JP2002362018A - Imaged forming method, liquid composition, powder composition, recording liquid and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method, with which a high quality image having a high image density can be recorded at high speed with neither feathering nor color boundary bleeding on a generally used plain paper. SOLUTION: This image forming method at least consists of a first process, in which a difference between the adhesive power of a sticking part and that of a non-sticking part is developed through the selective sticking of a liquid composition to at least the image forming part of a material to be recorded, a second process, in which a powder composition is stuck to a selectively stuck liquid composition, and a third process, in which a recording liquid is stuck to the stuck powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selectively depositing a liquid composition on at least an image forming portion of a recording material to cause a difference in the adhesive strength between a deposited portion and a non-deposited portion. Attach the powder composition to the attached liquid composition,
The present invention relates to a novel image forming method for improving the quality of printed matter by attaching a recording liquid to the attached powder. The present invention also relates to a liquid composition, a powder composition, and a recording liquid used in the image forming method.

[0002]

2. Description of the Related Art A recording method for recording an image by using a recording liquid containing a coloring material as liquid droplets, such as an ink jet recording method, has been proposed.
It is excellent in that the printing mechanism is simple and no noise is generated. On the other hand, this image recording method has a problem in print quality that the image quality greatly changes due to the difference in the paper quality of the recording medium. In addition, when performing high-speed recording, because the absorption of the recording liquid into the recording medium is not in time,
In particular, in color printing, or when bleeding occurs at the color boundary, or when the recording medium after printing is ejected from the recording device,
Since the undried image is rubbed inside the apparatus, there is a problem that the recorded image is disturbed.

As a method for solving these problems, a method using recording liquid fixing particles has been proposed. JP 5
Japanese Patent Application Publication No. -96720 discloses an image forming apparatus and an image forming method in which water-absorbing resin particles are applied over the entire surface of a recording material and then printed to reduce bleeding and insufficient fixing during color printing. Japanese Patent Application Laid-Open No. 8-58225 discloses an image forming method and an image forming method in which bleeding and insufficient fixing during color printing are reduced by applying cationic resin particles over the entire surface of a recording material and then performing printing. Have been. However, these apparatuses and methods heat-fix the coated resin particles, so that the resin component also remains in the non-image area. Inconveniences such as curl and poor writing performance occur. In addition, since resin particles are coated on the entire surface, consumption of consumables is increased and printing cost is increased as compared with a method in which resin is not coated on non-image portions. Further, there is a problem that curl is caused by the internal stress of the resin component.

As a method for solving the above problem, Japanese Patent Laid-Open No.
Japanese Patent Application Publication No. 1-188963 discloses a recording method and apparatus in which water-absorbent resin particles are applied to the entire surface of a recording material, printed, and then the water-absorbent resin particles in a non-image portion are removed.
However, in order to remove the water-absorbing resin particles, it is necessary to attach them to a rubber roller or an adhesive roller, or to suck them using a suction means. And there is a defect in each case, when using a roller, if the amount of resin particles attached exceeds the allowable amount of the roller, it is necessary to replace the rubber roller or the adhesive roller, and the user must purchase a new member
Force exchange. On the other hand, when a suction means is used, the apparatus becomes large in structure and expensive.
Further, there is also a problem that the rubbing property is insufficient because there is no fixing means.

As a method of supplying the recording liquid fixing particles only to the image portion of the recording material, Japanese Unexamined Patent Publication No. Hei 6-92010 discloses printing after jetting fine particles and a binder polymer to an image forming portion of the recording material. Thus, an ink jet recording method for improving the printing quality on plain paper has been disclosed. However, in this method, since the recording liquid fixing particles are supplied as a solution, the recording liquid fixing particles are already wet with the solvent. In this state, the colorant in the recording liquid is hardly adsorbed to the recording liquid fixing particles when printing is performed, so that bleeding is likely to occur, and the effect of preventing bleeding is insufficient. Further, since the amount of the liquid adhering to the paper, that is, the total amount of the recording liquid fixing particle dispersion liquid and the recording liquid is large, drying is slow. Therefore, the drying and fixing properties of the recording liquid are insufficient. As described above, various proposals have been made, but no sufficient solution has been proposed yet.

[0006]

The present invention relates to the following 1 to 7:
With the goal. 1. Provided is an image forming method capable of recording an image with high image density and quality at high speed on a commonly used plain paper without feathering or color boundary bleeding. 2. Provided is an image forming method that does not cause image stains due to poor drying of a recording liquid and image stains due to insufficient abrasion of an image forming section even when printing is performed on plain paper. 3. Provided is an image forming method which does not cause uncomfortable feeling in a non-image portion and has good writability. 4. Provided is an inexpensive maintenance-free image forming method with a simple configuration. 5. An object of the present invention is to provide an image forming method suitable for double-sided printing, in which even when printing on plain paper, the recording liquid does not penetrate deep into the paper, and the image density when viewed from the opposite side to the image printing surface is low. 6. Even when printing on plain paper, it is possible to prevent deformation of the paper such as cockling and curl caused by the absorption of the recording liquid by the paper, improve the reliability of transport of the recording medium in the print recording device, and obtain Provided is an image forming method capable of facilitating the handling of a print recording medium. 7. Provided is an image forming method capable of improving the water resistance of an image obtained on a final recording medium.

[0007]

As a result of diligent studies, the present inventors have found that the above problems can be solved by the following inventions 1) to 15) (hereinafter referred to as inventions 1 to 15). 1) a step (first step) of causing a difference in the adhesive strength between an adhered portion and a non-adhered portion by selectively adhering a liquid composition to at least an image forming portion of a recording material; An image forming method comprising the steps of: adhering a powder composition to the liquid composition obtained (second step); and adhering a recording liquid to the adhering powder (third step). 2) The image forming method according to 1), further comprising a step (fourth step) of heating and melting the powder composition to which the recording liquid has adhered, following the first to third steps. 3) The image forming method according to 1) or 2), wherein the attaching unit in the first step is ejection by an inkjet head. 4) The image forming method according to any one of 1) to 3), wherein the adhesion unit in the second step is coating with a roller. 5) The image forming method according to any one of 1) to 4), wherein the attaching unit in the third step is ejection by an inkjet head. 6) characterized by containing at least a resin 1)
A liquid composition for a first step in the image forming method according to any one of claims 1 to 5. 7) The liquid composition according to 6), wherein the resin is contained in an emulsion state. 8) The powder composition for a second step in the image forming method according to any one of 1) to 5), which comprises at least a water-absorbing polymer. 9) The powder composition according to 8), wherein the water-absorbing polymer is at least one selected from the group consisting of polyacrylic acid, sodium polyacrylate, poly-N-vinylacetamide, and polyacrylamide. . 10) The powder composition for a second step in the image forming method according to any one of 1) to 5), which comprises at least a compound that adsorbs a coloring agent contained in a recording liquid. 11) The powder composition according to 10), wherein the compound that adsorbs the coloring agent contained in the recording liquid is a cationic compound. 12) The recording liquid for the third step in the image forming method according to any one of 1) to 5), wherein the recording liquid contains at least a coloring agent having adsorptivity to the powder composition. 13) The recording liquid according to 12), wherein the colorant is an anionic dye or an anionic pigment. 14) The recording liquid for the third step in the image forming method according to any one of 1) to 5), which comprises at least a component that dissolves or swells the powder composition. 15) A printed matter produced by using the image forming method according to any one of 1) to 5).

Hereinafter, the present invention will be described in detail. The image forming method of the present invention 1 includes at least the following first to
It comprises a third step. First: the step of selectively attaching the liquid composition to the image forming portion of the recording material. Second: the step of attaching the powder composition to the selectively attached liquid composition. Third: the attached powder. Step of Attaching Recording Liquid to Composition The image forming method of the second aspect of the present invention includes the following fourth step following the first to third steps. Fourth: Step of heating and melting the powder composition to which the recording liquid has adhered

The operation of each of the above steps will be described. In the first step, the liquid composition of the present invention is selectively attached to an image forming portion of a recording material. By causing the liquid composition to adhere to the recording material, a difference in adhesive strength is caused between the portion having the liquid composition and the portion having no liquid composition due to the viscosity of the liquid composition. The difference in the adhesive strength allows the powder composition described later to be selectively adhered only to the image forming portion. In the second step, the powder composition of the present invention is supplied to the liquid composition selectively adhered to the recording material in the first step. "Adhesion between liquid composition and powder composition">"Adhesion between powder composition and coating roller">"Adhesion between powder composition and recording material" holds In this case, the powder composition can be selectively adhered only to a portion where the liquid composition exists, that is, only to a portion where an image is formed in a subsequent step. As a result, a thin layer of the powder composition is selectively formed only on the image forming portion on the recording material. By selectively adhering the powder composition only to the image forming portion, the powder composition does not remain in the non-image portion unlike the prior art.
Accordingly, a printed matter having good writing characteristics without a sense of incongruity in the touch of the non-image portion can be obtained. Further, since the powder composition adheres only to the image forming portion, deformation of the recording material such as curl can be minimized. Further, since a step of removing the powder composition in the non-image area (suction, adsorption, etc.) is not required, an image forming method having a simple configuration can be provided.

In the third step, the recording liquid is supplied to the thin layer of the powder composition formed in the second step. At this time, if the powder composition contains a water-absorbing polymer, the recording liquid is absorbed by the powder composition and the viscosity of the recording liquid instantaneously increases,
If the powder composition contains a compound that adsorbs the coloring agent, a phenomenon occurs in which the coloring agent in the recording liquid is instantaneously adsorbed to the powder composition. Since these phenomena occur instantaneously, no unfixed colorant remains, and high-speed drying property is obtained. In addition, since the fluidity of the colorant is instantaneously lost, the occurrence of bleeding and color bleeding can be suppressed. Accordingly, printed matter free from image disturbance due to poor drying of the recording liquid and free from bleeding and color bleed can be obtained at high speed. Further, since the coloring agent is absorbed or adsorbed by the surface layer powder composition, the coloring agent remains on the surface layer of the recording material. For this reason, a printed matter having a much higher image density can be obtained as compared with the case where the colorant penetrates into the recording material. Further, since the recording liquid does not penetrate into the recording material, strikethrough of the recording liquid is effectively suppressed. Therefore, it is possible to obtain a high-quality double-sided printed matter in which the recording liquid does not show through. Further, since the recording material fibers are not excessively wet with the recording liquid, the waving (cockling) of the recording material is effectively suppressed. Therefore, it is possible to obtain a high quality printed matter with less cockling. As a fourth step, a step of heating and melting the powder composition to which the recording liquid has adhered can be added. For example, if the powder composition to which the recording liquid has been adhered is melted and fixed to the recording material by heat and pressure using a heat roller or the like, a printed matter having excellent fixability can be obtained.

At least a resin can be added to the liquid composition of the present invention. By containing the resin, the viscosity after adhering to the recording material is increased, and the difference in adhesive strength between the image forming portion and the non-image portion can be increased. Examples of the resin that can be added to the liquid composition include, in a natural system, gum arabic, gum guaran, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, vegetable polymers such as quince seed starch, alginic acid,
Carrageenan, algae-based macromolecules such as agar, gelatin, casein, albumin, animal macromolecules such as collagen, xanthene gum, microbial macromolecules such as dextran, or shellac, etc., in a semi-synthetic system, methylcellulose, ethylcellulose, hydroxy Pure synthesis of fibrous polymers such as ethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, starch polymers such as sodium starch glycolate and sodium starch phosphate, and seaweed polymers such as sodium alginate and propylene glycol alginate. In the system, polyvinyl alcohol, polyvinyl pyrrolidone, vinyl polymers such as polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid and alkali metal salts thereof,
Acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleate resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleate resin,
and alkali metal salts of β-naphthalenesulfonic acid formalin condensate.

It is preferable to add a resin emulsion to the liquid composition of the present invention from the viewpoint of the viscosity of the liquid. This is because the viscosity of the liquid composition needs to be such that it can be ejected from the ink jet head when it is applied to the recording material by the ink jet head. Also, as compared with the case where the resin is dissolved, the separation of the resin and the solvent easily occurs after the liquid composition adheres to the recording material, so that only the resin component remains on the surface of the recording material, and the adhesive strength is increased. Surface layer having a high surface roughness can be formed, which is a more preferable state for the selective adhesion of the powder composition. As the resin emulsion of the present invention, emulsification with a surfactant,
It is preferable to use a dispersed resin, and it is also preferable to use a capsule-type resin emulsion whose outer shell is made of acrylic acid, methacrylic acid, or the like. Examples of the resin component include an acrylic resin, a vinyl acetate resin, a vinyl chloride resin, a styrene resin, a butadiene resin, a styrene-butadiene resin, and an acryl-styrene resin.

As these resins, those having both a hydrophilic part and a hydrophobic part are preferable. The particle diameter of these resin components is not particularly limited as long as an emulsion is formed, but is preferably about 150 nm or less, more preferably about 5 to 100 nm. Examples of commercially available resin emulsions include Microgel E-1002 and E-Gel.
5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), Boncoat 5454 (styrene-acrylic resin emulsion, Dainippon Ink and Chemicals, Inc.) Company), S
AE-1014 (styrene-acrylic resin emulsion, manufactured by Zeon Corporation), Cybinol SK-20
0 (acrylic resin emulsion, manufactured by Seiden Chemical Co., Ltd.). Means for causing the liquid composition to adhere to the recording material include a coating roller, a spray, and an inkjet head. Among them, an inkjet head is preferably used from the viewpoint of image resolution.

The liquid composition of the present invention causes a difference in adhesive strength between an adhered portion and a non-adhered portion by selectively adhering to an image forming portion of a recording material. The term “part” refers to an area where the recording liquid adheres in a later step and its periphery. The reason for including the periphery is to provide a margin so that the recording liquid adheres to the liquid composition and the powder composition even when the position where the recording liquid is applied is deviated from the original position due to low mechanical precision. It is. In consideration of the ejection stability from the inkjet head, the viscosity of the liquid composition of the present invention at 25 ° C. is preferably 30 mPa · sec or less, and more preferably 10 mPa · sec or less.

The powder composition of the present invention contains spherical or irregular particles composed of a water-absorbing polymer as a main component, and may optionally contain a moisture-resistance improver. Instantly absorbs the recording liquid attached by containing a water-absorbing polymer,
The viscosity of the recording liquid can be instantaneously increased, and as a result, bleeding and color bleed can be effectively suppressed.
Further, since the fluid component of the recording liquid is instantaneously eliminated, a remarkable effect is exhibited also in high-speed drying. As the water-absorbing polymer, any polymer that absorbs water can be suitably used. Specific examples thereof include polyacrylic acid, sodium polyacrylate, polyalkyl oxides such as polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylamide, poly-N-vinylacrylamide, polypropylene glycol, glue, gelatin, and casein. , Albumin, alginic acid, sodium alginate, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl ether, polyvinylmethylcellulose, polyethylene glycol, glucose, xylose, sucrose, maltose, arabinose, α-
Cyclodextrin, starch and the like. Among them, polyacrylic acid, sodium polyacrylate, poly-N-vinylacetamide, and polyacrylamide are preferred from the viewpoint of image quality. Even if these polymers are used alone,
More than one species may be used in combination. Further, it may be used as a copolymer with another monomer. Examples of the moisture resistance improver include an alkylamine compound, an alkyl alcohol compound, and the like. Addition of these compounds can suppress aggregation of the powders without impairing the hygroscopicity.

The powder composition that can be used in the present invention can contain a compound that adsorbs the coloring agent contained in the recording liquid. By containing such a compound, the coloring agent contained in the recording liquid can be instantly adsorbed,
As a result, bleeding and color bleeding can be effectively suppressed. In addition, since the flowability of the colorant is instantaneously lost, a remarkable effect is exhibited also in high-speed drying. When the coloring agent is anionic, the compound adsorbing the coloring agent is preferably a cationic compound, and when the coloring agent is cationic, the compound adsorbing the coloring agent is an anionic compound. Is preferred. The cationic compound can be contained in the powder composition in various forms, but one preferable example is a form in which the powder itself is mainly composed of a cationic polymer compound. Specific examples thereof include polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymer, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium,
Examples include cationic polymer compounds such as polyamidine, polyamine sulfone, and cationic starch. These cationic polymer compounds do not need to be synthesized from a single monomer, but may be prepared by mixing and copolymerizing cationic monomers for the purpose of imparting moisture resistance or controlling fluidity. , Styrene, ethylene, propylene,
Those copolymerized with a monomer such as vinyl acetate can also be used. Further, the powder composed of these cationic polymer compounds may be used alone, but depending on the purpose,
Mix and use powders of various cationic polymer compounds, mix and use powders of polymer compounds such as polyethylene glycol and polyacrylamide, and mix and use pigments such as silica, titanium oxide, and zinc oxide You can also. It is preferable to mix silica or polymer compound particles having a crosslinked structure having a smaller particle diameter than the main component powder dissolved in the recording liquid, in order to impart moisture resistance and increase the fluidity of the powder.

The powder composition of the present invention may contain a higher alkylamine, a higher alkylammonium compound or a polyvalent amine compound. Powder comprising a cationic polymer compound as described above and a higher alkylamine,
A mixture with a higher alkyl ammonium compound or a polyvalent amine compound or a mixture with a nonionic polymer compound such as polyethylene glycol or polyacrylamide can also be used. However, in these methods, when the powder is stored under high humidity, a problem that a part of the powder absorbs and dissolves and the powders adhere to each other easily occurs. In order to prevent this problem of moisture absorption, it is preferable to use a powder mainly composed of an anionic polymer compound and to use a higher alkylamine or a higher alkylammonium compound as a counter ion of the anionic polymer compound.

Specific examples of the higher alkylamine or higher alkylammonium compound that can be used in the present invention include laurylamine, stearylamine, cetylamine, behenylamine, dimethylstearylamine, lauryltrimethylammonium, cetyltrimethylammonium, and stearyltrimethylammonium. , Behenyltrimethylammonium, dioctyldimethylammonium, distearyldimethylammonium, stearyldimethylbenzylammonium and the like.

Specific examples of the polyamine compound which can be used in the present invention include ethylenediamine, hexamethylenetetramine, piperazine, hexamethyleneimine,
Hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, heptaethyleneoctamine, nanoethylenedecamine, triethylenetetramine, triethylene-bis (trimethylene) hexamine, bis (3-
Aminoethyl) aminomethylenediamine, N, N'-bis (3-aminopropyl) putrescine, 1,4-diazacycloheptane, 1,5-diazacyclooctane,
1,4,11,14-tetraazacycloeicosane,
1,2-diaminopropan-3-ol, phenylenediamine, triaminobenzene, tetraaminobenzene,
Pentaaminobenzene and the like can be mentioned.

The particle size of the powder composition is preferably from 0.1 to 50 μm. Particle size 0.1
When the particle size is less than μm, the cohesion between the powders is so strong that the powders associate with each other to form a large lump, and the powders are easily scattered when applied to the intermediate transfer member. Is generated. If the particle size of the powder exceeds 50 μm, the resolution of the obtained image is reduced, and a high-quality image cannot be obtained. In order to enhance the moisture resistance of the powder composition, it is effective to include a moisture resistance enhancer. Since the moisture resistance enhancer protects the hydrophilic group of the water-absorbing polymer, the moisture resistance is improved. Further, when the recording liquid adheres, the moisture resistance enhancer is eluted into the recording liquid, so that the moisture resistance can be improved without hindering the absorption of the recording liquid. Examples of the moisture resistance enhancer include alkylamines, alcohols, glycols and the like. These may be used alone or in combination of two or more.

The recording liquid of the present invention can be used in water or oil, but from the viewpoint of safety, water is preferred. As the coloring agent to be contained in the recording liquid, it is preferable to use at least one of an anionic dye, a pigment or a disperse dye dispersed with an anionic dispersant, and a pigment having an anionic group on the surface. Examples of the anionic dye include dyes classified into acid dyes, direct dyes, and food dyes in the color index.

Specifically, as acid dyes and food dyes, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142 C.I. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97 106, 111, 114, 115, 134, 186 249, 254, 289 C . I. Acid Blue 9, 29, 45, 92, 249 C.I. I. Acid Black 1, 2, 7, 24, 26, 94 C.I. I. Food yellow 3,4 C.I. I. Food Red 7, 9, 14 C.I. I. Food black 1,2

As direct dyes, C.I. I. Direct Yellow 1, 12, 24, 26, 33, 44, 50, 86 120, 132, 142, 144 C.I. I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227 C.I. I. Direct Orange 26, 29, 62, 102 C.I. I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165 199, 202 C.I. I. Direct Black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 has high solubility, good color tone, and water resistance when recorded by the method of the present invention. This is an example of a dye that can be preferably used because of its good properties.

As the pigment used in the recording liquid of the present invention, organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo and the like can be used.
Thioindigo-based, perylene-based, isoindolenone-based, aniline black, azomethine-based, rhodamine B lake pigments and the like, and inorganic pigments such as carbon black, iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, and barium yellow , Navy blue, cadmium red, chrome yellow, and metal powder.

Examples of the pigment dispersant having an anionic group include polyacrylic acid, polymethacrylic acid, styrene acrylic resin, styrene maleic resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, β-naphthalene Sulfonic acid formalin condensate,
Carboxymethylcellulose, starch glycolic acid,
Examples include sodium alginate, pectic acid, hyaluronic acid and the like. These anionic dispersants are
Although it can be used in an acid form, an alkali metal salt such as sodium and potassium can also be used. As a pigment having an anionic group on the surface, carbon black having a carboxyl group or a sulfonic acid group can be mentioned as a typical example. Other examples include phthalocyanine-based pigments and anthraquinone-based pigments that have been oxidized or treated with fuming sulfuric acid to introduce carboxyl groups or sulfonic acid groups into some of the pigment particles.

The recording liquid of the present invention contains a colorant and water as main components, but may contain an organic solvent, a fungicide, a pH adjuster and the like. In particular, 1. To make the recording liquid have desired physical properties.
2. To prevent clogging of the nozzles of the recording head due to drying of the recording liquid; It is preferable to use a water-soluble organic solvent for the purpose of controlling the wettability of the recording liquid to the powder. Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,4. −
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol,
Polyhydric alcohols such as 1,2,4-butantriol, 1,2,3-butanetriol and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
Polyhydric alcohol alkyl ethers such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether And N-methyl-2-pyrrolidone, N
-Hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam and other nitrogen-containing heterocyclic compounds; amides such as formamide, N-methylformamide, formamide, N, N-dimethylformamide Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodieanol; propylene carbonate, ethylene carbonate, and γ-butyrolactone. Can be These solvents are used alone or in combination with water.

Examples of the pH adjuster include 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, acetic acid and the like can be used. When the powder is an anionic polymer having a higher alkylamine or a higher alkylammonium compound as a counter ion, it is particularly preferable to adjust the pH value of the recording liquid to 8.0 or more. As described above, the anionic polymer having a higher alkylamine or a higher alkylammonium compound as a counter ion is preferable in that the powder has moisture resistance. However, since the solubility of the powder itself in water is low, the pH value is low. This is because, when a recording solution having a low viscosity is used, the dissolution rate becomes slow, and it becomes difficult to perform high-speed image recording. When the pH value is adjusted to 8.0 or more using the above-mentioned pH adjuster, the basic component in the recording liquid undergoes an ion exchange reaction to increase the dissolution rate of the powder by the recording liquid. Printing record becomes possible.

An example of an image forming apparatus for implementing the image forming method of the present invention 1 will be described with reference to FIG. The recording material (1) is conveyed to a liquid composition head by a paper feed roller. Here, the liquid composition is selectively adhered to the image forming portion. Next, the powder composition is applied by a powder composition coating roller. The powder composition coating roller transfers the powder composition to a region on the recording material to which the liquid composition has adhered in a state where the powder composition has been physically or electrostatically adhered. The adhesive force between the liquid composition and the powder composition> the adhesive force between the powder composition and the coating roller> the adhesive force between the powder composition and the recording material is established, so that the liquid composition The powder composition does not adhere to portions where no recording material adheres, that is, regions where the recording material is exposed.
A rubber material such as silicone rubber is suitably used as a member of the roller. Next, the recording liquid is adhered by an ink jet head for a recording material to produce a printed matter. In FIG.
Further, by heat-pressing with a fixing roller, the powder composition is softened and melted, and the adhesion to the recording material is increased.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The following composition was used as the liquid composition. <Liquid composition 1> ・ Styrene-acrylic resin emulsion (resin content) 15 wt% (manufactured by Nippon Paint Co., Ltd., Microgel E-1002, E-5002) ・ Ethylene glycol 10 wt% ・ Potassium dehydroacetate (preservative) 0.3 wt・ Remaining amount of ion-exchanged water <Liquid composition 2> ・ 15 wt% of polyvinyl alcohol (resin content) ・ 10 wt% of ethylene glycol ・ 0.3 wt% of potassium dehydroacetate (preservative) ・ Remaining amount of ion-exchanged water

The following compounds were used as the powder composition. <Powder composition 1>-Polyacrylic acid (Nibo Chemical, Carbopol 2050) <Powder composition 2>-Polyvinylpyrrolidone (G120, K120) <Powder composition 3>-Sodium polyacrylate (Sanfresh ST-100MPS, manufactured by Sanyo Chemical) <Powder composition 4>-Polyacrylamide (Sacris N-1 manufactured by Sanyo Chemical) <Powder composition 5>-Poly-N-vinylacetamide (manufactured by Showa Denko; GX-205) <Powder composition 6>-Silica gel (Fine Seal X-45, manufactured by Tokuyama) <Powder composition 7>-Polyallylamine (Sanfix 555, manufactured by Sanyo Chemical Co., Ltd.) <Dispersion of powder composition 1> ・ Silica gel (Tokuyama, Fine Seal X-45) 15 wt% ・ Ethylene glycol 10 wt% ・ Potassium dehydroacetate (preservative) 0.3 t% · Ion-exchanged water Balance

The recording liquid having the following formulation was used. <Black recording liquid> C.I. I. Food black 2 (anionic pigment) 4wt% ・ Ethylene glycol 10wt% ・ Tetraethylene glycol 5wt% ・ Triethylene glycol monobutyl ether 5wt% ・ Potassium dehydroacetate (preservative) 0.3wt% ・ Remaining ion-exchanged water <Yellow record Liquid> C.I. I. Acid Yellow 17 (anionic dye) 2 wt% ・ Diethylene glycol 15 wt% ・ 1,6-hexanediol 5 wt% ・ Ethylene oxide added acetylene (surfactant) 1 wt% ・ Potassium dehydroacetate 0.3 wt% ・ Ion exchange water

<Magenta recording liquid> C.I. I. Acid Red 92 (anionic dye) 2.5 wt% ・ Diethylene glycol 15 wt% ・ 2-pyrrolidone 5 wt% ・ Polyoxyethylene alkyl ether (surfactant) 1 wt% ・ Potassium dehydroacetate 0.3 wt% ・ Ion-exchanged water Cyan recording liquid> I. Acid Blue 9 (anionic dye) 3 wt% ・ Glycerin 10 wt% ・ 2-pyrrolidinone 10 wt% ・ Polyoxyethylene alkyl ether (surfactant) 1 wt% ・ Potassium dehydroacetate 0.3 wt% ・ Ion-exchanged water

{Printing Experiment} A spray or ink-jet head is used as a means for applying the liquid composition, a brush or silicone rubber roller is used as a means for applying the powder composition, and a means for applying the recording liquid is used. Printing experiments were performed using a spray or an inkjet head, respectively. As the inkjet head, an on-demand type head using a piezoelectric element having 256 nozzles for each color was used. By operating these heads, the following test chart was printed on the following recording material using four colors of recording liquid. Test chart: A color chart including a black character portion (evaluating bleeding) and a color patch (evaluating color bleed, image density, recording liquid drying property, and abrasion property) was used. -Recording material: My paper (manufactured by NBS Ricoh) The produced printed matter was evaluated for the following items. I. Bleeding b. Color bleed c. Image density d. Ink dryness (recording liquid does not adhere to the finger when touching the patch) e. Uncomfortable feeling in non-image area (powder residual feeling) f. Writability of non-image part g. Scratch (colorant does not stick to fingers when strongly rubbing patches with fingers)

The following Table 1 shows the evaluation criteria for the above items (1) to (5).

[Table 1]

Example 1 The liquid composition 1 was sprayed from a spray nozzle to adhere the liquid composition 1 only to an area corresponding to an image portion of a test chart on a recording material. Next, the powder composition 1 was adhered from above using a brush. At this time, it was confirmed that there was no powder composition in the non-image area where the liquid composition did not adhere. Further, when the powder composition 1 adheres,
The color recording liquid was applied according to the test chart. Table 2 shows the evaluation results. When the powder composition was sprinkled over the entire surface with the liquid composition adhered to the image area, and the recording material was turned upside down and vibrated, the powder composition was applied to the area where the liquid composition was adhered. However, it was confirmed that the powder composition did not adhere to the region where the liquid composition was not present. That is, it was confirmed that there was a difference in the adhesiveness between the image area and the non-image area.

Example 2 The liquid composition 1 was sprayed from a spray nozzle, and the liquid composition 1 was applied only to the area corresponding to the image area of the test chart on the recording material. Next, the powder composition 1 was adhered from above using a brush. At this time, it was confirmed that there was no powder composition in the non-image area where the liquid composition did not adhere. Further, when the powder composition 1 adheres,
The color recording liquid was applied according to the test chart. Furthermore, it heat-pressed with the heat roller. Table 2 shows the evaluation results.

Example 3 The liquid composition 1 was jetted from an ink-jet head, and the liquid composition 1 was applied only to the area corresponding to the image area of the test chart on the recording material. Next, the powder composition 1 was adhered from above using a brush. At this time, it was confirmed that there was no powder composition in the non-image area where the liquid composition did not adhere. Further, a recording liquid of four colors was applied to the portion where the powder composition 1 was attached by spraying according to the test chart.
Table 2 shows the evaluation results.

Example 4 The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Then, the powder composition 1 was adhered from above using a roller made of silicone rubber. At this time, it was confirmed that there was no powder composition in the non-image area where the liquid composition did not adhere. Further, a recording liquid of four colors was applied to the portion where the powder composition 1 was attached by spraying according to the test chart. Table 2 shows the evaluation results.

Example 5 The liquid composition 1 was ejected from an ink-jet head, and the liquid composition 1 was applied only to an area corresponding to an image portion of a test chart on a recording material. Then, the powder composition 1 was adhered from above using a roller made of silicone rubber. At this time, it was confirmed that there was no powder composition in the non-image area where the liquid composition did not adhere. Further, the recording liquid of four colors was adhered to the place where the powder composition 1 was adhered by the ink jet head according to the test chart. Table 2 shows the evaluation results.

Example 6 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 2 was ejected from an ink jet head, and the liquid composition 2 was applied only to a region corresponding to an image portion of a test chart on a recording material. Then, the powder composition 1 was adhered from above using a roller made of silicone rubber.
Further, the recording liquid of four colors was adhered to the place where the powder composition 1 was adhered by the ink jet head according to the test chart. Table 2 shows the evaluation results.

Example 7 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Then, the powder composition 1 was adhered from above using a roller made of silicone rubber.
Further, the recording liquid of four colors was adhered to the place where the powder composition 1 was adhered by the ink jet head according to the test chart. Table 2 shows the evaluation results.

Example 8 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Next, the powder composition 2 was adhered from above using a roller made of silicone rubber.
Further, the recording liquid of four colors was applied to the place where the powder composition 2 was adhered according to the test chart with an ink jet head. Table 2 shows the evaluation results.

Example 9 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Next, the powder composition 3 was adhered from above using a roller made of silicone rubber.
Further, the recording liquid of four colors was applied to the place where the powder composition 3 was adhered using an ink jet head according to the test chart. Table 2 shows the evaluation results.

Example 10 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Next, the powder composition 4 was adhered from above using a roller made of silicone rubber.
Further, a recording liquid of four colors was adhered to the place where the powder composition 4 was adhered by an ink jet head according to a test chart. Table 2 shows the evaluation results.

Example 11 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Then, the powder composition 5 was adhered from above using a roller made of silicone rubber.
Further, a recording liquid of four colors was adhered to the place where the powder composition 5 was adhered by the ink jet head according to the test chart. Table 2 shows the evaluation results.

Example 12 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Next, the powder composition 6 was adhered from above using a roller made of silicone rubber.
Further, the recording liquids of four colors were applied to the place where the powder composition 6 was adhered according to the test chart with an ink jet head. Table 2 shows the evaluation results.

Example 13 A printing experiment was performed using the image forming apparatus shown in FIG. The liquid composition 1 was ejected from an ink jet head, and the liquid composition 1 was applied only to a region corresponding to an image portion of a test chart on a recording material. Next, the powder composition 7 was adhered from above using a roller made of silicone rubber.
Further, recording liquids of four colors were adhered to the places where the powder composition 7 was adhered according to the test chart with an ink jet head. Table 2 shows the evaluation results.

Comparative Example 1 In a state where the liquid composition was not adhered to the recording material, the powder composition 1 was applied to the entire surface of the recording material while applying an electric field. Further, recording liquids of four colors were applied by an ink jet head according to the test chart. The evaluation results are shown in Table 2. The powder remained in the non-image area, and writing with a felt-tip pen was impossible.

Comparative Example 2 In a state where the liquid composition was not adhered to the recording material, the dispersion 1 of the powder composition was adhered to an area corresponding to the image portion of the test chart using an ink jet head. Further, recording liquids of four colors were applied by an ink jet head according to the test chart. The results of the evaluation are shown in Table 2. The results showed that there was much bleeding and color bleed, the image density was low, and the recording liquid was in an undried state. This is because when the dispersion liquid 1 of the powder composition is adhered by an ink jet head, the powder adheres to the paper in a wet state and cannot absorb the recording liquid.

[0050]

[Table 2]

[0051]

According to the image forming method of the present invention 1, bleeding
No image or feathering, image stain due to poor drying of recording liquid
Can be eliminated. In addition, the powder composition is applied to the non-image area.
Since it does not adhere, there is no sense of incongruity in the feel and writeability
Can be good. According to the image forming method of the second aspect of the present invention,
Heating and melting the powder composition to which the recording liquid has adhered
Increases the abrasion of the image forming area
Can be. According to the image forming method of the third aspect, the liquid composition
Objects can be attached with high resolution and high positional accuracy
Therefore, a printed matter having high image quality can be obtained. Departure
According to the image forming method of Example 4, the powder composition is evenly distributed.
Printing with high image quality because it can be attached to all at once
You can get things. According to the image forming method of the fifth aspect,
If the recording liquid is applied with high positional accuracy and high resolution
Can produce high quality printed matter.
You. According to the liquid composition of the sixth aspect, adhesion of the liquid composition
It is possible to increase the difference in adhesive strength between the
To ensure that the powder composition adheres to the image area.
Can be. As a result, there is no image defect and high image quality
You can get printed matter. According to the liquid composition of the seventh invention,
If it is, the adhesive force between the adhered portion and the non-adhered portion of the liquid composition
Since the difference can be further increased, the powder
The composition can be more reliably adhered. The result
As a result, there is no image defect compared to the liquid composition of the present invention 6 and the image
A print having high image quality can be obtained. For powder composition
Due to the absorption or absorption effect of the recording liquid
Eliminates ringing and eliminates image stains due to poor drying of the recording liquid.
You can comb. According to the powder composition of the present invention 8, the powder
Bleeding or feathering due to the recording liquid absorption effect of the body composition
Eliminates ring and eliminates image stains due to poor drying of recording liquid
Can be According to the powder composition of the ninth aspect, the powder composition
Due to the particularly high absorption effect of the recording liquid by the composition, the present invention
No more bleeding and feathering than powder composition of No. 8
Image contamination due to poor drying of the recording liquid
You. According to the powder composition of the present invention 10, the powder composition
Bleeding and feathering due to the coloring agent adsorption effect in the recording liquid
To eliminate image stains caused by poor drying of the recording liquid
Can be. According to the powder composition of the eleventh invention, the powder composition
The present invention 10
Eliminates bleeding and feathering more than powder compositions
Image contamination due to poor recording liquid drying can be eliminated. Book
According to the recording liquid of the twelfth aspect, the colorant in the recording liquid has a powder composition.
Removes bleeding and feathering by being absorbed by objects
Image contamination due to poor drying of the recording liquid
You. According to the recording liquid of the thirteenth invention, the recording liquid is safe and has a high storage stability.
A good recording liquid can be obtained. In the recording liquid of the present invention 14,
According to this, the adhesion to the recording material is
Performance can be improved. Printed matter of the fifteenth invention
No bleeding or color bleed, high image density,
There is no image stain due to poor recording solution and there is no discomfort in the non-image area
In addition, a printed matter excellent in writability can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of an apparatus configuration for performing an image forming method according to the first embodiment of the present invention.

FIG. 2 is a diagram illustrating an example of an apparatus configuration for performing an image forming method according to the second embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Paper feed part 2 Ink jet head for liquid composition 3 Liquid composition coating roller 4 Ink jet head for recording liquid 5 Paper discharge part 6 Fixing roller

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2C056 EA05 FD20 HA41 HA42 HA46 2H086 BA01 BA02 BA15 BA17 BA35 BA53 BA55

Claims (15)

[Claims] A step of selectively causing a liquid composition to adhere to at least an image forming portion of a recording material to cause a difference in adhesive strength between an adhered portion and a non-adhered portion (first process); An image characterized by comprising a step (second step) of attaching a powder composition to a liquid composition adhered to a substrate and a step (third step) of attaching a recording liquid to the adhered powder. Forming method. 2. The method according to claim 1, further comprising a step (fourth step) of heating and melting the powder composition to which the recording liquid has adhered, following the first to third steps. Image forming method. 3. The method according to claim 1, wherein the attaching means in the first step is ejection by an inkjet head.
Or the image forming method according to 2. 4. The image forming method according to claim 1, wherein the applying means in the second step is coating by a roller. 5. The method according to claim 1, wherein the attaching means in the third step is ejection by an inkjet head.
5. The image forming method according to any one of items 1 to 4. 6. The liquid composition for a first step in the image forming method according to claim 1, wherein the liquid composition contains at least a resin. 7. The liquid composition according to claim 6, wherein the resin is contained in an emulsion state. 8. The powder composition for the second step in the image forming method according to claim 1, which contains at least a water-absorbing polymer. 9. The water-absorbing polymer is polyacrylic acid,
The powder composition according to claim 8, wherein the composition is at least one selected from the group consisting of sodium polyacrylate, poly-N-vinylacetamide, and polyacrylamide. 10. A recording medium comprising at least a compound which adsorbs a coloring agent contained in a recording liquid.
5. The powder composition for a second step in the image forming method according to any one of 5. 11. The powder composition according to claim 10, wherein the compound that adsorbs the coloring agent contained in the recording liquid is a cationic compound. 12. The method according to claim 1, further comprising a coloring agent having an adsorptivity to the powder composition.
6. The recording liquid for a third step in the image forming method according to any one of items 5 to 5. 13. The recording liquid according to claim 12, wherein the colorant is an anionic dye or an anionic pigment. 14. The composition according to claim 1, further comprising a component for dissolving or swelling the powder composition.
5. The recording liquid for a third step in the image forming method according to any one of 5. 15. A printed matter produced by using the image forming method according to claim 1.