JP2003285539A - Ink jet recording method and recorded image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink jet recording method capable of recording an image free from bleeding in boundary of the image and has small change in density and color of the image after an elapse of time as compared with those of the image just printed out, and a recorded image using the same. <P>SOLUTION: The ink jet recording method records on a recording body provided with an ink receiving layer on a water impermeable substrate by using an ink jet recording ink containing 5 to 50 mass% of a water-soluble organic solvent. The ink contains at least water, a water-soluble dye and the water-soluble organic solvent. The water-soluble organic solvent comprises at least 80 mass% of a water-soluble organic solvent having a flash point of 120 to 160°C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inkjet recording method and a recorded image used in a printer or the like.

[0002]

2. Description of the Related Art Ink-jet recording is a technique for ejecting minute droplets of ink to adhere to a recording sheet such as paper by various operating principles to record images, characters, etc. It has advantages such as noise and easy multicoloring.

With respect to clogging and maintenance of nozzles, which has been a problem in this system, the improvement has been made from both aspects of ink and apparatus, and it is now rapidly spreading to various fields such as various printers and facsimiles. .
The details are described in, for example, the trend of inkjet recording technology (edited by Koichi Nakamura, published by Nippon Kagaku Information Co., Ltd., March 31, 1995).

However, in the ink jet recording method, bleeding at the image boundary due to the penetration of ink into the recording medium becomes a problem. Inkjet recording body (recording paper)
For this purpose, various recording materials have been used. For example, plain paper, various coated papers in which a layer composed of a hydrophilic binder and an inorganic pigment is coated on a paper support (art paper, coated paper, cast coated paper, etc.), and further, these papers, transparent or opaque There is used a recording paper in which an ink receiving layer is coated as a recording layer on various plastic film supports or various supports in which both surfaces of paper are coated with a plastic resin.

Among them, a recording paper in which an ink receiving layer is coated as a recording layer on a paper, various transparent or opaque plastic film supports, or a support in which both sides of paper are coated with a plastic resin is used. Because it does not absorb, cockling (wrinkles) does not occur during printing,
High-quality images can be obtained.

The ink receiving layer is roughly classified into a so-called swelling type ink receiving layer mainly composed of a hydrophilic binder and a void type ink receiving layer having a void layer in the recording layer.

The void type ink receiving layer exhibits high ink absorbability because it has voids in the recording layer. For this reason, beading of an image is less likely to occur in a region where the ink ejection amount is larger than that in the swelling type, and thus the image quality is less deteriorated in a high image density region and is used in many scenes.

If the void-type ink receiving layer has a sufficient void volume with respect to the amount of ink, at least the surface of the void will appear dry immediately after printing even if the organic solvent remains in the void structure. It is also possible to roll it into a cylinder or stack prints on top of each other. Needless to say, the rolls are stored in a tubular shape or the prints are piled up and stored together with the high speed and large size of inkjet printing.
This is an important performance for an inkjet recording material.

Further, as an ink jet recording image,
The density of the printing dots is high, the color tone is bright and vivid, the absorption of the ink is fast, and the printing liquid does not flow or bleed even when the printing dots overlap.
Diffusion of printing dots in the horizontal direction of the image is not excessively large, and the periphery is smooth and does not blur (that is, there is no blur of the image). It is generally required that no change occurs, and these requirements are particularly great when used as a color proof.

When attention is paid to the relationship between the passage of time after printing and changes in color and density, the following points can be inferred as one of the causes. That is, the coloring material and the recording material in the ink are
It is known that the color tone changes with the evaporation of the volatile components in the recording liquid, and it is presumed that this causes the concentration and hue of each color to change with time.

As described above, such a phenomenon is caused by the fact that the printed images are overlapped with each other due to the high speed of the ink jet printing.
It is often rounded, but in that case, a color difference is likely to occur between the overlapped portion and the non-overlapped portion.

Further, with the increase in the size of ink jet printing, the size of the printed image is also increased. When the length of one side becomes 364 mm or more (the short side of B4 size), the printed image is often rolled and stored. A difference in color tone is likely to occur between the part exposed to the outside air and the part not exposed to the outside air.

Further, when the densities change at the same speed and at the same speed for each color, the color variation of the formed image is not noticeable, but when the balance of the densities of the respective colors is lost, the color variation becomes noticeable. It is estimated that the color changes with time.

Further, if there are so-called dark and light inks of the same color but different densities, and the densities of the dark color ink and the light color ink change, and the changing speeds are different, the dark color ink is formed over time after printing. There is also a problem (tone jump) that the gradation of the high density portion and the gradation of the low density portion formed by the light color ink are not connected, which causes deterioration of image quality over time.

As described above, it has been found that it is an important problem to reduce the fluctuation of the image density and the fluctuation of the color between the image immediately after printing and the aged image.

Further, when the recording medium is rolled and stored, it is necessary that the recording medium does not crack and the ink receiving layer does not come off.

Further, it is important that there is no fading even after being placed in a bright place for a long time after image formation. Especially, in the case of a multicolor image, fading does not occur uniformly, and a specific color is not fading much. However, if the fading of another color is severe, the color balance is lost and the image deterioration due to fading becomes more conspicuous.

[0018]

As described above, in the ink jet recording method, not only the portion exposed to the outside air and the outside air not exposed are bleeding at the image boundary due to the ink seeping into the recording medium. Color tone difference easily occurs in the part. Further, when the density changes at the same speed for each color, the color variation of the formed image is not noticeable, but when the balance of the density of each color is lost, the color variation becomes noticeable. It is presumed that color variation will occur.

When so-called dark and light inks having the same color but different densities are used, if the dark ink and the light ink have different densities and the changing speeds are different, the dark ink is formed with the lapse of time after printing. And the gradation of the high density part
There is also a tone jump in which the gradation of the low density portion formed by the light color ink is not connected, which causes deterioration of image quality over time.

Therefore, the stability of the image over time is an important issue. An object of the present invention is to provide an ink jet recording method having no image boundary blurring, an image immediately after printing and an aged image with little fluctuation in image density and color tone, and a recorded image using the same. is there.

[0021]

The inventors of the present invention have found that the variation in color of an image printed on a recording material having an ink receiving layer on a water-impermeable support is caused by the change of the water-soluble organic solvent in the ink. It was found that the higher the flash point is, the less likely it is to occur.

Further, the present inventors have found that the bleeding of an image printed on a recording medium having an ink receiving layer on a water-impermeable support is less likely to occur as the flash point of the water-soluble organic solvent in the ink is lower. Found.

Further, as a result of earnest studies, the inventors of the present invention have defined the range of the flash point of the water-soluble organic solvent in the ink and the amount of the water-soluble organic solvent in the ink, and It has become possible to solve the problems in the ink jet recording method such as the color variation of an image printed on a recording medium having an ink receiving layer on a transparent support, image bleeding, and fading during storage.

That is, the object of the present invention is achieved by adopting one of the following constitutions. [1] A recording material having an ink receiving layer on a water-impermeable support contains at least water, a water-soluble dye, and a water-soluble organic solvent, and 80% by mass or more of the water-soluble organic solvent has a flash point of 120. An ink jet recording method comprising recording using an ink jet recording ink which is a water soluble organic solvent at ˜160 ° C. and the amount of water soluble organic solvent in the ink is 5 to 50% by mass.

[2] The amount of the water-soluble organic solvent is 10 to 3
The inkjet recording method according to [1], wherein the content is 5% by mass.

[3] The ink receiving layer comprises at least a void-type ink receiving layer formed of a hydrophilic binder and inorganic fine particles on a water-impermeable support [1] or The inkjet recording method according to [2].

[4] The water-impermeable support is RC
(Resin coated) support or resin film support, The ink jet recording method described in any one of [1] to [3].

[5] The ink jet recording method according to any one of [1] to [4], wherein the ink is composed of two or more kinds of ink jet recording ink having density characteristics.

[6] The ink comprises an inkjet recording ink set containing at least a yellow inkjet recording ink, a magenta inkjet recording ink, a cyan inkjet recording ink, and a black inkjet recording ink. The inkjet recording method according to any one of [1] to [5].

[7] The inkjet recording method according to [6], wherein in the inkjet recording ink set, the amount of the water-soluble organic solvent in all inks is 10 to 35% by mass.

[8] The ink jet recording ink contains at least one compound represented by the general formulas (1) to (5) or a water-soluble copper phthalocyanine compound as a water-soluble dye. [1] to [7]
The inkjet recording method according to any one of 1.

[0032]

[9] 30-80% of the ink receiving layer
The ink jet recording method according to any one of [1] to [8], which comprises a void type receiving layer having a void ratio of.

[10] Recording and writing are performed by an on-demand method [1]-

The inkjet recording method according to any one of [9].

[11] The inkjet recording method described in any one of [1] to [10], wherein the recording / writing is performed by ejecting an inkjet recording ink by an electromechanical conversion method.

[12] Any one of [1] to [10], wherein the recording / writing is performed by ejecting ink for ink jet recording by an electric / heat conversion system.
Inkjet recording method according to item.

[13] 720 dpi (dot, power,
Inch; 1 inch is about 2.54 cm, and the recording density is not less than the number of pixel dots that can exist in the width) and not more than 2880 dpi, and the droplet volume is not less than 0.1 pl and less than 10 pl. The inkjet recording method according to any one of [1] to [12].

[14] The length of one side of the recording medium is 364 m
The inkjet recording method according to any one of [1] to [13], wherein the inkjet recording method is m or more.

[15] Any one of [1] to [14]
A recorded image recorded by using the inkjet recording method described in the item.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

[Support] As the water-impermeable support used in the present invention, a plastic resin film support,
Alternatively, a support (resin coated or RC support) in which both surfaces of paper are coated with a plastic resin film can be mentioned.

As the plastic resin film support, for example, polyester film, diacetate film, triacetate film, polyolefin film, alkyl film, polycarbonate film, polyvinyl chloride film, polyimide film, cellophane, Celluloid and the like or laminated films of these are mentioned. These resin films are usually transparent or semitransparent.

On the other hand, as a water-impermeable support in which one or both sides of paper which is a water-permeable support is coated with a plastic resin, preferably a support in which both sides of paper are coated with a polyolefin resin, It is a so-called RC paper.

Hereinafter, a support in which both surfaces of paper, which is a preferred support in the present invention, are coated with a polyolefin resin, that is, RC paper will be described.

The paper used for the support of the present invention is made of wood pulp as a main raw material, and if necessary, synthetic paper such as polypropylene is used in addition to wood pulp. LBKP, LBSP, NBKP, NBS as wood pulp
Any of P, LDP, NDP, LUKP and NUKP can be used, but LBKP and NBS with a large amount of short fibers
It is preferable to use more P, LBSP, NDP, and LDP. However, the ratio of LBSP and / or LDP is preferably 10 to 70%. As the above-mentioned pulp, a chemical pulp containing few impurities (sulfate pulp or sulfite pulp) is preferably used, and a pulp whose whiteness is improved by bleaching is also useful.

In the paper, for example, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancers such as starch, polyacrylamide and polyvinyl alcohol, and fluorescent whitening. Agents, dispersants, softening agents such as quaternary ammonium, and the like can be added as appropriate.

The freeness of pulp used for papermaking is CSF.
Is preferably 200 to 500 ml, and the fiber length after beating is preferably 30 to 70% of the sum of 24 mesh residue and 42 mesh residue defined in JIS P 8207. The 4-mesh residue is preferably 20% or less.

The basis weight of the paper is preferably 50 to 250 g, and particularly preferably 70 to 200 g. The paper thickness is 50
˜210 μm is preferable.

The paper can be given a high smoothness by calendering at the papermaking stage or after the papermaking. Paper density is 0.7
~ 1.2 g / m ² (JIS P 8118) is common. Further, the stiffness of the base paper is preferably 20 to 200 g under the conditions specified in JIS P 8143.

A surface sizing agent may be applied to the surface of the paper, and as the surface sizing agent, the same sizing agent that can be added to the base paper can be used.

The pH of the paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS P8113.

Next, the polyolefin resin coating both sides of this paper will be described. Examples of the polyolefin resin used for this purpose include polyethylene, polypropylene, polyisoprene, and polyethylene, but polyolefins such as ethylene- and propylene-based copolymers are preferable, and polyethylene is particularly preferable.

The particularly preferred polyethylene will be described below. The polyethylene that covers the front and back of the paper is mainly low-density polyethylene (LDPE) and / or
Alternatively, high density polyethylene (HDPE) may be used, but other LLDPE, polypropylene or the like may be partially used.

Particularly, for the polyolefin layer on the coating layer side, rutile or anatase type titanium oxide is added thereto,
Those with improved opacity and whiteness are preferred. The titanium oxide content is generally 1 to 20% by mass, preferably 2 to 15% by mass, based on the polyolefin. A coloring pigment having high heat resistance and a fluorescent brightening agent for adjusting the white background can be added to the polyolefin layer.

Examples of color pigments include ultramarine blue, navy blue,
Examples include cobalt blue, phthalocyanine blue, manganese blue, cerulean, tungsten blue, molybdenum blue, and anthraquinone blue.

Examples of the fluorescent whitening agent include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, and the like. Dialkyl stilbene etc. are mentioned.

The amount of polyethylene used on the front and back of the paper is selected so as to optimize the film thickness of the ink absorbing layer and the curl at low and high humidity after providing the back layer, but generally the polyethylene layer is used. Is 15 to 50 μm on the ink absorption layer side.
m and 10 to 40 μm on the back layer side. The ratio of polyethylene on the front and back sides is preferably set so as to adjust the curl that changes depending on the type and thickness of the ink receiving layer, the thickness of the inner paper, etc. Usually, the ratio of polyethylene on the front and back sides is about the thickness. It is 3/1 to 1/3.

Furthermore, it is preferable that the polyethylene-coated paper support has the following characteristics 1) to 8).

1) The tensile strength is JIS P 811.
The strength defined by 3 is preferably 19.6 to 294N in the vertical direction and 9.8 to 196N in the horizontal direction.

2) The tear strength is JIS P 811
0.20 to 2.94N in the longitudinal direction with the strength specified by 6.
The lateral direction is preferably 0.098 to 2.45N.

3) The compressive elastic modulus is preferably 9.8 kN / cm ² . 4) The opacity is preferably 80% or more, and particularly preferably 85 to 98% when measured by the method specified in JIS P8138.

5) As for whiteness, L ^* , a ^* , and b ^* defined by JIS P 8727 are L ^* = 80 to 96, a ^* = − 3 to
It is preferable that +5 and b ^* =-7 to +2.

[0062] 6) Clark stiffness, the support Clark stiffness in the carrying direction is 50~300cm ^2/100 of the recording paper is preferred.

7) The water content in the base paper is 4 to 1 with respect to the inside paper.
0% is preferable. 8) Gloss provided with ink receiving layer (75 degree specular gloss)
Is preferably 10 to 90%.

[Water-soluble dye] Examples of the water-soluble dye in the present invention include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes and diphenylmethane dyes. The invention can be used in combination with these. Among these, the compounds of the above general formulas (1) to (5) and the phthalocyanine dye (compound) are particularly desirable. Specific examples of water-soluble dye compounds are shown below. However, the compounds are not limited to these exemplified compounds.

First, the general formula (1) will be described. In the formula of the general formula (1), R ₁ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include an alkyl group (for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms). Groups), aromatic groups (eg, phenyl groups,
Naphthyl group, etc.), heterocyclic group (for example, 5- or 6-membered heterocyclic group having at least one atom selected from nitrogen atom, oxygen atom, and sulfur atom), alkoxy group (for example,
A linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms), an aryloxy group (eg a phenoxy group, a naphthyloxy group etc.), an acylamino group (eg a carbon number 1)
-10 alkanoylamino group, benzoylamino group, etc., acyloxy group (for example, alkanoyloxy group having 1 to 10 carbon atoms, benzoyloxy group, etc.), acyl group (for example, alkanoyl group having 1 to 10 carbon atoms, benzoyl group) Etc.), carbamoyl group (for example, unsubstituted carbamoyl group, alkylcarbamoyl group having 1 to 10 carbon atoms, dialkylcarbamoyl group having 2 to 20 carbon atoms, 7 to 2 carbon atoms)
0 N-alkyl-N-phenylcarbamoyl group, etc.),
Alkoxycarbonyl group (eg, alkoxycarbonyl group having 1 to 10 carbon atoms), sulfonylamino group (eg, alkanesulfonylamino group having 1 to 10 carbon atoms, benzenesulfonylamino group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl) Group, alkylsulfamoyl group having 1 to 10 carbon atoms, dialkylsulfamoyl group having 2 to 20 carbon atoms, N-alkyl-N- having 7 to 20 carbon atoms
Phenylsulfamoyl group, etc.), hydroxyl group, sulfonyl group (for example, alkanesulfonyl group having 1 to 10 carbon atoms, benzenesulfonyl group, etc.), alkylthio group (for example, alkylthio group having 1 to 10 carbon atoms), arylthio group (Eg, phenylthio group, etc.), ureido group (eg, unsubstituted ureido group, alkylureido group having 1 to 10 carbon atoms, dialkylureido group having 2 to 20 carbon atoms, phenylureido group, etc.), urethane group (eg, carbon Number 1
-10 alkoxycarbonylamino group, etc.), cyano group, sulfonic acid group and its salt, cyano group, carboxyl group and its salt, nitro group, amino group (for example, unsubstituted amino group, alkylamino having 1 to 10 carbon atoms) Base, carbon number 2
~ 20 dialkylamino group, anilino group, carbon number 7 ~
20 N-alkylanilino group, etc.), a mercapto group, or a halogen atom (eg, fluoro group, chloro group, bromo group, iodo group, etc.) and the like. R ₁ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₁ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

R ₂ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₂ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₂ is preferably a hydrogen atom, an alkyl group or an alkoxyl group.

M represents an integer of 1 to 5. n represents an integer of 1 to 4.

J represents a carbonyl group or a group represented by the above general formula (6). In the formula (6), R ₃ represents a substitutable substituent, for example, a hydroxyl group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkylamino group (eg, the number of carbon atoms). 1-10 alkylamino group, 2-20 carbon dialkylamino group, 1-10 carbon alkanolamino group, 2 carbon atoms
~ 20 alkanolamino groups, etc.), morpholino groups, piperazino groups, etc., including hydroxyl groups, fluorine atoms, chlorine atoms,
Ethanolamino group, diethanolamino group and morpholino group are preferred.

In the present invention, among the compounds represented by the general formula (1), the compounds shown below are particularly preferably used, and the light resistance of the ink jet image formed thereby can be further improved, and the ink jet The image quality can be improved.

[0070]

[Chemical 8]

Next, the general formula (2) will be described. In the formula of the general formula (2), R ₄ represents a hydrogen atom or a substitutable substituent, and the substitutable substituent is R ₁
Examples of the substitutable substituents described in 1. R ₅ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ .
R ₄ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₄ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

R ₅ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₅ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₅ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

G represents an integer of 1 to 5. h represents an integer of 1 to 5.

In the present invention, among the compounds represented by the general formula (2), the compounds shown below are particularly preferably used, and the light resistance of the ink jet image formed by them can be further improved, and the ink jet The image quality can be improved.

[0075]

[Chemical 9]

Next, the general formula (3) will be described. In the formula (3), R ₆ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₆ further includes a fused ring with a benzene ring (for example, a naphthalene ring, together with two or more adjacent carbon atoms on the benzene ring to be substituted,
Anthracene ring, quinoline ring, benzimidazole ring,
Benzthiazole ring, benzoxazole ring, etc.) and may be further substituted with a substitutable substituent.
R ₆ is preferably a hydrogen atom.

R ₇ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₇ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₇ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

R ₈ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₈ is preferably a hydrogen atom or a phenylcarboxyl group.

R ₉ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₉ is preferably a hydrogen atom or an alkyl group.

R ₁₀ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₁₀ is further a condensed ring with a benzene ring (for example, a naphthalene ring, an anthracene ring, a quinoline ring, a benzimidazole ring, a benzthiazole ring, a benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₁₀ is preferably a hydrogen atom or an aryloxy group.

P represents an integer of 1 to 4. q represents an integer of 1 to 5.

In the present invention, among the compounds represented by the general formula (3), the compounds shown below are particularly preferably used, and the light resistance of the ink jet image formed thereby can be further improved, and the ink jet The image quality can be improved.

[0083]

[Chemical 10]

Next, the general formula (4) will be described. In the formula (4), R ₁₁ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₁₁ further includes a fused ring with a benzene ring (for example, a naphthalene ring, together with two or more adjacent carbons on the benzene ring to be substituted,
Anthracene ring, quinoline ring, benzimidazole ring,
Benzthiazole ring, benzoxazole ring, etc.) and may be further substituted with a substitutable substituent.
R ₁₁ is preferably a hydrogen atom.

X represents a phenyl group or a naphthyl group, and is a substitutable substituent (eg, an alkyl group, an alkoxy group,
Aryloxy group, hydroxyl group, alkylthio group, arylthio group, mercapto group, sulfonyl group, sulfonic acid group and salts thereof, carboxyl group and salts thereof, amino group, alkylamino group, dialkylamino group, acylamino group,
Sulfonylamino group, ureido group, thioureido group, urethane group, oxamide group, carbamoyl group, sulfamoyl group, aryl group, heterocyclic group, cyano group, nitro group,
It may be substituted with a halogen atom or the like), and is preferably substituted with a sulfonic acid group and a salt thereof or a carboxyl group and a salt thereof.

Y represents hydrogen ion, sodium ion, potassium ion, lithium ion, ammonium ion or alkylammonium ion.

R represents an integer of 1 to 4. s represents an integer of 1 or 2.

R + s = 5. Z represents a substitutable substituent, represents a carbonyl group, a sulfonyl group or a group represented by the general formula (7), and preferably a group represented by the general formula (7).

In the formula (7), W ₁ and W ₂ represent halogen atoms, amino groups, hydroxyl groups, alkylamino groups and arylamino groups which may be different from each other. preferable.

In the present invention, among the compounds represented by the general formula (4), the compounds shown below are particularly preferably used, and the light resistance of the ink jet image formed thereby can be further improved, and the ink jet The image quality can be improved.

[0091]

[Chemical 11]

[0092]

[Chemical 12]

Next, the general formula (5) will be described. In the formula (5), R ₁₂ represents a hydrogen atom or a substitutable substituent, and the substitutable substituent is R
_The substitutable substituents described in ₁ are included. R ₁₂ is further a condensed ring with a benzene ring (for example, a naphthalene ring, an anthracene ring, a quinoline ring, a benzimidazole ring, a benzthiazole ring, a benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and is further substituted with a substitutable substituent. R ₁₂ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

R ₁₃ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₁₃ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and may be further substituted with a substitutable substituent, and a sulfonic acid group and a salt thereof and a carboxyl group and a salt thereof are preferable. R ₁₃ is preferably an alkyl group or an alkoxy group.

R ₁₄ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include the substitutable substituents described for R ₁ . R ₁₄ is further a condensed ring with a benzene ring (for example, a naphthalene ring, anthracene ring, quinoline ring, benzimidazole ring, benzthiazole ring, benzoxazole ring) together with two or more adjacent carbon atoms on the benzene ring to be substituted. Etc.) and may be further substituted with a substitutable substituent, and a sulfonic acid group and a salt thereof and a carboxyl group and a salt thereof are preferable. R ₁₄ is preferably a sulfonic acid group and its salt, or a carboxyl group and its salt.

R ₁₅ represents a hydrogen atom or a substitutable substituent, and examples of the substitutable substituent include an alkyl group (for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms) and an aromatic group. (Eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, at least one nitrogen atom,
5 or 6 having an atom selected from oxygen atom and sulfur atom
Membered heterocyclic group), an acyl group (for example, having 1 to 10 carbon atoms)
Alkanoyl groups, benzoyl groups, etc.), sulfonyl groups (eg, alkanesulfonyl groups having 1 to 10 carbon atoms, benzenesulfonyl groups, etc.) and the like. R ₁₅ is preferably a hydrogen atom or an acyl group.

T represents an integer of 1 to 5. u represents an integer of 1 to 4.

W represents an integer of 1 to 5. In the present invention, among the compounds represented by the general formula (5), it is particularly preferable to use the compounds shown below, which can further improve the light resistance of the inkjet image formed by the compounds, and the quality of the inkjet image. Can be increased.

[0099]

[Chemical 13]

The water-soluble copper phthalocyanine compound in the present invention is a copper phthalocyanine compound containing a water-soluble group, and the water-soluble group may be directly bonded to the phthalocyanine skeleton or may be bonded via a joint. Well, it may have a plurality of water-soluble groups. Further, it may have a substituent other than the water-soluble group. Specific examples of the water-soluble group include a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a hydroxyl group, and an ethylene oxide group. Preferred water-soluble groups include sulfonic acid groups or carboxylic acid groups,
Particularly preferred is a sulfonic acid group.

Specific examples of the water-soluble copper phthalocyanine compound include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199 and the like can be mentioned, but the present invention is not limited thereto.

The content of the water-soluble dye is 0.1 to 2
It is possible to select in the range of 0% by mass, and in order to obtain a photographic image, it is preferable to prepare and use so-called dark and light ink in which the dye contents are changed. Also, if necessary, red,
It is also preferable in terms of color reproduction to use special color inks such as green and blue.

[Water-Soluble Organic Solvent] The flash point of the water-soluble organic solvent is described in the guidebook for dangerous materials of the “Tokyo Disaster Prevention Guidance Association”, and the flash point that can be used in the present invention is 95 to 180 ° C. Examples of the water-soluble organic solvent include ethylene glycol (flash point 111.1 ° C.), glycerin (flash point 177 ° C.), diethylene glycol (flash point 123.
9 ° C), triethylene glycol (flash point 176.7)
℃), tripropylene glycol (flash point 130 ℃),
Triethylene glycol monomethyl ether (flash point 1
18 ° C.), 2-pyrrolidone (flash point 129 ° C.), and the like, but are not limited to the water-soluble organic solvents exemplified above. It can also be measured by the method described in "Government Ordinance on Regulation of Dangerous Goods" of "Fire Defense Law".

In the present invention, 8 in a water-soluble organic solvent is used.
0% by mass or more is the water-soluble organic solvent having a flash point of 120 to 160 ° C., and the amount of the water-soluble organic solvent in the ink is 5 to 50% by mass, preferably 10 to 35% by mass.

When using two or more kinds of inks having different light and shade characteristics in which the content of the water-soluble dye is changed, 80% by mass or more of the ink having the light and shade characteristics is 80% by mass or more of the water-soluble organic solvent in the ink. It is a water-soluble organic solvent having a flash point of 120 to 160 ° C., and the amount of the water-soluble organic solvent in the ink is 10 to 3
The content of 5% by mass is preferable for smooth gradation expression over time.

[Ink Receiving Layer] At least the void-type ink receiving layer formed of the hydrophilic binder and the inorganic fine particles used in the present invention is preferable because it has good ink absorption characteristics and can improve color bleeding.

The void-type ink receiving layer of the recording medium used in the present invention is preferably formed mainly of fine particles and a hydrophilic binder.

As the fine particles that can be used in the present invention, inorganic fine particles and organic fine particles can be used.
In particular, inorganic fine particles are preferable because they have high gloss, high color density, and easily obtain fine particles. Examples of such inorganic fine particles include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate,
Titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, water Aluminum oxide, lithopone,
Examples thereof include white inorganic pigments such as zeolite and magnesium hydroxide. The above-mentioned inorganic fine particles can be used as primary particles as they are, or can be used in the state of forming secondary aggregated particles.

In the present invention, from the viewpoint of obtaining a high quality print on an ink jet recording medium, alumina, pseudo-boehmite, colloidal silica or fine particle silica synthesized by a vapor phase method is preferable as the inorganic fine particles.

Of these, pseudo-boehmite alumina hydrate is preferable from the viewpoint of preventing bleeding of a printed image in a high humidity environment. As a typical example of this pseudo-boehmite, Japanese Patent Laid-Open No. 7-8
Alumina hydrate A described in Examples of 9221
Is mentioned. This alumina hydrate A was first produced into aluminum alkoxide by the method described in US Pat. No. 4,242,271, and the method described in US Pat. No. 4,202,870. Then hydrolyze the aluminum alkoxide with 30% in an oven.
Aging at 2 ° C. for 2 hours gives a colloidal sol of alumina. The alumina hydrate A is amorphous and has a flat plate shape, a BET specific surface area of 76 g / m, and a BET pore volume of 0.5.
It is 7 ml / g.

The reason why such pseudo-boehmite has a high ink receptivity is considered to be the fact that its pore radius and pore size distribution are in a range very suitable for ink receptivity. The pore size distribution of pseudo-boehmite has two or more maximums. The relatively large pores absorb the solvent component in the ink, and the relatively small pores adsorb the dye in the ink. One of the maximum pore size distributions of pseudo-boehmite has a pore radius of preferably 10 nm or less, more preferably 1 to 6 nm. The other maximum preferably has a pore radius of 10 to 20 nm.

In the present invention, the most preferable inorganic fine particles are fine particle silica synthesized by the vapor phase method. It is preferable in terms of color bleed, gloss, image density, and cost. The silica synthesized by this vapor phase method may have a surface modified with Al. The Al content of the vapor grown silica whose surface is modified with Al is preferably 0.05 to 5% by mass with respect to silica.

As the particle size of the above-mentioned inorganic fine particles, any particle size can be used, but it is preferable that the average particle size is 1 μm or less. If it is 1 μm or less, the glossiness and color developability are better, and therefore, in particular, 0.2 μm
The following is preferable, and 0.1 μm or less is most preferable. The lower limit of the particle size is not particularly limited, but from the viewpoint of manufacturing the inorganic fine particles, it is generally 0.003 μm or more, and particularly 0.005 μm.
The above is preferable.

The average particle size of the above-mentioned inorganic fine particles is obtained by observing the cross section and the surface of the void-type ink receiving layer with an electron microscope to find the particle size of 100 arbitrary particles, and calculating the simple average value (number average). Desired. Here, each grain size is represented by a diameter assuming a circle having the same projected area.

The dispersity of the fine particles is preferably 0.5 or less from the viewpoint of glossiness and color developability. When it is 0.5 or less, gloss and color developability at the time of printing are better. Particularly, 0.3 or less is preferable. Here, the dispersity of the fine particles is represented by a value obtained by observing the fine particles in the void-type ink receiving layer with an electron microscope and determining the standard deviation by the average particle diameter. .

The fine particles may be primary particles as they are or may be present in the porous film as secondary particles or higher-order aggregated particles, but the average particle diameter is observed by an electron microscope. The particle size of the independent particles that are formed in the void-type ink receiving layer.

The content of the above fine particles in the water-soluble coating liquid is 5 to 40% by mass, and particularly preferably 7 to 30% by mass.

The water-soluble binder contained in the void type ink receiving layer is not particularly limited, and conventionally known water-soluble binders can be used. Examples thereof include gelatin, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide and polyvinyl alcohol. Etc. can be used, but polyvinyl alcohol is particularly preferable.

Polyvinyl alcohol is a polymer that has an interaction with inorganic fine particles, has a particularly high retention for inorganic fine particles, and has a relatively small humidity dependency of hygroscopicity. Is relatively small, the suitability for cracking during coating and drying, which is the subject of the present invention, is excellent. As the polyvinyl alcohol preferably used in the present invention, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol having a cation-modified terminal or anion-modified polyvinyl alcohol having an anionic group, etc. Polyvinyl alcohol is also included.

The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 300 or more, and particularly has an average degree of polymerization of 1,000 to 5,000.
Those of are preferably used. Degree of saponification is 70 to 10
0% is preferable, and 80 to 99.5% is particularly preferable.

As the cation-modified polyvinyl alcohol, for example, a primary to tertiary amino group or a quaternary ammonium group as described in JP-A-61-10483 can be used as the main chain or side chain of the polyvinyl alcohol. The polyvinyl alcohols contained therein are obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl). ) Ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N
-(3-dimethylaminopropyl) methacrylamide,
Hydroxylethyltrimethylammonium chloride, trimethyl- (methacrylamidopropyl) ammonium chloride, N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide and the like can be mentioned.

The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol% with respect to vinyl acetate.

Polyvinyl alcohol may be used in combination of two or more types having different degrees of polymerization and different types of modification. In particular, when polyvinyl alcohol having a degree of polymerization of 2000 or more is used, the degree of polymerization is set in advance in the inorganic fine particle dispersion liquid.
5,000 or less polyvinyl alcohol is 0.05 to 10% by mass, preferably 0.1 to 5% by mass with respect to the inorganic fine particles.
It is preferable to add polyvinyl alcohol having a degree of polymerization of 2000 or more after the addition because there is no significant increase in viscosity.

The ratio of the fine particles to the water-soluble binder in the void type ink receiving layer is preferably 2 to 20 times in mass ratio. If the mass ratio is less than 2 times, not only the void ratio of the void-type ink receiving layer is lowered and it becomes difficult to obtain a sufficient void volume, but also an excessive amount of the water-soluble binder swells during inkjet recording to form voids. It becomes a factor to block the ink absorption speed. On the other hand, if this ratio exceeds 20 times, cracking tends to occur when the void-type ink receiving layer is applied as a thick film, which is not preferable. Particularly preferred ratio of fine particles to water-soluble binder is 2.5.
˜12 times, most preferably 3 to 10 times.

It is preferable to add a compound containing a zirconium atom or an aluminum atom in the molecule to the void type ink receiving layer using the above vapor phase method silica because color bleeding and bleeding are improved.

The compound having a zirconium atom in the molecule which can be used in the recording medium used in the present invention does not include zirconium oxide. Specific examples thereof include zirconium difluoride, zirconium trifluoride and zirconium tetrafluoride. , Hexafluorozirconate (eg potassium salt), heptafluorozirconate (eg sodium salt, potassium salt), heptafluorozirconate (eg sodium salt, potassium salt, ammonium salt), octafluorozirconate (eg Lithium salt), zirconium fluoride oxide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, hexachlorozirconate (eg sodium salt, potassium salt), zirconium oxychloride (zirconyl chloride), zirconium dibromide, Zirconium bromide, zirconium tetrabromide, bromide, zirconium oxide, a three-iodide zirconium,
Zirconium tetraiodide, zirconium peroxide, zirconium hydroxide, zirconium sulfate, zirconium p-toluenesulfonate, zirconyl sulfate, sodium zirconyl sulfate, zirconyl acid sulfate trihydrate, potassium zirconium sulfate, zirconium selenate, zirconium nitrate, nitric acid Zirconyl, zirconium phosphate, zirconyl carbonate, zirconyl ammonium carbonate, zirconium acetate, zirconyl acetate, zirconyl acetate acetate, zirconyl lactate, zirconyl citrate, zirconyl stearate, zirconium phosphate, zirconyl phosphate, zirconium zirconium isopropylate, zirconium Butyrate, zirconium acetylacetonate, zirconium acetate, bis (acetylacetonate) dichlorozirco Um, tris (acetylacetonato) chloro zirconium, and the like.

Among these compounds, zirconyl carbonate, zirconyl ammonium carbonate, zirconyl acetate, zirconyl nitrate, zirconium acid chloride, zirconyl lactate,
Zirconyl citrate is preferred, with ammonium zirconyl carbonate and zirconyl acetate being most preferred.

The compound containing an aluminum atom in the molecule which can be used in the present invention does not include aluminum oxide, and specific examples thereof include aluminum fluoride, hexafluoroaluminic acid (eg potassium salt), aluminum chloride, Basic aluminum chloride (eg, polyaluminum chloride), tetrachloroaluminate (eg,
Sodium salt), aluminum bromide, tetrabromoaluminate (eg potassium salt), aluminum iodide, aluminate (eg sodium salt, potassium salt, calcium salt), aluminum chlorate, aluminum perchlorate, thiocyan Aluminum acid sulfate, aluminum sulfate, basic aluminum sulfate, aluminum potassium sulfate (alum), ammonium aluminum sulfate (ammonium alum), sodium aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum hydrogen phosphate, aluminum carbonate, aluminum polysulfate silicate, aluminum formate, Aluminum acetate, aluminum lactate, aluminum oxalate, aluminum isopropylate, aluminum butyrate, ethyl acetate aluminum diisopropylate Rate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethyl acetoacetonate) and the like.

Of these, aluminum chloride, basic aluminum chloride, aluminum sulfate, basic aluminum sulfate and basic aluminum sulfate silicate are preferable,
Most preferred are basic aluminum chloride and basic aluminum sulfate.

The above compound was used as an ink jet recording paper 1.
Per m ² , usually 0.05 to 25 mmol, preferably 0.25 to 10 mmol, particularly preferably 0.5 to 5 m
Used in the mol range.

In the void type ink receiving layer using silica, it is preferable to add a silane coupling agent because it has an effect of reducing color bleed.

The silane coupling agent is preferably a compound having a quaternary ammonium salt and a di- or trialkoxysilanyl group. Examples of preferable silane coupling agents include (a) 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride,
(B) N-β- (N-vinylbenzylaminoethyl)-
γ-aminopropyltrimethoxysilane, (C) 3-
Examples thereof include (trimethoxysilyl) propyldimethylhydroxyethylammonium chloride and a silane coupling agent having a (d) imidazole group. These chemical formulas are shown below.

[0134]

[Chemical 14]

The curing of the silane coupling agent is carried out by converting a plurality of alkoxysilanyl groups into silanol groups in the presence of water (possible by the moisture in the air) so that the silane coupling agents are heated (preferably by heating). ) It is carried out by binding by a condensation reaction between silanol groups to form a crosslinked structure.

When these cationic substances are added to the coating liquid for the transparent porous layer, they may interact with the anionic charge on the surface of the inorganic fine particles such as silica to cause aggregation, but they are contained in the coating liquid for the crosslinking agent. In that case, there is no problem, and an effective amount can be added to improve the film quality of the transparent porous layer. The addition amount of the cationic substance is 0.0
It is preferably ¹ to 3.6 g / m ² , and 0.05 to
More preferably, it is about 2 g / m ² .

If the porosity that determines the properties of the void layer is low, the ink receptivity is low, and show-through occurs when the recording materials after printing are piled up or rolled up. If it is too high, the film becomes fragile and bends or folds. This causes cracking and peeling. A preferable porosity is 30 to 80%, and particularly 50 to 70%
Is preferred. The porosity can be obtained according to the following formula.

Porosity = 100 × absorption capacity per unit area / (total dry film thickness × unit area) The absorption capacity per unit area is 25 ° C. and 50% R for the recording medium.
After conditioning the humidity in an H 2 atmosphere for 24 hours, this sample is immersed in pure water for 10 seconds. Then, after 10 seconds, the sample was taken out of the water, the water on the surface was quickly removed with a filter paper, the mass before and after the immersion was measured, and the mass change was divided by the density of water and the sample area to obtain an ink per unit area. The absorption amount.

[Inkjet Recording Ink Set] The inkjet recording ink set in the invention includes at least a yellow inkjet recording ink, a magenta inkjet recording ink, a cyan inkjet recording ink, and a black inkjet recording ink. The ink set for inkjet recording refers to an ink set including a plurality of inks generally used for so-called color inkjet printing.

The ink set of the present invention has a flash point of 120 to 80% by mass in the water-soluble organic solvent of each ink.
More preferably, it is a water-soluble organic solvent at 160 ° C., the amount of the water-soluble organic solvent in the ink is 5 to 50% by mass, and the amount of the water-soluble organic solvent in the ink is 10 to 35% by mass.

Further, the ink set according to the present invention comprises 80% of all the inks in the ink set in the water-soluble organic solvent.
Mass% or more is the water-soluble organic solvent having a flash point of 120 to 160 ° C., and the amount of the water-soluble organic solvent in the ink is 5 to 50 mass%.
Is more preferable, and the amount of the water-soluble organic solvent in the ink is more preferably 10 to 35% by mass.

When the ink jet recording ink of the present invention contains at least one of the compounds represented by the general formulas (1) to (5) or the water-soluble copper phthalocyanine compound, the ink jet image formed is It is preferable because the light resistance can be improved. More preferably, at least two, and more preferably all of the ink jet recording inks of the ink jet recording ink set contain the compounds represented by the general formulas (1) to (5) or the water-soluble copper phthalocyanine compound. It is that you are. However, at this time, the ink jet recording ink set contains at least one compound represented by the general formulas (1) to (5) or a water-soluble copper phthalocyanine compound so that the ink set is a yellow, magenta, cyan, or black ink. Needless to say, is contained in the ink corresponding to each color.

The recording density at the time of recording in the present invention is 720 in order to obtain a high quality image of a photographic tone.
It is preferable that the value of dpi or more is 2880 dpi or less. It is preferable that the recording density is high in order to obtain a high-quality image having a photographic tone, but if it is too high, the amount of ink ejected to the recording medium increases, and beading and bleeding occur. If the volume of the droplet is too small, the stability during flight is poor, and if it is too large, beading, bleeding or deterioration of graininess occurs, so 0.1 pl or more and 10 pl or less are preferable.

[Substances, etc. Added to Inkjet Ink] The inkjet ink of the present invention may contain a surfactant for controlling the surface tension thereof. As the surfactant, for example, anionic, cationic, amphoteric and nonionic surfactants are used. Typically, the anionic surfactants are fatty acid salts, alkyl sulfates, alkyl sulfates, alkylbenzenes. Sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt,
Examples of cationic surfactants such as alkylnaphthalene sulfonic acid formalin condensate and polyoxyethylene alkyl sulfate ester salt include amine salts, tetraalkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, alkylpyridinium salts, and alkyl quinolines. Examples of the nonionic surfactants such as sodium salts include polyoxyethylene alkyl ethers, polyoxyethylene propylene block polymers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyls. Examples thereof include amine and ethylene oxide adducts of acetylene alcohol.

The amount of these surfactants added depends on the type of dye,
0.01 depending on the total mass of the ink, depending on the type and amount of the water-soluble organic solvent and other additives contained in the ink
The range of 5 mass% is preferred.

Further, the ink-jet ink of the present invention contains a viscosity adjusting agent suitable for each purpose for the purpose of improving ejection stability, compatibility with print heads and ink cartridges, storage stability, and other characteristics. , Adding specific resistance adjusting agent, film forming agent, ultraviolet absorber, antioxidant, antiseptic, antifungal agent, rust preventive agent, pH adjusting agent, dye dissolving aid, defoaming agent, metal chelating agent, etc. You can also

Specific examples of preferable preservatives and fungicides include, for example, sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate and 1,2-benz. Isothiazolidin-3-one (Axia Proxel CRL, Proxel BD, Proxel GXL, Proxel TN, Proxel XL-2
Etc.) and 4-chloro-3-methylphenol (Preventol CMK etc. from Bayer Co.).

Examples of pH adjusters include amines such as diethanolamine, triethanolamine, propanolamine and morpholine, and their modified products, inorganic salts such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and ammonium hydroxide. Examples thereof include quaternary ammonium hydroxide (tetramethylammonium and the like), carbonates such as potassium carbonate, sodium carbonate and lithium carbonate, and phosphates.

Examples of the dye dissolution aid include ureas such as urea, thiourea and tetramethylurea.

[Recording Method and Apparatus] The inkjet recording method of the present invention is preferably carried out by an on-demand method, and more preferably by ejecting ink by an electromechanical conversion method or an electrothermal conversion method. preferable. The electrical-mechanical conversion system includes, for example, electrical
A mechanical conversion method can be used. Examples of the electricity / heat conversion method include an electricity / heat conversion method using a heating element.

Further, in the present invention, even if a large-sized recording medium is used, there is no problem as in the conventional case.
In that sense, it can be said that the technique is suitable for forming an image of a large size with one side of 364 mm or more.

[0152]

EXAMPLES Examples of the present invention will be described below.
The invention is not limited to these examples.

Example 1 [Production of Recording Body 1] Moisture content 6%, basis weight 115 g / m
Low density polyethylene having a density of 0.92 was applied to the back side of the photographic base paper of No. ² by an extrusion coating method in a thickness of 35 μm. Then, a low-density polyethylene containing 5.5% of anatase type titanium oxide and having a density of 0.92 was applied to the surface side by an extrusion coating method in a thickness of 40 μm to prepare a support having both sides coated with polyethylene.

After corona discharge was performed on the surface to give a gelatin subbing layer of 0.1 g / m ² and on the back side, corona discharge was performed.
Styrene / butadiene latex layer with a thickness of 0.4 g /
It was applied so as to be m ² . In the latex layer on the back side, a silica matting agent having an average particle size of 3 μm and a cationic antistatic agent, a silicon dispersion liquid and a fluorine-containing surfactant are 10% by mass and 5% by mass, respectively, with respect to the binder resin.
2 mass% and 3 mass% are contained.

Next, a coating liquid for forming the ink absorbing layer was prepared as follows. Preparation of Titanium Oxide Dispersion-1 20 kg of titanium oxide having an average particle size of 0.25 μm (W-10 manufactured by Ishihara Sangyo Co., Ltd.), 150 g of sodium tripolyphosphate having a pH of 7.5, polyvinyl alcohol (PVA 235 manufactured by Kuraray Co., Ltd.) ) 500 g, cationic polymer (P
-1) 150 g and manufactured by San Nopco: Antifoam SN381
Was added to 90 L of an aqueous solution containing 10 g and dispersed with a high pressure homogenizer (manufactured by Sanwa Kogyo Co., Ltd.), and then the total amount was adjusted to 100 L to obtain a uniform titanium oxide dispersion liquid-1.

Preparation of Silica Dispersion-1 125 kg of vapor phase method silica (A300 manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 0.007 μm,
Using a jet stream inductor mixer TDS manufactured by Mitamura Riken Kogyo Co., Ltd., suction-disperse it in 620 L of pure water adjusted to pH = 2.5 with nitric acid at room temperature, and then make a total volume of 694 L with pure water to obtain silica. Dispersion-1 was prepared.

Preparation of silica dispersion-2 18 L of an aqueous solution (pH = 2.3) containing 1.29 kg of the cationic polymer (P-1), 4.2 L of ethanol and 1.5 L of n-propanol was added to silica. Dispersion-1 of 69.4 L was added with stirring, followed by boric acid 26
7.0 L of an aqueous solution containing 0 g and 230 g of borax was added, and 1 g of the above defoaming agent SN381 was added.

This mixed solution was dispersed with a high pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and the total amount was adjusted to 97 with pure water to prepare a silica dispersion liquid-2.

[0159]

[Chemical 15]

Preparation of Optical Brightening Agent Dispersion-1 Oil-soluble optical brightening agent UVITEX-O manufactured by Ciba-Geigy
400 g of B was dissolved in 9000 g of diisodecyl phthalate and 12 L of ethyl acetate under heating, and this was added to and mixed with 3500 g of acid-treated gelatin, cationic polymer (P-1), and 65 L of an aqueous solution containing 6000 ml of a 50% saponin aqueous solution, and Sanwa. The mixture was emulsified and dispersed using a high pressure homogenizer manufactured by Kogyo Co., Ltd., ethyl acetate was removed under reduced pressure, and then the total amount was adjusted to 100 L to prepare a fluorescent whitening agent dispersion liquid-1.

Preparation of Matting Agent Dispersion-1 Methacrylate ester matting agent MX-manufactured by Soken Kagaku Co., Ltd.
156 g of 1500H was added to 7 L of pure water containing 3 g of PVA235 and dispersed with a high-speed homogenizer to make the total amount 7.8 L to prepare Matting Agent Dispersion-1.

Preparation of coating liquid The coating liquid for the first layer, the second layer and the third layer was prepared by the following procedure.

First Layer Coating Liquid: Silica Dispersion Liquid-2 42
The following additives were sequentially mixed into 0 ml with stirring at 40 ° C.

[0164]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.7 ml   5% aqueous solution of polyvinyl alcohol (Kuraray Industries PVA235)                                                           500 ml   Optical brightener dispersion-1 22 ml   Titanium oxide dispersion-1 33 ml   Daiichi Kogyo Co., Ltd. latex emulsion AE-803 20 ml   Make up to 1000 ml with pure water.

Second Layer Coating Liquid: Silica Dispersion Liquid-2, 45
The following additives were sequentially mixed into 5 ml with stirring at 40 ° C.

[0166]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.5 ml   6% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA235)                                                           500 ml   Optical brightener dispersion-1 35 ml   Make up to 1000 ml pure and total volume.

Third Layer Coating Liquid: Silica Dispersion Liquid-2, 45
The following additives were sequentially mixed into 5 ml with stirring at 40 ° C.

[0168]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.7 ml   6% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA235)                                                           450 ml   Silicone dispersion (Toray Dow Corning Silicone BY-22-839) 16 ml   Saponin 50% aqueous solution 4 ml   Matting agent dispersion-1 10 ml   Make up to 1000 ml with pure water.

The coating solution obtained as described above was filtered with the following filter. First layer and second layer: TCP10 manufactured by Toyo Roshi Kaisha, Ltd. in two steps Third layer: TCP30 manufactured by Toyo Roshi Kaisha, Ltd. in two steps, then a support coated on both sides with polyolefin
Layer (wet film thickness 50 μm), second layer (wet film thickness 100 μm)
m) and the third layer (wet film thickness 50 μm) in this order.

For coating, each coating solution was coated at 40 ° C. with a three-layer slide hopper, and immediately after coating, it was cooled in a cooling zone maintained at 7 ° C. for 20 seconds, and then 20 to 30 ° C.
The recording medium 1 was obtained by successively drying for 45 seconds with the air of 45 ° C., for 90 seconds with the air of 45 ° C. and for 90 seconds with the air of 55 ° C.

The porosity of the obtained recording material was 48%. [Preparation of Yellow Ink-a (Ya)] The following components were mixed and sufficiently stirred, and then filtered using a membrane filter having a pore size of 0.45 μm to prepare Yellow Ink-a.

C. I. Direct Yellow 132 2.7% by mass 2-Pyrrolidinone 10.0% by mass Triethylene glycol-mono-n-butyl ether 10.0% by mass Tripropylene glycol 9.0% by mass Olfine E1010 (manufactured by Nisshin Chemical Co., Ltd.) 1.0 Mass% Proxel GXL (D) (manufactured by Avicia) 0.1 mass% Ion-exchanged water Adjusted to be 100 mass% in total amount of ink and added [Yellow ink-b to e (Yb to e) preparation] Ink The content of the water-soluble dye contained therein, the type and amount of the water-soluble organic solvent contained in the ink, and the type and amount of other additives contained in the ink were changed as shown in Table 1. e was produced.

[0173]

[Table 1]

* 1: Water-soluble dye content (mass%) * 2: Diethylene glycol-mono-n-butyl ether (flash point 77.8 ° C) * 3: 1,2-hexanediol (flash point 102 ° C) * 4 : Ethylene glycol (flash point 111.1 ° C) * 5: Diethylene glycol (flash point 123.9 ° C) * 6: 2-Pyrrolidinone (flash point 129 ° C) * 7: Triethylene glycol-mono-n-butyl ether (flash point 143.1 ° C) * 8: Tripropylene glycol (flash point 130 ° C) * 9: Glycerin (flash point 177 ° C) * 10: 1,2,6-hexanetriol (flash point 19
0.6 ° C) * 11: Olfine E1010 (mass%) * 12: Proxel GXL (D) (mass%) * 13: Urea (mass%) * 14: Total water-soluble organic solvent content * 15: Water-soluble organic Flash point of the solvent 120-160
C. Water-soluble organic solvent ratio [Preparation of image recording samples 1 to 5] Nozzle diameter 23 μm, driving frequency 5 kHz, number of nozzles per color 128, piezo head with same nozzle density 90 dpi, recording density 720 dpi × 720 dpi Ink was set in an on-demand type ink jet printer set so that the volume of each droplet was 7 pl, and 320 mm x 4
B1 size (2
57 mm × 364 mm) image pattern (OD value Y =
1) was produced.

<Evaluation of Solid Color Variation> The image of each of the obtained samples was immediately exposed to the outside on the printing surface and was rolled into a cylindrical shape so that a part of the printing surface did not touch the outside air. 23 ℃, 20%
After being left for 24 hours in the environment of RH, it was visually evaluated whether there was a difference in color tone and density at the boundary between the part exposed outside and the part coated inside.

⊚: Color tone and density difference are not seen at the boundary ○: Color tone and density difference are slightly seen at the boundary (practical level) ×: Color tone and density difference are seen at the boundary (practical use Improper level) <Evaluation of bleeding> Immediately apply 2 to the image obtained by the above method.
After standing in an environment of 3 ° C. and 80% RH for 48 hours, it was visually evaluated whether bleeding occurred at the boundary between the printed portion and the non-printed portion.

⊚: The boundary between the printed part and the non-printed part is clear ○: The boundary between the printed part and the non-printed part is slightly blurred (practical level) ×: The boundary between the printed part and the non-printed part is clearly blurred (practical Table 2 shows the evaluation results of the image recording samples 1 to 5.

[0178]

[Table 2]

In the evaluation of the solid color variations of the image recording samples 1 to 5, neither cracking of the recording material nor show-through of the ink due to curling of the recording material was observed, and the image was good even when rolled and stored.

[Preparation of Image Recording Samples 6 to 10] Light Yellow Ink-a to Light Yellow Ink-e (LY-
a to LY-e) Light yellow ink-a to light yellow ink-e
In the preparation of Light Ink-a to Light Yellow Ink-e in the same manner as in Preparation of Yellow Ink-a to Yellow Ink-e, except that the dye concentration is set to 1/4.
Was produced.

Image recording samples 6 to 10 were prepared in the same manner as the image recording samples 1 to 5 except that the image density was set to Y = 0.5, and the results of evaluation of solid color variation and bleeding were performed. It shows in Table 3.

[0182]

[Table 3]

In the evaluation of the solid color variation of the image recording samples 6 to 10, neither cracking of the recording material nor show-through of the ink due to curling of the recording material was observed, and the image was good even when rolled and stored.

[Preparation of Image Recording Samples 11 to 16] As shown in Table 4, a dark and light ink set was prepared by combining the yellow ink and the light yellow ink, and the nozzle diameter was 23 μm.
m, driving frequency 5 kHz, 12 nozzles per color
8. A yellow ink set was set in an on-demand type ink jet printer equipped with a piezo type head having the same color nozzle density of 90 dpi, a recording density of 1440 dpi × 1440 dpi, and a droplet volume per droplet of 7 pl, and 350 mm × A gradation chart of an A3 size (297 mm × 420 mm) image pattern was created on the recording medium 1 cut into 450 mm.

[0185]

[Table 4]

In creating the gradation chart, color conversion processing is performed so that the color of the original image is reproduced using the color chart included in the high-definition color digital standard image data (issued by the Japanese Standards Association). A gradation chart with halftone dots of 0% to 100% was created through a color conversion filter.

<Evaluation of Tone Jump> After the image of the obtained sample was left in an environment of 23 ° C. and 20% RH for 24 hours,
The gradation chart was visually evaluated for tone jumps.

B: No tone jump is seen. X: A tone jump is seen.

Table 5 shows the evaluation results of the image recording samples 11 to 16.

[0190]

[Table 5]

[Preparation of Magenta Inks a to e, Cyan Inks a to e, Black Inks a to e] In the preparation of the above yellow ink a, a water-soluble dye was used as C.I. I. Magenta Ink-a was prepared in the same manner as in Yellow Ink-a except that an equivalent mixture of Compound M-1 and Compound M-4 was used instead of Direct Yellow 132.
In the production of yellow inks-b to e, the water-soluble dye was replaced with C.I. I. Magenta inks b to e were prepared in the same manner as the preparation of yellow inks b to e, except that an equivalent mixture of the compound M-1 and the compound M-4 was used instead of the direct yellow 132.

In producing the above yellow ink-a,
The water-soluble dye is C.I. I. C. instead of Direct Yellow 132. I. Cyan ink-in the same manner as in the preparation of yellow ink-a except that Direct Blue 199 was used.
a, yellow ink-b to e, the water-soluble dye is C.I. I. C. instead of Direct Yellow 132.
I. Cyan inks-b-e are prepared in the same manner as in the preparation of yellow inks-b-e except that Direct Blue 199 is used.
Was produced.

In producing the above yellow ink-a,
The water-soluble dye is C.I. I. C. instead of Direct Yellow 132. I. In the preparation of Black Ink-a and Yellow Inks-b to e, the water-soluble dye was replaced with C.I. I. C. instead of Direct Yellow 132. I.
Yellow ink -b ~ except that Hood Black 2 was used
Black inks-b to e were prepared in the same manner as the preparation of e.

[Preparation of Image Recording Samples 17 to 31] Nozzle diameter 23 μm, drive frequency 5 kHz, number of nozzles per color 128, piezo type head having nozzle density 90 dpi of the same color is mounted, recording density 720 dpi × 720 dpi, 1
The ink is set in an on-demand type ink jet printer set so that the volume of droplets per droplet is 7 pl, and the recording medium 1 cut into 300 mm × 400 mm has a uniform solid B1 size (257 mm × 364 mm) image pattern of each color (each color OD value of M = 2, C = 2, K = 2) Image recording samples 17 to 31 were prepared.

Evaluation of solid color variation and bleeding was carried out in the same manner as the evaluation of image recording samples 1 to 5.

Table 6 shows the evaluation results of Samples 17 to 31.

[0197]

[Table 6]

In the evaluation of the solid color variation of the image recording samples 17 to 31, neither cracking of the recording material nor show-through of the ink due to curling of the recording material was observed, and the image was good even when rolled and stored.

[Preparation of Image Recording Samples 32 to 46] Light Magenta Ink-a to e, Light Cyan Ink-a to
Preparation of light black inks-a to e In the preparation of the above light yellow inks-a to e, the water-soluble dye was replaced with C.I. I. Light magenta inks a to e were prepared in the same manner as the light yellow inks a to e, except that an equivalent mixture of the compound M-1 and the compound M-4 was used instead of the direct yellow 132.

In the above light yellow inks a to e, the water-soluble dye is C.I. I. C. instead of Direct Yellow 132. I. Light cyan inks a to e were prepared in the same manner as light yellow inks a to e except that Direct Blue 199 was used.

In the preparation of the above light yellow inks a to e, the water-soluble dye is C.I. I. Direct yellow 1
32 instead of C.I. I. Light black inks a to e were prepared in the same manner as the light yellow inks a to e except that the food black 2 was used.

Nozzle diameter 23 μm, drive frequency 5 kHz
z, number of nozzles per color 128, nozzle density of the same color 90
Equipped with a piezo type head of dpi, recording density 720dp
i × 720 dpi, ink was set in an on-demand type ink jet printer set so that the volume of each droplet was 7 pl, and the recording medium 1 cut into 300 mm × 400 mm had a uniform solid B1 size (257 mm × 36 mm).
4 mm) image pattern of each color (OD value of each color LM =
1, LC = 1, LK = 1) Image recording samples 32-46 were prepared.

The solid color variation and the bleeding were evaluated in the same manner as the evaluation of the image recording samples 1 to 5.

Table 7 shows the evaluation results of Samples 32-46.

[0205]

[Table 7]

In the evaluation of the solid color variation of the image recording samples 32 to 46, cracking of the recording material and set-off of the ink due to curling of the recording material were not observed, and the image was good even when rolled and stored.

The dark and light ink sets 7 to 24 were combined by combining the respective dark and light inks as shown in Table 8, and the image recording sample 11 was prepared.
Image recording samples 47 to 64 were prepared in the same manner as in the preparation of .about.16 to evaluate the tone jump. The evaluation results are shown in Table 9.

[0208]

[Table 8]

[0209]

[Table 9]

Preparation of Recording Body 2 Coating solutions for the first layer, second layer and third layer were prepared by the following procedure.

First Layer Coating Solution: Silica Dispersion Liquid-2 600
The following additives were sequentially mixed into ml while stirring at 40 ° C.

[0212]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.5 ml   5% aqueous solution of polyvinyl alcohol (Kuraray Industries PVA235)                                                           250 ml   Optical brightener dispersion-1 25 ml   Titanium oxide dispersion-1 33 ml   Daiichi Kogyo Co., Ltd. latex emulsion AE-803 16 ml   Make up to 1000 ml pure and total volume.

Second Layer Coating Liquid: Silica Dispersion Liquid-2, 65
The following additives were sequentially mixed into 0 ml with stirring at 40 ° C.

[0214]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.6 ml   5% aqueous solution of polyvinyl alcohol (Kuraray Industries PVA235)                                                           300 ml   Optical brightener dispersion-1 35 ml   Make up to 1000 ml pure and total volume.

Third layer coating solution: silica dispersion-2, 650
The following additives were sequentially mixed into ml while stirring at 40 ° C.

[0216]   10% aqueous solution of polyvinyl alcohol (Kuraray Industry Co., Ltd .: PVA203)                                                           0.7 ml   5% aqueous solution of polyvinyl alcohol (Kuraray Industries PVA235)                                                           270 ml   Silicone dispersion   (Toray Dow Corning Silicone BY-22-839) 15 ml   Saponin 50% aqueous solution 5 ml   Matting agent dispersion-1 10 ml   Make up to 1000 ml pure and total volume.

The coating solution obtained as described above was filtered with the following filter. First layer and second layer: TCP10 manufactured by Toyo Roshi Kaisha, Ltd. in two stages Third layer: TCP30 manufactured by Toyo Roshi Kaisha, Ltd. in two stages, then a support coated on both sides with polyolefin
Layer (wet film thickness 60 μm), second layer (wet film thickness 680 μ)
m) and the third layer (wet film thickness 60 μm) in this order.

For coating, each coating solution was coated at 40 ° C. with a three-layer slide hopper, immediately after coating, cooled in a cooling zone kept at 7 ° C. for 20 seconds, and then blown with air at 20 to 30 ° C. for 30 seconds. , 45 ℃ for 60 seconds, 55 ℃ for 6
Recording body 2 was obtained by sequentially drying for 0 seconds.

The recording medium obtained had a porosity of 62%. Preparation of yellow inks f to k, magenta inks f to k, cyan inks f to k, and black inks f to k The following components were mixed and sufficiently stirred, and then the pore diameter was 0.45 μm.
The yellow ink-f was produced by filtering using an m membrane filter.

Compound Y-1 2.8 mass% 1,2-hexanediol 2.0 mass% 2-pyrrolidinone 10.0 mass% triethylene glycol-mono-n-butyl ether 5.0 mass% tripropylene glycol 10. 0% by mass Olphin E1010 (manufactured by Nissin Chemical Co., Ltd.) 1.0% by mass Proxel GXL (D) (manufactured by Avicia) 0.1% by mass ion-exchanged water contained in the ink adjusted to 100% by mass in total. The content of the water-soluble dye, the type and amount of the water-soluble organic solvent contained in the ink, and the type and amount of other additives contained in the ink are changed as shown in Tables 10 and 11, and yellow ink-g to k , Magenta ink-f ~
k, cyan ink-f to k, and black ink-f to k were prepared.

[0221]

[Chemical 16]

[0222]

[Chemical 17]

[0223]

[Chemical 18]

[0224]

[Chemical 19]

[0225]

[Table 10]

* 1: Water-soluble dye * 2: Water-soluble dye content (mass%) * 3: Diethylene glycol-mono-n-butyl ether (flash point 77.8 ° C) * 4: 1,2-hexanediol (flash point 102 ° C) * 5: Ethylene glycol (flash point 111.1 ° C) * 6: Diethylene glycol (flash point 123.9 ° C) * 7: 2-Pyrrolidinone (flash point 129 ° C) * 8: Triethylene glycol mono- n-Butyl ether (flash point 143.1 ° C) * 9: Tripropylene glycol monomethyl ether (flash point 121 ° C) * 10: Tripropylene glycol (flash point 130 ° C) * 11: Triethylene glycol (flash point 176.7)
℃) * 12: Tetraethylene glycol (flash point 173.9
℃) * 13: Glycerin (flash point 177 ℃) * 14: 1,2,6-hexanetriol (flash point 19
0.6 ° C)

[0227]

[Table 11]

* 15: Olfine E1010 (mass%) * 16: Proxel GXL (D) (mass%) * 17: Urea (mass%) * 18: Total water-soluble organic solvent content * 19: For water-soluble organic solvent Occupying flash point 120-160
C. Water-soluble organic solvent ratio [Preparation of image recording samples 65 to 88] Nozzle diameter 23 μ
m, driving frequency 5 kHz, 12 nozzles per color
8. A piezo type head having the same color nozzle density of 90 dpi is mounted, the recording density is 720 dpi × 720 dpi, and the ink is set in an on-demand type ink jet printer set so that the volume of the liquid droplet per droplet is 5 pl.
B1 size (257 mm × 364 mm) image pattern (OD value for yellow ink Y = 1, OD value for magenta ink M = 2, and cyan ink for cyan ink) OD value
C = 2, OD value in case of black ink K = 2) was prepared.

The obtained image recording sample was used as image recording sample 1
In the same manner as the evaluation of solid color variation and bleeding in the case of ~ 5,
Solid color variation and bleeding were evaluated. Table 12 shows the evaluation results.
Shown in.

Further, the light resistance was evaluated by the following method. <Evaluation of light resistance> X-rite 938 Spectrodensitio of each of the image sample obtained by exposing the obtained image of each sample with a Xe fade meter (70,000 lux) for 48 hours and the unexposed image sample.
meter (measuring conditions ANSI status T compliant,
C light source), yellow density in the case of yellow ink, magenta density in the case of magenta ink, cyan density in the case of cyan ink, and visible density in the case of black ink, and the light resistance was evaluated according to the following evaluation criteria.

Remaining rate (%) = (reflection density of exposed sample) ÷
(Reflection Density of Unexposed Sample) ⊚: Residual rate is 80% or more ◯: Residual rate is 50% or more and less than 80% ×: Residual rate is less than 50% Table 12 shows the evaluation results.

[0232]

[Table 12]

In the evaluation of the solid color variation of the image recording samples 65 to 88, cracking of the recording material and show-through of the ink due to curling of the recording material were not observed, and the image was good even when rolled and stored.

[Preparation of Color Ink Sets 25-32]
With the combinations shown in Table 13, the color ink set 25 to
32 was produced.

[0235]

[Table 13]

[Production of Image Recording Samples 89 to 96] A nozzle diameter of 23 μm, a driving frequency of 5 kHz, a nozzle number of 128 per color, a piezo type head having a nozzle density of 90 dpi of the same color is mounted, and a recording density of 720 dpi × 720 dpi, 1
The ink was set in an on-demand type ink jet printer set so that the volume of the droplet per droplet was 7 pl, and the recording medium 2 or recording medium 1 cut into 300 mm × 400 mm was filled with each color of B1 size (257 mm × 364 mm). An image, a two-color superimposed image in which all the respective inks were combined, and a three-color superimposed image in which all the respective inks were combined were prepared.

Image recording samples 89 to 96 were prepared by the following method.
Was evaluated. <Light resistance balance evaluation> ⊚: Remaining rate exceeds 80% in any of yellow, magenta, cyan, and black ◯: One of yellow, magenta, cyan, and black has a remaining rate of 80% or less ×: Yellow, magenta, cyan , 2 or more of black have a residual rate of 80% or less, or 1 or more of yellow, magenta, cyan, and black have a residual rate of 50% or less <Evaluation of mixed color bleed> Each sample obtained is 23 ° C., 80% R
After being left in the H environment for 48 hours, the boundary between the printed portion and the non-printed portion was observed, and bleeding was evaluated according to the following visual evaluation criteria.

⊚: No bleeding even in the three-color printing section ○: Slight bleeding in the three-color overlapping printing section, but no bleeding in two or less colors Δ: Bleeding is observed in the two-color overlapping printing section ×: Two-color overlapping printing There is much bleeding even on the parts. <Evaluation of mixed color and solid color variation> Immediately, the printed surface of the sample was exposed to the outside, and a part of the printed surface was rolled into a cylinder so as not to touch the outside air. After this was left in an environment of 23 ° C. and 20% RH for 24 hours, it was visually evaluated whether there was a difference in color tone and density at the boundary between the portion exposed outside and the portion coated inside.

⊚: Color tone and density difference are not seen in the boundary even in the three-color overlapping print section. ○: Color tone and density difference are slightly seen in the three-color overlapping print section, but there is a difference in the boundary section with two or less colors. Color tone and density difference are not seen. Δ: Color tone and density difference are seen at the boundary even in the two-color overlapping print section. ×: Color tone and density difference are clearly seen at the boundary in the two-color overlapping print section. However, Δ and × have problems in practical use.

The evaluation results are shown in Table 14.

[0241]

[Table 14]

From the results shown in Table 14, it was found that the image-recorded samples produced by the recording method of the present invention have excellent light resistance balance and further excellent color mixture bleeding and color mixture solid color variation.

[0243]

According to the present invention, there is provided an ink jet recording method in which there is no bleeding at the boundary of the image, and there is little fluctuation in image density or color fluctuation between the image immediately after printing and the aged image, and a recorded image using the same. You can do it.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 29/30 C09B 31/08 31/08 33/06 CLA 33/06 CLA 33/10 33/10 35 / 03 35/03 62/09 B 62/09 B41J 3/04 101Y F term (reference) 2C056 EA04 FC02 FC06 2H086 BA15 BA19 BA21 BA52 BA56 BA60 BA62 4H056 JA06 JB02 JD21 4J039 BC40 BC41 BC50 BC51 BC52 BC54 BC60 BC61 BC64 BC65 BC68 BC73 BC74 BC77 BC79 BE02 BE12 CA06 EA15 EA16 EA17 EA19 GA24

Claims (15)

[Claims] 1. A recording material having an ink receiving layer on a water-impermeable support contains at least water, a water-soluble dye and a water-soluble organic solvent, and 80% by mass or more of the water-soluble organic solvent is flammable. An ink jet recording method, comprising: recording using an ink for ink jet recording, which is a water soluble organic solvent having a point of 120 to 160 ° C. and an amount of the water soluble organic solvent in the ink is 5 to 50% by mass. 2. The ink jet recording method according to claim 1, wherein the amount of the water-soluble organic solvent is 10 to 35 mass%. 3. The ink receiving layer according to claim 1, wherein the ink receiving layer includes at least a void-type ink receiving layer formed of a hydrophilic binder and inorganic fine particles on a water-impermeable support. The inkjet recording method described in 1. 4. The ink jet recording method according to claim 1, wherein the water-impermeable support is an RC (resin coated) support or a resin film support. . 5. The ink jet recording method according to claim 1, wherein the ink is composed of two or more kinds of ink jet recording ink having density characteristics. 6. The ink is at least a yellow ink jet recording ink, a magenta ink jet recording ink, a cyan ink jet recording ink,
The inkjet recording method according to any one of claims 1 to 5, comprising an inkjet recording ink set containing a black inkjet recording ink. 7. The amount of the water-soluble organic solvent of all inks in the ink set for inkjet recording is 10.
The ink jet recording method according to claim 6, wherein the content is from 35% by mass to 35% by mass. 8. The ink-jet recording ink contains at least one of compounds represented by the following general formulas (1) to (5) or a water-soluble copper phthalocyanine compound as a water-soluble dye. The inkjet recording method according to claim 1. [Chemical 1] (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substitutable substituent. M represents an integer of 1 to 5 and n represents an integer of 1 to 4. J represents a carbonyl group or a general formula ( It represents a group represented by 6).) (In the formula, R ₄ and R ₅ each represent a hydrogen atom or a substitutable substituent. G represents an integer of 1 to 5 and h represents an integer of 1 to 5.) (In the formula, R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ each represent a hydrogen atom or a substitutable substituent. P represents an integer of 1 to 4, and q represents an integer of 1 to 5. It represents.) (In the formula, each R ₁₁ represents a hydrogen atom or a substitutable substituent. X represents a phenyl group or a naphthyl group. R represents an integer of 1 to 4; s represents an integer of 1 or 2; r +
Satisfies s = 5. Y is hydrogen ion, sodium ion,
It represents potassium ion, lithium ion, ammonium ion or alkylammonium ion. Z represents a carbonyl group, a sulfonyl group or a group represented by the general formula (7). ) [Chemical 5] (In the formula, R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ each represent a hydrogen atom or a substitutable substituent. T represents an integer of 1 to 5, u represents an integer of 1 to 4, and w Represents an integer of 1 to 5.) (In the formula, R ₃ represents a substitutable substituent.) (In the formula, W ₁ and W ₂ are a halogen atom, an amino group,
It represents a hydroxyl group, an alkylamino group or an arylamino group. ) 9. The ink jet recording method according to claim 1, wherein the ink receiving layer includes a void type receiving layer having a porosity of 30 to 80%. 10. The ink jet recording method according to claim 1, wherein the recording and writing are performed by an on-demand method. 11. The inkjet recording method according to claim 1, wherein the recording / writing is performed by ejecting an inkjet recording ink by an electromechanical conversion method. 12. The ink jet recording method according to claim 1, wherein the recording / writing is performed by ejecting ink for ink jet recording by an electrothermal conversion method. 13. A recording density of 720 dpi (dots per inch; 1 inch is about 2.54 cm, and the number of pixel dots that can exist in that width) or more and 2880 dpi or less, and a droplet volume is 0. 13. Recording according to claim 1 or more and less than 10 pl.
Inkjet recording method according to item. 14. The ink jet recording method according to claim 1, wherein the length of one side of the recording body is 364 mm or more. 15. A recorded image recorded by using the ink jet recording method according to any one of claims 1 to 14.