JPH06250335A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material excellent in curling property and pressure resistance by incorporating a specified coupler into photographic layers and laminating polyester layers. CONSTITUTION:At least one layer of photographic layers contains a coupler expressed by the formula. A transparent supporting body consists of laminated polyester layers having different equilibrium water contents. In the formula, R<1> is -CONR<4>R<5>, -NHCOR<4>, -NHCOOR<6>, NHSO2R<6>, -NHCONR<4>R<5>, -SO2NR<4>R<5>, or -NHSO2NR<4>R<5>, R<2> is H or substituent, R<3> is a substituent, X is hydrogen atom or a group which can be released by the reaction with the oxidant of an aromatic primary amine developing agent. 1 is an integer 0-3, R<4>, R<5> are hydrogen atoms, aromatic groups, aliphatic groups or heteroring groups, R<6> is an aromatic group, aliphatic group, or heteroring group. When 1 is 2 or 3, R<3> may be same or different or may be bonded to form rings. R<4> and R<5>, R<2> and R<3>, R<2> and X may be bonded to form rings.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material (hereinafter simply referred to as a color light-sensitive material) having improved curling characteristics, pressure resistance and image characteristics. Sometimes).

[0002]

2. Description of the Related Art In recent years, cameras have become smaller and simpler,
The portability has improved and the opportunity for taking pictures has increased significantly. However, further miniaturization has been desired by users, and miniaturization while maintaining high image quality has been widely studied. The so-called 135 size roll film for general use is loaded in the standard format patrone, which is an obstacle to making the camera thinner. In order to reduce the size of the cartridge, it is most effective and convenient to thin the film, that is, the light-sensitive material, and it can be achieved by making the thickness of the plastic film support of the light-sensitive material thinner than before. .

On the other hand, the standard size Patrone of 135 size is currently limited to 36 pictures. For one Patrone,
There is a desire to put more image information, and this can also be achieved by making the thickness of the support of the photosensitive material thinner than before.

By the way, as a plastic film support conventionally used for a light-sensitive material, triacetyl cellulose (TAC), polyethylene terephthalate (P) is used.
ET) is typical.

T which is mainly used for roll-shaped films
The AC film has a property that it has no optical anisotropy and high transparency, and further has an excellent property that it can be curled after development processing. However TAC
Since the film originally has a drawback of low mechanical strength, it cannot be thinned at present.

On the other hand, since PET film has excellent productivity, mechanical strength and dimensional stability, it is mainly used for a sheet-shaped film such as an X-ray film. However, in the roll form widely used as a photographic light-sensitive material, there are drawbacks that it is difficult to wind the curl even after the development processing and the handleability is poor, and its application range is limited.

As a method for improving the curl-up recovery property of a PET film, a copolymerized PET film in which hydrophilicity is imparted by using an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component has been proposed (special feature: Kaihei 1-
No. 244446). However, in this method, a large amount of the copolymerization component must be contained in order to obtain a sufficient curl recovery property, and the original properties such as excellent mechanical strength and dimensional stability of PET are lost. Therefore, the advantage over TAC is lost.

Further, Japanese Patent Laid-Open No. 4-93937 discloses a photographic light-sensitive material excellent in mechanical properties such as curl recovery, tear strength, and folding endurance by laminating polyesters having different water contents. Proposed.

As a result, excellent productivity, mechanical strength, dimensional stability, and the like of the PET film can be obtained, and recovery of curling can be obtained without much loss.

Further, Japanese Patent Laid-Open No. 4-235036 proposes to improve transparency, water absorption, mechanical properties and heat resistance by using a polyester film having a multilayer structure.

However, as a result of producing a color light-sensitive material by providing a photographic constituent layer on these supports, it was revealed that the image characteristics of the color forming dye of the cyan coupler change with time. That is, it was found that the maximum absorption wavelength changed with the lapse of time after the development processing. Therefore, there arises a problem that the printing conditions change with time, and variations in printing become large when printing is repeated.

[0012]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic color light-sensitive material excellent in curling property and pressure resistance, and to obtain a cyan dye image with aging after development processing. An object is to provide a silver halide color photographic light-sensitive material having stable color tone and density.

[0013]

The objects of the present invention have been achieved by the following. That is, in a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of at least one red-sensitive, green-sensitive, blue-sensitive photosensitive layer and a non-photosensitive layer on one side on a transparent support, At least one of the constituent layers contains a coupler represented by the following general formula [CI], and the transparent support is formed by laminating polyester layers having different equilibrium water contents. A silver halide color photographic light-sensitive material.

[0014]

[Chemical 2]

In the formula, R ¹ is --CONR ⁴ R ⁵ , --NHCOR ⁴ , --NHCO.
OR ⁶ , -NHSO ₂ R ⁶ , -NHCONR ⁴ R ⁵ , -SO ₂ NR ⁴ R ⁵ or -NHS
O ₂ NR ⁴ R ⁵ , R ² represents H or a substituent, R ³ represents a substituent, and X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized product of an aromatic primary amine developer. Where l is 0
Represents an integer of 3, R ⁴ and R ⁵ each represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, and R ⁶ represents an aromatic group, an aliphatic group or a heterocyclic group. l is 2 or 3
In this case, each R ³ may be the same or different, and may combine with each other to form a ring, and R ⁴ and R ⁵ , R ² and R ³ ,
R ² and X may combine with each other to form a ring.

To achieve the object of the present invention, it is particularly preferable that at least one of the polyester layers having different equilibrium water contents contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. It is a silver halide color photographic light-sensitive material characterized by being a copolyester.

The present invention will be described in detail below.

1) In the present invention, the equilibrium water content means the amount of water contained in the sample in the equilibrium state, expressed as a percentage with respect to the weight of the sample.

In the present invention, one embodiment in which the equilibrium water content of the polyester layer is different is preferably 0.1% or more,
More preferably 0.2% or more, particularly preferably 0.3% or more
It means having a difference in equilibrium water content of 2.0% or less. In another preferred embodiment, the equilibrium water content of at least one polyester layer is 0.5% or more, and the other at least one polyester layer is less than 0.5%. . Any method may be used to adjust the equilibrium water content, but it is preferable to adjust the equilibrium water content depending on the type of ester monomer, composition ratio, and degree of polymerization.

In the present invention, as an embodiment having different equilibrium water contents, among the polyester layers having different equilibrium water contents,
At least one polyester layer is preferably a copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a monomer component, and a polyester layer containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component When there are a plurality of the above, the polyester layers may have different equilibrium water contents due to the difference in the addition ratio of the copolymerization component.
Particularly, it is preferable that the polyester layer having a higher equilibrium water content contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, or is a copolymerized polyester having a high addition ratio of the copolymerization component. Less than,
A copolymerized polyester layer containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component is simply referred to as a "copolymerized polyester layer".

(A) Polyester Layer The polyester used in the polyester layer of the present invention is not particularly limited, but has excellent mechanical strength.
Polyesters containing aromatic dibasic acid and glycol as main constituents are preferred.

Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1 Examples thereof include 4,4-cyclohexanedimethanol and p-xylylene glycol.
Among these, terephthalic acid is preferable as the aromatic dibasic acid, and ethylene glycol is preferable as the glycol.

More preferably, the main content of repeating units of the polyester layer is 85 mol% or more, and further other copolymerization components are contained within a range that does not impair good properties such as excellent original mechanical strength of polyester. May be contained. Further, other polymers may be blended. If necessary, phosphoric acid, phosphorous acid, or their esters, inorganic particles (eg, silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.), dyes, UV absorbers, antioxidants, etc. are included. can do.

The polyester layer in the present invention may be a layer formed of a single layer or a layer formed of a plurality of layers by a known method.

The total thickness of the polyester layer is preferably 50 μm or less, and more preferably 40 to 25 μm in order to obtain a thickness and strength required for a conventional photographic support. .

(B) Copolymerized Polyester The copolymerized polyester according to the present invention, which is a polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, wherein the main constituent components of the polyester are aromatic dibasic acid and glycol. Suitable examples of the copolymerized polyester are

The aromatic dicarboxylic acid having a metal sulfonate group used in the present invention includes 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid and 4-sodium sulfoisophthalic acid.
Sodium sulfoisophthalic acid, 4-sodium sulfo-
Examples thereof include 2,6-naphthalenedicarboxylic acid, aromatic dicarboxylic acids shown below, and compounds obtained by substituting these sodiums with other metals such as potassium and lithium.

[0028]

[Chemical 3]

Among these, 5-sodium sulfoisophthalic acid and 4-sodium sulfo-2,6-naphthalenedicarboxylic acid are preferable.

The copolyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component in the present invention has a quantity of the aromatic dicarboxylic acid having a metal sulfonate group, which is detected by hydrolyzing the same. Is preferably 2 to 7 mol% with respect to the total ester bond units in the copolyester layer in order to sufficiently recover the curl and to obtain a photographic support excellent in mechanical strength. , And more preferably 4 to 5 mol%.

Aromatic dibasic acids preferably used in the present invention include terephthalic acid, isophthalic acid and 2,6-
Examples thereof include naphthalenedicarboxylic acid, and as the glycol, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,
4-cyclohexanedimethanol, p-xylylene glycol and the like can be mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable as the aromatic dibasic acid, and ethylene glycol is preferable as the glycol.

Preferred examples of the copolyester used in the present invention include a copolyester having terephthalic acid and ethylene glycol as main constituents, and 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents. A copolyester can be mentioned.

Further, the copolymerized polyester in the present invention may further contain polyalkylene glycol as a copolymerization component in addition to the main constituent component (particularly glycol) as long as the object of the present invention is not impaired.

Examples of the polyalkylene glycol include polyethylene glycol and polytetramethylene glycol, among which polyethylene glycol is preferred. The molecular weight of polyethylene glycol is usually 200 to 20,000, preferably 400 to 5,
It is 000.

The content of the polyalkylene glycol is preferably 3 to 10% by weight, more preferably 4 to 8% by weight, based on the total weight of the reaction product, in order to obtain sufficient curl recovery and mechanical strength. %. If it is less than 3% by weight, sufficient curling and curl recovery cannot be obtained, and if it exceeds 10% by weight, mechanical strength tends to deteriorate.

The copolymerized polyester used in the present invention may further contain other types of copolymerization components or may be blended with other polymers as long as the objects of the present invention are not impaired.

The copolymerized polyester having an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component is not particularly limited in its production method. For example, in the case of a polycondensation reaction after an ester exchange reaction, a transesterification reaction is performed. At times, a copolymerization component such as an aromatic dicarboxylic acid having a polyethylene glycol or a metal sulfonate group may be added, and then polycondensation may be continuously performed. After the transesterification reaction, these copolymerization components may be added to perform a polycondensation reaction. You may go.

Examples of the catalyst used for this transesterification include acetates, fatty acid salts, carbonates of metals such as manganese, calcium, zinc and cobalt. Among these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable.

Hydroxides, metal salts of aliphatic carboxylic acids, quaternary ammonium and the like may be added to the extent that the reaction is not inhibited and the polymer is not colored during the transesterification and / or polycondensation. Among them, sodium hydroxide, sodium acetate and tetraethylene hydroxyammonium are preferable, and sodium acetate is particularly preferable.

The copolyester used in the present invention is phosphoric acid, phosphorous acid,
And their esters and inorganic particles (for example, silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.), or the inorganic particles appropriately added after the polymerization.

The copolyester may contain various dyes, ultraviolet absorbers, antioxidants, etc., which are appropriately added at any stage of the transesterification reaction, the polymerization stage and the post-polymerization stage. It doesn't matter.

The type of the antioxidant is not particularly limited, and specific examples thereof include hindered phenol compounds, allylamine compounds, phosphite compounds and thioester antioxidants. . Among these, hindered phenol compounds are preferable.

The content of the antioxidant in the transparent support is usually 0.01 to 2 relative to the support in view of the effect of photographic performance and the turbidity of the polyester layer as the photographic support.
%, Preferably 0.1 to 0.5% by weight. The antioxidants may be used alone or in combination of two or more.

Further, the transparent support in the present invention is a transparent support coated with a photographic emulsion layer for the purpose of preventing a light piping phenomenon (edge fog) which occurs when light is incident from an edge. It is preferable to include a dye in the. The dye to be blended for such a purpose is not particularly limited in its type, but in the film forming process of the film, a dye having excellent heat resistance is preferable, and examples thereof include anthraquinone-based chemical dyes. You can As the color tone of the transparent support, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes can be mixed and used. As these dyes, dyes such as SUMIPAST manufactured by Sumitomo Chemical Co., Ltd., Diaresin manufactured by Mitsubishi Kasei Co., Ltd., and MACROLEX manufactured by Bayer can be used alone or in an appropriate mixture.

(C) Manufacture of photographic support As a method of manufacturing the photographic support of the present invention, for example,
As one method, the polyester described in (A) and the copolyester described in (B) are melt-extruded through separate extruders, filters, die and the like, and then, in a conduit of the molten polymer or in an extrusion die. A coextrusion method in which the unstretched film is biaxially stretched in the longitudinal direction and the transverse direction and heat-fixed is obtained by unbonding the film in a laminar flow and extruding, cooling and solidifying on a rotating cooling drum to obtain an unstretched film. is there. As another method, an unstretched film obtained by melt-extruding the polyester described in (A) from an extruder and cooling and solidifying on a cooling drum, or a uniaxially oriented film obtained by uniaxially stretching the unstretched film, or a commercially available polyester If necessary, the surface of the film or sheet is coated with an anchoring agent, an adhesive, etc., and then the copolymerized polyester described in (B) is extrusion laminated thereon, and then biaxially stretched, followed by heat setting. Extrusion lamination method and the like can be mentioned. Among these, the coextrusion method is preferable from the viewpoint of the ease of the manufacturing process.

The stretching conditions of the film cannot be uniformly specified because it varies depending on the copolymerization composition of the copolyester, but preferably in the longitudinal direction within the temperature range from the glass transition temperature (Tg) of the copolyester to Tg + 100 ° C. Stretching ratio 2.5 to 6.0 times, Tg to Tg + 100 ° K in transverse direction
The stretching ratio is 2.5 to 5.0 times in the temperature range. The biaxially stretched film obtained as above is usually 150 ° C to 250 ° C.
It is heat set at ℃ and cooled.

In this case, if necessary, the vertical direction and / or
Alternatively, it may be relaxed in the lateral direction.

The thickness of the photographic support of the present invention thus obtained is not particularly limited as long as it has the mechanical strength required for use as a photographic support, but is usually 30.
˜125 μm, preferably 40 to 120 μm, more preferably 50 to 100 μm.

Any number of layers constituting the support may be laminated, but from the viewpoint of complicating the production equipment, etc., two or four layers are generally preferable, and three layers are particularly preferable. In the case of three layers, each layer is not particularly limited, for example, the inner layer is a polyester layer, the layers on both sides of the inner layer may be a copolyester layer, or the inner layer is a copolyester layer,
The layers on both sides of the inner layer may be polyester layers,
The former is preferred.

The elastic modulus of the photographic support is preferably 450 Kg / mm ² or more, more preferably 500 Kg / m ^{2 in} order to obtain a strong photographic support which is a characteristic feature of polyester.
m ² or more.

Further, the curl recovery rate of the photographic support is preferably 50% or more, and more preferably 80% or more, in order to obtain sufficient transportability in the development processing when used as a photographic film. .

(D) Particularly Preferred Conditions for a Photographic Support Particularly preferred as a photographic support of the present invention is one in which the inner layer has a polyester layer, and both sides of the inner layer each have a copolyester layer. The thickness of the inner polyester layer is d _2, and the total thickness of the copolyester layer laminated on one side of the n _A layer (total thickness of n _A layers)
Average content (mol%) of aromatic dicarboxylic acid having a metal sulfonate group with respect to all acid components contained in the entire n _A layer, and average content (% by weight) of polyalkylene glycol based on the total weight of the reaction product. Respectively d
1, S1, and P1, and d3 and S for the copolyester layer laminated on the other surface of the n _B layer, respectively.
3 and P3, the following conditional expressions 1, 2 and 3
It is particularly preferable to satisfy both of the above.

Conditional expression 1; d2 ≦ 50 (μm) Conditional expression 2; 0.7 ≦ {(d1 + d3) / d2} ≦ 3 Conditional expression 3; {(S1 × P1 × d1) / (S3 × P3 × d
3)} ≧ 1.5 where n _A , n _B , d1, S1, P1, d3, S
3 and P3 are as follows, respectively.

N _A ; n _A ≧ 1 and a natural number n _B ; n _B ≧ 1 and a natural number d1; a copolyester layer laminated on one surface of the polyester layer with the n _A layer The thickness of each layer in
d1 ₁ , d1 ₂ , d1 ₃ , ..., d1 _nA-1 , d1 _nA ,

[0055]

[Equation 1]

It is

Therefore, according to this equation, it can be said that d1 is the total thickness of the copolyester layers laminated on the one surface of the polyester layer by n _A layers.

S1: The content (mol%) of the aromatic dicarboxylic acid having a metal sulfonate group with respect to all ester bonds in each layer of the copolyester layer laminated on the surface of the polyester layer by n _A layers is S1 ₁ , respectively. S
1 ₂ , S1 ₃ , ..., S1 _nA-1 , S1 _nA ,

[0059]

[Equation 2]

It is Therefore, according to this equation, S
It can be said that 1 is the content (mol%) of the aromatic carboxylic acid having a metal sulfonate group with respect to all ester bonds per unit thickness of the polyester layer.

P1: The content (% by weight) of the polyalkylene glycol reaction product in each layer of the copolyester layer laminated on the surface of the polyester layer with respect to the n _A layer was P1 ₁ , P1 ₂ , and P1 ₃ , ...
., P1 _nA-1 and P1 _nA ,

[0062]

[Equation 3]

It is Therefore, according to this equation, P
It can be said that 1 is the content rate (% by weight) based on the total weight of the reaction product of the polyalkylene glycol per unit thickness of the copolyester layer.

Further, d3, S3 and P3 correspond to d1, S1 and P1 of the copolyester laminated on the other surface of the polyester layer by the n _B layer.

D3;

[0066]

[Equation 4]

S3;

[0068]

[Equation 5]

P3;

[0070]

[Equation 6]

It is

In the present invention, the above conditional expressions 1, 2
And 3 are satisfied at the same time, and a photographic support satisfying at least one of the following conditional expressions 4, 5 and 6 is more preferable, and the above conditional expressions 1, 2 and 3 are more preferable. And conditional expression 4 below,
It is a photographic support satisfying 5 and 6.

Conditional expression 4; d2 ≦ 40 (μm) Conditional expression 5; 1.5 ≦ {(d1 + d3) / d2} ≦ 2.5 Conditional expression 6; {(S1 × P1 × d1) / (S3 × P3 × d
3)} ≧ 2 (where, n _A , n _B , d1, S1, P1, d3, S
3 and P3 are as described above. In the case of a three-layer structure as in the present embodiment, it is preferable that the two outer layers outside the central layer have different intrinsic viscosities in addition to different thicknesses or composition ratios as described above. The viscosity difference ΔIV is preferably 0.02 to 0.5, more preferably 0.05 to 0.4, and particularly preferably 0.1 to 0.3.

The local variation in the thickness of the transparent support is 5 μm.
It is preferably m or less, more preferably 4 μm or less, and particularly preferably 3 μm or less. When the local variation in the thickness of the transparent support is within 5 μm, it is possible to more effectively prevent the occurrence of coating unevenness and drying unevenness when the photographic constituent layer is applied.

(E) Undercoat layer The surface of the transparent support of the invention on which the photographic constituent layers are formed is
If necessary, a surface activation treatment such as corona discharge and / or an undercoat layer can be applied prior to the formation of the photographic constituent layer.

As this undercoat layer, for example, JP-A-59-1 is used.
Suitable examples are the undercoat layers described in JP-A Nos. 9941, 59-77439 and 59-224841, and JP-B-58-53029. The undercoat layer provided on the surface of the transparent support opposite to the photographic constituent layer is also referred to as a back layer.

(F) Application to photographic film The photographic support of the present invention is particularly suitable as a photographic support for a photographic film used in the form of a roll.

2) The coupler represented by the general formula [CI] in the present invention will be described in detail.

[0079]

[Chemical 4]

In the above general formula [CI], R ¹ is -CONR
^{4 R 5, -NHCOR 4, -NHCOOR} 6, -NHSO 2 R 6, -NHCONR 4 R 5,
Represents —SO ₂ NR ⁴ R ⁵ or —NHSO ₂ NR ⁴ R ⁵ , R ² represents H or a substituent, R ³ represents a substituent, X represents a hydrogen atom or an aromatic primary amine developer oxidant Represents a group which is split off upon reaction with. l represents an integer of 0 to 3. R ⁴ and R ⁵ each represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group,
R ⁶ represents an aromatic group, an aliphatic group or a heterocyclic group,
Is 2 or 3, each R ³ may be the same or different and may be bonded to each other to form a ring, and R ⁴ and R ⁵ , R ² and R ³ , and R ² and X are bonded. May form a ring. The groups represented by R ^{2 to} R ⁶ include those having a substituent.

The compound represented by the general formula [CI] will be described in detail below.

R ⁶ is an aliphatic group having 1 to 30 carbon atoms,
An aromatic group having 6 to 30 carbon atoms and a heterocyclic group having 1 to 30 carbon atoms are preferable, and as R ⁴ and R ⁵ , those mentioned as preferable as a hydrogen atom and R ⁶ are preferable.

R ² is a hydrogen atom bonded to NH directly or through CO or SO ₂ , an aliphatic group having 1 to 30 carbon atoms,
Aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms,
-OR ⁷ , -COR ⁷ , -N <(R ⁷ ) (R ⁸ ), -CON <(R ⁷ ) (R ⁸ ), -S
^{_{O 2 N <(R 7)}} (R 8), - CO 2 R 9, -SO 2 R 9, -PO (OR 9) 2, -PO
(R ⁹⁾ ₂ or _{^{-SO 2 OR 9 (R 7,}} R 8 and R ⁹ are the same as defined in R ^4, R ⁵ and R ⁶ of said respective, R ⁷ and R ⁸ join to May form a heterocycle.)
Is preferred. The substituent represented by R ₂ includes those having a substituent.

Typical examples of R ³ are halogen atom, hydroxy group, amino group, carboxyl group, sulfo group, cyano group, aromatic group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, Ureido group, acyl group, acyloxy group, aliphatic oxy group,
Aromatic oxy groups, aliphatic thio groups, aromatic thio groups, aliphatic sulfonyl groups, aromatic sulfonyl groups, sulfamoylamino groups, nitro groups, imide groups and the like,
The number of carbon atoms contained in R ³ is preferably 0-30. l = 2
At this time, examples of cyclic R ³ include a dioxymethylene group and the like.

R ¹ is particularly preferably —CONR ⁴ R ⁵ , l is preferably 0, and R ² is directly bonded to NH —COR ⁷ , —COOR ⁹ , —
^{_{SO 2 R 9, -CON <(}} R 7) (R 8), - SO 2 N <(R 7) (R 8) are particularly preferred, more preferred, bond directly NH -COOR ^9,
—COR ⁷ and —SO ₂ R ⁹ , with —COOR ⁹ being most preferred.

Further, those which form a dimer or higher multimer through R ^{1 to} R ³ and X are also included in the general formula [CI].

Specific examples of the coupler represented by the general formula [CI] are disclosed in JP-A-60-237448, 61-153640 and 61-14555.
No. 7, No. 62-85242, No. 62-123157, No. 62-123158,
No. 63-93754, No. 63-208042, RD-29015 and the like, and can be synthesized by the method described therein.

To add the coupler to the light-sensitive material, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling point organic solvent or an alkali dispersion method added as an alkaline solution is used depending on the physical properties (eg, solubility) of the coupler. Various methods such as a latex dispersion method, a solid dispersion method of directly adding as a fine solid, and the like can be used.

The amount of coupler added is usually 1.0 × 10 ^{−3 to} 1.0 mol, preferably 5.0 × 10 ³ mol per mol of silver halide.
It is in the range of ^-3 mol to 8.0 x 10 ^-1 mol.

The coupler represented by the general formula [C-I] is
It may be used in combination with other cyan couplers, but in that case, the ratio of the coupler represented by the general formula [C-I] is preferably 10 mol% or more.

Next, typical specific examples of the coupler represented by the general formula [C-I] will be shown, but the present invention is not limited thereto.

[0092]

[Chemical 5]

[0093]

[Chemical 6]

[0094]

[Chemical 7]

[0095]

[Chemical 8]

[0096]

[Chemical 9]

[0097]

[Chemical 10]

[0098]

[Chemical 11]

[0099]

[Chemical 12]

[0100]

[Chemical 13]

[0101]

[Chemical 14]

[0102]

[Chemical 15]

[0103]

[Chemical 16]

-Photographic Constituting Layer- The silver halide color photographic light-sensitive material of the present invention can be a full-color photographic light-sensitive material. A full-color photographic light-sensitive material generally has a red-sensitive layer containing a cyan coupler, a green-sensitive layer containing a magenta coupler, and a blue-sensitive layer containing a yellow coupler. Each of these photosensitive layers may be a single layer or may be composed of a plurality of layers. The coupler of the present invention is preferably used in the red-sensitive layer.

The stacking order of the photosensitive layers is not particularly limited,
Various stacking orders can be taken according to the purpose. For example, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer can be laminated in that order from the support side. can do.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivity. Further, for the purpose of improving color reproduction, in addition to the three layers of red-sensitive layer, green-sensitive layer and blue-sensitive layer, a fourth or more photosensitive layer having a color-sensitivity can be provided. Regarding the layer structure using a fourth or more color-sensitive photosensitive layer, JP-A Nos. 61-34541, 61-201245 and 61-198236,
No. 62-160448, which can be referred to.

In this case, the fourth or more photosensitive layers having color sensitivity may be arranged at any laminating position. Further, the fourth or more color-sensitive photosensitive layer may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer.

The silver halide emulsion of the present invention includes silver chloride, silver bromide, silver iodide or mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodide and silver chloroiodobromide. Etc. can be applied. These silver halide emulsions are produced by a usual method, and an ammonia method, a neutral method, an acidic method, a halogen conversion method, a function addition method, a uniform precipitation method, or the like can be applied. The average diameter of the particles is not limited, but 0.01 μm to 5 μm is preferable. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed using a conventional method. The chemical sensitization includes gold sensitization using a gold complex salt, reduction sensitization using a reducing substance, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or so-called activated gelatin, and cyclic sensitization. A sensitization method using a salt of a noble metal belonging to Group VIII of the table can be used.

The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. As the method, cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine, and carbocyanine can be used alone or in combination, or can be used in combination with a styryl dye or an aminostilbene compound.

The silver halide emulsion used in the present invention includes stabilizers, antifoggants, surfactants, defoamers, antistatic agents, hardeners, film physical property improvers, brighteners and stain inhibitors. ,
Additives such as an ultraviolet absorber and an anti-irradiation agent can be included. About these various additives
All those described in Research Disclosure Volume 176, No. 17643 (1978) can be used.

The coating silver amount of the silver halide color photographic light-sensitive material in the present invention is not particularly limited, but is 10 in terms of silver amount.
g / m ² or less, preferably 3 g / m ² or more, 7 g / m ² or less, particularly preferably 3 g / m ² or more. Also, the amount of silver relative to the gelatin binder is not particularly limited, but depending on the high-sensitivity emulsion layer, the low-sensitivity emulsion layer, and other purposes, the silver amount (weight) / gelatin (weight) ratio used in the range of 0.01 to 5.0 Preferably.

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention.

As the yellow coupler, known couplers such as US Pat. Nos. 3,933,051, 4,022,620 and 4,32 are known.
No. 6,024, No. 4,401,752, No. 4,248,961, No. 58-10
739, British Patents 1,425,020, 4,314,023, 4,51
Those described in 1,649, European Patent 249,473A, etc. can be preferably used.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat.
4,310,619, 4,351,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, (RD) 24220 (198)
June 4), JP-A-60-33552, (RD) No. 24230 (1984)
June), JP-A-60-43659, 61-72238, 60-357.
No. 30, No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International publication WO8
Those described in 8/04795 and the like are particularly preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in US Pat. No. 4,163,670, Japanese Patent Publication No. 57-3.
Those described in 9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. US patent
A coupler that corrects unnecessary absorption of a coloring dye by the fluorescent dye released at the time of coupling described in 4,744,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 which has a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

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

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820, 4,080,211 and 4,367,28.
No. 2, 4,409,320, 4,576,910, British patent 2,102,1
No. 73 etc.

A coupler that releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are described in JP-A-57 / 1982.
-151944, 57-154234, 60-184248, 63-3734
Preferred are those described in US Pat. No. 6, U.S. Pat. Nos. 4,248,962 and 4,782,012.

As couplers which release a nucleating agent or a development accelerator imagewise upon development, British Patent 2,097,140 can be used.
No. 2,131,188, JP-A-59-157638, and 59-170840.
Those described in No. 10 are preferable.

Other couplers that can be used in the color light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
No. 8,393, No. 4,310,618, multiequivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds, or DIR redox releasing redox compounds, European Patent 173,
No. 302A, a coupler releasing a multicolored dye after release, (RD) Nos. 11449 and 24241, and a bleaching accelerator releasing coupler described in JP-A No. 61-201247, U.S. Pat.
And a coupler releasing a leuco dye described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are described in (RD) 17643 and (RD) 308119 below. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G item Colored coupler 1002 VII-G item VII G item DIR Coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residues 1001 VII-F Release coupler Alkali-soluble coupler 1001 VII-E The additive used in the present invention is described in RD308119XIV. It can be added by a dispersion method.

In the above color photographic material, it is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers,
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. It is possible to mix and use various kinds of synthetic hydrophilic polymer substances such as

The color light-sensitive material of the present invention is
JP-A-53-109604, JP-B-57-6576, JP-A-60-45248
No., U.S. Pat.No. 4,947,196, International Publication No. 90/04254,
91/11750, 91/11816, 92/08165, 92/082
It may have a transparent magnetic layer as shown in No. 27 and the like.

The optical density of the transparent magnetic layer of the present invention is preferably 1.0 or less, more preferably 0.75 or less, and particularly preferably 0.02 to 0.30.

In the present invention, the magnetic layer is a layer formed by dispersing ferromagnetic powder in a binder.

The coating amount of the magnetic powder is 50 mg or less, preferably 20 mg or less, and particularly preferably 0.1 mg to 5 mg as the amount of iron per 100 cm ^{2 of the} silver halide color light-sensitive material.

Examples of the ferromagnetic powder include γ-Fe ₂
O ₃ powder, Co deposited γ-Fe ₂ O ₃ powder, Co deposited Fe ₃ O ₄ powder, Co deposited FeOx (4/3 <x <3/2) powder, other Co-containing iron oxide,
Examples of other ferrites such as hexagonal ferrites include M-type and W-type hexagonal Ba ferrites and Sr.
Examples thereof include ferrite, lead ferrite, Ca ferrite, and solid solutions or ion substitutes thereof.

With the color light-sensitive material of the present invention, a color image can be obtained by subjecting the color light-sensitive material to a usual color development treatment after exposure. The basic steps of the negative-positive method are color development, bleaching and fixing steps, and the basic steps of the reversal development method are the first developing solution, white exposure or fogging agent treatment, color development, bleaching,
Each step of fixing. Among these treatment methods, there are a treatment method in which each of the basic steps is performed independently, and a treatment method in which two or more steps are performed in a single treatment using a treatment liquid having these functions. For example, a one-bath color processing method using a processing solution containing a color developing agent and a ferric salt bleaching component and a thiosulfate fixing component (see JP-B-35-1885),
Alternatively, there is a one-bath bleach-fixing method in which a bleach-fixing solution containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching component and a thiosulfate fixing component is used.

The photographic processing method of the color light-sensitive material of the present invention is not particularly limited, and any processing method can be applied. The following method can be given as a typical example.

(1) After color development, bleach-fixing treatment is carried out,
A method of further washing with water and stabilizing treatment, if necessary.

(2) A method of separately performing bleaching and fixing after color development, and further washing with water and stabilizing treatment, if necessary.

(3) A method of performing pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, and washing with water.

(4) A method of performing color development, washing with water, complementary color development, stopping, bleaching, fixing, washing with water, and stabilization.

(5) A method of processing a low silver content silver halide photographic light-sensitive material using an amplifier agent such as peroxide or cobalt complex salt.

The processing temperature can be as high as 30 ° C. or higher, or at room temperature.
It may be a low temperature of 20 ° C or lower. Generally, the processing temperature is 20 ~
70 ℃ is adopted. The set temperature in each processing step may be the same or different.

[0139]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example-1 (Preparation of Support Nos. 1 to 10 of the present invention and Comparative Support No.
11 and 12) 0.1 part by weight of calcium acetate hydrate was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. 28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (SIP) (concentration 35% by weight) (5 mol% / total ester bond component), polyethylene glycol (PEG ) (Number average molecular weight 3000) 8.1 parts by weight (7% by weight / polymer), Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant (0.5% by weight / polymer) 0.05 parts by weight antimony trioxide, trimethyl phosphate 0.13 parts by weight of ester was added.
Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester.

Each of the copolyester and the commercially available polyethylene terephthalate (intrinsic viscosity 0.65) was vacuum dried at 150 ° C. and melt-extruded at 285 ° C. using three extruders. To form a laminated unstretched film. At this time, the extrusion amount of each material was adjusted and the thickness of each layer was changed as shown in Table 1. Then 85 ℃
Then, the film was stretched 3.5 times in the vertical direction by 3.5 times in the horizontal direction, further stretched 3.5 times in the horizontal direction at 95 ° C, and then heat-set at 210 ° C to obtain a biaxially stretched support (supports Nos. 1 to 10) having a thickness of 80 μm. It was

The equilibrium water content of the copolyester and the polyester film used for preparing the support Nos. 1 to 10 was measured as follows.

The copolymerized polyester was melt-extruded at 285 ° C. using one extruder and solidified for rapid cooling on a cooling drum to obtain a laminated unstretched film, which was 3.5 times in the vertical direction at 85 ° C. The film was stretched, further stretched 3.5 times in the transverse direction at 95 ° C., and then heat-set at 210 ° C. to prepare a biaxially stretched film having a thickness of 80 μm.

This film was conditioned under an atmosphere of 23 ° C. and 55% RH for 3 days, and then a trace moisture meter (C manufactured by Mitsubishi Kasei Co., Ltd.) was used.
Equilibrium water content was measured at a drying temperature of 150 ° C. using A-05 type).

As a result, the water content of the polyester layer film was 0.4%, and the water content of the copolyester layer film was
It was 0.9%.

<Elastic Modulus> After leaving the support in a room whose temperature was controlled at 23 ° C. and 55% RH for 4 hours or more, a sample width of 10 mm,
Cut to a length of 200 mm, make 100 mm between chucks, and pull speed 10
It was determined by conducting a tensile test at 0 mm / min.

<Transparency> The haze of the support is measured according to JIS K-671.
Measured according to 4. Practically 3% as a photographic support
The following is preferable, but all of Support Nos. 1 to 12 were 3% or less.

<Rewind property> Sample size 12 cm x
Wind a 35mm support on a core with a diameter of 10mm, 55 ℃, 20% RH
It is processed for 3 days under the conditions of, and the curl is attached. After that, it is released from the core, immersed in pure water at 38 ° C. for 15 minutes, and then dried with a hot air dryer at 55 ° C. for 3 minutes while applying a load of 50 g. The load was removed, the sample was hung vertically, the distance between both ends of the sample was determined, and it was evaluated how much the original distance was restored to 12 cm.

The results are shown in Table 1.

[0150]

[Table 1]

From the results shown in Table 1, a film made of a single material of triacetyl cellulose and a polyester is inferior in either the roll recovery property or the elastic modulus, but the film obtained by laminating the polyester and the copolyester is wound. It can be seen that a support having a good recovery rate and elastic modulus can be obtained.

Example-2 (Support Nos. 13 to 21 of the present invention) 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (ethylene diglycol solution) and polyethylene glycol were added in the amounts shown in Table 2. And a copolymerization ratio so that each was polymerized in the same manner as in Example 1 to obtain polyesters (hereinafter, referred to as polyesters A-13 to 21). Polyester A-1 was prepared in the same manner as the support No. 6 prepared in Example 1.
Using 3 to 21 and commercially available polyethylene terephthalate, the layer thickness ratio is polyester A-13 to 21 / polyester / polyester A-13 to 21 = 2/1/1, and the thickness is 80 μm. An axially stretched support was obtained (Support Nos. 13 to 21).

For the polyesters A-13 to 21, materials for measuring equilibrium water content were prepared in the same manner as in Example 1, and the equilibrium water content was measured. The results are shown in Table 2.

Table 2 shows the results of measurement of the roll-back recovery rate, elastic modulus, and haze of Supports Nos. 13 to 21.

[0155]

[Table 2]

From this, it was found that the support obtained by laminating the polyesters A-13 to 21 and the commercially available polyester was better than the commercially available polyester support in both curling recovery rate and elastic modulus.

Example 3 (Support Nos. 22 to 29 of the present invention) The weight of SIP and PEG added to the copolyester prepared in Example 1 was the same, and the torque at the end of the polymerization was changed. Polymers having different intrinsic viscosities were obtained in the same manner except that the intrinsic viscosities were changed (Support Nos. 22 to 29). Using each of the obtained copolyesters and commercially available polyethylene terephthalate, a biaxially stretched film having a thickness of 80 μm shown in Table 3 was obtained by adjusting the thickness ratio and the intrinsic viscosity of each layer shown in Table 3. No.22-29). The characteristic values of these supports are shown in Table 3.

For each of the copolyesters, a material for measuring equilibrium water content was prepared in the same manner as in Example 1,
The equilibrium water content was measured and found to be almost 0.9%.

[0159]

[Table 3]

<Intrinsic Viscosity> The intrinsic viscosity was measured using an Ubbelohde viscometer. Using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane with a weight ratio of about 55:45 (flow time adjusted to 42.0 ± 0.1 seconds), dissolve the sample and adjust the concentration to 0.2, 0.6,
A 1.0 (g / dl) solution (temperature 20 ° C.) was prepared. The specific viscosity (η _sp ) at each concentration (C) was obtained by an Ubbelohde viscometer, and the intrinsic viscosity [η] was extrapolated to zero concentration by the following formula.

[0161]

[Equation 7]

After preparing the light-sensitive material, the silver halide emulsion layer and / or the gelatin back layer on both sides, which are coated on the support of the light-sensitive material, are treated with bankreatin or an aqueous solution of sodium hypochlorite. Even if the film as the support peeled off by using is cut out and evaluated in the same manner, the same intrinsic viscosity can be obtained, so after peeling the support in this way after the preparation of the photosensitive material, each layer is scraped off. Alternatively, the intrinsic viscosity of the obtained sample may be measured.

The same applies to the equilibrium water content, and after the support is peeled off after the preparation of the light-sensitive material, each layer may be scraped off to measure the equilibrium water content of the obtained sample.

Example 4 (Coating of Undercoat Layer) The first and second undercoat layers were provided on both sides of the above-mentioned support Nos. 1 to 12 as follows. In the following, the transparent support having the undercoat layer may be simply referred to as a transparent support.

First Undercoat Layer Resin solution 10 for undercoat layer obtained by emulsion polymerization of the following composition
0 parts by weight, 0.2 parts by weight of the following surfactants, hexamethylene-
A coating liquid for an undercoat layer consisting of 0.3 part by weight of 1,6-bis (ethyleneurea) and 900 parts by weight of water was applied so as to have a wet film thickness of 20 μm, and then dried.

<Composition> 2-Hydroxyethyl methacrylate 75 parts Butyl acrylate 90 parts t-Butyl acrylate 75 parts Styrene 60 parts Sodium dodecylbenzene sulfonate 6 parts Ammonium persulfate 1 part Water 700 parts <Surfactant>

[0167]

[Chemical 17]

Second subbing layer Next, a coating solution for the subbing layer consisting of 10 parts by weight of gelatin, 0.2 parts by weight of saponin and 1,000 parts by weight of water was applied to a wet film thickness of 20 μm, and then dried.

(Coating of Magnetic Layer) The following magnetic layer was provided on one surface of the support.

<Magnetic Layer> γ-Fe ₂ O ₃ 200 mg / m ² (Coercive force: 330 Oe, specific surface area 32 m ² / g) Gelatin 3.0 g / m ² Sodium di- (2-ethylhexyl) sulfosuccinate 200 mg / m ² Bisvinylsulfonylmethane 30 mg / m ² WAX-1 60 mg / m ² (Preparation of silver halide color photographic light-sensitive material) A photographic constituent layer having the composition shown below is provided on the transparent support 1 to form a multi-layer color film. A sample 101, which is a photosensitive material, was prepared.

(Composition of Photographic Constituting Layer) The coating amount of silver halide and colloidal silver is g / m ² in terms of metallic silver.
The amount expressed in units, and for couplers and additives, g
/ M the amount expressed in ^two units, for Matazo sensitizing dye shown in mol per mol of silver halide in the same layer.

First layer; antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) (Silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm) (silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.54 Cyan coupler (C-2) 0.08 Colored cyan coupler (CC-1) 0.021 DIR compound (D-2) 0.020 High boiling point Solvent (Oil-1) 0.53 Gelatin 1.30 4th layer; Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm) (Silver iodide content 8.0 mol%) 0.62 Silver iodobromide emulsion (Average grain size) 0.38 μm) (Silver iodide content 8.0 Le%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 -4 Sensitizing dye (SD-2) 1.2 × 10 -4 Sensitizing dye (SD-3) 1.6 × 10 -5 Sensitizing dye (SD-4 ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.08 Colored cyan coupler (CC-1) 0.030 DIR compound (D-2) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm) (silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ⁻⁴ Sensitizing dye (SD -2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-1) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6 layers; intermediate layer compound (SC-1) 0.09 high boiling solvent (Oil-2) 0.11 gelatin 0.80 7th layer; low sensitivity green sensitive layer silver iodobromide emulsion (average grain size 0.38 µm) (silver iodide content 8.0 mol%) 0.80 sensitizing dye (SD-4) 7.4 × 10 -5 sensitizing dye (S -5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.41 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2) 0.33 Gelatin 1.95 8th layer; medium-speed green-sensitive layer Silver iodobromide emulsion (Average grain size 0.52 μm) (Silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-5) 2.4 × 10 ^-4 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Magenta coupler (M-2) ) 0.12 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 9th layer; High sensitivity green sensitive layer Iodine Silver bromide emulsion (average grain size 1.0 μm) (silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-5) 1.4 × 10 ^-4 Sensitizing dye (SD-6) 1.4 × 10 ^-4 Magenta coupler (M-2) 0.10 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 10th layer; Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer; Low sensitivity blue sensitive layer Silver iodobromide emulsion (Average grain size 0.38 μm) 0.22 (Silver iodide content 8.0 mol%) Silver iodobromide emulsion (Average grain size 0.27 μm) 0.03 (Silver iodide content 2.0 mol%) Sensitizing dye (SD-7) 4.2 × 10 ^-4 Sensitizing dye (SD-8) 6.8 × 10 ^-5 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer; Mid-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm) 0.30 (silver iodide content 8.0 mol%) Sensitizing dye (SD-7) 1.6 × 10 ^-4 Sensitizing dye (SD-8) 7.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer; high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm) 0.85 (iodination Content of 8.0 mol%) Sensitizing dye (SD-7) 7.3 × 10 -5 Sensitizing dye (SD-8) 2.8 × 10 -5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) 0.046 Gelatin 0.80 15th layer; 1st protective layer Silver iodobromide (average grain size 0.08 μm) 0.40 (silver iodide content 1.0 mol%) UV absorber (UV-1) 0.026 UV absorber (UV-2) 0.013 High Boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer; 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate ( Average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 The above-mentioned light-sensitive materials further include compounds SU-1 and Su-.
2. Viscosity modifier, Hardener H-1, H-2, Stabilizer ST-
1, antifoggant AF-1, AF-2 (weight average molecular weight 1
0,000 and 1,100,000), Dyes AI-1, A
Contains I-2 and compound DI-1 (9.4 mg / m ² ).

The above UV-1, Oil-1, SC-1, O
il-2, Oil-3, SD-1, SD-2, SD-3, S
D-4, C-1, C-2, CC-1, D-1, D-2, M-
1, M-2, CM-1, D-3, SC-2, HS-1, SD-
5, Y-1, SD-6, SD-7, SD-8, UV-2, W
AX-1, SU-1, Su-2, H-1, H-2, ST-1,
The structures of AF-2, AI-1, AI-2 and compound DI-1 are shown below.

[0174]

[Chemical 18]

[0175]

[Chemical 19]

[0176]

[Chemical 20]

[0177]

[Chemical 21]

[0178]

[Chemical formula 22]

[0179]

[Chemical formula 23]

[0180]

[Chemical formula 24]

[0181]

[Chemical 25]

[0182]

[Chemical formula 26]

Each photosensitive layer used in Sample 101 (third, fourth, fourth)
All of the silver iodobromide emulsions (5, 6, 7, 8, 9, 12, 13, 14 layers) were tetradecahedral normal crystal monodisperse emulsions having an internal high iodine type core-shell structure.

Next, samples 102 to 130 were prepared by changing the support and the cyan couplers of the third layer, the fourth layer and the fifth layer as shown in Table 4 with respect to the sample 101.

[0185]

[Table 4]

(Development of silver halide color photographic light-sensitive material) Samples 101 to 130, which are color light-sensitive materials, are 135 size 2
It was cut into a standard of 4 shots, stored in a film cartridge, and loaded into the camera shown in FIG. The solid exposure and the automatic winding and feeding of the film were performed in a state where the magnetic head with the track number 26 having the length of 35 mm which is the same as the width of the film was in contact. After the completion, processing was performed according to the processing steps shown below.

[0187]

[Table 5]

In Table 5, the replenishing amount is 1 m ² of the photographic light-sensitive material.
It is the value per hit.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof were prepared as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g potassium hydroxide 1.0 g Water was added to make 1 liter, and the pH was adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water was added to make 1 liter, and the pH was adjusted with ammonia water
Adjusted to 6.0.

<Fixer> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and the pH was adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and add potassium hydroxide or 20%
The pH was adjusted to 10.18 with sulfuric acid.

<Bleach replenisher> Water 700 ml 1/3 Diaminopropane tetraacetate Iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Ammonia water or glacial acetic acid was used to adjust the pH to 4.0. After that, water was added to make 1 liter.

<Fixing replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Ammonium water or glacial acetic acid was used to adjust the pH to 6.5 and then water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

For each of the samples 101 to 130 obtained by the development processing, the density unevenness due to the influence of the pressing of the magnetic head was examined, but no unevenness was observed at all.

Also, regarding the curl characteristics (rolling recovery rate and elastic modulus), 112 and 124 are inferior, and in the base containing a polyester having a hydrophilic group, a triacetyl cellulose base (Sample No. 111, 123) is used. It was confirmed that there was no change and there was no problem.

Example-5 Samples 101 to 130 used in Example-4 were subjected to the same development treatment as in Example-4 after white wedge exposure.

With respect to each of the treated samples, a portion having a red density of 1.0 was measured using PDA-65 type manufactured by Konica.

Next, the developed sample was allowed to stand at room temperature for 1 week, then left to stand for 2 more weeks, and again the density at the place where the spectral density was measured again before was measured.

Table 6 shows the decrease in concentration from the first measurement at each measurement time point as ΔD ¹ _R and ΔD ² _R.

[0204]

[Table 6]

From these results, it can be seen that, in any of the samples of the present invention, there is no fluctuation in the concentration after leaving for 1 week and after leaving for 2 weeks, but the concentration is stable in the first week like Sample Nos. 101 to 112. You can see that there are things that cause a decline.

In the experiment using the comparative coupler, in the triacetyl cellulose film (Sample No. 111) and the polyethylene terephthalate film (Sample No. 112), the red density was decreased by 1 week and 2 weeks after the development treatment. However, it is known that a polyethylene terephthalate film base has a problem in curling characteristics, and is not preferable as a support.

On the other hand, when the comparative coupler is used for the base (Sample Nos. 101 to 112) using the copolyester having a good curling property, the change in red density with aging for one week is large, which is not preferable.

On the other hand, by using the cyan coupler of the present invention, a color light-sensitive material having an improved density variation with time can be obtained, and the color dye image from the coupler of the present invention depends on the base. Clearly not affected.

Example-6 Support No. 1 of the present invention prepared in Example-2 and Example-3
Using Nos. 3 to 29, Nos. 131 to 164 having the same photographic constituent layers as those of No. 101 or No. 113 were coated were prepared as shown in Table 7.

Then, Table 7 shows the results of evaluation of the concentration decrease over time in the same manner as in Example-5.

[0211]

[Table 7]

From Table 7, it can be seen that the samples using the base of the copolymerized polyester of the present invention and the cyan coupler of the present invention have improved density fluctuation over time.

[0213]

According to the present invention, a silver halide color photographic light-sensitive material having excellent curling properties, pressure resistance, mechanical strength and having no change in the density of a colored dye image over time can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a camera used in an embodiment of the present invention.

[Explanation of symbols]

 10 Shooting lens 20 Filmed film 30 Winding shaft 40 Magnetic head 50 Patrone

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having, on one side on a transparent support, a photographic constituent layer comprising at least one red-sensitive, green-sensitive, blue-sensitive photosensitive layer and a non-photosensitive layer, respectively. A transparent support comprising a coupler represented by the following general formula [C-I] and at least one polyester layer having a different equilibrium water content from each other. A silver halide color photographic light-sensitive material characterized by: [Chemical 1] Wherein, R ¹ represents ^{-CONR 4 R 5, -NHCOR 4,} -NHCOOR 6, -NHS
_{^{O 2 R 6, -NHCONR 4 R}} 5, represents -SO ₂ NR ⁴ R ⁵ or _{^{-NHSO 2 NR 4 R 5, R}} 2 represents H or a substituent, R ³ represents a substituent, X is hydrogen Atom or a group which is released upon reaction with an oxidized product of an aromatic primary amine developer, l represents an integer of 0 to 3, and R ⁴ and R ⁵ are each a hydrogen atom, an aromatic group, an aliphatic group or It represents a heterocyclic group, and R ⁶ represents an aromatic group, an aliphatic group or a heterocyclic group. When l is 2 or 3, each R ³ may be the same or different, and may be bonded to each other to form a ring, and R ⁴ and R ⁵ , R ² and R ³ , R ² and X.
May combine to form a ring. ] 2. At least one polyester layer among the polyester layers having different equilibrium water contents is a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. Item 1. A silver halide color photographic light-sensitive material according to Item 1.