JP2990315B2 - Silver halide photographic material - Google Patents

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 light-sensitive material, and more particularly to an infrared-sensitive color photographic element, in which a finished image has no color turbidity and continuously outputs images with a laser printer. However, the present invention relates to a silver halide photographic light-sensitive material capable of stably obtaining a high-quality color image.

[0002]

BACKGROUND OF THE INVENTION Today in the field of electronics, C
2. Description of the Related Art The remarkable progress of image pickup devices such as CDs and magnetic recording media has made it possible to take pictures with the same ease as conventional pictures using silver halide, and immediately transfer them to a television to enjoy them. In the field of printing and plate making, due to advances in scanners and image processing equipment, after reading the original image with a scanner, you can easily perform editing, correction, contrast, scaling, etc. while looking at the color display. Is now available.

[0003] However, simply displaying an image on a television screen is still insufficient, and an image recorded on paper is required. Various methods such as a thermal transfer method, an ink jet method, and an electrophotographic method are used. Has been put to practical use. Even in such fields, the rich gradation of silver halide photographic materials is outstanding compared to other systems and has excellent descriptive power, but conventional silver halide photographic materials have , Blue, green and red photosensitive silver halide emulsion layers, it is difficult to obtain a light source suitable for recording on the silver halide emulsion layers.

For exposing a silver halide photographic light-sensitive material for the above purpose, gas lasers such as helium / neon, argon ion, and helium / cadmium have been widely used. However, these lasers have disadvantages such as being large, expensive, and short in life. On the other hand, a method using a non-linear optical element using a semiconductor laser is known, but the conversion efficiency is not sufficient, and an appropriate wavelength when viewed from the side of the silver halide photographic material. Due to problems such as lack of light, they had not been put to practical use.

However, by using a silver halide emulsion sensitive to infrared rays and using a semiconductor laser, an image can be easily obtained with an inexpensive and small exposure apparatus.

However, silver halide photographic materials having sensitivity to infrared light have the disadvantage that the absorption wavelength of the infrared spectral sensitizing dye broadens on the short wavelength side, and the resulting image tends to be turbid. was there.

[0007] Further, when a light emitting diode or a semiconductor laser is continuously operated as an infrared light source, there is a problem that the image density fluctuates. One of the factors is that the light emission wavelength and light intensity of the light source change with temperature. It is thought that.

On the other hand, for example, Japanese Patent Application Laid-Open No. 61-137149 specifies the difference in emulsion sensitivity between layers of a light-sensitive material, the contrast, the layer structure, the spectral characteristics of a filter layer, and the like.
JP-A-3-138642, JP-A-3-120535 or JP-A-3-13838 discloses that a specific infrared sensitizing dye is used to deeply narrow a spectral wavelength region to improve color turbidity by decomposing an image. Etc. are disclosed.

However, these prior arts do not sufficiently improve the color turbidity when a continuous image is output, and have a high sensitivity and a stable high image quality for laser printing. Was strongly desired.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a halogenation for laser printing which is free from color turbidity and can obtain a high-sensitivity, stable and high-quality color image even when images are continuously output using a laser printer. An object of the present invention is to provide a silver photographic light-sensitive material. Other objects will be apparent from the following description.

[0011]

The object of the present invention has been found to be achieved by the following, and has led to the present invention. (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [1], [ 2] and at least one of the sensitizing dyes selected from [3] and a macrocyclic compound containing a hetero atom (however,
A silver halide photographic light-sensitive material containing a combination of at least one of those having a mercaptotetrazole structure) .

[0012]

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In the formula, Z ₁ and Z ₂ each represent an atom group necessary for forming a heterocyclic ring, and the heterocyclic ring includes 5 to 6 atoms including a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom.
And a condensed ring having a substituent may be bonded to these rings.

Examples of the heterocycle include thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole,
Benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthoimidazole, 4-quinoline, pyrroline, pyridine, tetrazole, indolenine, benzoindolenine, indole, tellurazole,
Benzotellurazole, naphthotellurazole nucleus and the like can be mentioned.

R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. Each of these groups may have a substituent. For example, in the case of an alkyl group, it may be any of linear, branched, and cyclic having 1 to 8 carbon atoms.

Examples of the alkyl group substituent include a halogen atom (bromine, chlorine, fluorine, etc.), a hydroxy group,
Cyano group, alkoxy group, substituted or unsubstituted amino group,
One or more carboxylic acids, sulfonic acids, etc. may be substituted.

Examples of the alkenyl group include a vinylmethyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. R ₃ and R ₄ represent a hydrogen atom, a lower alkyl group or an aralkyl group, and when R ₃ is a hydrogen atom,
R ₄ or R ₂ may be linked to form a 5- to 6-membered ring, and when R ₄ is a hydrogen atom, R ₃ is linked to another R ₃ to form a hydrocarbon ring or a heterocyclic ring. Is also good.

K and m represent 0 or 1, and L represents an integer of 3 or more. X represents an acid anion and n represents 0 or 1.

[0019]

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In the formula, Z ₁ and Z ₂ each represent an atom group necessary for forming a heterocyclic ring, and the heterocyclic ring has the same meaning as Z ₁ and Z _{2 in the} above general formula [1]. R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and have the same meanings as R ₁ and R _{2 in} the general formula [1]. R ₄
Is an alkyl group, an alkenyl group, an alkynyl group or an aryl group (for example, a phenyl group which may have a substituent)
Represents R ₃ represents a hydrogen atom, a lower alkyl group or an aryl group, and R ₃ and other R ₃ may be linked to form a hydrocarbon ring or a heterocyclic ring.

Q is a sulfur atom, oxygen atom, selenium atom or =
R ₅ represents NR ₅ has the same meaning as R _4. L represents 2 or 3, k and m represent 0 or 1, X represents an acid anion, and n represents 0 or 1.

[0022]

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In the formula, Z ₁ represents an atom group necessary for forming a heterocyclic ring, and the heterocyclic ring is represented by Z ₁ or Z _{2 in the} above-mentioned general formula [1].
Other than the same as, for example, thiazoline, thiazolidine,
Benzothiazoline, naphthothiazoline, selenazoline,
Selenazolidine, benzoselenazoline, naphthoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline, benzimidazoline, naphthimidazoline and the like. R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

[0024] R ₃ is a hydrogen atom, a lower alkyl group, in addition to an aryl group, it may form a hydrocarbon ring or a heterocyclic ring linked and the R ₃ and the other R _3. Q is a sulfur atom, an oxygen atom, a selenium atom or = NR _4, R ₄ mother alkyl group, an alkenyl group, an alkynyl group or an aryl group. L is 2 or
In 3, k represents 0 or 1.

(2) In a silver halide photographic light-sensitive material having two or more red-sensitive layers having a light-sensitive maximum at 720 nm or more,
This is achieved by the silver halide photographic material as described in the above item (1), wherein the red-sensitive layer having a longer wavelength contains at least one macrocyclic compound containing a hetero atom. Hereinafter, the present invention will be described in detail.

Among the spectral sensitizing dyes represented by the general formula [1], particularly useful sensitizing dyes can be represented by the following general formulas [4], [5] and [6].

[0027]

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In the formula, Z ₁ and Z ₂ each represent an atomic group necessary for forming a 5- or 6-membered heterocyclic ring which may have a substituent, and R ₁ and R ₂ are each an alkyl group; In the aryl group, these groups may have a substituent. R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. X represents a counter ion.

[0029]

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In the formula, Z ₁ and Z ₂ each represent an atom group necessary for forming a thiazole, oxazole, selenazole, pyridine, quinoline or tellurazole ring, and these heterocycles have a substituent. You may. Z ₃ represents a group of atoms necessary to form a 5- to 6-membered carbocyclic ring, R ₁ and R ₂ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted rule group, and R ₁ is R ₄ , R ₂ may be combined with R ₅ to form a ring. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₃ represents a heterocyclic ring which may have a substituent. X represents a counter ion.

[0031]

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In the formula, Z ₁ represents an atom group necessary for forming a benzothiazole, benzoxazole, benzoselenazole, benzimidazole or benzotellurazole ring, and these rings have a substituent. Is also good. Z ₂ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring which may have a substituent.

[0033] From L ₁ L ₅ also has have a substituent represents a methine group, R _1, R ₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted Aruru group, R ₁ is R ₄ and
R ₂ may be combined with R ₅ to form a ring. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R ₃ is an optionally substituted alkyl group having up to 4 carbon atoms, m represents 1-2, n represents 0-1 and X represents a counter ion.

Hereinafter, the general formulas [1] to [6] of the present invention will be described.
Are shown below, but the present invention is not limited to these.

[0036]

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[0037] _{No. Z 1 Z 2 R 1 R} 2 Y 1 Y 2 X - 1 S O C 2 H 5 C 2 H 5 H 6,7- benzo _{I 2 S O C 2 H 5} (CH 2) 3 SO ₃ ^- 6,7-benzo 4,5-benzo _{- 3 S O C 2 H 5} (CH 2) 3 SO 3 - H 6-C 6 H 5 - 4 S O C 2 H 5 (CH 2) 2 COO - 5 _{, 6-CH 3 6-Cl} - 5 O S C 2 H 5 C 2 H 5 4,5- benzo 4,5-benzo Br 6 S S undefined undefined H H I 7 S S undefined undefined 5, 6-SCH ₃ 5,6-SCH ₃ ８8 SS 〃 〃 〃4,5-benzo ９9 SS 〃 〃5-SCH ₃ H 〃10 SS 〃C ₃ H ₇ 5-CH ₃ 6-Cl 〃11 SS 〃 CH ₂ COOH H H 〃 12 S S C ₂ H ₄ OH C ₂ H ₄ OH H H 〃 13 OSC ₂ H ₅ C ₂ H ₅ H 6 -CH ₃ 〃 14 S S C ₂ H ₅ (CH ₂ ) ₃ SO ₃ ^- 6-Cl H 〃 _{15 S S C 2 H 5 C} 2 H 5 5,6-SCH 3 5-OCH 3, 6-CH 3 〃 _{No. Z 1 Z 2 R 1 R} 2 Y 1 Y 2 X ^- 16 SS CH ₃ CH ₃ 4,5-benzo 4,5-benzo * PTS 17 SS C ₂ H ₅ C ₂ H ₅ 〃 HI 18 SS 〃 〃 〃 6-CH ₃ 〃 19 SS 〃 undefined undefined 5-OCH ₃ 〃 20 S S Undefined undefined 5, 6-CH ₃ 〃 _{21 S S (CH 2) 4} SO 3 K (CH 2) 4 SO 3 - 5,6-OCH 3 5,6-CH 3 - 22 S S (CH 2) 3 SO ₃ ^- C ₄ H ₉ 6,7- benzo _{5-OCH 3 - 23 S O} C 5 H 11 (CH 2) 2 SO 3 - 5,6-CH 3 6-OCH 3 - 24 S S (CH 2) 3 OH (CH ₂ ) ₄ SO ₃ 5,6-CH ₃ 5,6-CH ₃ − (* PTS is paratoluenesulfonic acid)

[0038]

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[0039] _{No. Z 1 Z 2 R 1 R} 2 Y 1 Y 2 X - 25 S O C 2 H 5 CH 3 H H I 26 S O 〃 C ₂ H ₅ 〃 4,5-benzo 〃 27 S O 〃 〃 6-CH ₃ 6-CH ₃ 〃 28 SO 〃 〃 5-OCH ₃ 6-CH ₃ 〃 29 OO 〃 〃 HH 〃 30 OO 〃 〃 5,6-benzo 5,6-benzo 〃 31 S S CH ₃ CH ₃ 5-SCH ₃ 5-SCH ₃ 〃

[0040]

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[0041]

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[0042]

[Table 1]

[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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The above-described infrared-sensitive sensitizing dye is described in, for example, FM Hammer, The Chemistry of Heterocylic.
Compounds, Vol. 18, (The Cyanine Dyes and Related
Compounds) (A. Weissherger ed. Interscience, N
ew York 1964).

Next, the macrocyclic compound containing a hetero atom of the present invention is a 9-membered or more macrocyclic compound containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom as a hetero atom. Particularly preferred compounds include crown ether compounds. These compounds are described in CJPedersen, Journal of American chemical So
ciety vol.86 (2495), 7017-7036 (1967), GWGokel,
SH, Korzeniowski, “Macrocyclic polyethr synthesi
s ", Springer-Verlag. (1982), Ed. Oda, Shono, Tabushi," Chemistry of Crown Ethers "Chemistry Dojin (1978), Tabushi, et al.," Host-Guest "Kyoritsu Shuppan (1979), Sasaki, Koga, Synthetic Organic Chemistry, Vol. 45 6), 571-582 (1987).

Hereinafter, specific examples of the macrocyclic compound containing a hetero atom used in the present invention will be shown, but the present invention is not limited thereto.

[0053]

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[0054]

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[0055]

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The macrocyclic compound containing a hetero atom used in the present invention may be, in addition to the compounds described above, the S-cyclic compounds described in Japanese Patent Application No. 3-82798, pages 13 to 18 by the same applicant as the present inventors. -9,
S-12-15, S-17,18, S-20, S-22-31, S-33-34, S-36
Etc. can be used.

To add the macrocyclic compound containing a hetero atom of the present invention to a hydrophilic colloid containing silver halide grains, water or a hydrophilic colloid such as methanol, ethanol, fluorinated alcohol, or N, N-dimethylformamide can be used. It may be added after dissolving in an organic solvent. The timing of addition may be any timing as long as it is before coating of the emulsion, but is preferably added before the end of chemical sensitization.

Regarding the order of adding the infrared-sensitive sensitizing dye and the macrocyclic compound, any of them may be added first, or they may be added simultaneously or as a mixed solution. The amount of the macrocyclic compound of the present invention varies depending on the type of the compound, but is usually 1
It is in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol, preferably 5 × 10 ^-6 to 1 × 10 ^-2 mol.

The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide and silver chloroiodobromide. You. Silver halide grains preferably used in the present invention are silver chlorobromide. More preferably, it is silver chlorobromide having a silver bromide content of 0.01 to 2 mol%, particularly preferably 0.1 to 2 mol%.
Mol% of silver chlorobromide. The composition of the silver halide grains is
The particles may be uniform from the inside to the outside of the particles, or the compositions of the inside and the outside of the particles may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous. Also, JP-A-1-1836
As described in Japanese Patent No. 47, a halogen may have a localized phase having a locally different halogen composition.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 in consideration of other photographic properties such as rapid processing and sensitivity.
It is in the range of μm. The particle diameter is represented by an average based on a projected area, wherein a spherical or approximate spherical particle diameter is a particle diameter, and a cubic particle is a ridge length, which is a particle diameter. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably, in the particle size distribution of silver halide grains, the coefficient of variation is 0.22 or less, more preferably
Monodispersed silver halide grains of 0.15 or less.

In the present invention, the silver halide grains used in the emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made. The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Octahedron, 14-hedron, 12
Particles having a shape such as a planar body can also be used. or,
The particles may be spherical, rod-like, plate-like, or the like. Further, particles having a twin plane may be used.

The silver halide emulsion used in the present invention and the silver halide photographic light-sensitive material according to the present invention can be combined with a yellow coupler, a magenta coupler, and a cyan coupler to obtain a halogen spectrally sensitized to a wavelength range of 400 to 900 nm. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

A dye which has no spectral sensitizing effect together with the sensitizing dye itself or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is added to the emulsion. You may make it contain.

In the present invention, as the yellow coupler, an acylacetanilide-based coupler can be preferably used. Among them, benzoylacetanilide compounds and pivaloylacetoanilide compounds are advantageous, and especially, the exemplified compounds described in JP-A-63-85631.
Y-1 to Y-146, exemplified compounds Y-1 to Y-98 described in JP-A-63-97951, and exemplified compounds Y described in JP-A-1-156748 (pages 67 to 78). -1 to Y-24 and the like are preferably used.

As the magenta coupler which can be used in the present invention, there may be mentioned oil-protected indazolone-based or cyanoacetyl-based couplers, preferably 5-pyrazolone-based and pyrazoloazole-based couplers such as pyrazolotriazoles. The magenta coupler preferably used in the present invention includes magenta couplers represented by the following formulas [MI] and [M-XI].

[0066]

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In the formula, Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy and the like.

Specific examples of the compound represented by the general formula [MI] include M-1 to M-61 described in JP-A-63-167360, page 5, lower right column to page 9, lower left column, and special examples. No. 1 of Kaisho 62-166339
No. 1-4, 6, 8-17, 19-24, 26-43, 45-59, 61 among the compounds described in the upper right column of page 8 to the upper right column of page 32.
To 104, 106 to 121, 123 to 162, and 164 to 223.

[0070]

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In the formula, Ar represents an aryl group, X represents a halogen atom, an alkoxy group or an alkyl group, and R represents a group that can be substituted on a benzene ring. n represents 1 or 2. When n is 2, R may be the same group or different groups. Y represents a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amine-based color developing agent.

In the general formula [M-XI], Y is a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine-based color developing agent, for example, a halogen atom, an alkoxy group, an aryloxy group, Examples include an acyloxy group, an arylthio group, an alkylthio group, and a 5- to 6-membered heterocyclic group. Here, Y does not represent a hydrogen atom.

The coupler represented by the general formula [M-XI] includes, for example, Compound No. 218 described in JP-A-63-52138.
To No. 244 and the like, and further, U.S. Pat.
No. 8, No. 3,061,432, No. 3,062,653, No. 3,127,269,
3,311,476, 3,152,896, 3,419,391, 3,5
19,429, 3,555,318, 3,684,514, 3,888,68
No. 0, 3,907,571, 3,928,044, 3,930,861,
No. 3,930,866, No. 3,933,500, JP-A-49-29639,
49-111631, 49-129538, 50-13041, 52-589
No. 22, No. 55-62454, No. 55-118034, No. 56-38043,
No. 57-35858, No. 60-2953, No. 60-23855, No. 60-6064
No. 4, UK patent 1,247,493, Belgian patent 789,116,
No.792,525, West German Patent 2,156,111, JP-B-46-60479
And No. 57-36577.

As the cyan coupler, a phenol cyan coupler and a naphthol cyan coupler can be used. The cyan coupler preferably used in the present invention includes cyan couplers represented by the following general formulas [CI] and [C-II].

[0075]

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In the formula, R ₁ represents an alkyl group having 2 to 6 carbon atoms. R ₂ represents a ballast group. Z represents a hydrogen atom or an atom or group which can be removed by reaction with an oxidized form of a color developing agent. The alkyl group represented by R ₁ may be linear or branched, and includes those having a substituent.

The ballast group represented by R ₂ has a size and shape that gives the coupler molecules sufficient bulk to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to other layers. Organic group.

Preferred examples of the ballast group are those represented by the following general formula.

[0079]

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R ₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent. General formula (C-
Specific examples of the cyan coupler represented by I) include the exemplified compounds PC-1 to PC-19 described on pages 116 to 119 of JP-A-1-156748 and JP-A-62-249151. Exemplified compounds C-1 to C-28, Japanese Patent Publication No. 49-11572,
61-3142, 61-9652, 61-9653, 61-39045
And cyan couplers described in JP-A Nos. 61-50136, 61-99141 and 61-105545.

[0081]

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In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

R ₃ may form a ring together with R ₁ . Z represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent.

In the cyan coupler represented by the general formula [C-II], the alkyl group represented by R ₁ preferably has ₁ to 32 carbon atoms, and may be linear or branched. Also includes those having a substituent. The aryl group represented by R ₁ is preferably a phenyl group, including those having a substituent. The alkyl group represented by R ₂ has 1 carbon atom
To 32 are preferred, and these alkyl groups may be linear or branched, and include those having a substituent. The cycloalkyl group represented by R ₂ preferably has 3 to 12 carbon atoms, and these cycloalkyl groups include those having a substituent. The aryl group represented by R ₂ is preferably a phenyl group, including those having a substituent. The heterocyclic group represented by R ₂ is preferably a 5- to 7-membered heterocyclic group, including those having a substituent, and may be condensed.

R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R ³ is preferably a hydrogen atom.

The ring formed by R ₁ and R ₃ together is
5- to 6-membered rings are preferred, for example,

[0088]

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The group capable of leaving by reaction with an oxidized form of the color developing agent represented by Z in the general formula [C-II] includes a halogen atom, an alkoxy group, an aryloxy group,
Examples include an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryl An oxy group and an alkoxy group.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula [C-II-A].

[0091]

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In the formula, R _A1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom.

R _A2 has the same meaning as R _{1 in} formula [C-II]. X _A represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Typical specific examples of the cyan coupler represented by the general formula [C-II] include the exemplified compounds C-1 to C-25 described in JP-A-63-96656, No. 156748 # 124
Exemplified compounds PC-II-1 to PC-II- described on pages 127 to 127
Other than 31, JP-A-62-178962, page 7, lower right column to page 9, lower left column, JP-A-60-225155, page 7, lower left column to page 10, lower right column,
JP-A-60-222853, page 6, upper left column to page 8, lower right column and JP-A 59-185335, page 6, lower left column to page 9, upper left column, 2,5-diacylamino And cyan cyan couplers.

When the above-mentioned couplers and the like are added to a silver halide emulsion by an oil-in-water type emulsification / dispersion method, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of about 150 ° C. or higher, if necessary. Dispersion means such as a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, etc., as a stirrer, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution and dissolving in combination with a boiling point and / or a water-soluble organic solvent. After emulsifying and dispersing, a desired photographic constituent layer (hydrophilic colloid layer) may be added.

After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

Examples of the high-boiling organic solvent used for this purpose include phthalic acid esters such as dibutyl phthalate, di- (2-ethylhexyl) phthalate, dinonyl phthalate, dicyclohexyl phthalate, and the like. Phosphoric acid esters such as ethylhexyl) phosphate, di-phenyl-cresyl phosphate, and trihexyl phosphate; organic acid amides such as diethyl lauramide and dibutyl lauramide; phenols such as dinonylphenol and p-dodecylphenol;
Hydrocarbons such as decalin and dodecylbenzene, and esters such as 1,4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane and dinonyl adipate are preferably used. Above all, phthalic acid, phosphoric acid, and other organic acid esters are more preferably used. These high-boiling organic solvents may be used alone or in combination of two or more.

Examples of the water-insoluble and organic solvent-soluble polymer used for dispersing the coupler and the like include (1) vinyl polymer and copolymer (2) polycondensate of polyhydric alcohol and polybasic acid (3) open polymer Polyester obtained by a repolymerization method (4) Others include polycarbonate resin, polyurethane resin, polyamide resin and the like.

The number average molecular weight of these polymers is not particularly limited, but is preferably 200,000 or less, more preferably
5,000 to 100,000. The ratio of the polymer to the coupler (polymerization ratio) is preferably from 1:20 to 20: 1, and more preferably from 1:10 to 10: 1.

In the light-sensitive material according to the present invention, various compounds can be used to enhance the durability of the image dye.

In the present invention, by dissolving and dispersing together with the coupler and adding to the light-sensitive material of the present invention,
Various compounds that change the spectral absorption of the dye formed can be used.

In addition, the fluorescent dye releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide photographic light-sensitive material of the present invention,
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation and for the purpose of adjusting sensitivity.

The silver halide photographic light-sensitive material according to the present invention includes a color fogging inhibitor, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a development accelerator, a development retarder, and a fluorescent brightener. , A matting agent, a lubricant, an antistatic agent, a surfactant and the like can be optionally used.

The emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
A sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, or the like can be used alone or in combination.

The silver halide emulsion of the present invention is subjected to chemical ripening for the purpose of preventing fog during the production process, storage, or photographic processing of the photographic material, or maintaining chemical ripening for the purpose of maintaining stable photographic performance. An antifoggant or stabilizer can be added at the time and / or after the completion of chemical ripening and before coating the silver halide emulsion.

It is advantageous to use gelatin as a binder for the silver halide photographic light-sensitive material used in the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic high molecular substances such as homo- or copolymers can also be used.

The photographic constituent layers of the silver halide photographic light-sensitive material according to the present invention include baryta paper or paper laminated with an α-olefin polymer or the like, and a paper support from which the α-olefin layer can be easily separated from the paper support. Reflection in which a white pigment is contained or coated on a film made of a semi-synthetic or synthetic polymer such as a flexible reflective support such as synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide. It can be applied to a support, a metal, or a rigid body such as ceramics. Also 12
A thin reflective support having a thickness of 0 to 160 μm can also be used.

As the white pigment, a colorless and / or organic white pigment can be used, and preferably an inorganic white pigment, for example, a sulfate of an alkaline earth metal such as barium sulfate, or an alkali such as calcium carbonate. Examples include earth metal carbonates, finely divided silica, silicas of synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. Barium sulfate and titanium oxide are preferred as white pigments.

The silver halide light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, charging, etc.). It may be applied via one or more undercoating layers to improve antistatic properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties and / or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion according to the present invention, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

The silver halide photographic light-sensitive material of the present invention can form an image by performing a color development process known in the art.

The color developing agent used in the color developing solution in the development processing of the silver halide photographic light-sensitive material of the present invention includes:
Includes aminophenolic and p-phenylenediamine derivatives that are widely used in various color photographic processes.

In the color developing solution applied to the development processing of the silver halide photographic light-sensitive material of the present invention, a known developing solution component compound is added in addition to the above-mentioned aromatic primary amine color developing agent. be able to.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Also, as an alternative to the water washing process,
Stabilization processing may be performed.

In the image forming method according to the present invention, the developing apparatus used for developing the silver halide photographic light-sensitive material is a roller transport type in which the light-sensitive material is conveyed with rollers interposed between the processing tanks. Also,
An endless belt system in which a photosensitive material is fixed to a belt and conveyed, or a system in which a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank, and the photosensitive material is conveyed may be used.

[0117]

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

Example 1 Magenta coupler M-1 and dye image stabilizer (ST-1, ST-
2, ST-3), high boiling organic solvent (DNP) and ethyl acetate 60
Add 20 ml of surfactant (SU-1) 7m
The resulting mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 1 using an ultrasonic homogenizer to prepare a magenta coupler dispersion. This dispersion was mixed with an infrared-sensitive silver halide emulsion coated with the following composition, and the coating liquid was adjusted to prepare Samples 101 to 118.

H-1 and H-2 were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

Addition amount of protective layer (g / m ² ) Gelatin 1.00 Anti-binder (F-1) 0.002 Infrared-sensitive layer Gelatin 1.40 Infrared-sensitive silver chlorobromide emulsion (Em-IR1) 0.170 Magenta coupler (M- 1) 0.35 dye image stabilizer (ST-1) 0.15 dye image stabilizer (ST-2) 0.15 dye image stabilizer (ST-3) 0.15 DNP 0.20 anti-irradiation dye (AI-1) 0.01 support Body Polyethylene laminated paper (Preparation method of infrared-sensitive silver halide emulsion) The following (Solution A) and (Solution B) were controlled at pAg = 6.5 and pH = 3.0 in 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C. While simultaneously adding over 30 minutes while adding the following (solution C) and (solution D) at pAg = 7.
3. Simultaneous addition over 180 minutes while controlling pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added
200ml (Solution C) Sodium chloride
102.7 g Potassium bromide 1.0 g Add water 600 ml (D solution) Silver nitrate 300 g Add water 600 ml after completion of addition and desalinate using Kao Atlas 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate. After that, the mixture was mixed with an aqueous gelatin solution to obtain a monodispersed cubic emulsion EMP-1 having an average particle size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol%.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain an infrared-sensitive silver halide emulsion (Em-IR1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Add STAB-1 at the time when optimal sensitometric performance is obtained. The temperature was lowered to stop chemical ripening, but STAB
Three minutes before the addition of -1 sensitizing dye according to the present invention (exemplary compound) was added at 1 × 10 ⁻⁴ mol / mol AgX and a macrocyclic compound containing a hetero atom (exemplary compound) at 0.7 g / mol AgX. Then, the following coating liquids shown in Table 2 were prepared.

[0124]

[Table 2]

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

The sample thus obtained was scanned with a laser printer (about 830 nm gallium aluminum arsenide semiconductor laser) at a scanning speed of 1.6 m / sec with a laser beam having a beam diameter of 80 μm at a pitch of 100 μm. Images were output continuously after output, and the first sample and the sample 1 hour later were processed according to the following processing steps.

Processing temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds (color developing solution) Pure water 800ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene 1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid Sodium salt 1.0 g N-ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 100 ml and adjust to pH = 10.10.

(Bleaching / fixing solution) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make a total volume of 100 ml. Adjust to pH = 5.7 with potassium or glacial acetic acid.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Add water to make the total volume 100 ml, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The concentration of the obtained sample was determined, and the difference (ΔD) between the sample output first and the sample one hour later was determined and evaluated.

Further, a separate gallium / aluminum / arsenic semiconductor laser having a wavelength of 780 nm was used for exposure, and the treatment was performed in the following treatment steps.

When the wavelength at the time of exposure was 830 nm, the sensitivity was compared between the samples to determine the sensitivity.
The relative sensitivity is expressed as

The results obtained are shown in Table 3 below.

[0136]

[Table 3]

As is clear from the table, Samples 101 to 104 have ΔD
And the density fluctuation when the exposure apparatus is operated continuously is large. Sample 105 is improved in image stability when scanning exposure is performed continuously by the combined use of dyes.
The difference in sensitivity due to the difference in wavelength is small.

It can be seen that ΔD is small and a stable image can be obtained by the combined use of the infrared sensitizing dye of the present invention and a hetero-macrocyclic compound. Also, it can be seen that ΔS is large and the spectral sensitivity on the short-wave side is good. This indicates that the factor of color turbidity is remarkably improved.

Further, Samples 106, 117 and 112 and Samples 114, 115 and 1
As can be seen by comparing 16, the general formulas [4], [5],
By using [6], it can be seen that ΔD and ΔS are small and the effect is more exhibited.

When supersensitization was performed with the hetero-macrocyclic compound containing a heterocycle of the present invention, Samples 106, 109 and 118 and Samples 119, 120 and 121
As can be seen from the comparison, it can be understood that the use of the crown ether is more effective.

Example 2 A coating solution was prepared in the same manner as in Example 1, and multilayer silver halide photographic materials 201 to 205 were prepared using the constituent layers shown in Tables 4 and 5 below.

(Preparation of Blue-Sensitive Silver Halide Emulsion Layer)
Average particle size in the same manner as EMP-1 except that the addition time of (Solution) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
A monodispersed cubic emulsion EMP-2 having a coefficient of variation of 0.05 and a silver chloride content of 99.5% was obtained.

The following compounds were used at 50 ° C. for EMP-2.
For 90 minutes with a blue-sensitive silver halide emulsion (Em-
B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX Sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (B
Average particle size in the same manner as in EMP-1 of Example 1 except that the addition time of (Solution) and the addition times of (Solution C) and (Solution D) were changed.
A monodispersed cubic emulsion having a particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

This emulsion was mixed with the following compound at 60 ° C. for 90 minutes.
Red-sensitive silver halide emulsion (Em-R) after chemical ripening
I got

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX

[0147]

[Table 4]

[0148]

[Table 5]

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

[0152]

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[0153]

Embedded image

The obtained sample was placed on a laser printer (about 78
0nm gallium aluminum arsenic semiconductor laser)
Then, the exposure amount was appropriately changed, and the processing was performed in the processing steps described in Example 1 to form a yellow color patch. The density of the obtained sample was measured using an optical densitometer (model PDA-65 manufactured by Konica Corporation), and the G concentration at a B concentration of 1.8 (G
D) was determined and color turbidity was evaluated. Table 6 shows the obtained results.

[0155]

[Table 6]

From Table 6, it can be seen that the use of the compound of the present invention reduces the color turbidity and achieves the effects of the present invention.

Example 3 Samples 301 to 304 were prepared in the same manner as in Example 1 except that a silver chlorobromide emulsion having a silver bromide content of 10 mol% was used in preparation of Samples 102, 105, 106 and 107 in Example 1. Was prepared.

In the same manner as described above, a silver chlorobromide emulsion having a silver bromide content of 70 mol% was used.
Samples 309 to 312 were prepared using a 0 mol% silver chloride emulsion.

The sample thus produced was evaluated in the same manner as in Example 1.

Samples 305 to 318 were processed according to the following processing steps in order to obtain an optimum image.

[0161] (Processing solution composition) Color developer benzyl alcohol 15 ml ethylene glycol 15 ml potassium sulfite 2.0 g potassium bromide 0.7 g sodium chloride 0.2 g potassium carbonate 30.0 g hydroxylamine sulfate 3.0 g polyphosphoric acid (TPPS) 2.5 g N-ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water Adjust the total volume to 100 ml and adjust the pH to 10.20 with potassium hydroxide or sulfuric acid. Bleaching-fixing solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Add water to make a total volume of 100 ml, and adjust the pH to 7.0 with potassium carbonate or glacial acetic acid. Adjust to 1. The results obtained are shown in Table 7 below.

[0162]

[Table 7]

As is clear from Table 7, even in the silver chloride emulsion or the silver chlorobromide emulsion having a high silver bromide content, the color turbidity was small and the density difference when continuously outputting images was small. The effect was obtained. Further, it was found that the effect was more exhibited when the silver bromide content was 0.05 mol%.

[0164]

According to the present invention, a silver halide photographic light-sensitive material having no color turbidity and having stable and high image quality even when images are continuously output by a laser printer can be obtained.

Continuation of front page (56) References JP-A-4-25833 (JP, A) JP-A-3-20730 (JP, A) JP-A-1-138552 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) G03C 1/20 G03C 1/22 G03C 1/28

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [1], [1] Macrocyclic compounds containing at least one of the sensitizing dyes selected from 2] and [3] and a hetero atom
(Excluding those having a mercaptotetrazole structure
A) a silver halide photographic material comprising at least one of the following: Embedded image In the formula, Z ₁ and Z ₂ each represent an atom group necessary for forming a heterocyclic ring, and R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R ₃ and R ₄ represent a hydrogen atom, a lower alkyl group or an aralkyl group, and when R ₃ is a hydrogen atom, it may be linked to R ₄ or R ₂ to form a 5- to 6-membered ring, and R ₄ In the case of a hydrogen atom, R ₃ may be linked to another R ₃ to form a hydrocarbon ring or a heterocyclic ring. k and m are 0 or 1
And L represents an integer of 3 or more. X is an acid anion and n is 0
Or represents 1. Embedded image In the formula, Z ₁ and Z ₂ each represent an atomic group necessary for forming a heterocyclic ring, and R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R ₄ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group, R ₃ represents a hydrogen atom, a lower alkyl group, in addition to an aryl group, R ₃ and another R ₃ and are linked to a hydrocarbon ring or heterocyclic A ring may be formed. Q is R ₅ represents a sulfur atom, an oxygen atom, a selenium atom or = NR ₅ has the same meaning as R _4. L is 2 or 3 and k, m
Represents 0 or 1, X represents an acid anion, and n represents 0 or 1. Embedded image In the formula, Z ₁ represents a group of atoms necessary to form a heterocyclic ring,
R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R ₃ represents a hydrogen atom, a lower alkyl group or an aryl group, and R ₃ and other R ₃ may be linked to form a hydrocarbon ring or a heterocyclic ring. Q is a sulfur atom, an oxygen atom, a selenium atom or = NR _4, R ₄ is <br/> kill group, an alkenyl group, an alkynyl group or an aryl group. L represents 2 or 3, and k represents 0 or 1. 2. A silver halide photographic material having two or more red-sensitive layers having a maximum light sensitivity at 720 nm or more, wherein the red-sensitive layer having a longer wavelength contains at least one macrocyclic compound containing a hetero atom. 2. The silver halide photographic light-sensitive material according to claim 1, wherein