JP2003082251A - Condensed-ring pyrazolyl azo dye and silver halide color photosensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide dyes having absorption properties excellent in color reproduction property as dyes of three primary colors and having sufficient fastness to light, humidity and active gas in the environment and to provide silver halide color photosensitive materials containing image forming compounds releasing the dyes. SOLUTION: The silver halide photosensitive material comprises the dye represented by general formula (I) [wherein R1 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group and R2 , R3 , R4 and R5 are each hydrogen atom or a substituent group and R2 and R3 together may form a ring and R4 and R5 together may form a ring; G1 to G4 are each C(R6 ) or nitrogen atom; R6 is hydrogen atom or a substituent group].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel condensed ring pyrazole azo dye and a color light-sensitive material containing an image-forming compound which releases the dye.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material for forming a color image has been mainly used, and specifically, an ink jet recording material, a heat transfer recording material, and an electrophotographic recording material. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are widely used. Color filters are used to record and reproduce color images in imaging devices such as CCDs and CMOSs in photographing devices and in LCDs and PDPs in displays. With these color image recording materials and color filters, in order to reproduce or record full color images,
Dyes (pigments) of the three primary colors of so-called additive color mixing method and subtractive color mixing method are used, but they have absorption characteristics that can achieve a preferable color reproduction range, and they are robust enough to withstand various use conditions and environmental conditions. The actual situation is that there is no such pigment, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method for continuously ejecting droplets and an on-demand method for ejecting droplets according to an image information signal. There are a method of ejecting liquid, a method of generating bubbles in the ink by heat to eject a droplet, a method of using ultrasonic waves, or a method of sucking and ejecting a droplet by electrostatic force. Further, as the ink for inkjet recording,
Water-based ink, oil-based ink, or solid (melting type) ink is used.

The dye used in such ink jet recording ink has good solubility or dispersibility in a solvent and high density recording is possible.
Good hue, active gas in light, heat and environment (N
It is robust against SOx as well as oxidizing gases such as Ox and ozone, has excellent fastness to water and chemicals, has good fixability to the image receiving material and does not bleed, and is stored as an ink It is required to have excellent properties, be non-toxic, have high purity, and be available at low cost. However, it is extremely difficult to search for a dye that meets these requirements at a high level.
In particular, when a dye having a good cyan hue and being robust against light, humidity and heat, especially when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles Robustness against oxidizing gases such as ozone in the environment is strongly desired.

In color copiers and color laser printers utilizing the electrophotographic system, toners in which a coloring material is dispersed in resin particles are generally widely used. As the performance required for color toner, absorption characteristics that can realize a preferable color gamut, especially Over HeadPro
high transparency (transparency), which is a problem when used as an injector (hereinafter referred to as OHP), and various robustness under the environmental conditions used during toner production, image formation, and the like. Toners in which pigments are dispersed as particles as colorants are disclosed in JP-A-62-157051, JP-A-65-255956 and JP-A-6-118715, but these toners are excellent in light fastness, Since it is insoluble, it easily aggregates, which causes problems such as a decrease in transparency and a change in hue of the transmitted color. On the other hand, toners using a dye as a coloring material are disclosed in JP-A-3-276161, JP-A-7-209912 and JP-A-8-
As disclosed in No. 123085, these toners, on the contrary, have high transparency and no hue change, but have problems in light resistance and heat resistance.

The heat-sensitive transfer recording has advantages that the apparatus is small and the cost can be reduced, the operation and maintenance are easy, and the running cost is low. As the performance required for dyes used in thermal transfer recording, absorption characteristics capable of achieving a preferable color reproduction range, heat resistance during image formation, compatibility of heat transferability and fixability after transfer, various types of obtained images Although fastness is mentioned, none of the dyes hitherto known satisfy these performances. For example, for the purpose of improving fixability and light fastness, a heat-sensitive transfer recording material and an image forming method in which a heat-diffusible dye is chelated by a transition metal ion previously added to an image-receiving material are disclosed in JP-A-6-63.
No. 0-2398, etc., but the chelating dye formed has an unsatisfactory absorption property, and there is an environmental problem due to the use of a transition metal.

Since a color filter is required to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a color filter can be manufactured by sequentially repeating a method of forming a pattern by subjecting a dyeable photoresist to pattern exposure and development, and then dyeing with a filter dye, for all filter colors. U.S. Pat.
The color filter can also be produced by the method using a positive resist described in JP-A-8,501 and JP-A-6-35182. These methods have a high transmittance because of using a dye, and the optical characteristics of the color filter are excellent, but there is a limit to the light resistance and heat resistance of the dye, and a dye having excellent transparency and high transparency is used. Was wanted. On the other hand, a method of using an organic pigment having excellent light resistance and heat resistance instead of the dye is widely known, but it is difficult to obtain optical characteristics like a dye with a color filter using the pigment.

The dyes used in each of the above-mentioned applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under manufacturing conditions, image forming conditions and environmental conditions used, for example, light resistance, heat resistance, humidity resistance, resistance to oxidizing gases such as ozone, etc. It has good resistance to chemicals such as sulfurous acid gas and has a large molar extinction coefficient.

Up to now, most of the cyan dyes used in the above-mentioned applications have been phthalocyanine dyes excellent in hue and light fastness, but they are sufficient for oxidizing gas, especially ozone. Improvement is desired because it does not have robustness. Japanese Unexamined Patent Publication No. 2000-303009 discloses a technique for imparting resistance to an oxidizing gas by using tetrasulfophthalocyanine, which uses sulfophthalimide as a raw material, but has a sufficient level of robustness against ozone. Has not arrived.

On the other hand, a color diffusion transfer photographic method using an image forming compound which gives an azo dye having a diffusivity different from that of the image forming compound itself as a result of development under basic conditions has been well known in the art. For example, as an image-forming compound that releases a cyan dye, US Pat.
It is described in No. 13,635, No. 4,273,708 and the like.

However, all of the compounds shown in these prior art documents have a nitro group at the para position of the phenylazo group, and it is known that they are reduced and discolored during development processing. . In addition, azo dyes having a nitro group generally have photo-reducing properties, so that the light fastness of images is not good. Furthermore, when these image-forming compounds are contained in the same layer as the photosensitive silver halide emulsion, a phenomenon of suppressing silver development may be observed, and it is presumed that the cause is also due to the nitro group. There is.

As a cyanazo dye image-forming compound using an aniline-based diazo component having no nitro group, JP-A-53-6
No. 6227, No. 60-93434, No. 60-87134, No. 60-257579, etc., the dyes released from the compounds described in these documents are pale colors as cyan dyes. It has drawbacks such as insufficient color reproducibility and an additional use of an image forming compound in order to obtain a good gray balance.

In order to overcome the above drawbacks,
Azo dyes disclosed in JP-A-3-14042, JP-A-7-219180, JP-A-60-14243 and JP-A-11-125888 are known, but further improvements in hue and light fastness are possible. Was wanted. Among these, the compound releasing the benzoisothiazolylazo dye described in JP-A-11-125888 was the most excellent in terms of hue and light fastness, but the image forming compound described in the patent was developed in an alkaline treatment liquid. When applied to a color diffusion image forming method which is characterized in that development is carried out, there is a problem that sufficient transfer density cannot be obtained due to insufficient transferability of the release dye.

As a result of various studies on the condensed ring pyrazolylazo dyes, the present inventors have found that in combination with a phenol coupler containing a condensed ring structure, the 1-H form is, for example, Egyp
tJChemical (2000), 43 (2), 165-175, Chemical Pap. (19
96), 50 (6), 341-344, etc., and is a pale dye as a cyan dye, whereas a condensed ring pyrazolylphenolazo in which the nitrogen atom at the 1-position is substituted with an alkyl group, an aryl group, or the like. It has been found that the dye exhibits good hue and fastness as a cyan dye, and exhibits good performance when applied to the above-mentioned color diffusion image forming method.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the present invention provides 1) a novel dye compound having a specific structure which can be a useful organic compound used in industrial, agricultural, medical, academic, etc. or an intermediate thereof, and 2) has a color reproducibility as a dye of three primary colors. Providing a novel dye having excellent absorption characteristics and having sufficient fastness to active gas in light, heat, humidity and environment, and 3) formation of an image (especially cyan image) which releases the dye. Provide compounds 4)
Provided is a silver halide color photographic light-sensitive material having improved color reproducibility, light fastness and color developability by the image forming compound,
5) It is an object of the present invention to provide an image forming method using the silver halide color photographic light-sensitive material.

[0016]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention can effectively achieve the above-mentioned object by the following (1) to (7) and sufficiently improve the drawbacks of the prior art. Found. (1) A dye represented by the following general formula (I).

[0017]

[Chemical 5]

In the formula, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₂ ,
R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, R ₂
And R ₃ and R ₄ and R ₅ may be bonded to each other to form a ring. G _{1 to} G ₄ each represent C (R ₆ ), or a nitrogen atom, and R ₆
Represents a hydrogen atom or a substituent. (2) A dye represented by the following general formula (II).

[0019]

[Chemical 6]

In the formula, R ₁ and G _{1 to} G ₄ are as defined above, and R ₇ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
A cyano group, an acylamino group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group or an aminocarbonylamino group, R ₈ represents a hydrogen atom or -NHZ, Z represents an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group. (3) A silver halide photographic light-sensitive material characterized by containing at least one image forming compound represented by the following general formula (III) on a support. General formula (III) (Dye-X) _q- Y In the formula, Dye represents a dye represented by the following general formula (I ') or a precursor thereof, and X represents R in the following general formula (I').
Bound to at least one of ₁ to R _6, corresponding or reverse correspondingly to the developing shows a mere bond or a linking group X-Y bond is cleaved, Y is the reaction of the photosensitive silver salt having a latent image on the image-wise Represents a group having a property of causing a difference in diffusibility of dye components by cleaving the XY bond corresponding to or opposite to. q is 1 or 2, and when q is 2, each Dye-X may be the same or different.

[0021]

[Chemical 7]

In the formula, R _{1 to} R ₅ and G _{1 to} G ₄ are as defined above, and R ₉ represents a hydrogen atom, a monovalent cation or a hydrolyzable group. (4) In the silver halide photographic light-sensitive material according to the item (3), Dye in the general formula (III) is the general formula (I ′).
In place of, a silver halide photographic light-sensitive material characterized by being a dye represented by the following general formula (II ′) or a precursor thereof.

[0023]

[Chemical 8]

In the formula, R ₁ , R ₇ , R ₈ , R ₉ and G _{1 to} G ₄ are as defined above, and at least one of R ₁ , R ₆ , R ₇ and R ₈ is bonded to X. (5) An image forming method, which comprises developing the silver halide color photographic light-sensitive material according to the item (3) or (4) by developing an alkali processing solution. (6) An image forming method, which comprises thermally developing the silver halide color photographic light-sensitive material described in (3) or (4). (7) Image formation, which comprises developing the silver halide color photographic light-sensitive material according to item (3) or (4) in the presence of an alkali with a sparingly soluble metal salt and a complexing agent for the metal salt. Method.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION A compound represented by the following general formula (I), general formula (II), general formula (III), general formula (I ') or general formula (II') used in the present invention. Will be described in more detail. In the general formula (I), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group, and more preferably an alkyl group.

The alkyl group represented by R ₁ has 1 to 30 carbon atoms.
, Preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, straight-chain, branched or cyclic, substituted or unsubstituted alkyl group (for example, trifluoromethyl, methyl, ethyl, propyl, isopropyl, butyl). , T-butyl,
t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like).

The alkenyl group represented by R ₁ has 2 to 3 carbon atoms.
A substituted or unsubstituted alkenyl group having 0, preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms, such as vinyl, 1-methylvinyl, cyclohexen-1-yl, etc. Represents The alkynyl group represented by R ₁ has 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms.
And more preferably a substituted or unsubstituted alkynyl group having 2 to 6 carbon atoms (eg, ethynyl, 1-propynyl, etc.)
Represents The aryl group represented by R ₁ has 6 to 30 carbon atoms,
Preferably it has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
10 represents a substituted or unsubstituted alkynyl group (eg, phenyl, naphthyl, anthryl, etc.).

The heterocyclic group represented by R ₁ has 1 to 30 carbon atoms.
, Preferably a substituted or unsubstituted heterocyclic group having 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms (as the hetero atom, for example, at least one or more of nitrogen, oxygen and sulfur, preferably 1 3 to 12 including 9 to 9
A monocyclic or condensed ring of a member ring, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, 2-morpholinyl, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2 -Benzoxazolyl, 1,2,4-thiadiazol-5-yl, 1,2,
4-oxadiazol-5-yl). Examples of the substituent of the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₁ include the following R ₂ to
The substituents mentioned in the explanation of R ₅ can be mentioned.

R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, and R ₂ and R ₃ and R ₄ and R ₅ may be bonded to each other to form a ring. The substituent represented by R _{2 to} R ₅ has 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms,
More preferably, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (eg, trifluoromethyl, methyl,
Ethyl, propyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl,
Octyl, 2-ethylhexyl, dodecyl, etc.), a C2-C30, preferably C2-C12, more preferably C2-C6 chain or cyclic alkenyl group (for example, vinyl, 1-methyl). Vinyl, cyclohexene-1
-Yl etc.), having 2 to 30 carbon atoms, preferably 1 to 1 carbon atoms
12, more preferably an alkynyl group having 2 to 6 carbon atoms (eg ethynyl, 1-propynyl, etc.), 6 to 6 carbon atoms.
An aryl group having 30, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.),

1 to 30 carbon atoms, preferably 1 to 1 carbon atoms
2, more preferably an acyloxy group having 1 to 7 carbon atoms (eg, acetoxy, propionyloxy, benzoyloxy, etc.), 1 to 30 carbon atoms, preferably 1 carbon atom
To 12 more preferably a carbamoyloxy group having 1 to 6 carbon atoms (for example, N, N-dimethylcarbamoyloxy and the like), 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms
More preferably a carbonamide group having 1 to 7 carbon atoms (eg, formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide, etc.), 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms.
More preferably a sulfonamide group having 1 to 6 carbon atoms (eg, methanesulfonamide, ethanesulfonamide, benzenesulfonamide, etc.), having 1 to 30 carbon atoms,
It preferably has 1 to 12 carbon atoms, and more preferably 1 carbon atom.
A carbamoyl group of 6 (eg, N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.);

C0-30, preferably C0-C3
12, more preferably a sulfamoyl group having 0 to 6 carbon atoms (for example, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), 1 to 30 carbon atoms, preferably Has 1 to 12 carbon atoms
More preferably an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.), having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably carbon number 6-10 aryloxy groups (for example, phenoxy, 4-methoxyphenoxy, naphthoxy, etc.), C7-30, preferably C7-15, more preferably C7-10 aryloxycarbonyl groups. (For example, phenoxycarbonyl, naphthoxycarbonyl, etc.), having 2 to 30 carbon atoms,
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
An alkoxycarbonyl group of ~ 6 (eg, methoxycarbonyl, ethoxycarbonyl, etc.),

C1-C30, preferably C1-C3
12 more preferably an N-acylsulfamoyl group having 1 to 6 carbon atoms (eg, N-acylsulfamoyl, N-
Benzoylsulfamoyl etc.), having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 12 carbon atoms.
An alkylsulfonyl group having 6 carbon atoms (for example, methylsulfonyl, ethylsulfonyl, 2-methoxyethoxysulfonyl, etc.), 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms
More preferably an arylsulfonyl group having 6 to 10 carbon atoms (for example, benzenesulfonyl, p-toluenesulfonyl, etc.), having 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms.
12, more preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms (for example, methoxycarbonylamino,
Ethoxycarbonylamino, etc.),

C6-30, preferably 6-15
More preferably an aryloxycarbonylamino group having 6 to 10 carbon atoms (for example, phenoxycarbonylamino etc.), having 0 to 30 carbon atoms, preferably 0 to 12 carbon atoms.
More preferably an amino group having 0 to 6 carbon atoms (for example,
Amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxy group, hydroxy group, sulfo group, mercapto group, having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms
More preferably an alkylsulfinyl group having 1 to 6 carbon atoms (for example, methylsulfinyl, ethylsulfinyl, etc.), having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms.
More preferably an arylsulfinyl group having 6 to 10 carbon atoms (for example, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.),
An alkylthio group having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms (eg, methylthio, ethylthio, cyclohexylthio, etc.),

C6-30, preferably 6-15
More preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, naphthylthio, etc.), and 1 carbon atom.
To 30, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms ureido group (for example, ureido, 3-
Methylureide, 3,3-dimethylureido, etc.), a heterocyclic group having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms (as a hetero atom, for example, nitrogen, oxygen and It contains 1 to 9, preferably 1 to 3, sulfur and the like and has 3 to 12 membered ring, preferably 5 to
7-membered monocyclic or condensed ring, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholyl, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2- Benzoxazolyl, etc.),

C1-C30, preferably C1-C3
12 or more preferably an acyl group having 1 to 7 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), 0 to 30 carbon atoms, preferably 0 to 12 carbon atoms
And more preferably a sulfamoylamino group having 0 to 6 carbon atoms (for example, N-methylsulfamoylamino, N-
Phenylsulfamoylamino etc.), carbon number 3 to 30
, Preferably a C 3-12, more preferably a C 3-6 silyl group (eg, trimethylsilyl, triethylsilyl, etc.) and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). . The above-mentioned substituents may further have a substituent, and examples of the substituent include the substituents mentioned here. Further, these substituents may be bonded to each other to form a condensed ring.

G _{1 to} G ₄ each represent C (R ₆ ) or a nitrogen atom, and R ₆ represents a hydrogen atom or a substituent. The substituent represented by R ₆ has the same meaning as the substituent described in the description of R _{2 to} R ₅ . G _{1 to} G ₄ are preferably selected such that the sum of the σ _p values of R ₆ is 0 to 2, and more preferably 0.5 to 1.5. As a result of intensive studies, we have come to the conclusion that C (R ₆ ) and N have almost the same electron effect when the σ _p value of R ₆ is 0.5. Therefore, G _{1 to} G ₄
When represents a nitrogen atom, σ _p = 0.5 is used for calculation.

Here, the Hammett's substituent constant σ _p value will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L.A. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants calculated by Hammett's law include σ _p value and σ _m
There are values, and these values can be found in many common books, for example J. A. Dean, "Lan
ge's Handbook of Chemistr
y ”12th edition, 1979 (McGraw-Hil
l) and "Chemical Area" special edition, No. 122, 96-103
Page, 1979 (Nankodo), Chemical Review (91
Volume), pp. 165-195 (1991), etc.
In the present invention, each substituent is represented by Hammett's substituent constant σ
_{Although it is} limited or explained by _p , this does not mean that the value known in the literature found in the above-mentioned book is limited only to a certain substituent, and even if the value is unknown in the literature, Hammett's rule It goes without saying that it also includes a substituent that will be included in the range when measured based on

A preferred combination of R _{2 to} R ₅ is, for example, (R ₂ , R ₃ , R ₄ , R ₅ ) = (acylamino group, hydrogen atom,
Acylamino group, hydrogen atom; each acylamino group may be the same or different), (acylamino group, hydrogen atom, hydrogen atom, acylamino group; each acylamino group may be the same or different) Good), (acylamino group, hydrogen atom, alkyl group, hydrogen atom), (acylamino group, hydrogen atom, alkoxy group,
(Hydrogen atom), (acylamino group, hydrogen atom, halogen atom, hydrogen atom), (acylamino group, hydrogen atom, hydrogen atom, alkyl group), (acylamino group, hydrogen atom, hydrogen atom, alkoxy group), (acylamino group, Hydrogen atom,
Hydrogen atom, halogen atom) and the like, but the embodiment represented by the general formula (II) is most preferable.

In the general formula (II), R ₁ and G _{1 to} G ₄ are as defined above, and R ₇ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group. , Cyano group, acylamino group, acyl group,
Alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, alkoxycarbonylamino group and aminocarbonylamino group, R ₈ represents a hydrogen atom or -NHZ, Z is an acyl group, an alkoxycarbonyl group, It represents an aminocarbonyl group, an alkylsulfonyl group and an arylsulfonyl group. (Detailed description of the substituents described for R ₇ and Z is the same as that described for R _{2 to} R ₅ above.) R ₇ is preferably an acylamino group, a carbamoyl group or a sulfamoyl group, and It is preferably an acylamino group. R ₈ is preferably —NHZ, and Z = alkylsulfonyl group or arylsulfonyl group is more preferable.

Next, image formation represented by the general formula (III)
The compound will be described. In the general formula (III), Dye is
The general formula (I ′) {preferably the general formula (II ′)}
R represents a dye or its precursor represented by₁~ R₈and
G₁~ G_FourRepresents the same as the above. R₉Is hydrogen atom, monovalent tick
It represents an on or hydrolyzable group. R₉Unit price represented by
Examples of cations include Na⁺, K⁺, NH_Four ⁺, N (CH₃)_Four ⁺
And so on. R ₉And a hydrolyzable group represented by
Examples thereof include an acyl group and a sulfonyl group.
It (A detailed description of the acyl group and the sulfonyl group is given above.
R₂~ R_FiveIs synonymous with what was described in the explanation of. )

Q is 1 or 2, and when q is 2, Dye-
X may be the same or different, but q is preferably 1. X is bonded to at least one of R _{1 to} R _{8 in} the above general formula (I ′) or general formula (II ′),
Represents a mere bond or a linking group in which the XY bond is cleaved in response to development or in reverse correspondence, and the linking group represented by X is -N (J ₁ )-
(J ₁ represents a hydrogen atom, an alkyl group or a substituted alkyl group), —SO ₂ —, —CO—, an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group,
Representative examples are substituted naphthylene groups, -O-, -SO-, and groups obtained by combining two or more of these divalent residues, and among these, preferred ones are -NJ ₁ -SO ₂ -,- NJ ₁ -CO- or -J _2-
(L) _k- (J ₃ ) _r- is a group represented by J ₂ and J ₃ each represents an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group or a substituted naphthylene group, and L Is -O-, -SO-, -SO _2- , -CO-, -SO ₂ NH-, -NHSO ₂
Represents-, -CONH-, -NHCO-, k represents 0 or 1, and r represents 1 or 0. Also, -NJ ₁ -SO ₂ -or -NJ ₁ -CO- and -J _2-
A combination of (L) _k- (J ₃ ) r- is also preferable. In the general formula (1), the bonding mode of Dye and Y is Dye-SO ₂ N.
Particularly preferred is the HY form.

Next, Y will be described. Y represents a group having the property of cleaving the Y--X bond corresponding to or inversely corresponding to the photosensitive silver halide having a latent image. Such groups are known in the field of photographic chemistry utilizing diffusion transfer of dyes, and are described, for example, in US Pat.
No. 184852).

Y will be described in detail (however, X is included in each formula shown below). (1) Examples of Y include a negative-acting releaser that releases a photographically useful group in response to development.

As Y classified into the negative-acting releaser, a releaser group which releases a photographically useful group from an oxidant is known. The following formula (Y-1) is mentioned as a preferable example of Y of this type.

[0045]

[Chemical 9]

In the formula, β represents a group of non-metal atoms necessary for forming a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle. α represents —OZ ₂ or —NHZ ₃ , where Z ₂ represents a hydrogen atom or a group that produces a hydroxyl group by hydrolysis,
₃ represents a hydrogen atom, an alkyl group, an aryl group, or a group capable of generating an amino group by hydrolysis. Z ₁ is an optionally substituted alkyl group, aryl group, aralkyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, sulfonyl group, acylamino group, sulfonylamino group, carbamoyl group, A sulfamoyl group, a ureido group, a urethane group, a heterocyclic group or a cyano group, a halogen atom, a represents a positive integer, and when a is 2 or more, Z _{1 s} may be the same or different. good. For formula (Y-1), -X is-
NHSO a group represented by ₂ Z ₄ Z ₄ represents a divalent group.

More preferred groups of the formula (Y-1) include the following formula (Y-2) or formula (Y-3).

[0048]

[Chemical 10]

In the formula, Z ₂ and X have the same meanings as described in formula (Y-1). Z ₅ and Z ₆ represent an alkyl group, an aryl group or an aralkyl group, and these may have a substituent. More preferably, Z ₅ is a secondary or tertiary alkyl group, and one having a sum of carbon numbers of Z ₅ and Z ₆ of 20 or more and 50 or less is preferable.

Specific examples of these are shown in US Pat. No. 4,055,4.
28, 4,336,322, JP-A-51-113.
No. 624, No. 56-16131, No. 56-71061
No. 56, No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, and No. 57-40.
No. 43, No. 59-60439, Japanese Patent Publication No. 56-1765.
No. 6 and No. 60-25780.

Another example of Y is formula (Y-4).

[0052]

[Chemical 11]

In the formula, α, X, Z ₁ and a have the same meanings as described in the formula (Y-1). β'represents a group of non-metal atoms necessary to form a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle.

In the group represented by the formula (Y-4), α is -O.
Z ₂ in which β ′ forms a naphthalene skeleton is preferred. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Further, as a releaser releasing a photographically useful group by a reaction similar to the formula (Y-1) or the formula (Y-2), JP-A-51-104343 and JP-A-53-46730.
No. 54-130122, No. 57-85055,
53-3819, 54-48534, 49-
No. 64436, No. 57-20735, Japanese Patent Publication No. 48-3
2129, 48-39165, and U.S. Pat. No. 3,44.
The groups described in 3,934 are mentioned.

The compound releasing the photographically useful group from the oxidant by another reaction mechanism is represented by the formula (Y-5) or (Y-
Examples include hydroquinone derivatives represented by 6).

[0057]

[Chemical 12]

In the formula, β'is the formula (Y-4) and Z ₂ is the formula (Y-4).
-1) has the same meaning as described above, Z ₇ has the same meaning as Z ₂ , and
Z ₈ represents a substituent described in Z ₁ or a hydrogen atom. Z ₂ and Z ₇ may be the same or different. Specific examples of this type are described in US Pat. No. 3,725,062.

Examples of this type of hydroquinone derivative releaser having a nucleophilic group in the molecule are also included. Specifically, it is described in JP-A-4-97347.

Another example of Y is US Pat. No. 3,44.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. No. 3,844,785, U.S. Pat. D. The hydrazine derivative described in No. 128, page 22 may be mentioned.

Further, as the negative acting releaser, the following formula (Y-7) can be mentioned.

[0062]

[Chemical 13]

In the formula, Coup represents a group capable of coupling with an oxidized product of p-phenylenediamines and p-aminophenols, that is, a group known as a photographic coupler. Specific examples are described in British Patent 1,330,524.

(2) Next, as Y, there can be mentioned a positive-working releaser which releases a photographically useful group in the opposite manner to development.

The positive-acting releaser may be a releaser that exhibits a function when reduced during treatment. As a preferable example of Y of this type, the following formula (Y-
8).

[0066]

[Chemical 14]

In the formula, EWG represents a group that receives an electron from a reducing substance. N represents a nitrogen atom, W is an oxygen atom, a sulfur atom or -MZ ₁₁ - represents the EWG is the N-W bond is cleaved after receiving electrons. Z ₁₁ represents an alkyl group or an aryl group. Z ₉ and Z ₁₀ represent a mere bond or a substituent other than a hydrogen atom. A solid line represents a bond, and a broken line represents that at least one of them is bonded.

Among the groups represented by formula (Y-8), formula (Y-9) is preferred.

[0069]

[Chemical 15]

In the formula, O represents an oxygen atom (that is, (Y-
8) W is an oxygen atom), Z ₁₂ forms a heterocycle containing an N—O bond, and Z ₁₂ − is formed following the cleavage of the N—O bond.
Represents an atomic group having the property of breaking an X bond. Z ₁₂ may have a substituent and a saturated or unsaturated ring may be condensed. Z ₁₃ represents -CO- or -SO ₂ -
Represents

Among the groups represented by the formula (Y-9), the group represented by the formula (Y-10) is more preferable.

[0072]

[Chemical 16]

In the formula, Z ₁₄ represents an alkyl group, an aryl group or an aralkyl group, Z ₁₅ represents a carbamoyl group or a sulfamoyl group, Z ₁₆ represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group or an aryl group. It represents an oxy group, an arylthio group, a halogen atom, a cyano group, or a nitro group, and b represents an integer of 0 to 3. The substitution position of the nitro group in the formula is ortho or para to the nitrogen atom. It is most preferable that Z ₁₅ is a carbamoyl group or a sulfamoyl group substituted with an alkyl group having 12 to 30 carbon atoms.

A specific example of Y of this type is disclosed in JP-A-62-2.
15,270, U.S. Pat. No. 4,783,396.

Further, as a positive-acting releaser which is subjected to another reduction and exhibits a function, US Pat. No. 4,139,379
And BEND described in No. 4,139,389
Compounds and Ca described in British Patent No. 11,445
rquin compound, JP-A-54-126535, JP-A-5-
The releaser of 7-84553 is mentioned.

When these reducible releasers represented by Y represented by the formula (Y-8) are used, a reducing agent is used in combination, but L containing a reducing group in the same molecule is used.
DA compounds are also included. This is US Pat. No. 4,551,
No. 423.

There is also a type of positive-working releaser that is incorporated as a reductant in a light-sensitive material and deactivates when oxidized during processing. As this type of releaser, Japanese Patent Laid-Open No. 51-63618 and US Pat.
Fields compounds described in Japanese Patent No. 79 are also disclosed in JP-A-49-11162.
No. 8, 52-4819, and U.S. Pat. No. 4,199,35.
The Hinshaw compounds described in No. 4 are mentioned.

As an example of this type of Y, the formula (Y-11)
Can also be mentioned.

[0079]

[Chemical 17]

In the formula, Z ₁₇ and Z ₁₉ represent a hydrogen atom or a substituted or unsubstituted acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, Z ₁₈ represents an alkyl group,
Represents an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, Z ₂₀ , Z
₂₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Specifically, JP-A-62
-245270 and 63-46450.

As a positive-acting releaser having another mechanism, a thiazolidine type releaser can be mentioned. Specifically, U.S. Pat. No. 4,468,451 and JP-A-7-1599.
62. Specific examples of the dyes represented by formulas (I) and (II) and the image-forming compound represented by formula (III) of the invention are shown below, but the invention is not limited thereto. .

[0082]

[Chemical 18]

[0083]

[Chemical 19]

[0084]

[Chemical 20]

[0085]

[Chemical 21]

[0086]

[Chemical formula 22]

[0087]

[Chemical formula 23]

[0088]

[Chemical formula 24]

[0089]

[Chemical 25]

[0090]

[Chemical formula 26]

[0091]

[Chemical 27]

Next, a method for synthesizing the dyes represented by the general formulas (I) and (II) and the image forming compound represented by the general formula (III) will be described. The dyes represented by the general formulas (I) and (II) are obtained by the following route, that is, a diazo coupling reaction of a phenol component or naphthol which is a coupler component and an amino form (A) of a condensed pyrazole which is a diazo component. Can be synthesized by.

[0093]

[Chemical 28]

The coupler component phenols or naphthols can be prepared, for example, by a general method for synthesizing silver halide color photographic 4-equivalent couplers (see, for example, US Pat. No. 2,772,162).
No., No. 2,895,826, No. 4,690,889, etc.)
Can be easily synthesized. The amino form (A) of condensed ring pyrazoles is, for example, J. Org. Chem., 57 (5), 1563-7; 19.
It can be synthesized by the method described in 92 or the reaction route shown below.

[0095]

[Chemical 29]

In the formula, a compound represented by (B) {X is a halogen atom (fluorine, chlorine, bromine, iodine etc.), an alkylsulfonyloxy group (eg methylsulfonyloxy, trifluoromethanesulfonyloxy etc.) or an arylsulfonyloxy Represents a group (eg, benzenesulfonyloxy, p-toluenesulfonyloxy, p-bromobenzenesulfonyloxy, etc.) and the like. }, A commercially available compound can be used. For example, J. Heterocyclic Chem., 18,
183; 1981 and Nat. Acad. Sci. Letters., 18, 15-16; 1995, and methods similar thereto. The diazotization of the amino form (A) of condensed ring pyrazoles and the diazo coupling reaction of the formed diazonium salt with phenols or naphthols are carried out under general conditions (eg Maruzen Co., Ltd., edited by The Chemical Society of Japan, New Experimental Chemistry). Lecture 14, Synthesis and Reaction of Organic Compounds III1525-152
6 and Diazo Chemistry / Heinrich Zollinger, Weinheim; N
ewYork; Basel; Cambridge; Tokyo (1995): VCH). In addition, the general formula (III)
The image-forming compound represented by can be synthesized, for example, by a method similar to the method described in JP-A-60-28651 and JP-A-11-125888. Specific synthetic examples of typical dyes and image-forming compounds of the present invention are shown below, but other dyes and image-forming compounds can be similarly synthesized.

Synthesis of Compound Example DYE-3 DYE-3 was synthesized according to the following scheme.

[0098]

[Chemical 30]

Synthesis of Compound c To a solution of 150 g (3.26 mol) of N-methylhydrazine in 600 ml of tetrahydrofuran was added dropwise 111 g (0.65 mol) of benzyloxycarbonyl chloride at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. The reaction solution was poured into 1500 ml of ethyl acetate / 1500 ml of water and the layers were separated. The organic layer was washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure to give compound b 105 g (0.58 mmol). 78 g (0.43 mol) of the compound b thus obtained and 60 g (0.4 g) of commercially available 2-chloro-3-cyanopyridine (compound a)
(3 mol) was stirred under a nitrogen stream at 150 ° C. for 1 hour. The reaction solution was extracted with 500 ml of ethyl acetate / 500 ml of water, the organic layer was washed with water and brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel chromatography (developing solvent: dichloromethane / methanol = 50/1) and then recrystallized from hexane to give compound c (29.4 g, 0.1 m).
ol).

Synthesis of Compound d 23.0 g (8%) of the above compound c was added to 300 ml of a 30% solution of hydrobromic acid in acetic acid.
1.5 mmol) was added, and the mixture was stirred at room temperature for 3 hours. Ethyl acetate 1000 ml / hexane 200 ml was added to the reaction solution, and the precipitated crystals were filtered and dried to give compound d 17.9 g (78.2 mmo
l) got.

Synthesis of DYE-3 A mixture of compound d 1.0 g (4.37 mmol), compound e 1.0 g (3.40 mmol) and phosphoric acid 25 ml was added with sodium nitrite 0.3 (4.37 mmo).
l) was slowly added at 10 ° C. and then stirred at room temperature for 3 hours. The reaction solution was extracted with 300 ml of ethyl acetate / 300 ml of water, the organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel chromatography (developing solvent: dichloromethane / methanol = 10/1) to obtain DYE-3 0.15 g (0.33 mmol). The NMR data of DYE-3 and λmax in DMF are shown below. ¹ H NMR (DMSO-d ⁶ ): δ 11.95 (brs, 1H), 11.60 (s, 1H), 10.02
(s, 1H), 8.72 (d, 1H), 8.55 (d, 1H), 8.43 (s, 1H), 7.97
(d, 1H), 7.85-7.80 (m, 2H), 7.23 (t, 1H), 4.16 (s, 3H),
3.11 (s, 3H), 2.28 (s, 3H) λmax (DMF) = 634nm

Synthesis of Compound Example DYE-4 DYE-4 was synthesized according to the following scheme.

[0103]

[Chemical 31]

Synthesis of Compound f To a solution of 86 g (0.79 mol) of phenylhydrazine in 200 ml of dimethylacetamide, 50 g (0.36 mol) of compound a was slowly added at room temperature, and the mixture was stirred at 50 ° C. for 1 hour. The reaction solution was cooled to room temperature, then slowly poured into 800 ml of 1N hydrochloric acid water, and the precipitated crystals were filtered. The crystals were washed with water and acetonitrile and dried by blowing air at 40 ° C to give compound f52.5g.
(0.25 mmol) was obtained.

Synthesis of compound g 25.0 g (1%) of the above compound f was added to 300 ml of a 30% acetic acid solution of hydrobromic acid.
(19 mmol) was added and the mixture was stirred at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, 1000 ml of ethyl acetate / 500 ml of hexane was added, and the precipitated crystals were filtered and dried to give compound g.
22.5 g (77.3 mmol) was obtained.

Synthesis of DYE-4 A mixture of 1.27 g (4.37 mmol) of compound g, 1.0 g (3.40 mmol) of compound e and 25 ml of phosphoric acid was added to 0.3 ml of sodium nitrite (4.37 mm).
ol) was slowly added at 10 ° C., and then the mixture was stirred at room temperature for 3 hours. The reaction solution was extracted with 300 ml of ethyl acetate / 300 ml of water, the organic layer was washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel chromatography (developing solvent: dichloromethane / methanol = 10/1) to obtain DYE-4 0.18 g (0.35 mmol). The DYE-4 NMR data and λmax in DMF are shown below. ¹ H NMR (DMSO-d ⁶ ): δ 11.96 (brs, 1H), 11.62 (s, 1H), 10.05
(s, 1H), 8.75 (d, 1H), 8.56 (d, 1H), 8.44 (s, 1H), 7.98-
7.80 (m, 3H), 7.35-7.13 (m, 6H), 3.12 (s, 3H), 2.28 (s, 3
H) λmax (DMF) = 639nm

Synthesis of Compound Example CC-3 CC-3 was synthesized according to the following scheme.

[0108]

[Chemical 32]

Synthesis of Compound I To a mixture of 22.9 g (0.1 mol) of compound d and 100 ml of phosphoric acid was slowly added 7.2 g (0.104 mol) of sodium nitrite at 0 ° C., and the mixture was stirred at that temperature for 30 minutes to prepare a diazo solution. Was prepared. Compound h 36.7g (0.8mol), sodium acetate 500g, dimethylacetamide 150ml, methanol 300ml, water 7500ml
The above diazo solution was slowly added to the mixture of 10 ° C. or lower, and the mixture was stirred at room temperature for 3 hours. The reaction liquid was poured into 1.5 liters of saline, and the precipitated crystals were filtered and dried to obtain 35 g (0.055 mol) of compound I.

Synthesis of Compound j To a mixture of 35 g (0.055 mol) of Compound I, 200 ml of acetonitrile and 5 ml of dimethylacetamide, 40 ml (0.43 mol) of phosphorus oxychloride was added dropwise at 40 ° C., and the mixture was stirred at 60 ° C. for 3 hours. After the reaction solution was cooled to room temperature, it was slowly poured into 1.5 liters of ice water. The precipitated crystals were filtered and dried to obtain 15 g (0.024 mol) of compound j.

Synthesis of CC-3 13.1 g (20.8 mmol) of compound j and 13.2 g (20.8 mmo of compound k
After adding 10.3 ml (104 mmol) of α-picoline to a solution of 60 ml of dimethylacetamide in l) at 10 ° C., the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1 liter of ethyl acetate / 1 liter of dilute hydrochloric acid and the layers were separated. The organic layer was washed with aqueous sodium hydrogen carbonate (twice) and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. Silica gel chromatography of the concentrated residue "
Purification with (developing solvent: dichloromethane / methanol = 15/1) gave 6.5 g of CC-3 (5.4 mmol, mp = 195-197 ° C.).

The dye of the present invention may be used as an image recording material for forming an image, particularly a color image,
Specifically, including the ink jet type recording material described in detail below, a heat sensitive recording material, a pressure sensitive recording material, a recording material using an electrophotographic method, a diffusion transfer type silver halide photosensitive material, a printing ink, a recording pen, etc. And preferably a diffusion transfer type silver halide light-sensitive material used in the embodiment of the general formula (III). In addition, solid-state image sensor such as CCD, LCD,
Records color images used in displays such as PDP
It can be applied to color filters for reproduction and dyeing solutions for dyeing various fibers. The dye of the present invention is used by adjusting physical properties such as solubility, dispersibility, and heat transferability suitable for its use with a substituent. Further, the dye of the present invention can be used in a dissolved state, an emulsified dispersed state, or a solid dispersed state depending on the system used. The dye of the present invention can be used as a dye having various hues, but is particularly useful as a cyan dye.

[Inkjet Recording Ink] The inkjet recording ink can be prepared by dissolving and / or dispersing the dye of the present invention in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. 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 accelerators, ultraviolet absorbers, preservatives,
Known additives such as antifungal agents, pH adjusting agents, surface tension adjusting agents, defoaming agents, viscosity adjusting agents, dispersants, dispersion stabilizers, rust preventives and chelating agents can be mentioned. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the water phase during the preparation.

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

The drying inhibitor 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 derivative, glycerin. , Lower alkyl ethers of polyhydric alcohols such as trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 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 preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. These drying inhibitors are contained in the ink in an amount of 10 to 50% by mass.
It is preferable to contain.

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

The ultraviolet absorber is used for the purpose of improving the storability of images. Examples of the ultraviolet absorber include JP-A-58-185677 and JP-A-61-190537.
Japanese Patent Laid-Open No. 2-782 and Japanese Patent Laid-Open No. 5-97075.
And benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784,
Japanese Unexamined Patent Publication No. 5-194843, U.S. Pat. No. 32,144
No. 63, etc., benzophenone compounds, JP-B-48-30492, JP-A-56-21141,
Cinnamic acid compounds described in JP-A-10-88106 and the like, JP-A-4-298503 and 8-534.
No. 27, No. 8-239368, No. 10-18.
No. 2621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. A compound which absorbs ultraviolet rays and fluoresces, which is represented by the compounds described in No. 24239 and stilbene compounds and benzoxazole compounds, that is, a so-called fluorescent brightening agent can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Hydroquinones as organic anti-fading agents,
Alkoxyphenols, dialkoxyphenols,
There are phenols, anilines, amines, indanes, chromanes, alkoxyanilines, heterocycles and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No.
17643, items VII, I through J, ibid. 1516
2, the same No. 18716, page 650, left column, same No. 36
544, page 527, ibid. 307105, page 872,
Same No. The compounds described in the patent cited in 15162 and pages 127 to 13 of JP-A No. 62-215272.
The compounds included in the general formulas of the representative compounds and the compound examples described on page 7 can be used.

As the antifungal agent, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-
Examples thereof include 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are 0.02 to 0.02 in the ink.
It is preferable to use 1.00% by mass.

The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. The pH
The adjusting agent has a pH of 6 to 10 for the purpose of improving the storage stability of the inkjet ink.
It is preferable to add it so that it becomes, and it is more preferable to add it so that it may become pH 7-10.

Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. still,
The surface tension of the inkjet ink using the dye of the present invention is preferably 20 to 60 mN / m. 25-45
mN / m is preferred. The viscosity of the inkjet ink using the dye of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust to 20 mPa · s or less. Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkylsulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate. 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) which is an acetylene-based polyoxyethylene oxide surfactant is used.
Products & Chemicals) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Furthermore, Research Disclosure N, pages (37) to (38) of JP-A-59-157,636.
o. What was mentioned as a surfactant of 308119 (1989) can also be used.

As the defoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent typified by EDTA, or the like can be used if necessary.

When the dye of the present invention is dispersed in an aqueous medium, JP-A No. 11-286637, Japanese Patent Application Nos. 2000-78491 and 2000-8025.
9. As described in 2000-62370, the colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application No. 2000-7
It is preferable to disperse the dye of the present invention dissolved in a high boiling point organic solvent in an aqueous medium, such as 8454, 2000-78491, 2000-203856, and 2000-203857. The specific method for dispersing the dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount thereof are preferably those described in the above patent. it can. Alternatively, the azo dye may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. As a dispersing device, a simple stirrer or impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) A specific commercially available device is a Gohlin homogenizer, a microfluidizer, DeBEE2000
Etc.) can be used. Regarding the method for preparing the above ink jet recording ink, in addition to the above-mentioned patents, JP-A-5-148436, 5-295312, 7-97541, 7-82515, and 7-118.
584, JP-A-11-286637, Japanese Patent Application 2000
The details are described in the respective publications of -87539, and can be used for the preparation of an inkjet recording ink using the dye of the present invention.

As the aqueous medium, a mixture containing water as a main component and a water-miscible organic solvent added may be used, if desired. Examples of the water-miscible organic solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric 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 (For example, 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. 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, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, Acetone) is included. The water-miscible organic solvent may be used in combination of two or more kinds.

In the present invention, it is preferable that the dye of the present invention is contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the ink for ink jet recording. Further, in the inkjet ink, other dyes may be used in combination with the dye of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

The ink jet recording ink using the dye of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full-color image, magenta tone ink, cyan tone ink,
In addition, a yellow tone ink can be used, and a black tone ink may be further used to adjust the tone. Any applicable yellow dye can be used. For example, an aryl or heterylazo dye having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as a coupling component (hereinafter referred to as a coupler component); for example, a coupler component Azomethine dyes having open-chain type active methylene compounds and the like; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Quinophthalone dye as a seed,
Examples thereof include nitro / nitroso dyes, acridine dyes and acridinone dyes.

Any magenta dye can be used as the applicable magenta dye. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example, arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. Examples thereof include dyes.

Any applicable cyan dye can be used. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having phenols, naphthols, heterocycles such as pyrrolotriazole as coupler components, cyanine dyes, oxonol dyes, Examples thereof include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes. Each of the above dyes may be one that exhibits yellow, magenta, and cyan colors only after a part of the chromophore is dissociated, in which case the counter cation is an alkali metal or an inorganic cation such as ammonium. It may be an organic cation such as a pyridinium or a quaternary ammonium salt, or a polymer cation having a partial structure of them.
Examples of applicable black materials include disazo, trisazo, and tetraazo dyes, and carbon black dispersions.

[Inkjet recording method] In the inkjet recording method using the dye of the present invention, energy is applied to the ink for inkjet recording to obtain a known image receiving material, that is, plain paper or resin-coated paper, for example, JP-A-8-16.
No. 9172, No. 8-27693, No. 2-27.
6670, 7-276789 and 9-3.
No. 23475, Japanese Patent Laid-Open No. 62-238783,
JP, 10-153989, A and 10-21747.
No. 3, gazette 10-235995, gazette 10-33.
No. 7947, No. 10-217,597, No. 10
Inkjet dedicated paper, film, electrophotographic co-paper, cloth, glass, etc.
Images are formed on metal, ceramics, etc.

When forming an image, a polymer latex compound may be used together for the purpose of imparting glossiness, water resistance and improving weather resistance. The latex compound may be applied to the image receiving material before, after, or at the same time as the application of the colorant, so that the place of addition is also in the image receiving paper, It may be in the ink or may be used as a liquid substance of the polymer latex alone. Specifically, Japanese Patent Application 2000-363090,
2000-315231, 2000-354380, 2000-343944, 200
The methods described in 0-268952, 2000-299465, and 2000-297365 can be preferably used.

Recording papers and recording films used for ink jet printing using the ink of the present invention will be described below. Supports for recording paper and recording film are chemical pulp such as LBKP and NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mixing additives such as fixing agent, cationic agent, paper strengthening agent,
Those manufactured by various devices such as a Fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, synthetic paper or plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 10 to 250 g.
/ M ² is desirable. The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. In the present invention, as the support,
A paper and a plastic film having both surfaces laminated with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support is
It 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 inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic acid anhydride obtained by the dry production method and hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

As the aqueous binder contained in the ink receiving layer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide, polyalkylene oxide derivative. Water soluble polymer such as styrene butadiene latex,
Examples thereof include water-dispersible polymers such as acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing 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. Regarding the polymer mordant, JP-A-48-28325 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The water-proofing agent is effective for making the image water-proof, and as the water-proofing agent, a cationic resin is particularly desirable. As such a cationic resin, polyamide polyamine epichlorohydrin, polyethyleneimine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by mass based on the total solid content of the ink receiving layer, and particularly 3
It is preferably from 10 to 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferable.

The surface active agent functions as a coating aid, a peeling property improving agent, a sliding property improving agent or an antistatic agent. For the surfactant, see JP-A-62-173463.
No. 62-183457. An organic fluoro compound may be used instead 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). Regarding organic fluoro compounds, JP-B-57-9053 (columns 8 to 17), JP-A-61-2
It is described in each publication of 0994 and 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners,
Preservatives, pH adjusters, matting agents, hardeners and the like can be mentioned. The ink receiving layer may be one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat 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. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, organic pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins.

Examples of the aqueous binder contained in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

Polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-1
It is described in each publication of No. 36648 and No. 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 or curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink using the dye of the present invention is not limited to an ink jet recording system, and a known system, for example, a charge control system for ejecting the ink by utilizing electrostatic attraction,
A drop-on-demand method (pressure pulse method) that uses the oscillating pressure of the piezo element, an acoustic inkjet method that radiates ink by converting an electric signal into an acoustic beam, and ejects the ink using radiation pressure, and heats the ink. It is used for a thermal ink jet system or the like that forms bubbles and utilizes the generated pressure. Inkjet recording system,
The method includes a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a method of using colorless and transparent inks.

[Color Toner] As the binder resin for the color toner into which the dye of the present invention is introduced, all commonly used binders can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, etc. may be mentioned. Inorganic fine powder or organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. It is preferable that these have a number average primary particle diameter of 10 to 500 nm, and further, 0.1 to 20% by mass is added to the toner.

As the releasing agent, all the releasing agents which have been conventionally used can be used. Specific examples thereof include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, and microcrystalline wax / carnauba wax / sazol wax / paraffin wax. The addition amount of these is preferably 1 to 5% by mass in the toner.

The charge control agent may be added if necessary, but a colorless one is preferable from the viewpoint of color developability. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin coated carrier in which the surface of the magnetic material particles is coated with a resin may be used. The volume average particle diameter of the carrier is preferably 30 to 150 μm.

The image forming method to which the toner using the dye of the present invention is applied is not particularly limited. For example, a method of repeatedly forming a color image on a photosensitive member and then transferring the image to form an image, Examples include a method in which images formed on a photoreceptor are successively transferred to an intermediate transfer member or the like, a color image is formed on the intermediate transfer member or the like, and then transferred to an image forming member such as paper to form a color image.

[Heat-sensitive transfer material] The heat-sensitive recording material has been transferred corresponding to the ink sheet in which the dye of the present invention is coated on the support together with the binder, and the heat energy applied from the thermal head according to the image recording signal. It consists of an image-receiving sheet that fixes the dye. The ink sheet is prepared by dissolving the dye of the present invention together with a binder in a solvent or by dispersing the dye in a solvent in the form of fine particles to prepare an ink liquid, coating the ink on a support, and appropriately drying the ink. Can be formed. For the preferable binder resin, ink solvent, support and image-receiving sheet that can be used, see JP-A-7-137.
Those described in No. 466 can be preferably used.

In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of recording a full-color image, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image and a magenta image may be formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are successively applied on a support to form a yellow image. In addition, an ink sheet containing a black image forming substance may be further formed, if necessary.

[Color Filter] The color filter can be formed by first forming a pattern with a photoresist and then dyeing it, or in JP-A-4-1635.
52, JP-A-4-128703, and JP-A-4-175753, there is a method of forming a pattern with a photoresist containing a dye. As a method used when introducing the dye of the present invention into a color filter, any of these methods may be used, but preferred methods are described in JP-A-4-175753 and JP-A-6-35182. A positive resist composition containing a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating it on a substrate, exposing it through a mask to develop the exposed portion. Then, a positive type resist pattern is formed, the whole surface of the positive type resist pattern is exposed, and then the positive type resist pattern after exposure is cured to form a color filter. Further, a black matrix can be formed according to a conventional method to obtain an RGB primary color system or Y, MC complementary color system color filter.

Regarding the thermosetting resin, the quinonediazide compound, the crosslinking agent, and the solvent used in this case, and the amounts used thereof, those described in the above publication can be preferably used.

[Diffusion Transfer Type Silver Halide Photosensitive Material] The above-mentioned general formula (II
I) Method of adding image forming compound and amount thereof, emulsion and other additives (materials), mode of photosensitive element, image receiving element, processing element, color diffusion transfer method (development with processing solution and heat development) ) And the exposure method, the matters described in paragraph Nos. [0088] to [0150] of JP-A No. 11-125888 can be applied as they are to the light-sensitive material of the present invention and the image forming method using the same.

[0152]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 First, a method for preparing silver halide will be described. The following eight types of silver halide emulsion grains (emulsion-A to emulsion-F) and emulsions-T and U were prepared by the following emulsion grain preparation methods.

Preparation of emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.034 mg of lead acetate.
And deionized gelatin with Ca content of 100ppm or less
In 1000 ml of gelatin aqueous solution containing g, the temperature is adjusted to 7
While maintaining the temperature at 5 ° C., a 0.4 M silver nitrate aqueous solution and a 0.4 M potassium bromide aqueous solution are controlled by a double jet method while controlling the addition rate of the potassium bromide aqueous solution so that the pBr becomes 1.60, and the silver nitrate aqueous solution 300 ml Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (sphere equivalent diameter) of about 0.7 μm were produced.

The core chemical sensitization was carried out under the following conditions. 1. Tank: A hemispherical bottom shape in which the metal surface is coated with Teflon (registered trademark) in a thickness of 120 μm with a fluororesin material FEP developed by Du Pont. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

Sodium thiosulfate 1 was added to the preparation liquid of Emulsion-A.
mg, and 90 mg of potassium tetrachloroaurate and potassium bromide 1.
Add 3 ml of an aqueous solution prepared by dissolving 2 g in 1000 ml of water, and add 75
The chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. 0.1 to the emulsion solution chemically sensitized in this way
After adding 5M potassium bromide, 0.9M silver nitrate aqueous solution and 0.9M potassium bromide aqueous solution were controlled to have a pBr of 1. While adjusting the addition rate of the potassium bromide aqueous solution so as to be 30, the silver nitrate aqueous solution 6
70 ml was added over 70 minutes. This emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to obtain a uniform particle size with an average particle size (sphere equivalent diameter) of about 1.2 μm. Further, octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to this internal latent image type core / shell emulsion.
Was added to 1000 ml of water, and 3 ml of an aqueous solution was added.
An octahedral internal latent image type direct positive emulsion was prepared by adding mg of poly (N-vinylpyrrolidone), heating and ripening at 60 ° C., and then adding 0.005M potassium bromide.

Preparation of Emulsions B to F (octahedral internal latent image type direct positive emulsion): In the preparation method of Emulsion A, the addition time of the aqueous solution of silver nitrate and the aqueous solution of potassium bromide was changed, and further the amount of chemicals added was changed. Then, an octahedral internal latent image type direct positive silver halide emulsion having an average grain size (equivalent sphere diameter) shown in Table 1 and having a uniform grain size was obtained.

[0158]

[Table 1]

Preparation of Emulsion-T (hexagonal tabular internal latent image type direct positive emulsion): 0.05M potassium bromide in 1.2 liters of gelatin aqueous solution containing 0.7% by weight of gelatin having an average molecular weight of 100,000 or less. In addition, 1.4 containing the above gelatin
33 ml of each was simultaneously mixed by the double jet method for 1 minute while vigorously stirring the M silver nitrate aqueous solution and the 2M potassium bromide aqueous solution. During this period, the gelatin aqueous solution was kept at 30 ° C. Furthermore, 300 ml of a gelatin solution containing 10% by mass of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, 25% by mass aqueous ammonia solution was added, and aging was performed at 75 ° C. After completion of the aging, after neutralizing ammonia, 5 mg of lead acetate (added in an aqueous solution) was added, and a 1 M silver nitrate aqueous solution and a 1 M potassium bromide aqueous solution were accelerated while maintaining a pBr of 2.5 (at the time of termination). The flow rate was 6 times the flow rate at the start) and the mixture was added by the double jet method (the amount of the silver nitrate aqueous solution used was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto to obtain 750 g of hexagonal tabular form. Core particles were obtained. The obtained hexagonal tabular core particles have an average projected area circle-equivalent diameter of 0.9 μm and an average thickness of 0.20.
.mu.m, and 95% of the total projected area was occupied by hexagonal tabular grains.

Next, the core chemical sensitization was performed under the following conditions. 1. Tank: Fluororesin material F developed by DuPont on the metal surface
Hemispherical bottom shape with Teflon coating with a thickness of 120 μm by EP. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

200 g of the hexagonal tabular core emulsion was mixed with 13 parts of water.
00 ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C., 3,6-dithia-
0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 2.4 ml of an aqueous solution prepared by dissolving 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) Was added and the mixture was heated at 75 ° C. for 180 minutes for chemical sensitization. In the same manner as when the core particles were prepared, the core particles thus chemically sensitized were mixed with a 2M silver nitrate aqueous solution and 2.
Double jet method at an accelerated flow rate (flow rate at the end is 3 times the flow rate at the start) while controlling the addition rate of the 5M aqueous solution of potassium bromide so that the pBr is 2.2. (The amount of the silver nitrate aqueous solution used was 810 ml).

After adding 0.3 M potassium bromide, this emulsion was washed with water by a conventional flocculation method and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area circle equivalent diameter of 2.0 μm, an average thickness of 0.38 μm, an average volume size of 1.3 (μm) ³ , and 88% of the total projected area are hexagonal tabular grains. It was occupied by particles. Next, 100 mg of sodium thiosulfate and 4 parts of sodium tetraborate were added to this hexagonal tabular internal latent image type core / shell emulsion.
15 ml of an aqueous solution prepared by dissolving 0 mg in 1000 ml of water was added, and further 20 mg of poly (N-vinylpyrrolidone) was added,
The grain surface was chemically sensitized by heating at 100 ° C. for 100 minutes to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-U (Hexagonal tabular internal latent image type direct positive emulsion): 0.15 mol% iodine was uniformly contained in the outer shell of Emulsion-T, and the outer shell formation amount was further increased. By increasing the average projected area circle equivalent diameter is 2.5
The average grain size was 0.45 μm, the average volume size was 1.7 (μm) ³ , and 88% of the total projected area was occupied by hexagonal tabular grains. Next, AgI corresponding to 0.04 mol% of the amount of silver required for grain formation at the start of shell chemical sensitization of this hexagonal tabular internal latent image type core / shell emulsion.
After adding the fine grain emulsion-X, the same shell chemical sensitization as in the emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-X (AgI fine grain emulsion) 0.5 g of potassium iodide and 26 g of gelatin were added to water and stirred into a solution kept at 35 ° C., while stirring, 80 ml of a silver nitrate aqueous solution containing 40 g of silver nitrate and 39 g of iodine. 80 ml of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the aqueous silver nitrate solution and the potassium iodide solution were each 8 ml / min at the start of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 ml was completed in 5 minutes. After the formation of particles was completed in this way, soluble salts were removed by a precipitation method at 35 ° C. Next, the temperature was raised to 40 ° C., 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with a caustic soda. The resulting emulsion has a finished amount of 7
The particles were monodispersed AgI fine particles having an average diameter of 0.015 μm at 30 g.

Emulsions A to F, T and U were used as described below to prepare a comparative photosensitive element (Sample 101) having the constitution shown in Tables 2 to 6 below. The sensitizing dye was added at the end of the shell chemical sensitization at the dye species, dispersion form, addition temperature and amount shown in Table 7 below.

[0167]

[Table 2]

[0168]

[Table 3]

[0169]

[Table 4]

[0170]

[Table 5]

[0171]

[Table 6]

[0172]

[Table 7]

[0173]

[Chemical 33]

[0174]

[Chemical 34]

[0175]

[Chemical 35]

[0176]

[Chemical 36]

[0177]

[Chemical 37]

[0178]

[Chemical 38]

[0179]

[Chemical Formula 39]

[0180]

[Chemical 40]

[0181]

[Chemical 41]

[0182]

[Chemical 42]

[0183]

[Chemical 43]

[0184]

[Chemical 44]

[0185]

[Chemical formula 45]

[0186]

[Chemical formula 46]

Preparation of Cover Sheet A transparent support having a thickness of 75 μm was coated in a layer structure as shown in Table 8 to prepare a cover sheet.

[0188]

[Table 8]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0190]

[Chemical 47]

[0191]

[Chemical 48]

The formulation of the alkaline treatment composition is shown below.   Silver nitrate 0.10g   Carbon black (manufactured by Dainichiseika Co., Ltd.) 160 g   Additive (27) 8.60g   Carboxymethyl cellulose Na salt 58.0 g   Benzyl alcohol 2.50g   Additive (28) 2.10g   1.90 g of potassium sulfite (anhydrous)   2.50 g of 5-methylbenzotriazole   1-p-tolyl-4-hydroxymethyl-4-methyl     -3-pyrazolidone 7.00 g   1-phenyl-4-hydroxymethyl-4-methyl     -3-Pyrazolidone 10.0 g   Potassium hydroxide 56.0 g   Aluminum nitrate 0.60g   Zinc nitrate 0.60g   Additive (29) 6.60g   Additive (14) 1.80g   1,2-benzisothiazolin-3-one 0.003 g

[0193]

[Chemical 49]

Preparation of Photosensitive Element Samples 102 to 109 In the same manner as the photosensitive element sample 101 except that the cyan dye-releasing compounds (1) and (2) were replaced by equimolar cyan releasing compounds shown in Table 9 below. Sample 102
~ 109 were created.

Image Evaluation The light-sensitive element sample was exposed to red monochromatic light from the emulsion layer side through a continuous wedge, and then overlapped with the cover sheet so that the thickness of the alkaline processing composition was 55 μm between both materials. The development was performed at 25 ° C using a pressure roller, and the minimum cyan reflection density (Dm
in), the maximum concentration (Dmax), the concentration change (ΔD _0.7 ) at the exposure dose given a concentration of 0.7 before the sample was irradiated with a 17,000 lux fluorescent lamp for 2 weeks, and the ozone gas concentration of the sample was 0.5 ppm. After leaving for 24 hours in the box set to, the change in density (ΔD _0.5 ) was measured at an exposure dose with a density of 0.5 before standing. Further, the hue as cyan was evaluated in three grades of very good (∘), good (Δ) and bad (x). The results are shown in Table 9.

[0196]

[Table 9]

[0197]

[Chemical 50]

From Table 9, the dyes of the present invention have equivalent or more hue, light fastness and ozone resistance as compared with the conventional cyan dyes, and the color diffusion containing the cyan dye image-forming compound defined in the present invention. It can be seen that the transfer photographic light-sensitive material exhibits excellent color forming properties.

Example 2 JP-A-11-125888, except that CC-4 of the present invention was used in place of the dye-donor compound (1) used in Example 1 described in JP-A-11-125888. Example 1 described in Japanese Patent Publication
When a light-sensitive material was prepared in the same manner as in 1., it was found that it showed good hue, wet-heat fastness, light-wet-heat fastness and color developability with respect to conventional coloring materials.

[0200]

The dye of the present invention is excellent in hue and
It has excellent fastness to light, moist heat, ozone, etc. and is suitable as a cyan dye. The silver halide photographic light-sensitive material of the present invention contains an image-forming compound which releases the above-mentioned dye, and exhibits excellent hue, fastness and color-forming property, and particularly, a color diffusion transfer photographic light-sensitive material. Is suitable as

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 487/04 141 C07D 487/04 141 143 143 G03C 8/10 502 G03C 8/10 502 504 504 8/40 503 8/40 503 F term (reference) 4C050 AA01 BB05 CC08 EE03 FF01 GG04 HH01 4C065 AA04 AA05 BB05 CC01 DD03 EE02 HH01 HH08 JJ01 JJ09 KK09 LL06 PP03

Claims (7)

[Claims] 1. A dye represented by the following general formula (I). [Chemical 1] In the formula, R ₁ is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, and R ₂ and R ₃ and R ₄
And R ₅ may combine with each other to form a ring. G _{1 to} G ₄ each represent C (R ₆ ), or a nitrogen atom, and R ₆ represents a hydrogen atom or a substituent. 2. A dye represented by the following general formula (II). [Chemical 2] In the formula, R ₁ is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group, G _{1 to} G ₄ are each
C (R ₆ ) or a nitrogen atom is shown, and R ₆ is a hydrogen atom or a substituent. R ₇ is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, cyano group, acylamino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, alkoxycarbonylamino group or aminocarbonylamino group R ₈ represents a hydrogen atom or —NHZ, and Z represents an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group. 3. A silver halide photographic light-sensitive material comprising a support and at least one image forming compound represented by the following general formula (III). General formula (III) (Dye-X) _q- Y In the formula, Dye represents a dye represented by the following general formula (I ') or a precursor thereof, and X represents R in the following general formula (I').
Bound to at least one of ₁ to R _6, corresponding or reverse correspondingly to the developing shows a mere bond or a linking group X-Y bond is cleaved, Y is the reaction of the photosensitive silver salt having a latent image on the image-wise Represents a group having a property of causing a difference in diffusibility of dye components by cleaving the XY bond corresponding to or opposite to. q is 1 or 2, and when q is 2, each Dye-X may be the same or different. [Chemical 3] In the formula, R ₁ is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, and R ₂ and R ₃ and R ₄
And R ₅ may combine with each other to form a ring. G _{1 to} G ₄ each represent C (R ₆ ), or a nitrogen atom, and R ₆ represents a hydrogen atom or a substituent. R ₉ represents a hydrogen atom, a monovalent cation or a hydrolyzable group. 4. The silver halide photographic light-sensitive material according to claim 3, wherein Dye in the general formula (III) is represented by the following general formula (II ′) instead of the general formula (I ′). A silver halide photographic light-sensitive material, which is a dye or a precursor thereof. [Chemical 4] In the formula, R ₁ , R ₉ and G _{1 to} G ₄ are as defined above, and R ₇ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group,
An acylamino group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group or an aminocarbonylamino group, R ₈ represents a hydrogen atom or -NHZ, and Z represents an acyl group. Represents a group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group. X is bonded to at least one of R ₁ , R ₆ , R ₇ and R ₈ . 5. An image forming method comprising developing the silver halide color photographic light-sensitive material according to claim 3 or 4 by developing an alkali processing solution. 6. An image forming method comprising thermally developing the silver halide color photographic light-sensitive material according to claim 3 or 4. 7. An image forming method comprising developing the silver halide color photographic light-sensitive material according to claim 3 or 4 in the presence of an alkali with a sparingly soluble metal salt and a complexing agent for the metal salt. .