JP2003011486A - Pretreatment liquid for recording material and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording method capable of obtaining an image, excellent in the reproducibility of a fine line or the like, not generating any oozing at the boundary of color, good in color tone, high in the density of an image as well as the quality of the image, excellent in water-resistant property, and not generating any strike-though of ink, further, hardly generating curl, cockling or the like, and a pretreatment liquid for the recording material, which is employed for the recording method. SOLUTION: In the image recording method wherein the pretreatment liquid for the colorless or light color recording material containing a compound for making a coloring agent in the recording liquid consisting of the coloring agent and a solvent for dispersing or resolving the coloring agent insoluble is applied on the recording material and, thereafter, the recording liquid is discharged as the drips of the liquid to form the image by adhering the same to the recording material, the pretreatment liquid for the recording material contains cationic resin, whose cationic degree (a colloid equivalent value by polyvinyl potassium sulfate reagent) defined in this sentence is 3-7 meq/g (pH 4.0).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment liquid for a recording material of an image recording method and an inkjet image recording method.

[0002]

2. Description of the Related Art In recent years, ink jet printers have become popular due to their advantages of low noise and low running cost, and color printers capable of printing on plain paper have been put on the market. Conventionally, dyes with high solubility have been mainly used as colorants in inks for office inkjet printers due to problems such as ink clogging, but posters that require water resistance and light resistance are created. Therefore, the use of inks containing a pigment as a colorant is also increasing. Further, when a color image is printed on an ordinary paper by an ink jet printer, in order to suppress bleeding at the color boundary such as a two-color overlapping portion, a surfactant or the like is added to the ink to enhance the ink permeability. However, since feathering occurs in characters and fine lines in that case, ink having low permeability is used only when printing black characters. However, the suppression of bleeding at color boundaries and the prevention of feathering on characters and thin lines are still insufficient.

Therefore, in order to solve such a problem, a recording material in which a material for fixing a dye in the ink is previously coated when an image is formed on the surface of a recording material such as plain paper is recorded. To use a recording material having a white pigment or a water-soluble polymer coated on the material or the surface thereof is disclosed in JP-A-56-867.
89, JP-A-55-144172, JP-A-55-81992, JP-A-52-53012 and JP-A-56-89594. These are recording materials that have undergone special processing,
In order to deal with a general recording material such as plain paper, JP-A-56-89595 discloses that a recording material is preliminarily sprayed with a polymer solution of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate or the like. An ink jet recording method has been proposed in which ink is jetted onto a portion where the polymer solution is attached to print. However, with these polymer solutions, feathering could not be suppressed and the water resistance was not improved at all. Also, an inkjet recording in which a pretreatment liquid for a recording material containing a compound that insolubilizes a dye in the ink is ejected onto the recording material, and then the ink is ejected to a portion of the recording material to which the pretreatment liquid adheres for printing. The method is disclosed in JP-A-64-63185 and JP-A-8-201.
No. 59 or Japanese Patent Laid-Open No. 8-20161. However, even in these methods, in order to stably jet the pretreatment liquid, it is necessary to reduce the viscosity of the pretreatment liquid, so that the concentration of the compound that insolubilizes the dye must be reduced. In order to obtain a sufficient image quality improving effect with such a pretreatment liquid, it is necessary to apply a relatively large amount of the pretreatment liquid, and thus curling or cockling of the recording material is likely to occur. In particular, there is a problem in that the amount of water adhering to the two-color overlapping portion is large and not only cockling but also strikethrough of ink is large.

Further, in JP-A-8-142500, a colorless liquid composition containing at least a silicone compound such as silicone oil and a cationic compound is applied to a recording medium and then a recording containing an anionic compound is carried out. An image forming method has been proposed in which ink is applied by an inkjet recording method. However, the area where the silicone compound adheres has extremely low ink permeability, so the image area dries slowly, and when high-speed printing is performed by this image forming method, low penetrability and poor wettability to the recording medium occur. There has been a problem that image quality is remarkably deteriorated, such as coalescence of adjacent dots and white stripes in the solid image portion along the head main scanning direction. Further, this colorless liquid composition does not have stable recording characteristics because the silicone oil is decomposed or phase separation occurs when it is stored for a long period of time.

Further, Japanese Patent Laid-Open No. 10-250 by the present applicant
No. 216, a colorless or light-colored image recording promoting liquid containing a compound for insolubilizing a colorant in a recording liquid, which is composed of a colorant and a solvent that disperses or dissolves the colorant, is applied to a recording material and then recorded. In a method of forming an image by ejecting a liquid as droplets and adhering the liquid to a recording material, an image recording method is proposed in which the image recording promoting liquid contains a predetermined surfactant. According to this method, the surfactant in the image recording promoting liquid improves permeability and wettability, so that the drying property of the image is improved and high-speed recording can be supported. This promotes the permeation of the material into the paper, causing problems such as increased strike-through, reduced image density, and feathering.

Although various proposals have been made in this way, a recording method capable of high-quality recording at high speed on plain paper has not yet been established.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above problems and to provide excellent reproducibility of fine lines and the like on various recording materials and good color tone without bleeding at color boundaries. It is another object of the present invention to provide an inkjet recording method capable of obtaining an image having high image quality and excellent water resistance. Another object of the present invention is to provide an inkjet recording method in which curling, cockling, etc. are less likely to occur, an image having a high image density is obtained, and ink strike-through does not occur. A further object of the present invention is to provide a pretreatment liquid for a recording material, which can be used in an inkjet recording method to obtain the above image.

[0008]

As a result of earnest research, the inventors of the present invention have found that by using a cationic resin having a predetermined structure, excellent reproducibility of fine lines and the like, no color boundary bleeding, and good color tone Based on the finding that an image with excellent image quality and water resistance can be obtained, curling, cockling, etc. are less likely to occur, and an image with high image density can be obtained, and an image with less ink strikethrough can be realized, I solved all the problems. The present invention is based on such findings. That is, before the image is formed by ejecting the recording liquid containing the anionic component as a droplet and adhering it to the recording material,
A pretreatment liquid that is applied to a recording material by an applying means that is in contact with the recording material, and is a component that insolubilizes an anionic component in the recording liquid. It is achieved by a pretreatment liquid for a colorless or light-colored recording material, which is characterized by containing a cationic resin having an equivalent value, which will be described later in detail, of 3 to 7 meq / g (pH 4.0).

The cationic resin has a weight average molecular weight of 10
It is preferably in the range of 00 to 100,000, more preferably 2000 to 50,000, still more preferably 2000 to 3
Thousands are preferred. When the weight average molecular weight is more than 100,000, it is difficult to dissolve in the solvent, so that the pretreatment liquid becomes non-uniform and uneven image quality is likely to occur. On the other hand, when the weight average molecular weight is less than 1000, the effects of preventing bleeding and improving water resistance are small, which is not preferable. Further, in order to obtain high reactivity with the anionic component, the pH of the cationic resin should be 4
It is preferable that the cation degree is 3 meq / g or more, and more preferably 3.5 meq / g. The cation degree is determined by colloid titration using a polyvinyl potassium sulfate reagent. The details can be obtained by the following procedure. That is, 90 ml of deionized water was placed in a conical beaker, 10 ml of a 500 ppm aqueous solution (converted to a dry product) was added, the pH was adjusted to 4.0 with an aqueous hydrochloric acid solution, and the mixture was stirred for about 1 minute. Next, add toluidine blue indicator 2-3
Add dropwise, N / 400 polyvinyl potassium sulfate reagent (N /
Titrate with 400 PVSK). The titration rate is 2 ml / min, and the end point is when the test water changes from blue to magenta and is held for 10 seconds or more. Cation degree is the cation degree (meq / g) = (N / 400 PVSK titer) x (N / 400P
VSK titer) / 2. The higher the degree of cation is, the stronger the cation is, and the more efficient the reaction with the anionic component in the recording liquid is, the more the amount of pretreatment liquid required can be reduced, causing curling and cockling of the recording material. It becomes possible to obtain a high quality image. The cationic resin is preferably ionically dissociated at a high rate in the pretreatment liquid in consideration of the reactivity with the anionic component in the recording liquid. Therefore, the counterion of the cationic resin is It must be a monovalent anion selected from halogen ions, nitrate ions, nitrite ions, and acetate ions.

Examples of means for applying the pretreatment liquid to the recording material by abutting it include roller coating and a coating method using a wire bar or a blade. With these methods,
It is possible to uniformly apply a high-viscosity pretreatment liquid for a recording material, which could not be applied by the droplets from the head, to the recording material. Further, the pretreatment liquid for the recording material applied by the contact imparting means has various additives that could not be added to the pretreatment liquid for the recording material used for the droplets from the head. Can also be added, and the flexibility in formulating the pretreatment liquid for the recording material can be greatly expanded.

In particular, when the means for contacting the recording material and applying the pretreatment liquid is a roller coating means, it is possible to apply a very small amount of the high-viscosity pretreatment liquid, and a simple structure is provided. Therefore, the applying unit can be manufactured at low cost and compactly, which is preferable.

As described above, it is possible to use a high-viscosity pretreatment liquid which has not been used in the pretreatment method of ejecting liquid droplets from the conventional head. That is, the pretreatment liquid can contain a high concentration of the cationic resin. By depositing a thin layer with a high concentration, the amount of deposit can be small and the cationic resin remains near the surface, so that the image quality is remarkably improved and curling, cockling, etc. of the recording material can be suppressed. Specifically, the content of the above cationic resin contained in the pretreatment liquid is preferably 10 to 80% by weight. If it is less than 10% by weight, the reproducibility of fine lines, reduction of feathering and color boundary blurring, improvement of image density, reduction of strikethrough density, etc. cannot be sufficiently obtained, and 80% by weight. If the amount is larger than the above, physical property changes due to evaporation of the solvent component and the like change significantly, and it becomes difficult to uniformly apply a predetermined amount.

The viscosity of the pretreatment liquid is 10 to 1 with a B type viscometer.
It is preferably 0000 mPa · s (25 ° C., rotor No. 4, rotation speed 30 rpm), and more preferably 10 to 1000 mPa · s. The pretreatment liquid is present on the surface of the recording material, and has an effect of image quality improvement such as reproducibility of fine lines, improvement of water resistance, and prevention of bleeding due to ionic interaction with an anionic component in the recording liquid. However, the viscosity of the pretreatment liquid is 10 mPa · s
If it is less than the above range, the pretreatment liquid penetrates into the inside of the recording material, and the effect of preventing feathering and color boundary bleeding is small. In this case, if a large amount of the pretreatment liquid is applied in order to obtain a sufficient image quality improving effect, the pretreatment liquid permeates into the recording material, and the coloring agent permeates into the recording material. This causes a decrease in image density. Further, the solvent component contained in the pretreatment liquid easily causes curling and cockling of the recording material. On the contrary, the viscosity of the pretreatment liquid is 10,000 mP
If it is larger than a · s, it is difficult to apply it uniformly to the recording material, which is not preferable.

The pretreatment liquid may contain various solvents in order to adjust it to a desired viscosity. As a solvent,
Water is particularly preferable from the viewpoint of excellent solubility of the above-mentioned cationic resin, safety of the pretreatment liquid, and cost. Water content is 5
It is preferably about 80% by weight. If it is less than 5% by weight, it is difficult for the cationic resin to dissolve stably, and 80% by weight
If it is larger than this, image bleeding tends to occur, and curling and cockling of the recording material easily occur, which is not preferable.

Further, if the viscosity changes due to evaporation of solvent components such as water in the pretreatment liquid, the amount applied to the recording material also changes, and it is not possible to ensure a constant image quality. In addition to preventing drying, the pretreatment liquid for the recording material should have the desired physical properties, to improve the dissolution stability of compounds and other additives that insolubilize the colorant in the recording liquid, and to pretreat the recording material. The following water-soluble organic solvents can be used for the purpose of stabilizing the coating properties of the liquid. The content of the water-soluble organic solvent is preferably in the range of 5 to 70% by weight. If it is less than 5% by weight, the effect of stabilizing the viscosity by suppressing evaporation and the effect as a dissolution aid are insufficient, and if it is more than 70% by weight, strikethrough and image bleeding are induced, which is not preferable.

That is, as the water-soluble organic solvent, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6- Hexanetriol, 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 tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, N-methyl-2
-Pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, nitrogen-containing heterocyclic compounds such as ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, etc. Amides, monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and other amines, dimethyl sulfoxide, sulfolane, thiodiethanol, and other sulfur-containing compounds, propylene carbonate, ethylene carbonate, γ-butyrolactone, etc. Can be used. These solvents may be used alone or in combination with water together with water.

Of these, particularly preferred are diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerol, 1,2,6-hexanetriol, 1,2,4.
-Butanetriol, petriol, 1,5-pentanediol, N-methyl-2-pyrrolidone, N-hydroxyethylpyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone. A high solubility of a compound that insolubilizes the colorant and other additives and an excellent effect of preventing coating failure due to water evaporation can be obtained.

Further, it is preferable that the pretreatment liquid for the recording material contains a monohydric alcohol, whereby it is possible to prevent the occurrence of coating unevenness due to foaming of the pretreatment liquid for the recording material, and the recording material is recorded. An image having a uniform density can be obtained by forming an image by applying the pretreatment liquid of the material to the recording material by abutting it, and then ejecting the recording liquid as droplets and adhering it to the recording material. .

The pretreatment liquid of the present invention is disclosed in JP-A-8-1425.
It is suitable for high-speed recording as compared with the case of using a colorless liquid composition containing a silicone compound and a cationic compound, which is described in JP-A-00-00. That is, in the liquid composition, the area where the silicone compound is adhered has extremely low ink permeability, so the image area dries slowly, and when high-speed printing is performed by this image forming method, in addition to low penetration, the ink composition does not easily penetrate into the recording medium. Since the wettability is poor, unification of adjacent dots occurs, and white streaks occur in the solid image portion along the main scanning direction of the head. Since the pretreatment liquid of the present invention contains water and a water-soluble solvent as the main solvent, it does not adversely affect the wettability and the penetrability of the recording liquid to which the pretreatment liquid is applied and the recording liquid. Therefore, good image quality can be obtained even when high-speed recording is performed. Further, the various components constituting the pretreatment liquid of the present invention are stable, and their characteristics do not change even after long-term storage.

Further, the pretreatment liquid of the present invention contains 0.1 to
It is preferable to contain 5% by weight of antiseptic and fungicide. Since the pretreatment liquid is applied while being in contact with the recording material, contaminant-causing substances such as paper powder are easily mixed in, and the pretreatment liquid is altered, which causes a change in the amount of adhesion due to alteration and a decrease in the image quality improving effect itself. Sometimes. Therefore, 0.1-5
By adding the weight% of antiseptic / antifungal agent, a pretreatment liquid capable of stably acting for a long period of time can be obtained. Antiseptic and antifungal agents include sodium benzoate, sodium pentachlorophenol, and 2-pyridinethiol-
1-Oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Proxel CRL, Proxel BDN, Proxel GXL, available from Abisha) can be used. If the addition amount is less than 0.1% by weight, the antiseptic and antifungal effect is insufficient, and if it is more than 5% by weight, the image quality is deteriorated.

The pretreatment liquid for the recording material of the present invention includes
It is preferable to add a binder resin for improving the fixing property. Examples of the binder resin include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins and the like.

Further, the pretreatment liquid for the recording material of the present invention may contain a surfactant. When a pretreatment liquid containing a cationic resin and a surfactant is applied to a recording material such as plain paper and then the recording liquid is adhered to the recording material, the surface sizing agent on the recording material is distributed irregularly. Due to less wetting, it is possible to obtain an image with high image density and high image density with less feathering, excellent reproducibility of fine lines and the like, and no color boundary bleeding. It is considered that this is because the recording liquid uniformly permeates the recording material and the coloring material becomes insoluble and stays near the surface of the recording material. As the surfactant, for example, sodium dodecylbenzene sulfonate,
Anionic surfactants such as sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfates, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, myristyl dimethyl benzyl ammonium chloride, chloride Benzalkonium, lanolin ethyl sulfate fatty acid aminopropylethyldimethylammonium, cationic surfactants such as didecyldimethylammonium chloride, amphoteric surfactants such as imidazoline derivatives, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, poly Oxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alk Amides, poly solution was ethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, nonionic surfactants ethylene oxide addition products of acetylene alcohol, fluorine-based surfactants, and the like. Specific examples of the solvent other than the surfactant include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether. Low water solubility such as alkyl and aryl ethers of polyhydric alcohols, lower alcohols such as ethanol and 2-propanol, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol Examples of the polyhydric alcohol include, but are not limited thereto as long as they can be dissolved in the pretreatment liquid and adjusted to desired physical properties.

The content of the above compound in the pretreatment liquid is preferably 0.1 to 50% by weight. In order to ensure the uniformity of the pretreatment liquid, a cationic surfactant is particularly preferable among the surfactants. As a result, the wettability between the recording liquid and the surface of the recording material is improved, and an image having high image quality and high image density and excellent water resistance is obtained. Examples of the cationic surfactant include Ionet D46, Ionet LEC, Secryl VN, Sunstat 1200, Sunstat KT-305C, Cation G-50, Ionet RK-15 (above Sanyo Chemical Industries, Ltd.) and the like.

Specifically, as the kind of the cationic resin having a cation degree of 3 to 7 meq / g (pH 4.0) for insolubilizing the anionic component in the recording liquid, dicyandiamide / formalin other than epichlorohydrin / dimethylamine addition polymer is used. Heavy polycondensate, dicyandiamide / diethylenetriamine heavy polycondensate, dimethyldiallylammonium chloride / SO ₂ copolymer, diallylamine salt / SO ₂ copolymer,
Dimethyldiallylammonium chloride polymer, polymer of allylamine salt, dialkylaminoethyl (meth)
It may also contain acrylate quaternary salt polymer, polyallylamine, cationic epoxy, polyethyleneimine, polyacrylamide, poly (meth) acrylic acid ester, vinylformamide, cationic resin emulsion, and cationic resin polyvalent metal salt. It is possible.

As these cationic resins, commercially available products can be used, and specifically, Sunstat E-81.
8, Sunfix 70, Sunfix 555C, Sunfix LC-55, Sunhooks PAC-700
Conch, Sanyo Elion A-3, Sunfix 41
4, Sunfix 555, Sunfix PRO-1
00, Sunfix 555US, Cellopol YM-5
00 (above Sanyo Chemical Industry Co., Ltd.), # 675, #F
R-2P, # 1001 (all manufactured by Sumitomo Chemical Co., Ltd.), LUPASOL SC61B (manufactured by BASF) and the like can be mentioned. In addition, ZP-700 (vinyl formamide type), MP-184 (polyacrylate type),
MP-173H (Polymethacrylate ester type), MP
-180 (polymethacrylic acid ester type), MX-02
10 (Polymethacrylate ester type), MX-8130
(Polyacrylic acid ester type), E-395 (Polyacrylic acid ester type), E-305 (Polyacrylic acid ester type), Q-101 (Polyamine type), Q-311
(Polyamine type), Q-501 (Polyamine type), Q-
105H (dicyandiamide type), Neo-600 (polyacrylamide type), (all manufactured by Hymo Co., Ltd.), Super Flock 2490 (polyacrylate type), Super Flock 3180, 3380, 3580, 388.
0, 3390, 3590, 3500, SD2081 (polyacrylamide), Acofloc C498T, C49
8Y (Polyacrylic ester type), Super Flock 1500, 1600, Acofloc C481, C48
3, C485, C488, C480 (polymethacrylic acid ester), Acofloc C567, C573, C
577, C581 (polyamine-based), (all manufactured by Mitsui Cytec Co., Ltd.) and the like.

As the cationic resin emulsion, ACRYT UW319-SX, ACRYT RKW-460,
Akrit RKW-400SX, Akrit RKW-4
50SX, Akrit RKW-450 (all manufactured by Taisei Kako Co., Ltd.) and the like can be mentioned. As the polyvalent metal salt of the cationic resin polyvalent metal salt, magnesium nitrate hexahydrate,
Magnesium acetate / tetrahydrate, calcium nitrate / tetrahydrate, calcium acetate / monohydrate, calcium chloride / anhydrous, calcium lactate / pentahydrate, calcium formate / anhydrous, magnesium benzoate / trihydrate Japanese products, magnesium sulfate, heptahydrate and the like can be mentioned.

Since the reactivity between the cationic resin in the pretreatment liquid and the anionic component in the recording liquid is most efficient in the liquid phase, the applying means for contacting the pretreatment liquid with respect to the recording material It is preferable to print with the recording liquid after the pretreatment liquid is applied and before the pretreatment liquid is dried. If high reactivity can be secured, the amount of pretreatment liquid used can be further reduced, and the image quality can be improved without causing curling or cockling of the recording material.

[0028] preferably 0.5g / m ² ~10g / m ² as a deposition amount of the recording material of the pretreatment liquid of the recording material can be suppressed thereby better curl of the recording material. If it is less than 0.5 g / m ² , the image quality improving effect is insufficient, and if it is more than 10 g / m ² , the recording material causes curling or cockling, and the adhered amount is too large, and the strike-through density is high. Increase.

The pretreatment liquid of the present invention preferably has a colloid equivalent value of 1 to 5 meq / g at pH 4.0 when diluted 2000 times with ion-exchanged water.

Next, the recording liquid used in the image recording method of the present invention will be described. The recording liquid comprises at least an anionic compound, a colorant, and a solvent that dissolves or disperses the colorant. The anionic compound in the recording liquid is an anionic dye, a pigment or dye dispersed with an anionic dispersant,
It is at least one colorant selected from pigments having anionic groups and anionic colored fine particles. Since the coloring agent has an anionic group as a functional group or the anionic component is adsorbed on the coloring agent, the reaction between the anionic component and the cationic resin prevents the coloring component from being contained in the recording liquid. It can be efficiently retained on the surface of the recording material, thus improving image density, reducing strikethrough density, and feathering.
Various image quality improving effects such as boundary blur prevention can be obtained.

As the anionic dyes, water-soluble dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes and food dyes in the color index and having excellent water resistance and light resistance are preferable. Specific examples of these dyes include acid dyes and food dyes such as 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, 9
2,97,106,111,114,115,134,
186, 249, 254, 289, C.I. 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. Hood red 7,9,1
4, C.I. I. Food black 1 and 2, C.I. as a direct dye. I. Direct Yellow 1, 12, 24, 26, 3
3,44,50,86,120,132,142,14
4, 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 2
6,29,62,102, C.I. I. Direct Blue 1,2,6,15,22,25,71,76,79,8
6,87,90,98,163,165,199,20
2, C.I. I. Direct Black 19,22,32,3
8, 51, 56, 71, 74, 75, 77, 154, 1
68,171, C.I. I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 21,
23, 24, 25, 28, 29, 32, 36, 40, 4
1,45,49,51,53,63,64,65,6
7, 70, 73, 77, 87, 91, C.I. I. Basic Red 2,12,13,14,15,18,22,2
3,24,27,29,35,36,38,39,4
6,49,51,52,54,59,68,69,7
0, 73, 78, 82, 102, 104, 109, 11
2, 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, C.I. as a reactive dye.
I. Reactive Black 3,4,7,11,12,1
7, 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, 25, 26, 32, 37, 44, 4
6,55,60,66,74,79,96,97, C.I.
I. Reactive blue 1,2,7,14,15,2
3,32,35,38,41,63,80,95 etc. can be used.

Particularly in the present invention, anionic acid dyes and direct dyes can be preferably used. It is also preferable to use a dye developed for ink jet, and as such a dye, for example, Projet Fast Black2 and Projet manufactured by Abisha Co., Ltd. are used.
Fast Cyan2, Projet Fast Mag
enta2, Projet Fast Yellow 2 and the like.

The pigment used in the present invention may be an inorganic pigment or an organic pigment without any particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method or a thermal method can be used. The organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments,
A thioindigo pigment, an isoindolinone pigment, a quinofuraron pigment, etc.), a dye chelate (for example, a basic dye type chelate, an acid dye type chelate, etc.), a nitro pigment, a nitroso pigment, and aniline black can be used. Specifically, for color, C.I. I. Pigment Yellow 1
(Fast Yellow G), 3,12 (Disazo Yellow AAA), 13, 14, 17, 24, 34, 35, 3
7, 42 (yellow iron oxide), 53, 55, 81, 83 (disazo yellow HR), 95, 97, 98, 100, 1
01, 104, 108, 109, 110, 117, 12
0,138,153, C.I. I. Pigment Orange 5,
13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scallet), 23, 31, 38, 48: 2
(Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48: 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52 : 2,53: 1,5
7: 1 (Brilliant Carmine 6B), 60: 1, 6
3: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 101 (Bengala), 104, 1
05, 106, 108 (cadmium red), 112,
114, 122 (quinacridone magenta), 123, 1
46, 149, 166, 168, 170, 172, 17
7,178,179,185,190,193,20
9, 219, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 3
8, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue E), 16, 17: 1, 56, 6
0, 63, C.I. I. Pigment Green 1, 4, 7,
There are 8, 10, 17, 18, 36 and so on.

These pigments are preferably dispersed with an anionic dispersant. As the anionic dispersant, polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer Coal, styrene-methacrylic acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid-
Acrylic acid alkyl ester copolymer, styrene-α-
Methylstyrene-acrylic acid copolymer, styrene-α-
Methylstyrene-acrylic acid copolymer-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinylethylene copolymer Examples thereof include a combination, a vinyl acetate-maleic acid ester copolymer, a vinyl acetate-crotonic acid copolymer, a vinyl acetate-acrylic acid copolymer and the like. Besides these, known anionic dispersants used for preparing conventionally known pigment dispersions can be used.

According to a preferred embodiment of the present invention, these copolymers have a weight average molecular weight of 3,000 to 50,000.
Is preferable, and more preferably 5,000 to 3
10,000, most preferably 7,000 to 15,000
Is. The addition amount of the dispersant may be appropriately added as long as the pigment is stably dispersed and the other effects of the present invention are not lost. The dispersant is preferably in the range of 1: 0.06 to 1: 3, more preferably in the range of 1: 0.125 to 1: 3.

In these cases, the pigment is preferably added to the recording liquid as a pigment dispersion obtained by dispersing the pigment in an aqueous medium with a dispersant.

In another preferred embodiment of the present invention, the surface of a pigment (for example, carbon) is treated with an anionic resin or the like to make it dispersible in water, or a graft pigment or a sulfone is formed on the surface of the pigment (for example, carbon). A processed pigment or the like which has an anionic functional group such as a group, a carboxyl group or a hydroxyl group added thereto and can be dispersed in water can be used. Further, the pigment may be contained in microcapsules having an anionic group so that the pigment can be dispersed in water.

Another aspect of the present invention is colored fine particles. The colored fine particles are obtained by coloring a styrene-acrylic resin, a polyester resin, a polyurethane resin or the like with an oil dye, a disperse dye or a pigment.

A resin emulsion may be added to the recording liquid of the present invention. The resin emulsion means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. Examples of the resin component of the dispersed phase include acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, and styrene resin.

According to a preferred embodiment of the present invention, this resin is preferably a polymer having both a hydrophilic portion and a hydrophobic portion. The particle size of these resin components is not particularly limited as long as it forms an emulsion,
It is preferably not more than about 5 nm, more preferably about 5 to 100 nm.

These resin emulsions can be obtained by mixing resin particles with water, optionally together with a surfactant.

Commercially available resin emulsions include Microgel E-1002 and E-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, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Zeon Corporation), Cybinol SK-200 (acrylic resin emulsion, Saiden Chemical Co., Ltd.) Manufactured), etc.

The recording liquid used in the present invention preferably contains a resin emulsion so that the resin component accounts for 0.1 to 40% by weight of the recording liquid, and more preferably 1 to 2.
It is in the range of 5% by weight.

The resin emulsion has the property of thickening and aggregating, and has the effect of suppressing the penetration of the coloring component into the inside of the recording material and further promoting the fixing to the recording material. Further, depending on the type of resin emulsion, a film is formed on the recording material, which has the effect of improving the abrasion resistance of the printed matter.

The recording liquid may contain sugar. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose,
Examples include xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose. Here, the polysaccharide means a sugar in a broad sense, and α-cyclodextrin,
It is meant to include substances widely existing in nature such as cellulose.

Further, examples of derivatives of these sugars include reducing sugars of the above-mentioned sugars (for example, sugar alcohol {general formula H
OCH ₂ (CHOH) _n CH ₂ OH (representing an integer of n = 2 to 5)}, oxidizing sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioacids, and the like. Sugar alcohol is particularly preferable, and specific examples thereof include maltitol, sorbitol and the like.

The content of these sugars is 0.1 to 0.1% of the recording liquid.
A range of 40% by weight, preferably 0.5 to 30% by weight is suitable.

Water is used as the main component of the recording liquid, but in order to make the recording liquid have the desired physical properties, to prevent the recording liquid from drying, and to improve the dissolution stability of the colorant. The water-soluble organic solvent described above as the water-soluble organic solvent used in the pretreatment liquid for the recording material can be used for the above purposes. Among them, particularly preferable water-soluble organic solvents include diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, petriol,
1,5-Pentanediol, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethylimidazolidinone are mentioned, and by using these, high solubility of the colorant can be obtained. It is possible to obtain an excellent effect in preventing the ejection characteristics from being deteriorated due to the property and water evaporation.

Further, a surfactant can be added to the recording liquid, whereby the surface tension of the recording liquid is adjusted to improve the permeability of the recording material, and the recording liquid to the head member of the ink jet printer is improved. The ejection stability of the recording liquid can be improved by improving the wettability. The surfactant is not particularly limited, but examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl sulfate, polyoxyethylene alkyl ether sulfate salt, and dialkyl sulfosuccinate. Is mentioned.

Examples of the nonionic surfactant include, for example,
Examples thereof include, but are not limited to, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide. The surfactants may be used alone or in combination of two or more.

A penetrant other than the surfactant may be added to the recording liquid for the purpose of adjusting the surface tension. Examples of such penetrants include 2-ethyl-1,3-hexanediol and 2 , 2,4-Trimethyl-1,3-pentanediol, and other polyhydric alcohols, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol mono Butyl ether, alkyl and aryl ethers of polyhydric alcohols such as tetraethylene glycol chlorophenyl ether, polyoxyethylene polyoxypropylene block copolymer, fluorine-based surfactant,
Lower alcohols such as ethanol and 2-propanol may be mentioned.

Furthermore, a hydrophilic polymer compound can be added to the pretreatment liquid or recording liquid for the recording material in order to adjust the viscosity. Vegetable polymers such as gum arabic, traggan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, alginic acid, carrageenan, seaweed macromolecules such as agar, gelatin, casein, albumin, collagen, etc. Animal-based polymers, microbial polymers such as xanthene gum and dextran, or fibrin-based polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc. in semi-synthetic systems, such as shellac, sodium starch glycolate, starch Starch-based polymers such as sodium acid ester, sodium alginate, seaweed-based polymers such as propylene glycol alginate, polyvinyl alcohols such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl methyl ether in pure synthetic systems, non-crosslinked polyacrylamide, Polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, β- Examples thereof include alkali metal salts of naphthalene sulfonic acid formalin condensates and polymer compounds having a side chain of a salt of a cationic functional group such as quaternary ammonium or amino group.

Further, conventionally known additives for recording liquids can be added to the recording liquid of the present invention. For example, as antiseptic and fungicides, sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Avisha Proxel CR
L, Proxel BDN, Proxel GXL) and the like can be used. It is possible to add a pH adjusting agent, a rust preventive agent, etc. to the pretreatment liquid as well as the recording liquid. As the pH adjuster, any substance can be used as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared, and examples thereof include diethanolamine and triethanol. Amines such as amines, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, lithium carbonate, carbonic acid Examples thereof include alkali metal carbonates such as sodium and potassium carbonate. Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uramildiacetate. Examples of the rust preventive agent include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like. In addition, a water-soluble ultraviolet absorber, a water-soluble infrared absorber, etc. can be added depending on the purpose.

[0054]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to the drawings. FIG. 1 shows an example of an embodiment of the ink jet recording method of the present invention. A sheet 6 is sent out by a sheet feeding roller 7 and a pretreatment liquid 1 is uniformly and thinly coated on the sheet by an application roller 4 and a counter roller 5. . The pretreatment liquid is drawn up by the drawing-up roller 3 and uniformly applied to the application roller 4 by the film thickness control roller 2. While being coated with the pretreatment liquid, the sheet is sent to the recording scanning unit having the recording head 20. From the end portion (A portion in the figure) of the pretreatment liquid application operation to the recording scan start portion (B portion in the figure)
Since the length of the paper path to the sheet is set longer than the length in the paper feeding direction, the application of the pretreatment liquid can be completely completed when the paper reaches the recording scan start portion. In this case, since the pretreatment liquid can be applied before the intermittent feed operation during the recording scan, the pretreatment liquid can be applied continuously at a constant speed, and uniform application without unevenness is possible. In this embodiment, the paper that needs pre-processing is supplied from the lower cassette, and the paper that is unnecessary or not processed is supplied from the upper cassette, which is convenient for providing a long paper path. is there.

FIG. 2 shows another embodiment of the present invention.
It is possible to provide a compact device as compared with the above embodiment. The paper 6 is sent out by the paper feed roller 7, and the pretreatment liquid 1 is uniformly and thinly applied to the paper by the application roller 4 and the counter roller 5. The pretreatment liquid is drawn up by the drawing-up roller 3 and uniformly applied to the application roller 4 by the film thickness control roller 2. While being coated with the pretreatment liquid, the paper passes through the recording scanning unit having the recording head 20 and is fed until the paper is completely coated with the pretreatment liquid. When the paper is completely coated with the pretreatment liquid, the paper starts again. Is returned to the recording scan start point. The completion of coating can be detected and controlled, for example, by providing a paper detecting means (not shown) which is usually used near the exit of the pretreatment liquid coating device. When the paper is returned to the print scanning position again, it is possible to position the paper by providing a similar paper detecting means near the print scanning unit. Alternatively, the length of the paper may be given as information in advance to calculate and determine the feed amount of the motor. When the paper is returned, if the same route as the one sent is returned, the trailing edge of the paper will re-enter the pretreatment liquid application device, causing problems such as uneven coating, stains, and paper jams. Can be solved by switching the direction with the paper guide 31 (to the position of the dotted line in the figure) and returning it to the paper guide 34 side.

FIG. 3 shows an example of a sequence for carrying out the ink jet recording method of the present invention. When receiving a print command from a host machine such as a PC, this apparatus starts head cleaning work and pretreatment liquid application work at the same time, and starts recording operation when all preparations are completed. In this case, even if the image data transfer is for one scan,
It may be a plurality of scans or one page. Since the pretreatment liquid application work is performed concurrently with the normal preparation work, the throughput is hardly reduced even if the pretreatment liquid application work is performed. In this case, the work and sequence for preparation are not limited to those in this embodiment.

FIG. 4 shows another example of the sequence. When receiving a print command from a host machine such as a PC, this apparatus performs head cleaning work, jetting check, and image data transfer, and puts all other than paper into a print ready state and outputs a ready signal. When the ready signal is received, the pretreatment liquid application work is started, and the recording operation is started when the paper is ready. In this case, the image data may be transferred for one scan, a plurality of scans, or one page.
The case of pages is the most advantageous in terms of variations in the elapsed time after application. Also in this case, the work and sequence for preparation are not limited to those in this embodiment.

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. In addition, the amounts (%) of the respective components described in the examples are solid contents and are based on weight unless otherwise specified.

Example 1 After mixing and stirring with the following formulation, the pH was adjusted to 10.5 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore size of 0.1 μm to obtain a recording liquid. [Yellow recording liquid 1] C.I. I. Acid Yellow 23 1% by weight Projet Fast Yellow 2 (manufactured by Avisha) 1% by weight Glycerin 5% by weight Ethylene glycol 20% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 1% by weight 2,2,2 4-Trimethyl-1,3-pentanediol 1% by weight Sodium benzoate 0.4% by weight Ion-exchanged water Remaining amount

[0060] [Magenta recording liquid 1]   C. I. Acid Red 52 1% by weight   Projet Fast Magenta 2 (manufactured by Abisha) 1% by weight   Glycerin 5% by weight   20% by weight of ethylene glycol   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2,2,4-Trimethyl-1,3-pentanediol 1% by weight   Sodium benzoate 0.4% by weight   Deionized water remaining

[0061] [Cyan recording liquid 1]   C. I. Acid Blue 91% by weight   Projet Fast Cyan 2 (manufactured by Abischa) 1% by weight   Glycerin 5% by weight   20% by weight of ethylene glycol   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2,2,4-Trimethyl-1,3-pentanediol 1% by weight   Sodium benzoate 0.4% by weight   Deionized water remaining

[0062] [Black recording liquid 1]   C. I. Direct black 168 3% by weight   Glycerin 5% by weight   20% by weight of ethylene glycol   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2,2,4-Trimethyl-1,3-pentanediol 1% by weight   Sodium benzoate 0.4% by weight   Deionized water remaining

Further, the following composition was stirred and mixed to prepare a pretreatment liquid 1 for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 1 for recording material] Dicyandiamide / formalin polycondensate (polymerization average molecular weight 3000) 8% by weight Glycerin 5% by weight Ethylene glycol 15% by weight Ionet D46 (Sanyo Chemical Co., Ltd. quaternary ammonium type cationic surfactant) 1% by weight Sodium benzoate 1% by weight Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Example 2 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore size of 0.8 μm to obtain a recording liquid. [Yellow recording liquid 2] Yellow pigment dispersion liquid 1 33.3% by weight (pigment 5% by weight) Glycerin 5% by weight Diethylene glycol 15% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 1% by weight 2-Ethyl-1,3-hexanediol 2% by weight Sunpack AP (san-ai petroleum fungicide) 0.4% by weight ion-exchanged water Remaining amount Note: Yellow pigment dispersion 1 C.I. I. Pigment Yellow 74 (average particle size 96 nm) 15 wt% Formalin condensate of naphthalene sulfonate 3 wt% Ion-exchanged water Remaining amount

[0065] [Magenta Recording Liquid 2]   Magenta pigment dispersion 1 33.3 wt% (pigment 5 wt%)   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining     Note: Magenta pigment dispersion 1       C. I. Pigment Red 122 (average particle size 120 nm) 15% by weight       Styrene-acrylate-methacrylic acid diethanolamine salt copolymer                                                                 3% by weight       Deionized water remaining

[0066] [Cyan recording liquid 2]   Cyan pigment dispersion 1 33.3 wt% (pigment 5 wt%)   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining     Note: Cyan pigment dispersion 1       C. I. Pigment Blue 15: 3 (average particle size 123 nm) 15% by weight       Styrene-acrylate-methacrylic acid diethanolamine salt copolymer                                                                 3% by weight       Deionized water remaining

[0067] [Black recording liquid 2]   Black pigment dispersion 1 33.3 wt% (pigment 5 wt%)   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining     Note: Black pigment dispersion 1       Carbon black average particle size 99 nm 15% by weight       Formalin condensate of naphthalene sulfonate 3% by weight       Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 2 for recording material] Dicyandiamide / diethylenetriamine polycondensate (polymerization average molecular weight 5000) 80% by weight glycerin 5% by weight 1,5-pentanediol 5% by weight Softanol 70 (Nonionic surfactant manufactured by Nippon Shokubai) 1 Wt% Pentachlorophenol sodium 0.1 wt% Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Example 3 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow recording liquid 3] C.I. I. Acid Yellow 23 1% by weight C.I. I. Direct Yellow 142 1% by weight N-methyl-2-pyrrolidone 7% by weight Diethylene glycol 15% by weight Dialkylsulfosuccinate 1% by weight 2-Ethyl-1,3-hexanediol 1% by weight Pentachlorophenol sodium 0.4% by weight Deionized water remaining

[0070] [Magenta recording liquid 3]   C. I. Acid Red 254 2% by weight   N-methyl-2-pyrrolidone 7% by weight   Diethylene glycol 15% by weight   Dialkyl sulfosuccinate 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   Pentachlorophenol sodium 0.4% by weight   Deionized water remaining

[0071] [Cyan recording liquid 3]   C. I. Acid blue 249 2% by weight   C. I. Direct Blue 199 1% by weight   N-methyl-2-pyrrolidone 7% by weight   Diethylene glycol 15% by weight   Dialkyl sulfosuccinate 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   Pentachlorophenol sodium 0.4% by weight   Deionized water remaining

[0072] [Black recording liquid 3]   Black pigment dispersion 2 33.3% by weight (pigment 5% by weight)   N-methyl-2-pyrrolidone 7% by weight   Diethylene glycol 15% by weight   Dialkyl sulfosuccinate 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   Pentachlorophenol sodium 0.4% by weight   Deionized water remaining     Note: Black pigment dispersion 2       Carbon black average particle size 99 nm 15% by weight       Styrene-acrylate-methacrylic acid diethanolamine salt copolymer                                                                 3% by weight       Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 3 for recording material] Epichlorohydrin / dimethylamine addition polymer (counter ion is acetate ion: polymerization average molecular weight 5000) 75% by weight glycerin 2.5% by weight 1,6-hexanediol 1.5% by weight Softanol 120 (Nonionic surfactant manufactured by Nippon Shokubai Co., Ltd.) 1% by weight 2-pyridinethiol-1-oxide sodium 5% by weight triethanolamine appropriate amount ion-exchanged water residual amount

Example 4 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow Recording Liquid 4] C.I. I. Acid Yellow 23 1% by weight C.I. I. Direct Yellow 86 1% by weight Glycerin 5% by weight Triethylene glycol 15% by weight Softanol 120 (Nippon Shokubai nonionic surfactant) 1% by weight Diethylene glycol monobutyl ether 3% by weight 2-pyridinethiol-1-oxide sodium 0.4% by weight Deionized water remaining

[0075] [Magenta recording liquid 4]   C. I. Reactive Red 180 2% by weight   C. I. Acid Red 52 1% by weight   Glycerin 5% by weight   Triethylene glycol 15% by weight   Softanol 120 (Nonionic surfactant made by Nippon Shokubai) 1% by weight   Diethylene glycol monobutyl ether 3% by weight   2-Pyridinethiol-1-oxide sodium 0.4% by weight   Deionized water remaining

[0076] [Cyan recording liquid 4]   C. I. Acid blue 249 2% by weight   C. I. Reactive Blue 7 1% by weight   Glycerin 5% by weight   Triethylene glycol 15% by weight   Softanol 120 (Nonionic surfactant made by Nippon Shokubai) 1% by weight   Diethylene glycol monobutyl ether 3% by weight   2-Pyridinethiol-1-oxide sodium 0.4% by weight   Deionized water remaining

[0077] [Black recording liquid 4]   Anionic surfactant dispersion type carbon black (manufactured by Fuji dye company)       Average particle size 110nm 5% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 2% by weight   2-Pyridinethiol-1-oxide sodium 0.4% by weight   Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 4 for recording material] Dimethyldiallylammonium chloride / SO ₂ copolymer (counter ion is nitrate ion: polymerization average molecular weight 10000) 10% by weight glycerin 5% by weight diethylene glycol 15% by weight 2-pyrrolidone 55% by weight ADEKA Pluronic L31 (Asahi Denka Co., Ltd. ethylene oxide-propylene oxide nonionic surfactant) 1% by weight sodium sorbate 1% by weight triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Example 5 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow recording liquid 5] C.I. I. Acid Yellow 23 1% by weight Projet Fast Yellow 2 (manufactured by Avisa) 1% by weight Glycerin 5% by weight Diethylene glycol 15% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 2% by weight sodium sorbate 0. 4% by weight deionized water remaining

[0080] [Magenta recording liquid 5]   C. I. Acid Red 52 1% by weight   Projet Fast Magenta 2 (manufactured by Abisha) 1% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 2% by weight   Sodium sorbate 0.4% by weight   Deionized water remaining

[0081] [Cyan recording liquid 5]   C. I. Acid Blue 91% by weight   Projet Fast Cyan 2 (manufactured by Abischa) 1% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 2% by weight   Sodium sorbate 0.4% by weight   Deionized water remaining

[0082] [Black recording liquid 5]   Sulfonic acid group-bonded carbon black dispersion average particle size 122 nm 5% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 2% by weight   Sodium sorbate 0.4% by weight   Deionized water remaining

Further, the following compositions were stirred and mixed to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 5 for recording material] diallylamine salt / SO ₂ copolymer (polymerization average molecular weight 15000) 50% by weight glycerin 5% by weight triethylene glycol 5% by weight 2-pyrrolidone 5% by weight sodium dehydroacetate 0.4% by weight % Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Example 6 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow Recording Liquid 6] C.I. I. Acid Yellow 23 1% by weight C.I. I. Direct Yellow 142 1% by weight Glycerin 5% by weight Diethylene glycol 15% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 1% by weight 2-ethyl-1,3-hexanediol 1% by weight Sunpack AP (San-ai petroleum fungicide) 0.4% by weight deionized water remaining

[0085] [Magenta Recording Liquid 6]   C. I. Acid Red 254 2% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

[0086] [Cyan recording liquid 6]   C. I. Acid blue 249 2% by weight   C. I. Direct Blue 199 1% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

[0087] [Black recording liquid 6]   Carboxyl group-bonded carbon black dispersion average particle size 128 nm                                                                 5% by weight   Glycerin 5% by weight   Diethylene glycol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 6 for recording material] Dimethyldiallylammonium chloride polymer (counter ion is chloride ion: polymerization average molecular weight 8000) 50% by weight glycerin 10% by weight Sunpack AP (antifungal agent manufactured by Sanai Petroleum) 0.4 Weight% Cation G-50 (Sanyo Chemical Co., Ltd. Alkyldimethylbenzylammonium chloride cation surfactant) 1 weight% Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Example 7 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow recording liquid 7] C.I. I. Acid Yellow 23 1% by weight C.I. I. Direct Yellow 86 1% by weight Glycerin 10% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 1% by weight 2-ethyl-1,3-hexanediol 1% by weight 2-pyrrolidone 2% by weight Sun Pack AP (san-ai oil fungicide) 0.4% by weight deionized water remaining

[0090] [Magenta recording liquid 7]   C. I. Reactive Red 180 2% by weight   C. I. Acid Red 52 1% by weight   Glycerin 10% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   2-pyrrolidone 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

[0091] [Cyan recording liquid 7]   C. I. Acid blue 249 2% by weight   C. I. Reactive Blue 7 1% by weight   Glycerin 10% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   2-pyrrolidone 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

[0092] [Black recording liquid 7]   Polymer dispersant-dispersed carbon black (manufactured by Dainichiseika Co., Ltd.)       Average particle size 118 nm 5% by weight   Glycerin 10% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   2-ethyl-1,3-hexanediol 1% by weight   2-pyrrolidone 2% by weight   Sunpack AP (san-ai oil antifungal agent) 0.4% by weight   Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, which was adjusted to have a pH of 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 7 for recording material] Polymer of allylamine salt (polymerization average molecular weight 20000) 50% by weight glycerin 5% by weight diethylene glycol 15% by weight Cation G-50 (Sanyo Kasei Co., Ltd. aralkyl dimethylbenzylammonium chloride cation surface-active agent) Agent) 1% by weight sodium dehydroacetate 0.4% by weight triethanolamine appropriate amount 2-pyrrolidone residual amount

Example 8 After mixing and stirring with the following formulation, the pH was adjusted to 9 with a 10% aqueous solution of lithium hydroxide. Then, the color recording liquid was filtered through a membrane filter having an average pore diameter of 0.1 μm, and the black recording liquid was filtered through a membrane filter having an average pore diameter of 0.8 μm to obtain a recording liquid. [Yellow recording liquid 8] C.I. I. Acid Yellow 23 1% by weight C.I. I. Direct Yellow 86 1% by weight Glycerin 5% by weight 1,5-Pentanediol 15% by weight Polyoxyethylene (3) sodium tridecyl ether acetate (anionic surfactant) 1% by weight Sodium dehydroacetate 0.4% by weight Ion-exchanged water Remaining amount

[0095] [Magenta recording liquid 8]   C. I. Reactive Red 180 2% by weight   C. I. Acid Red 52 1% by weight   Glycerin 5% by weight   1,5-Pentanediol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   Sodium dehydroacetate 0.4% by weight   Deionized water remaining

[0096] [Cyan recording liquid 8]   C. I. Acid blue 249 2% by weight   C. I. Reactive Blue 7 1% by weight   Glycerin 5% by weight   1,5-Pentanediol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   Sodium dehydroacetate 0.4% by weight   Deionized water remaining

[0097] [Black recording liquid 8]   Anionic microencapsulated carbon black (manufactured by Dainippon Ink and Chemicals)       Average particle size 125nm 5% by weight   Glycerin 5% by weight   1,5-Pentanediol 15% by weight   Polyoxyethylene (3) tridecyl ether sodium acetate       (Anionic surfactant) 1% by weight   Sodium dehydroacetate 0.4% by weight   Deionized water remaining

Further, the following compositions were mixed by stirring to prepare a pretreatment liquid for a recording material, and the pH was adjusted to 7 with triethanolamine. The viscosity at this time is shown in Table 1. [Pretreatment liquid 8 for recording material] Dialkylaminoethyl (meth) acrylate quaternary salt polymer (counter ion is nitrate ion: polymerization average molecular weight 10000) 50% by weight glycerin 10% by weight Sunpack AP (san-ai petroleum-proof mold Agent) 0.4% by weight Cation G-50 (Sanyo Kasei Co., Ltd. Alkyldimethylbenzylammonium chloride cationic surfactant) 2% by weight Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Next, with respect to the recording liquid and the pretreatment liquid for the recording material described in the above-mentioned examples, the pretreatment liquid for the recording material was applied to the my paper (N
Recording head 20 using laminated PZT having 128 nozzles with a diameter of 30 μm after being applied to BS Ricoh Co., Ltd.
With a droplet weight of 18 ng, printing was performed at a pixel density of 600 dpi and the following test was performed. The test results are shown in Table 1.

1) Image Density A solid image of the black recording liquid was printed, and after drying, the density of the solid image of the black recording liquid was measured by a reflection type color spectrophotometric densitometer (manufactured by X-Rite). 1.45 or more was marked with ⊚, 1.2 to 1.44 was marked with ◯, and less than 1.2 was marked with x.

2) Color boundary bleeding On the recording medium, magenta, cyan,
Black 0.5 mm line images were respectively formed, and the occurrence of color boundary bleeding that occurred when inks of different colors were adjacent to each other was visually observed. Similarly, the color is different when the magenta, yellow, and black 0.5 mm line images are formed in the cyan solid image and when the cyan, yellow, and black 0.5 mm line images are formed in the magenta solid image, respectively. The occurrence of boundary bleeding was observed. Almost no bleeding on the color boundary could be visually confirmed,
If there is no problem in practical use ◎, there is a slight occurrence of color boundary bleeding visually, △ if it is a level that may cause a problem depending on the usage condition such as small letters, and there is a visual occurrence of color boundary bleeding, usually When the use of was a problematic level, it was marked as x.

3) 0.5 mm line images of magenta, cyan, yellow, and black were respectively formed on the feathering recording medium, and the occurrence of feathering such as feathering along the wood fiber was observed with a 10 × magnifying glass. However, it can be confirmed when observed with a 10 times magnifying glass, but it is a level that can not be visually confirmed, ○ if there is no practical problem, it can be visually confirmed, and × if it is a problem level did.

4) Color tone Red, green, blue, yellow, magenta and cyan colors are printed, and after drying, the color tone is visually judged by 10 people. If it is a color tone that affects sharpness, it is marked as ×.

5) Reflection type color spectrophotometric densitometer (X-Rite)
A solid image was formed so that the density of each color of the recording liquid measured by the company) was 1.0. Visually observe this image from the back side, and if the colorant of the solid image is missing to the back side and it is at a level that cannot be used for double-sided printing, x, the colorant of the solid image is not missing to the back side, but the solid image and white background If the boundary of the part is clear and it is used for double-sided printing,
When the boundary between the solid image and the white background is almost unclear and there is no problem even if it is used for double-sided printing, ○, the boundary between the solid image and the white background is completely unclear, and there is no problem even if it is used for double-sided printing. When not present, it was judged as ◎.

6) Curl and Cockling When a solid image of the black recording liquid is printed and curling or cockling is scarcely observed, the result is ⊚. The case was rated as ◯, and the level that caused a problem in print quality was rated as x.

7) A solid image formed by the recording liquid of each color on a water-resistant recording medium is recorded at 30 ° C.
0.1 kg / cm after being immersed in the ion-exchanged water for 60 seconds
Press the filter paper with the pressure of ² . When the colorant does not transfer to the filter paper and there is no image bleeding, ◎, when the colorant slightly transfers to the filter paper, but when there is no image bleeding, ○, the colorant transfers to the filter paper, and image bleeding also occurs If yes, it was marked as x.

Next, the pretreatment liquid for the recording material described in the above example was set in the apparatus shown in FIG. 1 and the following tests were conducted. 8) Storability of pretreatment liquid for recording material While the pretreatment liquid for recording material is set in the apparatus of FIG.
It was left at 0 ° C. for 30 days, and after that, if it could be used without problems, it was marked with ◯, and if there was a problem, it was marked with ◯.

Comparative Example 1 A recording liquid was prepared in the same manner as in Example 1 and 1) to 5) were prepared in the same manner as in Example 1 except that the pretreatment liquid for the recording material was not used.
The test 7) was performed.

Comparative Example 2 A recording liquid was prepared in the same manner as in Example 2 and the same procedure as in Example 2 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

Comparative Example 3 A recording liquid was prepared in the same manner as in Example 3 and the same processes as in Example 3 were performed except that the pretreatment liquid for the recording material was not used, 1) to.
The tests 5) and 7) were performed.

COMPARATIVE EXAMPLE 4 A recording liquid was prepared in the same manner as in Example 4, and the same procedure as in Example 4 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

COMPARATIVE EXAMPLE 5 A recording liquid was prepared in the same manner as in Example 5, and the same procedure as in Example 5 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

Comparative Example 6 A recording liquid was prepared in the same manner as in Example 6 and the same procedure as in Example 6 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

Comparative Example 7 A recording liquid was prepared in the same manner as in Example 7, and the same procedure as in Example 7 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

Comparative Example 8 A recording liquid was prepared in the same manner as in Example 8 and the same procedure as in Example 8 was repeated except that the pretreatment liquid for the recording material was not used.
The tests 5) and 7) were performed.

Comparative Example 9 The pretreatment liquid for the recording material of Example 6 was jetted onto the recording material at a pixel density of 600 dpi by a recording head using a laminated PZT having 128 nozzles having a diameter of 30 μm. The recording liquid of each color in Example 6 was replaced with one nozzle having a diameter of 30 μm.
A recording head using a laminated PZT having 28 nozzles ejected onto a recording material with a droplet density of 18 ng and a pixel density of 600 dpi, and tests 1) to 8) were performed. The pretreatment liquid for the recording material was sprayed onto the portion of the recording material onto which the recording liquid of each color was sprayed.

Comparative Example 10 In the same manner as in Comparative Example 9 except that the pretreatment liquid 9 for the recording material was used in place of the pretreatment liquid for the recording material of Example 6,
The tests 1) to 8) were performed. The viscosity of this liquid is shown in Table 1. [Pretreatment liquid 9 for recording material] Dimethyldiallylammonium chloride polymer (counter ion is chloride ion: polymerization average molecular weight 8000) 2% by weight glycerin 10% by weight Sunpack AP (antifungal agent manufactured by Sanai Petroleum) 0.4 Weight% Cation G-50 (Sanyo Chemical Co., Ltd. Alkyldimethylbenzylammonium chloride cation surfactant) 1 weight% Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Comparative Example 11 The procedure of Comparative Example 9 was repeated except that the pretreatment liquid 10 for the recording material was used in place of the pretreatment liquid for the recording material of Example 6.
The tests 1) to 8) were performed. The viscosity of this liquid is shown in Table 1. [Pretreatment liquid 10 for recording material] Dimethyldiallylammonium chloride polymer (counter ion is chloride ion: polymerization average molecular weight 2000) 1% by weight glycerin 10% by weight Sunpack AP (antifungal agent manufactured by San-ai Petroleum) 0.4 Weight% Cation G-50 (Sanyo Chemical Co., Ltd. Alkyldimethylbenzylammonium chloride cation surfactant) 1 weight% Triethanolamine Appropriate amount Ion-exchanged water Remaining amount

Examples 9 to 18 Using the inks described in Example 6 and the pretreatment liquid for the recording material, the following recording media were subjected to the tests 1) to 7). The test results are shown in Table 1. Example 9: Xerox Paper R; Xerox Paper R
(Size 8s, Air permeability 20s) Example 10: AUSTRALIAN PAPER (Australia); REFLE
X (Size 25s, Air permeability 4s) Example 11: NBS Ricoh Co., Ltd .; NBS copy printing paper 90K (Size 60s, air permeability 68s) Example 12: Canon PB paper (Size 21s, Air permeability 8s) Example 13: NBS Ricoh Co., Ltd .; NBS copy printing paper 45K (size degree 11s, air permeability 45s) Example 14: Honshu Paper Co., Ltd .; Yamayuri (size degree 12s, air permeability 21s) Example 15: manufactured by Ricoh Co., Ltd .; paper source PPC paper type S
(Size: 22 s, Air permeability: 13 s) Example 16: Xerox Co .; P paper (Size: 24 s, Air permeability 19 s) Example 17: Xerox: Multi Ace (Size: 25 s, Air permeability 17 s) Example 18: Xerox 4024 manufactured by Xerox Co.
Paper (size 32s, air permeability 21s)

[0120]

[Table 1]

[0121]

(1) Effect of claim 1 In the pretreatment liquid for a recording material according to claim 1, the cation degree (colloid equivalent value by the polyvinyl potassium sulfate reagent) defined in the present specification is 3 to. 7 meq / g (pH 4.
By including the cationic resin of 0), it is possible to obtain an image that is remarkably improved, such as feathering and boundary bleeding, image density improvement, strikethrough density reduction, etc., regardless of the recording material type. .

(2) Effect of claim 2 In the pretreatment liquid for a recording material according to claim 2, since the content of the cationic resin is in the range of 10 to 80% by weight, only a small amount of use is required. It is possible to achieve both the reproducibility of fine lines, the reduction of feathering and color boundary blurring, the improvement of image density, the reduction of strike-through density, and the curling of the recording material and the suppression of cockling. Further, it is difficult for the physical properties to change due to the influence of the use environment, and stable characteristics can be obtained for a long time.

(3) Effect of claim 3 In the pretreatment liquid for a recording material according to claim 3, the viscosity at 25 ° C. is in the range of 10 to 10000 mPa · s, so that the recording material can be stably applied. In addition, since it can be kept near the surface of the recording material, the required amount of pretreatment liquid can be reduced, and the curl and cockling of the recording material can be prevented and the image quality can be greatly improved. You can

(4) Effect of claim 4 In the pretreatment liquid for the recording material of claim 4, the cation degree (colloid equivalent by polyvinyl potassium sulfate reagent) defined in the text when diluted 2000 times with ion-exchanged water is used. value)
Is 1 to 5 meq / g (pH 4.0),
Regardless of the type of recording material, it is possible to suppress feathering, boundary bleeding, and the like, and obtain an image that is significantly improved, such as improved image density and reduced strikethrough density.

(5) Effect of claim 5 In the pretreatment liquid for a recording material according to claim 5, water is added in an amount of 5 to 8
By containing 0% by weight, the cationic resin can be stably and uniformly dissolved, and feathering can be reduced.

(6) Effect of claim 6 The pretreatment liquid for a recording material according to claim 6 contains a water-soluble organic solvent in an amount of 5 to 70% by weight, whereby the effect of stabilizing the viscosity by suppressing evaporation is obtained. In addition, the cationic resin can be dissolved stably and uniformly, and the image quality such as feathering can be improved.

(7) Effect of claim 7 The pretreatment liquid for a recording material according to claim 7 contains 0.1 to 5% by weight of an antiseptic / antifungal agent, and Contamination of the processing liquid can be prevented, and thus a stable image quality improving effect can be obtained even after long-term use.

(8) Effect of claim 8 In the ink jet recording method of claim 8, after applying the pretreatment liquid according to any one of claims 1 to 6 to the recording material by the abutting means for contacting, the pretreatment liquid is applied. Printing with the recording liquid before drying increases the reactivity between the cationic resin and the anionic component in the recording liquid, and increases the reaction efficiency. It is possible to improve image quality without causing curling or cockling of the recording material.

(9) Effect of Claim 9 In the ink jet recording method of Claim 9, the anionic component which reacts with the cationic resin in the pretreatment liquid is a pigment in which an anionic dye or an anionic dispersant is dispersed. Alternatively, since it is either a dye, a pigment having an anionic group, or anionic colored fine particles, the coloring component in the recording liquid will effectively stay on the recording material due to the reaction with the cationic resin. It is possible to improve and reduce the strikethrough density.

(10) Effect of Claim 10 In the ink jet recording method of Claim 10, since the abutting applying means is the roller applying means, it becomes possible to uniformly apply the high-concentration cationic resin. ,
The applying means can be manufactured at low cost.

(11) Effect of Claim 11 In the ink jet recording method of Claim 11, the amount of the pretreatment liquid deposited on the recording material is 0.5 g / m ^{2 to} 10 g /
Since it is m ² , curling and cockling to the recording material can be suppressed, and a sufficient image quality improving effect can be obtained.

As described above, the present invention provides a pretreatment liquid having very excellent characteristics. Since the pretreatment liquid has a high viscosity, the pretreatment liquid can be applied by being brought into contact with the recording material, and its excellent characteristics can be obtained.
That is, by using a high-concentration cationic resin and a high-viscosity pretreatment liquid, a high-concentration and thin layer is deposited, so that the cationic resin stays in the vicinity of the surface with a small amount of adhesion and the image quality is significantly improved. The curling and cockling of the recording material can be suppressed. Further, since the pretreatment liquid is applied to the recording material in advance, it is possible to uniformly obtain a good image regardless of the type and characteristics of the recording material.

[Brief description of drawings]

FIG. 1 is a side sectional view of an apparatus showing an example of an embodiment of the present invention.

FIG. 2 is a side sectional view of an apparatus showing another example of the embodiment of the present invention.

FIG. 3 shows an example of a sequence for carrying out the inkjet recording method of the present invention.

FIG. 4 is another example of a sequence for carrying out the inkjet recording method of the present invention.

[Explanation of symbols]

1 Pretreatment Liquid 2 Film Thickness Control Roller 3 Pumping Roller 4 Coating Roller 5 Counter Roller 6, 17 Paper 7, 18 Paper Feeding Roller 8 Paper Feeding Tray 11, 12, 13, 14, 15, 16, 32, 33 Paper Feeding Roller 20 Recording head 21 Ink cartridge 22 Carriage shaft 23 Carriage 31 Paper guide 34 Paper return guide

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobutaka Nagata             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Keiji Murakami             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Nobuyo Nagai             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2C056 EA13 HA42                 2H086 BA01 BA02 BA53 BA59 BA61                       BA62                 4J039 AD03 AD04 AD08 AD09 AD15                       BC09 BC13 BC50 BE01 BE02                       BE12 BE19 BE22 CA06 GA24

Claims (11)

[Claims] 1. Before forming an image by ejecting a recording liquid containing an anionic component as a droplet and adhering it to a recording material, before applying the recording liquid to the recording material by an application means that contacts the recording material. The treatment liquid is a component that insolubilizes the anionic component in the recording liquid and has a cation degree (colloidal equivalent value by the polyvinyl potassium sulfate reagent) of 3 to 7 meq / g.
A pretreatment liquid for a colorless or light-colored recording material, which contains a cationic resin (pH 4.0). 2. The content of the cationic resin is 10-8.
The pretreatment liquid for a recording material according to claim 1, wherein the pretreatment liquid is 0% by weight. 3. A viscosity of 10 to 10,000 mPa · s (2
3. The pretreatment liquid for a recording material according to claim 1, wherein the pretreatment liquid is 5 ° C.). 4. The recording material according to claim 1, which has a colloid equivalent value of 1 to 5 meq / g (pH 4.0) when diluted 2000 times with ion-exchanged water. Pretreatment liquid. 5. The pretreatment liquid for a recording material according to claim 1, wherein the pretreatment liquid contains 5 to 80% by weight of water. 6. The pretreatment liquid for a recording material according to claim 1, which contains a water-soluble organic solvent in an amount of 5 to 70% by weight. 7. The pretreatment liquid for a recording material according to claim 1, wherein the preservative and antifungal agent is contained in an amount of 0.1 to 5% by weight. 8. After applying the pretreatment liquid according to any one of claims 1 to 7 to a recording material by an applying means that abuts,
Apply the recording liquid to the recording material before the pretreatment liquid dries,
An ink jet recording method, which comprises insolubilizing an anionic compound in a recording liquid. 9. The anionic compound in the recording liquid according to claim 8 is at least selected from an anionic dye, a pigment or dye dispersed with an anionic dispersant, a pigment having an anionic group, and anionic colored fine particles. An ink jet recording method, which is one colorant. 10. The ink jet recording method according to claim 8, wherein the abutting application means is roller coating. 11. A method of applying a pretreatment liquid for a recording material to the recording material.
Wearing amount is 0.5g / m ²-10g / m²Is characterized by
The inkjet according to any one of claims 8 to 10.
Recording method.