JP2003136832A - Ink jet recording system, ink jet recording liquid, and ink jet recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording system suitable to print a medical or particularly the diagnostic object of an X-ray image and to provide an ink jet recording liquid and an ink jet recording medium. SOLUTION: The ink jet recorder 100 records by ink jetting on the ink jet recording medium 4 by injecting the ink jet recording liquid from the nozzle of a recording head 120. The ink jet recording liquid contains a bidentate water soluble dye coordinate bondable with metal ion. The ink jet recording medium is a transparent sheet containing the complex formable metal ion exhibiting a black color in reaction with the water soluble dye.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the industrial field of X-ray diagnostic imaging in medicine. In particular, the present invention relates to an inkjet recording system, an inkjet recording liquid, and an inkjet recording medium for printing an X-ray image for diagnostic purposes.

[0002]

2. Description of the Related Art For the past 100 years since the discovery of X-rays, a screen film system (SF system) combining a fluorescent intensifying screen and an X-ray film has been used for X-ray image formation.

That is, when X-rays are applied to a fluorescent intensifying screen, blue or green visible light is emitted in proportion to the X-ray intensity, and the light exposes the silver halide photographic film, and after development processing. An X-ray image is obtained as a silver image. However, although the image quality of the SF system is extremely good,
In order to obtain an image, a developing process using water is necessary, and the developing solution and fixing solution are generated as waste liquid. This is not environmentally friendly. Further, the development process involving water is extremely complicated and a troublesome work.

In recent years, in radiographic imaging, Computed Radiography (CR) has replaced the SF system.
Systems such as flat panel X-ray detectors (FPD) for extracting digital electric signals of X-ray images have appeared. Also, new modalities such as X-ray CT and MRI are provided for image diagnosis as digital images (see FIG. 5).

In these digital medical imaging systems,
Since no conventional X-ray film is used for capturing an image, there is no complicated process such as development processing, and an X-ray image can be quickly obtained on a monitor such as a cathode ray tube (CRT) display or a liquid crystal display panel. be able to.

However, since there is a limit to the image density area that can be drawn on a CRT display and the emission brightness of the CRT display is greatly reduced in less than a year, there are inconveniences such as scrutinizing an X-ray image and a conference or inspecting. In the case of using it as a form consent, it is necessary to obtain a hard copy of the X-ray image. Also, a large liquid crystal display panel is required to display a medical image, which is very expensive.

Therefore, as a method for obtaining this hard copy, an electric signal of an X-ray image obtained from a CR or FPD is replaced with a laser light intensity and printed on a conventional silver halide film, and a development process is performed to form an image. There is a way to do it. Further, in recent years, a silver salt dry film which uses an organic acid silver salt and does not require a conventional wet treatment has been used.

[0008]

However, this uses expensive silver as in the conventional SF system, and the manufacturing process is complicated and the manufacturing cost is high.

On the other hand, as a method for forming an image with a dye without requiring silver resources, there are a thermal transfer system and a sublimation printer. However, in the case of the thermal transfer described above, the ink of the recorded image is transferred from the ink ribbon to the outermost surface of the film, and there is a problem that the ink is peeled off depending on the handling.

Further, in the case of a sublimation printer, there is a problem that a sufficient density is not obtained as a medical diagnostic image, and there is also a problem that a waste such as an ink ribbon is generated after image formation like thermal transfer.

In order to solve the above-mentioned drawbacks of the thermal transfer or sublimation type printer, the existence of an ink jet printer can be mentioned. An ink jet printer forms an image by continuously ejecting a small amount of liquid ink and landing it on an ink jet recording medium by utilizing, for example, a piezoelectric effect of crystals according to an input electric signal. Therefore, it is not necessary to dispose of the used ink ribbon unlike the thermal transfer system or the sublimation printer. Further, in order to obtain an image with good gradation such as a silver salt photograph, an ink having a plurality of densities is used, and further an ink jet recording medium having an ink absorbing layer is used in order to increase the ink absorbing amount of the medium. Particularly when recording on a medium having a void type ink receiving layer, since an image is formed by the ink absorbing layer (image receiving layer) inside the void type ink receiving layer, no inconvenience such as ink transfer occurs.

This ink jet printer does not use expensive silver resources. In addition, since no development processing agent or the like is used, no running cost is required. Further, in order to draw an image that is most suitable for the purpose of use of the image, a digital image signal obtained from a CR or FPD is used by using an optimum ink and recording medium, and by using an appropriate recording medium having an ink receiving layer. It is possible to draw an X-ray image having excellent image quality.

Here, for the ink jet image, an ink jet recording liquid in which a dye is dissolved in water is used. The non-aqueous solvent ink jet recording liquid which does not use water has drawbacks such as odor of the solvent and high material cost. The ink jet recording liquid in which a dye is dissolved in water is ejected from the ink head of an ink jet printer as a predetermined amount of droplets onto a recording medium having an ink receiving layer to draw an image. Even after the image formation, water, which is a solvent of the inkjet recording liquid, still exists, and there is a drawback that so-called "ink bleeding" occurs when the inkjet image is stored in an environment where the solvent is difficult to evaporate and the humidity is high. This drawback is the greatest drawback of an ink jet recorded image using an ink jet recording liquid containing a dye.

On the other hand, medical images used for diagnosis are required by law to be stored for at least 5 years in Japan, and depending on the case, they may be stored for 5 years or longer. If image deterioration occurs due to ink bleeding during this storage period, the sharpness of the image deteriorates and the image becomes deteriorated, and the image diagnosed immediately after printing cannot be read again. Can't reach

The present invention has been made in view of the above problems, and provides an ink jet recording system, an ink jet recording liquid, and an ink jet recording medium suitable for medical treatment, particularly for printing X-ray images for diagnostic purposes. The purpose is to

[0016]

[Means for Solving the Problems] That is, the following (1)
This is solved by each of the solving means described in (17) to (17).

(1) An invention according to claim 1 is an ink jet recording system for ejecting ink jet recording liquid from a nozzle onto an ink jet recording medium to carry out ink jet recording, wherein the ink jet recording liquid comprises:
The ink jet recording medium contains a water-soluble dye capable of forming a coordinate bond with a metal ion in two or more positions, and the inkjet recording medium contains a metal ion capable of forming a complex that exhibits a black color by reacting with the water-soluble dye. An inkjet recording system characterized by being a sheet.

That is, in the present invention, the image is recorded on the transparent medium by forming the metal complex dye in the ink jet recording medium. Since this metal complex dye has a large molecular weight, diffusion is less likely to occur as compared with conventional dyes, and the storability of a black image formed on a transparent recording sheet used for medical image diagnosis is extremely good.

(2) An invention according to claim 2 is an ink jet recording system for ejecting ink jet recording liquid from a nozzle onto an ink jet recording medium to carry out ink jet recording, wherein the ink jet recording liquid is metal ions and 2 A first inkjet recording liquid containing a water-soluble dye capable of coordinating at a coordinate or higher, and a second inkjet recording liquid containing a compound containing a metal ion capable of forming a complex that exhibits a black color by reacting with the dye; A control unit that controls the ejection of the ink jet recording liquid from the nozzle, the control unit ejecting the first ink jet recording liquid onto the ink jet recording medium, and then ejecting the ink jet recording medium. Jetting the second inkjet recording liquid to at least an image forming region, An ink jet recording system characterized and.

That is, in the present invention, an image is recorded on a transparent medium by forming a metal complex dye on the ink jet recording medium with the first ink jet recording liquid and the second ink jet recording liquid. Since this metal complex dye has a large molecular weight, diffusion is less likely to occur as compared with conventional dyes, and the storability of a black image formed on a transparent recording sheet used for medical image diagnosis is extremely good.

(3) In the invention according to claim 3, the water-soluble dye is a dye represented by the above general formulas (1) to (6).
The ink jet recording system according to claim 1 or 2, wherein: [In the formulas (1) to (5), X1 and X2 each have a group that forms a dye through a conjugated system, and represent at least a bidentate chelate-forming group or an atom group, and Y is 5 Represents a group of atoms forming a six-membered or six-membered aromatic carbocycle or heterocycle. In the formula (6), R1, R2 and R3 are hydrogen atoms,
It represents a halogen atom or a monovalent substituent, and n represents 0, 1 or 2. (4) The invention according to claim 4 is the inkjet recording system according to any one of claims 1 to 3, wherein the metal ion is a transition metal ion-containing compound.

(5) The invention according to claim 5 is characterized in that the ink jet recording liquid is an aqueous ink jet recording liquid containing 10% by weight or more of water. The inkjet recording system according to claim 1.

(6) The invention according to claim 6 has a heating means for heating the ink jet recording medium after ejecting the ink jet recording liquid onto the ink jet recording medium. Claim 5
The inkjet recording system according to any one of 1.

(7) The invention according to claim 7 is for preventing transfer of thermal energy generated from the heating means to the recording head for ejecting the ink jet recording liquid and the means for supplying the ink jet recording liquid. The ink jet recording system according to claim 6, further comprising:

(8) The invention according to claim 8 records a monochrome image having a maximum transmission image density of 2.60 or more and 4.00 or less, according to any one of claims 1 to 7. The described inkjet recording system.

(9) The invention according to claim 9 is characterized in that the concentration of the water-soluble dye in the ink jet recording liquid used is from 3 to 6 inclusive. The inkjet recording system according to any one of 1.

(10) The invention according to claim 10 is the ink jet recording system according to any one of claims 1 to 9, which is used for forming an X-ray image.

(11) An eleventh aspect of the present invention is an ink jet recording liquid used in the ink jet recording system according to any one of the first to ninth aspects, wherein the ink jet recording liquid is a metal ion and two or more bidentates. The inkjet recording liquid is characterized by containing a water-soluble dye capable of coordinate bond with.

(12) The invention according to claim 12 is characterized in that the water-soluble dye is a dye represented by the general formula (1) to (6). Is. [X1 and X2 in Formulas (1) to (5)]
Represents an at least bidentate chelate-forming group or group of atoms having a group which forms a dye through a conjugated system, and Y represents an atom forming a 5- or 6-membered aromatic carbocycle or heterocycle. Represents a group of. R in the formula (6)
1, R2 and R3 represent a hydrogen atom, a halogen atom or a monovalent substituent, and n represents 0, 1 or 2. (13) The invention according to claim 13 is characterized in that the ink jet recording liquid is an aqueous ink jet recording liquid containing 10% by weight or more of water. The inkjet recording liquid described above.

(14) The invention according to claim 14 is an ink jet recording medium used in the ink jet recording system according to any one of claims 1 to 9, wherein the ink jet recording medium is composed of a transparent resin. A backing layer having fine particles dispersed therein is formed on the non-recording surface of the support, and an ink receiving layer having voids is formed on the recording surface of the support. And an inkjet recording medium.

(15) According to a fifteenth aspect of the present invention, the ink receiving layer comprises an image receiving layer for carrying an image and a solvent absorbing layer for absorbing the solvent of the ink jet recording liquid. 15. The inkjet recording medium according to claim 14, wherein:

(16) The invention according to claim 16 is characterized in that the ink receiving layer contains a metal ion-containing compound capable of forming a complex by reacting with a water-soluble dye. 15. The inkjet recording medium according to any one of 15.

(17) The invention according to claim 17 is composed of a colorless or blue-colored resin having rounded corners at four corners and having a thickness of 75 μm or more and 250 μm or less, and at least one surface thereof is a void type ink receiving layer. The inkjet recording medium according to any one of claims 14 to 16, wherein the inkjet recording medium comprises at least one layer.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention relating to an inkjet recording system, an inkjet recording liquid, and an inkjet recording medium will be described in detail below with reference to the drawings. The present invention is not limited to the specific examples shown in the embodiments.

<Inkjet Recording System> FIG. 2 shows the basic structure of the inkjet recording system according to the embodiment of the present invention. That is, the "inkjet recording system" of the present embodiment is composed of three members, "inkjet recording liquid", "inkjet recording device" and "inkjet recording medium".

<Inkjet Recording Apparatus> FIG. 1 is a block diagram for explaining the functional blocks relating to image recording of the medical inkjet recording apparatus. This inkjet recording device receives an input image signal and performs image processing if necessary. That is, there are image interpolation when the pixel size of the input image and the pixel size of the output image are different, and processing for printing the image in an arbitrary size. After image processing, control of ink supply, ink ejection from the recording head, conveyance of the inkjet recording medium, etc. is performed based on the data signal.

Specifically, the medical ink jet recording apparatus 100 of this embodiment is a recording head unit 120 as recording means for recording an image by ejecting ink.
have.

The control means 101 controls each part of the medical ink jet recording apparatus 100 of this embodiment. Also,
The control unit 101 also controls the amount of ink adhered to the inkjet recording medium, which is a feature of this embodiment.

An image processing unit 110 receives an image signal from an external medical imaging device or storage device and executes necessary image processing. The image signal input from the outside may be via various networks. The image signal processed by the image processing means 110 is sent to the control means 101.

The recording head unit 120 is provided with a plurality of recording heads 120a to 120d of black inks K1 to K4 of different densities (four kinds as an example in FIG. 1) arranged in a line, and the control means 101 is provided. A printhead control signal corresponding to the image signal is supplied. These recording heads 120a to 120d may be integrated or may be provided individually. In this way, by forming an image using multiple types of different black ink,
As an image for medical diagnosis, a high-quality, multi-tone image can be obtained. The ink ejecting mechanism of the ink jet recording head may use a piezo effect or an ink jet method using a bubble forming force generated when ink is instantaneously heated. The types of preferable ink will be described later.

As will be described later, a first ink jet recording liquid containing a water-soluble dye capable of coordinating with a metal ion at two or more positions as an ink jet recording liquid, and a complex which reacts with the dye to give a black color A second inkjet recording liquid containing a compound capable of forming a metal ion;
Is used, the recording head is capable of ejecting these two types of inkjet recording liquids.

Reference numeral 131 is a carrying roller for carrying the ink jet recording medium 4 in the main scanning direction. Further, 132 is a heat transfer blocking means for blocking heat conduction to the inkjet recording medium 4, and 133 is a heating roller for heating the inkjet recording medium 4.

Reference numeral 140 is a recording head conveying means for conveying the recording head in the sub-scanning direction. Here, the transport roller 1
31 conveys the ink jet recording medium 4 in the direction of arrow A based on the ink jet recording medium conveyance signal. Further, the recording head unit 12 is movable in a direction B orthogonal to the carrying direction of the inkjet recording medium 4.
A recording head transport unit 140 that moves 0 is arranged.

Here, the recording head conveying means 140 moves the recording head unit 120 in the direction of the arrow B based on the recording head conveying signal, and each recording head 120a-12a.
0d forms an image on the inkjet recording medium 4 based on the recording head control signal. An image signal is sent from the image processing unit 110 to the control unit 101, and an image signal from an external photographing device or storage device is input to the image processing unit 110. The image processing may be input via a network.

<Description of Inkjet Recording Liquid (Ink)> As a dye contained in the inkjet recording liquid used in this embodiment, a metal 2 having a specific structure is used.
A dye capable of coordinating with a dentate or higher is used. Examples of such a dye include those represented by the general formula (1) represented by the above chemical formula.
The dyes represented by (6) to (6) are preferable.

In the general formulas (1) to (5), X1 and X2 represent groups forming a dye through a conjugated system, and at least 2
Represents a group or group of atoms capable of forming a chelate at a locus,
Y represents a group of atoms forming a 5- or 6-membered aromatic carbocycle or heterocycle.

In the general formula (6), X3 represents a group of atoms which can be bonded via a conjugated system, and Z1 and Z2 each represent a group of atoms forming a nitrogen-containing heterocycle containing at least one nitrogen atom. The heterocycles may be different or the same.

In the general formulas (1) to (3) and the general formula (6), R1, R2 and R3 are hydrogen atoms, halogen atoms or 1
Represents a valent substituent, and n represents 0, 1 or 2. X1 is particularly preferably represented by the following general formula (7):
X2 is particularly preferably represented by the following general formula (8).

[0049]

[Chemical 3]

In the formula, Z and Z'represent a group of atoms forming an aromatic nitrogen-containing heterocycle substituted with a group containing at least one chelatable nitrogen atom. Y represents a group of atoms forming an aromatic carbocycle or a heterocycle, and the ring may further have a substituent or may have a condensed ring. Specific examples of the ring include benzene ring, pyridine ring, pyrimidine ring, furan ring, thiophene ring, thiazole ring, imidazole ring, naphthalene ring, 3H-pyrrole ring, oxazole ring, 3H-pyrrolidine ring, oxazolidine ring, imidazolidine. Ring, thiazolidine ring, 3H
-Indole ring, benzoxazole ring, benzimidazole ring, benzthiazole ring, quinoline ring, isoquinoline ring, indolenine ring, barbitur ring, thiobarbitur ring, rhodanin ring, hydantoin ring, pyrazolidinedione ring, pyridinedione ring And so on. These rings may form a condensed ring with another carbon ring (for example, a benzene ring) or a heterocycle (for example, a pyridine ring).
Substituted atoms and substituents on the condensed ring include alkyl groups, aryl groups, acyl groups, amino groups, nitro groups, cyano groups, acylamino groups, alkoxy groups, hydroxy groups, alkoxycarbonyl groups, halogen atoms and the like. The group may be further substituted.

In the formula (6), X3 represents a group of atoms capable of forming a dye by bonding via a conjugated chain. Specifically, it is a 5- or 6-membered carbon ring or heterocycle. A group of atoms forming the group or those represented by the following general formula (9) are preferable.

[0052]

[Chemical 4]

In the formula, X4 and X5 each represent a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, etc., which may be the same or different. May be. When X3 forms a 5- or 6-membered carbocycle or heterocycle, the ring may be a monocycle or a condensed ring, and specifically, a pyrrole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a furan ring, a thiophene ring. , Imidazole ring, benzimidazole ring, pyrazoloyimidazole ring, pyrazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzthiazole ring, isoxazole ring, isothiazole ring, triazole ring, benzotriazole ring, pyrazolotriazole ring, tetrazole Ring, thiadiazole ring, pyrazolotetrazole ring, oxadiazole ring, pyrazolotriazole ring, rhodanine ring, hydantoin ring, thiohydantoin ring, barbitur ring, thiobarbitur ring, oxazoline ring, oxazolidinedione ring, pyridinedione ring, Oxyin Examples include dol ring, pyrazolidinedione ring, quinoline ring, isoquinoline ring, 5-pyrazolone ring, oxazolone ring, isoxazolone ring, indandione ring, hydroxypyridone ring, pyrazolopyridone ring, pyrazolopyrrole ring, pyrazolopyrazole ring and the like. To be

The above carbocycle or heterocycle may be unsubstituted or substituted, and as the substituent atom and the substituent, a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group) Group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (For example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.) ), A cyano group, an acylamino group (for example, an acetylamino group, a propionylamino group, etc.), Kiruchio group (e.g., methylthio group,
Ethylthio group, n-butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group (eg 3-methylureido group, 3,3-). Dimethylureido group, 1,3-dimethylureido group etc.), sulfamoylamino group (dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group ( For example, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfon group). Group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group , Nitroso group, amine oxide group (eg pyridine oxide group), imide group (eg phthalimido group etc.), disulfide group (eg benzene disulfide group, benzothiazolyl-2-disulfide group etc.), heterocyclic group (eg pyridyl group, benz group) Imidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.), carboxyl group, sulfo group and the like. Z1 and Z2 each represent a group of atoms forming a nitrogen-containing heterocycle containing a nitrogen atom, which may be the same or different from each other, specifically, a pyrrole ring,
Pyridine ring, pyrimidine ring, triazine ring, imidazole ring, benzimidazole ring, pyrazoloyimidazole ring, pyrazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzthiazole ring, isoxazole ring, isothiazole ring, triazole ring, benzotriazole ring Ring, pyrazolotriazole ring, tetrazole ring, thiadiazole ring, pyrazolotetrazole ring, oxadiazole ring, pyrazolotriazole ring, pyridinedione ring, oxindole ring, pyrazolidinedione ring,
Quinoline ring, isoquinoline ring, 5-pyrazolone ring, oxazolone ring, indandione ring, isoxazolone ring,
Examples thereof include an indandione ring, a hydroxypyridone ring, a pyrazolopyridone ring, a pyrazolopyrrole ring, and a pyrazolopyrazole ring, and the following general formula (1)
Those represented by 0) to (15) are particularly preferable.

[0055]

[Chemical 5]

In the general formulas (10) to (15), R4,
R5, R6, R8 and R9 are hydrogen atom, halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.) or monovalent substituent (eg alkyl group, aryl group, heterocyclic group, acyl group, amino group, nitro group) Group, cyano group, acylamino group,
Represents a dialkylamino group, an alkoxy group, a hydroxy group, an alkoxycarbonyl group), and R7 represents a hydrogen atom or a monovalent substituent (for example, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a nitro group, a cyano group). , Acylamino group, dialkylamino group, alkoxy group, hydroxy group, alkoxycarbonyl group). R1 and R2 have the same meanings as R1 and R2 below.

In the general formulas (1) to (3) and the general formula (6), R1, R2 and R3 each represent a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom) or a monovalent substituent.
Examples of the monovalent substituent include an alkyl group, an alkoxy group, a cyano group, an alkoxycarbonyl group, an aryl group, a heterocyclic group, a carbamoyl group, a hydroxy group, an acyl group and an acylamino group. n represents 0, 1 or 2.

Specific compound examples of the dye of the present embodiment are shown below, but the present embodiment is not limited to these.

[0059]

[Chemical 6]

[0060]

[Chemical 7]

[0061]

[Chemical 8]

The water-based ink jet recording liquid of the present embodiment is one containing 10% by weight or more of water. And you may contain an organic solvent. 1 at room temperature in this solvent
In this embodiment, a dye that dissolves by weight or more is a water-soluble dye.

Examples of the water-soluble organic solvent used for the ink jet recording liquid in this embodiment include alcohols (eg, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, secondary butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc., polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, di) Propylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, Propylene glycol monophenyl ether, etc., amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylene) Pentamine, Lyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl) -2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-
Examples thereof include imidazolidinone and the like), sulfoxides (for example, dimethyl sulfoxide and the like), sulfones (for example, sulfolane and the like), urea, acetonitrile, acetone and the like.

If desired, a surfactant may be added to the ink. Surfactants preferably used in the ink include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycol. , Nonionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers,
Examples include cationic surfactants such as alkylamine salts and quaternary ammonium salts.

In addition to the above, the ink contains an antiseptic agent, an antifungal agent and a pH.
It is also possible to add an adjusting agent, a viscosity adjusting agent, etc., if necessary. In the water-based inkjet recording liquid as described above, the dye can be used as it is if it is soluble in the solvent system. On the other hand, when it is an insoluble solid as it is, the dye is dispersed in various dispersing machines (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ong mill, etc.). Can be used to make fine particles, or the dye can be dissolved in a soluble organic solvent, and then dispersed in the solvent together with a polymer dispersant and a surfactant. Furthermore, when it is a liquid or a semi-molten substance which is insoluble as it is, it can be dispersed as it is or in a soluble organic solvent and dispersed in the solvent system together with the polymer dispersant and the surfactant.

A specific method for preparing such an aqueous ink jet recording liquid is described in, for example, JP-A-5-148436.
No. 5, No. 5-295312, No. 7-97541, No. 7
Reference can be made to the methods described in -82515, 7-118584 and the like.

Embodiments of the compound containing a metal capable of forming a complex with the above compound in the present embodiment will be described. This compound can be represented by the following general formula (16).

[0068]

[Equation 1]

In this general formula (16), M is a metal and X is
Is an anionic ligand, Y is a neutral ligand, Z is a counter ion, 1 is a natural number of 1 to 5, m is a natural number of 1 to 6, and n is
-2 to 2 (n ≠ 0), o, p, and q represent integers of 0 to 6.

The compound of the general formula (16) will be described in detail below. Examples of the metal ion represented by M ^{l +} include silver (I), aluminum (III), gold (III), cerium (III, IV), cobalt (II, III), chromium (III),
Copper (I, II), europium (III), iron (II, III),
Gallium (III), Germanium (IV), Indium (I
II), lanthanum (III), manganese (II), nickel (I
I), palladium (II), platinum (II, IV), rhodium (I
I, III), ruthenium (II, III, IV), scandium (III), silicon (IV), samarium (III), titanium (I
V), uranium (IV), zinc (II), zirconium (IV)
And the like. Among these, in the case of a bidentate dye, a transition metal ion capable of coordinate-bonding at a 4-dentate or 6-dentate is preferable, and in the case of a tridentate dye, at a 6-dentate Transition metal ions capable of coordinate bond are preferred.

Particularly preferable transition metal ions are zinc (II), nickel (II), cobalt (II, III),
Copper (II), Rhodium (II, III), Ruthenium (II, II)
I), palladium (II) and platinum (II, IV) are more preferable.

As the anion ligand represented by X ^m- , halide ion, hydroxy ion, nitrate ion, carboxylate, cyano ion, peroxo ion, acetylacetonato ion and its derivative, and salicylaldehyde phenolate can be used. Ions and their derivatives, glycinato ion, thiocyanate ion, azide ion, carbonate ion, oxalate ion, sulfate ion, oxalato ion and the like can be mentioned. The neutral ligand represented by Y is ammonia, water, triphenylphosphine, ethylenediamine, 1,3-propanediamine,
2,2'-bipyridine, 1,10-phenanthroline,
Glycinamide, diethylenetriamine, 2,2 ',
2 ″ -terpyridyl, triethylenetetramine and the like can be mentioned.

Further, the counter ion represented by Z ⁿ becomes an anion or a cation as necessary in order to make the charge neutral. Examples of such anions include halide ions (fluoride, chloride, bromide, iodide and other ions), sulfite ion, sulfate ion, alkyl or aryl sulfonate ion, nitrate ion, nitrite ion, perchlorate ion, carboxylate. (Acetate, trifluacetate, stearate, etc.),
Examples thereof include succinate, benzoate, hexafluorophosphate, tetrafluoroborate, and the like. As cations, lithium (I), sodium (I),
Examples of each cation include potassium (I), ammonium and phosphonium.

Specific examples of the metal ion-containing compound capable of reacting with the dye to form a complex as described above include zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, nickel chloride (II) and nickel sulfate ( II), nickel nitrate (II), nickel acetate (II), nickel stearate (II), bis (2,4-pentanedionato) diaqua nickel (I
I), bis (dimethylglyoximato) nickel (I
I), bis (3-methoxycarboni-2,4-tetodecanedionate) nickel (II), tris (glycinamide) nickel (II) tetraphenylborate, cobalt chloride (II), cobalt acetate (II) ), Cobalt thiocyanate (II), hexaamminecobalt (III) chloride, tris (ethylenediamine) cobalt (III) chloride, c
is-dichlorotetraamminecobalt (III) chloride, ammonium tetranitrodiaminecobalt (III) acid, potassium hexacyanocobaltate (III), copper (II) chloride, copper (II) sulfate, copper tetrafluoroborate (I
I), bis (ethylenediamine) copper (II) sulfate, rhodium (II) chloride, rhodium (II) sulfate, dirhodium tetraacetate (II), hexaammine rhodium (III) chloride, potassium hexacyanorhodate (III) , Ruthenium (III) bromide, hexaammine ruthenium (III) bromide,
Potassium hexacyanoruthenium (II), palladium (II) sulfate, ammonium tetrachloropalladium (II), tetraamminepalladium (II) chloride, tetraammineplatinum (II) chloride, bisethylenediamineplatinum (II) chloride, hexaammine Platinum (IV) chloride, tris (ethylenediamine) platinum (IV) chloride, and the like can be mentioned.

The ink jet recording liquid containing the compound represented by the above general formula (16) has a content of 0.1
-40% by weight is preferable, and more preferably 1-20% by weight. The above-mentioned organic solvent, surfactant, preservative, antifungal agent, pH adjusting agent, viscosity adjusting agent and the like can be added to the ink jet recording liquid as required.

The flying viscosity of the ink jet recording liquid of the present embodiment is preferably 40 cps or less, more preferably 30 cps or less. The surface tension during flight is 20
It is preferably dyn / cm or more, more preferably 25 to 80 dyn / cm.

In order to obtain the ink jet recording liquid as described above in the present embodiment, it is preferable that the whole ink jet recording liquid contains 10% by weight or more of water. If the amount is less than this, the properties of the contained water do not appear, and it cannot be said that the aqueous inkjet recording liquid can be used easily.

<Inkjet recording medium> The above general formula (16) can be dispersed in the ink receiving layer of the recording sheet. Hereinafter, regarding the recording sheet, FIG.
Refer to and describe.

The ink jet recording medium used in this embodiment is characterized in that it draws a substantially black image using an ink jet recording liquid. It has four rounded corners and a thickness of 75 μm or more and 250 μm or less. An inkjet recording medium having at least one void-type ink receiving layer 402 on at least one surface, which is made of a colorless or blue colored resin (transparent support 401) having a thickness (FIG. 3A).
reference).

The ink jet recording medium used in this embodiment is in the form of a sheet having an area of 15 cm × 10 cm or more, and if the corners of the sheet are sharp, there may be some safety problems. Rounded corners are attached to the four corners. If the thickness is less than 75 μm, the sheet sags and is difficult to handle. On the other hand, if the thickness is more than 250 μm, the sheet becomes heavy when carried in layers. Conventionally used X-ray films are colorless and transparent or blue colored films, and therefore preferably made of a colorless or blue colored resin so that the user does not feel uncomfortable.

Further, this ink jet recording medium has at least one void-type ink receiving layer on at least one side, and the side not coated with the ink receiving layer is mechanically transportable in a printer or when stacked. In order to prevent the films from sticking to each other, it is a preferred embodiment to have a backing layer 403 as a surface to be matted.

The ink jet recording medium used in this embodiment can be achieved by increasing the porosity of the ink receiving layer 402 as much as possible, and by matting the surface to form irregularities. In addition, a white metal oxide such as titanium oxide or lead oxide can be added to the layer inside or under the ink receiving layer. In addition, a layer is provided on the back side having no ink receiving layer, and a metal oxide such as titanium oxide or lead oxide is dispersed therein, and the ink receiving layer 40
2 can be provided on both sides of the support 401.

Support 40 for this ink jet recording medium
The material of No. 1 is polyester such as polyethylene phthalate, cellulose ester such as nitrocellulose and cellulose acetate, polysulfone, polyimide,
Polycarbonate or the like can be used.

The sheet-shaped ink jet recording medium is preferably colored blue. This blue coloring has the effect of preventing the eyes from being dazzled by excessive transmitted light from a portion without an image when observing the image with transmitted light, and also has the effect of making a black image look more preferable. Then, it is necessary to provide the ink receiving layer 402 on at least one surface of this sheet-shaped inkjet recording medium.

For this reason, it is necessary to improve the adhesiveness of the ink receiving layer 402 by subjecting the support 401 of the ink jet recording medium to corona discharge treatment, flame treatment, ultraviolet irradiation treatment and the like.

The ink receiving layer 402 has a porosity of 40 to 90%.
It is a layer of a three-dimensional mesh structure. Its three-dimensional mesh structure
However, silica fine particles with an average particle size of 20 nm or less or organic substances
Silica formed from fine particles and water-soluble resin
The weight ratio of the fine particles or organic fine particles to the water-soluble resin is
The preferred range is 1.2: 1 to 12: 1. Three-dimensional net
The pores that form the pores of the eye structure have an average diameter of 5-40 nm.
The pores that form the voids have a pore volume of 0.3-1 ml / g.
To do. Silica fine particles are inorganic silicic acid, the surface of which is 1 nm^Two
Has 2 to 3 silalol groups per 3D network structure
Has a particle size of 10 to 100 nm in which silica fine particles are aggregated.
Preferably consisting of chains formed by the joining of secondary particles
Yes. The fine particles here are, for example, colloidal silica and silica silicate.
Lucium, zeolite, kaolinite, halosite, white
Mica, talc, calcium carbonate, calcium sulfate, oxidation
Aluminum etc. can be mentioned. Water-soluble resin
Rivinyl alcohol is preferred. Preferred water
Examples of soluble resins include gelatin and JP-A-7-276789.
It is disclosed in the gazette and the like. Ink receiving layer is 50 ~ 500m ^Two
It is preferable to have a specific surface area of / g. Ink absorption
The amount is 20cc / m^Two~ 50cc / m^TwoIs preferred. Again the sheet
To prevent sheets from sticking together
Disperse on the surface matte particles with an average particle size of 5-100 μm
can do. And a surfactant for antistatic
Can also be added.

On the surface without the ink receiving layer 402,
In addition to gelatin, a water-soluble resin can be applied to prevent curling. To this layer, antistatic processing, mat processing for preventing sticking, coloring with blue, and metal oxide particles such as titanium oxide particles and zinc oxide particles can be added.

It is preferable that the void layer of the ink jet recording film of this embodiment contains a cationic polymer for the purpose of improving the water resistance and bleeding resistance of the image. As the cationic polymer used in the present embodiment, for example, a cationic polymer having a primary to tertiary amino group and a quaternary ammonium group can be used, but discoloration during image storage and deterioration of light resistance are possible. A cationic polymer having a quaternary ammonium salt group is preferred because it has a small amount of dye and a high dye fixing property.

Further, if necessary, JP-A-57-366 can be used.
No. 92, Basic Latex Polymer, Japanese Patent Publication No. 4-1
No. 5744, JP-A Nos. 61-58788 and 62-17.
Polyallylamine described in Japanese Patent No. 4184, etc.
A weak alkali metal acid salt described in JP-A-1-47290 can be used in combination. The cationic polymer preferably used in this embodiment is obtained as a homopolymer of the following quaternary ammonium salt group-containing monomer or a copolymer with other monomers. Next, specific examples of monomers having a quaternary ammonium salt group that are preferably used will be given.

[0090]

[Chemical 9]

[0091]

[Chemical 10]

Next, specific examples of the monomer copolymerizable with the above-mentioned monomer will be given, but the present embodiment is not limited to these.

[0093]

[Chemical 11]

[0094]

[Chemical 12]

Specific examples of the cationic polymer having a quaternary ammonium salt group which is preferably used are given below, but the present embodiment is not limited to these. The numbers indicate the mole percentage of monomer.

[0096]

[Chemical 13]

[0097]

[Chemical 14]

[0098]

[Chemical 15]

The cationic polymer may be water-soluble or latex particles obtained by emulsion polymerization, but in the present embodiment, it is preferable to use a water-soluble cationic polymer. Further, among the water-soluble cationic polymers, a cationic polymer having an average molecular weight of 50,000 or less is preferable because it is less likely to aggregate with the inorganic fine particles and the glossiness is less likely to deteriorate. More preferably, the average molecular weight is 30,000 or less. The lower limit of the average molecular weight is not particularly limited, but is about 2000 or more in terms of water resistance and moisture resistance. The average molecular weight here is a number average molecular weight, and refers to a polystyrene conversion value determined by gel permeation chromatography. It is preferable that the above-mentioned cationic polymer is 0.5 times or more in mass ratio with respect to the hydrophilic binder used in the recording layer, since sufficient water resistance and moisture resistance can be obtained. Also,
Due to the film forming property of the void layer and the like, it is preferably 2 times or less. The upper limit of the amount used is not particularly limited, but is preferably 3 g / m ² or less from the viewpoint of ink absorbency, curl of the recording film, and the like.

When reading a transmission X-ray image, many films are often handled in a short time. At this time, if the front and back of the image can be seen at a glance, the complexity is released. For this purpose, for example, a notch may be placed on the right shoulder of the seat to easily identify the front and back.

As shown in FIG. 3 (b), the ink receiving layer of the ink jet recording medium in this embodiment is preferably composed of an image receiving layer 402a and a solvent absorbing layer 402b, and this image receiving layer is also used. Forming the ink bleeding prevention layer 402c on the layer 402a is a further preferable embodiment.

The image receiving layer 402a is a layer (also referred to as an ink absorbing layer or dye absorbing layer) on which a large amount of dye for image formation is dyed, and the solvent absorbing layer 402b is a solvent of the landed ink selective. The layer which is occluded by the ink and the two layers which are adjacent to each other separate the dye and the solvent thereof in the ink jet recording medium immediately after printing and recording. The structure of these two layers can be realized by changing the type of fine particles used, the particle size thereof, and the content of a mordant such as a cationic polymer.

In this embodiment, the bleeding prevention layer 4 is used.
Having 02c is a preferred embodiment. The bleeding prevention layer 402c is a water-soluble polymer or a water-insoluble polymer binder in which a water-absorbing gel is dispersed, or a filler such as silica for absorbing the water-soluble polymer and the ink to facilitate drying. The thing containing is included. The bleeding prevention layer is applied on the image receiving layer 402a to prevent bleeding when the ink lands.

In the ink receiving layer 402, the general formula (1
The compound represented by 6) may be contained. Regarding this content, 5% to 100% of the weight of fine particles such as colloidal silica can be added. When the amount of this additive is small, the color density cannot be sufficiently obtained when the ink jet recording liquid is a water-soluble dye only. On the other hand, if the amount of the additive is too large, the color of the metal ion becomes visible, which causes a problem. The additive is optimized depending on the kind of the compound represented by the general formula (16) and the purpose of use of the inkjet recording system, but 20% to 60% is more preferable range with respect to the weight of fine particles such as colloidal silica. Is.

Ink receiving layer 40 in this embodiment.
Regarding the compound represented by the general formula (16) to be added to 2,
One kind may be used alone, or a plurality of compounds may be mixed and used in consideration of the image color tone.

With respect to the dye of the ink jet recording liquid used in this embodiment, it is possible to prepare an ink jet recording liquid which develops black with a combination of several kinds or a single kind.

The black color in the present embodiment is the black color of a silver salt image usually seen in the X-ray photographs of conventional silver salt photographs, or a black color close to it. In other words, from bluish cold black toning to slightly yellowish warm black toning,
It does not necessarily have to be a solid black color. A monochromatic image exhibiting a black color in which the color tone does not change at least with respect to the change in density is a preferable mode in the present embodiment.

The kind of dye concentration of the ink jet recording liquid used in this embodiment is preferably 3 kinds or more and 6 kinds or less in order to obtain a smooth image gradation. Three
If the number is smaller than the number of types, it is difficult to obtain a sufficiently smooth density gradation. When the number of types exceeds 6, the improvement in smoothness of the density gradation is small and a problem such as enlargement of the apparatus occurs. Here, in order to have smooth gradation in the image part,
For example, when four kinds of density ink is used in this part, if the image density obtained with the lowest dye density is 1, then 1:
It is preferable to use an inkjet recording liquid having a dye concentration capable of obtaining an image density in a ratio of 2: 4: 8 or 1: 1.5: 3: 9. Using these inks, a smoother image gradation can be obtained in the image gradation portion by a method such as error diffusion.

The maximum image density obtained by the inkjet recording system in this embodiment is 2.60 or more and 4.00 or less. This can be measured with a conventional diffusion densitometer. In order to obtain a sufficiently wide gradation in a medical diagnostic image, the maximum density of the image needs to be 2.60. The object to be diagnosed is 1 mm
A wider gradation is required to identify the following smaller ones. However, even when the maximum image density is higher than 4.00, no matter how intensely transmitted light is observed, there is a limit in its discriminating ability, which only imposes an unnecessary load on the inkjet recording system.

The ink jet recording method in this embodiment may be an on-demand method or a continuous method, but the on-demand method is more preferable.

As the ink ejection method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method ( For example, a thermal inkjet type, an inkjet type using the force of bubble formation, etc., an electrostatic suction type (for example, electric field control type, slit jet type, etc.), and a discharge type (for example, spark jet type, etc.) As an example: About 64 to 512 nozzles are suitable for medical inkjet. The ink drop velocity is more than 2 m / s and preferably 20 m / s. The appropriate amount of ink ejected from one drop is 1 picoliter to 50 picoliters.

In the ink jet recording system used in this embodiment, a black-colored image is formed by a compound containing a metal ion and a water-soluble dye capable of coordinate-bonding with a metal ion at two or more positions. At this time, the above dye reacts with the metal ion to produce a metal complex dye.
This chemical reaction instantly proceeds even at room temperature. However, there is some unevenness in the area where the image density is very high, and the ejection of the inkjet recording liquid is slightly uneven. Further, when the compound containing a metal ion is dispersed in the inkjet recording medium, it cannot be said that there is no unevenness. Therefore, in order to accelerate the progress of the metal complex reaction, it is a preferable embodiment to heat or heat the image portion after the image formation (see FIG. 4).

This heating or heating method is generally of the thermal energy conduction type, radiation type or convection type. The conductive type is a type that heats a substance by bringing it into contact with, for example, a heated drum (a heating roller 133 or the like). The radiation type is, for example, heating a substance by irradiating far infrared light from an infrared heater 134 or the like. The convection type is a heating method in which hot air or the like is applied to a substance from an air nozzle 135 or the like.

In the present embodiment, any of the above three types may be used. Alternatively, the combination is more preferable. The convection type requires the release of heated air. Further, the conductivity type is likely to raise the temperature of the recording apparatus itself. For the radiant type, to partially overheat the above 2
The heating method is easier than the other methods and is the most preferable heating method in the present embodiment.

On the other hand, the ink head is always filled with ink, and if this ink dries, the fine nozzles of the ink head will be blocked. Therefore, it is necessary to minimize the influence of this heating function on the ink head. It is a preferable aspect that the inkjet recording system of the present embodiment has a function of reducing factors such as warm air and infrared light emitted by the heating function that cause the ink head to dry. Specifically, this is realized by providing a heat transfer blocking roller 132 or the like as a heat transfer blocking means between the heating function and the ink head, or by providing a wall such as a plate or an air curtain. It

Further, in order to reduce such drying, it is necessary to prevent the temperature of the entire printer from rising. Therefore, the present embodiment is characterized in that after the printing and heating are finished, the drying function is automatically stopped when a set time elapses under the control of the control means 101 or the like. That is, the above radiation type can be realized by stopping the far infrared emission. The conductive type can be realized by, for example, turning off the heater of the heating roller 133. The convection type can be realized by turning off the power of the blower fan. These functions can be stopped manually, or the functions can be set in the recording device so that the functions are stopped after a certain period of time, and the functions can be automatically activated. When the temperature surrounding the recording device is low, the temperature sensor built into the recording device detects the external temperature, and for example, only the heating of the heating roller is continued and only the far infrared heater power is cut off. It is a preferable embodiment to draw out to.

The X-ray image in the present embodiment is a so-called simple radiographed image of the chest, abdomen, limbs, etc., which is usually photographed using an X-ray tube in the radiology department of a medical facility, and magnified radiographs and contrasts For example, shooting, and stereoscopic shooting.
For these X-ray images, an image once taken by the screen film system can be taken out as a digital image signal by a so-called film digitizer, and the image can be re-recorded by the inkjet recording system of the present embodiment. Further, it can be obtained by recording an image signal from a computed radiography or a flat panel X-ray detector. Also, using the Internet, etc., receive digital X-ray image signals from a remote location,
You can also get the image. Furthermore, with this system,
Magnetic resonance imaging (MRI) images that do not use X-rays can also be printed side by side with X-ray images. These printed medical images are used for image diagnosis, conferences, education, and informed consent.

[0118]

EXAMPLES Specific examples of the above-described embodiment will be described below. <1. Preparation of inkjet recording medium> visible light density 0.18
A 175 μm thick polyester base colored in blue was used as a transparent support 401, and both surfaces thereof were subjected to corona discharge treatment. First, a backing layer 4 containing a surfactant in a gelatin film for preventing curling and antistatic.
03 was applied. And using the liquid of the following composition,
The ink receiving layer 402 was formed on the surface of the other support.

The composition of the coating liquid for the ink receiving layer is shown below. <1.1 Medium sample> ・ Dry silica fine particles (average particle size: 7 nm, silalol groups 2-3)
/ Nm ² : 1 kg of Aerosil A300) ・ Polyvinyl alcohol (saponification degree 88%, degree of polymerization 3500: PVA23
5 kg of Kuraray) is prepared. After the above composition was added to and dispersed in 15 kg of water, the pH was adjusted to 4.0 to obtain a coating liquid.

Then, a medium sample was obtained after coating the above film with a wet film thickness of 350 μ and drying. <1.2 Medium sample> Nickel chloride was added to the above coating composition liquid.
A medium sample in which 5 kg was added to form an ink receiving layer,
It was obtained by coating in the same manner as the medium sample.

<1.3 Medium Sample> Further, a coating solution having the following composition was prepared, and the above blue transparent base was used to prepare a wet film thickness.
A coating of 350 μm was applied, and a medium sample was obtained after drying.・ 0.5kg of nickel chloride ・ Alumina fine particles (average particle size: 13nm, Aluminum Oxide
C) 1kg, polyvinyl alcohol (saponification degree 88%, degree of polymerization 3500: PVA23
5 kg of Kuraray) is prepared.

The above composition was added to 14 kg of water and dispersed, and then the pH was adjusted to 4.0 to obtain a coating solution. <1.4 medium sample> ・ Dry silica fine particles (average particle size: 7 nm, silalol groups 2-3)
/ Nm ² : 1 kg of Aerosil A300) ・ Polyvinyl alcohol (saponification degree 88%, degree of polymerization 3500: PVA23
5 kg of Kuraray) is prepared.

After the above composition was added to and dispersed in 15 kg of water, the pH was adjusted to 4.0 to obtain a coating liquid A.・ Dry silica fine particles (average particle size: 7 nm, silalol groups 2-3)
/ Nm ² : 1 kg of Aerosil A300) ・ Polyvinyl alcohol (saponification degree 88%, degree of polymerization 3500: PVA23
5 Prepare 0.5 kg of Kuraray and 0.2 kg of Mor-1 (Tokyo Kasei).

After the above composition was added to 15 kg of water and dispersed therein, the pH was adjusted to 4.0 to obtain a coating liquid B. Coating solution A is applied to a blue base support that has been coated with a backing layer and a wet film thickness of 200μ
After coating and drying, a coating solution B having a wet film thickness of 150 μ was further applied and dried to obtain a medium sample having a two-layer structure of an ink receiving layer and a solvent absorbing layer.

The water absorption of the above ink jet recording medium is
It was 35 g / m ² . In this, the medium having only the ink receiving layer from which the backing layer was peeled off was dipped in water at about 15 ° C., pulled up after 1 minute, and the water absorption amount was determined from the weight before and after the immersion.

<2. Preparation of ink><2.1Ink> 240 g of CI Food Black, 250 g of glycerin, 3 g of Emulgen 911 (manufactured by Kao Corporation), 1000 g of ion-exchanged water, diluted with a liquid containing no dye of the above ink composition Then, a black ink having a density of 5% was used as a reference for a density ratio of 1. Inks of various densities were prepared based on this density to obtain inks.

<2.2 Ink> 50 g of nickel chloride,
150 g of triethylene glycol and 10 g of isopropanol
0 g of the ink was finished with 1000 g of ion-exchanged water to obtain an ink having the above ink composition.

<2.3 Ink> 8 g of dye [D-1], dye
8 g of [D-8], 8 g of dye [D-13], 6 g of dye [D-5], 200 g of triethylene glycol, 20 g of isopropanol, 1 g of triethanolamine, 1000 g of ion-exchanged water Finishing, a black ink having a concentration of 5%, which was diluted with a liquid containing no dye of the above ink composition, was used as a standard for a concentration ratio of 1. Inks of various densities were prepared based on this density to obtain inks. The ink obtained here did not have an unpleasant odor.

<3. Inkjet recording device (printer)> An on-demand inkjet printer with a nozzle hole diameter of 24 μm, 256 nozzle heads, a drive frequency of 12 kHz, an ink ejection speed of 6 m / sec, 7 picoliter droplets, and 360 dots / 25.4 mm was used. . Further, a printer in which an infrared heater was installed so that the maximum surface temperature after printing was 50 ° C. for 2 seconds was also used. This ink head was used for ink in the image density area. The error diffusion method was used for the image gradation part.

<4. Taking a test image> Toshiba Corporation X-ray tube DRX-29031H whose rotating anode is tungsten
An image was taken using a chest phantom made by Kyoto Kagaku Co., Ltd. with a focus size of 2 mm and an X tube voltage of 125 kV. Read size 175 after shooting with Konica's Regius 150
The image signal was read in μm. After performing gradation correction suitable for the image, this 12-bit gradation image signal was obtained.

<5. Printing of medical image> The above image signals were input to the printer using the printer, the ink, and the ink jet recording medium to obtain the chest monochrome images of test images Nos. 1 to 16. The image density in the lung field is 1.5, and the maximum density in the non-image area is 2.8.
was gotten. Moreover, no particular odor was felt from the obtained image.

<6. Evaluation of image storability of test image print sample> Two sets of the above print images were prepared. 21 pairs
It was stored at ± 2 ° C and 30 ± 5% RH. This environment is a few
In general, the condition is such that blurring does not substantially occur in the image for months. The other set was stored at 80 ± 2 ° C. and 70 ± 5% RH for 7 days to test for image bleeding. Normally, there are almost no such image storage conditions. Although it is not scientifically clear that this condition corresponds to the actual passage of time, it is a condition used as an accelerated test for bleeding occurrence.

Image blurring due to image bleeding was observed centering on the simulated blood vessel image in the upper left lung field of the sample stored under the above two conditions for 7 days. The results are shown in Table 1 below.
Comparison of images stored at 80 ° C based on those stored at 21 ° C.
There is no image blur (image blurring) and the equivalent of the two is ◎, although it seems that there is some blurring, but something that you do not notice immediately 〇, some blurring starts, but image deterioration is The one that was not felt was evaluated as Δ, and the one where the blur of the image deterioration was clear was evaluated as X. The observations were made on a light box with a brightness of 8000 lx.

[0134]

[Table 1]

As shown in Table 1, better results could be obtained in the examples of the present invention than in the comparative examples.

[0136]

As described in detail above, it is possible to realize an ink jet recording system, an ink jet recording liquid, and an ink jet recording medium suitable for medical treatment, particularly for printing X-ray images for diagnostic purposes.

[Brief description of drawings]

FIG. 1 is a block diagram showing an electrical configuration of an inkjet recording apparatus that constitutes an inkjet recording system according to an embodiment of the present invention.

FIG. 2 is a system explanatory diagram showing an example of an inkjet recording system according to an embodiment of the present invention.

FIG. 3 is a configuration diagram showing a configuration of an inkjet recording medium that constitutes an inkjet recording system according to an exemplary embodiment of the present invention.

FIG. 4 is a configuration diagram showing how an inkjet recording medium constituting the inkjet recording system according to the embodiment of the present invention is heated.

FIG. 5 is a configuration diagram showing a system configuration of a medical digital image diagnostic system.

[Explanation of symbols]

4 Inkjet recording medium 100 Medical inkjet recording device 101 control means 110 image processing means 120 recording head unit 131 Conveyor roller 132 Heat transfer prevention means (heat transfer prevention roller) 133 heating roller

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41J 3/04 101Z F term (reference) 2C056 EA05 ED07 FC01 FC06 HA46 HA47 2H086 BA02 BA05 BA14 BA15 BA24 BA31 BA53 BA56 BA59 BA62 4J039 BA39 BC05 BC06 BC12 BC19 BC33 BC34 BC40 BC44 BC50 BC51 BC54 BC55 BC59 BC65 BC73 BC75 BC79 BE06 CA03 EA19 EA44 EA47 GA24

Claims (17)

[Claims] 1. An inkjet recording system for performing inkjet recording by ejecting an inkjet recording liquid onto an inkjet recording medium from a nozzle, wherein the inkjet recording liquid is an aqueous solution capable of coordinate-bonding with a metal ion in two or more positions. Inkjet recording medium, which contains a functional dye, wherein the inkjet recording medium is a transparent sheet containing a complex-forming metal ion that reacts with the water-soluble dye to form a black color. 2. An ink jet recording system for ejecting ink jet recording liquid onto an ink jet recording medium from a nozzle to perform ink jet recording, wherein the ink jet recording liquid is water-soluble which can coordinate-bond with metal ions at two or more sites. Inkjet recording liquid containing a reactive dye, a second inkjet recording liquid containing a compound containing a metal ion capable of forming a complex that exhibits a black color by reacting with the dye, and the inkjet recording liquid is ejected from the nozzle. And a control means for performing control for causing the first inkjet recording liquid to be ejected onto the inkjet recording medium, and then the second control means for ejecting the first inkjet recording liquid onto at least an image forming area of the inkjet recording medium. An inkjet printer characterized by ejecting an inkjet recording liquid. Recording system. 3. The water-soluble dye is represented by the following general formulas (1) to (6).
3. The inkjet recording system according to claim 1, wherein the inkjet recording system is a dye represented by [Chemical 1] [In the formulas (1) to (5), X1 and X2 each have a group that forms a dye through a conjugated system, and represent at least a bidentate chelate-forming group or an atom group, and Y is 5 Represents a group of atoms forming a six-membered or six-membered aromatic carbocycle or heterocycle. In the formula (6), R1, R2 and R3 each represent a hydrogen atom, a halogen atom or a monovalent substituent, and n represents 0, 1 or 2. ] 4. The metal ion according to claim 1, wherein the metal ion is a transition metal ion-containing compound.
The inkjet recording system according to any one of 1. 5. The inkjet recording system according to claim 1, wherein the inkjet recording liquid is an aqueous inkjet recording liquid containing 10% by weight or more of water. 6. The inkjet recording medium according to claim 1, further comprising heating means for heating the inkjet recording medium after ejecting the inkjet recording liquid onto the inkjet recording medium. Inkjet recording system. 7. A heat transfer inhibiting means for inhibiting transfer of thermal energy generated from the heating means to a recording head for ejecting the inkjet recording liquid and a means for supplying the inkjet recording liquid. 7. The inkjet recording system according to claim 6, wherein: 8. The maximum density of a transmission image is 2.60 or more and 4.0.
The inkjet recording system according to any one of claims 1 to 7, wherein a monochrome image of 0 or less is recorded. 9. The inkjet recording system according to any one of claims 1 to 8, wherein the type of concentration of the water-soluble dye in the inkjet recording liquid used is 3 or more and 6 or less. . 10. The ink jet recording system according to claim 1, which is used for forming an X-ray image. 11. An inkjet recording liquid for use in the inkjet recording system according to claim 1, wherein the inkjet recording liquid is a water-soluble dye capable of coordinate-bonding with a metal ion in two or more positions. An ink jet recording liquid comprising: 12. The water-soluble dye is represented by the following general formula (1):
The inkjet recording liquid according to claim 11, which is a dye represented by any one of (6) to (6). [Chemical 2] [In the formulas (1), (1) to (5), X1 and X2 each have a group that forms a dye through a conjugated system, and represent at least a bidentate chelate-forming group or a group of atoms, Y is 5
Represents a group of atoms forming a six-membered or six-membered aromatic carbocycle or heterocycle. In the formula (6), R1, R2, R
3 represents a hydrogen atom, a halogen atom or a monovalent substituent, and n
Represents 0, 1 or 2. ] 13. The inkjet recording liquid according to claim 11, wherein the inkjet recording liquid is a water-based inkjet recording liquid containing 10% by weight or more of water. 14. The inkjet recording medium used in the inkjet recording system according to claim 1, wherein the inkjet recording medium has a support made of a transparent resin, An ink jet recording medium, wherein a backing layer having fine particles dispersed therein is formed on a non-recording surface of the body, and an ink receiving layer having voids is formed on the recording surface of the support. 15. The ink receiving layer comprises an image receiving layer for carrying an image and a solvent absorbing layer for absorbing a solvent of an inkjet recording liquid. Inkjet recording medium. 16. The ink jet recording according to claim 14 or 15, wherein the ink receiving layer contains a metal ion-containing compound capable of forming a complex by reacting with a water-soluble dye. Medium. 17. A colorless or blue-colored resin having rounded corners at four corners and having a thickness of 75 μm or more and 250 μm or less, and at least one surface having at least one void type ink receiving layer. Claim 14
The inkjet recording medium according to claim 16.