition according to the present invention, the dispersion becomes unstable after the cationic compound is adsorbed on the surface of the fine particles, and the fine particles aggregate due to a change in concentration when the solvent component permeates on the recording medium. Therefore, it is considered that it is easy to remain near the surface.

As a result, it is considered that the following excellent effects can be obtained. That is, in an image area where the amount of applied ink is large, such as a shadow portion or a solid portion, an image excellent in color uniformity with little white haze and color unevenness can be obtained. Also,
Since the cationic compound is adsorbed to the surface of the fine particles very efficiently compared to the coated paper, and the color is developed, the amount of the anionic fine particles can be reduced. The abrasion resistance of the printed portion is also improved. A more preferred zeta potential is -10 to -85 mV. With a liquid composition in this range, the boundary between dots becomes less noticeable when solid printing is performed, so that a good image with less stripes due to head scanning can be obtained. Can be
Furthermore, when a liquid composition containing anionic fine particles having a zeta potential in the range of -15 to -65 mV is used, it is possible to obtain an image having extremely excellent coloring properties irrespective of the type of paper.

PH of anionic liquid composition of the present invention
Is preferably in the range of 7 to 12 at around 25 ° C. from the viewpoints of storage stability and adsorptivity of the cationic compound. Within this pH range, the stability of the cationic compound does not significantly decrease when mixed with the cationic ink, so that strong aggregation of the cationic compounds does not occur, and the saturation of the recorded image is reduced. Can be effectively prevented from dropping or becoming a dull image. Further, when the content is in the above range, the dispersibility of the anionic fine particles is good, so that the storage stability of the liquid composition and the stability of ejection from the recording head can be maintained satisfactorily. Furthermore, when mixed with the ink, the cationic substance is sufficiently adsorbed on the surface of the anionic fine particles, and in order to suppress excessive penetration of the coloring material into the inside of the recording medium, an ink jet recorded matter having excellent coloring properties is obtained. can get. More preferably, the pH range of the liquid composition is from 8 to 11,
Within this range, corrosion of the recording head due to long-term storage can be extremely effectively prevented, and the scratch resistance of the printed portion is further improved.

(Anionic Fine Particles) Next, the components constituting the anionic liquid composition according to the present invention will be described. In order to achieve the above-mentioned effects, the anionic fine particles mentioned as the first component preferably have an anionic surface in the state of the particles themselves when dispersed in the liquid composition. When mixed with a cationic ink by making the surface anionic, the cationic coloring material can be adsorbed on the particle surface, and the coloring material is suppressed from excessively penetrating into the recording medium.
An ink jet recorded matter having a sufficient image density can be obtained. On the other hand, when the surface of the fine particles is not anionic, and in the liquid composition, and is present separately from the water-soluble anionic compound, the coloring material aggregates around the anionic compound, Since the coloring properties of the coloring material itself are impaired, it is difficult to achieve coloring properties comparable to those of coated paper for inkjet. Therefore, the fine particles used in the liquid composition according to the present invention need to have an anionically charged surface. However, not only fine particles that are essentially anionic, but also are inherently electrostatically cationic. Alternatively, neutral fine particles can be used as long as the fine particles have a surface anionized by the treatment.

The anionic fine particles suitably used in the present invention are sufficient to achieve the object of the present invention as long as the fine particles formed on the recording medium have pores formed in the aggregate. For this reason, the material type of the fine particles is not particularly limited. If specific examples are given as examples, for example, anionized silica, titania, zirconia,
Examples include boria, silica boria, ceria, magnesia, silica magnesia, calcium carbonate, magnesium carbonate, zinc oxide, and the like, and composite fine particles, organic fine particles, and inorganic-organic composite fine particles thereof. In the liquid composition of the present invention, these can be used alone or in combination of two or more.

The anionic fine particles used in the present invention are, like the above-described cationic fine particles, dynamically dispersed from the viewpoint of color development, uniformity of color and storage stability of the ink after printing. Those having an average particle diameter in the range of 0.005 to 1 μm measured by a light scattering method are suitable. More preferably, the average particle diameter is in the range of 0.01 to 0.8 μm. When such fine particles are used, the abrasion resistance and texture after printing on a recording medium are particularly preferable. More preferably, the average particle diameter is from 0.03 to 0.1.
Such fine particles are preferred because such fine particles are easily formed effectively in the target fine particle radius region in the fine pores of the fine particle aggregate formed on the recording medium.

(Physical Properties and Shape of Pore of Anionic Fine Particles) The anionic fine particles as described above used in the present invention can efficiently form fine pores of fine particle aggregates formed on a recording medium. At the same time, from the viewpoint of efficiently adsorbing the coloring material on the surface of the fine particles themselves, the maximum fine particle radius of the fine particles in the aforementioned nitrogen adsorption / desorption method is 2 to 12 nm, and the total fine pore volume is 0.3 ml / g or more. Are preferred. More preferably, the fine particles having a maximum pore radius of 3 to 10 nm and a total pore volume of 0.3 ml / g or more have fine pores of the fine particle aggregate formed on the recording medium. This is preferable because it is easily formed effectively in the hole radius region.

When the BET specific surface area of the fine particles used in the present invention is in the range of 70 to 300 m ² / g, the coloring material can be converted into a monomolecular state by a sufficient amount of adsorption points of the coloring material on the surface of the fine particles. This effectively leaves the recording medium in the vicinity of the surface of the recording medium, contributing to the improvement of the coloring property.

Further, the shape of the fine particles used in the present invention is as follows.
Fine particles can be dispersed in ion-exchanged water and dropped on a collodion film to prepare a measurement sample, which can be determined by observing with a transmission electron microscope. In the present invention, when forming fine particle aggregates on a recording medium, fine particles have a directionality in which primary particles having a needle shape, a flat plate shape, or a spherical shape have a direction in which pores are formed in the aggregates. A non-spherical shape such as a rod-like or necklace-like shape that forms secondary particles connected together can be suitably used. According to the findings of the present inventors, the flat shape has better dispersibility in water than the needle shape, and the pore volume is small because the orientation of the fine particles becomes random when a fine particle aggregate is formed. It is more preferable because it becomes larger.

The content of the anionic fine particles in the liquid composition as described above depends on the type of the substance to be used.
The optimum range may be appropriately determined, but is not more than 0.
The range of 1 to 40% by mass is a preferable range for achieving the object of the present invention, more preferably 1 to 30% by mass, and further preferably 3 to 15% by mass. Within such a range, an image with excellent color development can be stably obtained regardless of the type of paper, and the storage stability and ejection stability of the liquid composition are particularly excellent.

(Base) As described above, the anionic liquid composition according to the present invention contains a base and has a pH of 7 to 10.
Although it is preferable that the base is adjusted to 12, the base as the second component ionizes the surface of the anionic fine particles and increases the surface potential, thereby improving the dispersion stability in the liquid and improving the ink stability. It plays a role in improving the adsorptivity of the cationic compound (cationic colorant) in the liquid and adjusting the viscosity of the liquid composition. The base suitably used in the present invention, when combined with the anionic fine particles used, has a desired p
There is no particular limitation as long as physical properties such as H, zeta potential and fine particle dispersibility can be obtained, and any of the following inorganic compounds and organic compounds can be freely used.

Specifically, for example, sodium hydroxide,
Lithium hydroxide, sodium carbonate, ammonium carbonate,
Ammonia, sodium acetate, ammonium acetate, morpholine, monoethanolamine, diethanolamine,
Triethanolamine, ethyl monoethanolamine,
Alkanolamines such as normal butyl monoethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, normal butyldiethanolamine, dinormalbutylethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine can be used. Among these, particularly, a base having a primary dissociation constant pkb of 5 or less in water is preferably used because it is particularly excellent in dispersion stability of anionic fine particles and adsorptivity of a cationic compound (cationic coloring material). .

The mixing ratio between the anionic fine particles (A) and the base (B) in the liquid composition of the present invention is A: B on a mass basis.
= 200: 1 to 5: 1, more preferably 150: 1 to 1
A ratio of 8: 1 is preferable because the dispersion stability of the anionic fine particles and the adsorptivity of the cationic compound to the surface of the fine particles are excellent.

(Other components) Next, other components constituting the anionic liquid composition will be specifically described. The anionic liquid composition of the present invention contains the above-mentioned anionic fine particles as an essential component, preferably contains the above-described base, and, in addition, usually contains water as a liquid medium. Water-soluble organic solvents, humectants and other additives as listed in the section of the product, for example,
Additives such as a viscosity adjuster, a pH adjuster, a preservative, various surfactants, an antioxidant, an evaporation promoter, a water-soluble anionic compound and a binder resin may be appropriately added.

Examples of the surfactant include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkyl allyl sulfonates, polyoxyethylene alkyl ethers, and polyoxyethylene. Examples include nonionic surfactants such as alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohols, and acetylene glycols. In the present invention, one or more of these may be appropriately selected. Can be used. Among the above, particularly, acetylene alcohols and acetylene glycols can be suitably used for exhibiting excellent effects on permeability to plain paper and high foaming property. The amount used depends on the surfactant used,
0.05 to 5% by mass with respect to the total amount of the liquid composition is preferable because sufficient permeability can be ensured.

(Surface Tension of Liquid Composition) The anionic liquid composition of the present invention is more preferably colorless or white, but may be toned in accordance with the color of the recording medium.
Further, as a preferable range of various physical properties of the liquid composition as described above, the surface tension at 25 ° C. is 10 to 60 mN / m.
(Dyn / cm), more preferably 10 to 40 mN / m
(Dyn / cm) and the viscosity at 25 ° C. is 1 to 30.
mPa · s (cP).

(Method of Dispersing Fine Particles in Liquid Composition) As a method of dispersing the liquid composition of the present invention containing the fine particles, a method generally used can be selected from the methods used for dispersion. . As a device to be used, a gentle mixer such as a homomixer or a rotary blade is more preferable than a grinding type disperser such as a ball mill or a sand mill. The shear stress varies depending on the viscosity, amount or volume of the liquid composition, but is preferably in the range of 0.1 to 100.0 N / m ² . If a strong shear stress exceeding the above-mentioned range is applied, phenomena such as gelation of the liquid composition and a change in crystal structure may occur, which is not preferable. Further, when the content is in the range of 0.1 to 20.0 N / m ^2, the pore structure of the fine particles themselves can be prevented from being destroyed, and the pore volume can be prevented from being reduced.

The dispersion time varies depending on the amount of the dispersion, the size of the container, the temperature of the dispersion, and the like.
If the time is 0 hour or less, the pore structure of the fine particles can be controlled within the above range. During the dispersion treatment, the temperature of the dispersion may be kept within a certain range by cooling or keeping the temperature. The preferred temperature range varies depending on the dispersion treatment method, material or viscosity, but is 10 to 100 ° C. If the ratio is lower than the lower limit of the above range, the dispersion treatment is insufficient, or aggregation of fine particles occurs. If it is higher than the upper limit of the above range, gelation of the liquid or change in the crystal structure of the fine particles may occur.

<Aqueous Ink> [Anionic Ink] Next, the aqueous anionic ink constituting the ink set of the present invention to be combined with the cationic liquid composition described above will be described. Here, the ink set refers to a combination of the liquid composition of the present invention and at least one or more anionic inks containing an anionic substance (anionic colorant). Further, a combination of at least one type of ink obtained by removing the liquid composition of the present invention from this ink set is referred to as an ink subset. The anionic ink used in the present invention uses a water-soluble dye containing an anionic group as a coloring material or, in the case where a pigment is used as a coloring material, a combination of an anionic compound (this is also the present invention). Is referred to as an anionic colorant). The anionic ink as described above used in the present invention further includes, in addition thereto, water, a water-soluble organic solvent and other components, for example,
A viscosity adjuster, a pH adjuster, a preservative, a surfactant, an antioxidant and the like are included as necessary. Hereinafter, each component of these inks will be described.

(Water-soluble dye) Examples of the water-soluble dye having an anionic group used in the present invention include water-soluble acid dyes, direct dyes, and reactive dyes described in Color Index. There is no particular limitation if it exists. Also, even those not listed in the color index,
There is no particular limitation as long as it has an anionic group such as a sulfone group and a carboxyl group. The water-soluble dyes mentioned here include those having a pH dependence of solubility.

(Pigment) As another form of the aqueous anionic ink, a pigment and an anionic compound are used in place of the water-soluble dye having an anionic group as described above.
The ink may include water, a water-soluble organic solvent, and other components such as a viscosity adjuster, a pH adjuster, a preservative, a surfactant, and an antioxidant, if necessary. Here, the anionic compound may be a dispersant for the pigment, or when the dispersant for the pigment is not anionic, an anionic compound other than the dispersant may be added. Of course, even when the dispersant is an anionic compound, the dispersant may be further added with another anionic compound.

The pigment that can be used in the present invention is not particularly limited. For example, the following pigments can be suitably used. First, the carbon black used in the black pigment ink is a carbon black manufactured by a furnace method or a channel method, and has a primary particle size of 15 to 40.
mμm, specific surface area by BET method is 50 to 300 m ² /
g, DBP oil absorption of 40 to 150 ml / 100 g, volatile matter of 0.5 to 10% by mass, and pH value of 2 to 9 are preferable.

For example, as described in No.
2300, no. 900, MCF88, No. 40, N
o. 52, MA7, MA8, No. 2200B (or more,
Mitsubishi Kasei), RAVEN 1255 (Colombia), REG
AL 400R, REGAL 660R, MOGUL L (above, made by Cabot), Color Black FW1, Color Black FW1
8, Color Black S170, Color Black S150,
Commercial products such as Printex 35 and Printex U (all manufactured by Degussa) can be used. Further, a prototype newly manufactured for the present invention may be used.

Examples of the pigment used in the yellow ink include CI Pigment Yellow 1 and CI Pigment Ye
llow 2, CI Pigment Yellow 3, CI Pigment Yell
ow 13, CI Pigment Yellow 16, CI Pigment Ye
llow 83 and the like.

Examples of the pigment used as the magenta ink include CI Pigment Red 5 and CI Pigment Red.
7, CI Pigment Red 12, CI Pigment Red 48
(Ca), CI Pigment Red 48 (Mn), CI Pigme
nt Red 57 (Ca), CI Pigment Red 112, C.I.
I. Pigment Red 122 and the like.

Examples of the pigment used as the cyan ink include CI Pigment Blue 1 and CI Pigment Blue.
2, CI Pigment Blue 3, CI Pigment Blue 1
5: 3, CI Pigment Blue 16, CI Pigment Blue
22, CIVat Blue 4, CIVat Blue 6, and the like. In addition, as for the coloring materials of any of the above colors, those newly manufactured for the present invention can be used.

(Pigment Dispersant) As a pigment dispersant which can be used in the ink used in the present invention, a water-soluble dispersant having a function of stably dispersing a pigment in water or an aqueous medium due to the presence of an anionic group. Any resin can be used. In particular, those having a weight average molecular weight in the range of 1,000 to 30,000 are preferred. More preferably, it is in the range of 3,000 to 15,000. Specifically, for example, styrene, styrene derivatives,
Vinyl naphthalene, vinyl naphthalene derivative, α, β-
Selected from hydrophobic monomers such as aliphatic alcohol esters of ethylenically unsaturated carboxylic acids, or acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid and fumaric acid derivatives Examples include a block copolymer, a graft copolymer or a random copolymer composed of two or more monomers, or a salt thereof. These resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved.

Further, a homopolymer comprising a hydrophilic monomer or a salt thereof may be used. It is also possible to use water-soluble resins such as polyvinyl alcohol, carboxymethyl cellulose, and naphthalenesulfonic acid formaldehyde condensate. However, when an alkali-soluble resin is used, there is an advantage that the viscosity of the dispersion can be reduced and the dispersion is easy. The water-soluble resin is preferably used in the range of 0.1 to 5% by mass based on the total amount of the ink.

The pigment ink which can be used in the present invention is constituted by dispersing or dissolving the above pigment and water-soluble resin in a water-soluble medium. An aqueous medium suitable for the pigment-based ink that can be used in the present invention is a mixed solvent of water and a water-soluble organic solvent. The water is not general water containing various ions, but deionized water (deionized water). ) Is preferred.

When the dispersant is not an anionic polymer, it is preferable to further add an anionic compound to the ink containing the pigment described above. Examples of the anionic compound suitably used in the present invention include, in addition to the high-molecular substances such as the alkali-soluble resins described in the section of the pigment dispersant, low-molecular-weight anionic surfactants as described below. it can.

Specific examples of the low molecular weight anionic surfactant include, for example, disodium lauryl sulfosuccinate, disodium polyoxyethylene lauroylethanolamide ester sulfosuccinate, disodium polyoxyethylene alkyl sulfosuccinate, carboxylation Polyoxyethylene lauryl ether sodium salt, carboxylated polyoxyethylene tridecyl ether sodium salt, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether triethanolamine sulfate, polyoxyethylene alkyl ether sodium sulfate, sodium alkyl sulfate, alkyl Examples include, but are not limited to, triethanolamine sulfate. The preferred amount of the anionic substance as described above is in the range of 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total amount of the ink.

(Self-dispersible Pigment) As a pigment that can be used in anionic ink, a self-dispersible pigment that can be dispersed in water or an aqueous medium without using a dispersant can also be used. . The self-dispersion type pigment has at least one kind of anionic hydrophilic group bonded directly or via another atomic group to the pigment surface. Examples of the anionic hydrophilic group include, for example, at least one kind selected from the following hydrophilic groups, and further another atomic group is an alkyl group having 1 to 12 carbon atoms, a substituent. And a naphthyl group optionally having a substituent. _{-COOM, -SO 3 M, -SO 2} NH 2, -PO 3 HM,
—PO ₃ M ₂ (M in the above formula represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium)

The pigment anionically charged by the introduction of a hydrophilic group on the surface of the pigment has excellent water dispersibility due to repulsion of ions. A stable dispersion state is maintained without adding any of these. It is particularly preferable when the pigment is carbon black.

(Additional Components in Ink) In addition to the above components, a surfactant, an antifoaming agent, a preservative, or the like may be added to the ink in order to obtain an ink having desired physical properties as required. And a commercially available water-soluble dye or the like can be further added.

Examples of the surfactant include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkyl allyl sulfonates, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl esters. , Polyoxyethylene sorbitan alkyl esters, non-ionic surfactants such as acetylene alcohol and acetylene glycol, and one or more of these can be appropriately selected and used. Among the above, particularly, acetylene alcohols and acetylene glycols can be suitably used for exhibiting excellent effects on permeability to plain paper and high foaming property. The amount used depends on the amount of the dispersant added,
Desirably, the content is 0.01 to 5% by mass based on the total amount of the ink.
At this time, the surface tension of the ink at 25 ° C. was 10 mN /
m (dyn / cm) or more, more preferably 2
It is preferable to determine the amount of the activator to be added so as to be 0 mN / m or more, more preferably 30 mN / m or more, and so that the surface tension becomes 70 mN / m or less. Because
In the ink jet recording system used in the present invention,
This is because it is possible to effectively suppress the occurrence of print distortion (deviation of the impact point of the ink droplet) due to the wetting of the nozzle tip.

As a method of preparing a pigment-based ink as described above, first, a pigment is added to an aqueous solution containing at least a pigment-dispersing resin and water, followed by stirring.
Dispersion is performed using a dispersing means described later, and centrifugation is performed as needed to obtain a desired dispersion. Next, the above-mentioned components are further added to the dispersion and stirred to form an ink.

When an alkali-soluble resin is used, it is preferable to add a base to dissolve the resin. At this time, it is preferable that the amount of the amine or the base for dissolving the resin is at least one time the amount of the amine or the base obtained by calculation from the acid value of the resin. The amount of the amine or the base can be calculated by the following equation.

(Equation 1)

Further, if premixing is carried out for 30 minutes or more before the dispersion treatment of the aqueous solution containing the pigment, the dispersion efficiency of the pigment is improved. This premixing operation improves the wettability of the pigment surface and promotes the adsorption of the dispersant on the pigment surface.

The bases to be added to the dispersion when the alkali-soluble resin is used include, for example, organic amines such as monoethanolamine, diethanolamine, triethanolamine, amine methylpropanol and ammonia, potassium hydroxide, and the like. It is preferable to use an inorganic base such as sodium hydroxide.

On the other hand, the dispersing machine used for preparing the pigment ink may be any commonly used dispersing machine, and examples thereof include a ball mill and a sand mill.
Among them, a high-speed sand mill is preferable, for example,
Examples thereof include a super mill, a sand grinder, a bead mill, an agitator mill, a Glen mill, a dyno mill, a pearl mill, a Kobol mill (all trade names) and the like.

The ink used in the present invention may contain, if necessary, a water-soluble organic solvent, a surfactant,
Additives such as an H preparation agent, a rust inhibitor, a fungicide, an antioxidant, an evaporation promoter, a chelating agent, and a water-soluble polymer may be added.

The liquid medium for dissolving or dispersing the coloring material which can be used in the present invention is preferably a mixture of water and a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Amides such as dimethylformamide and dimethylacetamide, ketones such as acetone, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycolide, ethylene glycol, propylene glycol, butylene glycol, An alkylene group such as ethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol or the like containing 2 to 6 carbon atoms. Sharp glycol, glycerol, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) lower alkyl ethers of polyhydric alcohols, such as ethers, N- methyl-2
Examples include cyclic amide compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, 2-pyrrolidone, and ε-caprolactam, and imide compounds such as succinimide.

In general, the content of the water-soluble organic solvent is preferably from 1 to 40% by mass, more preferably from 3 to 30% by mass% with respect to the total mass of the ink. Also,
When the content of water in the ink is in the range of 30 to 95% by mass, the solubility of the coloring material is good, the increase in the viscosity of the ink can be suppressed, and the fixing property is sufficiently satisfied. Can be done.

Although the anionic ink used in the present invention can be used as a general aqueous writing instrument, it is particularly suitable when applied to an ink jet recording method of a type in which the ink is ejected by the bubbling phenomenon of the ink due to thermal energy. It is characterized in that the ejection becomes extremely stable and no satellite dots are generated. However, in this case, the thermal properties (for example, specific heat, thermal expansion coefficient, and thermal conductivity) may be adjusted.

[Cationic Ink] Next, the aqueous cationic ink constituting the ink set of the present invention in combination with the anionic liquid composition described above will be described. Here, the ink set refers to a combination of the liquid composition of the present invention and at least one or more inks containing a cationic substance (cationic colorant). Also, a combination of at least one or more inks excluding the liquid composition of the present invention from this ink set is called an ink subset. The cationic ink used in the present invention, as a coloring material, using a water-soluble dye containing a cationic group, or when using a pigment as a coloring material,
It is preferable to use a cationic compound in combination (this combination is also referred to as a cationic coloring material in the present invention). The ink as described above used in the present invention further includes water, a water-soluble organic solvent and other components such as a viscosity modifier, p
An H adjuster, a preservative, a surfactant, an antioxidant and the like are included as necessary. Hereinafter, each component of these inks will be described.

(Water-soluble dye) The water-soluble dye having a cationic group used in the present invention is not particularly limited as long as it is a water-soluble dye described in, for example, Color Index. In addition, there is no particular limitation on those not described in the color index as long as they have a cationic group. The water-soluble dyes mentioned here include those having a pH dependency of solubility.

(Pigment) As another form of the ink used in the present invention, a pigment and a cationic compound are used in place of the above-mentioned water-soluble dye having a cationic group, and water, a water-soluble organic solvent and other Components, such as viscosity modifiers,
The ink may include a pH adjuster, a preservative, a surfactant, an antioxidant, and the like as necessary. Here, the cationic compound may be a dispersant for the pigment, or if the dispersant for the pigment is not cationic, a cationic compound other than the dispersant may be added. Of course, even when the dispersant is a cationic compound, another cationic compound may be further added. The pigment that can be used in the present invention is not particularly limited, and the pigment described in the section of the anionic ink can be suitably used.

(Pigment Dispersant) The pigment dispersant in the ink used in the present invention may be any water-soluble resin having a function of stably dispersing the pigment in water or an aqueous medium due to the presence of a cationic group. Can be used. As a specific example, what is necessary is just what is obtained by superposition | polymerization of a vinyl monomer, and at least one part of the obtained polymer has cationic property. Examples of the cationic monomer for constituting the cationic moiety include salts of the following tertiary amine monomers and quaternized compounds thereof.

N, N-dimethylaminoethyl methacrylate [CH ₂ ＣC (CH ₃ ) —COO—C ₂ H ₄ N (CH ₃ ) ₂ ], N, N-dimethylaminoethyl acrylate [CH ₂ ＣＨCH—COO _{-C 2 H 4 N (CH 3} ) 2], N, N- dimethylaminopropyl methacrylate _{[CH 2 = C (CH 3} ) -COO-C 3 H 6 N (CH 3) 2], N, N- dimethyl aminopropyl acrylate _{[CH 2 = CH-COO-} C 3 H 6 N (CH 3) 2], N, N- dimethylacrylamide _{[CH 2 = CH-CON (} CH 3) 2], N, N- dimethyl methacrylamide _{[CH 2 = C (CH 3} ) -CON (CH 3) 2], N, N- dimethylaminoethyl acrylamide _{[CH 2 = CH-CONHC 2} H 4 N (CH 3) 2], N, N- dimethylamino methacrylamide [CH ₂ = C ( _{H 3) -CONHC 2 H 4 N} (CH 3) 2], N, N- dimethylaminopropyl acrylamide _{[CH 2 = CH-CONH-} C 3 H 6 N (CH 3) 2], N, N- dimethylamino Propyl methacrylamide [CH ₂ ＣC (CH ₃ ) —CONH—C ₃ H ₆ N (CH ₃ ) ₂ ] and the like.

In the case of a tertiary amine, compounds for forming a salt include hydrochloric acid, sulfuric acid, and acetic acid. Compounds used for quaternization include methyl chloride, dimethyl sulfate, benzyl chloride, and the like. Epichlorohydrin and the like. Among them, methyl chloride, dimethyl sulfate and the like are preferable in preparing the dispersant used in the present invention. The tertiary amine salt or the quaternary ammonium compound as described above behaves as a cation in water, and under neutralized conditions, acidity is a stable dissolution region.
The content of these monomers in the copolymer is preferably in the range of 20 to 60% by mass.

Examples of other monomers used in the composition of the polymer dispersant include acrylic acid esters having a hydroxy group such as 2-hydroxyethyl methacrylate and acrylic acid esters having a long ethylene oxide chain in the side chain; Examples of hydrophobic monomers such as styrene-based monomers and water-soluble monomers soluble in water near pH 7 include acrylamides, vinyl ethers, vinylpyrrolidones, vinylpyridines, and vinyloxazolines. As the hydrophobic monomer, a hydrophobic monomer such as styrene, a styrene derivative, vinyl naphthalene, a vinyl naphthalene derivative, an alkyl ester of (meth) acrylic acid, or acrylonitrile is used. In the polymer dispersant obtained by copolymerization, a water-soluble monomer is used in order to make the copolymer stably exist in an aqueous solution.
The hydrophobic monomer is used in an amount of 20 to 4% by mass in order to enhance the dispersing effect of the copolymer on the pigment.
It is preferable to use it in the range of 0% by mass.

(Self-dispersing Pigment) In the case of a cationically charged pigment, at least one hydrophilic group bonded directly or via another atomic group is selected from the following quaternary ammonium groups. Are combined. However, the present invention is not limited to these.

[0152]

In the above formula, R represents a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group. The above cationic groups include, for example, NO3- and CH3COO- as counter ions.

As a method for producing a cationically-charged self-dispersion pigment having a hydrophilic group bonded thereto as described above, for example, a method of bonding an N-ethylpyridyl group having the following structure is exemplified. To explain, 3
-Amino-N-ethylpyridinium bromide.

The pigment charged cationically by the introduction of a hydrophilic group on the surface of the pigment has excellent water dispersibility due to repulsion of ions. A stable dispersion state is maintained without adding any of these. In particular, it is preferable that the pigment is carbon black.

(Additional Components in Ink) In addition to the above components, a surfactant, an antifoaming agent, a preservative, or the like may be added to the ink in order to obtain an ink having desired physical properties as required. And a commercially available water-soluble dye or the like can be further added.

As the surfactant, primary, secondary and tertiary amine salt type compounds, specifically, hydrochlorides such as laurylamine, cocoamine, stearylamine and rosinamine, acetates and the like; quaternary ammonium Salt type compound, specifically, lauryl trimethyl ammonium chloride,
Cetyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, etc .; pyridinium salt compounds, specifically, cetylpyridinium chloride, cetylpyridinium bromide, etc .; imidazoline-type cationic compounds, specifically Is 2
-Heptadecenyl-hydroxyethylimidazoline and the like;
Ethylene oxide adducts of higher alkylamines, specifically, cationic surfactants such as dihydroxyethylstearylamine, and amphoteric surfactants that exhibit cationicity in a certain pH range can also be used. Specifically, for example, an amino acid type amphoteric surfactant; R-NH-
CH ₂ —CH ₂ —COOH type compounds; betaine type compounds, specifically, carboxylate type amphoteric surfactants such as stearyl dimethyl betaine and lauryl dihydroxyethyl betaine, as well as sulfate ester type, sulfonic acid type, An amphoteric surfactant such as a phosphate ester type is exemplified. Also,
Examples of the nonionic surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohols, and acetylene glycols. In the present invention, one or more of these can be appropriately selected and used. Among the above, particularly, acetylene alcohols and acetylene glycols can be suitably used for exhibiting excellent effects on permeability to plain paper and high foaming property. The amount used varies depending on the surfactant used, but is 0.05 to
5% by mass is preferable because sufficient permeability can be ensured.

(Surface Tension of Ink) Further, the cationic ink used in the present invention has the following properties in order to improve the ink permeability of the printed matter recorded on plain paper and the like, and at the same time, to improve the matching with the ink jet head. As the physical properties of the ink itself, the surface tension at 25 ° C. is preferably 10 mN / m or more, more preferably 20 mN / m or more.
0 mN / m or less, more preferably 30 to 68 mN / m.
m is preferable, and the viscosity is 15 cP or less, preferably 10 mPa · s (cP) or less, more preferably 5 mPa
-It is desirable to adjust to s (cP) or less.

<Method for Forming a Colored Part on a Recording Medium> Next, a method for forming a colored part on a recording medium of the present invention will be described. The method for forming a colored portion on a recording medium according to the present invention includes: (i) a step of applying an anionic or cationic aqueous ink containing a coloring material to the recording medium; and (ii)
Applying a liquid composition containing fine particles, the surface of which has the opposite polarity to the polarity of the ink in a dispersed state, to a recording medium, wherein the surface of the recording medium includes an aqueous ink and The liquid composition is provided so as to be in contact with each other in a liquid state. Hereinafter, a method for applying the liquid composition and the aqueous ink configured as described above to a recording medium will be described.

The method of forming a colored portion on a recording medium according to the present invention includes the step (ii) of applying the liquid composition as described above on the recording medium, and the step of (ii) using a colorant containing an anionic or cationic material. (I) applying a water-based aqueous ink to a recording medium, in which case a liquid composition is applied to the colored portion forming region of the recording medium, or to the colored portion forming region and the vicinity thereof, The ink and the liquid composition are applied so as to contact each other in a liquid state. The term “colored portion forming region” as used herein refers to a region where ink dots are attached, and the vicinity of the colored portion forming region refers to a region that is about 1 to 5 dots outside the region where ink dots are attached. Refers to

In the method of forming a colored portion on a recording medium of the present invention, if the liquid composition of the present invention and the aqueous ink come into contact with each other in a liquid state on the recording medium,
These may be provided by any method. Therefore, it does not matter which of the liquid composition and the ink is applied first on the recording medium. For example, step (i) may be performed after performing step (ii), or step (ii) may be performed after performing step (i). Step (i)
, It is also preferable to perform the step (ii) and then perform the step (i) again. In addition, when the liquid composition is first applied to the recording medium, the time from when the liquid composition is applied to the recording medium to when the ink is applied onto the recording medium is particularly limited. However, it is preferable that the ink be applied to the recording medium almost simultaneously or within a few seconds in order to make them come into contact with each other in a liquid state.

(Recording Medium) The recording medium used in the above-described method of forming a colored portion on the recording medium of the present invention is not particularly limited, and conventionally used copy paper. So-called plain paper such as bond paper is preferably used. Of course, a coated paper specially prepared for ink jet recording or a transparent film for OHP is also preferably used. Further, it can be suitably used for general high-quality paper and glossy paper.

(Method of Applying Liquid Composition) As a method of applying the liquid composition of the present invention onto a recording medium, for example, a method of applying the liquid composition to the entire surface of the recording medium by a spray or a roller may be considered. More preferably, it is preferable to carry out the ink jet method capable of selectively and uniformly applying the liquid composition only to the colored portion forming region or the colored portion forming region to which the ink is applied and the vicinity of the colored portion forming region. . In this case, various ink jet recording methods can be used, but a method of discharging droplets using bubbles generated by thermal energy is particularly preferable.

<Inkjet Recording Apparatus> Next, the inkjet recording apparatus of the present invention will be described. An ink jet recording apparatus according to the present invention includes an ink container that contains an anionic or cationic aqueous ink containing a coloring material, a first recording unit including an ink jet head that ejects the ink, Liquid composition,
Preferably, a liquid composition storage section containing a liquid composition containing fine particles whose surface is charged in the opposite polarity to the aqueous ink in a dispersed state, and an inkjet head for discharging the liquid composition And a second recording unit.

Hereinafter, these will be described. FIG. 1 is a schematic perspective view showing an example of a schematic configuration of an inkjet printing apparatus to which the present invention has been applied. In FIG. 1, reference numeral 1 denotes a cartridge constituting a print head for discharging ink to perform printing, and reference numeral 2 denotes a cartridge constituting a liquid composition discharge head for discharging a liquid composition. In the illustrated example, four inks of different colors are used.
One print cartridge 1 and one liquid composition discharging cartridge 2 are used.

Each of the cartridges 1 for printing has a structure in which an ink tank portion is provided at an upper portion and an ink discharge portion (printing portion) is provided at a lower portion. The liquid composition cartridge 2 has a structure in which a liquid composition tank portion is provided at an upper portion and a liquid composition discharge portion is provided at a lower portion. Further, the cartridges 1 and 2 are provided with connectors for receiving drive signals and the like. 3 is a carriage.

On the carriage 3, four print head cartridges (print heads) 1 for printing with inks of different colors and one liquid composition discharge head cartridge (liquid composition discharge head) 2 are provided. Is mounted. The carriage 3 is provided with a connector holder for transmitting a signal for driving the print head 1 and the liquid composition discharge head 2 and the like. The head cartridges 1 and 2 are connected via the connector holder. Is electrically connected to

Each print head 1 stores inks of different colors, for example, yellow (Y), magenta (M), cyan (C), and black (B) inks. In this drawing, from the left side of the drawing, print head cartridges (print heads) 1Y, 1M, 1C, and 1B for yellow, magenta, cyan, and black inks are shown.
And a liquid composition discharge head cartridge (liquid composition discharge head) 2 containing the liquid composition is mounted on the right end.

In FIG. 1, reference numeral 4 denotes a scanning rail which extends in the main scanning direction of the carriage 3 and slidably supports the carriage, and reference numeral 5 denotes a driving belt which transmits a driving force for reciprocating the carriage 3. . 6 and 7, 8 and 9
Are transport roller pairs that are arranged before and after the print position of the print head, respectively, for nipping and transporting the recording medium 10. The recording medium 10, such as paper, is guided and supported at a printing position by a platen (not shown) for regulating a printing surface flat in a press-contact state. At this time, the ejection port forming surfaces of the head cartridges (heads) 1 and 2 mounted on the carriage 3 protrude downward from the carriage 3 and are positioned between the recording medium transport rollers 7 and 9, and the platen (non- (Shown) in parallel with the recording medium 10 pressed against the guide surface.

A recovery unit 11 is provided near the home position set on the left side of the print area of the ink jet printing apparatus shown in FIG. The recovery unit 11 includes four caps 12 corresponding to four print heads (head cartridges) 1Y, 1M, 1C, and 1B and one cap corresponding to one liquid composition ejection head (head cartridge) 2. The cap 13 is provided so as to be able to move up and down in the vertical direction.

When the carriage 3 is at the home position, the ejection openings of the heads 1 and 2 are joined by pressing the corresponding caps 12 and 13 against the ejection opening forming surfaces of the heads 1 and 2. Sealing (capping)
Is done. By capping, thickening and sticking of the ink due to evaporation of the ink solvent in the discharge port is prevented, and occurrence of defective discharge is prevented.

The recovery unit 11 is provided with each cap 1
A suction pump 14 communicating with the cap 2 and a suction pump 15 communicating with the cap 13 are provided. These pumps 14, 1
Reference numeral 5 is used to execute a suction recovery process by capping the ejection port forming surfaces with caps 12 and 13 when ejection failure occurs in the print head 1 and the liquid composition ejection head 2. Further, the recovery unit 11 is provided with two wiping members (blades) 16 and 17 made of an elastic member such as rubber. The blade 16 is held by a blade holder 18, and the blade 17 is held by a blade holder 19.

In the schematic diagram of the present invention, the blade holders 18 and 19 are respectively raised and lowered by a blade raising and lowering mechanism (not shown) driven by using the movement of the carriage 3, whereby the blades 16 and 19 are moved. 17
Is a wiping position (a wiping position that protrudes (ascends) for wiping ink or foreign matter attached to the ejection port forming surfaces of the heads (cartridges) 1 and 2) and a retracted (down) position that does not contact the ejection port forming surfaces (standby position). ) And go up and down. In this case, the blade 1 for wiping the print head 1
The blades 6 for wiping the liquid composition discharge head 2 and the liquid composition discharge head 2 are configured to be able to move up and down independently of each other.

Then, when the carriage 3 moves from the right side (print area side) in FIG. 1 to the home position side,
Alternatively, when moving from the home position side to the print area side, the blade 16 comes into contact with the ejection port forming surface of each print head 1 and the blade 17 comes into contact with the ejection port forming surface of the liquid composition ejection head 2, thereby causing relative movement. As a result, the wiping operation of the discharge port forming surfaces is performed.

FIG. 2 is a schematic perspective view showing a print head (cartridge) 1 having a structure in which an ink discharge section and an ink tank are integrated. Note that the liquid composition discharge head 2 is
It has substantially the same configuration as the print head 1 except that the liquid to be stored and used is a liquid composition. In FIG. 2, the print head 1 has an ink tank 21
And a head-side connector 23 for receiving a signal for driving the ink discharge unit 22 and outputting a remaining ink amount detection signal. have. The connector 23 is provided at a position aligned with the ink tank unit 21.

The print head 1 has a discharge port forming surface 81 on the bottom side (the recording medium 10 side) in FIG. 2, and the discharge port forming surface 81 is formed with a plurality of discharge ports. A discharge energy generating element that generates energy necessary for discharging ink is disposed in a liquid path portion that communicates with each discharge port.

The print head (head cartridge) 1 is an ink jet printing means for performing printing by discharging ink, and is constituted by a replaceable ink jet cartridge in which an ink discharge section 22 and an ink tank 21 are integrated. The print head 1 is an ink-jet printing unit that discharges ink using thermal energy, and includes an electrothermal converter for generating thermal energy. Further, the print head 1 performs printing by discharging ink from a discharge port using a pressure change generated by growth and shrinkage of bubbles caused by film boiling caused by thermal energy applied by the electrothermal transducer. It is.

FIG. 3 shows an ink discharge section 22 (liquid composition discharge section 2) of the print head 1 (liquid composition discharge head 2).
FIG. 2A is a partial perspective view schematically showing the structure of FIG. In FIG. 3, a plurality of ejection openings forming surfaces 81 facing a recording medium (print paper or the like) 10 with a predetermined gap (for example, about 0.5 to 2.0 mm) are provided at a predetermined pitch. A discharge port 82 is formed, and an electrothermal converter (heat-generating resistor or the like) 8 for generating energy for ink discharge along a wall surface of each liquid path 84 communicating the common liquid chamber 83 and each discharge port 82.
5 are provided.

The plurality of ejection ports 82 are
Are arranged in a positional relationship such that they are arranged in a direction intersecting with the moving direction (main scanning direction). In this manner, the corresponding electrothermal transducer 85 is driven (energized) based on the image signal or the ejection signal to cause the ink in the liquid passage 84 to boil, and the ink is ejected from the ejection port 82 by the pressure generated at that time. A print head 1 is configured.

FIGS. 4 to 6 are schematic diagrams showing the wiping operation of the ink jet printing apparatus described above. FIG. 4 shows a case where the carriage 3 moves from the print area side to the home position side. In FIG. 4, the print head 1 and the liquid composition discharge head 2 on the carriage 4 move from the right side (print area side) toward the home position as shown in FIG. Then, like (B),
First, the ink blade 16 between the ink cap 12 and the liquid composition cap 13 is raised,
Each print head 1Y, 1
M, 1C and 1B are sequentially wiped.

Further, as shown in FIG. 4C, after each print head 1 has passed over the blade 17 for liquid composition, the blade 17 for liquid composition is raised, and as shown in FIG. Then, the ejection port forming surface of the liquid composition ejection head 2 is simultaneously wiped. 4 blades 16 for ink
After wiping the first print head 1 and further ending the wiping of the liquid composition discharge head 2 by the blade 17 for the liquid composition path, the respective blades 16 and 17 descend and wait at the standby position.

In FIG. 4, the wiping is performed by the blades 16 and 17 when the carriage 3 moves from the right side (print area) in FIG. 1 to the home position side where the recovery unit 11 is located. The direction is not limited to this, and wiping may be performed when the carriage 3 moves from the home position side to the right side (print area side) as shown in FIG.

In FIG. 5A, in FIG. 5A, the print head 1 is raised by simultaneously raising the blade 16 for ink and the blade 17 for liquid composition and moving the carriage 3 rightward (toward the print area). And the liquid composition discharge head 2 are simultaneously wiped (B), and at the same time when the wiping of the liquid composition discharge head 2 is completed, only the blade 17 for the liquid composition is lowered to stand by, and the blade 17 for the ink remains as it is. Of the print head 1 is performed (C). Finally, as shown in FIG. 5D, when the wiping of all the print heads 1 is completed, the blade 16 for ink is lowered to complete a series of wiping operations.

By employing the wiping direction described with reference to FIG. 5, the droplets removed by the wiping and adhering to the blades 16 and 17 are scattered by the elasticity of the blades to the transport portion of the recording medium 10, and The danger of inadvertently soiling the recording medium 10 can be eliminated.

Further, as shown in FIG. 6, the wiping direction of the print head 1 and the wiping direction of the liquid composition discharge head 2 may be different. In FIG. 6, for example,
As shown in (A) and (B), when the carriage 3 moves from the home position side to the right side (print area side), the print head 1 is wiped with the blade 16 for ink, and (C) and (D). As shown in (1), when the carriage 3 moves from the print area side to the home position side, only the liquid composition ejection head 2 may be wiped by the liquid composition blade 17.

By adopting such a wiping direction, the ink scattered by the elastic force of the blade 16 adheres to the liquid composition discharge head 2 or conversely, the blade 1
The inconvenience (danger) that the liquid composition scattered by the elastic force of 7 adheres to the print head 1 can be eliminated or greatly reduced.

In FIG. 1, the print head 1
Cap 12 and the cap 13 for the liquid composition discharge head 2 are separated and made independent (dedicated), and the suction pumps 14 and 15 connected to these caps 12 and 13 are also used for the print head 1. And for the liquid composition ejection head 2 were separately (dedicated). Thus, in the caps 12 and 13 and the pumps 14 and 15, these waste liquids can be treated without bringing the ink and the liquid composition reactive with the ink into contact with each other, and maintain high reliability. It becomes possible.

FIG. 7 is a schematic diagram showing a collection system for collecting the ink and the liquid composition discharged from the pumps 14 and 15 into the waste ink tank. In FIG. 7, the waste ink sucked from the print head 1 by the suction pump 14 connected to the cap 12 and the waste liquid sucked from the liquid composition discharge head 2 by the suction pump 15 connected to the cap 13 go out of the printing apparatus. In order to prevent leakage, they are collected and stored in the waste liquid tank 24 through independent paths.

The waste liquid tank 24 is configured so that a porous absorber 25 is filled therein, and the absorber 25 absorbs and holds the waste liquid. This waste liquid tank 24
It is provided in the printing apparatus main body. In FIG. 7, the waste ink conduit 2 from the suction pump 14 for the printhead 1 is shown.
6 and the waste liquid conduit 27 from the suction pump 15 for the liquid composition discharge head 2 are connected to both ends of the waste liquid tank 24 at positions separated from each other as shown in the figure. By doing so, the liquid composition and the ink in the waste liquid tank 24 come into contact with each other only when the liquid is sufficiently absorbed in the absorber 25, and thus the amount of the liquid that the porous absorber 25 can absorb and hold. Can be sufficiently secured.

FIG. 8 shows an arrangement in which, in the waste liquid recovery system of FIG. 7, the absorbers 25 in the waste liquid tank 24 are arranged in upper and lower tiers, ink is absorbed by the lower absorber 25A, and the upper absorber 25
It is a schematic diagram which shows the waste-liquid collection | recovery system comprised so that B might absorb a liquid composition. According to the configuration of FIG. 8, even when the lower ink absorber 25A overflows, the upper absorber 25
The dye in the ink reacts and is fixed by the upper absorber 25B due to B and the liquid composition absorbed therein, so that the ink does not leak out and stain the inside and outside of the printing apparatus.

As another form of the ink jet recording apparatus, an ink containing section containing an anionic or cationic aqueous ink containing a coloring material, and the liquid composition of the present invention, preferably the above aqueous ink, are used. Is a liquid composition storage section containing a liquid composition containing fine particles whose surfaces are charged in the opposite polarity in a dispersed state; an aqueous ink stored in the ink storage section; and the liquid composition storage section. And an ink jet head for independently ejecting the liquid composition contained in the unit. Hereinafter, these will be described.

FIG. 10 shows such a cartridge 100.
In the drawing, reference numeral 1003 denotes an ink storage unit that stores ink, and 1005 denotes a liquid composition storage unit that stores a liquid composition. As shown in FIG. 11, the cartridge is configured to be detachable from a recording head 1101 that ejects each of the ink and the liquid composition, and when the cartridge 1001 is mounted on the recording head 1101, the liquid composition and the Ink is configured to be supplied to the recording head 1101.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, and the one in which they are integrated as shown in FIG. Can be

In FIG. 15, reference numeral 1500 denotes a recording unit, in which an ink storage section containing ink, for example, an ink absorber is stored, and the ink in the ink absorber has a plurality of orifices. Head part 1
It is configured to be ejected from 501 as ink droplets. As a material of the ink absorber, for example, polypropylene or polyurethane can be used. 1502
Is an atmosphere communication port for communicating the inside of the recording unit with the atmosphere.

Further, as another embodiment of the recording unit used in the present invention, the ink and the liquid composition are stored in respective storage sections in one ink tank, and each of the ink and the liquid composition is stored. A recording unit integrally provided with a recording head for discharging, specifically, for example, as shown in FIG. 12, a liquid composition in a container 1201L, a black ink in a container 1201Bk, Cyan and magenta color inks are stored in color ink storage units 1201Y, 1201M and 1201C, respectively.
Further, the recording head 120 is configured so that the ink flow paths are divided so that each ink can be ejected individually.
3 is provided.

FIG. 16 is a schematic perspective view showing a schematic configuration of another embodiment of the ink jet printing apparatus according to the present invention. In FIG. 16, reference numeral 4 denotes a scanning rail that extends in the main scanning direction of the carriage 3 and slidably supports the carriage. Reference numeral 5 denotes a drive belt that transmits a driving force for reciprocating the carriage 3. Also, 6, 7 and 8, 9
Are transport roller pairs that are arranged before and after the print position of the print head, respectively, for nipping and transporting the recording medium 10.

The recording medium 10 such as paper is guided and supported by a platen (not shown) for regulating the printing surface flat at the printing position in a press-contact state. At this time,
The ejection port forming surfaces of the head cartridges (heads) 1 and 2 mounted on the carriage 3 protrude downward from the carriage 3 and are located between the recording medium transport rollers 7 and 9.
Recording medium 1 pressed against a guide surface of a platen (not shown)
It faces in parallel to 0.

In FIG. 16, a total of six head cartridges are positioned and mounted on the carriage 3.
In the present embodiment, the yellow print head 1Y, the magenta print head 1M, the cyan print head 1C, the black print head 1B, the liquid composition discharge head 2, the second Of black print heads 1BB. The liquid composition discharge head 2 discharges a liquid composition reactive with a coloring material in the ink onto the recording medium 10.

The second black print head 1BB at the right end is a print head that uses black ink used in sub-scanning printing in reciprocating printing. In other words, the liquid composition ejection head 2 is arranged next to (to the right of) the black print head 1B in each of the above-described embodiments, and the black print head 1BB is arranged next (to the right end). Have been.

In FIG. 16, a recovery unit 11 is disposed on the left side of the print area. In the recovery unit 11, the print heads 1Y and 1Y are arranged from left to right in accordance with the arrangement of the head cartridges 1 and 2. 1M, 1C, 1
A cap 12 for capping B is sequentially arranged, and then (on the right) a cap 13 for capping the liquid composition discharge head 2 is arranged, and further on the right (right end).
Is provided with a cap 12 for capping the second black print head 1BB.

Each of the caps is provided so as to be able to move up and down in the vertical direction. When the carriage 3 is at the home position, the caps 12 and 13 corresponding to the ejection port forming surfaces of the heads 1 and 2 are respectively provided. By being pressed, the ejection ports of the heads 1 and 2 are sealed (capped), thereby preventing the ink from thickening and sticking due to the evaporation of the ink solvent in the ejection ports, thereby preventing the occurrence of ejection failure. .

The recovery unit 11 includes the caps 1 and
A suction pump 14 communicating with the cap 2 and a suction pump 15 communicating with the cap 13 are provided. These pumps 14, 1
Reference numeral 5 is used to execute a suction recovery process by capping the ejection port forming surfaces with caps 12 and 13 when ejection failure occurs in the print head 1 and the liquid composition ejection head 2. Further, a blade 17 for the liquid composition ejection head 2 is disposed between the fifth liquid composition cap 13 from the left end and the sixth (right end) black ink cap 12, and the right end of the right end cap 12. A blade 16 for each print head 1 is arranged on the (print area side).

The blade 17 is the blade holder 1
The blade 16 is held by a blade holder 18. In this embodiment, the blade holders 18 and 19 are respectively raised and lowered by a blade raising and lowering mechanism (not shown) driven by using the movement of the carriage 3, whereby the blades 16 and 17 are connected to the ejection ports of the heads 1 and 2. It moves up and down between a position protruding for wiping ink and foreign matter adhering to the forming surface (wiping position) and a retracted position (standby position) not in contact with the ejection port forming surface. In this case, the blade 16 for wiping the print head 1 and the blade 17 for wiping the liquid composition discharge head 2 are configured to be able to move up and down independently of each other.

FIG. 17 is a schematic diagram showing the wiping operation of the ink jet printing apparatus of FIG. In FIG. 16, after the print head blade 16 protrudes (ascends) as shown in FIG. 16A, each head mounted on the carriage 3 moves from the right side (print area side) toward the home position. come. The raised print head blade 16 sequentially wipes the print head 1 as the carriage 3 moves to the left as shown in FIG. Then, as shown in (C), when the liquid composition ejection head 2 comes before (to the right of) the blade 16 for the print head, the blade 16 retreats (downs) to the standby position, and Contact with the liquid composition discharge head 2 is prevented.

Further, when the carriage 3 moves leftward and the liquid composition discharge head 2 passes through the print head blade 6, as shown in FIG. 4D, the print head blade 6 and the liquid composition discharge head Both blades 17 protrude (raise). As the carriage 3 moves to the left, the blade 17 moves as shown in FIG.
The wiping of the liquid composition discharge head 2 by the wiping and the wiping of the right end print head 1BB by the blade 16 are simultaneously performed. After the wiping of all the heads 1 and 2 is completed, as shown in FIG.
Is retracted (downward), and waits at the standby position.

In the embodiment shown in FIGS. 16 and 17, when the carriage 3 moves from the print area side (right side) to the home position side where the recovery unit 11 is located, the blade 16 is used.
Although the wiping by 17 is performed, the wiping direction is not limited to this, and the wiping may be performed when moving from the home position side to the right side (print area side).

The ink jet printing apparatus shown in FIG.
The liquid composition ejecting head 2 ejects the liquid composition according to the present invention having a reactivity with the coloring material in the ink to the recording medium 10, and the ink ejected from each print head 1 and the recording medium 10 It is configured so that a recorded matter can be formed by contacting the above. On the recording medium 10, the coloring material in the ink reacts with the liquid composition, so that the coloring material in the ink is adsorbed on the surface of the fine particles in a monomolecular state, and the fine particles form an image. And an image having excellent color uniformity can be obtained.

FIG. 18 is a schematic perspective view showing a schematic configuration of another embodiment of the present invention. In FIG. 18, a recording medium 106 inserted at a paper feed position of the inkjet printing apparatus 100 is transported by a feed roller 109 to a printable area of the inkjet cartridge 103. A platen 108 is provided on the back surface of the print medium in the printable area.

The carriage 101 has two guide shafts 10.
4 and 105, the cartridge 103 having the head unit can reciprocally scan the print area. Each unit described below can be mounted on the carriage 101. That is, the inkjet cartridge 103 including an ink jet head for ejecting ink and liquid composition of each of a plurality of colors, and an ink tank for supplying the ink or liquid composition to each ink jet head is mounted. For example, four colors of black (Bk), cyan (C), magenta (M), and yellow (Y) can be used as a plurality of colors of ink.

At the left end of the area where the carriage 101 can move, a recovery system unit 110 having a wiping mechanism described later is provided below the area, and the ejection port of each ink jet head is capped at the time of non-printing or the like. Etc. become possible. This left end position is called the home position of each ink jet head. Reference numeral 107 denotes a switch unit and a display element unit. The switch unit is used for turning on / off the power of the inkjet printing apparatus, setting various print modes, and the like, and the display element unit displays various states of the printing apparatus. It is.

FIG. 19 is a schematic diagram illustrating a mechanism for wiping and wiping operation of another embodiment of the recovery system unit 110 in the above-described ink jet printing apparatus. The ink jet cartridge 103 shown in FIG.
BK1, 20S, and 20BK2 (tanks for Y, M, and C inks are not shown), and the head unit 102 is an inkjet head for each ink, that is, black ink heads 200BK1, 200BK2, and a liquid composition head 200S. , Cyan ink head 200C, magenta ink head 200M, and yellow ink head 2
00Y.

As shown in FIG. 19, each of the blades 118A and 118B and the wiping member 1 for wiping or wiping the discharge port surface of the ink jet head.
Reference numeral 17 is provided for each ink jet head. The blades 118A and 118B and the wiping member 117 corresponding to each of these heads can operate integrally during the wiping or wiping operation. That is, at the timing when the ink jet cartridge 103 is located at the home position and the wiping or wiping operation is performed, the ink cartridge 103 rises to a position where it can come into contact with the discharge port surface and the cover plate, and then the wiping direction indicated by an arrow in the drawing. , The discharge port surface can be wiped by the two blades 118A and 118B. On the other hand, in the wiping direction indicated by the arrow in the figure,
The wiping member 117 performs a wiping operation on the ejection port surface to remove a mixture of the liquid composition and the ink attached to the ejection port surface.

FIG. 20 is a view showing the discharge port surface 205 of the ink jet head 200 according to the present embodiment. A mixture 201 of the liquid composition and the ink is provided around the discharge port 206.
Shows a state where is attached. As shown in the figure,
In this embodiment, in each inkjet head, the arrangement of the ejection ports 206 is two rows, and the arrangement of the ejection ports in each row is shifted from each other by １ ／ of the ejection port pitch. As a result, a resolution of 2 that can be realized when the ejection port
Double resolution printing can be performed.

FIGS. 21A and 21B are a front view and a side view, respectively, showing a mechanism for the wiping and wiping operations shown in FIG. Incidentally, in FIG.
The illustration of the inkjet head 200Y and the like is omitted, and the head 200B facing the blades 118A and 118B and the like is omitted.
Only K1 is shown. In particular, as is clear from FIG.
Two of 18A and 118B are provided, and the difference is provided in the height. In the present embodiment, as an example, the wiping member 1
Reference numeral 17 denotes a recovery unit 11 which is formed by using a porous sintered urethane, Rubicell Clean (trade name, manufactured by Toyo Polymer Co., Ltd.), and wrapping it around an arm made of ABS resin.
It is obtained by attaching it to the base of No. 0 via a spring not shown. The contact pressure between the discharge port surface 205 and the wiping member 117 is set to be 100 g for a contact length of 4 mm. If this contact pressure is too large, the discharge port surface 2
05 may be damaged, while if it is small, a sufficient wiping effect cannot be obtained. Therefore, it is desirable to set it to about 1 to 100 g / mm, more preferably, 5 to 30 g / mm.
g / mm.

The rubber member used for the blades 118A and 118B is a urethane rubber made from a polyol having an ether bond as a raw material in the illustrated example. Instead of this, the blade has good water resistance, solvent resistance and abrasion resistance. Elastic members such as chlorinated butyl rubber, HNBR, natural rubber,
Isoprene rubber, butyl rubber, styrene rubber, nitrile rubber, silicon rubber and the like can also be used. As shown in the figure, the number of blades is two, and the first blade 118A has a thickness of 0.6 mm, a degree of freedom of 5.0 mm,
The object with the penetration amount of 1.4 mm, the second blade 118B,
1.0mm thickness, 10.0mm free length, 0.8m penetration
m. Note that these members and set values are not particularly limited, and can be freely set according to the liquid composition, the ink, the configuration of the recording apparatus, and the like.

FIGS. 22A to 22D are diagrams for explaining the wiping operation of the ink jet head according to the present embodiment. During wiping, blade 118A,
Holder 110A holding 118B and wiping member 117
Move in the direction of the arrow in the figure (FIG. (A)), the first blade 118A comes into contact with the discharge port surface 205 (FIG. (B)), and the holder 110A further moves, thereby causing the second blade to move. 118B also comes into contact with the discharge port surface 205 (FIG. 3 (c)). Foreign matter such as a mixture of the liquid composition and ink adhered to the discharge port surface 205 as described above is removed by abutting these two blades and relative sliding with the discharge port surface in that state. Can be. Then, when the holder 110A further moves in the same direction, the contact of the blade is released ((d) in the figure), and the wiping is completed. As shown in FIG. 3C, the wiping member 117 is similarly deformed by the deformation of the blade 118B caused by the contact of the second blade 118B having a longer free length with the discharge port surface 205, whereby the wiping member 117 is similarly deformed. The wiping member 117 does not come into contact with the discharge port surface 205, and only wiping is performed.

FIGS. 23A to 23C are diagrams illustrating the wiping operation of this embodiment. The wiping operation is performed by the holder 110
A is performed by the movement in the direction opposite to the movement shown in FIG. That is, as the holder 110A moves from the initial state shown in FIG. 23A in the direction of the arrow shown in FIG. 23B, the wiping member 117 comes into contact with the discharge port surface 205,
Thus, the wiping operation is performed, and the mixture of the liquid composition and the ink described above can be removed. Then, when the holder 110A further moves in the same direction, the contact is released ((c) in the figure), and the wiping operation ends. In the wiping operation, both the blades 118B and 118A come into contact with the discharge port surface 205 and the wiping is performed at the same time, as is apparent from FIG.

In the recording apparatus used in the present invention,
In the above description, an ink jet recording apparatus that ejects ink droplets by applying thermal energy to ink and a liquid composition has been described as an example. However, a piezoelectric ink jet recording apparatus using a piezoelectric element can be similarly used.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on mass unless otherwise specified. The zeta potential in the text is determined by dispersing the liquid composition with ion-exchanged water so that the solid content concentration of the fine particles becomes 0.1%, and then measuring the zeta potential with a zeta potential measuring device (BI-ZETA plu manufactured by Brookhaven).
s, liquid temperature 20 ° C., using an acrylic cell). The pH was measured using a pH meter (Horiba Seisakusho Co., Ltd., Castany pH) at a liquid temperature of 25 ° C.
It measured using the meter D-14). After dispersing the liquid composition in ion-exchanged water so that the average particle diameter of the fine particles becomes 0.1%, the particle size distribution analyzer (BI-90, manufactured by Brookhaven, Inc.) is used. , A liquid temperature of 20 ° C, and an acrylic cell).

First, the preparation of the liquid composition of the present invention will be described. After mixing and dissolving each of the following components, the mixture was pressure-filtered with a membrane filter having a pore size of 1 μm (trade name, Fluoropore Filter, manufactured by Sumitomo Electric Industries, Ltd.),
Liquid compositions A, B, C and D of the present invention were obtained. Further, the pore radius distribution and the pore volume of the liquid composition were pretreated according to the following procedure, the sample was put into a cell, vacuum degassed at 120 ° C. for 8 hours, and omnisorb 1 manufactured by Cantachrome Co., Ltd. was used. It was measured by the nitrogen adsorption desorption method. The pore radius and pore volume were determined by the method of Barrett et al. (J. Am. Chem. Soc., Vol. 7).
3, 373, 1951). (1) The liquid composition is dried at 120 ° C. for 10 hours in an air atmosphere, and the solvent is evaporated to dryness. (2) The dried product is heated from 120 ° C. to 700 ° C. in one hour, and then baked at 700 ° C. for three hours. (3) After firing, the fired product is gradually returned to normal temperature, and the fired product is ground in an agate mortar and powdered.

(Synthesis Example of Alumina Hydrate) Aluminum dodecoxide was produced by the method described in US Pat. No. 4,242,271. Next, U.S. Pat.
According to the method described in JP-A-02,870, the aluminum dodecoxide was hydrolyzed to produce an alumina slurry. Water was added to the alumina slurry until the solid content of the alumina hydrate became 8.2%. Alumina slurry p
H was 9.7. Add 3.9% nitric acid solution and adjust pH
Was adjusted to obtain a colloidal sol under the aging conditions shown in Table 1. The colloidal sol was spray-dried at 83 ° C. to produce alumina hydrates A to D. The surface of each of the alumina hydrates was positively charged in water and showed cationicity. Further, these alumina hydrates were dispersed in ion-exchanged water and dropped on a collodion film to prepare a measurement sample, and when observed with a transmission electron microscope, all of the particles were plate-shaped fine particles.

[0222]

[Table 1]

[0223]

The pH of the liquid composition A obtained above was 3.
8, and the zeta potential was +38 mV. Further, an ink tank is filled with the liquid composition A, and the temperature is 60 ° C./Dry·
No sediment was observed in the ink tank even after the one-month storage test, and the ejection stability from the recording head was good. Further, the fine particle aggregate obtained from the liquid composition A has a pore volume of 0.9 to 0.9 in a pore radius of 3 to 30 nm.
It was 6 ml / g, and the pore volume in the range exceeding 30 nm was 0.005 ml / g. The pore volume in the range of 3 to 20 nm is 0.94 ml / g,
The pore volume in the range exceeding 0.02 was 0.02 ml / g.

[0225]

The pH of the liquid composition B obtained above was 3.
7, and the zeta potential was +41 mV. Further, an ink tank was filled with the liquid composition B, and the temperature was 60 ° C./Dry·
No sediment was observed in the ink tank even after the one-month storage test, and the ejection stability from the recording head was good. Further, the fine particle aggregate obtained from the liquid composition B has a pore volume of 0.4 to 0.4 in a pore radius of 3 to 30 nm.
It was 5 ml / g, and the pore volume in the range exceeding 30 nm was 0.001 ml / g. The pore volume in the range of 3 to 20 nm is 0.44 ml / g,
The pore volume in a range exceeding 0.01 was 0.01 ml / g.

[0227]

The pH of the liquid composition C obtained above was 3.
7, and the zeta potential was +39 mV. Also, the ink tank is filled with the liquid composition C, and the temperature is 60 ° C./Dry·
No sediment was observed in the ink tank even after the one-month storage test, and the ejection stability from the recording head was good. The fine particle aggregate obtained from the liquid composition C has a pore volume of 0.9 to 0.9 in a pore radius of 3 to 30 nm.
It was 0 ml / g, and the pore volume in the range exceeding 30 nm was 0.01 ml / g. The pore volume in the range of 3 to 20 nm was 0.83 ml / g, and the pore volume in the range exceeding 20 nm was 0.08 ml / g.

[0229]

The pH of the liquid composition D obtained above was 4.
2, and the zeta potential was +36 mV. Further, an ink tank is filled with the liquid composition D, and the temperature is 60 ° C./Dry·
No sediment was observed in the ink tank even after the one-month storage test, and the ejection stability from the recording head was good. The fine particle aggregate obtained from the liquid composition D has a pore volume of 0.7 to 0.7 when the pore radius is in the range of 3 to 30 nm.
It was 9 ml / g, and the pore volume in the range exceeding 30 nm was 0.05 ml / g. The pore volume in the range of 3 to 20 nm was 0.70 ml / g, and the pore volume in the range exceeding 20 nm was 0.14 ml / g.

Next, the production of the ink subsets 1 and 2 used in Examples and Comparative Examples of the present invention will be described. <Preparation of Ink Subset 1> The components shown below were mixed, sufficiently stirred and dissolved, and then pressure-filtered with a fluoropore filter (trade name, manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.45 μm. Obtaining black, yellow, magenta and cyan dye inks, Bk1, Y1, M1 and C1,
The combination consisting of these dye inks was designated as ink subset 1.

[Black Ink Bk1] C.I. I. Direct Black 195 2.5 parts ・ 2-Pyrrolidone 10 parts ・ Glycerin 5 parts ・ Isopropyl alcohol 4 parts ・ Sodium hydroxide 0.4 part ・ Water 78.1 parts

[0233]

[0234]

[0235]

<Preparation of Ink Subset 2> A pigment dispersion was prepared from the following components, and a black ink Bk2 was prepared using the dispersion. Further, using the same pigment dispersion, yellow, magenta and cyan pigment inks,
Y2, M2 and C2 were obtained, and the combination of these pigment inks was designated as ink subset 2.

[Black Ink Bk2] (Preparation of Pigment Dispersion) Styrene-acrylic acid-ethyl acrylate copolymer (acid value 140, weight average molecular weight 5,000) 1.5 parts Monoethanolamine 1.0 Parts ・ Diethylene glycol 5.0 parts ・ Ion exchange water 81.5 parts

The above components were mixed, and mixed in a water bath.
Heat to ° C. to completely dissolve the resin. 10 parts of newly produced carbon black (MCF88, manufactured by Mitsubishi Kasei) and 1 part of isopropyl alcohol were added to this solution,
After premixing for 0 minutes, dispersion treatment was performed under the following conditions. -Disperser: sand grinder (Igarashi Kikai)-Grinding media: zirconium beads, 1 mm diameter-Filling ratio of grinding media: 50% (volume ratio)-Grinding time: 3 hours Further centrifugation (12,000 rpm, 20) Minutes)
Was performed to remove coarse particles to obtain a dispersion.

(Preparation of Black Ink Bk2) Using the above-described pigment dispersion, components having the following composition ratios were mixed to prepare a pigment-containing ink, which was designated as black ink Bk2. -30.0 parts of the above pigment dispersion-10.0 parts of glycerin-5.0 parts of ethylene glycol-5.0 parts of N-methylpyrrolidone-2.0 parts of ethyl alcohol-48.0 parts of ion-exchanged water

[Yellow ink Y2] Black ink B
The carbon black (MCF8) used in the preparation of k2
A pigment-containing yellow ink Y2 was prepared in the same manner as in the preparation of the black ink Bk2, except that Pigment Yellow 74 was used in place of 10 parts of the ink (manufactured by Mitsubishi Chemical Corporation).

[Magenta Ink M2] Black Ink B
The carbon black (MCF8) used in the preparation of k2
A pigment-containing magenta ink M2 was prepared in the same manner as in the preparation of the black ink Bk2, except that Pigment Red 7 was used in place of 10 parts of the ink.

[Cyan ink C2] Black ink Bk
Carbon black (MCF8
8, a pigment-containing cyan ink C2 was prepared in the same manner as in the preparation of the black ink Bk2 except that 10 parts of Pigment Blue 15 were used instead of 10 parts.

Examples 1 to 8 The liquid compositions A to D of the present invention obtained as described above, and the ink subset 1
(Bk1, Y1, M1, and C1) and ink subsets 2 (Bk2, Y2, M2, and C2) were used to perform printing in the combinations shown in Table 2 below. This was designated as Examples 1 to 8 of the present invention.

[0244]

[Table 2]

Example 1 in which the liquid compositions A to D and the ink subsets 1 and 2 are used in combination as described above
In the method of forming colored portions of Nos. To 8, recording was performed on PPC paper (manufactured by Canon). Further, as the ink jet recording apparatus used at that time, a recording apparatus similar to that shown in FIG. 1 was used, and a color image was formed using five recording heads shown in FIG. At this time, the liquid composition was first applied and attached on recording paper first, and then ink was attached.

Specifically, three-pass fine printing for printing the print area by three scans was performed. At this time, the liquid composition was applied to a pixel position where any one of yellow, magenta, cyan, and black inks was applied for each pass. That is, the logical sum of the print data of yellow, magenta, cyan, and black for each pass was used as the application data of the liquid composition. The type of the fine mask at the time of the fine printing is not particularly limited, and a known technique can be used.

The recording head used here was 600 dpi.
And a driving frequency of 9.
6 kHz. When a 600 dpi head was used, the ejection amount per dot was 15 ng for the yellow, magenta, cyan ink and liquid composition, and 30 ng per dot for the black ink. These recording conditions are the same throughout the examples and comparative examples.

(Comparative Examples 1 and 2) Using only ink subsets 1 and 2, printing was performed as shown in Table 3 below.

[Table 3]

The recording head used in recording using only the ink subset 1 and the ink subset 2 (Comparative Examples 1 and 2) had a recording density of 600 dpi, and the driving conditions were a driving frequency of 9.6 kHz. . 60
When the 0 dpi head is used, the ejection amount per dot is about 15 ng for each of yellow, magenta and cyan inks, and about 30 ng per dot for black ink. Recording was performed under the same conditions as described above.

[Evaluation Method and Evaluation Criteria] Example 1 above
-8 and the recorded images obtained in Comparative Examples 1 and 2 were evaluated by the following evaluation methods and evaluation criteria. Table 4 shows the results.

(Evaluation Method of Recorded Image) (1) Chromogenicity High-definition XYZ, CIELAB, RGB standard images (SHI
PP) (Supervision: High-definition Standard Image Creation Committee, published by The Institute of Image Electronics Engineers of Japan) were printed using an RGB color chart using a printer, and the color charts were measured. The evaluation of the color development was performed by calculating the three-dimensional spread of the color distribution (hereinafter referred to as the color gamut volume in the text) by the method described in the technical description and compared. At that time, image processing for forming a printed image was performed under the same conditions, and colorimetry was measured 24 hours after printing using a GRETAG spectroline with a light source of D50 and a viewing angle of 2 °. The evaluation criteria are shown below. The ratio of the color gamut volume to the print image of only the ink subset (Comparative Examples 1 and 2) was used as an evaluation criterion.

AAA: The color gamut volume ratio is 1.7 times or more AA: The color gamut volume ratio is 1.5 to less than 1.7 times A: The color gamut volume ratio is 1.4 to less than 1.5 times BB: Color The gamut volume ratio is from 1.2 to less than 1.4 times B: The gamut volume ratio is from 1.0 to less than 1.2 times C: The gamut volume ratio is less than 1.0 times

Separately from this, an image was formed by printing with ink subset 1 using ink-jet coated paper (trade name: color BJ paper LC-101, manufactured by Canon Inc.). The ratio of the color gamut volume to the printed matter of No. 1 was 1.3 times.

(2) Uniformity After printing solid images of the yellow, magenta, cyan and black inks using the above-described printer, the color uniformity of white haze and color unevenness was visually evaluated. . In particular, colors having poor uniformity were evaluated. The evaluation criteria are as follows. A: Almost no white haze or color unevenness occurs. B: White haze and color unevenness are slightly visible along the paper fibers,
It is a level with virtually no problem. C: White haze and color unevenness are remarkably observed along the fiber of the paper.

(3) Unevenness Using the above-described printer, solid images of inks of each color of yellow, magenta, cyan and black were printed, and the unevenness was visually evaluated. In particular, a color with poor unevenness was evaluated. The evaluation criteria are as follows. A: There is almost no uneven streaks. B: Streaks are slightly visible for each head scan, but there is practically no problem. C: White stripes are remarkably visible for each head scan.

(4) Scratch Resistance Solid images of inks of each color of yellow, magenta, cyan and black were printed using the printer described above.
16 hours after printing, put the silk paper on the printing part,
A weight of 3.5 cm x 3.5 cm is placed on top of it,
15 cm / sec. While applying a pressure of 0 g / cm ³ . The abrasion resistance of the printed portion was evaluated by pulling the silk paper at the speed shown in FIG. In particular, colors having poor abrasion resistance were evaluated. The evaluation criteria are as follows. A: Ink drop hardly occurs. B: Ink slightly adheres to the silbon paper, but the color fading of the printed portion is not noticeable. C: A large amount of ink adheres to the silk paper, and the color of the printed portion is clearly discolored.

(5) Texture After printing solid images of yellow, magenta, cyan and black inks using the above-described printer, the texture of the recording medium was visually evaluated. The evaluation criteria are as follows. A: Both the printed portion and the non-printed portion have no uncomfortable feeling and leave the texture of plain paper. B: The texture differs between the printed portion and the unprinted portion, or the entire recording medium greatly differs from the texture of plain paper.

[0258]

[Table 4]

(Examples 9 to 15) In order to examine the effect on the image quality due to the type of the recording medium to be used, an ink set composed of a combination of the liquid composition A and the ink subset 1 prepared above was used. An image output test was performed using seven types of “plain paper” widely distributed under the following trade names 1) to 7). At the time of image formation, each of the four color inks constituting the ink subset 1 and the liquid composition A were printed on each of these plain papers in the same manner as in Examples 1 to 8, and Examples 9 to 15 were printed. Recorded image. Then, the obtained images were evaluated in the same manner as in Examples 1 to 8, and the results are shown in Table 5 below.

Recording media 1) Canon: PB paper 2) Canon: Brilliant White paper 3) Union Camp: Great White Inkjet 4) Hammermill: Jet Print 5) Xerox 6) Hewlett Packard: Bright White Inkjet Paper 7) Aussdat Ray: Ray Jet

[0261]

[Table 5]

As a result, as shown in Table 5, in the method of forming a colored portion in Examples 9 to 15, as shown in Table 5, regardless of the type of the recording medium, coloring, uniformity, uneven streaks, and abrasion resistance It was confirmed that satisfactory images could be obtained in both properties and textures.

[0263]

As described above, according to the present invention,
In particular, when color ink jet recording is performed on plain paper, a method for measuring the properties of pores due to the liquid composition that enables excellent color development and uniformity of color to be obtained, while maintaining the texture of plain paper A liquid composition capable of obtaining excellent color developability and color uniformity comparable to ink-jet coated paper, and having less uneven streaks in a solid image portion and an ink jet recorded image having excellent scratch resistance in a printed portion. Provided are an ink set combining a liquid composition, a method for forming a colored portion on a recording medium, and an ink jet recording apparatus. The liquid composition provided by the present invention not only enables the provision of the above-described excellent image, but also has excellent ink jet recording characteristics such as storage stability and ejection stability from a recording head.

[Brief description of the drawings]

FIG. 1 is a partially cutaway perspective view schematically showing an inkjet printing apparatus to which the present invention is applied.

FIG. 2 is a schematic perspective view of the head cartridge in FIG.

FIG. 3 is a partial perspective view schematically illustrating a structure of an ink ejection unit of the head cartridge in FIG.

4A and 4B are schematic diagrams showing a wiping operation of the ink jet printing apparatus of FIG. 1, wherein FIG. 4A shows movement of each head from a print area side to a home position and rise of an ink blade, and FIG. Wiping,
(C) shows the wiping of the liquid composition discharge head, and (D) shows the descent of each blade.

5A and 5B are schematic diagrams showing a wiping operation of the ink jet printing apparatus of FIG. 1; FIG. 5A is an elevation of each blade, FIG. 5B is a movement of each head from a home position to a print area side, and FIG. (D) shows the lowering of the blade for the liquid composition, and (D) shows the lowering of the blade for the ink, respectively.

6A and 6B are schematic diagrams showing a wiping operation of the ink jet printing apparatus of FIG. 1, wherein FIG. 6A is an elevation of an ink blade, and FIG. Wiping,
(C) shows the movement of each head from the print area side to the home position side, the standby of the ink blade and the rise of the liquid composition blade, and (D) the movement of each head to the home position side and the liquid composition ejection head. Are shown, respectively.

FIG. 7 is a schematic diagram showing a waste liquid collecting system of the inkjet printing apparatus of FIG. 1;

FIG. 8 is a schematic diagram showing a partially modified example of the waste liquid recovery system of FIG. 7;

FIG. 9 is a schematic cross-sectional view illustrating a state of a colored portion when inkjet recording is performed on coated paper.

FIG. 10 is a schematic view showing one embodiment of an ink cartridge according to the present invention.

FIG. 11 is a schematic diagram of a recording head on which the ink cartridge of FIG. 10 is mounted.

FIG. 12 is a schematic view showing one embodiment of a recording unit according to the present invention.

FIG. 13 is a schematic cross-sectional view illustrating a state of a colored portion of an inkjet image according to the present invention.

FIG. 14 is a schematic process diagram illustrating a process of forming a colored portion of an ink jet recorded image according to the present invention.

FIG. 15 is a perspective view of a recording unit.

FIG. 16 is a partially broken perspective view schematically showing one embodiment of an ink jet printing apparatus according to the present invention.

17A and 17B are schematic diagrams illustrating a wiping operation of the ink jet printing apparatus of FIG. 16, wherein FIG.
(C) lowers the ink blade, (D) raises both blades after the liquid composition has reached the proper position, (E) wipes the liquid composition and the second black ink head, (F) Indicates the lowering of both blades, respectively.

FIG. 18 is a schematic perspective view showing an inkjet printing apparatus according to one embodiment of the present invention.

19 is a schematic diagram for explaining a mechanism for wiping and wiping operation in the inkjet printing apparatus of FIG.

20 is a diagram illustrating a discharge port surface of an inkjet head and a mixture of a liquid composition and ink attached to the discharge port surface in the embodiment of FIG. 18;

21 (a) and (b) are a front view and a side view, respectively, of the mechanism shown in FIG.

FIGS. 22A to 22D are diagrams illustrating a wiping operation of the embodiment of FIG.

23 (a) to (c) are diagrams illustrating a wiping operation of the embodiment of FIG. 19;

[Explanation of symbols]

1: print head (ink ejection head cartridge) 2: liquid composition ejection head (liquid composition ejection head cartridge) 3: carriage 4: guide shaft (scanning rail) 5: drive belt 6, 7, 8, 9: transport roller 10: Recording medium 11: Recovery unit 12: Cap (for print head) 13: Cap (for liquid composition discharge head) 14: Suction pump (for ink) 15: Suction pump (for liquid composition) 16: Blade ( 17: Blade (for liquid composition discharge head) 18, 19: Blade holder 20, 20Bk1, 20S, 20BK2: Ink tank 21: Liquid storage tank section 22: (Ink) discharge section 22A: (Liquid composition) Material) discharge unit 23: head side connector 24: waste liquid tank 25: absorber 26: waste ink conduit 7: Waste liquid conduit 81: Discharge port forming surface 82: Discharge port 83: Common liquid chamber 84: Liquid path 85: Electrothermal converter (heating resistor, etc.) 100: Inkjet printing device 101: Carriage 102: Head unit 103: Inkjet Cartridges 104, 105: Guide shaft 106: Recording medium 107: Switch section and display element section 108: Platen 109: Feed roller 110: Recovery unit 110A: Holder holding blade and wiping member 117: Wiping member 118A, 118B: Blade 200, 200Bk, 200Bk1, 200BK2, 2
00S, 200Y, 200M, 200C: Inkjet head 201: Mixture of body composition and ink 205: Discharge port surface 206: Discharge port 901: Base paper 903: Ink receiving layer 905: Porous fine particles 907: Adhesive 909: Ink Penetration section 1001: cartridge 1003: ink storage section 1005: liquid composition storage section 1101: recording head 1201: recording unit 1203: recording head 1301: recording medium 1302: void 1303: fine particles 1305: coloring material 1307, 1309: fine particle aggregation Object 1400: Colored part 1401: Reaction part 1402: Ink outflow part 1403: Recording medium 1404: Colorant 1405: Void 1406: Liquid composition 1407: Pool 1413: Ink 1415: Aggregate 1500: Recording unit 1501: Head part 1502: Atmospheric communication hole

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masao Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (Reference) 2C056 EA04 FA03 FC01 FC02 2H086 BA02 BA05 BA51 BA53 BA55 BA59 BA60 4J039 BA12 BA16 BA22 BA24 BA30 BA31 BA32 BA35 BD03 BE01 BE22 EA15 EA16 EA17 EA19 EA20 EA36 EA41 EA42 EA44 EA47 GA24

Claims (45)

[Claims] After pre-treating a liquid composition containing at least fine particles and a solvent in the order of the following (1) to (3),
A step of measuring the pore properties of fine particle aggregates formed from the liquid composition by vacuum degassing at 20 ° C. for 8 hours by a nitrogen adsorption / desorption method; Method of measuring physical properties: (1) The liquid composition is dried at 120 ° C. for 10 hours in an air atmosphere to evaporate almost the solvent, and then dried; (2) The dried product is heated from 120 ° C. to 700 ° C. in 1 hour. After the temperature is raised, baking is performed at 700 ° C. for 3 hours; and (3) After the baking, the above-mentioned baked product is gradually returned to normal temperature to powder the baked product. 2. A liquid composition which is applied to a recording medium together with an ink containing a coloring material to form a colored portion on the recording medium, wherein the liquid composition comprises a solvent and the coloring material When the pore physical properties of a fine particle aggregate formed from the liquid composition are measured by the method according to claim 1, the fine particle aggregate has a pore radius of 3 nm. 0.4 m pore volume in the region of ３０30 nm
1 / g or more, and a liquid composition characterized by having a pore volume of 0.1 ml / g or less in a region where the pore radius exceeds 30 nm. 3. A pore volume in a region having a pore radius of 3 nm to 20 nm is 0.4 ml / g or more, and a pore radius is 20 n
The liquid composition according to claim 2, wherein the pore volume in a region exceeding m is 0.1 ml / g or less. 4. The ink according to claim 2, wherein the ink is an anionic or cationic aqueous ink, and the liquid composition contains, in a dispersed state, fine particles whose surface is charged in the opposite polarity to the aqueous ink. An aqueous liquid composition as described. 5. The liquid composition according to claim 2, wherein the fine particles are fine particles that adsorb the coloring material on the surface of the fine particles while preventing aggregation of the coloring material in the ink when forming the colored portion. 6. The liquid composition according to claim 2, wherein the zeta potential is from +5 to +90 mV. 7. The liquid composition according to claim 2, further comprising an acid, wherein the pH is adjusted to 2 to 7. 8. The acid having a first-order dissociation constant pKa in water of 5
The liquid composition according to claim 7, which is: 9. The liquid composition according to claim 2, wherein the zeta potential is -5 to -90 mV. 10. The liquid composition according to claim 2, further comprising a base, wherein the pH is adjusted to 7 to 12. 11. A first-order dissociation constant pKb of a base in water
The liquid composition according to claim 10, wherein is less than or equal to 5. 12. The fine particles have an average particle diameter of 0.005.
The liquid composition according to claim 2 or 3, wherein the liquid composition has a size in a range of from 1 to 1 µm. 13. An ink set independently comprising an ink containing a coloring material and a liquid composition containing fine particles reactive with the coloring material, wherein the liquid composition according to claim 2 is provided. An ink set, which is a composition. 14. The fine particle aggregate having a pore radius of 3 nm to 2 nm.
The pore volume in the region of 0 nm is 0.4 ml / g or more;
The pore volume in the region where the pore radius exceeds 20 nm is 0.1%.
The ink set according to claim 13, wherein the ink set is not more than ml / g. 15. An aqueous liquid composition wherein the ink is an anionic or cationic aqueous ink, and wherein the liquid composition contains, in a dispersed state, fine particles whose surface is charged to the opposite polarity to the aqueous ink. Claim 13 or 1 which is
4. The ink set according to 4. 16. The ink set according to claim 13, wherein the ink is at least one selected from yellow ink, magenta ink, cyan ink, black ink, red ink, blue ink, and green ink. 17. The ink set according to claim 13, wherein the inks separately include a yellow ink, a magenta ink, and a cyan ink. 18. The ink set according to claim 13, wherein the inks separately include a yellow ink, a magenta ink, a cyan ink, and a black ink. 19. The ink according to claim 1, wherein the ink is anionic and the liquid composition has a zeta potential of +5 to +90 mV.
The ink set according to any one of items 3 to 18, wherein 20. The ink according to claim 13, wherein the ink is anionic, the liquid composition contains an acid, and the pH of the liquid composition is adjusted to 2 to 7. set. 21. The ink set according to claim 20, wherein the first dissociation constant pKa of the acid in the liquid composition in water is 5 or less. 22. The ink according to claim 1, wherein the ink is cationic and the liquid composition has a zeta potential of -5 to -90 mV.
The ink set according to any one of items 3 to 18, wherein 23. The ink according to claim 13, wherein the ink is cationic, the liquid composition contains a base, and the pH of the liquid composition is adjusted to 7 to 12. set. 24. The ink set according to claim 23, wherein the primary dissociation constant pKb of the base in the liquid composition in water is 5 or less. 25. The ink set according to claim 13, wherein the fine particles dispersed in the liquid composition have an average particle diameter in a range of 0.005 to 1 μm. 26. The ink according to claim 13, wherein the ink has an anionic property and contains an anionic compound.
The ink set according to any one of the above. 27. The ink set according to claim 26, wherein a water-soluble dye having an anionic group is contained as the anionic compound. 28. The ink set according to claim 26, wherein the anionic compound includes a pigment having an anionic group on the surface. 29. The ink set according to claim 26, wherein the ink contains a pigment and an anionic compound which is a dispersant for the pigment. 30. The ink according to claim 13, wherein the ink has a cationic property and contains a cationic compound.
26. The ink set according to any one of items 25 to 25. 31. A method comprising: (i) applying an ink containing a coloring material to a recording medium; and (ii) applying the liquid composition according to claim 2 to the recording medium. A method for forming a colored portion on a recording medium. 32. A method comprising: (i) applying an ink containing a coloring material to a recording medium; and (ii) applying the liquid composition according to claim 3 to the recording medium. A method for forming a colored portion on a recording medium. 33. An aqueous liquid composition in which the ink is an anionic or cationic aqueous ink and the liquid composition contains fine particles whose surface is charged to the opposite polarity to that of the ink in a dispersed state. 31 or 32.
3. The method for forming a colored portion on a recording medium according to item 1. 34. The method according to claim 31, wherein the step (i) is performed after the step (ii) is performed. 35. After performing the step (i), the step (i)
The method for forming a colored portion on a recording medium according to any one of claims 31 to 33, wherein i) is performed. 36. After performing the step (i), the step (i)
The method for forming a colored portion on a recording medium according to any one of claims 31 to 33, wherein i) is performed, and then step (i) is performed again. 37. The ink jet recording method according to claim 31, wherein the application of the ink to the recording medium in the step (i) is performed by discharging the ink from an orifice according to a recording signal. A method for forming a colored portion on a recording medium according to the above. 38. The method for forming a colored portion on a recording medium according to claim 37, wherein the ink jet recording method is a method of ejecting ink by applying thermal energy to the ink. 39. The ink jet recording method according to claim 31, wherein the application of the liquid composition to the recording medium in the step (ii) is performed by discharging the liquid composition from an orifice according to a recording signal. A method for forming a colored portion on a recording medium according to claim 1. 40. The method for forming a colored portion on a recording medium according to claim 39, wherein the ink jet recording method is a method in which thermal energy is applied to the liquid composition to discharge the liquid composition. 41. A liquid containing the liquid composition according to claim 2, wherein an ink containing section containing an ink containing a color material, a first recording unit provided with an ink jet head for discharging the ink, and An ink jet recording apparatus comprising: a composition storage section; and a second recording unit including an ink jet head for discharging the liquid composition. 42. An ink containing section containing an ink containing a coloring material, the liquid composition containing section according to claim 2, and the ink contained in the ink containing section and the liquid composition containing section. An ink jet recording apparatus, comprising: an ink jet head for independently discharging a contained liquid composition. 43. The ink jet recording apparatus according to claim 41, wherein the ink jet head is a thermal ink jet head for ejecting liquid by applying thermal energy. 44. The liquid composition according to claim 2, which is applied to a recording medium together with an anionic or cationic ink containing a coloring material and is used to form a colored portion on the recording medium. Thus, the formation of the colored portion is such that the liquid composition and the ink come into contact with each other in a liquid state, and the surface of the fine particles of the liquid composition has a molecular state in which the coloring material in the ink has in the ink. A liquid composition characterized by being adsorbed or bonded while maintaining substantially the same molecular state. 45. The liquid composition according to claim 3, which is applied to a recording medium together with an anionic or cationic ink containing a coloring material and used to form a colored portion on the recording medium. Thus, the formation of the colored portion is such that the liquid composition and the ink come into contact with each other in a liquid state, and the surface of the fine particles of the liquid composition has a molecular state in which the coloring material in the ink has in the ink. A liquid composition characterized by being adsorbed or bonded while maintaining substantially the same molecular state.