JP2009226642A - Formation method of inkjet image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording method which enables forming of an image free from the generation of impact interference of ink droplets even if inkjet recording is performed on rapid discharge conditions. <P>SOLUTION: An ink set of yellow ink containing at least, one kind of water-soluble yellow dye, magenta ink containing at least, one kind of water-soluble magenta dye and cyan ink containing at least, one kind of water-soluble cyan dye, featuring that the counter ion of the water-soluble dye of each ink is lithium ion and/or ammonium, is used. After a first dot impacts on the surface of an image receiving material, a second dot of the ink with a different color phase from the first dot, is discharged within 50 ms. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for forming an inkjet image.

  The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording. Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inkjet inks, good solubility in solvents such as water, high-density recording is possible, hue is good, light, heat, in the environment It is robust against active gases (SOx, etc. in addition to oxidizing gases such as NOx and ozone), has excellent fastness to water and chemicals, has good fixability to image receiving materials, and is difficult to bleed, ink It is required to have excellent storage stability, no toxicity, high purity, and availability at low cost.

  In particular, it is a dye that is fast to light, humidity, and heat, and in particular, when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, it is oxidative such as ozone in the environment. It is strongly desired to be robust against gas and excellent in water resistance.

  Dyes that are highly robust against such various external environments have been disclosed (see, for example, Patent Documents 1 and 2).

  On the other hand, in recent years, an inkjet system has been increasingly used when printing out digital images taken with a digital camera or a portable camera. In order to increase the number of processed sheets per unit time, the recording time is shortened by increasing the ink ejection frequency or by high-density recording with multiple nozzles.

  However, many inks using high-fastness dyes as described above do not easily penetrate into the image receiving material. When high-speed recording is performed using ink with poor permeability, the next ink is ejected to an adjacent location before the ink droplet landed on the image receiving material penetrates into the image receiving layer. The two ink droplets may coalesce, and the quality of the resulting image may be significantly reduced. Such coalescence of ink droplets is hereinafter referred to as “droplet interference”.

  As a method for improving the permeability of the ink, for example, a method of decreasing the surface tension of the ink by increasing the amount of the surfactant added is known to those skilled in the art. However, an unnecessarily large increase in the amount of the surfactant tends to cause bubbles in the ink and may deteriorate the discharge performance. In addition, even when the surface tension is reduced more than necessary, the ink may easily drip from the nozzle, or it may become difficult to form a meniscus of the ink in the nozzle, thereby affecting the discharge property. It is difficult to increase the amount of

  It is also known to those skilled in the art to improve ink permeability by adding specific water-soluble organic solvents such as 1,2-hexanediol, 2-pyrrolidone and triethylene glycol monobutyl ether. However, it is known that the composition of the solvent in the ink affects the ink ejection property, the drying property on the nozzle, the storability of the resulting image, and the bleeding of the image when stored under high humidity conditions. However, the present situation is that no solvent composition satisfying all the performances has been found.

  On the other hand, phthalocyanine dyes are often used for cyan inks, but high-fastness phthalocyanine dyes often have low solubility in water. In order to improve the water solubility of a dye having low water solubility, it has been disclosed that the counter ion of the dye is a lithium ion (see, for example, Patent Document 3). This method is effective in the case of a cyan single color, but in the secondary color or tertiary color in which a plurality of inks are mixed, if the counter ion of the dye contained in the other ink is other than lithium ions, As a result of the exchange, the water solubility of the phthalocyanine dye is lowered, the penetration speed with respect to the image receiving material is lowered, and droplet ejection interference may occur in high-speed recording. Here, droplet ejection interference refers to ink droplets ejected from the nozzles landing on the image receiving material and before the ink droplets penetrate into the image receiving layer. It means that liquids are united by contact. The above problem is noticeable in blue and green in which other colors such as cyan, magenta and yellow are mixed.

  For this reason, a counter ion that does not cause precipitation between inks is selected (for example, Patent Document 4). Here, the water solubility of the dye is improved by lithium ions when the water-soluble group of the dye is an ionic hydrophilic group having a low pKa such as a sulfonic acid group. However, when the water-soluble group is a sulfonic acid group, the interaction between the dye and the mordant polymer contained in the image receiving layer for fixing the dye is weak, so that the dye can easily move and print. Changes in hue immediately after the image and bleeding of the image when the recorded image is stored under high humidity conditions are likely to occur.

  In contrast, when the water-soluble group of the dye is a carboxyl group having a relatively high pKa, the interaction between the dye and the mordanting polymer becomes stronger, but on the other hand, the water-solubility of the lithium salt of the carboxylic acid is greatly reduced. In addition, this may cause ejection failure due to precipitation of dyes. These phenomena were particularly remarkable in the case of a yellow dye.

Accordingly, a yellow ink using a yellow dye having a carboxyl group in the molecule and having a high water solubility even if it is a lithium salt, and the counter ion of the dye in all the inks is lithium. There has been a demand for a method of forming an inkjet image using an ink set which is an ion.
JP 2007-77256 A JP 2007-138124 A JP 2003-213167 A JP 2004-307819 A

  An object of the present invention is to provide an inkjet image forming method capable of forming an image that does not cause droplet ejection interference even when inkjet recording is performed under high-speed ejection conditions.

<1> a yellow ink containing at least one water-soluble yellow dye, a magenta ink containing at least one water-soluble magenta dye, and a cyan ink containing at least one water-soluble cyan dye, and Using an ink set in which the counter ions of the water-soluble dye in each ink are lithium ions and / or ammonium ions,
Within 50 ms after the first dot hits the surface of the image receiving material,
At the position where it contacts the first dot,
A method for forming an inkjet image, wherein a second dot is ejected from an ink having a hue different from that of the first dot.
<2> The inkjet image according to <1>, wherein 70 mol% or more of the counter ions of the water-soluble dye in the yellow ink, magenta ink, and cyan ink are lithium ions and / or ammonium ions. Forming method.
<3> The method for forming an inkjet image according to <1> or <2>, wherein the ink set further includes a black ink containing at least one water-soluble black dye.
<4> At a position where the first dot contacts the first dot within 30 ms after landing on the surface of the image receiving material,
The method for forming an inkjet image according to any one of <1> to <3>, wherein the second dot is ejected from an ink having a hue different from that of the first dot.
<5> At a position where the first dot contacts the first dot within 10 ms after landing on the surface of the image receiving material,
The method for forming an inkjet image according to any one of <1> to <4>, wherein the second dot is ejected from an ink having a hue different from that of the first dot.

<6> 50% by mass or more of the water-soluble yellow dye contained in the yellow ink has at least one carboxyl group in the molecule, described in any one of the above items <1> to <5> Method of forming an inkjet image.
<7> The above items <1> to <6, wherein 50% by mass or more of the dye contained in each ink in the ink set has a noble oxidation potential of the dye of more than 1.0 V (vs SCE). The method for forming an inkjet image according to any one of the above.
<8> 50% by mass or more of the water-soluble yellow dye contained in the yellow ink contains at least one selected from the group consisting of a compound represented by the general formula (Y-I) and a salt thereof. The method for forming an inkjet image according to any one of <1> to <7> above.

(In the formula, G represents a heterocyclic group, n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When 2, R, X, Y, Z, Q, G represents a monovalent or divalent substituent, and at least one represents a divalent substituent, and when n is 3, R, X , Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent, and at least two represent a divalent substituent or at least one represents a trivalent substituent.

<9> The water-soluble yellow dye represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y -4) and at least one selected from the group consisting of a compound represented by formula (Y-5) and a salt thereof, the method for forming an inkjet image as described in <8> above.

(Wherein R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atom constituting a 5- to 8-membered nitrogen-containing heterocycle. M represents a hydrogen atom or a cation, and m ₁ represents an integer of 0 to 3.)

(Wherein R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. M ₂₁ and m ₂₂ each independently represents an integer of 0 to 3.)

(In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle independently, M represents a hydrogen atom or a cation, and m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.)

(Wherein R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle independently, M represents a hydrogen atom or a cation, and m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.)

(Wherein R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₄ represents a divalent linking group, G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, M represents a hydrogen atom or a cation, and m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.)

<10> Formula (Y-1), Formula (Y-2), the general formula (Y-3), Formula (Y-4), the general formula (Y-5), G, G 1 and G _The method for forming an inkjet image according to <9>, wherein the nitrogen-containing heterocycle composed of ₂ is an S-triazine ring.

<11> The <9> or <10>, wherein the water-soluble yellow dye represented by the general formula (Y-1) is a compound represented by the following general formula (Y-6) Method of forming an inkjet image.

(In the formula, R ₁ , R ₂ , Y ₁ and Y ₂ each represent a monovalent group, and X ₁ and X ₂ each independently represent an electron-withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl A group, a substituted or unsubstituted heterocyclic group, and M represents a hydrogen atom or a cation.)
<12> The above <1> to <11, wherein 50% by mass or more of the water-soluble cyan dye contained in the cyan ink is a phthalocyanine dye having a structure represented by the following general formula (C-1): The method for forming an inkjet image according to any one of the above.

(In General Formula (C-1), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ are each independently (= C (J ₁ )-and or N =), (= C (J ₂ )-and / or -N =), (= C (J ₃ )-and / or -N =), (= C (J ₄ )-and / or -N =) J _{1 to} J ₄ each independently represents a hydrogen atom and / or a substituent (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) ring {A ring: (A), B ring: (B), C ring: (C), Ring D: At least one of the four (D)} s is preferably an aromatic hydrocarbon ring, more preferably two or more are aromatic hydrocarbon rings A ring, B ring, C When any ring of the ring and ring D is a hetero ring, the pyridine ring is also Ku If preferred .J ₁ through J ₄ pyrazine ring is a substituted group is preferably an electron-withdrawing substituent, at least one of further J ₁ through J ₄ is or J ₁ through J ₄ (At least one of the substituents possessed by has an ionic hydrophilic group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.)
<13> The above <1> to <12, wherein 50% by mass or more of the water-soluble magenta dye contained in the magenta ink is a water-soluble azo dye having a structure represented by the general formula (M-1). The method for forming an inkjet image according to any one of the above.

(In the general formula (M-1), A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. Do B ₁ and B ₂ represent -CR ₁₃ = and -CR ₁₄ =, respectively? Or one of them represents a nitrogen atom and the other represents —CR ₁₃ ═ or —CR ₁₄ ═ each of R ₁₁ and R ₁₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, An aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, each group further having a substituent. also good _.G, R _{13, R 14,} each independently, a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl , Heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group , An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group Alkyl and arylsulfonylamino groups, nitro groups, alkyl and arylthio groups, alkyl and arylsulfonyl groups, alkyl and arylsulfinyl groups, sulfamoyl groups, heterocyclic Represents a group or an ionic hydrophilic group. Each group may be further substituted. Also, R ₁₃ and R _11, or even to form a 5- or 6-membered ring and R ₁₁ and R ₁₂ are bonded However, general formula (M-1) has at least one ionic hydrophilic group.)
<14> 50% by mass or more of the water-soluble black dye contained in the black ink is a water-soluble azo dye having a structure represented by the following general formula (B-1). The method for forming an inkjet image according to any one of 13>.

(In the above general formula (B-1), A and B each independently represents an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group. And B is a divalent group.) T ₁ and T ₂ each represent ═CR ₄₃ — and —CR ₄₄ ═, or either one is a nitrogen atom and the other is ═CR ₄₃ — or —CR _44. V ₁ , R ₄₃ and R ₄₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, or a carbamoyl group. Group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group Si group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and Represents an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and each group may be further substituted, R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkyl group, Represents a quinyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, and each group further has a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms, and R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may combine to form a 5- to 6-membered ring. )

<15> In any one of the above items <1> to <14>, wherein an image is formed on the image receiving material having an ink receiving layer containing porous white inorganic pigment particles on a support. The method for forming an inkjet image as described.

  According to the present invention, it is possible to provide an inkjet image forming method capable of forming an image without causing droplet ejection interference even when inkjet recording is performed under high-speed ejection conditions.

The inkjet image forming method of the present invention will be described below.
The inkjet image forming method of the present invention comprises a yellow ink containing a water-soluble yellow dye, a magenta ink containing a water-soluble magenta dye, and a cyan ink containing a water-soluble cyan dye, Using an ink set in which the counter ion of the water-soluble dye is lithium ion and / or ammonium ion,
A second dot made of ink having a hue different from that of the first dot is ejected to a position where the first dot comes into contact with the first dot within 50 ms after landing on the surface of the image receiving material.
The “first dot” is a dot ejected from any one of the yellow ink, magenta ink, and cyan ink when forming an image by an inkjet method, and the hue is not particularly limited. . The “second dot” means a dot of ink ejected from another ink having a different hue from the ink used for the first dot.
In the present invention, the formation of the ink jet image is achieved by continuously ejecting ink for ink jet recording onto the image receiving material. Therefore, the “first dot and the second dot” means the image formation. It also includes two dots that are hit after each other at an arbitrary time.

The present invention uses an ink set having an ink containing lithium ions and / or ammonium ions as a counter ion of a water-soluble dye, and the first dot has a hue within 50 ms after landing on the surface of the image receiving material. When forming an image by ejecting a second dot with a different point to the position where it comes into contact with the first dot, there is no droplet ejection interference, especially in the secondary colors of green and blue. It is possible to form an image that does not. Further, when a yellow dye is used as the water-soluble dye, the effect of preventing droplet ejection interference is particularly remarkable.
After the first dot has landed on the surface of the image receiving material, the time interval for discharging the second dot to the position where it comes into contact with the first dot is the landing of the first dot from the viewpoint of speeding up image recording. Within 30 ms is preferable, and within 10 is more preferable.
Hereinafter, an ink set used in the present invention and a method for forming an inkjet image will be described.

<Ink set>
The ink set according to the present invention includes inks having water-soluble dyes having yellow, magenta, and cyan hues, and can include other inks such as black ink as necessary.
First, the water-soluble dye contained in the ink will be described below.

[Water-soluble dye]
In the ink jet image forming method of the present invention, an ink set in which counter ions of water-soluble dyes contained in all inks are lithium ions and / or ammonium ions (hereinafter also referred to as specific counter ions) is used. It is characterized by.
The counter ions need to be lithium ions and / or ammonium ions. Among them, lithium ions and ammonium ions are preferable, and lithium ions are particularly preferable.
70 mol% or more of the counter ions are preferably the specific counter ions, more preferably 75 mol% or more, and particularly preferably 80 mol% or more.
By setting the content of mol% of the specific counter ion within the above range, even when different counter ions exist and exchange with counter ions in the water-soluble dye occurs, droplet ejection interference between different colors hardly occurs. This is preferable because an ink having good penetrability tends to be obtained.

In addition, the ink used in the inkjet image forming method of the present invention includes yellow, magenta, cyan, and black dyes having oxidation potentials higher than 1.0 V (vs SCE). It is preferable to use 50% by mass or more of the entire dye in the image to provide image fastness.
The oxidation potential is preferably as noble, more preferably noble than the oxidation potential of 1.1 V (vs SCE), and most preferably noble than 1.15 V (vs SCE).
The proportion of the dye having an oxidation potential nobler than 1.0 V (vs SCE) in the whole dye is preferably as high as possible, more preferably 60% by mass or more, and most preferably 70% by mass or more.
Further, the oxidation potentials of yellow, magenta, cyan and black dyes are preferably not so different from each other in terms of the balance at the time of fading, preferably within 0.3V, and more preferably within 0.25V. .

  The value of the oxidation potential represents the ease of transfer of electrons from the sample to the electrode. The larger the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation. Represent. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group.

  The value of the oxidation potential, which will be described in detail below, means the potential at which the compound is an anode in voltammetry and the electron of the compound is extracted, and is considered to approximately match the energy level of HOMO in the ground state of the compound. Yes.

  The inventors have studied the ozone fastness of the colored image. As a result, there is a correlation between the oxidation potential of the compound used in the colored image and the ozone fastness, and the oxidation potential value is higher than that of the saturated calomel electrode (SCE). It has been found that ozone fastness is improved by using noble compounds.

  The reason why the ozone fastness of the colored image is improved can be explained by the relationship between the HOMO (highest occupied orbit) and LUMO (lowest empty orbit) of the compound and ozone gas. That is, it is considered that the colorant is oxidized by the reaction of the colorant HOMO and the ozone gas LUMO, and as a result, the ozone fastness of the colored image is lowered. The reactivity with ozone gas may be lowered by lowering the HOMO.

  A person skilled in the art can easily measure the value (Eox) of the oxidation potential. Regarding this method, see, for example, P.I. Delahay, “New Instrumental Methods in Electrochemistry” (1954 Interscience Publishers) and A.D. J. et al. "Electrochemical Methods" by Bard et al. (1980 John Wiley & Sons) and "Electrochemical Measurement Method" by Akira Fujishima et al. (1984, Gihodo Publishing Co., Ltd.).

The measurement of the oxidation potential will be specifically described.
The oxidation potential is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ mol · dm ^{−3 in} a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Dissolve and measure as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography.
The supporting electrolyte and solvent to be used can be selected appropriately depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Akira Fujishima et al., “Electrochemical measurement method” (published by Gihodo Publishing Co., Ltd., 1984), pages 101 to 118.

  The value of the oxidation potential may be deviated by several tens of mil volts due to the influence of the inter-liquid potential difference or the liquid resistance of the sample solution, but the potential measured by calibrating with a standard sample (for example, hydroquinone). The reproducibility of the value of can be guaranteed.

The oxidation potential in the present invention is in N, N-dimethylformamide containing 0.1 mol · dm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the compound is 1 × 10 ⁻³ mol · dm ⁻³ ). The SCE (saturated calomel electrode) is used as the reference electrode, the graphite electrode is used as the working electrode, and the platinum electrode is used as the counter electrode, and values measured by direct current polarography are used. When the dye is hardly soluble in N, N-dimethylformamide, water may be added within a range of 1% or less.

  The dye used in the present invention may have any structure as long as it satisfies the above oxidation potential. In particular, the yellow dye has a noble structural potential because it has a noble oxidation potential (low HOMO). The dye structure necessary for satisfying the oxidation potential will be described in detail below.

  In the present invention, in order to lower the reactivity with ozone as an electrophile, it is desirable to introduce an electron withdrawing group into the dye skeleton to make the oxidation potential more noble. Therefore, using Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of a substituent, the σp value is as in nitro, cyano, sulfinyl, sulfonyl, and sulfamoyl groups. It can be said that the oxidation potential can be made more noble by introducing a large substituent.

Hammett's substituent constant σp value will be described briefly.
Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo).

In addition to the above-described substituents, the oxidation potential can be made noble as the number of atoms having high electronegativity generally increases as the constituent atoms of the chromophore.
Therefore, for example, when an unsaturated heterocycle is used as a constituent of a chromophore rather than an aryl group, the oxidation potential can be made noble. Examples of the heteroatom having a high electronegativity include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is particularly preferable.

Accordingly, the dye used in the present invention is preferably one in which the chromophore is composed of a heteroatom, one containing an unsaturated heterocycle, or one containing an electron-withdrawing group.
Preferred chromophores composed of heteroatoms include azo dyes, azomethine dyes, phthalocyanine dyes and the like, with azo dyes being particularly preferred.
As the unsaturated heterocycle, a 5- or 6-membered unsaturated heterocycle is preferable, and a thiophene ring, furan ring, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazole ring, thiadiazole ring. And oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like. The unsaturated heterocycle may form a condensed ring with a hydrocarbon ring or a heterocycle.
In the case of a nitrogen-containing heterocycle, the nitrogen atom may be quaternized. Further, with respect to the heterocycle that can be tautomeric, even when only one tautomer is described, other tautomers are also included. Of these, preferred are a thiazole ring, an isothiazole ring, a pyrazole ring, a thiadiazole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. Most preferred are an isothiazole ring, a pyrazole ring, a 1,2,4-thiadiazole ring, a 1,3,4-thiadiazole ring, and a pyridine ring.

  As a preferable electron-withdrawing substituent, a substituent having a Hammett's σp value of 0.4 or more is preferable, a substituent of 0.45 or more is more preferable, and a substituent of 0.50 or more is most preferable. Further, when a plurality of electron-withdrawing groups are present as substituents on the chromophore, the sum of the σp values of the substituents is preferably 0.50 or more, more preferably 0.60 or more, and 0.70 The above is most preferable. Specific examples of the electron-withdrawing group having σp of 0.40 or more are described in J. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo) I can do it.

-Water-soluble yellow dye-
The water-soluble yellow dye used in the inkjet image forming method of the present invention is not particularly limited as long as the counter ion of the water-soluble group is lithium ion and / or ammonium ion, but suppresses bleeding under high humidity conditions. In this respect, it is preferable that the molecule has at least one carboxyl group as a water-soluble group.
In particular, 50% by weight or more of the water-soluble yellow dye contained in the yellow ink preferably has at least one carboxyl group in the molecule as a water-soluble group in order to suppress bleeding under high humidity conditions. .
Further, the yellow dye having at least one carboxyl group in the molecule as the water-soluble group and / or the yellow dye having an oxidation potential nobler than 1.0 V (vs SCE) is 50% by weight or more of the whole yellow dye, respectively. It is preferable that

  As the yellow dye used in the yellow ink of the present invention, it is preferable that 50% by mass or more has at least one selected from the group consisting of a compound represented by the following general formula (Y-I) and a salt thereof. Of the dyes represented by the formula (Y-I), lithium salts and / or ammonium salts having at least one carboxyl group in the molecule are preferred.

(In the formula, G represents a heterocyclic group, n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When 2, R, X, Y, Z, Q, G represents a monovalent or divalent substituent, and at least one represents a divalent substituent, and when n is 3, R, X , Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent, and at least two represent a divalent substituent or at least one represents a trivalent substituent.

Hereinafter, the general formula (YI) will be described in more detail.

  In the general formula (Y-I), preferable examples of the substituent of G are preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group. Are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine, thiazoline and sulfolane.

  When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

  C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butyl) Phenyl, 2,4-di-t-amylphenyl), hetero-2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2 -Methoxyethoxy, 2-methylsulfonylethoxy), aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyl) Oxy, acylamino groups (eg, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), anilino groups ( For example Phenylamino, 2-chloroanilino), ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (eg, N, N-dipropylsulfamoylamino), alkylthio groups (eg, , Methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino) Alkylsulfonylamino group and arylsulfonylamino group (for example, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutyl) Carbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl) ), An alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4- Methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenyl) Carbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg Carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  In the general formula (Y-I), examples of preferred substituents of Q, R, X, Y and Z will be described in detail.

  When Q, R, X, Y and Z represent a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. Examples of the monovalent substituent include halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryl Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

  Hereinafter, Q, R, X, Y, and Z will be described in more detail.

  The halogen atom represented by Q, R, X, Y and Z represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

  The alkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is preferable. Examples of the alkyl group include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

  The cycloalkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

  The aralkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aralkyl include benzyl and 2-phenethyl.

  The alkenyl group represented by Q, R, X, Y and Z represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferred examples include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

  The alkynyl group represented by Q, R, X, Y and Z is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

  The aryl group represented by Q, R, X, Y and Z is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoyl. Aminophenyl. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent.

  The heterocyclic group represented by Q, R, X, Y and Z is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. A group, which may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

  The alkoxy group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

  The aryloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  The silyloxy group represented by Q, R, X, Y and Z is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

  The heterocyclic oxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

  The acyloxy group represented by Q, R, X, Y and Z is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An oxy group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

  The carbamoyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

  The alkoxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

  The aryloxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples thereof include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

  The amino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of the group include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

  The acylamino group represented by Q, R, X, Y and Z is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

  The aminocarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

  The alkoxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

  The aryloxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

  The sulfamoylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

  The alkyl and arylsulfonylamino groups represented by Q, R, X, Y and Z are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

  The alkylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

  The arylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. As an example of the substituent, the G may further have a substituent. And the same substituents as mentioned when they are small groups. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

  The heterocyclic thio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

  The sulfamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

  The alkyl and arylsulfinyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

  The alkyl and arylsulfonyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

  The acyl group represented by Q, R, X, Y and Z is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable, and examples of the substituent include a group in which G can further have a substituent. Examples are the same as the substituents sometimes mentioned. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

  The aryloxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

  The alkoxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

  The carbamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

  The phosphino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

  The phosphinyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

  The phosphinyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

  The phosphinylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

  The silyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

  Examples of the azo group represented by Q, R, X, Y, and Z include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. I can do it.

  Examples of the imide group represented by Q, R, X, Y, and Z include N-succinimide and N-phthalimide.

When Q, R, X, Y and Z represent a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene) and an alkenylene group (eg, ethenylene, propylene). Nylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1, 3,5-triazine-2, 4-diyl group, pyrimidine-2, 4 -Diyl group, pyrimidine-4,6-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR'- (R 'is a hydrogen atom, alkyl group or aryl group) _{, -S -, - SO 2 -} , - SO- , or a combination thereof (e.g., _{-NHCH 2 CH 2 NH -, -} NHCONH- , etc.) is good is Arbitrariness.

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

  Examples of the substituent are the same as those described for G above.

The alkyl group and aryl group of R ′ have the same meanings as the examples of the substituent of G.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. (For example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.).

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (Y-I), preferred examples of n are 1 or 2, with 2 being particularly preferred.

  In the general formula (Y-I), a preferred example of the substituent for X is an electron-withdrawing group. In particular, it is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and more preferably an electron-withdrawing group having a σp value of 0.30 or more. The upper limit is 1.0 or less electron withdrawing group.

  Specific examples of X which is an electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphono group Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, A halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a heterocyclic group, a halogen atom, Azo group or selenocyane Group.

  Preferred examples of X include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, 6 to 6 carbon atoms 18 arylsulfonyl groups, C 0-12 sulfamoyl groups, C 1-12 halogenated alkyl groups, C 1-12 halogenated alkyloxy groups, C 1-12 halogenated alkylthio groups, carbon A halogenated aryloxy group having 7 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms substituted with two or more other electron-withdrawing groups having a σp of 0.20 or more, Fine nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

  More preferably, they are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.

  Particularly preferable as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and the most preferable one is a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms. It is.

  In the general formula (YI), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;

  Detailed examples of the substituent represented by Z are the same as the corresponding examples of the substituent described in the example of the heterocyclic group represented by G, and preferred examples are also the same.

  A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In the general formula (YI), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted group. The arylsulfonyl group is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group, and particularly preferably a hydrogen atom.

  In general formula (YI), R represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon number. A 4-12 heterocyclic group is preferred, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, a secondary or tertiary alkyl group is particularly preferred, and a t-butyl group is most preferred. .

  In general formula (Y-1), Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted group. A heterocyclic group having 4 to 12 carbon atoms in total is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms and / or a branched alkyl group is preferable, and particularly a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. And a hydrogen atom is most preferable.

  Regarding the preferred combination of substituents of the dye represented by the general formula (Y-I) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

Particularly preferred combinations as the dye represented by the general formula (Y-I) of the present invention include the following (A)
It includes ~ (g).

(I) G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) R is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total. Among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon atom having 4 to 12 carbon atoms. Of these, a heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, particularly a hydrogen atom or an alkyl group having 1 to 8 is preferable, and a hydrogen atom is most preferable. preferable.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted aryl group or a substituted heterocyclic group, and among them, a substituted aryl group is particularly preferred.

(F) Q is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, particularly a hydrogen atom, A substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

(G) n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 2.

  Of the azo dyes represented by the general formula (Y-I), dyes represented by the following general formulas (Y-1) to (Y-5) are preferable.

Hereinafter, the general formula (Y-1) will be described in detail.
General formula (Y-1)

R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.
The monovalent group represents a hydrogen atom or a monovalent substituent. As an example of a monovalent substituent, it is synonymous with the monovalent substituent example of R, X, Y, and Z in the said general formula (YI), and its preferable example is also the same. m ₁ represents an integer of 0 to 3.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ will be described in more detail.

Examples of the substituents for R ₁ and R ₂ are independently the same as the examples of R in the general formula (Y-I), and preferred examples are also the same.

Examples of substituents for Y ₁ and Y ₂ are independently the same as the examples of Y in the general formula (Y-I), and preferred examples are also the same.

Examples of substituents for Z ₁ and Z ₂ are independently the same as the examples of Z in the general formula (Y-I), and preferred examples are also the same.

Hereinafter, the G and m ₁ will be described in more detail.

  G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

  Preferred examples of the 5- to 8-membered nitrogen-containing heterocycle represented by G are S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, and among them, S-triazine A ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

m ₁ represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of the preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

  Hereinafter, the M will be described in more detail.

  M represents a hydrogen atom or a cation.

The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-1) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-1) of the present invention includes the following (A) to (F).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted Unsubstituted heterocyclic groups having a total carbon number of 4 to 12 are preferable, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is most preferred.

(E) G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and preferable examples of the 5- to 8-membered nitrogen-containing heterocycle include S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, and pyridine ring. , An imidazole ring, a pyrazole ring, or a pyrrole ring, among which an S-triazine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

(F) m ₁ represents an integer of 0 to 3, and when the —OM group is substitutable in the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferred, Among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

(G) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

Hereinafter, the general formula (Y-2) will be described in detail.
General formula (Y-2)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₁ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ , 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-2) will be described in more detail.

In the general formula (Y-2), preferable examples of the substituent for R ₁ and R ₂ are the same as the examples of the substituent for R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (Y-1). The preferred examples are also the same.

In Formula (Y-2), preferable examples of the substituents of _{X 1} and _{X 2} are the same as the examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In Formula (Y-2), preferable examples of the substituents of _{Z 1} and _{Z 2} are the same as the examples of the substituents of _{Z 1} and _{Z 2} described for formula (Y-1), preferred examples are also the same It is.

Preferred examples of Formula (Y-2) in, G ₁ and G ₂ are the same as the examples of G described for Formula (Y-1), and preferred examples thereof are also the same.

In the general formula (Y-2), m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and in the structure of a preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ , − When the OM group can be substituted, 0 to 2 are preferable, and 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are most preferable.

  In general formula (Y-2), the preferable example of M is synonymous with the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In the general formula (Y-2), preferred examples of the substituent for R ₁₁ and R ₁₂ are the same as the examples of the substituents for R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (Y-1). Preferred examples are -OM group (M is a hydrogen atom or cation), substituted or unsubstituted amino group; alkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, substituted or unsubstituted Examples thereof include a substituted alkylthio group having 1 to 12 carbon atoms and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.

In the general formula (Y-2), the divalent linking group represented by L ₁ is an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene. Group (eg, ethynylene, propynylene), arylene group (eg, phenylene, naphthylene), divalent heterocyclic group (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, pyrimidine- 4,6-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR- (R is a hydrogen atom, alkyl group or aryl group), -S-,- It is preferably SO ₂ —, —SO— or a combination thereof (for example, —NHCH ₂ CH ₂ NH—, —NHCONH—, etc.).

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

Examples of the substituent are the same as the substituents of _{R 1,} R 2, _{Y 1} and _{Y 2} in the formula (Y-1).

The alkyl group and aryl group of R are synonymous with the substituent examples of R ₁ , R ₂ , Y ₁ and Y _{2 in} the general formula (Y-1).

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-, -SO _2- or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.) and more preferably a.

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  Regarding the preferred combination of substituents of the dye represented by formula (Y-2) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-2) of the present invention includes the following (A) to (H).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted Unsubstituted heterocyclic groups having a total carbon number of 4 to 12 are preferable, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is most preferred.

(D) G ₁ and G ₂ may be the same or different and represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₁ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, the general formula (Y-3) will be described in detail.
General formula (Y-3)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₂ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-3) will be described in more detail.

In formula _{(Y-3), R 1} , R 2, Y 1, and preferred examples of the substituents of _{Y 2} are, _R 1 described for Formula _{(Y-1), R 2} , Y 1, and Y It is the same as the example of a substituent of ₂ , and a preferable example is also the same.

In formula (Y-3), preferable examples of the substituents of _{X 1} and _{X 2} are the same as examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-3), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In the general formula (Y-3), preferable examples of m ₃₁ and m ₃₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (Y-2), and preferable examples are also the same.

  In general formula (Y-3), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-3), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described above for Formula (Y-2), preferable examples thereof are also the same It is.

In General Formula (Y-3), the divalent linking group represented by L ₂ has the same meaning as the example of L ₁ described in General Formula (Y-2), and the preferred examples are also the same.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-3) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by formula (Y-3) of the present invention includes the following (i) to (h).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted Unsubstituted heterocyclic groups having a total carbon number of 4 to 12 are preferable, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₃₁ and m ₃₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₂ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, the general formula (Y-4) will be described in detail.
General formula (Y-4)

R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₃ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-4) will be described in more detail.

In formula (Y-4), preferable examples of the substituents of _{Y 1,} and _{Y 2,} and examples of the substituents of the _R 1 described in the general formula _{(Y-1), R 2} , Y 1, and _{Y 2} It is the same, and a preferable example is also the same.

In formula (Y-4), preferable examples of the substituents of _{X 1} and _{X 2} are the same as examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-4), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In General Formula (Y-4), preferred examples of m ₄₁ and m ₄₂ are the same as the examples of m ₂₁ and m ₂₂ described in General Formula (Y-2), and preferred examples are also the same.

  In general formula (Y-4), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-4), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described above for Formula (Y-2), preferable examples thereof are also the same It is.

In the general formula (Y-4), examples of the divalent linking group represented by L ₃ are the same as the examples of L ₁ described in the general formula (Y-2), and preferred examples are also the same. .

  Regarding the preferred combination of substituents of the dye represented by formula (Y-4) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-4) of the present invention includes the following (A) to (H).

(I) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and most preferably a hydrogen atom.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is most preferred.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₄₁ and m ₄₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₃ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, Formula (Y-5) will be described in detail.
General formula (Y-5)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₄ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

  m51 and m52 each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-5) will be described in more detail.

In formula _{(Y-5), R 1} , preferred examples of the substituents of R 2, _{Y 1} and _{Y 2} are, _R 1 described for Formula _{(Y-1), R 2} , Y 1, and _{Y 2} And the preferred examples are also the same.

In formula (Y-5), preferable examples of the substituents of _{Z 1} and _{Z 2} are the same as examples of the substituents of _{Z 1} and _{Z 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-5), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In the general formula (Y-5), preferable examples of m ₅₁ and m ₅₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (Y-2), and preferable examples are also the same.

  In general formula (Y-5), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-5), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11} and _{R 12} described for Formula (Y-2), preferable examples thereof are also the same It is.

In formula (Y-5), examples of the divalent linking group represented by L ₄ are the same as the examples of L ₁ described for Formula (Y-2), and preferred examples thereof are also the same .

  Regarding the preferred combination of substituents of the dye represented by formula (Y-5) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by formula (Y-5) of the present invention includes the following (A) to (H).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted Unsubstituted heterocyclic groups having a total carbon number of 4 to 12 are preferable, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is most preferred.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₄₁ and m ₄₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group; an alkylamino group having 1 to 12 carbon atoms, and 6 carbon atoms To an arylamino group having 1 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. Among them, an unsubstituted amino group and an alkylthio group having 1 to 12 carbon atoms are preferable. Are preferably an alkylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. An amino group, a dialkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon number 12 alkylthio group are preferable.

(H) L ₄ is a divalent linking group and preferably has an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably an electron-withdrawing group of 0.30 or more. It is an electron withdrawing group of 1.0 or less. Among them, an alkylsulfonyl group having 1 to 12 carbon atoms: {—SO ₂ — (CH ₂ ) n —O ₂ S—; an integer where n = 1 to 10}, an arylsulfonyl group having 6 to 18 carbon atoms: {— SO ₂ —Ar—O ₂ S—; Ar is preferably a substituted or unsubstituted aryl group, most preferably an alkylsulfonyl group having 1 to 12 carbon atoms, an alkylsulfonyl group: {—SO ₂ — (CH ₂ ) n a n = 1 to 5 integer}; -O ₂ S-.

Formula (Y-1), Formula (Y-2), the general formula (Y-3), Formula (Y-4), the general formula (Y-5), G, composed of _{G 1} and _{G 2} The nitrogen-containing heterocycle is preferably an S-triazine ring from the viewpoint of storage stability of the dye in the ink.

  Of the water-soluble yellow dyes represented by the general formula (Y-1), a dye represented by the general formula (Y-6) is preferable.

Hereinafter, Formula (Y-6) will be described in detail.

R ₁ , R ₂ , Y ₁ , and Y ₂ each represent a monovalent group, and X ₁ and X ₂ each independently represent an electron-withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An aryl group or a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ and M will be described in detail.

Examples of the substituents of R _{1, R} 2, _{Y 1,} and _{Y 2} is the same as the examples of the substituents of the general formula _R 1 described in (Y-1) _in, R 2, _{Y 1,} and _{Y 2} There are also preferred examples.

Examples of the substituents of X ₁ and X ₂ are the same as examples of the substituents of X ₁ and X ₂ described in Formula (Y-1) and preferable examples thereof are also the same.

Examples of the substituents of Z ₁ and Z ₂ are the same as examples of the substituents of Z ₁ and Z ₂ described in Formula (Y-1) and preferable examples thereof are also the same.

The example of M is the same as the example of M demonstrated in the said general formula (Y-1), and its preferable example is also the same.

As for the preferred combination of substituents of the dye represented by the general formula (Y-6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

A particularly preferable combination as the coloring matter represented by the general formula (Y-6) of the present invention includes the following (A) to (E).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted Unsubstituted heterocyclic groups having a total carbon number of 4 to 12 are preferable, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferred, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is most preferred.

(E) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

  In the present invention, it is represented by the general formulas (YI), (Y-1), (Y-2), (Y-3), (Y-4), (Y-5) and (Y-6). In the case where the compound needs hydrophilicity, it preferably has 2 or more ionic hydrophilic groups in the molecule, more preferably 2 to 10 ionic hydrophilic groups, and 3 to 6 It is particularly preferred to have one ionic hydrophilic group.

  The ionic hydrophilic group may be any as long as it is an ionic dissociation group. Specific examples include a sulfo group, a carboxyl group (including salts thereof), a hydroxyl group (may be a salt), a phosphono group (may be a salt), or quaternary ammonium.

A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable.
When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them A carboxyl group or a hydroxyl group is selected as the ionic aqueous group, and a combination of lithium ion and / or ammonium ion is particularly preferred as the counter ion in the present invention.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  In this invention, the compound represented by the following general formula (Y-6-I) is preferable among the compounds represented by the said general formula (Y-6).

General formula (Y-6-I):

In formula (Y-6-I), R ₁ , R ₂ , Y ₁ , Y ₂ , W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ represents a monovalent group, and X ₁ and X ₂ each independently represents an electron-withdrawing group having a Hammett σp value of 0.20 or more. M represents a hydrogen atom or a cation. However, at least one of W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ , W ₂₅ is an ionic hydrophilic group or ionic hydrophilic It is a group having a group as a substituent.

  In the present invention, the general formula (Y-6-I) will be described in detail.

In the present invention, in the general formula (Y-6-I), W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are In formula (Y-6), it is synonymous with the example of the monovalent group demonstrated by Y < ₁ >, Y < ₂ >, Z < ₁ >, Z < ₂ >.

Preferred W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group , Alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (Including salts thereof), hydroxyl group (may be salt), phosphono group (may be salt) or quaternary ammonium, among which hydrogen atom, halogen atom, alkyl group, sulfo group (including salts thereof), Preferred are a carboxyl group (including salts thereof), a hydroxyl group (may be a salt) (including salts thereof), and a hydrogen atom. A sulfo group (including salts thereof), a carboxyl group (including a salt thereof) comprises preferably, especially _{W 11, W 12, W 13} , at least one sulfo group (their salts of _{W 14} and _{W 15} ), Carboxyl groups (including salts thereof) and at least one of W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ is a sulfo group (including salts thereof), carboxyl group (including salts thereof) Is preferred.

In the present invention, the general formula _(Y-6-I), X 1, X 2 mother Formula (Y-6) in an _X 1, _{X 2} and synonymous, and preferred examples are also the same .

In the present invention, the general formula _(Y-6-I), Y 1, Y 2 mother Formula (Y-6) in a _Y 1, _{Y 2} and synonymous, and preferred examples are also the same .

In the present invention, in formula _(Y-6-I), R 1, R 2 has the same meaning as _R 1, _{R 2} in Formula (Y-6), and preferred examples thereof are also the same.

  In the present invention, in the general formula (Y-6-I), M is synonymous with M in the general formula (Y-6), and preferred examples are also the same.

  A particularly preferable combination as the compound represented by the general formula (Y-6-I) of the present invention includes the following (A) to (F).

(I) R ₁ and R ₂ may be the same or different, and are preferably a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group, particularly preferably a secondary or tertiary alkyl group, t- A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, and a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms Preferred and most preferred is a cyano group.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom and a methyl group are most preferable.

(D) W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are hydrogen atoms, halogen atoms, alkyl groups, sulfo groups (their salts are ), Carboxyl groups (including salts thereof), hydroxyl groups (may be salts) (including salts thereof), hydrogen atoms, sulfo groups (including salts thereof), carboxyl groups (including salts thereof). In particular, at least one of W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ and W ₁₅ is a sulfo group (including a salt thereof), a carboxyl group (including a salt thereof), and W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are preferably sulfo groups (including salts thereof) and carboxyl groups (including salts thereof).

(E) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(F) In the present invention, the compound represented by the general formula (Y-3-I) preferably has two or more ionic hydrophilic groups in the molecule, and has 2 to 16 ionic hydrophilic groups. It is more preferable to have a group, and it is particularly preferable to have 3 to 5 ionic hydrophilic groups.

  As the ionic hydrophilic group, a carboxyl group (including salts thereof) or a hydroxyl group (may be a salt) is preferable.

  When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them Lithium ions and / or ammonium ions are preferable, and lithium ions are particularly preferable.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-6-I) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substitutions are possible. More preferred are compounds in which the group is the preferred group, and most preferred are compounds in which all substituents are the preferred groups.

The general formulas (Y-I), (Y-1), (Y-2), (Y-3), (Y-4), (Y-5), (Y-6), (Y-6) The water-soluble dye represented by I) preferably has a maximum absorption wavelength (λmax) of 380 to 490 nm in H ₂ O, and has a λmax of 400 to 480 nm, from the viewpoint of color reproducibility. More preferably, it has a λmax at 420 to 460 nm.

-Water-soluble cyan dye-
The cyan dye used in the inkjet image forming method of the present invention is not particularly limited as long as the counter ion of the water-soluble group is lithium ion and / or ammonium ion, but obtains good image storage stability under various environments. For this purpose, it is preferable that the oxidation potential of the dye is nobler than 1.0 V (vs SCE). The cyan dye having an oxidation potential nobler than 1.0 V (vs SCE) is preferably 50% by weight or more of the whole cyan dye.

  As the cyan dye used in the cyan ink of the present invention, 50% by mass of the dye is preferably a lithium salt and / or an ammonium salt of a dye represented by the following general formula (C-1).

In general formula (C-1), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ correspond to each other independently and independently (= C (J ₁₎ - or -N =), (= C ( J 2) - or -N =), (= C ( J 3) - or -N =), (= C ( J 4) - or -N =) Represents. J _{1 to} J ₄ each independently represents a hydrogen atom or a substituent. (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ), at least one of the four rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} is an aromatic hydrocarbon It is preferably a ring, and more preferably two or more are aromatic hydrocarbon rings.
When any ring of A ring, B ring, C ring and D ring is a hetero ring, a pyridine ring or a pyrazine ring is preferable.
When J ₁ through J ₄ is a substituent, preferably an electron-withdrawing substituent, further at least one of _J 1 through J ₄ is or Among the _{substituents J} 1 through J ₄ has at least One preferably has a substituent that imparts solubility (an ionic hydrophilic group when the dye is water-soluble, and a hydrophobic group when the dye is oil-soluble).
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
In the general formula (C-1), when any ring of the A ring, the B ring, the C ring, and the D ring is an aromatic hydrocarbon ring, the aromatic hydrocarbon ring is represented by the following general formula (I) Preferably there is.

In general formula (I), * represents a bonding position with the phthalocyanine skeleton. G represents -SO-Z ₁ , -SO ₂ -Z ₁ , -SO ₂ NZ ₁ Z ₂ , -CONZ ₁ Z ₂ , -CO ₂ Z ₁ , -COZ ₁ , or a sulfo group. t represents an integer of 1 to 4. Among general formulas (I), G is preferably —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₁ Z ₂ , —CONZ ₁ Z ₂ , —CO ₂ Z ₁ , or —COZ. ₁ , particularly preferred is the case where G is —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₁ Z ₂ , and most preferred is that G is —SO ₂ —Z. _{This is} the case of ₁ . t is preferably 1 or 2, and most preferably 1.
Z ₁ may be the same or different, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted An aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.
Z ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted It represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferred. Most preferred.
In the general formula (C-1), when any ring of A ring, B ring, C ring, and D ring is an aromatic hydrocarbon ring, at least one aromatic ring is represented by the following general formula (II) It is particularly preferred.

In general formula (II), * represents a bonding position with the phthalocyanine skeleton. G has the same meaning as in formula (I), and preferred, particularly preferred and most preferred are the same. t ₁ is 1 or 2, with 1 being most preferred.

  Preferable specific examples of the dye represented by the general formula (C-1) include compounds described in JP-A-2007-138124, [0582] to [0652].

-Water-soluble magenta dye-
The magenta dye used in the method for forming an inkjet image of the present invention is not particularly limited as long as the counter ion of the water-soluble group is lithium ion and / or ammonium ion, but obtains good image storage stability under various environments. For this purpose, it is preferable that the oxidation potential of the dye is nobler than 1.0 V (vs SCE). The magenta dye having an oxidation potential nobler than 1.0 V (vs SCE) is preferably 50% by weight or more of the total magenta dye.

  As the magenta dye used in the magenta ink of the present invention, 50% by mass or more of a lithium salt and / or an ammonium salt of a dye represented by the following general formula (M-1) is preferable.

In the general formula (M-1), A represents a residue of a 5-membered heterocyclic diazo component A-NH ₂ . B ₁ and B ₂ are each -CR ₁₃ =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. G, R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl substituted with a group or heterocyclic group And an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.

Preferable specific examples of the dye represented by the general formula (M-1) include compounds described in JP-A 2007-138124, [0489] to [0563].

As described above, the inkjet image forming method of the present invention is an ink having ink in at least three colors of a yellow ink, a magenta ink, and a cyan ink each containing a water-soluble yellow dye, a water-soluble magenta dye, and a water-soluble cyan dye. Done with a set,
Further, from the viewpoint of color reproducibility and image quality, it is preferable to use an ink set having a black ink containing a water-soluble black dye.
The water-soluble black dye is not particularly limited, but is not particularly limited as long as the counter ion of the water-soluble group is a lithium ion and / or an ammonium ion, but preferably has a counter ion of 70 mol% or more. In order to obtain good image storage stability under various environments, the oxidation potential of the dye is preferably nobler than 1.0 V (vs SCE), so that the oxidation potential is 1.0 V (vs SCE). It is preferable that the black dye which is noble is more than 50% by weight of the whole black dye.

  The black dye used in the black ink of the present invention is preferably a lithium salt and / or ammonium salt of a dye represented by the following general formula (B-1) at 50% by mass or more.

In the general formula (B-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =. V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or aryl Sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or sulfo Represents a group, and each group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or An arylsulfonyl group and a sulfamoyl group are represented, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

  Preferable specific examples of the dye represented by the general formula (B-1) include compounds described in JP-A 2007-138124, [0669] to [0772].

  Other dyes may be used in combination with the yellow dye, magenta dye, cyan dye, and black dye within the scope of the present invention for the purpose of adjusting the hue and fading speed. Specific examples of suitable dyes for use in combination include, for example, [0473] to [0481] (combination dyes for yellow dyes) and [0570] to [0578] (combination dyes for magenta dyes) in JP-A-2007-138124. ), [0660] to [0664] (combination dye of cyan dye), and [0779] to [0792] (combination dye of black dye).

[ink]
The ink in the present invention is an ink used for ink jet recording (hereinafter also referred to as ink jet recording ink), and can be prepared by dissolving the water soluble dye in an aqueous medium containing the water soluble dye. . Further, if necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are added directly to the ink liquid.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.

  The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, - sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is preferably used for the purpose of allowing ink jet ink to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-211141, Cinnamic acid compounds described in, for example, Kaihei 10-88106, JP-A-4-298503, 8-53427, 8-239368, 10-182621, JP-A-8- No. 501291, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, a neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added so that the inkjet ink has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink in the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. In addition, the viscosity of the inkjet ink in the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.
The dye content in the inkjet recording ink is preferably 0.1 to 20 parts by mass, and 0.5 to 15 parts by mass for each dye in 100 parts by mass of the ink. More preferred is 1.0 part by mass or more and 10 parts by mass or less.
In the ink for inkjet recording according to the present invention, the dyes may be used alone or in combination of two. When using together, it is preferable that the sum total of content of dye is in the above-mentioned range.
For example, in the case of cyan inkjet recording ink, it is preferable to contain the phthalocyanine dye, but the phthalocyanine compound is contained in a proportion of 0.2 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the ink. It is preferable.

In the present invention, yellow, magenta, cyan, and black inks may be used in combination of two or more dyes. In that case, an oxidation potential of 50% by mass or more of the dyes in each ink is 1.0 V. More noble is preferred. In particular, since it is difficult to obtain a preferable black tone with a single dye, it is preferable to mix two or more kinds of dyes. However, the oxidation potential of each dye used in that case is nobler than 1.0 V. It is preferable. When two or more kinds of dyes are used in combination, the total dye content is preferably within the above range.
Further, as described above, it is important that 70 mol% or more of the counter ions of the water-soluble groups of all the dyes in each ink are lithium ions and / or ammonium ions.

In recent years, yellow, magenta, and cyan inks are often composed of two or more types of inks having different dye concentrations for the purpose of improving the image quality. In the present invention, the dyes used in the light and dark inks are all oxidized. The potential is preferably nobler than 1.0V, more preferably nobler than 1.1V, and particularly preferably nobler than 1.15V.
Also in this case, it is necessary that the dark and light inks satisfy the scope of the present invention.

  In the present invention, when two or more kinds of different inks are used as the ink of the same hue, the density of the other kinds of ink is preferably 0.05 to 0.5 times the density of one kind of ink.

  In addition, for controlling ink properties, polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, cellulose derivatives such as ethyl cellulose, carboxyethyl cellulose, polysaccharides and derivatives thereof, other water-soluble polymers and polymer emulsions, cyclodextrins, macrocyclic amines , Dendrimers, crown ethers, urea and its derivatives, acetamide and the like can be used.

  Examples of chelating agents include ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid (IDA), ethylenediaminedi (o-hydroxyphenylacetic acid) (EDDDHA), nitrilotriacetic acid (NTA), dihydroxyethylglycine (DHEG), and trans-1 2-cyclohexanediaminetetraacetic acid (CyDTA), diethylenetriamine-N, N, N ′, N ′, N′-pentaacetic acid (DTPA), glycol ether diamine-N, N, N ′, N′-tetraacetic acid (GEDTA) ) And the like.

  Examples of the viscosity modifier include methyl cellulose, ethyl cellulose and derivatives thereof, glycerins and polyglycerin and polyethylene oxide and polypropylene oxide adducts thereof, and polysaccharides and derivatives thereof. Specific examples of these include glucose, fructose, mannitol, D-sorbitol, dextran, xanthan gum, curdlan, cycloamylose, maltitol and derivatives thereof.

  The ink set used in the method for forming an inkjet image of the present invention preferably contains a betaine compound as necessary in each color ink composition, and among them, a betaine surfactant having an oil-soluble group in particular. It is preferable. Among the betaine compounds, compounds represented by the following general formula are preferably used in the present invention.

  The betaine compound preferably used in the present invention is preferably a betaine-type surfactant having surface activity.

The betaine compound here refers to a compound having both a cationic site and an anionic site in the molecule.

  Examples of the cationic site include an aminic nitrogen atom, a nitrogen atom of a heteroaromatic ring, a boron atom having four bonds with carbon, and a phosphorus atom. Of these, an amine nitrogen atom or a nitrogen atom of a heteroaromatic ring is preferable. Among them, a quaternary nitrogen atom is particularly preferable.

  Examples of the anionic site include a hydroxyl group, a thio group, a sulfonamide group, a sulfo group, a carboxyl group, an imide group, a phosphoric acid group, and a phosphonic acid group. Among these, a carboxyl group and a sulfo group are particularly preferable. The charge of the molecule as a whole may be any of cation, anion, and neutral, but is preferably neutral.

  As the betaine compound, a compound represented by the following general formula (W-1) is preferably used.

General formula (W-1)
(R) _p -N- [L- (COOM) _q ] _r

In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L represents a divalent linking group. M represents a hydrogen atom, an alkali metal atom, an ammonium group, a protonated organic amine or a nitrogen-containing heterocyclic group, a quaternary ammonium ion group, and when M is a counter ion of an ammonium ion consisting of an N atom in the formula Represents a group which does not exist as a cation. q represents an integer of 1 or more, and r represents an integer of 1 to 4. p represents an integer of 0 or more and 4 or less, and p + r is 3 or 4. When p + r is 4, the N atom is a protonated ammonium atom (= N ⁺ =). When q is 2 or more, the COOMs may be the same or different. When r is 2 or more, L- (COOM) _q may be the same or different. When p is 2 or more, R may be the same or different.

  Preferable specific examples of the betaine compound include compounds described in [0810] to [0822] of JP-A-2007-138124.

  The betaine compound may be added in any amount as long as it exhibits the effects of the invention, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass in the ink composition.

  In the inkjet image forming method of the present invention, a colorless water-soluble planar compound having 10 or more delocalized π electrons in one molecule may be contained in the ink as a bronze improving agent. Preferable specific examples of the bronze improver include compounds described in JP-A-2005-105261 [0017] to [0025] and compounds described in JP-A 2006-249275 [0032]. .

  A preferable amount of the bronze improving agent may be added as long as the effect of the invention is exerted, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass in the ink composition.

In order to prevent intercolor bleeding between the cyan, magenta and yellow inks and the black ink in the ink set of the present invention, these inks may contain a pH buffering agent.
Any pH buffering agent may be used as long as it can stably maintain the pH of the ink at 7.0 to 9.5. When the pH of the ink is less than 7.0, bleeding between colors and uneven color are likely to occur, and the image fixing property is deteriorated. When the pH exceeds 9.5, the head member may be damaged.
Examples of pH buffering agents include potassium dihydrogen phosphate / sodium hydroxide, sodium tetraborate / hydrochloric acid, potassium dihydrogen phosphate / disodium hydrogen phosphate, ammonium chloride / ammonia, trisaminomethane / hydrochloric acid, Good buffer ACES, ADA, BES, Bicine, Bis-Tris, CHES, DISPO, EPPS, HEPES, HEPPSO, MES, MOPS, MOPSO, POPSO, TAPS, TAPSO, TES, Tricine with sodium hydroxide, potassium hydroxide, ammonia A combination of these is preferably used. Among these, a pH buffer agent using sodium hydroxide, potassium hydroxide, or ammonia as an alkali is particularly preferable. The effect of these pH buffers is particularly remarkable when the ink drop amount is 1 to 20 pl, preferably 2 to 18 pl. Moreover, the effect is favorable by a thermal inkjet system.

  The surface tension of cyan, magenta and yellow ink is preferably 20 to 70 mN / m, more preferably 25 to 60 mN / m at 20 ° C. If it is lower than 20 mN / m, bleeding on the paper becomes remarkable, and stable ejection tends to be difficult to obtain. On the other hand, if it is greater than 70 mN / m, ink penetration into the paper does not occur sufficiently, and the color developability of secondary colors such as blue, red, and green deteriorates, which tends to be undesirable. It is more effective when the surface tension of black ink at 20 ° C. is lower than any of the surface tensions of cyan, magenta, and yellow ink.

  The viscosity of cyan, magenta, yellow and black inks is the same for all inks, and is preferably 30 mPa · s or less at 20 ° C., more preferably 1.5 to 20 mPa · s, and the best results are obtained. When it is lower than 1.5 mPa · s, it is difficult to obtain discharge stability, and when it is higher than 20 mPa · s, clogging tends to be undesirable.

[Method of forming inkjet image]
The ink-jet image forming method of the present invention uses the ink set of the present invention described above to place the first dot at a position where it comes into contact with the first dot within 50 ms after landing on the surface of the image receiving material. Is an image forming method in which the second dots are ejected with inks having different hues, thereby enabling high-speed image formation, and the obtained image can be prevented from causing droplet ejection interference. .

  In the ink jet image forming method of the present invention, energy is supplied to the ink for ink jet recording of the ink set, and a known image receiving material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, 8 -27693, 2-276670, 7-276789, 9-323475, JP-A-62-238783, JP-A-10-153899, 10-217473, No. 10-235995, No. 10-337947, No. 10-217597, No. 10-337947, etc., dedicated inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, Images can be formed on ceramics, etc., but among these, the effects of the present invention can be maximized. The image-receiving material described later are most preferred.

  In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant. Therefore, even if the addition place is in the image receiving paper, It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, the methods described in Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, and 2000-268952 can be preferably used.

Hereinafter, image receiving materials such as recording paper and recording film used for forming an inkjet image using the ink of the present invention will be described. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, a porous white inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective in making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, benzophenone-based and benzotriazole-based ultraviolet absorbers, and the like. Of these, zinc sulfate is particularly preferred.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink in the present invention is not limited to the ink jet recording system, and is a known system, for example, a charge control system that ejects ink using electrostatic attraction, a drop-on-demand system (pressure pulse) that uses the vibration pressure of a piezo element. Method), an acoustic ink jet method in which an electrical signal is converted into an acoustic beam and applied to the ink and the ink is ejected using the radiation pressure, and a thermal ink jet method in which bubbles are formed by heating the ink and the generated pressure is used. Used for etc. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

  The present invention will be described more specifically with reference to the following examples. The scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

Example 1
<Preparation of ink set>
(Preparation of yellow ink Y-101)
After adding ion exchange water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared yellow ink (Y-101).

[Yellow ink: Y-101 prescription]
(Solid content)
Yellow dye (a lithium salt of yellow dye Y-1 represented by the following structural formula) 60.0 g / l
Proxel XL-2 (produced by AVECIA) 1.0 g / l
(Liquid component)
・ Glycerin 81g / l
・ Triethylene glycol 96g / l
・ Triethylene glycol monobutyl ether 91g / l
・ Propylene glycol 3g / l
・ Orphine E1010 (manufactured by Shin-Etsu Chemical) 20g / l

(Preparation of magenta ink M-101)
After adding ion exchange water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the magenta ink (M-101).

[Magenta ink M-101 prescription]
(Solid content)
Magenta dye (magenta dye M-1 represented by the following structural formula) 30.0 g / l
・ Urea 48.0g / l
Proxel XL-2 (produced by AVECIA) 1.0 g / l
(Liquid component)
・ Glycerin 84.0 g / l
・ Triethylene glycol 20.0 g / l
・ Triethylene glycol monobutyl ether 99.0 g / l
・ Propylene glycol 3.0g / l

(Preparation of cyan ink C-101)
After adding ion exchange water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared cyan ink (C-101).

[Cyan ink C-101 prescription]
(Solid content)
Cyan dye (cyan dye C-1 represented by the following structural formula) 54.0 g / l
・ Urea 41.0g / l
Proxel XL-2 (produced by AVECIA) 1.0 g / l
(Liquid component)
・ Glycerin 91g / l
・ Triethylene glycol 18g / l
・ Triethylene glycol monobutyl ether 94g / l
・ Propylene glycol 3g / l
・ 1,2-hexanediol 12g / l
・ 2-Pyrrolidone 27g / l
・ Orphine E1010 (manufactured by Shin-Etsu Chemical) 10g / l

(Preparation of black ink Bk-101)
After adding ion exchange water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared black ink (Bk-101).

[Black ink: Bk-101 prescription]
(Solid content)
Black dye 1 (main dye Bk-1 for black below) 62.0 g / l
・ Black dye 2 (black complementary color dye Bk-2 below)
Proxel XL-2 (produced by AVECIA) 1.0 g / l
(Liquid component)
・ Glycerin 83g / l
・ Triethylene glycol 8g / l
・ Triethylene glycol monobutyl ether 84g / l
・ Propylene glycol 3g / l
・ 1,2-hexanediol 16g / l
・ Orphine E1010 (manufactured by Shin-Etsu Chemical) 10g / l

(Preparation of ink set 1)
An ink set 1 composed of the yellow ink Y-101, the magenta ink M-101, the cyan ink M-101, and the black ink Bk-101 obtained above was produced.

<Image recording>
The ink set 1 (Y-101, M-101, C-101, Bk-101) of the present invention is filled in a Dry Minilab 400 ink cartridge manufactured by Fuji Film Co., Ltd., and an inkjet image receiving paper “Image” manufactured by Fuji Film Co., Ltd. Recording was performed in an environment of 23 ° C. and 50% RH using “Aya” roll paper.
At this time, recording was performed by changing the ejection conditions so that the size of the ink droplets ejected from the head was 2 pl, and the time of contact between two adjacent inks was 50 ms, 30 ms, and 10 ms, respectively.
-Evaluation criteria-
A: Adjacent dots of different colors each independently form a circular shape, and have the same shape as a single ejected dot.
B: Some coalescence is observed between adjacent dots of different colors, and droplet ejection interference is observed.
C: Adjacent dots of different colors are completely united.

(Comparative Example 1)
<Preparation of ink set>
(Preparation of yellow ink Y-102 and magenta ink M-101, and ink sets 2 and 3)
In the ink set of Example 1, yellow ink Y-102 was prepared in the same manner as in Example 1 except that the counter ion of yellow dye Y-1 in the preparation of yellow ink Y-101 was changed from lithium to potassium. Ink set 2 was produced.
In the ink set of Example 1, magenta ink M-102 was prepared in the same manner as in Example 1 except that the counter ion of magenta dye M-1 in the preparation of magenta ink M-101 was changed from lithium to potassium. Ink set 3 was produced.

<Image recording>
In Example 1, instead of using ink set 1, recording and evaluation were performed in the same manner except that comparative ink sets 2 and 3 were used.

(Evaluation)
The obtained image was observed with a microscope and evaluated according to the following criteria. The obtained results are shown in Table 1.

  From the results shown in Table 1 above, the ink set of the present invention can suppress the occurrence of droplet ejection interference at the contact portion of dots formed in different colors and perform image quality even when high-speed recording is performed. It was clear that the image was superior to the comparative example in terms of the transparency of the image.

Claims (15)

Each of the inks comprising: a yellow ink containing at least one water-soluble yellow dye; a magenta ink containing at least one water-soluble magenta dye; and a cyan ink containing at least one water-soluble cyan dye. In the ink set in which the counter ion of the water-soluble dye in the lithium ion and / or ammonium ion is used, the first dot comes into contact with the first dot within 50 ms after landing on the surface of the image receiving material. A method for forming an inkjet image, wherein a second dot is ejected from an ink having a hue different from that of the first dot. The inkjet image forming method according to claim 1, wherein 70 mol% or more of counter ions of the water-soluble dye in the yellow ink, magenta ink, and cyan ink are lithium ions and / or ammonium ions. The method for forming an inkjet image according to claim 1, wherein the ink set further includes a black ink containing at least one water-soluble black dye. The second dot made of ink having a hue different from that of the first dot is ejected at a position where the first dot contacts the first dot within 30 ms after landing on the surface of the image receiving material. The method for forming an inkjet image according to any one of claims 1 to 3. A second dot made of ink having a hue different from that of the first dot is ejected at a position where the first dot contacts the first dot within 10 ms after landing on the surface of the image receiving material. The method for forming an inkjet image according to any one of claims 1 to 4. 6. The inkjet image according to claim 1, wherein 50% by mass or more of the water-soluble yellow dye contained in the yellow ink has at least one carboxyl group in the molecule. Forming method. 7. The dye according to claim 1, wherein 50% by mass or more of the dye contained in each ink in the ink set has a noble oxidation potential of 1.0V (vs SCE). 2. A method for forming an inkjet image according to item 1. 50% by mass or more of a water-soluble yellow dye contained in the yellow ink contains at least one selected from the group consisting of a compound represented by the general formula (Y-I) and a salt thereof. The method for forming an inkjet image according to any one of claims 1 to 7.

(In the formula, G represents a heterocyclic group, n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When 2, R, X, Y, Z, Q, G represents a monovalent or divalent substituent, and at least one represents a divalent substituent, and when n is 3, R, X , Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent, and at least two represent a divalent substituent or at least one represents a trivalent substituent. The water-soluble yellow dye represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y-4). And at least one selected from the group consisting of a compound represented by the general formula (Y-5) and a salt thereof.

(Wherein R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atom constituting a 5- to 8-membered nitrogen-containing heterocycle. M represents a hydrogen atom or a cation, and m ₁ represents an integer of 0 to 3.)

(Wherein R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. M ₂₁ and m ₂₂ each independently represents an integer of 0 to 3.)

(In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle independently, M represents a hydrogen atom or a cation, and m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.)

(Wherein R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, G ₁ , G ₂ represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle independently, M represents a hydrogen atom or a cation, and m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.)

(Wherein R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₄ represents a divalent linking group, G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, M represents a hydrogen atom or a cation, and m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.) Formula (Y-1), Formula (Y-2), the general formula (Y-3), Formula (Y-4), the general formula (Y-5), G, composed of _{G 1} and _{G 2} The method for forming an inkjet image according to claim 9, wherein the nitrogen-containing heterocycle is an S-triazine ring. 11. The inkjet image according to claim 9, wherein the water-soluble yellow dye represented by the general formula (Y-1) is a compound represented by the following general formula (Y-6). Forming method.

(In the formula, R ₁ , R ₂ , Y ₁ and Y ₂ each represent a monovalent group, and X ₁ and X ₂ each independently represent an electron-withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl A group, a substituted or unsubstituted heterocyclic group, and M represents a hydrogen atom or a cation.) The water-soluble cyan dye contained in the cyan ink is 50% by mass or more of a phthalocyanine dye having a structure represented by the following general formula (C-1). 2. A method for forming an inkjet image according to item 1.

(In General Formula (C-1), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ are each independently (= C (J ₁ )-and or N =), (= C (J ₂ )-and / or -N =), (= C (J ₃ )-and / or -N =), (= C (J ₄ )-and / or -N =) J _{1 to} J ₄ each independently represents a hydrogen atom and / or a substituent (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) ring {A ring: (A), B ring: (B), C ring: (C), Ring D: At least one of the four (D)} s is preferably an aromatic hydrocarbon ring, more preferably two or more are aromatic hydrocarbon rings A ring, B ring, C When any ring of the ring and ring D is a hetero ring, the pyridine ring is also Ku If preferred .J ₁ through J ₄ pyrazine ring is a substituted group is preferably an electron-withdrawing substituent, at least one of further J ₁ through J ₄ is or J ₁ through J ₄ (At least one of the substituents possessed by has an ionic hydrophilic group. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.) 15. The water-soluble azo dye having a structure represented by the general formula (M-1) is 50% by mass or more of the water-soluble magenta dye contained in the magenta ink. 2. A method for forming an inkjet image according to item 1.

(In the general formula (M-1), A represents a residue of a 5-membered heterocyclic diazo component A-NH _2. Do B ₁ and B ₂ represent -CR ₁₃ = and -CR ₁₄ =, respectively? Or one of them represents a nitrogen atom and the other represents —CR ₁₃ ═ or —CR ₁₄ ═ each of R ₁₁ and R ₁₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, An aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, each group further having a substituent. also good _.G, R _{13, R 14,} each independently, a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl , Heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group , An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group Alkyl and arylsulfonylamino groups, nitro groups, alkyl and arylthio groups, alkyl and arylsulfonyl groups, alkyl and arylsulfinyl groups, sulfamoyl groups, heterocyclic Represents a group or an ionic hydrophilic group. Each group may be further substituted. Also, R ₁₃ and R _11, or even to form a 5- or 6-membered ring and R ₁₁ and R ₁₂ are bonded However, general formula (M-1) has at least one ionic hydrophilic group.) 14. The water-soluble azo dye having a structure represented by the following general formula (B-1) is 50% by mass or more of the water-soluble black dye contained in the black ink. The method for forming an inkjet image according to claim 1.

(In the above general formula (B-1),
A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group and B is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =. V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or aryl Sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or sulfo Represents a group, and each group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or An arylsulfonyl group and a sulfamoyl group are represented, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring. ) The inkjet image according to any one of claims 1 to 14, wherein an image is formed on the image receiving material having an ink receiving layer containing porous white inorganic pigment particles on a support. Forming method.