JPH06258789A - Photographic product - Google Patents

Abstract

PURPOSE:To enhance the quality of a photographic image photographed by the photographic product having an exposure function and a built a built-in photographic sensitive material. CONSTITUTION:At least one of the photosensitive layers of the silver halide color photographic sensitive material contains one of couplers represented by the general formula in which R1 is H or a substituent; Z is a nonmetallic atomic group necessary to form an optionally substituted or condensed 5-membered azole ring having 2 or 3 nitrogen atoms; and X is H or a group to be released by coupling with the oxidation product of a developing agent. A photographing optical system comprises a forward meniscus lens 26 having an aspherical convex front surface and a both convex spherical lens 27, and it has a focal length of 32mm, an aperture value of 11, and a shutter speed of 1/100sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic product containing a light-sensitive material having an exposure function, and in particular, improved photographic finish quality such as sharpness, color reproducibility, and image distortion in peripheral areas. Photographic products that have been created.

[0002]

2. Description of the Related Art In recent years, a photographic product having a color photosensitive material (color negative film) built-in has become popular under the trade name of a film unit with a lens. This freed us from the trouble of loading a film into an ordinary camera and the failure caused by a mistake in loading the film, and increased the opportunity for taking photographs due to its simplicity. Also with a strobe according to the purpose of shooting,
The telephoto type and super wide-angle type have been developed and put into practical use. The major feature of these photographic products is that they are inexpensive. Therefore, in order to easily perform the positioning and the optical axis alignment in mass production, the taking optical system is 1
Many use a single lens.

However, when a simple photographic optical system composed of a single lens as described above is used, the effects of spherical aberration and chromatic aberration are likely to occur, and sharpness, especially compared with the case of photographing with a normal camera, Improvement has been desired in terms of distortion of the peripheral image. In addition, "Sharpness Run Panoramic" (trade name) uses a wide-angle shooting optical system (focal length 25 mm) composed of two lenses to improve the distortion and sharpness of the peripheral image. However, since the production quantity is small, even if a two-lens taking optical system is used, it is not a big problem.

On the other hand, in order to improve the sharpness of color light-sensitive materials,
Generally, development inhibitor releasing couplers (so-called DIR couplers) are known to have an effect, and for example, Research Disclosure (RD) -17643VII-
Patents described in paragraph F, JP-A-57-151944,
57-154234, 60-184248, 60-37346, and U.S. Pat. No. 4,248,962.

The sharpness of the color light-sensitive material is improved by the above-mentioned D
In addition to improvements from direct factors such as the use of IR compounds and dyes, improvements from indirect factors are considered. One of them is the “color contrast effect” relating to sharpness. The visual increase in sharpness due to the color contrast effect is most prominent when the color saturation of the yellow, magenta, and cyan color images is increased.

As a method of improving the sharpness without using a DIR compound, for example, a method of thinning a hydrophilic colloid layer, a method of using a dye that absorbs scattered light during exposure, a lower layer or a base is used. A method of coloring or a method of changing the shape of the photosensitive silver halide grains has been proposed.

[0007]

However, in the above-mentioned methods, the enhancement of the imaging performance of the photographing optical system and the enhancement of the performance of the color light-sensitive material have only been individually studied, and particularly, the lens In the case of a product such as an attached film unit which is mass-produced in a form in which a color light-sensitive material is previously incorporated and sold at a low cost, an appropriate improvement measure has not been found.

An object of the present invention is to incorporate a light-sensitive material having improved photographic finish quality such as sharpness, color reproducibility, and image distortion in the peripheral area, in consideration of the performances of both the photographing optical system and the color light-sensitive material. To provide mold photo products.

[0009]

As a result of earnest research, it has been found that the present invention can achieve the above object by the following means. (I) At least one red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer are each provided on a support, and at least one of the three color-sensitive emulsion layers has the following chemical formula 4. A photographic product provided with an exposure function, which contains a silver halide color photographic light-sensitive material containing a coupler represented by the general formula (M) shown below, has a taking optical system composed of at least two lenses. At least one surface is an aspherical surface, and the focal length of the entire photographing optical system is 28 mm or more.

[Chemical 4] R ₁ in the formula represents a hydrogen atom or a substituent. Z is
It represents a group of non-metal atoms required to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

(II) The silver halide color photographic light-sensitive material of the photographic product described in (I) has at least one of the three color-sensitive emulsion layers, represented by the general formula (1) or " The compound represented by the general formula (2) shown in Chemical formula 6 is contained.

[Chemical 5] In the formula, A represents a coupler residue or a redox group, and L
₁ and L ₃ represent a divalent timing group, L ₂ is 3
It represents a timing group having a valent or higher valent bond, and PUG represents a photographically useful group. j and n each independently represent 0, 1 or 2, m represents 1 or 2, s represents the valence of L ₂ minus 1, and represents an integer of 2 or more. When a plurality of L ₁ , L ₂ or L ₃ are present in the molecule, they may all be the same or different. Further, the plurality of PUGs may be the same or different.

[Chemical 6] In the formula, A and PUG have the same meaning as in formula (I). L ₄ represents -OCO- group, -OSO- group, -OSO ₂ - group, -OC
S-group, -SCO- group, -SCS- group or -WCR ₁₁
It represents a group - R _12. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R ₁₁ and R
_12's each independently represent a hydrogen atom or a substituent, and include the case where they are linked to form a cyclic structure. L ₅ is a group that releases PUG by electron transfer along a conjugated system or L ₄
Represents a group defined by.

(III) In the silver halide color photographic light-sensitive material of the photographic product described in (I) or (II), the total film thickness from the emulsion layer closest to the support to the surface layer is 20 μm or less. (IV) The silver halide color photographic light-sensitive material of the photographic products described in (I) to (III) has a sensitivity of ISO 320 or more, and the total silver coating amount is 3 to 8 g / m ² . (V) The silver halide color photographic light-sensitive material of the photographic products described in (I) to (IV) has a sensitivity of ISO 640 or higher.

Further, when only a spherical single lens is used as the photographing optical system, the resolution of the peripheral portion is deteriorated by the spherical aberration, and it is difficult to correct the chromatic aberration. Since there is a limit to improvement, in the photographic product of the present invention, the taking optical system is composed of at least two lenses, at least one surface of these lenses is aspherical surface, and the focal length of the entire taking optical system is Is 28
mm or more.

The above-mentioned photographing optical system is preferably composed of a two-element lens composed of a front aspherical convex meniscus lens and a biconvex spherical lens, and the diaphragm is provided on the front surface of the lens, between the two lenses, or on the lens. Although it may be on the rear surface, it is preferably positioned on the rear surface of the lens from the viewpoint of ease of assembly and the like. The focal length of the photographing optical system is preferably 28 mm or more and 85 mm or less, more preferably 30 mm.
It is not less than 50 mm. If the focal length of the photographic optical system is less than 28 mm, as in "Sharp Run Panoramic", it is necessary to strictly control the surface accuracy of each lens in order to improve the image distortion in the peripheral area. At the same time, precision is required for positioning and optical axis alignment of each lens at the time of assembling, which is not suitable for mass-produced photographic products.

The color photographic light-sensitive material to be incorporated in the light-sensitive material-embedded photographic product provided with the exposure function of the present invention includes a light-sensitive layer closest to the support (including the same layer) to a surface layer opposite to the support. It is preferable that the total film thickness of the layer group is 20 μm or less in order to further improve the resolution, more preferably 19 μm or less, and further preferably 18 μm or less.

The total film thickness of the layer group from the light-sensitive layer closest to the support to the surface layer can be measured by cutting the light-sensitive material at 25 ° C. and 55% humidity and taking a photograph of its cross section. it can. To take a cross-sectional photograph, a method of taking a cross-sectional photograph using a scanning electron microscope after creating a cut surface of a dried photosensitive material with a microtome and coating the cut surface with gold, palladium, carbon, etc. To use.

The photographic product with a built-in photosensitive material provided with the exposure function according to the present invention has a photographing optical system composed of, for example, two lenses, an exposure mechanism such as a shutter mechanism, and a color photosensitive material (color negative film) wound up. A unit main body portion having a photographing function including a structure for the above, and a color photosensitive material which is previously stored in a roll shape in a film storage chamber formed in the unit main body portion. The color light-sensitive material may be incorporated in the form of a roll, or may be incorporated in a cartridge (cartridge).
Further, it is preferable that an empty cartridge is built in the unit main body portion in advance and the exposed color photosensitive material is wound around this cartridge for each photographing, but the present invention is not limited to this.

The photographing optical system used in the present invention may have a variable diaphragm or may have a fixed diaphragm. In order to handle a photographic product easily,
It is preferable to have a fixed aperture. The aperture value (F value) is preferably 8 or more and 16 or less, more preferably 1
It is 0 or more and 14 or less.

The shutter speed may be variable or fixed, but is preferably fixed like the diaphragm. Preferably 1/50 second to 1/250 second, more preferably 1/50 second.
80 seconds / 1/160 seconds.

In order to maintain sufficient sensitivity under cloudy weather at these aperture values and shutter speeds, the color photographic light-sensitive material incorporated in the light-sensitive material-equipped photographic product of the present invention has ISO 320 or higher. It is preferable to have sensitivity. ISO500 or more is more preferable, and ISO640 or more is more preferable. Further, all of these light-sensitive materials are ISO3200 or less, preferably ISO160.
It has a sensitivity of 0 or less.

Next, the compound of the general formula (M) according to the present invention will be described in detail. In formula (M), R ₁ represents a hydrogen atom or a substituent. Z has 2 to 3 nitrogen atoms
Represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 1 ring, and the azole ring is a substituent (including a condensed ring)
May have. X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

Among the coupler skeletons represented by the general formula (M) used in the present invention, preferable ones are 1H-imidazo [1,2-b] pyrazole and 1H-pyrazolo [1,5.
-B] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H
-Pyrazolo [1,5-d] tetrazole, which are represented by the following formulas (M-I), (M-II),
It is represented by (M-III) and (M-IV). The compound represented by (M-II) or (M-III) is preferable, and the compound represented by (M-II) is more preferable.

[0022]

[Chemical 7]

Substituents R ₁₁ , R ₁₂ , R in these formulas
₁₃ and X will be described in detail.

R ₁₁ is hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy Carbonyl group,
It represents an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg chlorine, bromine), an alkyl group (eg a straight chain or branched chain alkyl group having 1 to 32 carbon atoms),
An aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and more specifically, for example,
Methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group,
Carboxyl group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butyl). Phenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {α- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-
Butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-toctadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazole).

Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group or an acylamino group. Can be mentioned.

R ₁₂ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group or an acyl group. And a cyano group.

R ₁₃ is a group similar to the substituents exemplified for R ₁₁ , preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group and an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group. It is a base.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent, and if the splitting-off group is described in detail, for example, a halogen atom, an alkoxy group, or aryl. Oxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 member or There are 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, for example, a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl. An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio, 1
-Carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), a carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazole, pyrazolyl, triazolyl, tetrazolyl, 1,
2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), and an arylazo group (eg, phenylazo, 4-methoxyphenylazo). In addition to these, X is a leaving group bonded via a carbon atom, which is an aldehyde or a ketone.
In some cases, it may take the form of a bis-type coupler obtained by condensing an equivalent coupler. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Examples of the compound of the magenta coupler represented by the general formula (M) are shown in the following "Chemical formula 8" to "Chemical formula 18", but are not limited thereto.

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

References which describe a method for synthesizing the coupler represented by the general formula (M) are listed below. The above formula (M-
The compounds of I) are for example those disclosed in US Pat. No. 4,500,63.
No. 0, the compound of formula (M-II) is, for example, U.S. Pat. Nos. 4,540,654, 4,705,863, JP-A-61-65245, 62-209457 and 6-209.
The compound of formula (M-III) in 2-249155 is described in, for example, JP-B-47-27411 and US Pat. No. 3,72.
The compound of formula (M-IV) described in JP-A No. 5,067 can be synthesized, for example, by the method described in JP-A-60-33552.

The magenta coupler represented by formula (M) used in the present invention is preferably used in the green-sensitive emulsion layer. It can also be added to a non-photosensitive layer adjacent to the green-sensitive emulsion layer. The total amount of the magenta coupler added is 0.01 to 1.0 g / m ² , preferably 0.0.
5 to 0.8 g / m ² , more preferably 0.1 to 0.5 g
/ M ² . The method for adding the magenta coupler in the light-sensitive material according to the present invention is based on the method for other couplers described below, but the amount of the high boiling organic solvent used as the dispersion solvent is the weight relative to all the couplers added to the magenta coupler-containing layer. The ratio is 0 to 4.0, preferably 0 to 2.
0, more preferably 0.1 to 1.5, still more preferably 0.3 to 1.0.

Next, the compounds represented by the general formulas (1) and (2) will be described in detail. In the general formula (1), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues (for example, 5-pyrazolone type and pyrazolotriazole). Type or imidazole type coupler residues), cyan coupler residues (eg, phenol type, naphthol type, imidazole type or third type described in EP-A-249,453).
No. 04,001, such as a pyrazolopyrimidine type coupler residue) and a colorless coupler residue (for example, an indanone type or acetophenone type coupler residue). Also, U.S. Pat. No. 4,315,070,
No. 4,183,752, No. 4,174,969
No. 3,961,959, No. 5,171,22
No. 3 or the heterocyclic coupler residue described in JP-A-52-82423.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-2.
30135, 62-251746, 61-27.
8852, U.S. Pat. Nos. 3,364,022, 3,379,529, 3,639,417, 4,684,604 or J. Org. Che
m. , 29, 588 (1964).

In the general formula (1), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A or L ₁ of the compound represented by the general formula (1), and the ** mark represents the position of bonding with L ₁ or L ₂ .

[0050] Formula (T-1) * - ( W-CR 11 (R 12)) t - ** ( wherein, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ represents a hydrogen atom or a substituent, R ₁₃ represents a substituent, t represents 1 or 2. When t is 2, two -W-CR ₁₁ (R ₁₂ ) -s are the same or different. When R ₁₁ and R ₁₂ represent a substituent, and typical examples of R ₁₃ are R _{15 and} R _15, respectively.
Group, R ₁₅ CO- group, R ₁₅ SO ₂ - group, R ₁₅ (R ₁₆₎ NC
O- group, or _{R 15 (R 16) NSO 2} - group.
Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. )

Specific examples of the group represented by formula (T-1) include groups represented by the following "Chemical formula 19" and "Chemical formula 20".

[0052]

[Chemical 19]

[0053]

[Chemical 20]

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula.

Formula (T-2) * -Nu-Link-E-** (In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E is an electrophilic group. Represents Nu
Link is a group that can be more nucleophilically attacked to cleave the bond with **, and Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. ) Specific examples of the group represented by formula (T-2) include those represented by the following "Chemical formula 21" and "Chemical formula 22".

[0056]

[Chemical 21]

[0057]

[Chemical formula 22]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
9737, 58-209738 and the like,
It is a group represented by the general formula (T-3) represented by the following "Chemical Formula 23".

[0059]

[Chemical formula 23] (In the formula, * mark, ** mark, W, R ₁₁ , R ₁₂ and t have the same meanings as described for the general formula (T-1).
However, R ₁₁ and R ₁₂ may be bonded to each other to form a benzene ring or a heterocyclic ring. Also, R ₁₁ or R ₁₂
And W may combine to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. Z
_{When 1} is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and t is 2
Then two-[Z ₁ (R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ]-
May be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms. ) Specific examples of the general formula (T-3) are shown in the following "Chemical formula 24" to "Chemical formula 27".

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

(4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, the following groups are the connecting groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1).

General formula (T-4) * -OCO-** General formula (T-5) * -SCS-**

(5) Group Utilizing Iminoketal Cleavage Reaction For example, a linking group described in US Pat. No. 4,546,073, represented by the general formula (T-
It is a group represented by 6).

[0067]

[Chemical 28] (In the formula, * mark, ** mark and W have the same meanings as described in the general formula (T-1), and R ₁₄ has the same meaning as R _13. ) In the general formula (T-6) Specific examples of the group represented are the groups represented by the following "Chemical Formula 29".

[0068]

[Chemical 29]

In the general formula (1), L ₁ is preferably one represented by the general formulas (T-1) to (T-5), particularly preferably the general formulas (T-1) (T-3). And (T-4).

In the general formula (1), j is preferably 0.
Or 1.

In the general formula (1), the group represented by L ₂ represents a trivalent or higher valent timing group, and is preferably a group represented by the following general formula (T-L ₁ ) or (T-L ₂ ). is there.

General formula (T-L ₁ ) *-W- [Z ₁ (R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ] _t -CH
₂ - ** _{(wherein, W, Z 1, Z 2} , R 11, R 12, x, y and t
Represents the same meaning as described for formula (T-3). Further, the * mark represents the position at which it bonds to A- (L ₁ ) _j- in the general formula (1), and the ** mark represents the position at which it bonds to-(L ₃ ) _n -PUG. However, there are multiple R ₁₁ or R
At least one of the ₁₂ is a substituted or unsubstituted methylene group - represents the (L _{3) n} -PUG with binding group. ) As the general formula (T-L ₁ ), W is preferably a nitrogen atom, more preferably W and Z ₂ are bonded to each other to form a 5-membered ring, particularly preferably imidazole, or This is the case of forming a pyrazole ring.

General formula (T-L ₂ ) *-N- (Z ₃ -**) ₂ (wherein, * and ** are synonymous with general formula (T-L ₁ ). Z ₃ group Represents a substituted or unsubstituted methylene group, two Z ₃ groups may be the same or different, and two Z ₃ groups may combine to form a ring.) To the general formula (T-
Specific examples of L ₁ ) and (T-L ₂ ) are shown below, but the present invention is not limited thereto.

[0074]

[Chemical 30]

[0075]

[Chemical 31]

[0076]

[Chemical 32]

[0077]

[Chemical 33]

[0078]

[Chemical 34]

[0079]

[Chemical 35]

[0080]

[Chemical 36]

However, the groups mentioned in the specific examples herein may further have a substituent, and such a substituent is as follows.
For example, an alkyl group (for example, methyl, ethyl, isopropyl, tert-butyl, hexyl, methoxymethyl, methoxyethyl, chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl), an aryl group (for example, phenyl, Naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methoxyphenyl, 2,6-dimethylphenyl, 4-carboxyphenyl, 4-sulfophenyl), heterocyclic group (for example, 2-pyridyl, 4 -Pyridyl, 2-furyl, 2-thienyl, 2-pyrrolyl), halogen atom (eg chloro, bromo), nitro group, alkoxy group (eg methoxy, ethoxy, isopropoxy), aryloxy group (phenoxy), alkyn Thio group (for example, methylthio,
Isopropylthio, tert-butylthio), arylthio group (eg phenylthio), amino group (eg amino, dimethylamino, diisopropylamino), acylamino group (eg acetylamino, benzoylamino), sulfonamide group (eg methanesulfonamide, benzenesulfone) Amido), cyano group, carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (eg phenoxycarbonyl) or carbamoyl group (eg N-ethylcarbamoyl, N-phenylcarbamoyl).

Of these, an alkyl group, a nitro group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, and a carbamoyl group are preferable.

In the general formula (T-L ₁ ), the —CH ₂ — group adjacent to the ** mark may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.

In the general formula (1), m is preferably 1.

The group represented by L ₃ in formula (1) has the same meaning as L ₁ .

In the general formula (1), n is preferably 0 or 1, and particularly preferably 0.

The photographically useful group represented by PUG in the general formula (1) is specifically a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator, a fixing accelerator and the like. Examples of preferred photographically useful groups are described in US Pat. No. 4,24.
Useful photographic groups described in 8,962 (represented by the general formula PUG in the patent), JP-A-62-4935.
Dyes described in U.S. Pat. No. 3, (in the specification, the part of the leaving group released from the coupler), US Pat. No. 4,477,563.
Development inhibitor described in JP-A-61-201
247 and bleaching accelerators described in JP-A-2-55 (in the specification, a part of the leaving group released from the coupler). In the present invention, a development inhibitor is particularly preferable as the photographically useful group.

As the development inhibitor, the following chemical formula 3 is preferable.
7 ”to“ Formula 42 ”represented by the general formula (INH-1) to
It is a group represented by (INH-13).

[0089]

[Chemical 37]

[0090]

[Chemical 38]

[0091]

[Chemical Formula 39] (In the general formula (INH-6), R ₂₁ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group (eg, methyl, ethyl,
Propyl, phenyl). )

[0092]

[Chemical 40]

[0093]

[Chemical 41]

[0094]

[Chemical 42] (In the formula, * represents a position bonded to the group represented by L ₂ or L ₃ of the compound represented by the general formula (1). Further, ** represents a position bonded to the substituent, and the substituent represents Substituted or unsubstituted alkyl groups, aryl groups, heterocyclic groups, alkylthio groups, alkyl or aryloxycarbonyl groups, etc. are included, and groups that decompose in the processing solution during photographic processing are included in these substituents. Is preferred.)

Specific examples of the substituted or unsubstituted alkyl group include methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, tert-butyl, 2-ethylhexyl, 2-methylthioethyl, benzyl, 4-
Methoxybenzyl, phenethyl, 1-methoxycarbonylethyl, propyloxycarbonylmethyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2-cyanoethyloxycarbonylmethyl, 2,2-dichloroethyloxycarbonyl Examples include groups represented by methyl, 3-nitropropyloxycarbonylmethyl, 4-nitrobenzyloxycarbonylmethyl and 2,5-dioxo-3,6-dioxadecyl.

Examples of the substituted or unsubstituted aryl group include phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methylthiophenyl, 3-methoxycarbonylphenyl and 4-
(2-Cyanoethyloxycarbonyl) -phenyl and the like can be mentioned.

The substituted or unsubstituted heterocyclic group is 4
-Pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl, 2-tetrahydropyranyl, and the like.

Examples of the substituted or unsubstituted alkylthio group include methylthio, tert-butylthio and 1-methoxycarbonylethylthio.

Examples of the substituted or unsubstituted alkyl or aryloxycarbonyl group include methoxycarbonyl, butoxycarbonylmethoxycarbonyl, isopentyloxycarbonylmethoxycarbonyl, N-hexylcarbamoylmethoxycarbonyl and phenoxycarbonyl.

Of these, INH (development inhibitor) is preferably represented by the general formulas (INH-1), (INH-2),
(INH-3), (INH-4), (INH-9) and (INH-12), particularly preferably the general formula (I
NH-1), (INH-2) and (INH-3).

Further, the substituent bonded to INH is preferably an alkyl group, a substituted or unsubstituted phenyl group, or an alkyl or aryloxycarbonyl group.

The compound represented by the general formula (1) is particularly preferably a compound represented by the following general formula (1a) or (1b).

General formula (1a) A (L ₁ ) _j -W- [Z ₁ (R ₁₁ ) _x = Z
_{2 (R 12) y] t} -CH 2 -PUG general formula _{(1b) A-L 1 -N-} (Z 3 -PUG) symbol ₂ wherein the general formula (1), (T-L 1) and (T-
Synonymous with L ₂ ). In the general formula (1a), j is preferably 0 or 1. In formulas (1a) and (1b), L ₁ is preferably a —OC (═O) — group, and PUG is preferably a development inhibitor.

However, when a plurality of photographically useful groups have different functions, the timing group does not utilize intramolecular nucleophilic substitution.

The function of the photographically useful group means the function exhibited by a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator or a fixing agent.

Further, it is particularly preferable that the two or more PUGs released from the same compound are the same development inhibitor.

Next, the compound represented by formula (2) will be described. In the general formula (2), A and PUG have the same meaning as in the general formula (1). L ₄ is -OCO- group, -OSO
- based on -OSO ₂ - group, -OCS- group, -SCO- group, -
SCS- group or -WCR ₁₁ R ₁₂ - represents a group. Here, W, R ₁₁ and R ₁₂ have the same meaning as defined in the general formula (T-1) in the description of L ₁ of the compound represented by the general formula (1).

When L ₄ represents a --WCR ₁₁ R ₁₂ --group, a preferred example is when W represents an oxygen atom or a tertiary amino group, and more preferably L ₄ represents --OCH _2-.
A group or W and R ₁₁ or R ₁₂ represents a group forming a ring.

[0109] The L ₄ is -WCR ₁₁ R ₁₂ - preferably -OCO- group may represent a group other than, -OSO- group, -O
SO ₂ - is a group, particularly preferably -OCO- group.

The group represented by L ₅ represents a group which releases PUG by electron transfer along the conjugated system or a group defined by L ₄ . Group is represented by formula which releases PUG by electron transfer along a conjugated system (1) formula in the description of L ₁ of (T-
It has the same meaning as the group represented by 3). L ₅ is preferably a group which releases PUG by electron transfer along a conjugated system, and more preferably a group which can be bonded to L ₄ by a nitrogen atom.

Among the compounds represented by the general formula (2), preferred are compounds represented by the general formula (3) represented by the following "Chemical Formula 43" or the general formula (4) represented by the following "Chemical Formula 44". .

General formula (3)

[Chemical 43] (In the formula, A has the same meaning as in formula (1). R ₁₀₁ and R
₁₀₂ each independently represents a hydrogen atom or a substituent. R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or a substituent. INH represents a group having a development inhibiting ability. R ₁₀₅ is an unsubstituted phenyl group, a primary alkyl group, an alkylthio group, a primary alkyl group substituted with a group other than an aryl group, or —CO ₂ C (R ₁₀₁ ) (R ₁₀₈ ) CO ₂
It represents a group represented by R ₁₀₆ . However, at least one of R _{101 to} R ₁₀₄ is a substituent other than a hydrogen atom. )

General formula (4)

[Chemical 44]

In the general formula (4), A, INH and R ₁₀₅ have the same meanings as in the general formula (3). R ₁₁₁ , R ₁₁₂
And R ₁₁₃ each represent a hydrogen atom or an organic residue, and any two of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ may be a divalent group to be linked to form a ring. )

The compound represented by formula (3) will be described in more detail. In the general formula (3), A has the same meaning as in the general formula (1). R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or a substituent. Specific examples of the substituent include an aryl group (eg, phenyl, naphthyl, p-methoxyphenyl, p-hydroxyphenyl,
p-nitrophenyl, o-chlorophenyl), an alkyl group (for example, methyl, ethyl, isopropyl, propyl,
tert-butyl, tert-amyl, isobutyl, s
ec-butyl, octyl, methoxymethyl, 1-methoxyethyl, 2-chloroethyl, nitromethyl, 2-cyanoethyl, 2-carbamoylethyl, 2-dimethylcarbamoylethyl), halogen atom (eg fluoro, chloro, bromo, iodo), alkoxy Groups (eg methoxy, ethoxy, isopropyloxy, propyloxy,
tert-butyloxy, isobutyloxy, butyloxy, octyloxy, 2-methoxyethoxy, 2-chloroethoxy), aryloxy groups (eg phenoxy, naphthoxy, or p-methoxyphenoxy), alkylthio groups (eg methylthio, ethylthio, isopropylthio, Propylthio, tert-butylthio, isobutylthio, sec-butylthio, octylthio or 2-methoxyethylthio), arylthio groups (eg phenylthio, naphthylthio, or p-methoxyphenylthio), amino groups (eg amino, methylamino,
Phenylamino, dimethylamino, diethylamino, diisopropylamino, or phenylmethylamino),
A carbamoyl group (for example, carbamoyl, methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl,
Diisopropylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl, tert-butylcarbamoyl, phenylcarbamoyl or phenylmethylcarbamoyl etc.), sulfamoyl group (eg sulfamoyl, methylsulfamoyl, ethylsulfamoyl, isopropylsulfamoyl, phenylsulfamoyl,
Octylsulfamoyl, dimethylsulfamoyl, diethylsulfamoyl, diisopropylsulfamoyl, dihexylsulfamoyl or phenylmethylsulfamoyl), alkoxycarbonyl (eg methoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, tert- Butyloxycarbonyl, tert-amyloxycarbonyl, or octyloxycarbonyl), aryloxycarbonyl (eg phenoxycarbonyl or p-methoxyphenoxycarbonyl), acylamino group (eg acetylamino, propanoylamino, pentanoylamino, N
-Methylacetylamino, or benzoylamino),
A sulfonamide group (for example, methanesulfonamide, ethanesulfonamide, pentanesulfonamide, benzenesulfonamide or p-toluenesulfonamide),
Alkoxycarbonylamino groups (eg methoxycarbonylamino, isopropyloxycarbonylamino, t
ert-butoxycarbonylamino or hexyloxycarbonylamino), aryloxycarbonylamino groups (eg phenoxycarbonylamino), ureido groups (eg 3-methylureido, or 3-phenylureido), cyano groups or nitro groups.

R ₁₀₁ and R ₁₀₂ may be the same or different, but the sum of the formula weights of both is preferably less than 120. Moreover, an alkyl group, a halogen atom, and an alkoxy group are mentioned as a preferable substituent, and an alkyl group is preferable.

In formula (3), the groups represented by R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include methyl, ethyl, isopropyl, tert-butyl, isobutyl, hexyl and 2-methoxyethyl. R
₁₀₃ and R ₁₀₄ are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

In the general formula (3), the group represented by R ₁₀₅ is an unsubstituted phenyl group, a primary alkyl group, an alkylthio group, a primary alkyl group substituted with a group other than an aryl group, or —CO ₂ C (R ₁₀₇ ) (R ₁₀₈ ) CO ₂ R
Represents a group represented by ₁₀₆ . Examples of the alkyl group include ethyl, propyl, butyl, isobutyl, pentyl,
Examples include isopentyl, 2-methylbutyl, hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, heptyl, or octyl. Examples of the substituent include a halogen atom, an alkoxy group, an alkylthio group, an amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group, a cyano group or a nitro group. , R ₁₀₁ and R ₁₀₂ are specific examples of the respective groups.
Among the substituents mentioned in (1), those excluding the group containing an aryl group can be mentioned.

R ₁₀₆ represents an unsubstituted alkyl group having 3 to 6 carbon atoms (eg, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl). R ₁₀₇ , R
₁₀₈ is a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl,
Butyl, pentyl, hexyl, octyl) and R
₁₀₇ and R ₁₀₈ may be the same or different.

Further, R ₁₀₅ may be substituted with two or more kinds of substituents. The substituent of R ₁₀₅ is preferably fluoro, chloro, alkoxy group, carbamoyl group, alkoxycarbonyl group, cyano group or nitro group. Of these, an alkoxycarbonyl group is particularly preferable.

R ₁₀₅ is preferably a phenyl group,
Alternatively, a primary unsubstituted alkyl group having 2 to 6 carbon atoms,
R in CO ₂ C (R ₁₀₇ ) (R ₁₀₈ ) CO ₂ R _106
106 is an unsubstituted alkyl group having 3 to 6 carbon atoms, and R ₁₀₇ and R ₁₀₈ are both a hydrogen atom-containing group or a primary alkyl group substituted with the group mentioned above as a preferable substituent for R ₁₀₅ . Particularly preferred is a primary unsubstituted alkyl group having 3 to 5 carbon atoms or a primary alkyl group substituted with an alkoxycarbonyl group.

The group represented by INH in the general formula (3) represents a group having a development inhibitor, and specific examples thereof are the general formula (INH-1) mentioned in the description of PUG of the general formula (1).
(INH-13). The preferable range and the like are also the same as those in the general formula (1).

Next, the compound represented by formula (4) will be described in detail.

First, the case where each of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ represents a hydrogen atom or a monovalent organic group will be described.

When R ₁₁₂ and R ₁₁₃ represent a monovalent organic group, the organic group is preferably an alkyl group (eg methyl, ethyl) or an aryl group (eg phenyl). At least one of R ₁₁₂ and R ₁₁₃ is preferably a hydrogen atom, and particularly preferably when R ₁₁₂ and R ₁₁₃ are hydrogen atoms.

R ₁₁₁ represents an organic group and is preferably the following groups. Alkyl groups (eg methyl, isopropyl, butyl, isobutyl, tert-butyl, sec
-Butyl, neopentyl, hexyl), aryl groups (eg phenyl), acyl groups (eg acetyl, benzoyl), sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg ethylcarbamoyl, phenylcarbamoyl), sulfamoyl groups (eg Ethylsulfamoyl, phenylsulfamoyl), alkoxycarbonyl group (eg ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl, 4-methylphenoxycarbonyl), alkoxysulfonyl group (eg butoxysulfonyl, ethoxysulfonyl). , An aryloxysulfonyl group (eg, phenoxysulfonyl, 4-
Methoxyphenoxysulfonyl), cyano group, nitro group, nitroso group, thioacyl group (eg thioacetyl,
Neobenzoyl), thiocarbamoyl group (eg ethylthiocarbamoyl), imidoyl group (eg N-ethylimidoyl), amino group (eg amino, dimethylamino, methylamino), acylamino group (eg formylamino, acetylamino, N-). Methylacetylamino), alkoxy groups (eg methoxy, isopropyloxy), or aryloxy groups (eg phenoxy)
Is.

Further, these groups may further have a substituent, and examples of the substituent include the group mentioned as R ₁₁₁ , halogen atom (for example, fluoro, chloro, bromo), carboxyl group and sulfo group. To be

As R ₁₁₁ , the number of atoms other than hydrogen atoms is preferably 15 or less.

Further, R ₁₁₁ is more preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted or unsubstituted alkyl group.

Next, in the groups represented by R ₁₁₁ , R ₁₁₂ and R ₁₁₃ , the case where any two of these groups become a divalent group and are linked to form a ring will be described.

The size of the ring formed is preferably a 4- to 8-membered ring, more preferably a 4- to 6-membered ring.

The divalent group is preferably the following groups.

-C (= O) -N (R ₁₁₄ )-, -SO _{2
-N (R 114) -, -} (CH 2) 3 -, - (CH 2) 4
_{-, - (CH 2) 5} -, - C (= O) - (CH 2)
_2- , -C (= O) -N ( _R114 ) -C (= O)-,-
_{SO 2 -N (R 114) -C} (= O) -, - C (= O) -
_{C (R 114) (R 115} ) -, - (CH 2) 2 -O-CH
_2- .

Here, R ₁₁₄ and R ₁₁₅ are synonymous with the case where a hydrogen atom or R ₁₁₁ represents a monovalent organic group,
R ₁₁₄ and R ₁₁₅ may be the same or different.

Of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ , the remaining groups that do not participate as a divalent group represent a hydrogen atom or a monovalent organic group, and specific examples of the organic group are the same as those shown when R is not formed. _The same as in the case of ₁₁₁ , R ₁₁₂ , and R ₁₁₃ .

Any two of R ₁₁₁ , R ₁₁₂ , and R ₁₁₃
When two are combined to form a ring, preferably R ₁₁₂ and R
_{One of 113} is a hydrogen atom, and the remaining R ₁₁₂ to R ₁₁₃ form a ring with R _111. More preferably, the left end of the divalent group mentioned above is a nitrogen atom of the general formula (4). In this case, the right end is bonded to a carbon atom.

Further, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ preferably do not form a ring and each represents a hydrogen atom or a monovalent organic group.

In the general formulas (1) and (2), A and P
The formula weight of the residue excluding the group represented by UG is 64 or more 24
It is preferably 0 or less, more preferably 70 or more and 200 or less, and particularly preferably 90 or more and 180 or less.

Specific examples of the compounds represented by the general formulas (1) to (4) of the present invention are shown below, but the present invention is not limited thereto.

Regarding the compounds in which A represents a coupler residue in the general formula (1), the numbers prefixed with (CA) and those in the general formulas (2) to (4) in which A represents a coupler residue are described. Is a number with (CB) attached to its head, and those of general formulas (1) to (4) in which A represents a redox group are indicated with a number attached with (SA).

[0141]

[Chemical formula 45]

[0142]

[Chemical formula 46]

[0143]

[Chemical 47]

[0144]

[Chemical 48]

[0145]

[Chemical 49]

[0146]

[Chemical 50]

[0147]

[Chemical 51]

[0148]

[Chemical 52]

[0149]

[Chemical 53]

[0150]

[Chemical 54]

[0151]

[Chemical 55]

[0152]

[Chemical 56]

[0153]

[Chemical 57]

[0154]

[Chemical 58]

[0155]

[Chemical 59]

[0156]

[Chemical 60]

[0157]

[Chemical formula 61]

[0158]

[Chemical formula 62]

[0159]

[Chemical formula 63]

[0160]

[Chemical 64]

[0161]

[Chemical 65]

[0162]

[Chemical formula 66]

[0163]

[Chemical formula 67]

[0164]

[Chemical 68]

[0165]

[Chemical 69]

[0166]

[Chemical 70]

[0167]

[Chemical 71]

[0168]

[Chemical 72]

[0169]

[Chemical formula 73]

[0170]

[Chemical 74]

[0171]

[Chemical 75]

[0172]

[Chemical 76]

[0173]

[Chemical 77]

[0174]

[Chemical 78]

[0175]

[Chemical 79]

The compounds of the present invention can be synthesized by, for example, US Pat. Nos. 4,847,383, 4,770,990, 4,684,604, 4,886,736, and US Pat.
JP-A-60-218645 and 61-230135.
No. 2, Japanese Patent Application No. 2-307070, No. 2-170832,
The method described in JP-A-2-251192 or a similar method can be used.

Specific synthetic examples will be described below. (Synthesis Example 1) Synthesis of Exemplified Compound (CA-1) The compound was synthesized by the synthetic route shown in the following "Chemical Formula 80".

[0178]

[Chemical 80] CA-1a (3.40 g) represented by "Chemical Formula 80" above
Was reacted in thionyl chloride (30 ml) at 60 ° C. for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure. This residue was treated with CA-1b (7.48 g) and diisopropylethylamine (10.5 ml) in dimethylformamide (0.
℃) and stirred for 1 hour. Then add this solution to water (50
0 ml) and the resulting crystals were collected by filtration to obtain CA
-1c was obtained as a crude crystal of 9.8g. The structure was confirmed by NMR.

CA-1c (3.20 g) and CA-1d
(1.38 g) of 1,2-dichloroethane (30 ml)
The reaction was carried out for 1 hour. There, CA-1e (3.20
A solution of g) in ethyl acetate (20 ml) was added under water cooling, diisopropylethylamine (4.5 ml) was added subsequently, and the mixture was stirred for 1 hour.

The reaction was stopped with 1N hydrochloric acid, and chloroform (30 ml) was added to dilute the reaction solution. After that, the reaction solution was washed with water three times, and the organic layer was dried over sodium sulfate. The oily substance obtained by distilling off the organic solvent was subjected to silica gel column chromatography (ethyl acetate: hexane = 1: 1).
Exemplified compound CA-1 was purified by 1.
20 g was obtained. The structure was confirmed by NMR. m. p.
133.0-134.0 ° C.

(Synthesis Example 2) Synthesis of Exemplified Compound (CA-12) It was synthesized by the synthetic route shown in the following "Chemical Formula 81".

[0182]

[Chemical 81] CA-12a (10.7 g) and 37% formalin aqueous solution (30 ml) were reacted in acetic acid (100 ml) at 70 ° C. for 5 hours, and then the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (ethyl acetate: hexane = 2:
By purifying in 1), 6.4 g of CA-12b was obtained.
(Yield 53%) was obtained.

Next, CA-12b (3.2 g) and CA-1
2c (2.1 g) was suspended in chloroform (40 ml), zinc iodide (5.7 g) was added thereto, and the mixture was reacted at room temperature for 2 hours. Stop the reaction with 1N hydrochloric acid and chloroform 40 ml.
After diluting with, the reaction solution was washed twice with water. The organic layer was dried over sodium sulfate and concentrated, and the residue obtained was subjected to silica gel column chromatography (ethyl acetate: hexane = 1: 1).
Exemplified compound (CA-12) by purification in 4)
4.1 g (yield 25%) was obtained. The structure is NMR, mass,
Confirmed by elemental analysis.

(Synthesis Example 3) Synthesis of Exemplified Compound (CB-2) It was synthesized by the synthetic route represented by the following "Chemical Formula 82".

[0185]

[Chemical formula 82] CB-2a (10 mmol) was added to chloroform (30 m
l) and suspended therein, thionyl chloride (20 mmol)
Is added and reacted at 50 ° C. for 1 hour, and then the solvent is distilled off. The residue obtained here was added to a solution of CB-2b (10 mmol) and diisopropylethylamine (20 mmol) in dimethylformamide (30 ml), reacted for 1 hour, and then poured into ice water (200 ml). 50 ml of chloroform
Was added and stirred, then the aqueous phase was separated, and the organic layer was washed with water (100 m
CB-2c was obtained by further washing twice with l), drying over sodium sulfate and concentrating.

The CB-2c thus obtained was mixed with chloroform (30
ml), and nitrophenyl chlorocarbonate (1
0 mmol) was added and reacted for 1 hour, and then CB-2b (1
A solution of 0 mmol) in ethyl acetate (50 ml) is added, diisopropylethylamine (50 mmol) is further added, and the mixture is reacted for 1 hour. The reaction was stopped by adding 1N hydrochloric acid (10 ml) and then diluted with ethyl acetate (10 ml). The organic layer is washed with water, dried over sodium sulfate and concentrated. The obtained residue is purified by silica gel column chromatography (eluent ethyl acetate: hexane = 1: 3) to obtain 1.94 g (yield 23% yield) of Exemplified compound CB-2. m. p. 101.5-102.5 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (CB-3) The compound was synthesized by the synthetic route represented by the following "Chemical Formula 83".

[0188]

[Chemical 83] It can be synthesized using (CB-3a) as a raw material by the same method as for the exemplified compound CB-2. Yield 31%. m.
p. 68.0-69.0 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (CB-11) It was synthesized by a synthetic route represented by the following "Chemical Formula 84".

[0190]

[Chemical 84] (CB-11a) 200g and (CB-11b) 34.7
g was dissolved in ethyl acetate (500 ml), diisopropylethylamine (142 ml) was added thereto, and the mixture was stirred for 4 hours. The precipitated crystals were collected by filtration and washed with ethyl acetate to obtain 176 g (75%) of (CB-11c).

53.6 g of (CB-11c) and paraformaldehyde (27.9 g) were refluxed in a mixture of 1,2-dichloroethane (500 ml) and acetic acid (54 ml) under reflux.
Reacted for hours. After cooling to room temperature, the reaction solution was washed with water, dried over anhydrous sodium sulfate and concentrated. The obtained residue was purified by silica gel column chromatography using chloroform as an eluent to give (CB-11d) 2
Obtained 3.2 g (41.2%).

(CB-11d) 23.2 g and (CB-1
6.78 g of 1e) was dissolved in chloroform (250 ml), 26.88 g of zinc iodide was added thereto, and the mixture was stirred for 3 hours. After adding 1N hydrochloric acid, the reaction solution was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated, and the obtained residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 4) to give the exemplified compound (CB
-11) was obtained by 7.0 g (23.9%). m. p. 11
7.0 to 118.5 ° C.

Synthesis Example 6 Synthesis of Exemplified Compound (CB-13) It was synthesized by the same method as in Synthesis Example 5. m. p. 61.
5-63.0 ° C.

(Synthesis Example 7) Synthesis of Exemplified Compound (CB-19) The compound can be synthesized by the same method as in Synthesis Example 2 of JP-A-60-218645. Yield 7%. m. p. 115
° C.

(Synthesis Example 8) Synthesis of Exemplified Compound (SA-5) The compound was synthesized by the synthetic route represented by the following "Chemical Formula 85".

[0196]

[Chemical 85] 11.6 g of SA-5a (synthesized by a method similar to the method described in JP-A-61-230135) was added to 30 ml of thionyl chloride under water cooling and the reaction was continued at 50 ° C. for another hour. Excess thionyl chloride was distilled off under reduced pressure, and the precipitated crystals were washed with a small amount of ice-cold chloroform to give SA.
-5b was obtained as crude crystals. Then SA-5b 13.1g
To a solution of 7.2 g of SA-5c and 12.1 g of triethylamine in N, N-dimethylformamide (100 ml).
The mixture was added at 0 ° C., and further reacted at room temperature for 1 hour.

The reaction mixture was poured into an aqueous solution of 60 ml of 2N hydrochloric acid and 300 ml of ice water, and 300 ml of ethyl acetate was further added and stirred. The liquid was transferred to a separatory funnel, the oil layer was taken, and washed several times with water. The organic layer was dried over anhydrous sodium sulfate,
After concentration, the residue was purified by silica gel column chromatography (ethyl acetate-hexane = 1/4 to 1/1 (v /
(v) was used as an eluent) to obtain 3.7 g of Exemplified Compound SA-5 as an amorphous substance.

The compound represented by formula (1) or (2) of the present invention may be added to any layer in the light-sensitive material, but is preferably added to the light-sensitive emulsion layer and / or its adjacent layer. It is particularly preferable to add to the red-sensitive emulsion layer and / or the green-sensitive emulsion layer. When the same color-sensitive layer is divided into two or more layers having different sensitivities, they may be added to any of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer.

The total amount added to the light-sensitive material is 0.0
01-1.0 g / m ² , preferably 0.010-
0.5 g / m ² , more preferably 0.020 to 0.40
g / m ² , more preferably 0.030 to 0.30 g / m
^{Is 2} .

When the compounds of the general formula (1) and the general formula (2) are used in combination, the mixing ratio can be arbitrarily selected and there is no particular limitation. Further, the compound of the general formula (1) or the general formula (2) and a development inhibitor-releasing compound other than the present invention can be used in combination depending on the purpose.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a silver halide emulsion layer, provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a support. A silver halide photographic light-sensitive material is a unit photosensitive layer having a color sensitivity to any of blue light, green light and red light. In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer may be formed, for example, in JP-A-61-43.
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038, and a coupler and a DIR compound may be contained.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the publications, etc., a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H or the like.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. A silver halide emulsion layer having a lower photosensitivity than that of the silver halide emulsion layer may be disposed, and the photosensitivity may be sequentially decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
Nos. 63-89850 and BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochloroodor containing about 30 mol% or less of silver iodide. It is silver oxide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry (Focal Press, 19
66)), "Production and Coating of Photographic Emulsions" by Zelikmann et al.,
Published by Focal Press (VL Zelikman e
tal. , Making and Coating P
photographicEmulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628
No. 3,655,394 and British Patent No. 1,41
The monodisperse emulsions described in 3,748 are also preferred.

Tabular grains having an aspect ratio (circular equivalent diameter of silver halide grains / grain thickness) of about 3 or more can also be used in the present invention. Tabular grains are written by Gatov,
Photographic Science and Engineering (Gutoff, Photographic S
Science and Engineering), Volume 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520. No. 2,112,157 and the like, and can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image on both the surface and inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-
No. 133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises the light-sensitive silver halide emulsion grain size, grain size distribution, halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The amount of silver coated on the light-sensitive material of the present invention is 3 to 8 g.
/ M ² or less is preferable, and 4 to 7 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
European Patent Nos. 249,473A and 447,969A
Nos. 482,552A are preferable.

As the magenta coupler, in addition to the coupler represented by the general formula (M) of the present invention, 5-pyrazolone compounds and pyrazoloazole compounds other than the present invention may be used depending on the purpose. You can For example, U.S. Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
32, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-
No. 43659, No. 61-72238, No. 60-357.
No. 30, No. 55-118034, No. 60-18595
1, U.S. Pat. Nos. 4,500,630 and 4,54.
0,654, 4,556,630, International Publication W
The compounds described in O88 / 04795 can be used.

Examples of cyan couplers include phenol-based and naphthol-based couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in U.S. Pat. No. 4,849,639 and the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and US Pat.
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
46,368, JP-A-3-177837 and EP 423,727A are preferable. Also,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler releasing a development inhibitor is, in addition to the compounds represented by the above general formulas (1) and (2) of the present invention,
RD17643, VII-F section and No. Thirty
7105, Patents described in VII-F, JP-A-57
-151944, 57-154234, 60-
184248, 63-37346, 63-37.
350, U.S. Pat. Nos. 4,248,962 and 4,78.
2,012, European Patents 464,612A, 4th
Those described in No. 82,552A are preferable.

For example, R. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
The compounds described in JP-A-45687, which release a fogging agent, a development accelerator, a silver halide solvent and the like by a redox reaction with an oxidized product of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The photographic material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-272.
248, and 1, described in JP-A No. 1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various antiseptics or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-described conditions according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, it is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 15
0 to 500% is preferable.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-β-methoxyethylaniline, 3-methyl-4-amino-described in EP 410,450A.
N-ethyl-N-4-hydroxybutylaniline, 1- (4-amino-3-ethylphenyl) -2,5-bis- (2-hydroxyethyl) pyrrolidine described in JP-A-4-11255 and their derivatives. Sulfate, hydrochloride or p
-Toluene sulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, for example, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and catecholsulfonic acid, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol , Polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Iminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be added.

When the reversal processing is carried out, black and white development is usually carried out before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L (liter) or less per square meter of the light-sensitive material, and it is possible to reduce the bromide ion concentration in the replenishing solution by 50%.
It can be 0 ml or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Treatment Liquid Volume (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to
It is 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the surface of the photographic processing liquid in the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit developing treatment method described in No. 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The time of color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature and high pH and using a high concentration of color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are iron (III) complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebath.
Specific examples of useful bleaching accelerators include, for example, U.S. Pat. No. 3,893,858 and West German Patent 1,290,81.
2, No. 2,059,988, JP-A-53-3273.
No. 6, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53
-95631, No. 53-104232, No. 53-1
No. 24424, No. 53-141623, No. 53-28
No. 426, Research Declosure No. 1712
No. 9 (July 1978), compounds having a mercapto group or a disulfide group; JP-A-50-1401.
Thiazolidine derivatives described in No. 29; JP-B-45-85
06, JP-A-52-20832, and JP-A-53-3273.
5, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 96
6,410, 2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-40,943.
No. 49-59,644, and 53-94,927.
No. 54, 35-727, 55-26, 506.
No. 58-163940, and bromide ions. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858,
West German Patent No. 1,290,812, JP-A-53-95,
The compounds described in No. 630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, a combined use of a thiosulfate solution and a thiocyanate, a thioether compound, or thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294769.
The sulfinic acid compounds described in No. A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add imidazoles such as methylimidazole in an amount of 0.1 to 10 mol / L.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method of strengthening the stirring, a method of causing a jet stream of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and a rotating means described in JP-A-62-183461 are used. To improve the stirring effect, and further to move the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution to make the emulsion surface turbulent, thereby further improving the stirring effect, the entire processing solution. There is a method of increasing the circulation flow rate of. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the development processing of the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society.
of Motion Picture and Tel
Evolution Engineers, Volume 64, 24
It can be determined by the method described on pages 8-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. The problem arises. In the processing of the light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
Isothiazolone compounds and siabendazoles described in No. 8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles by Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology" (198
2 years) The bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In some cases, the washing treatment is further followed by a stabilizing treatment. As an example thereof, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. Can be mentioned. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic processor or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material according to the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. .

The silver halide color light-sensitive material according to the present invention contains various types of 1-color image forming materials for the purpose of promoting color development, if necessary.
-Phenyl-3-pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339 and JP-A-57-1.
44547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0272]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
The term "unit body with a photographing function" used in the following description refers to a constituent part of the photographic product with a built-in photosensitive material, which is a product of the present invention, excluding the color photosensitive material.

[Preparation of Unit Body with Photographing Function] Sample A of Photographing Unit Main Body FIG. 2 shows an external view of a lens-fitted film unit (photographic product with a light-sensitive material having an exposure function) according to the present invention. ing. This film unit with lens 2
Is composed of a unit main body 3 with a photographing function and an outer case 4 for housing the same. The outer case 4 is provided with holes for exposing the winding knob 5, the stroboscopic light emitting section 6, the shutter button 7, the lens hood 8, the object side viewfinder window 9a, the eyepiece side viewfinder window 9b, the number-of-images display panel 10, and the like. Therefore, the photographing operation can be performed with the camera housed in the outer case 4.

FIG. 3 shows the unit main body 3 with the photographing function.
It shows the state of disassembling. The unit main body 3 is composed of a main body base 12, a rear cover 13, and a front cover 14, and the main body base 12 has an exposure opening 16 arranged on the optical axis 15.
On both sides of the cartridge storage room 17 and film roll room 18
And are formed. The front surface of the outer wall of the cartridge storage chamber 17 has a shape projecting more forward than the front surface of the outer wall of the film roll chamber 18, and this portion can be used as a grip during photographing.

On the cartridge storage chamber 17, a winding knob 5 that engages with the axis of the cartridge is rotatably provided. The shaft center of the cartridge is engaged with the winding knob 5. On the front surface of the main body base 12, a strobe unit 22 including a battery 20 and a switch contact piece 21, a shutter mechanism with a shutter speed of 1/100 seconds, a film winding mechanism,
And an exposure unit 23 having a finder optical section and the like, and finally fixed by the front cover 14. The exposure unit 23 is attachable to and detachable from the main body base 12 by snap connection.

FIG. 1 is a sectional view of the photographing optical system portion of the exposure unit 23. Aperture aperture 25 corresponding to aperture value 11
A front aspherical convex meniscus lens 26 and a biconvex spherical lens 27 are provided on the optical axis 15 of the shutter cover 25 in which a is formed.
A photographic optical system with a two-lens configuration consisting of
The focal length of the entire photographing optical system is 32 mm. The two lenses 26 and 27 are inserted into a receiving cylinder 30 of the shutter cover 25 with a spacer 28 sandwiched therebetween, and an annular lens holder 31 is attached to the front surface of the receiving cylinder 30 so that the photographic optical system is formed. It is held by the exposure unit 23.

Therefore, in the photographing optical system of the unit main body sample A with the exposure function, the total focal length is 32 mm,
The lens configuration has two optical elements, a front aspherical convex meniscus lens and a biconvex spherical lens, an aperture value of F11, and a shutter speed of 1/100 second (fixed). In addition,
The focal length of the photographing optical system may be 28 mm or more, but if it exceeds 80 mm, the unit main body 3 with an exposure function is used.
Is considerably thick and is not very practical in view of the usage form of the photographic product targeted by the present invention. Also,
If the focal length is less than 28 mm, the manufacturing cost of the photographing optical system itself and the number of assembling steps increase in order to satisfactorily correct the distortion in the peripheral portion of the screen, which is not suitable for the photographic product of the present invention which is premised on cost reduction. .

Unit body sample B with photographing function This unit body sample B with photographing function has basically the same configuration as the unit body A with photographing function described above, except that the photographing optical system is as shown in FIG. Is different. That is, the spherical monocular lens 42 having a focal length of 32 mm is held between the front cover 41 and the exposure unit 40 in which the small hole 40a corresponding to the aperture value 11 is formed,
The aperture value is 11 and the shutter speed is 1/100 second (fixed).

[Preparation of Color Light-Sensitive Material] On the undercoated cellulose triacetate film support, each layer having the composition shown below was multilayer-coated to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ⁻³ HBS-1 0.16

Second Layer (Intermediate Layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 0.75

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.11 ExC-3 0.045 ExC-4 0.07 ExC-5 0.0050 ExC-7 0.001 CB-13 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0 .87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.0 × 10 ⁻⁴ ExS-2 1.2 × 10 ⁻⁵ ExS-3 4.0 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.055 ExC-4 0.085 ExC-5 0.007 CB-13 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.62 ExS-1 2.0 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁵ ExS-3 3.0 × 10 ⁻⁴ ExC-1 0.125 ExC-3 0.040 ExC-6 0.010 CB-13 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.60

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 polyethyl acrylate latex 0.19 gelatin 1.30

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.24 Emulsion B Silver 0.10 Emulsion C Silver 0.14 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ^-4 ExS-6 6.5x10 ^-4 ExM-1 0.005 M-13 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0 .80

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.94 ExS-4 2.0 × 10 ⁻⁵ ExS-5 1.4 × 10 ⁻⁴ ExS-6 5.4 × 10 ⁻⁴ M-3 0.08 M-16 0.08 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.29 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.011 ExM-1 0.016 M-21 0.046 M-20 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.57

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.10 HBS-1 0.055 gelatin 0.70

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 Emulsion D Silver 0.10 ExS-7 8.0 × 10 ⁻⁴ ExY-1 0.010 ExY− 2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.30 ExS-7 3.0 × 10 ⁻⁴ ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1 .13

Thirteenth Layer (First Protective Layer) UV-2 0.08 UV-3 0.11 UV-5 0.26 HBS-1 0.09 Gelatin 2.40

Fourteenth layer (second protective layer) Emulsion G Silver 0.10 H-1 0.37 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0 .10 B-3 0.10 S-1 0.20 gelatin 0.75

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt.

[0295]

[Table 1]

In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

[0297]

[Chemical 86]

[0298]

[Chemical 87]

[0299]

[Chemical 88]

[0300]

[Chemical 89]

[0301]

[Chemical 90]

[0302]

[Chemical Formula 91]

[0303]

[Chemical Formula 92]

[0304]

[Chemical formula 93]

[0305]

[Chemical 94]

[0306]

[Chemical 95]

[0307]

[Chemical 96]

[0308]

[Chemical 97]

[0309]

[Chemical 98]

[0310]

[Chemical 99]

[0311]

[Chemical 100]

[0312]

[Chemical 101]

For Sample 101, the magenta coupler (M-13) used in the seventh layer (low-sensitivity green-sensitive emulsion layer) was used as the comparative coupler (1), and the magenta coupler (M-3) used in the eighth layer. ), (M-16) as a comparison coupler (1),
In (2), the magenta coupler (M-2
Sample 102 was prepared in exactly the same manner as Sample 101, except that 1) and (M-20) were replaced with comparative couplers (2) and (3) in equimolar amounts, respectively. The comparative couplers (1), (2) and (3) are shown in "Chemical Formula 102".

[0314]

[Chemical 102]

The present invention used for Sample 101 in the third layer (low-sensitivity red-sensitive emulsion layer), the fourth layer (medium-sensitivity red-sensitive emulsion layer), and the fifth layer (high-sensitivity red-sensitive emulsion layer). Sample 101 except that the compound CB-13, which is preferably used in
Sample 103 was prepared in exactly the same manner as in.

Samples 101 to 103 include a light-sensitive layer closest to the support, and the total thickness of the layers provided on the opposite side of the support is 19.0 μm, the ISO sensitivity is about 800, and the total silver content is about 800. The coating amount was 7.7 g / m ² .

Sample 104 was prepared by increasing the coating amount of the thirteenth layer (first protective layer) to 1.5 times that of sample 101. The total film thickness of the layer group including the photosensitive layer closest to the support of Sample 104 and provided on the side opposite to the support was 20.
It was 2 μm.

Sample 105 was prepared by increasing the coating amount of the twelfth layer (high-sensitivity blue-sensitive emulsion layer) to 1.5 times that of sample 101. The total silver coating amount of sample 105 was 8.4 g /
It was m ² . (The film thickness was 19.7 μm.)

Samples 106, 107 and 108 were prepared by adjusting the grain size of the emulsion with respect to sample 101. The ISO sensitivities of the samples 106, 107 and 108 were about 600, 400 and 200, respectively.

[Preparation of Photographic Product Incorporating Photosensitive Material] Samples 101 to 1 obtained by preparing the above color photosensitive material.
08 was cut and processed, stored in a normal metal cartridge, and the cartridge was stored in the cartridge storage chamber 17 of the unit body samples A and B obtained in the preparation of the unit body with the exposure function.
Then, the color photosensitive material which was pulled out from the cartridge and formed into a roll was housed in the film roll chamber 18 to obtain a photographic product having a built-in photosensitive material.

[Preparation of Practical Skills, Development, and Preparation of Prints] Using these photographic products with a built-in light-sensitive material, in fine weather and under normal light (at this time, the illuminance was about 30,000 lux, and the so-called LV value was 13). A person was placed at a distance of 5 m in the center, and a landscape with mountains, forests and houses in the background was photographed.

The photographed color light-sensitive material was developed by the following method and printed on Fuji Color Paper SUPER FAV by a usual method. (Processing method) Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 3 minutes 00 seconds 38 ℃ Washing with water 30 seconds 24 ℃ Settling 3 minutes 00 seconds 38 ℃ Washing with water (1) 30 seconds 24 ℃ Washing with water (2 ) 30 seconds 24 ℃ Stabilization 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,12.0-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid Adjusted by) 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid 100.0 Sodium ferric trihydrate, Disodium salt of ethylenediaminetetraacetic acid 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0

(Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution 295.0 ml (700 g / liter) Acetic acid (90%) 3.3 Add water 1 0.0 liter pH (adjusted with aqueous ammonia and acetic acid) 6.7

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p 0.2-monononylphenyl ether (Average degree of polymerization: 10) Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-10.75-ylmethyl) piperazine Water was added to 1.0 liter pH 8.5

These color prints were evaluated on the basis of the following methods in five levels. A: Five ordinary people evaluated the impression of the entire print. B: Five experts from Fujifilm Ashigara Research Institute evaluated the sharpness of the central part. C: Five experts from Fujifilm Ashigara Research Institute evaluated the sharpness of the surrounding area. D: The color reproducibility was evaluated by five experts of the evaluation of Fujifilm Ashigara Laboratory. The evaluation criteria are shown below. 5: Particularly excellent 4: Excellent (satisfied) 3: Standard (almost satisfied) 2: Slightly inferior (somewhat dissatisfied) 1: Inferior (dissatisfied) Table 2 shows the evaluation results.

[0328]

[Table 2]

The usefulness of the present invention is apparent from Table 2.
That is, both the central part and the peripheral part show excellent sharpness,
The color reproducibility is good because No. 1 of the present invention. Only 9,11-16. Also, in the evaluation results of the general public, the sample of the present invention has a high evaluation result of 4 to 5, and together with the sharpness evaluation result of the expert, the general public's evaluation shows the sharpness of the print. It is clear that this is what you see.

[0330]

As described above, the photographic product containing a light-sensitive material according to the present invention has a red-sensitive emulsion layer, a green-sensitive emulsion layer,
And a silver halide color photographic light-sensitive material containing a coupler represented by formula (M) in at least one of the blue-sensitive emulsion layers, and at least one surface of the photographic optical system is aspherical. Since it is composed of two lenses and the total focal length is 28 mm or more, the features of the color photosensitive material and the features of the photographic optical system act synergistically, resulting in excellent resolution, especially in the peripheral area of the screen. It is possible to obtain a photographic product containing a light-sensitive material, in which distortion and chromatic aberration are remarkably improved.

With respect to the color light-sensitive material, the total film thickness from the emulsion layer closest to the support to the surface layer is set to 20 μm or less, or the ISO speed of the color light-sensitive material is set to 320 or more and the total silver coating amount is 3 μm. By setting the amount to 8 g / m ² , a photographic image of even better quality can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view of an essential part of a photographing optical system portion of a product of the present invention.

FIG. 2 is an external perspective view of a lens-fitted film unit.

FIG. 3 is an exploded perspective view of a unit main body with a photographing function.

FIG. 4 is a sectional view of an essential part of a photographing optical system part of a comparative product.

[Explanation of symbols]

 2 film unit with lens 23 exposure unit 25 shutter cover 25a aperture hole 26 front aspherical convex meniscus lens 27 biconvex spherical lens 28 spacer 40a aperture hole 42 spherical lens

Claims (5)

[Claims] 1. A support having at least one red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer, respectively.
A photographic product provided with an exposure function, which comprises a silver halide color photographic light-sensitive material containing a coupler represented by the general formula (M) shown in the following chemical formula 1 in at least one of the three color-sensitive emulsion layers, The photographing optical system is composed of at least two lenses, and at least one of these lenses is used.
The surface includes an aspherical surface and the focal length of the photographic optical system is 28 m.
A photographic product characterized by being m or more. [Chemical 1] R ₁ in the formula represents a hydrogen atom or a substituent. Z is
It represents a group of non-metal atoms required to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 2. The silver halide color photographic light-sensitive material comprises:
2. The compound according to claim 1, wherein at least one of the three color-sensitive emulsion layers contains a compound represented by the general formula (1) represented by the following chemical formula 2 or the general formula (2) represented by the chemical formula 3. Photo products. [Chemical 2] In the formula, A represents a coupler residue or a redox group, and L
₁ and L ₃ represent a divalent timing group, L ₂ is 3
It represents a timing group having a valent or higher valent bond, and PUG represents a photographically useful group. j and n each independently represent 0, 1 or 2, m represents 1 or 2, s represents the valence of L ₂ minus 1, and represents an integer of 2 or more. When a plurality of L ₁ , L ₂ or L ₃ are present in the molecule, they may all be the same or different. Further, the plurality of PUGs may be the same or different. [Chemical 3] In the formula, A and PUG have the same meaning as in formula (I). L ₄ represents -OCO- group, -OSO- group, -OSO ₂ - group, -OC
S-group, -SCO- group, -SCS- group or -WCR ₁₁
It represents a group - R _12. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R ₁₁ and R
_12's each independently represent a hydrogen atom or a substituent, and include the case where they are linked to form a cyclic structure. L ₅ is a group that releases PUG by electron transfer along a conjugated system or L ₄
Represents a group defined by. 3. The silver halide color photographic light-sensitive material comprises:
The total film thickness from the emulsion layer closest to the support to the surface layer is 20
The photographic product according to claim 1 or 2, wherein the photographic product has a thickness of not more than μm. 4. The silver halide color photographic light-sensitive material comprises:
It has a sensitivity of ISO 320 or higher, and the total silver coating amount is 3 to 8
Photographic product according to any one of claims 1 to 3, characterized in that it is g / m ² . 5. The silver halide color photographic light-sensitive material comprises:
The photographic product according to any one of claims 1 to 4, which has a sensitivity of ISO 640 or higher.