JPS61200540A - Photosensitive material - Google Patents

Abstract

PURPOSE:To increase the photographic sensitivity and image quality of a photosensitive material by incorporating a specified low mol.wt. coupler into at least one of the blue-, green- and red-sensitive layers of the photosensitive material having at least one of the color-sensitive layers as a layer consisting of plural layers having higher and lower photographic sensitivities arranged so that a layer having high photographic sensitivity and different color sensitivity is held between the layers. CONSTITUTION:A low mol.wt. coupler having 250-450mol.wt. is incorporated into at least one of the blue-, green- and red-sensitive layers of a photosensitive material having at least one of the color-sensitive layers are a layer consisting of plural layers having higher and lower photographic sensitivities arranged successively from the support side so that a layer having high photographic sensitivity and different color sensitivity is held between the layers. Since the plural layers have at least one emulsion layer having different color sensitivity and high photographic sensitivity between them, a layer having high photographic sensitivity can be placed at a position higher than the original position to increase the photographic sensitivity and to also increase the developability. Since the low mol.wt. coupler is used, the sharpness as well as the photographic sensitivity is increased and the graininess can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to photographic light-sensitive materials, particularly silver halide color light-sensitive materials.

2. Prior Art In general, silver halide color photographic light-sensitive materials consist of three types of photographic silver halide that have been selectively spectrally sensitized to have sensitivity to blue light, green light, and red light on a support. For example, in a silver halide photographic light-sensitive material for color negatives, -S is coated with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer,
A red-sensitive silver halide emulsion layer is coated in this order, and a blue-sensitive silver halide emulsion layer is usually placed between a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer. A bleachable yellow filter is provided to absorb the blue light that passes through it. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. It is also known that each of these photosensitive silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive halogenated emulsion layer consisting of two layers having different sensitivities. In these silver halide color photographic materials GI 4, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and a color developing agent is produced. A dye image is formed by the reaction of the oxidation product of the base drug with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indadulones or cyanocouplers are typically used to form cyan, magenta and yellow dye images, respectively. A 7-cetyl magenta coupler and an acylacetamide yellow coupler are used, and these dye-forming couplers are contained in the light-sensitive silver halide emulsion layer.

In recent years, silver halide color photographic materials with high sensitivity and high image quality have been desired in this industry. In other words, opportunities to take photographs under poor conditions with little light, such as indoors, or using telephoto lenses or zoom lenses, where camera shake is likely to occur, are increasing, and silver halide color photographic materials are becoming smaller format. Accordingly, there is a strong demand for the development of silver halide color 15-true optical materials that are highly sensitive and have excellent image quality such as sharpness and graininess.

However, it is difficult to achieve both high sensitivity and improved image quality. First, the following are known layer structures for achieving high sensitivity. In a layer structure in which each of the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the blue-sensitive silver halide emulsion layer are sequentially coated on the top. ,
Regarding some or all of the photosensitive silver halide 7L agent layer,
A high-sensitivity silver halide grain layer containing a diffusion-resistant coupler (hereinafter referred to as a high-sensitivity emulsion layer) and a low-sensitivity halogen layer containing a diffusion-resistant coupler that develops colors of substantially the same hue as a layer having substantially the same color sensitivity There is a layer structure (normal layer structure) in which the silver oxide grain layer (hereinafter referred to as a low-sensitivity emulsion layer) is separated and layered adjacently.According to this 111-layer structure, During exposure, one photosensitive silver halide emulsion layer not only absorbs the amount of exposure light by another photosensitive silver halide emulsion layer located further away, but also causes developer to diffuse during development. In other words, in such a normal layer structure, the green phosphorescent halogenated emulsion layer and the red halogenated emulsion layer located in the lower layer (on the support side) This is disadvantageous in increasing the sensitivity of the photosensitive silver halide emulsion layer.

In addition, in silver halide color optical materials, image quality,
It is desired to improve quality such as sensitivity and storage stability, as well as shorten development time and improve convenience, and various studies are being conducted for this purpose. In particular, as color cameras become more compact and the screen size of one frame of photosensitive material becomes smaller, there is a strong desire to improve image quality. This is because, when obtaining color prints of the same size, unless the image quality is improved in proportion to the enlargement magnification from the photosensitive material, the resulting photographs will be grainy and have blurred details.

In general, halogenated ji! A photosensitive material is a compound (hereinafter referred to as a "coupler") that generates a dye through a campling reaction with an oxidized form of a developing agent produced during development of the photosensitive silver halide, together with a photosensitive silver halide.
It consists of a protective colloid containing The coupler is
It is dissolved in a high boiling point solvent with a boiling point of 175°C (under 1 atm) or higher and dispersed in the protective colloid layer! It is imaginary and contained.

It is known that the sharpness is improved as the thickness of the protective colloid layer becomes thinner, and the sharpness is improved depending on the application method and the hardness of the protective colloid layer.
The thickness of the layer has been gradually reduced through improvements in single agents and protective colloids. However, if the amount of protective colloid is excessively reduced in order to make the layer thinner, the high boiling point solvent contained in the layer will gradually ooze out, so this breakthrough is desired.

In order to prevent such oozing of high-boiling point solvents, it is necessary to increase the amount of protective colloid according to the total weight of the coupler and high-boiling point solvent contained in the protective colloid layer, and research is conducted under these constraints. has been progressing. As a result of this research, a method using polymer coupler latex has been proposed.

However, it is still not sufficient in terms of color development efficiency, and there has been a strong desire to develop a new technology that can improve sharpness without reducing color development efficiency.

C.1 Objective of the Invention An object of the present invention is to provide a photographic material that is highly sensitive and has improved image quality, particularly grain softness and sharpness.

21 Structure of the invention and its effects, that is, the present invention has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and at least one of these silver halide emulsion layers is sensitive to each other. These multiple layers consist of a layer with low sensitivity and a layer with high sensitivity arranged in order when viewed from the support side, and between these layers there is a halogenated layer with different color sensitivity and high sensitivity. In a photographic light-sensitive material having at least one silver emulsion layer, at least one light-sensitive silver halide emulsion layer has a molecular weight of 25.
This invention relates to a photographic material characterized by containing a low molecular weight coupler having a molecular weight of 0 to 450.

According to the present invention, the plurality of layers have different color sensitivities! Since it has a structure in which at least one emulsion layer of S degree is arranged (hereinafter referred to as "reverse layer structure"), it is possible to obtain 15 degrees by placing the high-sensitivity layer above its original position. , high sensitivity, and further improvement in developability can be realized.

Moreover, according to the present invention, one emulsion Jω contains the above-mentioned low molecular weight coupler, but since this low molecular weight coupler has a small molecular weight of 250 to 450,
Compared to known couplers, when the number of moles is the same (that is, when Dmax is about the same), the heavy equipment becomes considerably smaller. Therefore, DIIIIIIX
By reducing the amount of coupler while maintaining sufficient g! By forming a film, it is possible to improve sharpness and furthermore to prevent the phenomenon of sweating.

In addition, the low molecular weight coupler used in the present invention has a faster reaction rate of camping than the polymer coupler latex, thereby providing sufficient color development efficiency and shortening the development processing time.

The present inventor studied conventional photographic light-sensitive materials and found that, for example, in a color photosensitive material prepared by dissolving a coupler in a high-boiling solvent and coating it in a state dispersed in a protective colloid solution, there are problems during coating and during development. In order to prevent the coupler from moving, a large atomic weight group called a ballast group was required to make the coupler non-diffusive. For this reason, the molecular weight of the coupler incorporated in the window material is usually as large as 500 or more.

The present inventors particularly found that when the coupler core does not contain an alkali-easily soluble group such as a carboxyl group or a sulfo group, even if the molecule fft (MW) of the coupler is 450 or less, the coupler and the dye obtained by development are The present invention was achieved by discovering that both are non-diffusible. However, if the MW is less than 250, the coupler will easily diffuse in the protective colloid layer, so the MW of the coupler should be 250.
Further, in the present invention, if the molecular weight of the coupler is set to 300 to 400, the effects of the present invention can be achieved even better. Incidentally, the coupler having a molecular weight of 250 to 450 according to the present invention is referred to as "
``Low molecular weight couplers.''

As mentioned above, the low molecular weight coupler of the present invention is extremely excellent in improving sharpness, especially by making the emulsion layer thinner. It is an unexpected and remarkable fact that by using such a low molecular weight coupler, in addition to the above-mentioned high sensitivity, sharpness can be improved and graininess can be significantly improved.

In the present invention, the above-mentioned "multiple layers consist of a low-sensitivity layer and a high-sensitivity layer arranged in order when viewed from the support side"
means that when the plurality of layers is three or more, the positions of any two of the three or more layers are in the order of the layer with the lowest sensitivity and the layer with the highest sensitivity with respect to the support. means.

Preferably, the most sensitive layer is located farthest from the support, and even more preferably, the most sensitive layer is located farthest from the support.

In addition, the above-mentioned "silver halide emulsion layers with different color sensitivities and high sensitivity" refers to the above-mentioned "silver halide emulsion layers with different color sensitivities" when the silver halide emulsion layers themselves are composed of multiple layers.
Of the plurality of layers, it refers to the layer that is not the lowest in sensitivity,
Preferably, it refers to the layer with the highest sensitivity.

The above-mentioned "between both layers (between multiple layers)" means that the multiple layers are 3
In the case of more than two layers, it means that it may be between any two layers among the three or more layers, but preferably,
The sensitivity difference between the plurality of layers described above, which is between the most sensitive layer among the plurality of layers and the layer less sensitive than the most sensitive layer, is 1 layer gECE: exposure amount) It is preferably 0.1 to 2.0, more preferably 0.4 to 1.2. Further, in the present invention, when a medium-sensitivity emulsion layer is provided, the sensitivity difference between the cough-speed emulsion layer and the high-sensitivity emulsion layer is preferably 0.2 to 1.5 as logE, more preferably 0.4. ~1.0, and the sensitivity difference between the cough sensitivity emulsion layer and the low sensitivity emulsion layer is 0.1~1.0.
Preferably, it is 0.

Among the color-sensitive halogenated 1R emulsion layers, it is preferable that the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer are arranged in the same direction when viewed from the support side. , a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order.

Regarding the type of silver halide emulsion layer composed of a plurality of layers described above, it is preferable that at least a green-sensitive layer is composed of a plurality of layers having different sensitivities, and further at least a green-sensitive layer and a red-sensitive layer. Preferably, the layer is composed of a plurality of layers each having a different sensitivity. Further, it is preferable that the most sensitive red-sensitive layer is located between a plurality of green-sensitive layers having different sensitivities.

Next, the above? ! Preferred examples of the layer order of the silver halide emulsion layers when the number of layers is two are shown in FIGS. 1 to 6. In these figures, only the layer structure of the photosensitive emulsion layer is shown, and non-photosensitive layers such as filter layers are omitted (however,
Supports are indicated by hunting. ).

1. Only the blue-sensitive layer (B) is a highly sensitive blue-sensitive layer (BM
) and a low-sensitivity blue-sensitive layer (BL) of 2N: The layer configurations shown in FIGS. 1(a) and (b) are preferable, and the layer structure shown in FIG. 1(b) is particularly preferable.

(2) When only the green photosensitive layer (G) is composed of a high-sensitivity layer (GM) and a low-sensitivity FfJ (OL): The layer configuration shown in FIG. 2 is preferred.

■, Blue photosensitive J'! (B) and the green photosensitive layer (G) are high-sensitivity layers (B, GH) and low-sensitivity Fi (BL, GL).
): The layer configurations shown in FIGS. 3(a) to 3(d) are preferable, and the layer structures shown in FIGS. 3(b) to 3(d) are particularly preferable.

■The green photosensitive layer (G) and the red sensitive N (R) are high sensitivity layers (GM, RH) and low sensitivity! (CL, RL)
When composed of: Figure 4 is preferable.

■, the blue-blue sensitive layer ('B) and the red-sensitive layer (R) are the high-sensitivity layer (BN, R)l) and the low-sensitivity 1 (BL, RL)
): Figures 5(a) and 5(b) are preferred, and Figure 5(b) is particularly preferred.

Vl, the blue-sensitive layer (B), the green-sensitive layer (C) and the red-sensitive layer (R) are all local sensitivity layer (BH1G, R11) and low sensitivity layer (Bt-CL), respectively.

6(a) to (d) are preferable, especially those in FIG. 6(b) to
(d) is preferred.

Above, a specific example in which the plurality of layers is two layers has been shown, but when the plurality of layers is three or more layers, it is preferable that the layers other than the layer with the highest sensitivity are adjacent to each other. When there are three layers, it is preferable that the medium speed layer and the low speed layer are adjacent to each other, and in particular, from the support side, the low speed layer,
Preferably, the order is medium speed layer.

Moreover, the above-mentioned one halogenated emulsion layer with different color sensitivity is used as two emulsion layers.
In the case where the above layers are adjacent to each other, it is preferable to provide a non-photosensitive hydrophilic colloid layer (intermediate layer) between them.

In addition, when a green-sensitive layer and a red-sensitive layer are located closer to the support than the blue-sensitive layer, there is a gap between the blue-sensitive layer and the green-sensitive layer, and between the blue-sensitive layer and the super-sensitive layer. It is preferred that the intermediate layer between the red-sensitive layers, the green-sensitive layer, and/or the red-sensitive layer have a yellow filter effect.

As the above-mentioned low molecular weight couplers used in the present invention, those represented by the following general 2I are preferred.

General formula 1: % formula % () (However, Coup is the turnip mother nucleus component, and X is the above general formula I
A group or atom that can be separated by the reaction between the coupler and the oxidized color developing agent, Y is a substituent (substituent or atom) introduced into the coupler core device tA, n is an integer of n≧], and n When ≧2, the plural Ys may be the same or different from each other.) In this general formula 1, the coupler core is, for example, benzoylacetanilide, pivaloylacetanilide, 1-phenyl-5 - pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetylcoumarone, acetoacetonitrile, indasilone, phenol, naphthol. Specifically, as X,
Examples include those listed as x1 to x6 described below. As Y, for example, R'-R'2. J-fl”
, R', and those exemplified as R1-R21 include those other than hydrogen atoms.

Among the low molecular weight couplers represented by the above general formula I, if the sum of the atomic weights of X is A, the sum of the atomic weights of Y is B, and the sum of the atomic weights of Couρ is C, C0(n+1) (however, n represents the number of Y) is particularly desirable in that the coupler is difficult to crystallize and the dye generated during development is difficult to move in the layer. If it is 1,
A dye produced by a reaction with an oxidized form of a color developing agent (CD),
That is, CD=Coup-(Y)n exhibits more non-diffusivity due to the presence of Y in the molecule. Therefore, of the layer containing low molecular weight couplers! It is possible to maintain a higher level of ¥ theory.

Previous practical coupler cores have been structurally limited due to the stereotype that all practical couplers contained in known protective colloids require large groups to be non-diffusible. The coupler molecular weight is larger than the range of the present invention, and therefore the protective colloid layer cannot be made thinner, and no improvement in sharpness can be expected.

The low molecular weight couplers of the present invention require less weight to achieve the same color strength than known internal couplers, thereby allowing the thin layer formation that is the object of the present invention. Also,
In order to obtain sufficient color development, the ratio of the sum of the coupler weight and the high boiling point solvent weight to the protective colloid weight should be 0.5.
~l, 5, more preferably 0.8 to 1.5,
This improvement in color development is achieved regardless of the ratio of the ffi amount of the boiling point solvent to the weight of the coupler, and the color development of known internal couplers is dependent on the weight of the protective colloid relative to the coupler weight and the weight of the high boiling point solvent. This is unexpected considering that it doesn't happen.

The color light-sensitive material according to the present invention comprises at least one layer of a protective colloid containing a high boiling point solvent dispersed in a protective colloid in which photosensitive silver halide and the low molecular weight coupler of the present invention are dissolved in a support. It is configured.

The improvement in sharpness achieved using low molecular weight couplers is
Image quality is obtained both in the protective colloid layer containing the low molecular weight coupler and in other color image forming layers in the color sensitization process. In color photosensitive materials, light is reflected at the interface between the support and the protective colloid layer and the interface between the protective colloid layer and air11.
I is known, and when a transparent support is used, reflection is also added at the interface between the support and the air layer on the side of the support on which the color arbitrary layer is not coated. Since the protective colloid layer according to the present invention is made thin, light that once enters color photosensitive material #1 is repeatedly reflected within the protective colloid layer (11
! It is multiplexed and attenuated. Therefore,
In layers thinned with low molecular weight couplers and other layers, since the deterioration of sharpness is effectively prevented! Y sharpness is improved.

Desirable compositions of the photographic window optical material according to the present invention include: one or more blue-sensitive silver halide emulsion layers containing a yellow coupler and one or more green-sensitive silver halide emulsions containing a magenta coupler; layer, and one or more red-sensitive silver halide emulsion layers containing a cyan coupler. In this case, at least one of the blue-sensitive silver halide emulsion layers preferably contains a low molecular weight yellow coupler.

In this case, the sharpness of both layers can be improved without improving the green-sensitive silver halide emulsion layer or the red-sensitive silver halide emulsion layer. Visually judging the print as a final image, the improvement in magenta image obtained with the green-sensitive silver halide emulsion layer is judged to be the most improved when the sharpness is improved to the same extent.

On the contrary, improvements in the blue-sensitive layer are hardly noticeable as improvements in the final image; nevertheless, in the present invention, it is surprising that improvements in the blue-sensitive layer result in significant improvements in the final image. be.

For the same reason, it is desirable that at least one of the green-sensitive silver halide emulsion layers contains a low molecular weight magenta coupler.

With this configuration, dye images can be obtained not only from the green-sensitive silver halide emulsion layer but also from the red-sensitive silver halide emulsion layer located below it! Sharpness is further improved.

Therefore, when a photographic window optical material is composed of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers (
At least a blue-sensitive silver halide emulsion layer, more preferably a blue-sensitive and a green-sensitive silver halide emulsion layer, most preferably a blue-sensitive, a green-sensitive and a red-sensitive silver halide emulsion layer. It is desirable that all of them contain the low molecular weight couplers of the present invention.

Further, when the silver halide emulsion layer having the same color sensitivity is composed of two or more layers, from the above viewpoint, it is desirable that at least the upper layer contains the coupler of the present invention.

On the other hand, in photographic window materials, the technology of using two or more photosensitive layers in order to photograph subjects with a wide range of illuminance is widely known, and also for the purpose of realizing the demand for higher sensitivity.
It is used in commercially available silver halide color photosensitive materials. In this technique, the lowest sensitivity layer has the largest contribution to image density, and the most coupler is often used.The weight of the coupler added to the second layer usually increases the film thickness of the EI FJ. Therefore, in such a case, if the low molecular weight coupler of the present invention is used in the lowest sensitivity emulsion layer, the effects of the present invention will be found.

That is, from this point of view, at least the blue-sensitive silver halide emulsion layer is composed of two or more silver halide emulsion layers, and the silver halide emulsion layer with the lowest sensitivity among these silver halide emulsion layers has a low sensitivity. Molecule ■It is desirable that a yellow coupler be contained.

Further, at least the green-sensitive silver halide emulsion layer is composed of two or more silver halide emulsion layers, and the silver halide emulsion layer having the lowest sensitivity among these silver halide emulsion layers contains a low molecular weight magenta coupler. It's better to stay.

The low molecular weight coupler of the present invention may be any compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, phenylenediamine jA 8, aminophenol F4, etc.) during color development. Although not specified, those containing an alkali easily soluble group such as a carboxyl group or a sulfo group may be undesirable. Examples of low molecular weight couplers include magenta couplers such as pyrazolotriazole couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers such as acylacetamide couplers ( For example, there are benzoylacetanilides, pivaloylacetanilides, etc., and cyan couplers include naphthol couplers, phenol couplers, etc. The coupler connects silver ions to ′i:,j
L, 4-equivalent or 2-equivalent may be used.

Further, the photographic performance can be further improved by using 2 t4 or more of the low molecular weight couplers of the present invention. An example of a combination in this case is a method of using couplers in which the coupling speed of one coupler is 1.3 to 15 times the coupling speed of the other coupler. Here, the coupling speed of the couplers can be determined by mixing two types of 1N couplers A and B that give different dyes that can be clearly differentiated from each other, adding milk RTL+47, and developing the color. By measuring each pigment in the resulting color image, it can be determined as a relative value.

Maximum to coupler: 5jf (DA) max,,
If we express the color development of the concentration DA at the intermediate stage and the color development of the coupler 3 (D++) max, , D, then the ratio of the reaction activity of the double force puller RA/R is
1 is represented by the following 2.

In other words, the coupling activity ratio RA/ R11 is calculated.

The low molecular weight couplers used in the present invention will now be described in detail. .

First, it is preferable that the low molecular weight coupler for yellow has hendiylacetanilide as a core, especially the general formula (2): (atom), X' is a group or atom that can be separated by the reaction between the coupler of this general formula (2) and the oxidized product of the color developing agent.) However, in this general formula, , R', R'', R', the sum of the atomic weights of R' and X' is preferably 30 to 210, and 50
-165 is more desirable.

In the above general formula (3), R1, RZ, R2, and R4 may be the same or different, for example, a hydrogen atom, a halogen atom,
Alkyl groups (e.g. methyl, ethyl, isopropyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, etc.), oryloxy groups (e.g. phenoxy), acylamino groups (e.g. acetylamino) , trifluoroacetylamino group, etc.),
Examples include sulfonamino groups (eg, methanesulfonamino groups, benzenesulfonamino groups, etc.), carbamoyl groups, sulfamoyl groups, alkylthio groups, alkylsulfonyl groups, alkoxycarbonyl groups, ureido groups, and cyanogen groups. x1 has the same meaning as the above-mentioned X, and preferable examples include a hydrogen atom, a halogen atom, and those represented by the following general formula.

General formula: ,1゜,・'n(0)5-B・' In this general formula, A represents an oxygen atom or a sulfur atom, and B represents a nonmetal necessary to form an aryl ring or a heterocycle. Represents an atomic group, R4 represents a nonmetallic atomic group necessary to form a 5- or 6-membered heterocycle with the nitrogen atom, and these rings may be further fused with an aryl ring or a heterocycle , D represents an organic group (e.g. alkyl group, aryl group) or an atom (e.g. halogen atom), b represents O or a positive integer, when b is plural, D
may be the same or different, D is 10-1-S
-1-COO-1-CON H-5-5OZNI+-1
NHCON! l-1-SO2-5-CO-1-N
II C0-1-oco-5N HS O□-5-N
It may contain a linking group such as H-.

Specific examples of the above yellow couplers are given below.

L Double [MW Tsuji Azuki L Go (MW-Sword)] Ll (MW'-340) Shil L Double (MW"=434) NO□ L Two Dan (MW=379) r Ll (MW=405) z Ll [MW=4 factors] Shit L" (MW1=1410) Shi2 Ll (MW〈*) E welcome (MW hakama 361) y-11 (MW=401) y-12 [MW=369) Yellow couplers having pivaloylacetanilide as a core are also preferred, and in particular, yellow couplers of the following general formula (2) can be used.

General formula ■: Here, the sum of the atomic weights of R', Rh and Xt is 35~
230 is preferable, and 80-185 is more preferable.

R5 and R6 have the same meaning as R' and R'' described above, and may be the same or different, such as hydrogen atom, halogen atom, alkyl group (e.g. methyl group, ethyl group, isopropyl group, etc.), alkoxy group. (e.g. methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g. phenoxy group, etc.), acylamino group (e.g.
For example, acetylamino group, trifluoroacetylamino group, etc.), sulfonamino group (for example, methanesulfonamino group, benzenesulfonamino group, etc.), carbamoyl group, sulfamoyl group, alkylthio method, alkylsulfonyl group, alkoxycarbonyl group, ureido group, An example is a cyano group.

X2 has the same meaning as the above-mentioned "X", and the same thing is exemplified.

Specific examples of the yellow coupler of general formula (2) are as follows.

L trouble (MW'=358) L square MW-%] L distortion [MW''-440] J Ni square (MW: 442) L two 17 (MW 44) As a yellow coupler, a benzoylacetanilide type color develops. It is preferable because it has a high concentration and can be made into a thinner layer.

Preferred low molecular weight magenta couplers used in the present invention are those having pyrazolotriazole as a core, and in particular, the general formula (2): (However, R', -J-R'' and R9 are all the above-mentioned R
1 and x1 have the same meaning as x+ above. ) is a magenta coupler. However, in this general formula (2), it is desirable that the sum of the atomic weights of R, -J-R'' and R? and x1, which is X, is 150 to 340, and 2
00 to 300 is more preferable, R' and R@ are, for example, a hydrogen atom, an alkyl group which may have a substituent (
For example, J represents a bond, -0-1-S-1 -N-, R11+ represents a hydrogen atom or an alkyl group, or R9 represents, for example, a hydrogen atom.X is preferably a hydrogen atom, a halogen atom, or a group of the following general formula.

General formula: 5-R1! In this general formula, Rl is a halogen atom, an alkyl group (e.g. methyl group, ethyl group), an alkoxy group (e.g. methoxy group, ethoxy group), an acylamino group (e.g. acetamido group, benzamide group), an alkoxycarbonyl group (e.g. methoxy carbonyl group), anilino group (e.g. 2-chloroanilino group, 5-acetamidoanilino group), N-alkylcarbamoyl group (e.g. N-methylcarbamoyl group), ureido group (e.g. N-methylureido group), cyano group, aryl A group or atom selected from a group (e.g. phenyl group, naphthyl 2.%), N, N-dialkylsulfamoyl group, nitro group, hydroxy group, carboxyl group, oryloxy group, and g is 2 or more. When R1+ may be the same or different.

Rfil stands for (Q or represents an unsubstituted alkyl group (e.g., butyl group, methyl group, etc.), aralkyl group (e.g., hensyl group, etc.), alkenyl group (e.g., allyl group, etc.), or cyclic alkyl group (e.g., cyclopentyl group, etc.) , Substituents include halogen atoms, alkoxy groups (
(e.g., butoxy group, methyloxycarbonyl group, etc.), acylamino) L (e.g., ace]amide group, tetradicanamide group, etc.), flukoxycarbonyl group (methoxycarbonyl group, etc.), N-furkylcarbamoyl group (N-methylcarbamoyl group, etc.) ), ureido group (ethylureido group, etc.), cyan group, aryl group (phenyl group, etc.), nitro group, alkylthio group (methylthio group, etc.), alkylsulfinyl group (ethylsulfenyl group, etc.), alkylsulfone group, anilino group , a sulfonamide group (such as an ethylsulfonamide group), an N-alkylsulfamoyl group, an aryloxy group, and an acyl group (such as an acetyl group).

A specific example of this low molecular weight magenta coupler is the following dance.

Double EMW''=, Otsu 9] C5)l17 m-2 (MW=333) m-3 (MW’; 3Q5) CH.

■HC7! m-4 (MW#333) m-5 (MW#266) m-6 [MW#375] m-7 (MV/"-344) ) Su (MW!=i293) H(1! Enili (MW=D) 1 firefly (MW=269) 1 mountain (MW#275) 11 1.4 r 1, 1 cMw=: eaves] NtlSOzCIh 1 Strained (MW #438) In addition to the above, other magenta couplers having 1-phenyl-5-pyrazolone or pyrazolobenzimidazole as a core are preferable, and in particular those represented by the following general formulas (1) and (2)
The following can be mentioned.

General formula V: General formula ■: Here, RI3
and R14 are all the same as R1 described above, and ×4 is synonymous with X described above. R13, (R'").

The sum of the atomic weights of and

In the above general formulas V and (1), RI3 is, for example, an acylamino group (e.g., propanamide group, benzamide group), anilino group (e.g., 2-chloroanilino group, 5-acetamidoanilino group), or ureido group (e.g., phenylureido group, butaneureido group). R+4 includes, for example, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxycarbonyl group, an alkoxycarbonyl group, a nitro group, an aryloxy group, a cyano group, or an acylamino group; The same ones as X3 mentioned above can be mentioned. f is an integer from O to 4, and when f is 2 or more, each R'' may be the same or different,
A specific example of this magenta coupler is as follows.

rn 16 (MW=343) m-17 [MW=425] Machi±(MW咄τ) Nisei [MW=4303 Machi-20 (MW-417) As a Mazenk coupler, θ [1kibi-ra] shown in the general formula ■ Dulotriazole-based dyes are preferable because the dye obtained by development does not absorb unnecessary blue light, has a high color development rate of 7, and can be made into a thinner layer.

The cyan couplers that can be used in the present invention preferably have phenol or naphthol as a core, and those of the following general formulas (1) and (2) are particularly preferred.

General formula (2): XS General formula (2): In this general formula, RIS to R1' are all the same as R1 above, and y, S, and xh are all the same as X above. In general formula (2), the sum of the atomic weights of R1S% R'' to R1'' and XS is preferably 165 to 350, and 20
0 to 300 is more preferable, and in general formula (2), R
The sum of the atomic weights of I6 to R2+ and X″ is 115 to 310
is preferable, and 160 to 265 are more preferable.

Examples of RIS include hydrogen atoms, aliphatic groups (e.g., alkyl groups such as methyl, isopropyl, acyl, cyclohexyl, and octyl), alkoxy groups (e.g., methoxy, isopropoxy, pentadecyloxy), and aryloxy groups (e.g., phenoxy, β). -ter L-butylphenoxy group), an acylamido group, a sulfonamide group, a ureido group, or a carbamoyl group shown in the following formula.

-NH-CO-G -NH-3o, -G -N HCON H-G G' In the formula, G and G' may be the same or different, and each hydrogen atom (however, G%G' is a hydrogen atom), an aliphatic group having 1 to 8 carbon atoms, preferably 4 carbon atoms
~8 represents a straight-chain or branched alkyl group, a cyclic alkyl group (e.g. cyclopropyl, cyclohexyl, norbornyl, etc.), or an aryl group (e.g. phenyl, naphthyl, etc.), where the above alkyl group, aryl group is Halogen atoms (e.g., fluorine, chlorine, etc.), nitro groups, cyano groups, amino groups (e.g., amines, alkylamino, dialkylamino, anilino, N-alkylanilino, etc.), alkyl groups (e.g., those mentioned above), aryl groups (e.g. phenyl, 7cetylaminophenyl, etc.)
, alkoxycarbonyl groups (e.g., butyloxycarbonyl), acyloxycarbonyl groups, amide groups (e.g., acetamide, methanesulfonamide, etc.), imide groups (e.g., succinimide, etc.), carbamoyl groups (
(e.g. N,N-diethylcarbamoyl, etc.), sulfamoyl groups (e.g., N,N-diethylsulfamoyl, etc.), alkoxy groups (e.g., ethoxy, butyloxy, octyloxy, etc.), aryoloxy groups (e.g., phenoxy, methylphenoxy, etc.) ) etc. In addition to the above substituents, RIS may contain commonly used substituents. RR6 is, for example, a hydrogen atom,
It is selected from an aliphatic group, especially an alkyl group or a carbamoyl group represented by the above-mentioned abbreviation. R17, R1, R1
9, R■ and R2+ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Specific examples of b + 7 include an alkylthio group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, and a carbamyl group.

Hydrogen atoms, halogen atoms (e.g. chloro, brome, etc.)
, primary, secondary or tertiary alkyl groups (e.g. methyl, propyl, isopropyl, n-butyl, nibutyl, tert-butyl, -xyl, 2-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl 2-( 2,4,6-toIJchlorophenyl)ethyl, 2-7minoethyl, etc.),
Alkylthio groups (e.g. octylthio, etc.), aryl groups (e.g. phenyl, 4-methylphenyl, 2,4.6
-dolichlorophenyl, 3,5-schif'romophenyl,
4-trifluoromethylphenyl, 2-tolylfluoromethylphenyl, 3-trifluoromethylphenyl, naphthyl, 2-chloronaphthyl, 3-ethylnaphthyl, etc.)
, heterocyclic groups (e.g. benzofuranyl group, furanyl group,
thiazolyl group, benzothiazolyl group, naphthothiazolyl group, oxasilyl group, benzoxasilyl group, 1-phthoxazolyl group, pyridyl group, quinolinyl group, etc.), amino group (e.g. amino, methylamino, diethylamine, phenylamino, tolylamino, 4-cyanophenylamino) , 2-trifluoromethylphenylamino, benzothiazolamino, etc.), carbonamide groups (alkylcarbonamide groups such as ethylcarbonamide, etc.; phenylcarbonamide 1', 2,4.6-drichlorophenylcarbonamide, 4 -Arylcarbonamide groups such as methylphenylcarbonamide, 2-ethoxyphenylcarbonamide, etc.; thiazolylcarbonamide, benzothiazolylcarbonamide, oxasilylcarbonamide, benzoxacylylcarbonamide, imidazolylcarbonamide, benzimidapril heterocyclic carbonamide groups such as carbonamide, etc.), sulfonamide groups (alkylsulfonamide groups such as butylsulfonamide, phenylethylsulfonamide, etc.; phenylsulfonamide, 2,4.6-)lichlorophenylsulfonamide , 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide, etc.; thiazolylsulfonamide,
heterocyclic sulfonamide groups such as benzothiazolylsulfonamide, imidapril sulfonamide, benzimidazolylsulfonamide, pyridylsulfonamide, etc.), sulfamyl W (such as propylsulfamyl,
Alkylsulfamyl groups such as octylsulfamyl; arylsulfamyl groups such as phenylsulfamyl, 2,4.6-dolychlorophenylsulfamyl, 2-methoxyphenylsulfamyl; thiazolylsulfamyl groups; heterocyclic sulfamyl groups such as benzothiazolylsulfamyl, benzothiazolylsulfamyl, oxacylsulfamyl, benzimidazolylsulfamyl, pyridylsulfefamyl, etc.) and carbamyl groups (such as ethylcarbamyl, octylcarbamyl, etc.) , etc.; alkylcarbamyl groups such as phenylcarbamyl, 2,4,6-drifuclophenylcarbamyl, etc., and thiazolylcarbamyl, benzothiazolylcarbamyl, oxacylylcarbamyl R11, R1? , R10 and R11
Specifically, those listed in R17 can be mentioned, respectively, and J is 5 and or 6 like Shimoshiki.
It represents a nonmetallic atom necessary to form a membered ring, ie, a benzene ring, a cyclosexene ring, a cyclopentene ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyridine ring, a virol ring, etc. Among these, a benzene ring is preferred.

xS, x'' are preferably hydrogen atoms, halogen atoms and -
〇-2-S-1-N=N- is a group (e.g., alkyl, aryl, heterocycle) bonded to the cuff ring position, and preferred examples of the cough group include alkoxy,
Examples include aryloxy, alkylthio, and arylthio groups. These groups are further 10-5-S-1-NH-1
-CON H-1-COO-2-5O,NH-1-SO
-1-SO, -1○ via substituent (e.g. alkyl, aryl, heterocycle)
It may have.

Specific examples of cyan couplers are as follows.

! -1 (MV/, :glare) and-2 (MW-Shima) (J Three pieces [MW-pcs] Beggar-4 (MW#3E7) OCR1C○0CHs Dan Nidan (MWLt386) OCI (ICONHCH.

In addition, in the present invention, in the present invention, known couplers may be included in combination with the low molecular weight couplers of each color mentioned above.
However, in this case, it is desirable to use the low molecular weight coupler according to the present invention in an amount of 50 to 100 parts per 100 parts of the total coupler amount.

These couplers have -C with 2X10-' mole to 5X10-' mole of if in one layer of silver halide emulsion.
mol, preferably 1X10-'' mol to 5X10-' mol.

The silver halide photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, and the like.

Further, the silver halide photographic material of the present invention may be one for jBa or one for multicolor.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver arsenide, silver iodobromide, silver iodochloride, silver chlorobromide, and R chloride. Any material used in silver halide emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acidic method, neutral method, and ammonia method. The grains may be grown all at once, or The method for producing and growing the primary particles that may be grown after producing the seed particles may be the same or different.

In the halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Also, considering the n-field growth rate of silver halide crystals, Alternatively, it may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and yAg in the mixing pot, or the halogen composition of the particles may be changed using a conversion method after growth. .

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are formed with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, and rhodium salts in the process of grain formation and/or grain growth. or complex salts, iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and reduction-sensitized nuclei can be added to the inside of the particles and/or on the surface of the particles by using GoS in an appropriate reducing atmosphere. Can be granted.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains, or they may be left as they are contained. This can be done based on the method described in the issue.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. Any ratio between the (1,0°0] plane and the (1,l,1) plane can be used.Also, particles with a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed. It's okay.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. In other words, compounds containing sulfur that can react with ions,
A sulfur enhancement method using activated gelatin, a selenium enhancement method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal i1 anger method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically enhanced to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The exacerbating dye may be used alone or in combination of two or more types. Together with the exacerbating dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the aggravating effect of the aggravating dye may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Silver halide is used during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening, for the purpose of preventing fog during storage or photographic processing, and/or keeping photographic performance stable. Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the oil-in-water emulsion dispersion method preferably used for dispersing couplers in the present invention, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 15
Gelatin (gelatin water) is dissolved in a high boiling point organic solvent of 0°C or higher, in combination with a low boiling point and/or water-soluble organic solvent as necessary.
After emulsifying and dispersing a surfactant in a wood-philic binder such as a liquid using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, the desired hydrophilic colloid is added. A step of removing the low-boiling organic solvent may be added at the same time as the zero dispersion liquid or dispersion, which may be added into the layer.

Examples of high boiling point organic solvents include phenol derivatives, phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesates, etc. that do not react with the oxidized form of the developing agent.
An organic solvent having a temperature of 50° C. or higher is used.

Anionic surfactants, nonionic surfactants, and cations can be used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. A surfactant can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The antifoggant agent may be used in the emulsion layer itself, or may be used in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

The photosensitive material of the present invention contains Fr! in the hydrophilic colloid layers such as the protective layer and the intermediate layer. It may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging due to rubbing, etc., and to prevent deterioration of the image due to UV light.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an anti-irradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the halogenated radical photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the light-sensitive material, improves the additivity, and creates a bond between the light-sensitive materials. Mantle agents can be added to prevent sticking.

Sliding Pj of a photosensitive material using the silver halide emulsion of the present invention
Lubricants can be added to reduce chafing.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

A light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, other layers include a baryta layer or an α-olephne polymer, etc., a flexible reflective support such as paper or synthetic paper, cellulose acetate, It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and %bJRN.

The silver halide material of the present invention can be prepared directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
The coating may be coated via one or more subbing layers to improve wear resistance, hardness, antihalation properties, friction properties, and/or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Dollion coatings and curtain coatings are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, T-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic light-sensitive material 1 of the present invention by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in color developing solution 17! from about 0.1 g to about 30 g for color developer IE, preferably from about 1 g to about 1.5 g for color developer IE.
Use at a concentration of g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
- A dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent.Among these, a particularly useful example is N,N''-diethyl-p-phenylenediamine. hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N,N”
-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline 6HH salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, An alkaline agent such as potassium carbonate, an alkali metal g6R salt, an alkali metal bisulfite, an alkali metal thiocyan fJi salt, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, and the like can be optionally contained. The pH value of this color developer is usually 7 or higher, most commonly about 1
0 to about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the salts of the metal complexes oxidize the metallic silver produced during development and convert it into silver halide, and at the same time color the uncolored areas of the coloring agent. Its composition is that metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid (4) Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (6) Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching solution used for the sodium acetate salt contains the above-mentioned metal complex salt of the organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as rehalogenated ffl+, metal salts, and chelate cuts such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, borate, oxalate, acetate, carbonate, phosphate, etc.
+ Normal bleaching of buffering agents, alkylamines, polyethylene oxides, etc.? What is known to be added at night can be added as appropriate.

Furthermore, the fixing solution is ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, Mekju! IN! Sulfites such as sodium sulfate, and various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may contain one or more types of pH buffering agents.

E, Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

A multilayer color photosensitive material was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support (BS). (However, sensitizing dyes 1 to ■ are shown below.)
.

1st layer: Halesian prevention layer (All) Gelatin layer containing black colloid 2nd layer: Intermediate layer (IL) 0.5g of gelatin and 0.045g of 2.5-Z [
-0.045g of dibutyl phthalate in which octylhydroquinone was dissolved was added in 1. (The intermediate layer contained per unit.

3rd F! : For red-sensitive low-sensitivity disintegrated emulsion layer... (RL-1) amount 1.79 g /=Coupler A...0.06 mol Coupler C per 1 mol of silver... ...0.0 per mole of 1 carp.
003Mole coupler D・・・・・・0 for 1 mole of iR
．． 003 Moltricresyl phosphate coating amount 0.3 cc/m 4th layer: Red malignant high sensitivity emulsion layer (RH-1)
'See 1.4
g/Ikabrar F・・・・・・・・・0.0125 mol per 1 mole of S 6 Kabratricresyl Phosphus) Coating amount 0, 2cc/+d 5th layer: Intermediate layer (IL) 2nd Same as the layer 6th N = green malignant low-grade emulsion stone (GL-1)
Amount 1. Og/n? Coupler 8-1...0.08 mole per 1 mole of coupler M...0.08 mole per mole of 1 coupler
．． 008 mole coupler D...i0.
0015 Moltricresyl phosphonate coating amount 1.4 cc/n (7th layer: Green angry fossa sensitive emulsion layer...(G, -1)
Amount 1.6g/m Coupler B-1...0.0 per mole per bar
2 mole coupler M...0.0 per mole of silver
03 Moltricresyl phosphate coating amount 0.3cc/m 13th TI! i:Ixo-Phil” -Ji (IL)
A gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

9th layer: Blue-sensitive low-sensitivity emulsion layer... (BL-1
)Amount 0.5g/rr
? Coupler Y-1......0.125 mole tricresyl phosphate coating amount per 1 mole of silver 0.3 cc/l+ (10th layer: Blue sensitivity emulsion layer... ...(BH-1
) Amount 0.6g/m Coupler Y-1・・・・・・・・・0.04 per 1 mole
Coating amount of mol tricresyl phosphate 0.1 cc/rf 11th layer: Protective layer (Pro) Coating a gelatin layer containing trimethyl methacrylate particles (diameter 1.5 μ).

The coupler in each layer was prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding p-dodecylbenzenesulfonic acid sorta as an emulsifier, and heating and dissolving it.
The mixture was mixed with a heated 10% gelatin solution and emulsified in a colloid mill.

In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

The sample prepared using the above Shiroxi was designated as Sample 1 (Comparative Example).

Coupler A (MW=461) Coupler 13-1 (MWk7(X13Cε Coupler CUJWζm) Coupler D (MW”+Eω) ib Coupler F <Mw=笥]
(Fuo Coupler M (Mw: 9793 Coupler Y-1 (MW”=748) The silver halide coupler used in #41 and the composition of
Other than the changes shown in the table, the trial month 1 and 6 moves are 1 set fee 2 ~
I made one copy of 7.

In each test, the ratio of the total amount of coupler and tricresyl sulfate to Latin in each silver halide emulsion layer was kept constant (0.8).

(Margin below) The composition of the layer is shown below.

-2: Blue-sensitive high-sensitivity emulsion layer amount 0.6 g/cd Blur Y-12...0.04 per mole
Mollicresyl phosphate 2 cloth 1 0.05cc/--2: Blue-sensitive low-sensitivity emulsion layer cloth Silver amount 0.5 g/m Blur y-12...... per 1 mole of tl Coating amount of 0.125 molar resyl phosphate 0.15 cc/resistance-2 = green-sensitive high-temperature emulsion layer coating! F1 amount 1.0 g / tri coupler m-3
...... 0.02 mole of tricresyl phosphate coating amount per 1 mole 0.13 cc/IcL-2: Coating amount of silver in the green-sensitive low-sensitivity emulsion layer 0.6 g/Ikabura-2 m-3・・・・・・・・・0.08 mol per mol of 1lWCoupler D・・・・・・・・・0.0 per mol of granite
01 mol tricresyl phosphate coating amount 0.84cc/1rf R,+-2: Red sensitivity high sensitivity emulsion layer coating silver amount 1.3 g/cd Coupler c-4......Silver 0 per mole
．． 0125 mol coupler C...0.0016 mol tricresyl phosph, ate coating amount per 1 mol of SEA 0.14 cc/m RL-2: Coating amount of silver in red-sensitive low-sensitivity emulsion layer 1. 7g/n? Coupler c-6...0 per mole of silver
．． 06 mole coupler C......i0.06 mole per 1 mole.
Coupling amount of 0.003 mole tricresyl phosphate 0.21cc/rrf BN-3: BM 2 coupler y-12, etc. Same as BN-2 and BL-3 except that molar y-1 was changed:
Same as BL-2 except that coupler y-12 of BL-2 was replaced with equimolar y-x.

G) 1-3: GH-2 coupler m-3 with equimolar m
Same as G9-2 except for changing to -12.

OL3: Same as GL-2 except that coupler m-3 of Gt-2 was replaced with equimolar m-12.

RN3: Same as R8-2 except that the coupler c-4 in Rs-2 was replaced with an equimolar amount of c-4.

RL-3: Same as RL-2 except coupler c-6 in RL 2 was replaced with equimolar c-7.

Each sample obtained was exposed to gradation light and subjected to the following color development process.

The development process used here was carried out at 38°C as described below.

1. Color development 3 minutes 15 seconds 2. Bleaching 6 minutes 30 seconds 3
,Washing・・・・・・・・・3 minutes 15 seconds 4,
Fixing: 6 minutes 30 seconds 5, Washing: 3 minutes 15 seconds 6,
Temperature: 3 minutes and 15 seconds The composition of the treatment liquid used in each step was as follows.

Color developer: Sodium nitrilotriacetate 0.1g Sodium sulfite 4.0g Sodium carbonate
30.0 g potassium bromide
1.4g Hydroxylamine sulfate 2.484-
(N-Ethyl-N-β hydroxyethylamino)-2-methyl-aniline sulfate 4.5g Add water
11 Bleaching solution: Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium iron salt 130.0 g Rice vinegar a
14. Omj! add water
11 Fixer: Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate <7
0%) 175.0ml! sodium bisulfite
Add 4.6g water/l/ Stabilizer: Formalin 3. Add QmJ water and calculate the relative sensitivity (S) for each sample obtained using blue light (B), green light (G) and red light (R), respectively.
RMS and MTF values were measured. The results are shown in Table 2.

Note that the relative sensitivity (S) is a relative value of the reciprocal of the exposure amount that gives a fog density of 10.1, and is expressed as a value with the sensitivity of BlG and R of sample No. 1 as 100.

The RMS value is 4 degrees of the minimum density + 1.2 with a circular scanning aperture of 2
+1il$ for the variation in density value that occurs when scanning with a 5μm microdecitometer! It is shown as a value 1000 times the deviation.

(Left below) From the above results, the present invention has significantly increased the number of demons!
It can be seen that not only the 'l-sensitivity is improved, but also the graininess (RMS value) is significantly improved.

[Brief explanation of drawings]

Figure 1(a), Figure 1(b), Figure 2, Figure 3(a),
Figure 3(b), Figure 3(C), Figure 3(d), Figure 4,
Figure 5(a), Figure 5(b), Figure 6(a), Figure 6(
b), FIG. 6(C), and FIG. 6(d) are respective schematic cross-sectional views of the N configuration of the photographic light-sensitive material based on the present invention. In addition, in the symbols shown in the drawings, B8... High-sensitivity blue photosensitive layer St-...
・・・・・・-Low sensitivity red sensitive layer CM・・・・・・・・・・・・・
...Highly sensitive green photosensitive layer CL-...
・・Low-sensitivity red-sensitive layer R□−・−・・・・・・・−・・
-High-sensitivity red-sensitive layer RL...--Low-sensitivity red-sensitive layer. Agent: Hiroshi Aisaka, Patent Attorney Figure 1 fo) fb) Figure 2 Figure 3

Claims (1)

[Claims] 1. It has blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, at least one of these silver halide emulsion layers is composed of a plurality of layers having mutually different sensitivities, and these plurality of layers are It consists of a layer of low sensitivity and a layer of high sensitivity arranged in order when viewed from the body side, and there is at least one silver halide emulsion layer having different color sensitivities and high sensitivity between these layers.
1. A photographic light-sensitive material in which at least one light-sensitive silver halide emulsion layer contains a low molecular weight coupler having a molecular weight of 250 to 450.