JP2000035647A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color reproducibility performance and the like by forming an invisible light sensitive silver halide emulsion layer and the like containing a specified compound, and a layer for cutting off infrared rays. SOLUTION: Each one or more red-, green-, and blue-sensitive silver halide emulsion layers containing couplers and the invisible light sensitive silver halide emulsion layer are formed on a support, and the latter emulsion layer contains an image quality enhancing agent and at least one of the compounds represented by formulae I or II in which each of Z11, Z12, Z21, and Z22 is a nonmetallic atomic group necessary to complete a 5- or 6-membered single ring or the like; each of R11, R12, R21, and R22 is an aliphatic group; each of R13-R17, and R23-R29 is an H atom or the like; R is an alkyl group or the like; each of (R11 and R13), (R14 and R16), (R17 and R12), (R21 and R23), (R24 and R26), (R25 and R27), (R26 and R28), and (R22 and R29) may combine with each other to form a 5- or 6-membered ring; each of x11 and x21 is ions necessary to cancel a charge in the molecule; each of m11 and m21 is the number of such ions; and each of n11 and n12, n21, and n22 is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having improved color reproducibility.

[0002]

2. Description of the Prior Art Since the release of Kodachrome by Eastman Kodak Company in 1935, various improvements have been made to color photography and its performance has been continuously improved. Improvements in the performance of color photographs include finer image structures, so-called graininess, sharpness, and color reproducibility. In the past, there have been several techniques for improving color reproducibility in the past, in which reproducibility has been dramatically improved. One of them is a colored coupler having an automatic mask function (US Pat. No. 2,455,17).
0, etc.).

[0003] Colored couplers are mainly used to improve the color reproducibility of negative films. Colored couplers have the effect of correcting unnecessary absorption of the three primary color dyes used in color films, yellow, magenta and cyan. With this colored coupler, unnecessary absorption of the coloring dyes of the color negative film can be corrected imagewise in the imagewise manner, and the color reproducibility can be greatly improved. In addition, more vivid color reproducibility is required. Particularly, in the case of a negative film, a development effect, that is, a multilayer effect is proposed as a technique for improving color purity (Belgian Patent No. 710,
344, German Patent No. 2,043,934, etc.). Furthermore, as an application of the multilayer effect, DI
R couplers (described in U.S. Pat. No. 3,277,554) have been developed. This DIR coupler greatly improved color purity reproducibility.

As described above, while aiming for higher color reproducibility, several techniques have been proposed for more faithfully reproducing colors as seen by humans. One of them is control of the spectral sensitivity distribution of a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer of a color film (described in JP-A-5-150411). Some techniques for improving color reproducibility that focus on the fact that the spectral sensitivity distribution of the cone of the human eye and the spectral sensitivity distribution of the color film are different have also been proposed. In general, the spectral sensitivity distribution of a color film is higher than that of the human eye in that the blue-sensitive layer has a maximum in sensitivity to long waves, the green-sensitive layer has a maximum in sensitivity to long waves, and the red-sensitive layer has considerable sensitivity. Has maximum sensitivity to long waves. The red cone of the human eye is 5
There is a region having a negative sensitivity near 00 nm. In this way, in order to match the spectral sensitivity distribution of the color film with the spectral sensitivity distribution of the human eye, it is possible to reproduce the spectral sensitivity distribution by the sensitizing dye and the so-called donor layer by skillfully controlling the layering effect. The difficult intermediate colors can be faithfully reproduced to some extent (Japanese Patent Laid-Open No. 61-345 / 1986)
No. 41).

With these techniques, the color reproducibility of a color film has become possible to reproduce the hue of a subject more faithfully.

As described above, the color reproducibility of color photographs has been steadily developed. However, it is a fact that next-generation color photographic materials are required to have a completely different dimension and a higher rank in color reproducibility.

[0007] The reason is that ordinary users take pictures,
This is because there are many opportunities to feel disappointed when getting the print. Opportunities for the general user to feel disappointed include, for example, when photographing fresh green trees, red flowers, distant mountains, and the like. When I photographed these scenes and got the finished prints, unlike what I had expected and remembered, the fresh green trees were dull, and the red flowers lost the subtle gradation of petals, so-called red blinds Many users feel disappointed if the distant mountains look hazy and lose their stereoscopic effect when viewed.

As described above, in color photography, simply reproducing the colors in a faithful and vivid manner is not satisfactory, and the scene when photographed is revived vividly. Is coming.

For this purpose, Japanese Patent Application No. 9-179656 describes that an infrared-sensitive layer is provided, and the information is added to a visible image to increase the amount of information and to improve specific color reproduction. Have been. Furthermore, it is described that by providing a layer that gives an interlayer effect together with the invisible photosensitive layer, not only a specific color but also excellent stability of various color reproduction is provided. However, since these were made to have photosensitivity in the infrared region, fog was caused by an infrared sensor installed in a transport system including an automatic developing machine and a camera. By optimizing the spectral sensitivity distribution of the invisible photosensitive layer, fogging can be suppressed to some extent, but various problems occur, such as desensitization.

JP-A-62-304898 discloses a method of improving sharpness by using tabular silver halide grains and adding colloidal silver to a protective layer.
Although this method improves the sharpness to some extent, its effect is not always sufficient. In addition, Japanese Patent Application Laid-Open No.
No. 6,117,793 and No. 9-274278, the infrared dye in the form of solid fine particles is incorporated in the photographic material, so that it is installed in a transport system including an automatic developing machine due to a small amount of coated silver. The light-shielding property of the infrared sensor is reduced, which makes it impossible to detect the position of the photosensitive material, thereby causing a conveyance failure. However, these are not sufficient as effects.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to improve the amount of information and color reproducibility, such as the greenness of trees, which are excellent in the descriptive power of scenes. It is another object of the present invention to provide a silver halide photographic light-sensitive material capable of reducing fog by an infrared sensor installed in a transport system.

[0012]

The above objects of the present invention have been attained by the following constitutions.

(1) One or more layers each of a red-sensitive silver halide emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer containing a coupler, and a blue-sensitive halogen containing a coupler on a support. A compound having a silver halide emulsion layer and an invisible light-sensitive silver halide emulsion layer, wherein the invisible light-sensitive silver halide emulsion layer is represented by the general formula (Ia) or (Ib), and A silver halide photographic material comprising at least one image quality improver and at least one infrared cut layer.

(2) One or more layers each of a red-sensitive silver halide emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer containing a coupler, and a blue-sensitive halogen containing a coupler on a support. A silver halide emulsion layer, and at least one of the three types of color-sensitive silver halide emulsion layers contains at least one compound represented by the above general formula [Ia] or [Ib]. And a silver halide photographic material having at least one infrared cut layer.

In a preferred embodiment of the silver halide photographic material, the infrared light cut layer contains at least one of black colloidal silver and an infrared dye.

Hereinafter, the present invention will be described in detail.

In the present invention, two configurations are employed to achieve the object. That is, the general formula [Ia] or [I
-B], wherein the compound represented by the formula (1) is contained in a non-visible light-sensitive silver halide emulsion layer;
At least one of the visible light-sensitive silver halide emulsion layers
This is the embodiment (2) contained in the layer. Hereinafter, description will be given along each component.

In the present invention, the invisible light-sensitive silver halide emulsion layer (invisible light-sensitive color reproduction improving layer) is a silver halide having a sensitivity maximum at a wavelength other than 400 to 680 nm of visible light. Means emulsion layer. The maximum light sensitive wavelength of the invisible light-sensitive silver halide emulsion layer is from 690 nm to
850 nm is preferred. The coating position of the invisible light-sensitive silver halide emulsion layer is preferably farther from the exposure light source than the layer for forming a dye image for the purpose of improving image quality.

The image improver contained in the invisible light-sensitive silver halide emulsion layer refers to a compound which produces or releases a substance useful for improving image quality imagewise according to the amount of exposure. Those that form a dye image according to the exposure amount, such as colored couplers, DIR couplers, bleach accelerator releasing couplers, and development accelerator releasing couplers, form a dye image according to the exposure amount and color correction dyes, Development inhibitors, bleaching accelerators, those which produce a substance useful for improving the image quality such as a development accelerator in an imagewise manner, and furthermore, such as a development inhibitor without forming a dye image like a development inhibitor releasing compound A substance which generates a substance useful for improving the image quality in an imagewise manner can be used. Of these, couplers are preferred.

In the present invention, the compound represented by the general formula [I-
a] or a compound represented by [Ib] (infrared sensitizing dye)
Is used.

In the general formula [Ia] or [Ib], a 5- or 6-membered monocyclic ring or a condensed nitrogen-containing heterocyclic ring completed by Z ₁₁ , Z ₁₂ , Z ₂₁ and Z ₂₂ is Examples thereof include benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole, quinoline, benzoxazole, naphthoxazole, phenanthrothiazole, thiadiazole, naphthopyridine and the like.

The aliphatic groups represented by R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ include, for example, methyl, ethyl, propyl, pentyl, sulfopropyl, hydroxyethyl, phenethyl, sulfobutyl And alkyl groups such as diethylaminosulfopropyl group, methoxyethyl group, naphthoxyethyl group, carboxymethyl group and carboxyethyl group, and alkenyl groups such as propenyl group.

As a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, —N (W ₁ ) W ₂ , —SR or a heterocyclic group represented by R _{13 to} R ₁₇ and R _{23 to} R ₂₉ For example, methyl group, ethyl group, propyl group, butyl group, alkyl group such as benzyl group, methoxy group, alkoxy group such as ethoxy group, phenoxy group, aryloxy group such as p-methylphenoxy group, phenyl group, aryl groups such as tolyl group, a diethylamino group, an anilino group, a piperidino group, -N such furyl amino group (W ₁₎ W ₂ group, methylthio group, phenylthio group, -SR such thienylthio group
And heterocyclic groups such as a thienyl group and a furyl group.

[0024] R ₁₁ and R _13, R ₁₄ and R _16, R ₁₇ and R _12, R
₂₁ and R ₂₃ , R ₂₄ and R ₂₆ , R ₂₅ and R ₂₇ , R ₂₆ and R ₂₈ , R ₂₂
And a 5-membered or 6-membered ring or a condensed ring thereof formed by connecting R ₂₉ and R ₂₉ to each other, for example, cyclohexene, cyclopentene, cyclohexecyclohexene, pyrroline,
2,3,4-tetrahydropyridine, piperidine and the like.

The ions represented by X ₁₁ and X ₂₁ include:
In addition to F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , and PF ₆ ⁻ , trifluoromethanesulfonic acid ion, p-toluenesulfonic acid ion and the like can be mentioned.

The compounds represented by the general formulas [Ia] and [Ib] include the following general formulas [Ie] and [I-
Compound (f) (infrared sensitizing dye) is more preferably used.

[0027]

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In the general formulas [Ie] and [If], Y ₅₁ , Y ₅₂ , Y ₆₁ and Y ₆₂ each represent an oxygen atom, a sulfur atom, a selenium atom or> NR. R represents an alkyl group, an aryl group or a heterocyclic group. R ₅₁ and R ₅₂
Represents an aliphatic group, and R ₆₁ represents a non-metallic atomic group required for bonding to the aliphatic group or R ₆₅ to complete a 5- or 6-membered ring. R ₅₃ and R ₅₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₅₅ and R ₆₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, Represents an alkylthio group or an amino group, and R ₆₃ and R ₆₄ are each a hydrogen atom, an alkyl group or a non-metallic atom required for bonding between R ₆₃ and R ₆₄ to form a 5- or 6-membered ring; Represents a group. R ₆₅ represents a hydrogen atom or a bond to R ₆₁ . A _{51 to} A ₅₈ and A _{61 to} A ₆₈ each represent a hydrogen atom or a replaceable group, and A _{51 to} A ₅₄ and A
_{55 to} A ₅₈ , A _{61 to} A ₆₄ , and A _{65 to} A ₆₈ may combine to form a ring. M ₅₁ and M ₆₁ each represent an ion required to cancel the charge in the molecule, and m ₅₁ and m ₆₁ each represent the number of ions required to cancel the charge in the molecule. p is 2
Or 3 is represented.

The compounds represented by formulas (Ie) and (If) will be described in more detail.

The general formula [Ie] and the general formula [I-
f), examples of the alkyl group, aryl group and heterocyclic group represented by R include those represented by the general formulas [Ia] and [I-
and b) the same as the examples of the alkyl group, the aryl group, and the heterocyclic group. Examples of the aliphatic group represented by R ₅₁ , R ₅₂ and R ₆₁ are the same as the examples of the aliphatic group represented by R ₁₁ in the general formula [Ia]. Examples of 5-membered or 6-membered ring and R ₆₁ and R ₆₅ to complete binding to the same as the examples of the ring and R ₁₁ and R ₁₃ of formula [I-a] is completed bonded to Is mentioned. Among the hydrogen atoms, alkyl groups, aryl groups and heterocyclic groups represented by R ₅₃ and R ₅₄ , examples of the alkyl group, the aryl group and the heterocyclic group include those represented by R ₁₃ in the general formula [Ia]. And the same as the examples of the alkyl group, the aryl group, and the heterocyclic group.

Of the hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, alkylthio groups and amino groups represented by R ₅₅ and R ₆₂ , alkyl groups,
Aryl group, a heterocyclic group, an alkoxy group, examples of the alkylthio group and an amino group, an alkyl group represented by R ₁₃ in the general formula [I-a], an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group, and Examples are the same as the examples of the amino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among the hydrogen atoms and alkyl groups represented by R ₆₃ and R ₆₄ , examples of the alkyl group include those represented by the general formula [Ia]
The same thing can be mentioned as examples of the alkyl group represented by R ₁₃ in.

Examples of the 5- or 6-membered ring formed by bonding between R ₆₃ and R ₆₄ include R in formula [Ia].
_The same examples of the ring formed by bonding between ₁₄ and R ₁₆ can be mentioned. Among the hydrogen atoms or the substitutable groups represented by A _{51 to} A ₅₈ and A _{61 to} A ₆₈ , the substitutable groups include a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methyl group and an ethyl group. Alkyl groups such as butyl group, trifluoromethyl group and isopropyl group; alkoxy groups such as methoxy group; aryl groups such as phenyl group and tolyl group; and carboxyl groups.

A _{51 to} A ₅₄ , A _{55 to} A ₅₈ , A _{61 to} A ₆₄ , A
The ring formed by bond between the ₆₅ to A _68, benzene, 2H-1,3-dioxole and the like.

Examples of the ions represented by M ₅₁ and M ₆₁ are the same as the examples of X _{11 in} the general formula [Ia].

In the compound represented by the aforementioned general formula [Ie] or [If], at least one of A _{51 to} A ₅₈ and A _{61 to} A ₆₈ is a chlorine atom, or A ₅₁ and A ₅₂ , A ₅₂ and A ₅₃ , A ₅₃ and A ₅₄ , A ₅₅ and A ₅₆ , A ₅₆ and A ₅₇ , A ₅₇ and A
₅₈ and _A61 and _A62 , _A62 and _A63 , _A63 and _A64 , _A65 and A
₆₆ , A ₆₆ and A ₆₇ , or a compound in which at least one of A ₆₇ and A ₆₈ is linked to each other to form a condensed naphthol ring are preferably used.

The following formulas [Ia] and [I-
b], [Ie], and [If] are representative of the compounds, but the present invention is not limited to these compounds (in addition, the general formula [Ia] ] And [Ib]
Specific examples of the compound represented by
Compounds A-1 to A-14 and B1 to B25 of No. 89 and Chemical No. The compound described as 13 can be mentioned. ).

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The silver halide color photographic light-sensitive material of the present invention forms a color image corresponding to the visible light of red, green and blue as in the prior art, and at the same time feels infrared light, that is, information by infrared light. In response to the above, there is an ability to adjust a color image formed by visible light.

In the present invention, it is effective that the layer containing the infrared sensitizing dye or the infrared sensitized silver halide emulsion is the highest sensitivity layer among photosensitive layers having the same color sensitivity and different sensitivities. Is large and preferable. Even if the layer is not the highest sensitive layer, a layer containing the largest amount of the color coupler, a layer containing the largest amount of the DIR compound, and a layer containing the largest amount of the colored coupler are also effective.

Furthermore, in the present invention, at least one red-sensitive layer and at least one green-sensitive layer, at least one green-sensitive layer and at least one blue-sensitive layer, and at least one blue-sensitive layer And at least one of the red-sensitive layers
Layers may be added to two layers having different color sensitivity, or at least one layer of a red photosensitive layer, at least one layer of a green photosensitive layer, and at least one layer of a blue photosensitive layer.
It may be added to three layers having different color sensitivity.

In the present invention, a layer which gives an interlayer effect to the invisible photosensitive layer may be provided. The layer which gives an interlayer effect as referred to herein means a layer having a function of lowering the concentration of the other photosensitive layer, which suppresses the coloring of the other layer according to the amount of exposure, and the color tone of the other layer. It is preferable to form an image inversely corresponding to the exposure amount. Examples of the former include a layer containing a so-called DIR compound that releases a development inhibitor or a precursor thereof by reaction with an oxidized developing agent, and examples of the latter include a layer containing a colored coupler. Can be

The present invention is characterized in that the silver halide photosensitive material has at least one infrared cut layer. Here, the infrared light cut layer refers to a layer provided so as not to cause fogging of the invisible photosensitive silver halide emulsion layer by an infrared sensor installed in a transport system such as an automatic developing machine or a camera. Refers to Therefore, the infrared light cut layer needs to be provided between the sensor light source and the invisible light-sensitive silver halide emulsion layer. When the sensor irradiation is from the back side, the infrared light cut layer may cut all infrared light, but when the sensor irradiation is from the emulsion surface, the infrared light cut layer Care must be taken not to impair the spectral sensitivity distribution of the silver halide emulsion layer as much as possible. In addition, as the irradiation direction of the sensor is mainly from the back side of the film, but there are those that irradiate from the front side,
It is preferable to provide two or more layers sandwiching the invisible light-sensitive silver halide emulsion layer. The installation position may be anywhere between the sensor light source and the invisible light-sensitive silver halide emulsion layer, but is preferably adjacent to the invisible light-sensitive silver halide emulsion layer.

In the present invention, the infrared light cut layer preferably contains black colloidal silver. Here, the black colloidal silver used in the present invention will be described.

As the colloidal silver, yellow colloidal silver for yellow filters and black colloidal silver for antihalation are generally known. In the present invention, the use of black colloidal silver is effective for the effect of the present invention. It is preferable because it is often played. However, colloidal silver (for example, brown-gray) which does not clearly have an absorption maximum wavelength in the visible region (400 nm to 700 nm) like yellow colloidal silver can obtain the same effect as the black colloidal silver. Accordingly, the black colloidal silver herein refers to black colloidal silver used for antihalation and colloidal silver having no absorption maximum wavelength in the visible region.

The black colloidal silver may be added to any layer other than the photosensitive silver halide emulsion layer and / or the outermost protective layer. The coating amount of the black colloidal silver may be any coating amount as long as the effect of the present invention can be obtained. However, when the infrared cut layer is provided between the invisible photosensitive emulsion layer and the support, it is preferably 0. 0.03 to ² g / m ² , more preferably 0.04 to 1 g / m ² , and still more preferably 0.05 to ² g / m ² .
1 g / m ² . Further, when the infrared cut layer is provided on the side opposite to the support, preferably 0.0005 to 0.2 g
/ M ² , more preferably 0.001 to 0.1 g / m ² , and still more preferably 0.005 to 0.1 g / m ² .

If the addition amount is too small, the effect of the present invention is not sufficient, and if it is too large, the effect on photographic properties may be increased.

These colloidal silver can be produced by a conventionally known method, for example, a method of reducing a soluble silver salt with hydroquinone in a gelatin solution as shown in US Pat. No. 2,688,601; 1,09
No. 6,921,914, a method of reducing a sparingly soluble silver salt with hydrazine described in US Pat.
It is possible to use a method of reducing silver with tannic acid as described in JP-A-5-134358, a method of forming silver particles by electroless plating as described in JP-A-5-134358, and the like. The method of adding these colloidal silver to the light-sensitive material is described in the above patent and British Patent No. 1,12.
No. 6,797, U.S. Pat. Nos. 4,460,679, 4,563,406, 3,333,960, and U.S. Defense Publication T900,010. It is possible.

In the present invention, it is preferable that the infrared light cut layer contains an infrared dye (a dye that absorbs infrared light). Hereinafter, these infrared dyes will be described.

As the infrared dye, a dye having an absorption at 700 to 1,400 nm is preferably used. The dye is not particularly limited as long as it has absorption in this wavelength range, but a compound represented by the following general formulas (A), (B), (C) and (D) is used. It can be suitably mentioned. First, the compound represented by the general formula [A] will be described.

[0071]

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In the formula, R ₁ and R ₂ represent alkenyl, cycloalkyl, aryl, heterocyclic, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl groups , An alkylsulfinyl group,
Arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxyl group or hydroxyl group, R _3, R ₄ represents a displaceable group, L ₁ ~L ₅ represents a methine group, n _1,
n ₂ represents n ₁ + n ₂ ≧ 3. k and m represent an integer of 0 to 4.

The alkenyl groups represented by R ₁ and R ₂ include, for example, vinyl, allyl, 1-propenyl,
Examples thereof include a 1,3-butadienyl group and a 2-pentenyl group. The alkenyl group includes those having a substituent, and examples of the substituent include a halogen atom (eg, chlorine, bromine, iodine, fluorine), an aryl group (eg, phenyl, naphthyl), a heterocyclic group (eg, pyrrolidyl, pyridyl) ,
Sulfinic acid group, carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (eg, amino, diethylamino), alkoxy group (eg, methoxy, ethoxy, butoxy, octyloxy, i-propoxy), aryloxy group (phenoxy, naphthyl) Oxy), carbamoyl groups (eg, aminocarbonyl, methylcarbamoyl, pentylcarbamoyl, morpholinocarbonyl,
Phenylcarbamoyl), amide group (eg, methylamide, benzamide, octylamide), sulfamoyl group (eg, sulfamoyl, methylsulfamoyl, phenylsulfamoyl, morpholinosulfonyl, butylsulfamoyl), sulfonamide group (eg, methanesulfonamide, Heptane sulfonamide, benzene sulfonamide), sulfinyl group (eg, alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, octylsulfinyl, etc., arylsulfinyl group of phenylsulfinyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, -Hydroxyethoxycarbonyl, octyloxycarbonyl), aryloxycarbonyl groups (e.g., pheno Cicarbonyl, naphthyloxycarbonyl), alkylthio groups (eg, methylthio, ethylthio, hexylthio), arylthio groups (eg, phenylthio, naphthylthio), alkylcarbonyl groups (eg, acetyl, ethylcarbonyl, butylcarbonyl, octylcarbonyl), arylcarbonyl groups (eg, Benzoyl, p-methanesulfonamidobenzoyl, p-
Carboxybenzoyl, naphthoyl), cyano group, ureido group (eg, methylureide, phenylureide),
And thioureido groups (eg, methylthioureido, phenylthioureido) and the like.

The aryl groups represented by R ₁ and R ₂ include
Examples include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and as the substituent,
For example, an alkyl group, wherein the R _1, alkenyl group represented by R _2, or R _1, the aforementioned groups mentioned as substituents for the alkenyl group represented by R ₂ are exemplified.

The heterocyclic groups represented by R ₁ and R ₂ include:
For example, a pyridyl group (2-pyridyl, 3-pyridyl, 4-
Pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-
Tetrafluoro-4-pyridyl, 3-nitro-2-pyridyl), oxazolyl group (5-carboxy-2-benzoxazolyl, 2-benzoxazolyl, 2-oxazolyl), thiazolyl group (5-sulfamoyl-2) -Benzothiazolyl, 2-benzothiazolyl, 2-thiazolyl), imidazolyl group (1-methyl-2-imidazolyl, 1-methyl-5-carboxy-2-benzimidazolyl), furyl group (3-furyl), pyrrolyl group (3-pyrrolyl) ), Thienyl group (2-thienyl), pyrazinyl group (2-pyrazinyl, etc.), pyrimidinyl group (2-pyrimidinyl, 4-chloro-2-pyrimidinyl), pyridazinyl group (2-pyridazinyl, etc.), purinyl group (8-purinyl) Etc.), isoxazolyl group (3-isoxazolyl etc.), selenazolyl group (5 Carboxy-2-selenazolyl, etc.), sulfolanyl group (3-sulfolanyl, etc.), piperidyl group (1-methyl-3-piperidyl, etc.), pyrazolyl group (3-pyrazolyl, etc.), tetrazolyl group (1-methyl-5-tetrazolyl, etc.) ), And the heterocyclic group includes those having a substituent. Examples of the substituent include an alkyl group, the alkenyl group represented by R ₁ and R ₂ , and R
Examples of the substituent of the alkenyl group represented by ₁ and R ₂ are given.

The cycloalkyl groups represented by R ₁ and R ₂ include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkylcarbonyl group represented by R ₁ and R ₂ include a methylcarbonyl group, an ethylcarbonyl group, an i-propylcarbonyl group, a t-butylcarbonyl group, an octylcarbonyl group and a dodecylcarbonyl group. .

The arylcarbonyl group represented by R ₁ and R ₂ includes, for example, a phenylcarbonyl group and a naphthylcarbonyl group.

Examples of the alkoxycarbonyl group represented by R ₁ and R ₂ include an ethoxycarbonyl group, an i-propoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, a dodecyloxycarbonyl group and the like.

The aryloxycarbonyl group represented by R ₁ and R ₂ includes, for example, a phenyloxycarbonyl group,
And a naphthyloxycarbonyl group.

The alkylsulfonyl groups represented by R ₁ and R ₂ include, for example, methylsulfonyl, ethylsulfonyl, i-propylsulfonyl, t-butylsulfonyl, octylsulfonyl, octadecylsulfonyl and the like. .

Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group. Examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, an i-propylsulfinyl group, a t-butylsulfinyl group, an octylsulfinyl group, and a dodecylsulfinyl group.

Examples of the arylsulfinyl group include a phenylsulfinyl group and a naphthylsulfinyl group. Examples of the carbamoyl group include an aminocarbonyl group, a methylcarbamoyl group, an ethylcarbamoyl group, an i-propylcarbamoyl group, a t-butylcarbamoyl group, a dodecylcarbamoyl group, a phenylcarbamoyl group, a 2-pyridylcarbamoyl group, a 4-pyridylcarbamoyl group, Examples include a benzylcarbamoyl group, a morpholinocarbonyl group, and a piperazinocarbonyl group.

Examples of the sulfamoyl group include aminosulfonyl, methylsulfamoyl, i-propylsulfamoyl, t-butylsulfamoyl, dodecylsulfamoyl, phenylsulfamoyl,
-Pyridylsulfamoyl group, 4-pyridylsulfamoyl group, morpholinosulfonyl group, and piperazinosulfonyl group.

Examples of the amino group include an amino group, a methylamino group, an ethylamino group, an i-propylamino group,
Examples include a t-butylamino group, an octylamino group, a dodecylamino group, a dimethylamino group, an anilino group, a naphthylamino group, a morpholino group, and a piperazino group.

Examples of the sulfonamide group include a methylsulfonamide group, an ethylsulfonamide group, an i-propylsulfonamide group, a t-butylsulfonamide group,
A dodecylsulfonamide group, a phenylsulfonamide group, and a naphthylsulfonamide group.

Examples of the amide group include a methylcarbonylamino group, an ethylcarbonylamino group, an i-propylcarbonylamino group, a t-butylcarbonylamino group,
A dodecylcarbonylamino group, a phenylcarbonylamino group, and a naphthylcarbonylamino group.

Examples of the ureido group include a methylureide group, an ethylureide group, an i-propylureide group,
-Butylureido group, dodecylureido group, phenylureido group, 2-pyridylureido group, and thiazolylureido group.

Examples of the thioureido group include a methylthioureido group, an i-propylthioureido group, a t-butylthioureido group, a dodecylthioureido group, a phenylthioureido group, a 2-pyridylthioureido group and a thiazolylthioureide group. No.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an i-propoxy group, a t-butyloxy group and a dodecyloxy group.

Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, an i-
Examples include a propylthio group, a t-butylthio group, and a dodecylthio group.

Examples of the arylthio group include a phenylthio group and a naphthylthio group.

Each of the groups represented by R ₁ and R ₂ includes those having a substituent. Examples of the substituent include an alkyl group, an alkenyl group represented by R ₁ and a group represented by R _1. Examples of the substituent of the alkenyl group include those exemplified above.

Of the groups represented by R ₁ and R ₂ , an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group,
It is an amino group, an alkoxy group, a cyano group, or a carboxyl group, particularly preferably an alkylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an alkoxy group, or a carboxyl group.

[0095] R _1, R ₂ represents a group substitutable, include those exemplified as the substituents for the alkyl group represented by an alkyl group and R ₁ represented by, for example R _1.

In the compound represented by the general formula [A],
The methine groups represented by L _{1 to} L ₅ include those having a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, i-propyl, t-butyl, 3-hydroxypropyl group, benzyl ), An aryl group (eg, phenyl), a halogen atom (eg, chlorine, bromine, iodine, fluorine atom), an alkoxy group (eg, methoxy, ethoxy), an acyloxy group (eg, methylcarbonyloxy, phenylcarbonyloxy) and the like.

The methine groups represented by L _{1 to} L ₅ can be linked to each other to form a ring. Preferred rings include, for example, a cyclohexene ring and a cyclopentene ring.

Specific examples of the compound represented by the formula [A] are shown below, but the present invention is not limited thereto.

[0099]

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[0100]

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[0101]

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[0102]

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The compound represented by the formula (B) will be described.

[0104]

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In the formula, R ₁ and R ₂ represent a substituent, and R ₃ and R ₄
Represents an m-carboxyphenyl group or an o-carboxyphenyl group. L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ represent a methine group, and n ₁ and n ₂ represent n ₁ + n ₂ ≧ 3.

In the compound represented by the general formula [B], the substituent represented by R ₁ and R ₂ is an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group,
Sulfonamide, amide, ureido, thioureido, alkoxy, aryloxy, alkylthio, arylthio, carboxyl and hydroxyl groups are preferred.

As the alkyl groups represented by R ₁ and R ₂ ,
Examples include a methyl group, ethyl group, propyl group, i-propyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, dodecyl group, pentadecyl group, eicosyl group and the like. The alkyl group includes those having a substituent, and examples of the substituent include those exemplified as the substituent of the alkenyl group represented by R ₁ and R ₂ in the general formula [A].

The aryl groups represented by R ₁ and R ₂ include
Examples include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and as the substituent,
For example, the of R _1, the alkyl group represented by R _2, or R _1, the aforementioned groups mentioned as substituents for the alkyl group represented by R ₂ are exemplified.

The alkenyl groups represented by R ₁ and R ₂ include vinyl, allyl, 1-propenyl, 1,3-
Butadienyl group, 2-pentenyl group and the like, and the alkenyl group includes those having a substituent. Examples of the substituent include those of the alkenyl group represented by R ₁ and R ₂ in the general formula [A]. What was mentioned as is mentioned.

As the heterocyclic groups represented by R ₁ and R ₂ ,
For example, those mentioned as examples of the heterocyclic group represented by R ₁ and R ₂ in the general formula [A] and the like are mentioned, and the heterocyclic group includes those having a substituent. The alkenyl groups represented by R ₁ and R ₂ in the general formula [A] and R ₁ and R ₂
Examples of the substituent of the alkenyl group represented by

Further, a cycloalkyl group, an arylcarbonyl group, an alkoxycarbonyl group represented by R ₁ and R ₂ ,
Aryloxycarbonyl group, arylsulfonyl group,
Arylsulfamoyl group, arylsulfinyl group,
Amino group, sulfonamide group, amide group, thioureido group, alkoxy group, aryloxy group, arylthio group and the like are also exemplified by the groups and substituents represented by R ₁ and R ₂ in the general formula [A]. Is mentioned.

Of the groups represented by R ₁ and R ₂ , preferably, an alkyl group, an aryl group, an alkylcarbonyl group,
An arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an alkoxy group, a cyano group, and a carboxyl group, particularly preferably an alkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an alkoxy group, and a carboxyl group It is.

In the general formula [B], the o-carboxyphenyl group and m-carboxyphenyl group represented by R ₃ and R ₄ include those having a substituent. As the substituent,
Examples thereof include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, an aryl group, a carboxyl group, and the like. Specific examples include those exemplified as the substituents of the alkyl group represented by R ₁ and R ₂ described above. Is mentioned.

Specific examples of the compound represented by the formula [B] are shown below, but the invention is not limited thereto.

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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The compound represented by formula (C) will be described.

[0121]

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In the formula, R ₁ and R ₂ represent a carboxyl group or a group having a carboxyl group, R ₃ and R ₄ represent a hydrogen atom or a substituent having no carboxyl group, and n represents 2 or more. In the general formula (C), examples of the substituent having no carboxyl group represented by R ₃ and R ₄ include an alkyl group,
Alkenyl groups, cycloalkyl groups, alkynyl groups, aryl groups, and heterocyclic groups are preferred. Examples of the alkyl group include methyl, ethyl, n
-Propyl, iso-propyl, t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-pentadecyl, eicosyl. The alkyl group includes those having a substituent,
As the substituent, for example, R _{1 of} the above general formula [A],
Those exemplified as the substituent of the alkenyl group represented by alkenyl groups and R _1, R ₂ represented by R ₂ are exemplified.

Hereinafter, specific examples of the compound represented by the formula [C] will be shown, but the present invention is not limited thereto.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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The compound represented by formula (D) will be described.

[0130]

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In the formula, n represents 1, 2 or 3. Specific examples of the compounds include, for example, the following compounds.

[0132]

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The dyes of the present invention described above are described, for example, in JP-A-48-62826, JP-A-49-5125 and JP-A-51-7.
Nos. 7327, 58-143342, 59-111
In a manner similar to the synthesis methods described in JP-A Nos. 641 and 64-40827, the compound can be easily synthesized by reacting a pyrazolone derivative with a methine chain source. For a synthesis example of the compound of the present invention, reference can be made to JP-A-2-1786.

As the infrared dye preferably used in the present invention, in addition to the compounds represented by the above formulas [A] to [D], those represented by the following formula [E] are particularly preferable.

[0135]

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In the formula, Z ¹ and Z ² each may be a condensed ring 5
Or a non-metallic atomic group necessary for forming a 6-membered nitrogen-containing heterocyclic ring, R ¹ and R ² each represent an alkyl group, an alkenyl group or an aralkyl group, and R ³ and R ⁵ each represent a hydrogen atom or And R ⁴ represents a halogen atom, an aryl group, -N
(R ⁶ ) represents (R ⁷ ), —SR ⁸ , —OR ⁹ or —SO ₂ R ¹⁰ , R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁷ represents an aryl group, a sulfonyl group or an acyl group Represents R ⁶ and R ⁷ may be linked to each other to form a 5- or 6-membered ring. R ⁸ and R ⁹ each represent an aryl group or a heterocyclic group, and R ¹⁰ represents an alkyl group, an aryl group, or a heterocyclic group. M ¹ and M ² each represent a hydrogen atom or a negative charge,
a and b each represent 0 or 1, and X represents an anion.
n represents 1 or 2, and is 1 when the dye forms an inner salt.

The compound represented by formula (E) will be further described.

In the formula, the optionally condensed 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ¹ or Z ² is an oxazole ring, isoxazole ring, benzoxazole ring, naphthoxazole ring, thiazole ring, Benzothiazole ring, naphthothiazole ring, indolenine ring, benzoindolenine ring,
Examples thereof include an imidazole ring, a benzimidazole ring, a naphthoimidazole ring, a quinoline ring, a pyridine ring, a pyrrolopyridine ring, and a floppyrrole ring.

The alkyl group represented by R ¹ , R ² , R ⁶ and R ¹⁰ is an unsubstituted alkyl group having 1 to 10, more preferably 1 to 6, carbon atoms (eg, methyl, ethyl, propyl, butyl) , Isobutyl, pentyl, hexyl). The aralkyl group represented by R ¹ and R ² is preferably an aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenylethyl) and has a substituent (eg, methyl, carboxy, methoxy, chloro atom). It may be. The alkenyl group represented by R ¹ and R ² is preferably an alkenyl group having 2 to 6 carbon atoms.
-A pentenyl group, a vinyl group, an allyl group, a 2-butenyl group, and a 1-propenyl group.

R ³ and R ⁵ may be linked to each other to form a 5- or 6-membered ring. Examples of such a ring include cyclopentene and cyclohexene. These rings have substituents (eg, methyl, t-butyl, phenyl)
May be provided. Examples of the halogen atom represented by R ⁴ include F, Cl, and Br.

The aryl group represented by R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ preferably has 6 to 12 carbon atoms, such as a phenyl group or naphthyl. The aryl group may be substituted, and any substituent may be used as long as it does not dissolve the dye during development. For example,
Examples include a methyl group, an ethyl group, a chloro atom, a methoxy group, and a methoxycarbonyl group.

The sulfonyl group represented by R ⁷ is 1 to 10
An alkyl or aryl sulfonyl group having the number of carbon atoms of, for example, a mesyl group, a tosyl group, a benzenesulfonyl group, and an ethanesulfonyl group can be given. The acyl group represented by R ⁷ is preferably an alkyl or aryl acyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, a propionyl group, and a benzoyl group.

R ⁶ and R ⁷ may be linked to each other to form a 5- or 6-membered ring. Examples of such a ring include piperidine, morpholine, piperazine and the like, and these rings have substituents (for example, methyl, phenyl,
Ethoxycarbonyl).

Examples of the anion represented by X include halogen ions (Cl, Br, I), p-toluenesulfonic acid ion, ethyl sulfate ion, PF ₆ ⁻ , BF ₄ ⁻ , and ClO ₄ ⁻ . n represents 1 or 2, and is 1 when the dye forms an inner salt.

The optionally condensed 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ¹ and Z ² is preferably a 5-membered nitrogen-containing heterocyclic ring in which a benzene ring or a naphthalene ring is condensed. And most preferably an indolenine ring. a and b are preferably 0. R ¹ and R ² are preferably alkyl groups. It is preferred that R ³ and R ⁵ are linked together to form a 5- or 6-membered ring. As R ⁴ , -N (R ⁶ ) (R
⁷ ), -SR ⁸ or -OR ⁹ is preferable, and -N (R ⁶ ) (R
⁷ ) is particularly preferred. R ⁶ is preferably an alkyl group or an aryl group, particularly preferably an aryl group. In R ⁴ a is -N (R ⁶⁾ (R ^7), R ⁶ and R ^7, at least one of the preferred case of aryl groups, more preferably R ⁶ and R ⁷ are both an aryl group. Most preferably, R ⁶ and R ⁷ are phenyl groups.

As a combination, preferably, a and b are 0 and a 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ¹ or Z ² may be a condensed benzene ring or a naphthalene ring. A 5-membered nitrogen-containing heterocyclic ring, wherein R ¹ and R ² are an alkyl group, and R ⁴ is —N (R ⁶ ) (R ⁷ ), —SR ⁸ or —OR
Case ⁹ Among them, more preferably, R ³ and R ⁵ are linked to form a 5- or 6-membered ring, and R ⁴ is —N (R ⁶ )
(R ⁷ ). Among them, particularly preferably, R ⁶ is
It is an alkyl group or an aryl group in which at least one of R ^{6 and} R ⁷ is an aryl group.

In the compound represented by the general formula [E],
The compound represented by the following general formula [F] is more preferably used.

[0148]

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In the formula, R ¹¹ and R ¹² each represent an alkyl group, an aralkyl group or an alkenyl group, and R ¹³ and R ¹⁵ each represent a hydrogen atom or an atom necessary for forming a 5- or 6-membered ring by bonding to each other. R ¹⁴ represents an aryl group, —N
^{(R 20) (R 21)} , - represents SR ²² or -OR ^23, R ²⁰
Represents a hydrogen atom, an alkyl group or an aryl group, R ²¹
Represents an aryl group, a sulfonyl group or an acyl group. or,
R ²⁰ and R ²¹ may be linked to each other to form a ring. R ²²
And R ²³ each represent an aryl group. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each represent an alkyl group, and R ¹⁶ and R ¹⁷ , R ¹⁸ and R
¹⁹ may be linked to form a ring.

The compound represented by formula (F) will be described in more detail.

In the formula, R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R
^The alkyl group represented by ¹⁹ and R ²⁰ has the same meaning as the alkyl group for R ^{1 and the} like described in the general formula [E]. R ¹⁶ and R
¹⁷ , R ¹⁸ and R ¹⁹ may be linked to each other to form a ring (for example, cyclohexane or the like). The alkenyl group and aralkyl group represented by R ¹¹ and R ¹² have the same meaning as the alkenyl group and aralkyl group of R ¹ and R ² . R ¹⁴ , R ²⁰ , R
^21, an aryl group represented by R ²² and R ²³ has the same meaning as the aryl group of R ⁴ or the like of the general formula [E].

The sulfonyl group or acyl group represented by R ²¹ has the same meaning as the sulfonyl group or acyl group for R ⁷ . R ¹⁴
Has the same meaning as the halogen atom for R ⁴ .
Ring formation by R ²⁰ and R ²¹ has the same meaning as the ring formation of R ⁶ and R ^7.

R ¹¹ and R ¹² are preferably an alkyl group. Preferably, R ¹³ and R ¹⁵ are linked to form a 5- or 6-membered ring. R ¹⁴ is ^{-N (R 20) (R 21} ), - SR 22 or -OR ²³ are ^{preferably, -N (R 20) (R} 21) is particularly preferred. R ²⁰ is preferably an alkyl group or an aryl group. At least one of R ²⁰ and R ²¹ of —N (R ²⁰ ) (R ²¹ ) in R ¹⁴ is preferably an aryl group, and more preferably both R ²⁰ and R ²¹ are aryl groups.
Most preferably, R ²⁰ and R ²¹ are phenyl groups.

Preferably, R ¹¹ and R ¹² are alkyl groups, and R ¹⁴ is —N (R ²⁰ ) (R ²¹ ), —S
It is the case of R ²² or -OR ^23. More preferably these, and R ¹³ and R ¹⁵ are linked to form a 5- or 6-membered ring, R ¹⁴
There is a case of ^{-N (R 20) (R 21} ). Among them particularly preferred, R ^20, R ²¹ is at least one of the preferred case of aryl groups, most preferably R ²⁰ and R ²¹ are both an aryl group.

As the substituent represented by A ^{1 to} A ⁸ , any group can be used as long as it can be substituted on the benzene ring. For example, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, etc., alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, , Propargyl group, etc.), aryl group (for example,
Phenyl group, naphthyl group, etc., heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, Pyrazolyl group, tetrazolyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy) Group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc., aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl Group,
Ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (For example, methylsulfonylamino group, ethylsulfonylamino group, n
-Butylsulfonylamino group, n-hexylsulfonylamino group, n-cyclohexylsulfonylamino group, n
-Octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylamino) Sulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., ureido group (for example, methylureido group, ethyl Ureido group, pentylureido group, cyclohexylureido group,
n-octylureido group, n-dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, n-
Pentylcarbonyl group, cyclohexylcarbonyl group,
n-octylcarbonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n
-Octylaminocarbonyl group, 2-ethylhexylaminocarbamoyl group, n-dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (for example, methylcarbonylamino group, ethylcarbonyl Amino group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, n-octylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthyl Aminocarbonyl group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethyl Hexylsulfonyl group, dodecyl sulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridyl sulfonyl group, etc.), an amino group (e.g., amino group, ethylamino group, dimethylamino group,
n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.),
Represents a cyano group, a nitro group, a carboxyl group, a hydroxyl group, or a hydrogen atom. A ¹ and A ² , A ² and A ³ , A ³ and A ⁴ ,
A ⁵ and A ⁶ , A ⁶ and A ⁷ , A ⁷ and A ⁸ can each form a ring. Preferred rings include, for example, a benzene ring, a pyridine ring and a thiophene ring.

The general formula [E] preferably used in the present invention.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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The compounds represented by the above general formulas [E] and [F] are described in US Pat. No. 3,671,648 and 2,09.
No. 5,854, JP-A-6-43583, and the following synthesis examples can be used for synthesis.

(Synthesis of Compound 1) 9.8 g of 1,2,3,3-tetramethyl-5-carboxyindolenium / p-toluenesulfonate, 1- [2,5-bis (anilinomethylene) Cyclopentylidene] -diphenylanilinium tetrafluoroborate 6 g, ethyl alcohol 100 ml, acetic anhydride 5 ml, triethylamine 1
0 ml was stirred at an external temperature of 100 ° C. for 1 hour, and the precipitated crystals were separated by filtration. Recrystallization was performed with 100 ml of methyl alcohol to obtain 7.3 g of compound 1.

Melting point: 270 ° C. or higher, λmax: 809.
1 nm g: 1.57 × 10 ⁵ (dimethyl sulfoxide) In addition to the compounds represented by the above general formulas [A] to [F], the infrared dye used in the present invention further includes the following general formula [G] , [H], [I], and [J].

[0170]

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In the formula, Q ¹ and Q ² represent a heterocyclic ring or a carbocyclic ring. M is a cation, a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion,
Represents an organic ammonium ion. Specific examples of the compound represented by the general formula [G] are shown below.

[0172]

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[0173]

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In the formula, Q ³ and Q ⁴ represent a heterocyclic ring or a carbocyclic ring. l ¹ and l ² each represent an integer of 0 or 1. M is a cation, and represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an organic ammonium ion. Specific examples of the compound represented by the general formula [H] are shown below.

[0175]

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[0176]

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In the formula, Ar ^{1 to} Ar ⁴ represent an aromatic group or a hydrogen atom. m is an integer of 0, 1, or 2, and L ^{1 to} L ³ represent a methine group. However, Ar ¹ and Ar ² are not simultaneously hydrogen atoms. Ar ³ and Ar ⁴ are not simultaneously hydrogen atoms. Specific examples of the compound represented by the above general formula [I] are shown below.

[0178]

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[0179]

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In the formula, Ar ^{1 to} Ar ⁴ represent an aromatic group or a heterocyclic aromatic group. X represents an ion required to neutralize the intramolecular charge, and l represents the number of ions required to cancel the intramolecular charge. Specific examples of the compound represented by the general formula [J] are shown below.

[0181]

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The dye for absorbing infrared light in the present invention is:
Λmax in the light-sensitive material is about 700 to 1100 nm, more preferably 800 to 1000 nm, and further preferably 8
Those having a thickness of 50 nm to 950 nm are preferably used.

The dye for absorbing infrared light in the present invention is:
It is preferably used in the form of solid fine particles dispersed. In order to make the solid fine particles dispersed, a dispersing machine such as a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill described in JP-A-52-92716 and WO 88/077944 is used. However, a vertical or horizontal medium disperser is preferable.

In any case, a solvent (eg, water, alcohol, etc.) may be allowed to coexist, and it is preferable to use a dispersing surfactant. As the dispersing surfactant, anionic surfactants described in JP-A-52-92716 and WO 88/04794 are mainly used. In addition, an anionic polymer, a nonionic or cationic surfactant can be used as necessary. Preferably, it is an anionic surfactant.

After dissolving a dye that absorbs infrared light in a suitable solvent, a poor solvent for the dye may be added to obtain a fine powder. Also in this case, the above-mentioned surfactant for dispersion may be used. Alternatively, it may be first dissolved by controlling the pH, and then microcrystallized by changing the pH.

The dye in the form of solid fine particles that absorbs infrared light used in the present invention can be dissolved or decolored rapidly in a developing solution, or has a low absorption in the visible region and is substantially non-elutable. Is preferably used. The term "substantially non-elutable dye" means that 95% or more and 100% or less of the coating weight of the dye is contained in the photographic material even after image formation. Of 9
Most preferably, 8% or more and 100% or less remain.

The dispersed particles of the solid fine particles of the dye absorbing infrared light in the dispersion have an average particle size of 0.005 to 10 μm, preferably 0.01 to 1 μm, and more preferably 0.01 to 1 μm.
0.5 μm, and sometimes 0.01 to 0.1 μm
m is preferable.

The dye in the form of solid fine particles dispersed in the present invention may be added to any layer other than the photosensitive silver halide emulsion layer and / or the outermost protective layer.

The coating amount of the dye in the form of solid fine particles dispersed in the present invention may be any coating amount as long as the effects of the present invention can be obtained, but the infrared cut layer is formed of the invisible photosensitive emulsion layer and the support. 0.001 to 1 when installed between
g / m ² , more preferably 0.005 to 0.5 g
/ M ² , more preferably 0.01 to 0.1 g / m ² . Also, when installing the side opposite to the support of the infrared cut layer is preferably 0.001 to 1 g / m ^2, more preferably a 0.005 to 0.5 / m ^2.

In the present invention, the couplers contained in the red, green and blue light-sensitive silver halide emulsion layers preferably have a spectral absorption maximum of a coloring dye formed from the coupler contained therein at least 20 nm away. Further, it is preferable to use a yellow coupler, a magenta coupler, and a cyan coupler.As the combination of the emulsion layer and the coupler, a yellow coupler and a blue photosensitive layer, a magenta coupler and a green photosensitive layer, and a cyan coupler and a red photosensitive layer are used. It is not limited, and other combinations may be used.

In the present invention, as a silver halide emulsion, Research Disclosure (hereinafter abbreviated as RD) No. 308119 can be used.

The following shows the places to be described.

[Item] [Page RD308119] Iodine composition 993 IA Section Production method 993 IA and 994 E Crystal wall Normal crystal 999 IA Twin crystal 999 IA Section Epitaxial 994 IA Section A Halogen composition uniform 993 IB Section Not uniform 993 IB Section Halogen conversion 994 IC Halogen substitution 994 IC Section Metal content 994 ID Monodispersion 990 IF Section Solvent addition 996 Item IF Latent image formation position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I- Section J Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additive used in such a process is RDNo. 17643, N
o. 18716 and no. 308119. The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23 to 24 648 to 649 H, I, J section Supersensitizer 996 IV-AE, J section 23 to 24 648 to 649 Antifoggant 998 VI 24 to 25 649 Stabilizer 998 VI 24 to 25 649 Known methods usable in the present invention Are also described in the above RD. The relevant sections are described below.

[Item] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I Section 25 650 Dye image stabilizer 1001 VII-J Section 25 Brightener 998 V 24 Ultraviolet absorber Section 1003 VIII-I, XIII -C section 25-26 Light absorber 1003VIII 25-26 Light scattering agent 1003VIII Filter dye 1003VIII 25-26 Binder 1003IX 26 651 Static inhibitor 1006XIII 27 650 Hardener 1004X 26 651 Plasticizer 1006XII 27 650 Lubricant 1006XII 27650 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in the light-sensitive material) Section 1001 XXB Various couplers can be used in the present invention, and specific examples thereof are described in the above RD. ing. The relevant sections are described below.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC to G Magenta coupler 1001 VII-D VIIC to G Cyan coupler 1001 VII-D VIIC to G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E The additives used in the present invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

RD308119VII is used for the light-sensitive material of the present invention.
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided.

The light-sensitive material of the present invention is manufactured by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (T
he Theory of The Photograph
ic Process Forth Edition)
Pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical So
city), vol. 73, p. 3, 100 (1951), known developers can be used, and the aforementioned RD17643, pp. 28-29, R.
The development can be carried out by a usual method described in D18716, page 615 and RD308119XIX.

[0201]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (The object of claim 1) The following composition was coated on a cellulose triacetate film support provided with an undercoat layer to prepare a sample 101 as a multilayer color photosensitive material.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material was 1 m ² unless otherwise specified.
Indicates the number of grams per unit. Further, silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is silver halide 1
It was shown in moles per mole.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Invisible photosensitive layer containing coupler Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye 1 -Ae-55 2.0 × 10 ^-4 Magenta coupler (M-1) 0.20 High boiling solvent (Oil-1) 0.34 Gelatin 0.90 4th layer: Intermediate layer Gelatin 0.40 5th Layer: Layer giving invisible photosensitive interlayer effect Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye (SD-3) 2.0 × 10 ^-4 DIR compound (D- 1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 0.9 Layer 6: Intermediate layer Gelatin 0.40 Seventh Layer: Low Sensitivity Red-Sensitive Layer Silver iodobromide emulsion A 0.80 Sensitizing dye (SD-1) 5.0 × 10 -5 Sensitizing dye (SD-2 ) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 2.0 × 10 ^-4 sensitizing dye (SD-5) 2.8 × 10 ^-4 Cyan coupler (C-1) 0.42 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.35 Gelatin 1.02 8th layer: Medium sensitivity red-sensitive layer Iodine Silver halide emulsion E 0.40 sensitizing dye (SD-3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 2.4 × 10 ^-4 sensitizing dye (SD-5) 4.5 × 10 ^-4 cyan coupler (C-1) 0.26 colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.01 high boiling solvent (Oil-1) 31 gelatin 0.78 ninth layer: high-sensitivity red-sensitive layer silver iodobromide emulsion G 1.51 sensitizing dye (SD-3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 3.1 × 10 ^-4 sensitizing dye (SD-5) 2.7 x 10 ^-4 cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.04 high Boiling solvent (Oil-1) 0.17 Gelatin 1.15 10th layer: Intermediate layer Color stain inhibitor (SC-1) 0.15 High boiling solvent (Oil-1) 0.15 Gelatin 0.80 11th layer : Low-sensitivity green-sensitive layer silver iodobromide emulsion B 0.21 sensitizing dye (SD-1) 5.9 × 10 ^-5 sensitizing dye (SD-6) 3.1 × 10 ^-4 sensitizing dye (SD -9) 1.8 × 10 ^-4 sensitizing dye (SD-11) 5.6 × 10 ^-5 magenta coupler (M-1) 0.20 Colored magenta Coupler (CM-1) 0.05 DIR compound (D-1) 0.02 High boiling organic solvent (Oil-2) 0.27 Gelatin 1.34 12th layer: Medium sensitive green-sensitive layer Silver iodobromide emulsion E 0.82 sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitizing dye (SD-6) 2.7 × 10 ^-4 sensitizing dye (SD-9) 1.7 × 10 ^-4 sensitizing Dye (SD-11) 4.8 × 10 ^-5 Magenta coupler (M-1) 0.21 Colored magenta coupler (CM-1) 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil) -2) 0.33 gelatin 0.89 13th layer: high-sensitivity green-sensitive layer silver iodobromide emulsion D 0.99 sensitizing dye (SD-6) 3.6 × 10 ^-4 sensitizing dye (SD-7) ) 7.0 × 10 ^-5 sensitizing dye ^{(SD-8) 4.8 × 10} -5 sensitizing dye ^{(SD-11) 6.2 × 10} -5 magenta Coupler (M-1) 0.05 Magenta coupler (M-2) 0.06 Colored magenta coupler (CM-2) 0.03 High boiling organic solvent (Oil-2) 0.25 Gelatin 0.88 14th layer: Intermediate layer High boiling organic solvent (Oil-1) 0.25 Gelatin 0.50 15th layer: Yellow filter layer Yellow colloidal silver 0.11 Color stain inhibitor (SC-1) 0.12 High boiling solvent (Oil-2) 0.16 gelatin 1.00 16th layer: intermediate layer Gelatin 0.36 17th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion B 0.37 sensitizing dye (SD-10) 5.6 × 10 ^{− 4} sensitizing dye (SD-11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 9.8 × 10 ^-5 yellow coupler (Y-1) 0.39 yellow coupler (Y-2) 14 DIR compound (D-5) 0.03 high Boiling point organic solvent (Oil-2) 0.11 Gelatin 1.02 18th layer: Medium-sensitivity blue-sensitive layer Silver iodobromide emulsion D 0.46 Silver iodobromide emulsion F 0.10 Sensitizing dye (SD-10) 5.3 × 10 ^-4 sensitizing dye (SD-11) 1.9 × 10 ^-4 sensitizing dye (SD-13) 1.1 × 10 ^-5 yellow coupler (Y-1) 0.28 yellow coupler ( Y-2) 0.10 DIR compound (D-5) 0.05 High boiling organic solvent (Oil-2) 0.08 Gelatin 1.12 19th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion D 04 silver iodobromide emulsion G 0.28 sensitizing dye (SD-11) 8.4 × 10 ^-5 sensitizing dye (SD-12) 2.3 × 10 ^-4 yellow coupler (Y-1) 0.04 Yellow coupler (Y-2) 0.12 High boiling organic solvent (Oil-2) 0.03 Gelatin 0.85 20th layer First protective layer Silver iodobromide emulsion (cubic average particle size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.03 UV absorber (UV-3) ) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling organic solvent (Oil-1) 0.44 High Boiling point organic solvent (Oil-3) 0.07 Gelatin 1.35 21st layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above-mentioned composition, compounds SU-1, SU-2, SU
-3, SU-4, viscosity modifier V-1, hardener H-1, H
-2, stabilizer ST-1, antifoggant AF-1, AF-
2. Two kinds of AF-3, weight average molecular weight: 10,000 and weight average molecular weight: 1,100,000, dye AI-
1, AI-2, AI-3, compounds FS-1, FS-2,
The preservative DI-1 was appropriately added to each layer.

[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube. or,
Each emulsion was optimally subjected to gold, sulfur and selenium sensitization.

Emulsion name Average AgI content Average grain size Crystal habit Diameter / thickness ratio Silver iodobromide emulsion A 2.0 mol% 0.32 μm Normal crystal 1.0 Silver iodobromide emulsion B 6.0 mol% 42 μm twin tabular plate 4.0 silver iodobromide emulsion D 8.0 mol% 0.70 μm twin tabular plate 5.0 silver iodobromide emulsion E 6.0 mol% 0.60 μm twin tabular plate 4.0 iodobromide Silver Emulsion F 2.0 mol% 0.42 μm twin flat plate 4.0 Silver iodobromide emulsion G 8.0 mol% 0.90 μm twin flat plate 3.0 Silver iodobromide emulsions A, B and F contain iridium 1 × 10 ^-7 mo
It contains 1/1 molAg.

As shown in Table 1, Samples 102 to 106 were prepared by adding black colloidal silver and / or infrared dye to each layer of the Sample 101 to form infrared cut layers. or,
A sample 107 in which the third layer was not provided for the sample 102 was manufactured.

[0221]

[Table 1]

Next, each of the obtained samples was cut into a 135 standard, stored in a patrone, loaded into a camera (Konica Hexer, manufactured by Konica), and simultaneously photographed with a tree against the back of trees under daylight under daylight. This was subjected to color development processing (CNK-4 manufactured by Konica) using an automatic developing machine, and dried to obtain a film sample. This automatic developing machine has two pairs of infrared light emitting element and light receiving element at the film insertion port, and when the infrared rays are cut off as the photographic material is inserted, the transport roller starts and the film is automatically removed from the developing tank. It is a mechanism to transport to Konica Color Paper Type QAA6
The printing was performed by using a color paper developing process (CPK-2-21 manufactured by Konica) using a stretching machine Klomega. In the case of baking, adjustment was made so as to obtain a Macbeth chart of 18% gray.

(Evaluation) The green reproduction of the trees was visually observed according to the following criteria.

×: Dim Δ: Slightly dull ○: Vivid reproduction ◎: Bright and vivid reproduction

The fog of the infrared sensor was visually observed according to the following criteria.

×: There is obvious sensor fog △: There is some sensor fog, but there is no noticeable ○: There is sensor fog that cannot be seen visually ◎: There is almost no sensor fog .

The results are shown in Table 2.

[0228]

[Table 2]

As is evident from Table 2, the printed image obtained by the silver halide photographic light-sensitive material of the present invention has a good reproduction of "green reproduction of trees" and a reduced "infrared sensor fog". It can be seen that both have been improved. In addition, as a result of subjectively evaluating the prints obtained from the samples 101 to 107 by 20 observers, all the 20 people answered that the prints obtained from the present invention are more preferable.

Example 2 (Subject to claim 2) The following composition was coated on a cellulose triacetate film support provided with an undercoat layer to prepare a sample 201 as a multilayer color photosensitive material.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.80 Sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitization Dye (SD-2) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 2.0 × 10 ^-4 sensitizing dye (SD-5) ) 2.8 × 10 ^-4 cyan coupler (C-1) 0.42 colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.01 high boiling solvent (Oil-1) 0.35 Gelatin 1.02 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide Emulsion E 0.40 Sensitizing dye (SD-3) × 10 ^-5 Sensitizing dye (SD-4) 2.4 × 10 -4 Sensitizing dye (SD-5) 4.5 × 10 -4 Cyan coupler (C-1) 0.26 Colored cyan coupler (CC- 1) 0.02 DIR compound (D-1) 0.01 High boiling solvent (Oil-1) 0.31 Gelatin 0.78 Fifth layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion G 1.51 Sensitized Dye (SD-3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 3.1 × 10 ^-4 sensitizing dye (SD-5) 2.7 × 10 ^-4 cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.02 High boiling solvent (Oil-1) 0.17 Gelatin 1.15 6th layer: Intermediate layer Gelatin 0.69 7 layer: low sensitivity green-sensitive layer silver iodobromide emulsion B 0.21 sensitizing dye (SD-1) 5.9 × 10 -5 sensitizing dye (S -6) 3.1 × 10 ^-4 Sensitizing dye (SD-9) 1.8 × 10 -4 Sensitizing dye (SD-11) 5.6 × 10 -5 Magenta coupler (M-1) 0.20 Colored magenta coupler (CM-1) 0.05 DIR compound (D-1) 0.02 High boiling organic solvent (Oil-2) 0.27 Gelatin 1.34 Eighth layer: Medium-sensitive green-sensitive layer Silver iodobromide Emulsion E 0.82 Sensitizing dye (SD-1) 5.0 × 10 ^-5 Sensitizing dye (SD-6) 2.7 × 10 ^-4 Sensitizing dye (SD-9) 1.7 × 10 ^-4 Sensitizing dye (SD-11) 4.8 × 10 ^-5 Magenta coupler (M-1) 0.20 Colored magenta coupler (CM-1) 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil-2) 0.33 gelatin 0.89 ninth layer: high-sensitivity green-sensitive layer silver iodobromide emulsion D 0.99 sensitizing dye (S -6) 3.6 × 10 ^-4 Sensitizing dye (SD-7) 7.0 × 10 -5 Sensitizing dye (SD-8) 4.8 × 10 -5 Sensitizing dye (SD-11) 6. 2 × 10 ^-5 Magenta coupler (M-1) 0.05 Magenta coupler (M-2) 0.06 Colored magenta coupler (CM-2) 0.05 High boiling organic solvent (Oil-2) 0.25 Gelatin 0 .88 10th layer: Yellow filter layer Yellow colloidal silver 0.11 Color stain inhibitor (SC-1) 0.12 High boiling point solvent (Oil-2) 0.16 Gelatin 1.00 11th layer: Low sensitivity blue sensitivity Layer Silver iodobromide emulsion B 0.37 sensitizing dye (SD-10) 5.6 × 10 ^-4 sensitizing dye (SD-11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 8 × 10 ^-5 yellow coupler (Y-1) 0.39 yellow coupler (Y-2) 0.14 DIR Compound (D-5) 0.03 High-boiling point organic solvent (Oil-2) 0.11 Gelatin 1.02 12th layer: Medium-sensitivity blue-sensitive layer Silver iodobromide emulsion D 0.46 Silver iodobromide emulsion F 0 .10 sensitizing dye (SD-10) 5.3 × 10 ^-4 sensitizing dye (SD-11) 1.9 × 10 ^-4 sensitizing dye (SD-13) 1.1 × 10 ^-5 yellow coupler ( Y-1) 0.28 Yellow coupler (Y-2) 0.10 DIR compound (D-5) 0.03 High boiling organic solvent (Oil-2) 0.08 Gelatin 1.12 13th layer: High sensitivity blue Sensitive layer Silver iodobromide emulsion D 0.04 Silver iodobromide emulsion G 0.28 Sensitizing dye (SD-11) 8.4 × 10 ^-5 Sensitizing dye (SD-12) 2.3 × 10 ^-4 Yellow coupler (Y-1) 0.04 Yellow coupler (Y-2) 0.12 High boiling organic solvent (Oil-2) 0.03 Gelatin 0.85 Fourteenth layer: First protective layer Silver iodobromide emulsion (average particle size 0.04 μm, silver iodide content 4.0 mol%) 0.30 Ultraviolet absorber (UV-2) 0.03 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling organic solvent (Oil) -1) 0.44 High boiling organic solvent (Oil-3) 0.07 Gelatin 1.35 Fifteenth layer: Second protective layer Alkali-soluble matting agent (Average particle size 2 μm) 0.15 Polymethyl methacrylate (Average particle size) 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above composition, compounds SU-1, SU-2 and SU
-3, SU-4, viscosity modifier V-1, hardener H-1, H
-2, stabilizer ST-1, antifoggant AF-1, AF-
2. Two kinds of AF-3, weight average molecular weight: 10,000 and weight average molecular weight: 1,100,000, dye AI-
1, AI-2, AI-3, compounds FS-1, FS-2,
The preservative DI-1 was appropriately added to each layer.

To the silver iodobromide emulsions B and D used in the seventh and ninth layers of the sample 201, compound 1-ae-55, which is an infrared sensitizing dye, was added 1.0 ×, respectively. 10
Samples 202 and 20 after adding ^-4 mol / mol of silver halide
3 was produced. Further, the infrared-sensitized halogenation obtained by adding compound 1-ae-55 to Emulsion E in an amount of 1.0 × 10 ⁻⁴ mol / mol of silver halide to the seventh and ninth layers. Samples 204 and 205 were prepared by adding 0.20 g / m ^{2 of} silver emulsion (a) in terms of silver. Furthermore, these samples 20
0.5 g of black colloidal silver in the sixth layer with respect to 1-205
/ M ² , and 0.05 g / m ² of the infrared dye A-10 in the tenth layer.
The added samples 206 to 210 were prepared. The obtained samples 201 to 210 are shown in Table 3 below.

[0233]

[Table 3]

Next, a print was obtained from the obtained sample in the same manner as in Example 1. Table 4 shows the results.

[0235]

[Table 4]

As is clear from Table 4, in the print image obtained by the silver halide photographic light-sensitive material of the present invention, "green reproduction of trees" was reproduced well, and "infrared sensor fog" was reduced. It can be seen that both have been improved. Further, as a result of subjectively evaluating the prints obtained from the samples 201 to 210 by 20 observers, all the 20 respondents answered that the print of the sample of the present invention was more preferable.

[0237]

According to the present invention, a silver halide which is excellent in the descriptive power of a scene (improves the amount of information such as green of trees and color reproducibility) and which can reduce the fog of an infrared sensor. It has a remarkably excellent effect that a photographic light-sensitive material can be provided.

Claims (3)

[Claims] 1. A light-sensitive silver halide emulsion layer containing a coupler, a green light-sensitive silver halide emulsion layer containing a coupler, and a blue light-sensitive halide containing a coupler, each having at least one layer on a support. A compound having a silver emulsion layer and an invisible light-sensitive silver halide emulsion layer, wherein the invisible light-sensitive silver halide emulsion layer is represented by the following general formula [Ia] or [Ib]; A silver halide photographic material comprising at least one enhancer and at least one infrared cut layer. Embedded image [Wherein, Z ₁₁ , Z ₁₂ , Z ₂₁ , and Z ₂₂ each represent 5 members or 6 members;
Represents a group of nonmetal atoms necessary to complete a membered monocyclic ring or a fused nitrogen-containing heterocyclic ring thereof. R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent an aliphatic group. _{R 13 ~R 17, R 23 ~R} 29 each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl _{group, -N (W 1) W 2} , -SR or heterocyclic group. Wherein R represents an alkyl group, an aryl group or a heterocyclic group, each of W ₁ and W ₂ represents an alkyl group, an aryl group or a heterocyclic group, linked to each other and W ₁ and W ₂ 5
A 6-membered or 6-membered nitrogen-containing heterocycle can also be formed. R
₁₁ and R ₁₃ , R ₁₄ and R ₁₆ , R ₁₇ and R ₁₂ , R ₂₁ and R ₂₃ , R ₂₄
And R ₂₆ , R ₂₅ and R ₂₇ , R ₂₆ and R ₂₈ , R ₂₂ and R ₂₉ can be linked to each other to form a 5- or 6-membered ring or a fused ring thereof. X ₁₁ and X ₂₁ each represent an ion required to cancel the charge in the molecule, and m ₁₁ and m ₂₁ each represent the number of ions required to cancel the charge in the molecule. n ₁₁ , n ₁₂ ,
n ₂₁ and n ₂₂ each represent 0 or 1. ] 2. A light-sensitive silver halide emulsion layer containing a coupler, a green light-sensitive silver halide emulsion layer containing a coupler, and a blue light-sensitive halide containing a coupler, each having at least one layer on a support. A silver emulsion layer, wherein at least one of the three color-sensitive silver halide emulsion layers contains at least one compound represented by the general formula [Ia] or [Ib], And a silver halide photographic material having at least one infrared light cut layer. 3. The silver halide photographic material according to claim 1, wherein the infrared light cut layer contains at least one of black colloidal silver and an infrared dye.