JP2003266916A - Ink set, ink-jet recording method, ink-jet recording apparatus, cartridge, and ink-jet recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set which can obtain a quality image without feathering and color bleeding even when printed on plain paper, can obtain a printed matter excellent in abrasion resistance, can obtain a high image density without the penetration of recording liquid into the depth of paper, can well do perfecting printing with an image density reduced when seen from a surface opposite to an image print surface, and can prevent image fouling by defective drying of the recording liquid, a recording method, recording apparatus, and recorded matter using the ink set and to provide an ink set which improves the water resistance of an image obtained on a recording medium and is excellent in stability with the passage of time without the propagation of mold, etc., in treatment liquid and the recording liquid even when stored for a long period, a recording method, a recording apparatus and a recorded matter using the ink set. <P>SOLUTION: In the ink set, the recording liquid containing a resin-coated coloring material and the treatment liquid containing fine particles reactive with the coloring material are combined. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set comprising a treatment liquid containing fine particles and a recording liquid containing a resin-coated coloring material, and a specific ink set for the ink set. A treatment liquid, a specified recording liquid for the ink set, an ink jet recording method for forming an image by adhering the treatment liquid and the recording liquid to a recording material,
The present invention also relates to an inkjet recording device, a cartridge containing the treatment liquid and the recording liquid, and an inkjet recorded product produced using the inkjet recording device.

[0002]

2. Description of the Related Art An ink jet recording method for recording an image by using a recording liquid containing a coloring material as droplets is excellent in that its printing mechanism is simple and noise is not generated. On the other hand, however, this image recording method has a problem that an image defect represented by character blurring (hereinafter, referred to as feathering) is likely to occur depending on a combination with a recording medium, and image quality is significantly deteriorated. Regarding this problem, attempts have been made to reduce feathering by suppressing ink permeability, but in this case, the ink is poor in dryness, so if you touch the printed material after printing, the ink may get in your hand, The image becomes dirty.

Further, when a color image is printed, inks of different colors are successively superposed, so that the color inks bleed or mix at the color boundary portion (hereinafter,
This is also called color bleeding), and there is also a problem that the image quality is greatly reduced. With respect to this problem, attempts have been made to reduce color bleeding by increasing the ink permeability, but in this case, the color material enters the inside of the recording medium, which lowers the image density, Ink oozes out to the back side of the recording material so much that double-sided printing cannot be performed properly. Therefore, an image forming method that solves these problems at the same time to improve the image quality is desired.

To solve these problems, a method has been proposed in which a treatment liquid containing fine particles is used together with the recording liquid.
For example, an inkjet recording method is disclosed in which a colorless liquid containing fine silica particles is adhered to a recording material, and then a non-aqueous recording liquid containing oil black is adhered (see, for example, Patent Document 1). Further, an inkjet recording method has been disclosed in which resin fine particles or titanium dioxide fine particles, or a solution containing these fine particles and a binder polymer is applied or sprayed before discharging a recording liquid containing a pigment and a resin (for example, Patent Document 1). 2).
In addition, an image forming an image on a recording material by separately ejecting a colorless inkjet treatment liquid containing an anionic metal oxide colloid and an ink containing a coloring material and not containing a resin component A forming method is disclosed (for example, refer to Patent Document 3).

However, although these proposals have been made, in Patent Documents 1 and 3 mentioned above,
In both cases, the recording liquid containing the anionic coloring material and the processing liquid containing the anionic fine particles are combined, so that the aggregation of the coloring material and the adsorption effect cannot be obtained, which is effective in suppressing feathering and color bleeding. Can't get Further, in Patent Document 2, since cationic titanium dioxide is combined with an anionic coloring material, there is a certain effect in aggregation and adsorption of the coloring material, but there is a point of suppressing feathering and color bleeding. Is not enough effect.

Further, there is disclosed an image forming method having a step of adsorbing a coloring material in the form of a single molecule in a droplet on the surface of fine particles and a step of causing aggregation of the fine particles adsorbing the coloring material on the surface ( See, for example, Patent Document 4.). Further, there is disclosed an ink set in which the pH of the mixed liquid when the ink and the liquid composition are mixed at a weight ratio of about 1: 1 is a pH that causes aggregation of the coloring material (see, for example, Patent Document 5). ). In addition, a liquid composition containing fine particles whose surface is charged in a polarity opposite to that of a water-based ink in a dispersed state is disclosed (for example, see Patent Document 6). However, although they all have a certain effect on the aggregation and adsorption of the coloring material, they are not sufficiently effective in suppressing feathering and color bleeding.

Further, these proposals using a processing liquid containing fine particles also have a problem in fixing property of the recording liquid. That is, when the treatment liquid and the recording liquid adhere to the recording material and the vehicle permeates the recording material, a mixture of the fine particles and the coloring material is deposited on the surface of the recording material. This deposited layer is mechanically weak,
Since it is easily removed by rubbing it with a finger, there is a problem of abrasion resistance such that the user's hand is stained with ink or the back surface of the printed matter is stained with the printed matter when the printed matter overlap each other.

A first liquid containing a polymer fine particle and / or a reaction agent which forms an aggregate when contacted with the ink composition due to insufficient abrasion resistance, and an ink composition containing the polymer fine particle. An ink jet recording method is disclosed in which the recording material is attached to the recording material to perform printing (for example, refer to Patent Document 7). In this configuration, the coloring material itself does not have the function of improving the abrasion resistance, and therefore it is necessary to add a large amount of polymer particles in order to obtain sufficient abrasion resistance. However, if a large amount of polymer particles is put, side effects such as deterioration of ejection stability, deterioration of storage stability, and increase of viscosity occur, and the problem cannot be solved yet. Also, a semi-transparent white ink composed of an inorganic oxide pigment, a dispersant and / or a polymer compound, a water-soluble organic solvent, and water is fixed to a recording material in advance, and an image is recorded with the water-soluble dye ink. Methods are disclosed (eg,
See Patent Document 8. ). Even in this configuration, since the coloring material itself does not have the function of improving the abrasion resistance, it is necessary to add a large amount of polymer particles to obtain sufficient abrasion resistance, and the problem has not been solved yet.

Further, after depositing a colorless or light-colored liquid containing two or more cationic groups per molecule on the recording medium, the liquid penetrates into the recording medium and exists in the medium, and There is disclosed an inkjet recording method in which an ink containing an anionic dye is attached to a portion where the liquid is attached to form an image immediately after the ink is removed from the surface (see, for example, Patent Document 9). Further, after depositing a colorless or light-colored liquid containing a polyvalent metal salt on the recording medium, the liquid penetrates into the recording medium and is present in the medium,
In addition, an inkjet recording method is disclosed in which an ink containing a dye having an acidic group is adhered to a portion where the liquid is adhered to form an image immediately after the ink has disappeared from the surface of the medium (see, for example, Patent Document 10). ). A colorless or quaternary ammonium salt or amine salt having on the recording medium one or more groups selected from the group consisting of alkyl groups, alkenyl groups and aryl groups having 4 or more carbon atoms in the molecule Immediately after the light-colored liquid has adhered and the liquid has penetrated into the recording medium, and the surface of the recording medium is apparently depleted, the ink containing the water-soluble dye having an acidic group is adhered to the adhered part of the liquid. An inkjet recording method is disclosed in which an image is formed by doing so (see, for example, Patent Document 11). However, in the methods described in these, since the treatment liquid containing no fine particles is used, the image density improvement, the character blurring reduction, and the color mixing reduction are insufficient. Further, since a dye other than the resin coating type is used as the coloring material, the abrasion resistance of the image forming portion is insufficient.

[0010]

[Patent Document 1] Japanese Unexamined Patent Publication No. 4-259590 (Claim 2, line 1, line 1 to line 7, claims [001]
0], [0015], [0022])

[Patent Document 2] Japanese Unexamined Patent Publication No. 6-92010 (Claim 1, [0010], page 2, column 1, line 2 to line 8)

[Patent Document 3] Japanese Patent Laid-Open No. 11-228890 (second
(Claim 1, Column 1, Line 1-Claim 27)

[Patent Document 4] Japanese Unexamined Patent Publication No. 2001-199149 (Page 2, Column 1, Line 13 to Claim 21 of Claim 2)

[Patent Document 5] Japanese Unexamined Patent Publication No. 2001-199150 (claim 1 on page 2, column 1, line 2 to line 9)

[Patent Document 6] Japanese Unexamined Patent Publication No. 2001-199151 (Claim 1 on page 2, column 1, line 2 to line 7)

[Patent Document 7] Special Table WO00 / 06390 (second
Claim 1) from the second line to the sixth line of the page

[Patent Document 8] Japanese Unexamined Patent Application Publication No. 2001-171095 (Claim 1 on page 2, column 1, line 2 to line 7)

[Patent Document 9] Japanese Patent No. 2667401 (claim 1 on page 1, column 1, line 2 to line 7)

[Patent Document 10] Japanese Patent No. 2675001 (Claim 1 on page 1, column 1, line 2 to line 7)

[Patent Document 11] Japanese Patent No. 2711098 (claim 1 on page 1, column 1, line 2 to line 9)

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain a printed matter excellent in abrasion resistance, which can obtain a high quality image free from feathering and color bleeding even when printed on plain paper. In addition, a high image density can be obtained without the recording liquid penetrating deep into the paper.
In addition, the image density when viewed from the side opposite to the image printed surface is low, double-sided printing can be performed well, and image stains due to poor drying of the recording liquid do not occur and the printed matter has an appropriate glossiness. To provide an ink set to be given, a recording method, a recording device, and a recorded matter using the ink set, and
Another object of the present invention is to improve the water resistance of an image obtained on a recording medium, without causing mold and the like to propagate in the treatment liquid and the recording liquid even during long-term storage, and an ink set excellent in stability over time. It is to provide a recording method, a recording device, and a recorded matter using this.

[0012]

As a result of intensive studies to achieve the above object, an ink set characterized by combining a treatment liquid containing fine particles with a recording liquid containing a resin-coated coloring material. The present invention has reached the present invention in which the above object can be effectively achieved.

The above-mentioned problems are (1) the combination of (1) a recording liquid containing a resin-coated coloring material and a processing liquid containing fine particles reactive with the resin-coated coloring material. And (2) "the ink set according to item (1), which produces an aggregate when the treatment liquid and the recording liquid come into contact with each other".

Further, the above-mentioned problem is (3) of the present invention, which is a treatment liquid used in the ink set described in the above (1), wherein the fine particles contained in the treatment liquid are cationic compounds. (4) "Treatment solution according to item (3), characterized in that the cationic compound is a cationic inorganic compound", (5) "Cationic inorganic The treatment liquid according to item (4), wherein the compound is a cationic silica ", (6)
"The treatment liquid according to any one of the items (3) to (5), wherein the treatment liquid contains water and a water-soluble solvent", (7) " The treatment liquid according to the above (6), which is a wetting agent and / or a penetrating agent ", (8)" The treatment liquid contains an antiseptic / antifungal agent, (3) The treatment liquid according to any one of (5) to (5), (9) "The treatment liquid contains a cationic surfactant, the above (3) to (3) The treatment liquid according to any one of item (5) ",
(10) “Recording liquid used in the ink set according to item (1), wherein the coloring material is a pigment”, (11) “Item (1) above” A recording liquid used in the ink set according to the above item, wherein the recording liquid contains a coloring material, water, and a water-soluble solvent ",
(12) "The recording liquid according to the item (11), wherein the water-soluble solvent is a wetting agent and / or a penetrating agent", and (13) "the recording liquid is an antiseptic / antifungal agent. It is achieved by the recording liquid described in the above item (11).

Further, the above-mentioned problem is (14) of the present invention, the ink set according to the above (1) or (2),
Alternatively, a combination of the treatment liquid according to any one of the items (3) to (9) and the recording liquid according to any one of the items (10) to (13) is used. An ink jet recording method for forming an image by forming an image on a recording material, comprising a step of attaching a treatment liquid to the recording material and a step of attaching the recording liquid to the recording material. Inkjet recording method ".

Further, the above-mentioned problems are (15) of the present invention, the ink set described in the above (1) or (2),
Alternatively, a combination of the treatment liquid according to any one of the items (3) to (9) and the recording liquid according to any one of the items (10) to (13) is used. An ink jet recording apparatus for forming an image by means of: a transporting section for transporting a recording material; an adhering section for adhering a treatment liquid to a recording material; and an adhering section for adhering a recording liquid to a recording material, And an ink jet recording apparatus characterized by forming an image on a recording material.

Further, the above-mentioned problems are (16) of the present invention, "the treatment liquid used in the ink set according to the above (1) or (2), or the above (3) to (9). (17) "The recording liquid used in the ink set according to the item (1) or (2), or the processing liquid cartridge containing the processing liquid according to any one of (1) to (7). This is achieved by a recording liquid cartridge containing the recording liquid according to any one of items 10) to (13).

Furthermore, the above-mentioned problem is (1) of the present invention.
8) The present invention can be achieved by "the inkjet recording material produced by using the inkjet recording device according to the item (15)".

Next, the present invention will be described in more detail. The mechanism of improving the image quality in the present invention is considered as follows. However, the present invention is not limited by the following description. When the treatment liquid containing the fine particles and the recording liquid containing the resin-coated coloring material are adhered to the recording material, a mixture of the fine particles and the resin-coated coloring material is deposited on the surface of the recording material, and the vehicle is Penetrates the recording material. At this time, since the resin-coated color material deposited on the recording material has a resin component itself, it is bound to the surrounding fine particles. Therefore, a mechanically strong film is formed and abrasion resistance is improved. Furthermore, the glossiness increases because a resin layer is formed on the surface. When neither the recording liquid nor the treatment liquid contains a resin component, the deposited layer composed of the fine particles and the coloring material becomes a mechanically very weak layer, and is easily removed when something contacts. As a result, the user's hands are stained with ink, and the back surface of the overlapped printed matter is stained with ink. In addition, recording liquid,
Alternatively, even if the treatment liquid contains polymer particles, if the coloring material itself does not have a resin component and does not have the function of improving the abrasion resistance, the surrounding area of the coloring material is increased to obtain sufficient abrasion resistance. To fill with polymer particles, it is necessary to add a large amount of polymer particles. A treatment liquid or a recording liquid to which a large amount of polymer particles are added will have lower ejection stability and storage stability, and will also have an increased viscosity. It is necessary to add a small amount of polymer particles in order to maintain ejection stability and storage stability, and to suppress the viscosity to an appropriate level, but in that case, sufficient abrasion resistance cannot be obtained and the problem cannot be solved. Absent. Further, when the reaction agent in the treatment liquid is a water-soluble resin instead of fine particles, the water-soluble resin forms an impermeable film on the recording material, which impedes the penetration of the vehicle. As a result, the drying property is deteriorated and the color bleeding is deteriorated.

To distinguish the resin-coated pigment from the polymer-dispersed pigment, a substance that selectively adsorbs to the resin is mixed with the recording liquid, and the coloring material component is analyzed with an analyzer such as a transmission electron microscope (TEM). It is better to use it to observe and judge the coating state. The resin-coated type is entirely covered with the resin, whereas the polymer-dispersed type has many parts not covered with the resin. Further, the resin-coated type and the polymer-dispersed type can be distinguished also from the weight ratio of the pigment and the resin (polymer). As a specific method, the pigment and the resin are deposited by changing the pH of the recording liquid, and an organic solvent is added to the deposited components to extract the resin. By this operation, the weight ratio of the pigment and the resin is obtained. In order for the resin to cover the surface of the pigment, the weight ratio of the resin / pigment may be 0.01 or more.

Further, when the recording liquid is dried and rubbed with a finger or a cloth, the resin-coated type is firmly fixed to the paper with the resin so that there is no color fading, whereas the polymer-dispersed type is used. Is not fixed firmly on the paper due to its low polymer content, so it can be distinguished from the fact that color fading occurs.

When the resin-coated coloring material of the present invention is used,
Since the coloring material itself has a resin component, a binding effect can be obtained with a very small amount of resin addition, and sufficient abrasion resistance can be obtained. Since the amount of resin added is small, there are no problems in terms of ejection stability, storage stability, and viscosity. The amount of resin added is preferably 0.01 wt% or more and less than 20 wt% with respect to the entire liquid, and 1 wt%
% Or more and less than 5 wt% is more preferable. 0.1 wt% or more and less than 200 wt% is preferable for the color material, and 10 w
It is more preferably t% or more and less than 50 wt%.

The recording liquid of the present invention contains a resin-coated coloring material. The resin may cover the entire surface of the coloring material or a part thereof. Further, the color material may be coated in the form of microcapsules, or the color material and the resin may be mixed.

As the coating resin, it is preferable to use a polymer having an affinity with the coloring material. Examples of resins include vinyl resins, polyester resins, polyurethane resins and the like. Among the resins, vinyl resins are preferred. Examples of vinyl resins include polymers of one or more monomers selected from the group consisting of styrene, (meth) acrylic acid and (meth) acrylic acid ester.

As the colorant used in the recording liquid of the present invention, either a dye or a pigment can be used, but when the fine particles are cationic, it is electrically neutralized by using an anionic dye or pigment. It is preferable in terms of image quality improvement because it is aggregated. It is also preferable to use a pigment rather than a dye. That is, when the pigment in the dispersed state is electrically neutralized as compared with the dye in the dissolved state, aggregation occurs more efficiently, so that the image quality can be improved.

The pigment used in the recording liquid used in the present invention is an organic pigment such as azo type, phthalocyanine type, anthraquinone type, quinacridone type, dioxazine type, indigo type, thioindigo type, perylene type, isoindrenone type, aniline black. , Azomethine-based, rhodamine B lake pigment, carbon black, etc., and inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark blue, cadmium red, chrome yellow, and metal powder. To be

Examples of the pigment dispersant having an anionic group include polyacrylic acid, polymethacrylic acid, styrene acrylic resin, styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic acid resin, β-naphthalene. Sulfonic acid formalin condensate,
Carboxymethyl cellulose, starch glycolic acid,
Examples thereof include sodium alginate, pectic acid and hyaluronic acid. These anionic dispersants are
The acid form can be used, but an alkali metal salt such as sodium or potassium can also be used.

Typical examples of the pigment having an anionic group on the surface thereof include carbon black having a carboxyl group or a sulfonic acid group. Other examples include those in which a phthalocyanine pigment or anthraquinone pigment is oxidized or treated with fuming sulfuric acid to introduce a carboxyl group or a sulfonic acid group into a part of the pigment particles.

As the water-soluble dye used in the present invention,
Dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes, and edible dyes in the color index, which have excellent water resistance and light resistance, are used. These dyes may be used as a mixture of a plurality of types, or may be used as a mixture with other dyes such as pigments as required. These colorants are added within a range that does not impair the effects of the present invention.

(A) Acid dyes and food dyes such as C.I. I. Acid Yellow 17,23,42,4
4,79,142 C.I. I. Acid Red 1,8,13,14,1
8, 26, 27, 35, 37, 42, 52, 82, 8
7, 89, 92, 97, 106, 111, 114, 11
5,134,186,249,254,289 C.I. I. Acid Blue 9,29,45,92,2
49 C.I. I. Acid Black 1,2,7,24,2
6,94 C.I. I. Food Yellow 3,4 C.I. I. Hood Red 7, 9, 14 C.I. I. Hood black 1,2

(B) C.I. I. Direct Yellow 1,12,24,2
6, 33, 44, 50, 86, 120, 132, 14
2,144 C.I. I. Direct Red 1,4,9,13,1
7, 20, 28, 31, 39, 80, 81, 83, 8
9,225,227 C.I. I. Direct Orange 26,29,62,1
02 C. I. Direct Blue 1,2,6,15,2
2,25,71,76,79,86,87,90,9
8, 163, 165, 199, 202 C.I. I. Direct Black 19,22,32,3
8, 51, 56, 71, 74, 75, 77, 154, 1
68,171

(C) C.I. I. Basic Yellow 1, 2, 11, 13,
14,15,19,21,23,24,25,28,2
9, 32, 36, 40, 41, 45, 49, 51, 5
3, 63, 64, 65, 67, 70, 73, 77, 8
7,91 C.I. I. Basic Red 2,12,13,14,
15, 18, 22, 23, 24, 27, 29, 35, 3
6,38,39,46,49,51,52,54,5
9,68,69,70,73,78,82,102,1
04, 109, 112 C.I. I. Basic Blue 1,3,5,7,9,2
1, 22, 26, 35, 41, 45, 47, 54, 6
2,65,66,67,69,75,77,78,8
9, 92, 93, 105, 117, 120, 122, 1
24, 129, 137, 141, 147, 155 C.I. I. Basic Black 2,8

(D) As a reactive dye, C.I. I. Reactive Black 3, 4, 7, 11,
12, 17 C.I. I. Reactive Yellow 1,5,11,1
3,14,20,21,22,25,40,47,5
1,55,65,67 C.I. I. Reactive Red 1,14,17,2
5,26,32,37,44,46,55,60,6
6,74,79,96,97 C.I. I. Reactive Blue 1,2,7,14,1
5,23,32,35,38,41,63,80,95
Etc. can be used.

The treatment liquid of the present invention contains fine particles. The fine particles may be an organic compound, an inorganic compound, or an organic-inorganic composite compound. The particle shape is also not particularly limited, and spherical, beaded,
It may be an irregular shape. As an organic compound,
Polystyrene, styrene-acrylic copolymer, polymethylmethacrylate, melamine resin, epoxy resin, silicone resin, benzoguanamine resin, polyamide resin, fluorine resin, α, β-unsaturated ethylenic monomer can be obtained by emulsion polymerization, etc. Examples thereof include polymers. The inorganic compounds are roughly classified into inorganic salts such as calcium carbonate and inorganic oxides such as silica (SiO ₂ ). Specific examples of the inorganic salt include calcium carbonate, calcium nitrate,
Calcium chloride, calcium sulfate, aluminum nitrate,
Examples thereof include aluminum chloride, aluminum sulfate, and iron sulfate, but are not limited thereto. When used as an aqueous treatment liquid, it is preferable to use one having a low solubility in water, such as calcium carbonate, calcium nitrate, or iron sulfate, because a dispersion can be easily obtained. Further, it is more preferable that these can be further subjected to a cationization treatment so as to further enhance the adsorbing ability and the aggregating ability of the coloring agent. A method of modifying with a cationic agent has been proposed in the prior art (Japanese Patent Laid-Open Nos. 10-129113 and 11-20301). Specific examples of the inorganic oxide include silica (S
Examples thereof include, but are not limited to, iO ₂ ), cationized silica, titanium dioxide, and alumina (Al ₂ O ₃ ).

The cationic fine particles of the present invention can be used if at least the particle surface is cationic. Examples of the cationic fine particles include cationic silica (cationic compound of silica (SiO ₂ )), alumina (Al
₂ O ₃ ), titanium dioxide, polymer particles having a cationic group introduced, and the like. In particular, when combined with an anionic coloring material, the adsorptive and cohesive action is good, and the image quality improving effect is high. Among the cationic fine particles, cationic silica is particularly preferable in terms of reactivity. The cationic silica can be used as long as the surface of silica is cationized. For cationization, a cationic compound may be introduced chemically or physically on the silica surface. For example, the surface treatment can be performed chemically by coupling an amino compound with the silanol group of silica or by reacting with an aluminum compound. Further, the surface treatment can be carried out physically by mixing silica and a cationic compound in a solvent, physically adsorbing the cationic compound, and then removing the solvent. At that time, as a specific example of the anionic silica used as the core material, S
T-ZL, ST-20, ST-30, ST-40, ST
-C, ST-N, ST-O, ST-S, ST-50, S
T-20L, ST-OL, ST-XS, ST-YL, S
T-XL, ST-UP, ST-OUP (above, Nissan Kagaku), Catalog SI-350, SI-500
(Above, made by DuPont), Nipgel AY-220,
AY-420, AY-460 (above, made by Nippon Silica) etc. are mentioned. Not limited to these methods, any one can be preferably used as long as the surface of silica is treated to be cationic.

Cationic fine particles can be obtained as a product, and as a cationized product of silica, ST-AK can be used.
(Manufactured by Nissan Chemical). As alumina, alumina sol 100, 200, 520 (all manufactured by Nissan Chemical)
Etc. Examples of titanium dioxide include the Titania series (made by Idemitsu Kosan). Some of these fine particles are already available as an aqueous dispersion.

The fine particles of the present invention may be cationic inorganic-organic composite fine particles, and any cationic inorganic-organic composite fine particles can be used.

The cationic inorganic-organic composite fine particles can be obtained by adsorbing a cationic organic compound on the surface of the inorganic fine particles or, conversely, adsorbing the cationic inorganic compound on the surface of the organic compound. For example, in the inorganic-organic composite fine particles coated with a cationic polymer, the inorganic fine particles are dispersed in a solvent such as water, and the cationic polymer is dispersed in water or a solution of a water-soluble organic solvent. It can be obtained by gradually adding. Specific examples of the cationic polymer include polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymer, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium, polyamidine. , Cationic amine compounds such as polyamine sulfone and cationic starch.

The amount of fine particles added is 0.01 to 50 of the processing liquid.
About wt% is preferable, and about 1 to 30 wt% is more preferable. When the content is 0.01 wt% or less, the image quality improving effect cannot be sufficiently obtained, and when the content is 50 wt% or more, the ejection stability cannot be sufficiently obtained. A plurality of cationic fine particles may be used in combination.

The average particle diameter of the fine particles is preferably 500 nm or less, more preferably 200 nm or less from the viewpoint of ejection stability. That is, when the thickness is 500 nm or more, clogging of the ejection head is likely to occur and ejection failure is likely to occur. The average particle diameter can be measured by an optical particle size distribution meter, and is represented by the particle diameter of 50% of particles.

The fine particles are dispersed in a vehicle containing water as a main component to form a treatment liquid. When dispersing, it is preferable to use a peptizing agent to stabilize the dispersion. The deflocculant is a substance that forms an electric double layer on the surface of the charged particles and electrostatically repels the electric double layer to prevent the particles from approaching each other and stabilize the dispersion. Since fine particles are positively charged from neutral to acidic, anion sources such as acetic acid, nitric acid, hydrochloric acid, formic acid, lactic acid, and their alkali metal salts, zirconium compounds such as zirconium oxychloride hydrate, and pyrophosphoric acid. Although sodium, sodium hexametaphosphate, taurine and the like are used as the peptizer, the present invention is not limited thereto.

The treatment liquid of the present invention can be produced by the following method. Fine particles, water and a peptizer are mixed to prepare a dispersion liquid. If necessary, add a water-soluble solvent and peptize with a peptizer. As the peptizer used at this time,
Examples thereof include a high-speed rotating high-shear type stirring peptizer, a dissolver, a colloid mill, a homogenizer, an ultrasonic peptizer, and the like. K. Auto homo mixer,
T. K. Homomic line flow, ultra homomixer, NNK colloid mill and the like can be mentioned. The number of rotations during peptization varies depending on the type and structure of the peptizer, but is 500
It is preferably from 1 to 10,000 rpm, and from 2000 to
More preferably, it is 8000 rpm. The temperature during peptization is preferably 5 to 100 ° C. The peptization time varies depending on the type and structure of the peptizer, but is preferably 0.01 to 48 hours.

In addition to the coloring material, a water-soluble organic solvent may be used for the purpose of making the treatment liquid and the recording liquid have desired physical properties or preventing clogging of the nozzle of the recording head due to drying. preferable. The water-soluble organic solvent includes a wetting agent and a penetrating agent. The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying.
Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propane. Diol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, glycerin, 1,2,6-
Hexanetriol, 2-ethyl-1,3-hexanediol, 1,2,4-butanetriol, 1,2,3-
Polyhydric alcohols such as butanetriol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Polyhydric alcohol alkyl ethers such as triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; Methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-
Pyrrolidone, 1,3-Dimethylimidazolidinone, ε-
Nitrogen-containing heterocyclic compounds such as caprolactam; formamide, N-methylformamide, formamide, N, N-
Amides such as dimethylformamide; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine and triethylamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, γ -Butyrolactone and the like. These solvents may be used alone or in combination with water.

The penetrant is added for the purpose of improving the wettability between the recording liquid and the treatment liquid or recording liquid and adjusting the permeation rate. As the penetrant, those represented by the following formulas (I) to (IV) are preferable. That is, a polyoxyethylene alkylphenyl ether type surfactant of the following formula (I), an acetylene glycol type surfactant of the formula (II), a polyoxyethylene alkyl ether type surfactant of the following formula (III) and a formula (IV Since the polyoxyethylene polyoxypropylene alkyl ether-based surfactant (1) can reduce the surface tension of the liquid, it can improve the wettability and the permeation rate.

[0045]

[Chemical 1] (R is a hydrocarbon chain having 6 to 14 carbon atoms which may be branched, k: 5 to 20)

[0046]

[Chemical 2] (M and n are 0-40)

[0047]

[Chemical 3] (R is a hydrocarbon chain having 6 to 14 carbon atoms which may be branched)

[0048]

[Chemical 4] (R is a hydrocarbon chain having 6 to 14 carbon atoms, m and n are numbers of 20 or less)

Other than the compounds of the above formulas (I) to (IV),
For example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl ether, and other polyhydric alcohol alkyl and aryl ethers, poly Nonionic surfactants such as oxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, lower alcohols such as ethanol and 2-propanol can be used, and diethylene glycol monobutyl ether is particularly preferable.

The treatment liquid of the present invention may contain a cationic surfactant such as a quaternary ammonium salt, a pyridinium salt or an imidazoline type compound. In particular,
Examples thereof include lauryl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl tributyl ammonium chloride, benzalkonium chloride, cetyl pyridinium chloride, 2-heptadecenyl hydroxyethyl imidazoline. The cationic surfactant has the effect of lowering the surface tension to improve the wettability with the recording material to form a fine particle layer promptly and to agglomerate the anionic coloring material, and is effective in improving the image quality.

The treatment liquid and the recording liquid of the present invention may contain an antiseptic / antifungal agent. By containing an antiseptic / antifungal agent, the growth of bacteria can be suppressed, and storage stability and image quality stability can be improved. As antiseptic and antifungal agents, sodium dehydroacetate, sodium sorbate,
2-Pyridinethiol-1-oxide sodium, isothiazoline compounds, sodium benzoate, sodium pentachlorophenol, etc. can be used.

The treatment liquid and the recording liquid of the present invention may contain a rust preventive agent. By containing the rust preventive agent, metal corrosion of the liquid contact surface such as the head can be prevented.
As the rust preventive, for example, acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like can be used.

As the pH adjuster, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid and acetic acid can be used.

The ink jet recording method of the present invention and the ink jet recording apparatus for carrying out the method will be described with reference to the drawings. The inkjet recording apparatus shown in FIG.
The processing liquid and the recording liquid are stored in the cartridge (20),
The treatment liquid and the recording liquid are supplied from the cartridge to the recording head. Here, the cartridge (20) is for processing liquid,
The recording liquid for each color is attached in a separated state.

The recording head is mounted on the carriage (18) and is guided by the timing belt (23) driven by the main scanning motor (24) to guide shafts (21), (2).
It is guided by 2) and moves. On the other hand, the recording material is placed by the platen at a position facing the recording head.

An enlarged view of the nozzle surface of the recording head is shown in FIG. A nozzle (31) for ejecting the treatment liquid is provided in the vertical direction, and the nozzles (32), (33), (34), (35) are provided.
A yellow recording liquid, a magenta recording liquid, a cyan recording liquid, and a black recording liquid are ejected from each of them.

Further, as shown in FIG. 3, in the recording head, it is possible to arrange all nozzles in the lateral direction. In the figure, reference numerals (36) and (41) are treatment liquid discharge nozzles, and nozzles (37), (38),
A yellow recording liquid, a magenta recording liquid, a cyan recording liquid, and a black recording liquid are ejected from (39) and (40), respectively. In the recording head of such an aspect,
Since the processing liquid discharge nozzles are provided at the left and right ends,
Printing can be performed on both the forward and backward paths in which the recording head reciprocates on the carriage. That is, it is possible to deposit the treatment liquid first and then deposit the color recording liquid on the forward pass and the return pass, or vice versa. Does not happen.

In the ink jet recording apparatus of the present invention, the treatment liquid and the recording liquid can be replenished by replacing the cartridge. Further, this cartridge may be integrated with the recording head.

4 and 5 show a cartridge capable of containing the processing liquid of the present invention and the recording liquid. The cartridge shown in FIGS. 4 and 5 can store either the processing liquid or the recording liquid.

It is most preferable that the recording liquid and the treatment liquid are discharged and overlapped by the print heads so that the recording liquid and the treatment liquid are overlapped at the same position. However, the application of the present invention is not limited to this range. For example, the treatment liquid is thinned and applied, and the recording liquid is superposed on the treatment liquid expanded by bleeding or the like, or the treatment liquid is applied only to the contour portion of the image,
The case of overlapping a part of the recording liquid is also included in the scope of the present invention.

[0061]

EXAMPLES The present invention will be described in detail below with reference to examples. <Method of Manufacturing Recording Liquid> The following recording liquid components were mixed and filtered with a 0.8 μm polytetrafluoroethylene-based fluororesin filter to manufacture each recording liquid. (1) Black recording liquid 1 Resin-coated black pigment 10.0 parts by weight (out of 10.0 parts by weight, resin part is 3.0 parts by weight) 1,3-butanediol 22.5 parts by weight Glycerin 7.5 Parts by weight Surfactant (I) 1.0 parts by weight 2-Pyrrolidone 2.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (2) Black recording liquid 2 Cabjet 300 (manufactured by Cabot, self-dispersion pigment) 10.0 parts by weight 1,3-butanediol 22.5 parts by weight glycerin 7.5 parts by weight Surfactant (I) 1.0 part by weight 2-pyrrolidone 2.0 parts by weight Part Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (3) Black recording liquid 3 CAVOJET 300 (Cabot, self-dispersion pigment) 10.0 Parts acrylic resin emulsion (manufactured by Avicia) 5.0 parts by weight 1,3-butanediol 22.5 parts by weight glycerin 7.5 parts by weight Surfactant (I) 1.0 parts by weight 2-pyrrolidone 2.0 Parts by weight sodium dehydroacetate 0.2 parts by weight sodium thiosulfate 0.2 parts by weight ion-exchanged water residual amount (4) black recording liquid 4 C.I. I. Food Black 2 3.0 parts by weight Glycerin 10.0 parts by weight Ethylene glycol 15.0 parts by weight Diethylene glycol 24.0 parts by weight Diethylene glycol monobutyl ether 4.0 parts by weight Sodium dehydroacetate 0.3 parts by weight Deionized water residual amount (5 ) Black recording liquid 5 C.I. I. Food Black 2 3.0 parts by weight Glycerin 5.0 parts by weight Ethylene glycol 5.0 parts by weight Diethylene glycol 15.0 parts by weight N-methyl-2-pyrrolidone 2.0 parts by weight Diethylene glycol monobutyl ether 3.0 parts by weight Sodium dehydroacetate 0.3 parts by weight Ion-exchanged water Remaining amount (6) Black recording liquid 6 Direct black 195 2.5 parts by weight 2-Pyrrolidone 10.0 parts by weight Glycerin 5.0 parts by weight Isopropyl alcohol 4.0 parts by weight NaOH 0.4 Part by weight Ion-exchanged water Remaining amount (7) Yellow recording liquid 1 Resin-coated yellow pigment 10.0 parts by weight (out of 10.0 parts by weight, resin part is 3.0 parts by weight) 1,3-butanediol 22. 5 parts by weight Glycerin 7.5 parts by weight Surfactant (I) 1.0 parts by weight 2-pyrrolidone 2.0 parts by weight Sodium dehydroacetate 0.2 parts Sodium thiosulfate 0.2 parts Ion-exchanged water Balance (8) Yellow recording liquid 2 C. I. Pigment Yellow 17 10.0 parts by weight 1,3-butanediol 22.5 parts by weight Glycerin 7.5 parts by weight Surfactant (I) 1.0 part by weight 2-pyrrolidone 2.0 parts by weight Sodium dehydroacetate 0.2 Parts by weight sodium thiosulfate 0.2 parts by weight ion-exchanged water residual amount (9) yellow recording liquid 3 C.I. I. Pigment Yellow 17 10.0 parts by weight Acrylic resin emulsion (manufactured by Avicia) 5.0 parts by weight 11,3-butanediol 22.5 parts by weight Glycerin 7.5 parts by weight Surfactant (I) 1.0 part by weight 2-Pyrrolidone 2.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (10) Yellow recording liquid 4 C.I. I. Acid Yellow 23 3.0 parts by weight Glycerin 10.0 parts by weight Ethylene glycol 15.0 parts by weight Diethylene glycol 24.0 parts by weight Diethylene glycol monobutyl ether 4.0 parts by weight Sodium dehydroacetate 0.3 parts by weight Deionized water residual amount (11 ) Yellow recording liquid 5 C.I. I. Acid Yellow 23 3.0 parts by weight Glycerin 5.0 parts by weight Ethylene glycol 5.0 parts by weight Diethylene glycol 15.0 parts by weight N-methyl-2-pyrrolidone 2.0 parts by weight Diethylene glycol monobutyl ether 3.0 parts by weight Sodium dehydroacetate 0.3 parts by weight Ion-exchanged water Remaining amount (12) Yellow recording liquid 6 ProjetFastYellow2 2.0 parts by weight Direct yellow 86 1.0 parts by weight β-thiodiglycol 8.0 parts by weight Ethylene glycol 8.0 parts by weight Acetinol EH (Kawaken Chemicals Co., Ltd.) 0.2 parts by weight Isopropyl alcohol 4.0 parts by weight Deionized water remaining amount

<Processing liquid preparation method> The following processing liquid components were mixed and filtered through a 0.8 μm polytetrafluoroethylene-based fluororesin filter to manufacture each processing liquid. (1) Treatment liquid 1 Polyallylamine-coated silica 15.0 parts by weight Glycerin 10.0 parts by weight Surfactant (I) 1.0 part by weight 2-Ethyl-1,3-hexanediol 2.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (2) Treatment liquid 2 Alumina (manufactured by Nissan Kagaku, alumina sol 520) 15.0 parts by weight (solid content) Glycerin 10.0 parts by weight Interface Activator (I) 1.0 part by weight 2-ethyl-1,3-hexanediol 2.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (3) treatment Liquid 3 Cationic silica (Nissan Chemical Co., Ltd., ST-AK) 15.0 parts by weight (solid content) Glycerin 10.0 parts by weight Surfactant (I) 1.0 parts by weight 2-ethyl- , 3-hexanediol 2.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Ion-exchanged water Remaining amount (4) Treatment liquid 4 Cationic silica (Nissan Chemical Co., Ltd., ST-AK) 15.0 parts by weight (solid content) Glycerin 10.0 parts by weight Surfactant (I) 1.0 part by weight 2-Ethyl-1,3-hexanediol 2.0 parts by weight Cation G50 (Sanyo Chemical Co., Ltd. cation system Surfactant) 4.0 parts by weight Sodium dehydroacetate 0.2 parts by weight Sodium thiosulfate 0.2 parts by weight Deionized water residual amount (5) Treatment liquid 5 Polyallylamine 5.0 parts by weight Glycerin 10.0 parts by weight Ethylene Glycol 11.0 parts by weight Diethylene glycol 20.0 parts by weight Diethylene glycol monobutyl ether 12.0 parts by weight Dehydroacetic acid sodium salt 0.1 part by weight Ion-exchanged water Balance (6) the treatment liquid _{6 Al (NO 3) 3 ·} 9H 2 O 5.0 parts by weight Glycerin 10.0 parts by weight of ethylene glycol 11.0 parts by weight diethylene glycol 20.0 parts by weight Diethylene glycol monobutyl ether 12.0 parts by weight Sodium dehydroacetate 0.1 parts by weight Ion-exchanged water Remaining amount (7) Treatment liquid 7 Quaternary ammonium compound (Cation G50, manufactured by Sanyo Kasei Co., Ltd.) 5.0 parts by weight Glycerin 10.0 parts by weight Part Diethylene glycol 20.0 parts by weight Ion-exchanged water Remaining amount (8) Treatment liquid 8 Cationic silica (Nissan Chemical Co., Ltd., ST-AK) 15.0 parts by weight Glycerin 7.5 parts by weight Diethylene glycol 7.5 parts by weight Nitric acid 0 .6 parts by weight deionized water remaining amount

<Image quality evaluation> The image quality of printed matter was evaluated as follows. (1) The image quality was evaluated by observing the feathered black character portion and comparing it with the rank sample. Rank 5 ... No bleeding at all Rank 4 ... Slight bleeding out Rank 3 ... There is bleeding out, but there is no problem in practical use Rank 2 ... Extensive bleeding out Rank 1 ... Extensive bleeding (2) Color bleed The image quality was evaluated by observing the boundary between black solid and yellow solid and comparing it with a rank sample. Rank 5: No color mixture Rank 4 ... Slight color mixture Rank 3 ... There is color mixture, but there is no problem in practical use Rank 2 ... Large amount of color mixture Rank 1 ... Large amount of color mixture (3) 1 hour of abrasion-resistant printing After that, the solid black portion was rubbed with a finger, and the presence or absence of ink transfer to the finger was observed. (4) Image density and strike-through density The optical density from the front surface and the optical density from the back surface of the solid black portion were measured to determine the image density and the strike-through density. (5) Dryability Immediately after printing, plain paper (My Paper, manufactured by NBS Ricoh) was pressed against the printed matter to observe the ink transfer of the black solid portion to the plain paper. (6) The waterproof printed matter was immersed in ion-exchanged water for 1 minute and then taken out, and the attached water was absorbed by a paper towel and naturally dried. The black solid image densities before and after the immersion were measured, and the change rate was determined and used as the fading rate. (7) Ejection stability The printed matter was observed, and the presence or absence of ejection failure was confirmed based on the presence or absence of image defects. (8) Glossiness The 60-degree glossiness of printed matter is measured by a glossiness meter (BYK Gardner, 450
1) was used.

Example 1 The ink jet recording apparatus shown in FIG. 1 was prepared by filling the treatment liquid cartridge with the treatment liquid 1, the yellow recording liquid cartridge with the yellow recording liquid 1, and the black recording liquid cartridge with the black recording liquid 1. It was attached to the and the printing evaluation experiment was performed. A printing test was performed using My Paper (plain paper, manufactured by NBS Ricoh) as a recording material. The printing was performed in the order in which the treatment liquid first adhered to the paper, and the recording liquid of each color adhered from the top. The printed matter printed was evaluated for feathering, color bleed, abrasion resistance, image density, strike-through density, drying property, and water resistance. The results are shown in Table 2.

(Examples 2 to 5) In Example 1, except that the treating liquid 1, the black recording liquid 1, and the yellow recording liquid 1 were used, respectively, the recording liquid and the treating liquid shown in Table 1 were used. The printing tests of Examples 2 to 5 were performed in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Examples 1 to 6) In Example 1, except that the treating liquid 1, the black recording liquid 1, and the yellow recording liquid 1 were used, respectively, the recording liquid and the treating liquid shown in Table 1 were used. The printing tests of Comparative Examples 1 to 6 were performed in the same manner as in Example 1. The results are shown in Table 2.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

As is clear from the detailed and specific description above, by using the recording liquid containing the resin-coated coloring material according to claim 1 of the present invention, a printed matter having good abrasion resistance can be obtained. To be Further, according to the second aspect of the present invention, feathering and color bleeding can be suppressed because the treatment liquid and the recording liquid generate aggregates. Further, according to claim 3 of the present invention, by using the cationic fine particles and the anionic coloring material, aggregation can be effectively generated, and feathering and color bleeding can be further suppressed. Further, according to claim 4 of the present invention, by using the cationic inorganic fine particles, aggregation can be more effectively generated, and feathering and color bleeding can be further suppressed. Further, according to claim 5 of the present invention,
By using the cationic silica, aggregation can be generated more effectively, and feathering and color bleeding can be further suppressed. Further, according to claim 6 of the present invention, the treatment liquid contains water and a water-soluble solvent,
It becomes less flammable and less irritating to the skin, increasing safety. Further, according to claim 7 of the present invention, the treatment liquid contains a wetting agent, whereby clogging of the head can be prevented,
By containing the penetrant, the liquid easily penetrates into the paper and the drying property can be improved. Further, claim 8 of the present invention
As a result, the treatment liquid contains an antiseptic / antifungal agent, whereby long-term storage stability is enhanced. Further, according to claim 9 of the present invention, the treatment liquid contains a cationic surfactant, whereby the cohesiveness is improved and feathering and color bleeding can be further suppressed. According to the tenth aspect of the present invention, by using a pigment as the coloring material in the recording liquid, the cohesiveness is improved, and feathering and color bleeding can be suppressed.
Further, according to claim 11 of the present invention, since the recording liquid contains water and a water-soluble solvent, the flammability is lowered and the skin irritation is lowered, so that the safety is enhanced. Further, according to claim 12 of the present invention, the recording liquid contains a wetting agent to prevent clogging of the head, and the inclusion of the penetrating agent allows the liquid to easily penetrate the paper to improve the drying property. it can. According to the thirteenth aspect of the present invention, the recording liquid contains an antiseptic / antifungal agent, whereby the long-term storage stability is enhanced.

[Brief description of drawings]

FIG. 1 is a diagram of an inkjet recording apparatus according to the present invention.

FIG. 2 is an example of a recording head according to the present invention.

FIG. 3 is another example of the recording head according to the present invention.

FIG. 4 is an external perspective view of a cartridge before being loaded in the recording apparatus according to the present invention.

FIG. 5 is a front sectional view of a cartridge according to the present invention.

[Explanation of symbols]

1 recording head 2 Main body case 7 Processing liquid and recording liquid common cartridge 16 gear mechanism 17 Sub-scanning motor 18 carriage 20 Recording liquid cartridge 21 Guide shaft 22 Guide shaft 23 Timing belt 24 main scanning motor 25 main scanning motor 26 Main scanning motor 27 Main scanning motor 31 Nozzle from which processing liquid is discharged 32 Nozzle for ejecting recording liquid 33 Nozzle that ejects recording liquid 34 Nozzle for discharging recording liquid 35 Nozzle for discharging recording liquid 36 Nozzle for discharging processing liquid 37 Nozzle for discharging recording liquid 38 Nozzle for discharging recording liquid 39 Nozzle for discharging recording liquid 40 Nozzle that ejects recording liquid 41 cartridge housing 42 liquid absorber 43 cases 44 Upper lid member 45 liquid supply port 46 seal ring 47 Air opening port 48 grooves 50 Cap member 51 Liquid leakage prevention protrusion 53 Cap member 55 Seal member 71 Cartridge positioning part 81 Cartridge attachment / detachment 81a Cartridge detachable finger hook 82 Indentation for attaching / detaching cartridge A space

Continued front page    F term (reference) 2C056 EA05 FA11 FC02 HA42                 2H086 BA02 BA05 BA55 BA59                 4J039 BA21 BE01 BE12 BE15 BE19                       BE22 BE33 CA06 EA33 EA36                       EA38 EA42 EA47 GA24

Claims (18)

[Claims] 1. An ink set comprising a combination of a recording liquid containing a resin-coated coloring material and a treatment liquid containing fine particles having reactivity with the resin-coated coloring material. 2. The ink set according to claim 1, wherein an aggregate is generated when the treatment liquid and the recording liquid come into contact with each other. 3. A treatment liquid used in the ink set according to claim 1, wherein the fine particles contained in the treatment liquid are cationic compounds. 4. The treatment liquid according to claim 3, wherein the cationic compound is a cationic inorganic compound. 5. The treatment liquid according to claim 4, wherein the cationic inorganic compound is cationic silica. 6. The treatment liquid according to claim 3, wherein the treatment liquid contains water and a water-soluble solvent. 7. The treatment liquid according to claim 6, wherein the water-soluble solvent is a wetting agent and / or a penetrating agent. 8. The treatment liquid according to claim 3, wherein the treatment liquid contains an antiseptic / antifungal agent. 9. The treatment liquid according to claim 3, wherein the treatment liquid contains a cationic surfactant. 10. A recording liquid for use in the ink set according to claim 1, wherein the coloring material is a pigment. 11. A recording liquid used in the ink set according to claim 1, wherein the recording liquid contains a coloring material, water, and a water-soluble solvent. 12. The recording liquid according to claim 11, wherein the water-soluble solvent is a wetting agent and / or a penetrating agent. 13. The recording liquid according to claim 11, wherein the recording liquid contains an antiseptic / antifungal agent. 14. An ink set according to claim 1 or 2, or a combination of the treatment liquid according to any one of claims 3 to 9 and the recording liquid according to any one of claims 10 to 13. An ink jet recording method for forming an image using a method, comprising a step of attaching a treatment liquid to a recording material,
And a step of adhering a recording liquid to a recording material, wherein an image is formed on the recording material. 15. The ink set according to claim 1 or 2, or a combination of the treatment liquid according to any one of claims 3 to 9 and the recording liquid according to any one of claims 10 to 13. An ink jet recording apparatus for forming an image by using a recording medium, comprising: a conveyance section for conveying a recording material, an adhesion section for adhering a treatment liquid to a recording material, and an adhesion section for adhering the recording liquid to the recording material. An ink jet recording apparatus, which forms an image on a recording material. 16. A treatment liquid cartridge containing the treatment liquid used in the ink set according to claim 1 or 2, or the treatment liquid according to any one of claims 3 to 9. 17. A recording liquid cartridge containing the recording liquid used in the ink set according to claim 1 or 2, or the recording liquid according to any one of claims 10 to 13. 18. An inkjet recorded matter produced by using the inkjet recording apparatus according to claim 15.