JPH07191429A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a preserable property with lapse of time, image quality and color image preservable property by incorporating a specific compd. into at least one layer of photosensitive silver halide emulsion layers on a specific base. CONSTITUTION:This photosensitive material contains the compd. expressed by formula A1-(TIME)a-DI and/or formula A2-(TIME)a-DI in the photosensitive silver halide emulsion layers and the thickness of the base is >=60 to <=110mum. In the formulas, A1 denotes a group which has a diffusion resistant group and eliminates (TIME)a-DI by reaction with the oxidant of an arom. primary amine developing agent; A2 denotes a group which has no diffusion resistant group and eliminates (TIME)a-DI by reaction with the oxidant of the arom. primary amine developing agent. TIME denotes the timing group to cleave DI after elimination from A; DI denotes a development restainer which is substantially deactivated after outflowing to a developer; (a) denotes 1 or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. Specifically, it is a silver halide color photograph that has excellent storage stability of the light-sensitive material, provides stable and good image quality and photographic properties, and has excellent development processability, and can be miniaturized or stored long in the cartridge. It relates to a photosensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter sometimes abbreviated as "light-sensitive material"), particularly a light-sensitive material for photographing, is used as a means for improving the image quality. The use of compounds) is well known and has been put to practical use. Examples of these DIR compounds include Research Disclosure (Research D
isclosure) No. 307105 (1989, No.
The patents described in V) and VII-F can be mentioned. Regarding the DIR compound according to the present invention, U.S. Pat. No. 4,782,012 and European Patent 522371A are described.
No. 3, JP-B-63-776, JP-A-3-89341,
Some of the similar compounds can be found in 3-78742 and 4-313750.

On the other hand, light-sensitive materials are generally produced by coating at least one light-sensitive silver halide emulsion layer on a plastic film support. Examples of the plastic film include fibrin-based polymers represented by tri (acetyl cellulose) (hereinafter referred to as “TAC”) and poly (ethylene terephthalate) (hereinafter referred to as “P”).
A polyester-based polymer represented by "ET") is used. These are, for example, Research Disclosure No. See 307105, XVII.

Photosensitive materials for photography using these supports include sheet-like materials such as cut films,
This is a general-purpose so-called 135 size roll film, which is typically 35 mm wide, is housed in a cartridge, loaded into a camera and used for photographing. Since this 135-sized standard format patrone has a conventional support thickness of about 120 μm, the length of the film that can be stored in the patrone is about 180.
The maximum number of shots taken is 36 in cm.
On the other hand, thinning, downsizing and simplification of handling have been promoted due to needs of portability and handling of cameras by general users. However, the current 135
It is necessary to reduce the size of the cartridge of the size including the diameter of the spool. In addition, a camera equipped with a continuous shooting mechanism has entered the market as the shooting mechanism of the camera has advanced. Therefore, there are some voices who want the appearance of a long film with a large number of shots in order to secure a photo opportunity.

To meet these needs, it is possible to reduce the thickness of the existing photographic light-sensitive material having a support having a thickness of 120 μm. However, the thinning of the support causes an imbalance in the balance of physical properties between the support and the constituent layers of the photosensitive layer,
For example, there is a drawback that curling occurs. In order to solve this problem, a photosensitive layer is provided on one side of a support having a thickness of 100 μm or less, and a back layer having a thickness of 3.5 to 15 μm is provided on the opposite side (the other side of the support). Is disclosed in JP-A-5-45783. Further, a photosensitive layer is provided on one side of a support having a thickness of 100 μm or less, and a back layer is provided on the opposite side, and at least 10% of the hardener used for the back layer is the hardener used for the photosensitive layer. Making them the same is disclosed in JP-A-5-45812.

Regarding the DIR compound, the above-mentioned US Pat. No. 4,782,012 and European Patent 52237 are mentioned.
1A, JP-B-63-776, JP-A-3-89341.
Nos. 3,78,742 and 4,313,750, as well as JP-A-3-198048 and 3,228048.
No. 4-251843, No. 4-278942, No. 4-278894, No. 4-280247, etc., describe similar compounds according to the present invention, and increase in fog and deterioration of sensitivity of a light-sensitive material over time. Large IIE with excellent storage stability and little deterioration in sharpness and gradation of own layer
(Inter-Image Effect) The image quality improving effect showing the effect is disclosed. Regarding the storability of the photosensitive material with time,
Although stability is certainly improved in low humidity conditions,
When stored under high humidity conditions, the stability is insufficient and unsatisfactory. It was found that the IIE effect was recognized also in the image quality and the effect was recognized in improving the color reproducibility, but the edge effect was not sufficient. Although the same effect is recognized for the sharpness, it was also revealed that the thinness of the support causes a decrease in the sharpness. Also,
It was also found that in continuous processing (running processing), fluctuations in photographic properties tend to occur.

[0007]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a photographic material in which the storability of the photographic material, particularly the storability under high humidity, is improved. The second purpose is to provide a light-sensitive material which provides image quality, particularly excellent sharpness and edge effect. A third object is to provide a light-sensitive material which provides stable photographic properties with little fluctuation in continuous processing. Another object of the present invention is to provide a light-sensitive material which can be miniaturized in the cartridge or can be stored in the cartridge long.

[0008]

The above object can be achieved by the silver halide color photographic light-sensitive material described below. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer has the following formula (1) and / or formula (2) A silver halide color photographic light-sensitive material containing a compound represented by the formula (1), wherein the thickness of the support is 60 μm or more and 110 μm or less. Formula (1) A _1- (TIME) _a -DI Formula (2) A _2- (TIME) _a -DI In the formula, A ₁ has a nondiffusible group and oxidizes the aromatic primary amine developer. Represents a group capable of leaving (TIME) _a -DI upon reaction with _a derivative, A ₂ has no diffusion-resistant group, and reacts with an oxidant of an aromatic primary amine developing agent to give (TIM
E) represents a group that leaves _a- DI, TIME represents a timing group that cleaves DI after leaving from A, DI represents a development inhibitor that is substantially deactivated after flowing out into a developer, and a represents Represents 1 or 2. two a when a is 2
IME represents the same or different.

The support has a thickness of 60 μm or more and 110 or more.
When the support is a poly (alkylene aromatic dicarboxylate) polymer having a thickness of not more than μm, which has been previously heat-treated before the coating of the silver halide photosensitive layer, the method described in JP-A No. 5-58200 mentioned above. -45783 and 5-45812, the above-mentioned object can be improved more effectively without limiting the film thickness of the back layer and the use of a hardener as disclosed in JP-A-5-45812, and the workability of the film can be improved. Improved processability could also be achieved by: The support having a thickness of 60 μm or more and 110 μm or less is made of a poly (alkylene aromatic dicarboxylate) polymer, has a glass transition temperature of 50 ° C. or more and 200 ° C. or less, and is coated with an undercoat layer after completion of molding of the support. Before coating or after coating the undercoat layer and before coating the silver halide photosensitive layer 4
The silver halide color photographic light-sensitive material as described above, which is a support heat-treated at a temperature of 0 ° C. or higher and lower than the glass transition temperature.

The present invention will be described in detail below. First, the compounds represented by Formula (1) and Formula (2) will be described in detail.

When A ₁ and A ₂ represent a yellow color image-forming coupler residue, for example, pivaloyl acetanilide type, benzoyl acetanilide type, malon ester type,
Examples include carbamoylacetamide type, malon ester monoamide type, benzimidazolyl acetamide type or cycloalkanoyl acetamide type coupler residues. Further, US Pat. Nos. 5021332 and 50213.
It may be a coupler residue described in No. 30 or European Patent No. 421221A. When A ₁ and A ₂ represent a magenta color image-forming coupler residue, examples thereof include a 5-pyrazolone type, a pyrazolobenzimidazole type, a pyrazolotriazole type, a pyrazoloimidazole type or a cyanoacetophenone type coupler residue. When A ₁ and A ₂ represent a cyan image-forming coupler residue, examples include phenol type or naphthol type. Further, it may be a coupler residue described in US Pat. No. 4,746,602 and European Patent 249453A. Further, A ₁ and A ₂ may be coupler residues that leave substantially no color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and elution type coupler residues described in European Patent Nos. 443530A and 444501A.

Preferred examples of A ₁ and A _{2 in} the formulas (1) and (2) are the following formulas (Cp-1) and (Cp-
2), (Cp-3), (Cp-4), (Cp-5),
(Cp-6), (Cp-7), (Cp-8), (Cp-
9) or a coupler residue represented by (Cp-10). These couplers are preferred because of their high coupling speed.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group. In the above formula, when the coupler residue is A ₁ , R ₅₁ ,
R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R
_At least one of ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a non-diffusible group which is selected to have a total carbon number of 8 to 40, preferably 10 to 30, otherwise carbon. The total number is preferably 15 or less. In the case of a bis-type, telomer-type or polymer-type coupler, any of the above substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon number may be out of regulation. The diffusion resistant group is a group which has a sufficiently large molecular weight in order to immobilize it in the layer to which the molecule is added.

In the above formula, when the coupler residue is A ₂ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ ,
The total number of carbon atoms contained in R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ and R ₆₃ is selected to be 0 to 15, preferably 0 to 10. Below, R _{51 to} R ₆₃ , b, d, e
And f will be described in detail. In the following, R ₄₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₃ . b represents 0 or 1. R ₅₄ represents a group having the same meaning as _{R 41, R 41 CO (R} 43) N-
Group, R ₄₁ SO ₂ (R ₄₃ ) N-group, R ₄₁ (R ₄₃ ) N-group, R
₄₁ S-group, R ₄₃ O-group, or R ₄₅ (R ₄₃ ) NCON
Represents an (R ₄₄ ) -group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each a group having the same meaning as R ₄₃ , R ₄₁ S
-Group, R ₄₃ O- group, R ₄₁ CO (R ₄₃ ) N- group, or R
₄₁ SO ₂ (R ₄₃ ) represents an N-group. R ₅₈ represents a group having the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as R _41, R ₄₁ CO
(R ₄₃ ) N-group, R ₄₁ OCO (R ₄₃ ) N-group, R ₄₁ SO
₂ (R ₄₃ ) N-group, R ₄₃ (R ₄₄ ) NCO (R ₄₅ ) N-group,
R ₄₁ O- group, R ₄₁ S- group, halogen atom, or R
₄₁ (R ₄₃ ) represents an N-group. d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents. R ₆₀ represents a group having the same meaning as R ₄₃ . R ₆₁ is R
Represents a group having the same meaning as ₄₃ . R ₆₂ is a group having the same meaning as R ₄₁ ,
R ₄₁ CONH-group, R ₄₁ OCONH-group, R ₄₁ SO ₂ N
H-group, R ₄₃ (R ₄₄ ) NCONH-group, R ₄₃ (R ₄₄ ) N
SO ₂ NH- group, R ₄₃ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ NH- group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CO (R ₄₄ ) N-group, R ₄₃ (R ₄₄ ) NCO-
_{Group, R 41 SO 2 (R 43} ) N- _{group, R 41 (R 43) NSO} 2 -
Group, R ₄₁ SO ₂ — group, R ₄₃ OCO— group, halogen atom,
A nitro group, a cyano group or R ₄₃ CO- group. e is 0
Represents an integer of 4 to 4. When there are plural R ₆₂ or R _63, they represent the same or different ones. f represents an integer of 0 to 3. When there are a plurality of R ₆₃ 's, they represent the same or different ones.

The definitions of an alkyl group, an aryl group and a heterocyclic group when the coupler residue is A ₁ will be described below. The alkyl group has 1 to 32 carbon atoms, preferably 1
To 22 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Representative examples are methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, cyclohexyl, 2-ethylhexyl, 1,1,
Examples include 3,3-tetramethylbutyl, n-dodecyl, n-hexadecyl, or n-octadecyl. The aryl group is an aryl group having 6 to 20 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl. Heterocyclic group has 1 to 2 carbon atoms
The hetero atom of 0, preferably 1 to 7, selected from a nitrogen atom, an oxygen atom or a sulfur atom, is preferably a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring.
Typical examples of the heterocyclic group include 2-imidazolyl, 2
-Benzimidazolyl, morpholino, pyrrolidino, 1,
2,4-triazol-2-yl group or 1-indolinyl may be mentioned.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CO (R ₄₈ ).
N-group, R ₄₇ (R ₄₈ ) NCO-group, R ₄₆ SO ₂ (R ₄₇ ) N
-Group, R ₄₇ (R ₄₈ ) NSO ₂ -group, R ₄₆ SO ₂ -group, R ₄₇
OCO- group, R ₄₇ CONHSO ₂ - group, R ₄₇ (R ₄₈₎ N
CONHSO ₂ — group, group having the same meaning as R ₄₆ , R
₄₇ (R ₄₈ ) N-group, R ₄₆ COO-group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined.

The definition of an alkyl group, an aryl group and a heterocyclic group when the coupler residue is A ₂ is described above. The alkyl group has 1 to 12 carbon atoms, preferably 1
~ 8 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Typical examples are methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, cyclohexyl, 2-ethylhexyl, or 1,1,
3,3-tetramethylbutyl may be mentioned. The aryl group is phenyl having 6 to 10 carbon atoms, preferably substituted or unsubstituted. The heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms, preferably selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, preferably a 3-membered to 8-membered ring. is there. Representative examples of the heterocyclic group include 2-imidazolyl, 2-benzimidazolyl, morpholino, pyrrolidino, 1,2,4-triazol-2-yl group or 1-indolinyl.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CO (R ₄₈ ).
N-group, R ₄₇ (R ₄₈ ) NCO-group, R ₄₅ SO ₂ (R ₄₇ ) N
-Group, R ₄₇ (R ₄₈ ) NSO ₂ -group, R ₄₆ SO ₂ -group, R ₄₇
OCO- group, R ₄₇ CONHSO ₂ - group, R ₄₇ (R ₄₈₎ N
CONHSO ₂ — group, group having the same meaning as R ₄₆ , R
₄₇ (R ₄₈ ) N-group, R ₄₆ COO-group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined. In the present invention, the compound represented by the formula (2) is preferable.

Next, the development inhibitor represented by DI will be described. Examples of the development inhibitor represented by DI include US Pat. Nos. 4,477,563, 5,021,331 and 4,
937179, 5,400,677, European Published Patent (EP) 336411A, 436109A,
No. 440466A, No. 446863A, No. 4479
21A, 451526A, 458315A,
Development inhibitors such as those described in U.S. Pat. Nos. 4,842,422A or 4,883,10A are included. Particularly preferably tetrazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-thiadiazolylthio, 1- (or 2
-) Benzotriazolyl, 1,2,4-triazole-
1- (or 4-) yl, 1,2,3-triazole-
1-yl, 1- (or 2-) tetrazolyl, 2-benzothiazolylthio, 2-benzimidazolylthio and derivatives thereof are included. Most preferred is 1- (or 2-) benzotriazolyl. DI is (TIM
E) shows the cleavage development inhibiting effect than _a, partially flows out from the photographic layer to a developing solution. DI that has flowed into the developing solution is decomposed and the development inhibiting effect is substantially lost. The rate of decomposition is 30 with a half-life
Seconds to 2 hours, preferably 2 minutes to 1 hour.
The decomposition reaction is typically carried out by alkali hydrolysis, decomposition by reaction with a chemical species (such as hydroxylamine) contained in the developing solution, or deactivation by substitution reaction of an adsorption group (such as mercapto group contained in DI). Particularly preferably, at least one of the substituents contained in DI has an ester bond. Examples of DI include the following.

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

Next, the group represented by TIME will be described. The group represented by TIME is A ₁ or A ₂ during development processing.
Any linking group capable of cleaving DI after further cleavage may be used. For example, US Pat.
Group utilizing the cleavage reaction of hemiacetal described in No. 96, No. 4652516 or No. 4698297,
Timing groups for causing a cleavage reaction by utilizing the intramolecular nucleophilic substitution reaction described in US Pat. Nos. 4,248,962, 4,847,185, 4,912,028 or 4,857,440, US Pat. Nos. 4,409,323, 503.
No. 4311, No. 5055385 or No. 44218.
No. 45, a timing group for causing a cleavage reaction by utilizing an electron transfer reaction, a group for causing a cleavage reaction by utilizing an iminoketal hydrolysis reaction, as described in US Pat. No. 4,456,073, or West German Patent 262
Examples thereof include a group capable of causing a cleavage reaction by utilizing the hydrolysis reaction of an ester described in No. 6317. Two TI
Examples of when MEs are connected (when a is 2) are U.S. Pat. Nos. 4,861,701, 5,026,628 and 50,
21322, European Published Patent (EP) No. 4992
79A and 438129A. TIME may also be a timing group that releases two DIs, examples of which include the timing groups described in EP-A-464612A. TIME binds to A ₁ or A _{2 at} a heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom. In the present invention,
The group represented by TIME is preferably a timing group which causes a cleavage reaction utilizing an electron transfer reaction along a conjugated system.

It is a preferred example that at least one TIME used in the formula (2) contains a diffusion resistant group. Total carbon number 8 to 40, preferably 10 to 22
Substituents are included. Preferred TIME includes the following formulas (T-1), (T-2) or (T-3). Formula (T-1) * -W- ( X = Y) j -C (R 21) R 22
-** Formula (T-2) * -W-CO-** Formula (T-3) * -W-LINK-E-** In the formula, * represents A ₁ in Formula (1) or Formula (2). Or represents a position to be bonded to A _2, and ** is DI or TIME
W represents an oxygen atom, a sulfur atom or> N—R ₂₃ , X and Y each represent a methine or nitrogen atom, and j represents 0, 1 or 2
And R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a substituent. Here, when X and Y represent a substituted methine, any substituent of each of the substituents, R ₂₁ , R ₂₂ and R ₂₃
It may be either a case where two substituents are linked to each other to form a cyclic structure (for example, a benzene ring or a pyrazole ring) or a case where no ring structure is formed. In Formula (T-3), E represents an electrophilic group, and LINK represents a linking group that sterically relates W and E so that they can undergo an intramolecular nucleophilic substitution reaction. The following are specific examples of TIME. In the present invention, TIME shown in Chemical formula 8 is particularly preferable.

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

Specific representative examples of the compounds represented by the formulas (1) and (2) used in the present invention are shown below, but the compounds are not limited thereto.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

[0051]

[Chemical 28]

The compound represented by the formula (1) or (2) of the present invention is described in US Pat.
7-151944, 58-162949, 60
-128444, 63-37350, JP-A-3-
198048, 3-228048, 4-251.
No. 843, No. 4-278942, No. 4-2799943.
No. 4,280,247 and No. 4-313750, and the method described in the patents cited as examples of the development inhibitor and the patents cited as examples of the timing group, or similar methods. it can.

The compounds represented by the formulas (1) and (2) of the present invention are used in at least one photosensitive silver halide emulsion layer constituting the photosensitive layer of the photosensitive material. The light-sensitive silver halide emulsion layer may be any light-sensitive layer such as a red-sensitive emulsion layer, a green-sensitive emulsion layer, a blue-sensitive emulsion layer, or a donor layer having a multi-layer effect having different color sensitivity and spectral sensitivity distribution. Good. Further, when the same color-sensitive layer is composed of a plurality of layers having two or more layers having different sensitivities, they can be used as any layers. Further, it may be used in combination with a non-photosensitive layer adjacent to these photosensitive layers such as an antihalation layer, an intermediate layer, a yellow filter layer and a protective layer.

The amount of the compounds represented by the formulas (1) and (2) of the present invention varies depending on the performance required for the light-sensitive material, but is 1.0 × 10 ⁻⁴ per 1 m ^{2 of} the layer to be added. ~ 1.
It is in the range of 0 g. Preferably 5.0 × 10 ^{−4 to} 0.5
g, more preferably 1.0 × 10 ^{−3 to} 0.
It is in the range of 2 g. The compounds represented by the formulas (1) and (2) may be used each alone in two or more layers, or may be used in combination of two or more.

As the compounds represented by the formulas (1) and (2), known DIR compounds can be used in combination depending on the performance required of the light-sensitive material. Known DIR compounds include, for example, RD. No. 17643, VII-F and
No. 307105, Patents described in VII-F, JP-A-57-151944, 57-154234, 60-184248, 63-37346, 63.
-37350, U.S. Pat. Nos. 4,248,962, 4,782,012, and European Patent 464,612A.
Nos. 482,552A and 499,279A can be used.

In the present invention, equations (1) and (2)
The compound represented by the formula (1) further has A ₁ or A ₂ and TIME described in the formula (1) and the formula (2), and DI is a development inhibitor exemplified in the following Chemical formula 29:
Specific representative examples of these compounds may be used in combination with the compounds shown in Chemical formulas 30 and 31 below.

[0057]

[Chemical 29]

[0058]

[Chemical 30]

[0059]

[Chemical 31]

In the present invention, equations (1) and (2)
The compound represented by can be introduced into the photosensitive material by applying various known dispersion methods described later. Further, it can be used by being mixed with or coexisting with various couplers and additives described later and introduced into the light-sensitive material.

The compounds represented by the formulas (1) and (2) of the present invention exhibit excellent performance in improving image quality such as sharpness and layering effect, and also exhibit excellent performance in edge effect. Further, it is possible to reduce the storability of the light-sensitive material with time, particularly the fluctuation of the photographic property and the deterioration of the image quality improving effect when it is stored under high humidity, and it is possible to provide the excellent effect of small fluctuation of the photographic property even in the continuous processing. These effects are obtained when the support is a thin film having a thickness of 60 to 110 μm and the support is a poly (alkylene aromatic dicarboxylate) polymer, and the silver halide photosensitive layer is used. When the support is heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition point before application, the remarkable effect is exhibited.

Next, the support will be described in detail. The support that can be used in the light-sensitive material of the present invention is a plastic film, and the above-mentioned RD. No. 17643-28
No. 18716, page 647, right column to page 648, left column, and ibid., No. 307105, page 879. Preferably a cellulose ester polymer film,
It is a transparent support represented by a polyester polymer film and a polycarbonate polymer film. Among them, a cellulose ester polymer film and a poly (alkylene aromatic dicarboxylate) -based polyester polymer film are preferable, and a poly (alkylene aromatic dicarboxylate) polymer film is particularly preferable, and a heat-treated film described later is most preferable.

In the present invention, the thickness of the above-mentioned film when used as a support for a photosensitive material is 60 μm or more and 110 μm or less. The thickness is preferably 70 μm
It is 100 μm or less. If the thickness is less than 60 μm, the flexural elasticity that can withstand the contraction stress of the photosensitive layer cannot be maintained, and a gutter-like curl occurs. This curling is not preferable because it causes scratches on the photosensitive material during the film packaging process, the feeding and rewinding process in the camera, the developing process and the like. On the other hand, if the thickness exceeds 110 μm, it becomes impossible to reduce the diameter of the cartridge and accommodate a long length of film, which corresponds to the thinning and miniaturization of the camera. Therefore, the thickness of the support is preferably 60 μm or more and 110 μm or less.

The poly (alkylene aromatic dicarboxylate) polymer (hereinafter abbreviated as the polyester of the present invention) which is particularly preferably used in the present invention will be described below. The naphthalate used in the description of the present invention means naphthalene dicarboxylate.

The preferred polyesters of this invention are formed with aromatic dicarboxylic acids and diols as essential components.
The aromatic dicarboxylic acid is a dicarboxylic acid having at least one benzene nucleus, and specific compounds thereof include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 1,4- or 1,5-or 2,6- or 2,7-naphthalenedicarboxylic acid, biphenyl-4,
4'-dicarboxylic acid, tetrachlorophthalic anhydride,

[0066]

[Chemical 32]

And the like. In addition to the essential aromatic dicarboxylic acid, dibasic acids that can be used as a copolymerization component include succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, and itacone. Acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid

[0068]

[Chemical 33]

And the like.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 Mention may be made of cyclohexanedimethanol. Other diols containing aromatic rings, catechol, resorcin,
Hydroquinone, 1,4-benzenedimethanol,

[0071]

[Chemical 34]

[0072]

[Chemical 35]

Etc. can be used. If necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or an ester thereof) at the same time in the molecule, and examples thereof include the following.

[0074]

[Chemical 36]

Among the polyesters composed of these diols and dicarboxylic acids, more preferred are homopolymers such as poly (ethylene terephthalate), poly (ethylene naphthalate) and poly (cyclohexanedimethanol terephthalate) (PCT). And 2,6-naphthalenedicarboxylic acid (NDCA) and terephthalic acid (TP) as particularly preferable essential aromatic dicarboxylic acids.
A), isophthalic acid (IPA), orthophthalic acid (OP
A), biphenyl-4,4'-dicarboxylic acid (PPD
C), ethylene glycol (EG) as a diol,
Cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BP
A), biphenol (BP), and para-hydroxybenzoic acid (PHB) as hydroxycarboxylic acid which is a copolymerization component.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized.

Among these, more preferable are:
Copolymer of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0.1 to 0.1: 0.9)
Is preferable, and 0.8: 0.2 to 0.2: 0.8 is more preferable. ), Terephthalic acid and ethylene glycol,
Copolymer of bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is 0.6: 0.4 to 0:
It is preferably between 1.0 and 0.5: 0.5-0.
1: 0.9 is preferable. ), Isophthalic acid, biphenyl-4,4'-dicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; biphenyl-4,4'-dicarboxylic acid in a molar ratio of 1 terephthalic acid).
0.1 to 0.5, 0.1 to 0.5, and more preferably 0.2 to 0.3 and 0.2 to 0.
3 is preferable. ), Terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to
0.7: 0.3 is preferable, and 0.9: is more preferable.
0.1-0.6: 0.4), terephthalic acid, copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is 0: 1.0-0.8:
0.2 is preferable, and more preferably 0.1: 0.9-
It is 0.7: 0.3. ), Para-hydroxybenzoic acid,
A copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is preferably 1: 0 to 0.1: 0.9, more preferably 0.9: 0.1 to 0.2: 0. Copolymers such as 8) are preferred. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as the acid component, first, a transesterification reaction is performed with the glycol component,
It can be synthesized by heating this under reduced pressure to remove the excess glycol component. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. For these polyester synthesis methods,
For example, Polymer Experiments Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136, "Synthetic Polymer V".
(Asakura Shoten, 1971) The description on pages 187 to 286 can be referred to. The preferred average molecular weight (weight) range for these polyesters is about 10,000 to 500,000. Furthermore, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized, or these polyesters may be copolymerized. A monomer having an unsaturated bond can be copolymerized therein to radically crosslink. Polymer blends obtained by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482 and 64-432.
5, JP-A-3-192718, Research Disclosure, 283, 739-41, 284, 779-8.
2, according to the method described in 294, 807-14,
It can be easily molded.

The glass transition temperature (Tg) in the present invention means that when 10 mg of a sample film is heated in a helium nitrogen stream at a temperature of 20 ° C./minute using a differential thermal analyzer (DSC), It is defined as the arithmetic mean temperature of the temperature at which eccentricity begins and the temperature returning to a new baseline.
However, when an endothermic peak appears, the temperature at which this endothermic peak has a maximum value is defined as Tg. The polyester of the present invention has a Tg of 50 ° C. or higher, but the use conditions thereof are not generally handled with sufficient caution, and in particular, the temperature is often exposed to 40 ° C. outdoors in the midsummer, in many cases. From this viewpoint, the Tg of the present invention is preferably 55 ° C. or higher in consideration of safety. More preferably, Tg is 70 ° C. or higher, and particularly preferably 80 ° C. or higher. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred. On the other hand, the upper limit of the glass transition temperature is 200 ° C. A polyester having a glass transition temperature of higher than 200 ° C. cannot provide a film having good transparency. Therefore, the Tg of the polyester used in the present invention needs to be 50 ° C. or higher and 200 ° C. or lower.

Examples of preferable specific compounds of the polyester used in the present invention are shown below, but the present invention is not limited thereto. Polyester compound example P-0: [terephthalic acid (TPA) / ethylene glycol (EG)) (100/100)] (PET) Tg = 80 ° C P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene Glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / Bisphenol A (BPA) (100/100)] Tg = 192 ° C. P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 12 ℃ P-7: TPA / EG / BPA (100/50/50) Tg = 105 ℃ P-8: TPA / EG / BPA (100/25/75) Tg = 135 ℃

P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. P-10: IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C P-11: NDCA / NPG / EG (100/70/30) Tg = 105 ° C P-12: TPA / EG / BP (100/20/80) Tg = 115 ° C P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P-14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50/50) Tg = 118 ° C. P-18: PAr / PET (60/40) Tg = 101 ° C. P-19: PEN / PET / PAr (50/25 25) Tg = 108 ℃ P-20: TPA / 5- sulfonium isophthalate (SIP) / EG (95/5/100) Tg = 65 ℃

The polyester support (film base) preferably has a thickness of 60 μm or more and 110 μm or less.
If it is less than 60 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, while if it exceeds 110 μm, it is inconsistent with the purpose of reducing the thickness for compactness. However, when used as a sheet-shaped photosensitive material,
It may have a thickness of more than 110 μm. Its upper limit is 300 μm. All of the polyesters of the present invention as described above have a strong bending elastic modulus, and make it possible to realize the original purpose of thinning the film. However, of these, PET and PEN had strong flexural elasticity, and using them, the film thickness required by conventional TAC of around 120 μm was reduced to 1
It is possible to reduce the thickness to 10 μm or less. Next, the polyester support of the present invention is preferably subjected to a heat treatment, in which case it needs to be performed at a temperature of 40 ° C. or higher and lower than the glass transition temperature for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather disorderly and conversely the free volume increases, and the molecules tend to flow, that is, the film is easily curled. Therefore, this heat treatment needs to be performed below the glass transition temperature. The heat treatment referred to in the present invention is once performed at 40 ° C. after being molded as a support.
After the temperature has been lowered to a temperature of less than 40 ° C. until the undercoat layer is coated, or after the temperature of the undercoat layer has been reduced to a temperature of less than 40 ° C. and before the silver halide photosensitive layer coating. It is preferable that the heat treatment is performed separately.

It is desirable to carry out this heat treatment at a temperature slightly below the glass transition temperature in order to shorten the treatment time.
The glass transition temperature is 0 ° C or higher and lower than the glass transition temperature, and more preferably 30 ° C below the glass transition temperature or higher and lower than the glass transition temperature. More preferably, it is not lower than the glass transition temperature and lower than the glass transition temperature by 15 ° C. On the other hand, when the heat treatment is performed under this temperature condition, the effect is recognized after 0.1 hour. Further, at 1500 hours or more, the effect is almost saturated. Therefore, it is preferable to perform the heat treatment for 0.1 hour or more and 1500 hours or less. In the method for heat-treating the polyester of the present invention, in order to shorten the time, it is previously heated to Tg or more for a short time (preferably, Tg is treated at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours), and then 40
It is also possible to perform heat treatment at a temperature of not less than ℃ and less than the glass transition temperature. In the heating method, the film roll may be left as it is in a heating warehouse for heat treatment, but it may be further transferred to a heating zone for heat treatment, and the latter is preferred in view of the suitability for production. Further, the roll core used in the heat treatment preferably has a structure in which an electric heater is built-in or a high-temperature liquid can be poured so that the film can be hollow or heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not have strength reduction or deformation due to heat,
Examples thereof include stainless steel and resin containing glass fiber.

The polyester of the present invention preferably contains various additives in order to further enhance its function as a photographic support. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber does not have absorption in the visible region, and the addition amount thereof is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight based on the weight of the polyester film. %. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. As a UV absorber, a benzophenone type such as 2,4-dihydroxybenzophenone, 2 (2'-hydroxy-3 ', 5'-di-
benzotriazoles such as t-butylphenyl) benzotriazole, salicylates such as methyl salicylate,
2,4,6-Tris [2'-hydroxy-4 '-(2 "
Examples thereof include triazine-based ultraviolet absorbers such as -ethylhexyloxy) phenyl] triazine.

Further, one of the properties which poses a problem when the polyester film of the present invention is used as a support for a photographic light-sensitive material is the problem of fogging caused by the high refractive index of the support. The polyester of the present invention, particularly the aromatic polyester has a high refractive index of 1.6 to 1.7, while the gelatin which is the main component of the photosensitive layer coated thereon has a refractive index of 1.50 to 1.50. It is smaller than this value, which is 1.55. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable. As the dye, from the above viewpoint, Diaresin manufactured by Mitsubishi Kasei, manufactured by Nippon Kayaku
The purpose can be achieved by mixing a commercially available dye such as Kayaset for polyester.
Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness according to the intended use, and the slipperiness imparting means is not particularly limited.
A general method is kneading an inactive inorganic compound or coating a surfactant. Examples of such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to, or an internal particle system capable of relatively reducing the precipitated particle size.

Further, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die. When any of these polymer films is used as a support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive silver halide emulsion layer). , The intermediate layer, the filter layer, etc.) are very difficult to adhere firmly. As conventional techniques attempted to overcome such difficulties, (1) chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
After performing surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a method of directly applying a photographic emulsion to obtain adhesive strength,
(2) There are two methods, that is, a method of forming an undercoat layer and coating a photographic emulsion layer on the undercoat layer after the surface treatment is performed once or without the surface treatment (for example, US Pat. No. 2,698,24).
No. 1, No. 2,764,520, No. 2,864,755
Issue No. 3,462,335 Issue No. 3,475,193
No. 3, 3, 431, 421, 3, 501, 301
Nos. 3,460,944, 3,674,531
No., British Patent Nos. 788,365, 804,005
No. 891, 469, Japanese Patent Publication No. 48-43122,
51-446, etc.).

Various arrangements have been made as to the constitution of the undercoat layer. A layer which adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is formed on the layer. The so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that is in good contact with the photographic layer as a layer, and applying only one layer of a resin layer containing both a hydrophobic group and a hydrophilic group. There is a single layer method.

Among the surface treatments of (1), corona discharge treatment is the most well-known method, and any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-20867, 49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.

The glow discharge treatment, which is the most effective surface treatment, is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578, 36-10336, and 45-.
22004, 45-22005, 45-240
40, 46-43480, U.S. Pat. No. 3,057,
No. 792, No. 3,057,795, No. 3,179,4
82, 3,288,638, 3,309,29
No. 9, No. 3,424, 735, No. 3, 462, 335
Issue 3, Issue 3,475,307, Issue 3,761,299
No., British Patent No. 997,093, JP-A-53-1292.
No. 62 or the like can be used.

Next, the undercoating method (2) will be described. All of these methods have been well researched. For example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first undercoating layer in the multi-layer method. , Itaconic acid, maleic anhydride, and other copolymers starting from monomers selected from polyesterimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers The properties of the two layers have been investigated mainly for gelatin.

In the single layer method, good support is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like.
Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various known gelatin hardening agents can be used in the undercoat layer of the present invention. Examples of gelatin hardening agents include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, epichlorohydrin resins, cyanuric chloride compounds (for example, Japanese Patent Publication Nos. 47-6151 and 47-33380). ,
54-25411, compounds described in JP-A-56-130740), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259 and 50-).
35807, JP-A-49-24435, 53-4.
Nos. 1221 and 59-18944),
Carbamoyl ammonium salt compounds (for example, JP-B-56-12853, JP-A-58-32699, JP-A-4)
9-51945, 51-59625, 61-9
No. 641), amidinium salt-based compounds (for example, compounds described in JP-A-60-225148), carbodiimide-based compounds (for example, JP-A-51-
Nos. 126125 and 52-48311), pyridinium salt compounds (for example, Japanese Examined Patent Publication No. 58-
50699, JP-A-52-54427, JP-A-57.
-44140, 57-46538), other Belgian patents 825,726, U.S. Pat. No. 3,321,313, JP-A-50-38540.
No. 52-93470, No. 56-43353, No. 58-113929, and the like.

The undercoat layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and graininess of the image are not substantially impaired. As a matting agent for inorganic fine particles, silica (SiO ₂ ) and titanium dioxide (T
iO ₂ ), calcium carbonate, magnesium carbonate and the like can be used. Examples of the organic fine particle matting agent include polymethylmethacrylate, cellulose acetate propionate, polystyrene, and US Pat. No. 4,142,89.
The treatment solution-soluble substances described in No. 4 and the polymers described in US Pat. No. 4,396,706 can be used. The average particle size of these fine particle matting agents is preferably 1 to 10 μm.

Other than the above, the undercoat layer may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by an extrusion coating method using a hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be coated simultaneously by the method described in "Coating Engineering", page 253 (1973, published by Asakura Shoten).

The binder for the back layer may be either a hydrophobic polymer or a hydrophilic polymer used in the undercoat layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye, an ultraviolet absorber and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt and a sulfonic acid salt, for example, JP-A-48-22017. JP-B-46-24159, JP-A-51-30725, JP-A-51-129216,
It is a polymer as described in JP-A-55-95942. Examples of the cationic polymer include JP-A-49
There are those described in JP-A-121523, JP-A-48-91165 and JP-B-49-24582. Further, ionic surfactants are also anionic and cationic, and are disclosed, for example, in JP-A-49-85826 and JP-A-4.
9-33630, U.S. Pat. No. 2,992,108,
U.S. Pat. No. 3,206,312, JP-A-48-878
No. 26, Japanese Patent Publication No. 49-11567, Japanese Patent Publication No. 49-11
Examples thereof include compounds described in JP-A No. 568 and JP-A No. 55-70837.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₂ , SnO ₂ , or Al.
₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ ,
It is fine particles of at least one crystalline metal oxide or a composite oxide thereof selected from V ₂ O ₅ . The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The lower limit is 10 ³ Ω
cm. The particle size is 0.002-0.7μ.
It is desirable that the thickness be m, particularly 0.005 to 0.3 μm.

Further, the silver halide color photographic light-sensitive material of the present invention may have a magnetic recording layer for recording various information. A known ferromagnetic material can be used. The magnetic recording layer can be provided as an upper layer (for example, a protective layer or an uppermost layer) of the support layer on the side where the photosensitive layer is coated, but it is preferably used for the back surface, and can be provided by coating or printing. Further, a space for optically recording may be provided in the photosensitive material for recording various information.

The smaller the hollow or spool in the center of the film used in the camera of the light-sensitive material of the present invention, the smaller the size. Can not. Therefore, in the present invention, the hollow portion or spool in the center of the film of the preferred film is 3 mm or more, and the upper limit is 1.
It is preferably 2 mm, more preferably 3 mm to 10 mm, particularly preferably 4 mm to 9 mm. Also, the smaller the winding inner diameter of the spool is, the more preferable. Therefore, in the present invention, the preferable inner diameter of the spool in the camera is 5 mm or more, and the upper limit is 15 mm, more preferably 6 mm to 13.5 mm, further preferably 7 mm to 13.5 mm, particularly preferably 7 mm. It is 13 mm.

In the present invention, the polyester support having a thickness of 60 μm or more and 110 μm or less, which is heat-treated at a temperature of 40 ° C. or more and less than the glass transition temperature before coating the above-mentioned photosensitive layer, is excellent in curl-eliminating property and mechanical strength. Therefore, it is particularly preferable. Therefore, it becomes possible to slim down the cartridge or load a longer film into the cartridge of the current 135 system. Further, it is possible to reduce scratching accidents during the manufacturing of photosensitive material, packaging processing, feeding of film in a camera, rewinding process and developing process. Further, the use of the above-mentioned heat-treated thin film has an effect of improving the storability, image quality and development processability of the light-sensitive material.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order 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. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are formed by sequentially exposing two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-206.
As described in 541, 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH)
/ 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
It can be installed in the order of / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
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 1. In addition, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even in the case of being composed of three layers having different sensitivities as described above, Japanese Patent Application Laid-Open No. 59-202464
In the same color-sensitive layer, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support. 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, in the case of four or more layers, the arrangement may be changed as described above. US 4,663,27 to improve color reproduction
1, same 4,705,744, same 4,707,436, JP-A-62-160448, same
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL or RL described in 63-89850, adjacent to or in proximity to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% silver iodide. 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 are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less, and the projected area diameter is about 1
It may be large-sized grains up to 0 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 (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid.
307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafki).
des, Chimie et Phisique Photographique, Paul Monte
l, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemi
stry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikm).
an, et al., Making and Coating Photographic Emulsi
on, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with 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 emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-63
The core / shell internal latent image type emulsion described in JP-A-264740 may be used, and its preparation method is described in JP-A-59-133542. 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. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain, US Pat.
852, a silver halide grain in which the grain inside is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition.
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 average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

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 development process, 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 may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area)
0.01 to 0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. 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, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. 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 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Right column 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); Japanese Patent Application No. 4 -134523 a coupler of the general formula (I) of claim 1; US 5,066,576 column 1, lines 45-55, a coupler of the general formula (I);
A coupler represented by the general formula (I) of paragraph 0008 of JP-A-4-274425; a coupler described in claim 1 of EP 498, 38A1 on page 40 (particularly D-35 on page 18); EP 447, 969A1 of page 4 Couplers represented by formula (Y) (especially Y-1 (page 17), Y-54 (page 41)); US
Couplers represented by formulas (II) to (IV) on lines 36 to 58 of column 4, 476, 219 (particularly II-17, 19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (lower right page 11), L-68 (lower right page 12), L-77 (lower right page 13); EP 456,257
[A-4] -63 (page 134), [A-4] -73, -75 (page 139); EP 486,965, M
-4, -6 (page 26), M-7 (page 27); M in paragraph 0024 of Japanese Patent Application No. 4-234120
-45; M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; M-22 in paragraph 0237 of JP-A-4-362631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35), 34,35 of JP-A-4-43345.
(Page 37), (I-1), (I-17) (pages 42 to 43); The coupler represented by formula (Ia) or (Ib) of claim 1 of Japanese Patent Application No. 4-236333. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

Examples of couplers in which the coloring dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,570, D
Those described in E 3,234,533 are preferable. The coupler for correcting the unwanted absorption of the coloring dye is a yellow color cyan dye coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8), CC described in US 4,833,069.
-13 (column 10), US 4,837,136 (2) (column 8), WO92 / 1
Colorless masking couplers of the formula (A) of claim 1 of 1575 (in particular the exemplified compounds on pages 36 to 45) are preferred.
Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 378,236A1
Compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of the (especially T-101 (page 30), T-104 (page 31), T-113 (page 36) ), T-13
1 (page 45), T-144 (page 51), T-158 (page 58)), a compound represented by the formula (I) described on page 7 of EP436, 938A2 (particularly D-49 (page 51)) ,
A compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly paragraph 0)
023 (23)), EP 440,195A2 formula (I), (I) described on page 5-6.
Compounds represented by I) and (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: Compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 (especially (60, 61) on page 61 and Japanese Patent Application No. 4
-325564, a compound of formula (I) according to claim 1 (particularly (7) of paragraph 0022); a ligand-releasing compound: a compound of formula LIG-X according to claim 1 of US 4,555,478 (particularly column 21-21). ~ Line 41 compound); Leuco dye releasing compound: U
S 4,749,641 columns 3-8 compounds 1-6; fluorescent dye releasing compounds: compounds represented by COUP-DYE in claim 1 of US 4,774,181 (especially compounds 7-11 in columns 7-10); development accelerators or fogging agents Emitted compounds: Compounds represented by formulas (1), (2) and (3) in column 3, US Pat. No. 4,656,123 (particularly (I-22) in column 25) and EP 450,637 A2, page 75, lines 36 to 38, E
xZK-2; A compound that releases a dye group only after it leaves:
Compounds of formula (I) in claim 1 of US 4,857,447 (especially Y-1 to Y-19 in columns 25 to 36).

The following additives are preferable as additives other than the coupler. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,9
3 (pages 140-144); Latex for impregnation of oil-soluble organic compounds:
Latex as described in US 4,199,363; Oxidizer developer Scavenger: Formula of column 2, lines 54-62 of US 4,978,606.
Compounds represented by (I) (especially I-, (1), (2), (6), (12)
(Columns 4-5), US 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3); stain inhibitor: EP
298321A, page 4, lines 30-33, formulas (I)-(III), especially I-47,72, I
II-1,27 (pages 24-48); Anti-fading agents: EP 298321A, A-6,7,2
0,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69
Pp. 118-), US 5,122,444 columns 25-38 II-1 to III-23,
In particular III-10, EP 471347A, pages 8-12, I-1 to III-4, especially I
I-2, US 5,139,931 columns 32-40 A-1 to 48, especially A-3
9,42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-46;
Formalin Scavenger: EP 477932A SC on pages 24-29
V-1 to 28, especially SCV-8; Hardener: H on page 17 of JP-A 1-214845
-1,4,6,8,14, US 4,618,573 column 13-23 formula (VII) ~
The compound (H-1 to 54) represented by (XII), the compound (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, especially H-
14, Compound described in claim 1 of US 3,325,287; Development inhibitor precursor: P-24,37,39 (6 to JP-A-62-168139)
Page 7); compounds according to claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US 4,923,790 columns 3-15 I-1 to III-43, especially II-1. , 9,10,18, III-25;
Stabilizers, antifoggants: Columns 6 to 16 of US 4,923,793 I
-1 ~ (14), especially I-1,60, (2), (13), column 4, US 4,952,483
5 to 32 compounds 1 to 65, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324;
Dye: a-1 to b-20, particularly a- on pages 15 to 18 of JP-A-3-156450
1,12,18,27,35,36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, E
FI-1 to F-II-43, especially FI-11 and FI, on pages 33 to 55 of P 445627A
I-8, EP 457153A, pages 17-28, III-1 to 36, especially III-1,3,
Fine crystal dispersion of Dye-1 to 124 of 8 to 26 of WO 88/04794, E
P 319999A pages 6-11, compounds 1-22, especially compound 1, EP
Compounds D-1 to 87 represented by formulas (1) to (3) of 519306A
(Page 3-28), compound 1 represented by formula (I) of US 4,268,622.
22 (columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by the formula (I) of US Pat. No. 4,923,788;
Compounds represented by formula (1) of 6-3335 (18b) ~ (18r), 101 ~
427 (pages 6-9), compounds of formula (I) of EP 520938A
(3) to (66) (pages 10 to 44) and compounds represented by formula (III)
HBT-1 to 10 (page 14), compounds (1) to (31) represented by formula (1) of EP 521823A (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Examined Fairness 2-32615, Actual Fairness 3
It is suitable for the film unit with a lens described in -39784. Suitable supports that can be used in the present invention are described, for example, in RD. No.17643, page 28, No.18716, 647
The right column of the page to the left column of the page 648 and the page 879 of the same No. 307105. 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, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as
The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A. Green et al.'S Photographic Science and Engineering. (Photogr. Sci. Eng.), Page 19, pages 2,124 to 129. It can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a 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 is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-
It can be calculated by (film thickness) / film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm to 20 μm. This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No.176
43, pages 28-29, ibid. No. 18716, 651 left column-right column, and ibid N
It can be developed by a usual method described on pages 880 to 881 of O.307105. The color developing solution used for 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. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are
The compounds described on page 28, lines 43-52 of EP 556700A are mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Add N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also do it. 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 processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, JP-A-63-216050 The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development step and the black-and-white development step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing and the like. 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 by using a high temperature, high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

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. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Among them, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III)
II) Complex salts and other aminopolycarboxylic acid iron (III) complex salts are preferable from the viewpoint of rapid processing 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 the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) 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 pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-124424,
53-141623, 53-28426, RD No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-53-32735;
Thiourea derivatives described in 3,706,561; DE 1,127,715, iodide salts described in JP-A-58-16235; DE 966,410, 2,74
Polyoxyethylene compounds described in 8,430; JP-B-45-
8836 Polyamine compounds; Others JP-A-49-40943,
Same 49-59644, same 53-94927, same 54-35727, same 55-26506, same
Compounds described in 58-163940; bromide ion can be used.
Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly US 3,89
Compounds described in 3,858, DE 1,290,812 and JP-A-53-95630 are preferable. Further, the compounds described in US 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 acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. 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, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Further, it is also preferable to use a combination of thiosulfate, thiocyanate, thioether compound and thiourea. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or
The sulfinic acid compounds described in EP 294769A are preferred. Further, addition of aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution is preferable for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole is used.
It is preferable to add 0.1 to 10 mol per liter.

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 treatment 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 process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460 or a stirring effect by using a rotating means of JP-A-62-183461 is used. Method of raising, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, the circulation flow rate of the entire processing solution There is a method of increasing it. Such a stirring improving means is effective in 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 light-sensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-6-191257.
It is preferable to have the photosensitive material conveying means described in 0-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Shortening the processing time,
It is particularly effective in reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive 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 system such as countercurrent, forward flow, and various other conditions Can be set in a wide range. Of 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 t
he Society of MotionPicture and Television Enginee
It can be determined by the method described in rs Volume 64, P.248-253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described 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 washing time can be set depending on the characteristics and use of the light-sensitive material, but in general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. For such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be applied. In addition, following the water washing treatment, there is a case where a further stabilization treatment is performed, and as an example,
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, 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 replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The photographic material of 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 a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compound, 3,342,599,
Research Disclosure No. 14850 and No. 15159
Schiff base type compounds described in US Pat. No. 3,719,492, and metal salt complexes described in US Pat. No. 3,719,492.
The urethane compound described in 35628 can be mentioned.
The photographic material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-1.
44547 and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can.

[0117]

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

Example 1 (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n 2 parts by weight of P.326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., and then extruded from a T-die 14
The film was longitudinally stretched 3.3 times at 0 ° C., and then 3.3 times at 130 ° C.
Double stretching was performed, and heat setting was further performed at 250 ° C. for 6 seconds. The thickness was 90 μm. -PET: A commercially available poly (ethylene terephthalate) polymer is biaxially stretched and heat-set according to a conventional method to have a thickness of 90 μm.
I got a film of m.・ TAC: Methylene chloride / methanol = 82/8 wt by a normal solution casting method of triacetyl cellulose
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used. Thickness is 122μm and 90μ
m.・ PEN / PET = 4/1 (weight ratio); PE in advance
The N and PET pellets were vacuum dried at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a twin-screw kneading extruder, and then pelletized. This polyester is
A film was formed under the same conditions as EN. The thickness was 90 μm.

(2) Coating of undercoat layer Each of the above supports is subjected to corona discharge treatment on both sides thereof, and then the undercoat liquid having the following composition is applied to provide the undercoat layer on the high temperature surface side during stretching. It was For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 cc Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g

An undercoat layer having the following composition was provided on the support TAC. Gelatin 0.2g Salicylic acid 0.1g Methanol 15cc Acetone 85cc Formaldehyde 0.01g

(3) Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layer of the above support was provided after undercoating. (3-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.1.
A fine powder of tin oxide-antimony oxide composite having a size of μm was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed with a stirrer, and then
Horizontal sand mill (trade name Dyno Mill; WILLYA. BACHOFEN
It was prepared by dispersing with AG) until the residence time reached 30 minutes.

(3-2) Preparation of Back Layer: The following formulation [A] was applied so that the dry film thickness would be 0.3 μm, and dried at 115 ° C. for 60 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness would be 1 μm.
It was dried at ℃ for 3 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion liquid 1 part by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight polyoxyethylene nonylphenyl ether 0.01 part by weight [coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8/2 weight ratio) 0.01 parts by weight Dispersion (average particle size 20 nm)

(4) Heat Treatment of Support After the undercoat layer and the back layer were applied and dried and wound by the above method, heat treatment was separately performed under the conditions shown in Tables 4 to 5 below. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound. On the other hand, the supports PEN, PET, P
A support which was not heat-treated at EN / PET = 4/1 (weight ratio) was also prepared.

(5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the composition shown below was multilayer-coated to prepare a multilayer color photosensitive 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 point organic solvent ExY: Yellow coupler H: Gelatin Hardener ExS; Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of 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.

(Samples 101 to 108; different supports as shown in Table 4) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS- 1 0.16

Second layer (intermediate layer) ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.030 UV-5 0.040 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 0.080 Gelatin 0.90

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.23 Emulsion B Silver 0.23 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.050 ExC-3 0.030 ExC-4 0.15 ExC-5 3.0 x 10 ^-3 ExC-7 1.0 x 10 ^-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.10 Gelatin 0.90

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.70 ExS-1 3.4 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.10 ExC-2 0.060 ExC-4 0.055 ExC-5 0.010 ExC-8 0.010 ExC-9 0.055 Cpd-2 0.023 HBS-1 0.11 Gelatin 0.60

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion D Silver 1.62 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.080 ExC-3 0.050 ExC-5 2.0 × 10 ^-3 ExC-6 0.010 ExC-8 0.010 ExC-9 0.025 Cpd-2 0.025 HBS-1 0.20 HBS-2 0.10 Gelatin 1.30

6th layer (intermediate layer) Cpd-1 0.090 P-2 0.25 HBS-1 0.05 polyethyl acrylate latex 0.15 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 0.24 Emulsion F Silver 0.24 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 5.0 × 10 ^-3 ExM-2 0.25 ExM-3 0.095 ExM-4 0.030 ExM-7 0.030 Comparative coupler (1) 0.015 E-1 5.0 × 10 ^-3 HBS-1 0.30 HBS-3 0.010 Gelatin 0.85

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion G Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.14 ExM-3 0.05 ExM-5 0.022 Comparative coupler (2) 0.010 E-1 5.0 × 10 ^-3 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion H Silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 Comparative coupler (2) 5.0 × 10 ^-3 ExM-1 0.020 ExM-4 0.030 ExM-5 0.022 ExM-6 0.030 Comparative coupler (1) 5.0 × 10 ^-3 Cpd-3 0.085 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.45

10th layer (yellow filter layer) Yellow colloidal silver Silver 7.5 × 10 ^-3 ExC-10 0.030 Cpd-1 0.10 Cpd-4 7.5 × 10 ^-3 L-2 0.50 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion I Silver 0.25 Emulsion J Silver 0.25 Emulsion K Silver 0.10 ExS-7 8.0 × 10 ^-4 ExC-7 0.010 ExY-1 5.0 × 10 ^-3 ExY-2 0.40 ExY-3 0.50 ExY-4 6.0 × 10 ^-3 ExY-6 0.10 HBS-1 0.30 Gelatin 1.65

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 1.30 ExS-7 3.0 × 10 ^-4 ExC-6 3.0 × 10 ^-3 ExY-2 0.15 ExY-3 0.065 ExY-4 5.0 × 10 ^-3 ExY-5 5.0 × 10 ^-3 Cpd-2 0.10 HBS-1 0.070 Gelatin 1.20

Thirteenth layer (first protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.20 UV-5 0.15 HBS-1 0.10 Gelatin 2.50

14th layer (second protective layer) Emulsion M Silver 0.10 H-1 0.33 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.24 Gelatin 0.70

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-4, B-4 to B- may be used. 6, F
-1 to F-18 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt. Cpd-4 was dispersed in a solid state according to the method described in International Patent No. 88-4794.

[0143]

[Table 1]

In Table 1, (1) Emulsions I to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to L were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) In the tabular grains, dislocation lines as described in JP-A-3-237450 are observed using a high voltage electron microscope.

The couplers and additives in each layer were dispersed in a gelatin solution by the method shown in Table 2. The addition method for each layer is shown in Table 3.

[0146]

[Table 2]

[0147]

[Table 3]

[0148]

[Chemical 37]

[0149]

[Chemical 38]

[0150]

[Chemical Formula 39]

[0151]

[Chemical 40]

[0152]

[Chemical 41]

[0153]

[Chemical 42]

[0154]

[Chemical 43]

[0155]

[Chemical 44]

[0156]

[Chemical formula 45]

[0157]

[Chemical formula 46]

[0158]

[Chemical 47]

[0159]

[Chemical 48]

[0160]

[Chemical 49]

[0161]

[Chemical 50]

[0162]

[Chemical 51]

[0163]

[Chemical 52]

[0164]

[Chemical 53]

Next, the comparative couplers (1) and (2) used in the seventh, eighth and ninth layers of the green-sensitive emulsion layer were used as the exemplified compounds D-15 and D-2 of the present invention, respectively. Samples 109 to 116 were prepared by replacing the molar amounts. Table 4
Shown in. Samples 117 to 120 were prepared by using a PEN support which was heat-treated before coating the photosensitive layer and replacing the above-mentioned couplers in the green-sensitive emulsion layer with the exemplified compounds of the present invention in equimolar amounts as shown in Table 5. . Furthermore, sample 10
1 to 108, the comparative couplers (1) and (2) used in the seventh to ninth green-sensitive emulsion layers were replaced with the couplers described in the cited patents shown in Chemical formulas 54 to 58 in equimolar amounts, and Sample 101 was used.
Samples 121 to 192 were prepared according to Representative examples of these are also shown in Table 5 above.

[0166]

[Table 4]

[0167]

[Table 5]

[0168]

[Chemical 54]

[0169]

[Chemical 55]

[0170]

[Chemical 56]

[0171]

[Chemical 57]

[0172]

[Chemical 58]

[0173]

[Chemical 59]

[0174]

[Chemical 60]

[0175]

[Chemical formula 61]

The prepared samples were cut and processed, and one set was subjected to the conditions of 5 ° C. and relative humidity of 35%, and the other set was set to 50 ° C.
After storing each for 5 days under the condition of relative humidity 80%, gradation exposure of white light is given, and the following color development processing is carried out.
The R, G, and B color densities of each sample were measured, the logarithm of the reciprocal of the exposure dose that gave the minimum density + 0.2 was calculated from the characteristic curve, and the samples were stored at high temperature and high humidity. The sensitivity difference (ΔS) between the time and the storage at low temperature and low humidity was determined. The results of the G concentration are shown in Tables 6 and 7.

Next, in order to examine the edge effect, line image exposure is performed with X-rays, and color development processing shown below is performed,
The obtained treated sample was scanned with a microdensitometer to measure the density with R, G, and B light. The maximum density-fog partial density (minimum density) of the line image of 30 μm is D ₁ ,
Letting D ₂ be the [average density in the central portion-fog partial density] of the line image of 1,000 μm, the respective (D ₁ -D ₂ ) / D ₁ obtained by measuring the density with R, G, and B light were obtained. Was used as a scale for evaluating the edge effect. The larger the numerical value, the greater the edge effect of the sample when observed with each of the R, G and B lights. The results obtained from the G light density measurement are also shown in Tables 6 and 7. For the description of an apparatus used to obtain a line image using X-rays, refer to "Apparatus for Making Equipment for Clear Photographic Image Formation by X-rays".
sharp Photographic Images with X-Rays) ", The Rev
iew of Scientific Instrument, Vol.38, No.11, P1619
~ 1622 (Nov.1967) can be referred to. Also,
For the edge effect, refer to "Development-Inhibito Release Inhibitor Release (DIR) Coupler
r-Releasing (DIR) Couplers in ColorPhotograph
y) ”, Photographic Science and Engineering, Vol.1
3, No. 2, P74-80 (March-April, 1969) can be referred to.

Further, the MTF pattern, which is a conventional method for sharpness as an image quality, is exposed and the MT of the magenta color image is exposed.
The F value was measured at a density of 1.0. The results are also shown in Tables 6 and 7.

On the other hand, the density of a sample obtained by separately subjecting it to grayscale exposure of white light was measured, and then the sample was stored at 70 ° C. and 80% relative humidity for 60 days, and then the density was measured again. The change (ΔDmin) was determined. The results are shown in Tables 6 and 7.

The color development processing used in this embodiment is shown below. Processing is Fuji Photo Film's automatic processor FP
-560B was modified and performed as follows. However, the processing of the photographed sample was carried out after running the separately image-wise exposed sample until it was replenished by 3 times the capacity of the color developing tank. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 40.0 ℃ 200 ml 5 liters Bleach 50 seconds 38.0 ℃ 140 ml 5 liters Bleach fixing 50 seconds 38.0 ℃ -5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ ― 3 liters Stability (2) 20 seconds 38.0 ℃ 560 ml 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material.

The stabilizing solution is a countercurrent system from (2) to (1),
The overflow of washing water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic developing machine and at the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 3.6 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Potassium carbonate 37.5 39.0 Potassium bromide 2.7 ― Potassium iodide 1.3 mg-hydroxylamine sulfate 3.5 5.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 6.0 10.5 Add water 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid Adjust) 10.05 11.0

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropaneferric acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 25 38 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.0

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (Adjust with ammonia water and acetic acid) 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

[0188]

The results of the samples shown in Tables 4 and 5 are summarized in Tables 6 and 7.

[0190]

[Table 6]

[0191]

[Table 7]

From Tables 6 and 7, the support of the present invention is represented by the formula (1) and / or (2) of the present invention on the support having a thickness of 90 μm in the range of 60 to 110 μm. A photosensitive material coated with a photosensitive layer containing a compound has excellent stability with little fluctuation in photographic sensitivity when the photosensitive material itself is stored under high temperature and high humidity, and has an edge effect and sharp image quality. Also shows a high value and has an excellent effect of improving the image quality. Furthermore, when the image after color development processing is stored under high temperature and high humidity, the density increase of the non-coloring part is small and the image quality and color image storability are excellent. Comparative samples 101 to 1
It is clear from the comparison between Sample No. 09 and Samples 110 to 120 according to the present invention. Even if the support has the same thickness of 90 μm, it is preferable that the support is made of a polyester material and that the support subjected to heat treatment before the application of the photosensitive layer is used for the samples 110 and 111 to 111, respectively. 116 and sample 111 and sample 112, sample 113 and sample 114, sample 1
This can be known from the comparison between 15 and sample 116.

Example 2 Samples 109 to 116 produced in Example 1 were slit into a width of 35 mm and a length of 1.8 m, perforated and incorporated into a unit as shown in FIG. 1 to produce a film-integrated camera. .

FIG. 1 shows a unit 1 of a film-integrated camera.
3 is a partial cross-sectional top view of FIG. Patrone 16
Spool 21 inside, and spool 2 in supply room 14
Two are provided. The film 18 is a film having a length of 1.8 m. In the unit 13, the unexposed film is wound and loaded on the spool 22 of the supply chamber 14. The film is pulled out each time the film is taken, and the spool 21 in the cartridge 16 of the winding chamber 15
It is designed to be rolled up. Reference numeral 17 is a photographing lens, and 20 is a photographing exposure frame of the subject. The following experiments were conducted using spool diameters of 11.0 mm and 8.0 mm.

The film-integrated type camera loaded with the above-prepared film was heated at 40 ° C. and 70% relative humidity for 24 hours, and was provided with a curl. The setting of the temperature and humidity is a condition assuming the outdoor in summer.

In the film-integrated type camera with a curled curl under the above conditions, the film was allowed to cool overnight in a room at 25 ° C. and 55% relative humidity, and then the tongue end of the film was pulled out by a jig. Develop with the automatic processor described in 1,
The workability of the film and the developability such as scratches and uneven processing were examined. The results are shown in Table 8.

[0197]

[Table 8]

From the results of Table 8, from the comparison between Sample 109 and Sample 110, it is preferable in the present invention that the use of a thin support is preferable from the viewpoint of workability of the film and reduction of troubles during the development processing of the film. I can know. Further, even in the case of a thin-layered support, it is preferable to use a support made of a polyester-based material which has been heat-treated before coating the photosensitive layer, for Samples 101, 111, 113, 115 and Sample 11.
It is clear from the comparison with 2, 114 and 116. In addition,
The thickness of the support of the sample 109 is 122 μm, and the length of 1.8 m is wound on the spool diameter of 11.0 mm. There is almost no gap between the film and the wall of the cartridge, and there is little room for winding a long film. Is 90
In the sample using the support of μm, there is room to wrap up a longer film, and in fact, a film having a length of 2.4 m is possible, which indicates that 50 shots can be taken. In addition, when using a pre-heated polyester support with a thickness of 90 μm and winding it up to a spool diameter of 8.0 mm, there is no problem in handling workability and processability of the film, which makes the cartridge slimmer. It shows that it is possible. Therefore, it suggests the possibility of downsizing the camera.

Example 3 The sample 106 produced in Example 1 was subjected to grayscale exposure with white light, and the sample 106 was processed using the new color developing solution described in Example 1. After that, the samples 101 to 108 were subjected to imagewise exposure, and a running treatment of a total of 10 m ² per day was continuously performed for 10 days, and then a grayscale exposure of white light was again given to the sample 106. The sample was color developed. The density of the processed sample is measured, and the logarithm of the reciprocal of the exposure amount that gives the density of minimum density + 0.2 is calculated from the characteristic curve, and the difference (ΔS) between the sensitivity values before and after the running process is calculated for G density. I asked. Further, the G density at the exposure amount point of logE = 1.5 is read from the sensitivity point to the high exposure amount side, and the density before the running process is D ₀ , the density after the running process is D ₁ , and the variation of the color density is calculated. It was determined as (D ₁ / D ₀ ) × 100.

Subsequently, Samples 114 to 117 to 120 were similarly processed by using Samples 109 to 120 for continuous treatment. Hereinafter, regarding samples 126, samples 121 to 12
8 and sample 129 to 136 for sample 134, sample 14
Samples 137 to 144 for sample No. 2 and sample 145 for sample 150
-152, sample 158 includes samples 153-160, sample 1
Samples 161-168 for 66 and sample 16 for sample 174
9 to 176, Sample 182 to Samples 177 to 184, and Sample 190 to Samples 185 to 192 were examined for variations in photographic properties during running processing in the same manner as described above. The results are shown in Table 9.

[0201]

[Table 9]

It can be seen from Table 9 that a photosensitive layer coated with a preheat-treated polyester system (PEN) of the present invention on a support having a thickness of 90 μm has the formula (1) and / or (2) of the present invention. The light-sensitive material using the compound represented, when the color developing solution is subjected to a low replenishing amount of running processing, before the start of the running processing and when processed with a solution in which the components in the processing solution have reached an equilibrium state It can be seen from the comparison with the comparative sample that the variation in the photographic properties with and is clearly small. It can also be seen that even for the compounds represented by the formulas (1) and (2) of the present invention, it is preferable to use the compounds described in the specific examples of the present invention as compared with known reference compounds.

Example 4 Thickness 1 of TAC support of Sample 109 prepared in Example 1
TAC with the thickness of 22 μm changed as shown in Table 10
As the support, the same photosensitive layer as that of Sample 109 was applied to prepare Samples 401 to 405. Next, the sample 114
Samples 406 to 411 were prepared by changing the thickness of the heat-treated PEN support of 90 μm in the same manner as shown in Table 10 only in the thickness.
Was produced. The heat treatment was performed under the same conditions.

The samples 401 to 411 thus prepared were examined for storability and image quality over time of the light-sensitive material in accordance with the method described in Example 1 together with the samples 109 to 110 and 114. The results are shown in the same Table 10.

[0205]

[Table 10]

From Table 10, in the present invention, the thickness of the support used for the light-sensitive material is in the range of 60 to 110 μm, and the storage property of the light-sensitive material at high temperature and high humidity over time, edge effect, sharpness, and after processing are shown. It can be seen that it is preferable for the image quality such as a small increase in D _min and the storability of color images. When the thickness of the support exceeds 110 μm, it becomes impossible to wrap a long film in the existing 135 size patrone as described in Example 2 above. Further, when the thickness was 50 μm, it was observed that even a polyester-based support could not have flexural elasticity to withstand the contraction stress of the photosensitive layer and a gutter-like curl was generated. It is thought that this is the cause of the deterioration of image quality such as sharpness and edge effect. On the other hand, in the TAC support, when the thickness is 50 μm, it is 35
It was found that a film having a perforation perforated by slitting it in a width of mm easily breaks from the perforation part if it is twisted and pulled a little, and it has been found that there is a great risk of causing a cutting failure at the time of development or the like. From the results of Table 10, the thickness of the support is preferably 70 to 100 μm.

Example 5 P-5, 6, described in the example of polyester compound, in accordance with the support production methods (1) to (4) described in Example 1.
7, 9, 10, 11, 12, 13, 17 and 19 of 10
A seed support was made. The heat treatment of these supports before coating the photosensitive layer is carried out at 10 from the glass transition temperature (Tg) described.
It was obtained by carrying out both for 48 hours at a temperature lower by ℃. These one
A sample was prepared by coating a photosensitive layer having the same composition as in Example 1 and Sample No. 118 on 0 type of support.

According to the method described in Example 1, these samples were examined for storability with time at high temperature and high humidity, edge effect and sharpness as image quality, and storability of color image. Values within the range of the results obtained for the samples 116 to 120 shown in Table 1 were obtained, and it was confirmed that these various performances were excellent.

[0209] Further, the film tongue end was taken out after the film was integrated with the film-integrated type camera in accordance with the method described in Example 2, but it was easy, and scratches were caused even in the development processing by the developing machine. Accidents during processing such as uneven development and folding of the trailing edge of the film were not observed.

Example 6 ExC-8 used in the third, fourth and fifth red-sensitive emulsion layers of Example 1 and Sample 119 was replaced by a compound D- represented by the formula (1) of the present invention. 6 or D-11, ExY-5 used in the twelfth blue-sensitive emulsion layer is D represented by the formula (1) of the present invention.
-4 or the sample prepared by substituting D-16 represented by the formula (2) in an equimolar amount, according to the running process described in Example 3, the change in photographic property was examined, and the sample numbers shown in Table 9 were obtained. Similar to Nos. 114 and 117 to 120, good results with small variations in sensitivity and color density were obtained.

[0211]

EFFECT OF THE INVENTION A silver halide color photograph using a support having a thickness of 60 μm or more and 110 μm or less and containing at least one photosensitive layer a compound represented by formula (1) and / or formula (2). The light-sensitive material is excellent in storability, image quality, and color image storability. The above performances are further improved when the support is a poly (alkylene aromatic dicarboxylate) polymer that has been heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature before coating the photosensitive layer.

[Brief description of drawings]

FIG. 1 shows an example of a partially cross-sectional top view of a unit of a film-integrated camera.

[Explanation of symbols]

 13 Unit 14 Supply Room 15 Winding Room 16 Patrone 17 Lens Unit 18 Film 20 Exposure Frame 21 Spool 22 Spool

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/305 // B32B 27/36 7421-4F C08J 5/18 CFD 9267-4F

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, and at least one light-sensitive silver halide emulsion layer.
The layer contains a compound represented by the following formula (1) and / or formula (2), and the thickness of the support is from 60 μm to 110 μm.
A silver halide color photographic light-sensitive material characterized by the following. Formula (1) A _1- (TIME) _a -DI Formula (2) A _2- (TIME) _a -DI In the formula, A ₁ has a nondiffusible group and oxidizes the aromatic primary amine developer. Represents a group capable of leaving (TIME) _a -DI upon reaction with _a derivative, A ₂ has no diffusion-resistant group, and reacts with an oxidant of an aromatic primary amine developing agent to give (TIM
E) represents a group that leaves _a- DI, TIME represents a timing group that cleaves DI after leaving from A, DI represents a development inhibitor that is substantially deactivated after flowing out into a developer, and a represents Represents 1 or 2. two a when a is 2
IME represents the same or different. 2. The support having a thickness of 60 μm or more and 110 μm or less is made of a poly (alkylene aromatic dicarboxylate) polymer and has a glass transition temperature of 50 ° C. or more and 200 ° C. or less, and molding of the support. 2. The support which has been heat-treated at a temperature of 40 ° C. or higher and lower than the glass transition temperature after completion of coating of the undercoat layer or after completion of coating of the undercoat layer and before coating of the silver halide photosensitive layer. Silver halide color photographic light-sensitive material.