JPH02219048A - Photographic sensitive material packaging unit imparted with photographing function - Google Patents

Abstract

PURPOSE:To improve the stability of preservation with age even under inferior external conditions by incorporating a DIR compd. into the photosensitive material and forming at least one of blue-, green- and red-sensitive layers of single layer constitution. CONSTITUTION:This packaging unit contains the silver halide color photographic sensitive material formed by having at least the blue-, green- and red-sensitive silver halide emulsion layers on a substrate and this photosensitive material contains the DIR compd., in addition, at least one of the blue-, green- and red- sensitive layers is made of the single layer constitution. The DIR compd. refers to the compd. which eliminates a development retardant or the compd. capable of releasing the development retardant by the reaction with the oxidant of a color developing agent. The place where the DIR compd. is added may be any place where influence can be exerted to the development of the silver halide in the emulsion layer of the single layer constitution. The preservable stability with age against inferior external condition is improved in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photographic light-sensitive material package and unit endowed with a photographing function, and in particular, the present invention relates to a photographic light-sensitive material package and unit that has a photographic function, and in particular has excellent tone reproducibility during storage over time.
The present invention relates to a photographic material packaging unit that is easy to handle and has a photographic function.

[Prior art]

Currently, color photographs are taken with color negative film and then enlarged and printed on color paper.
The positive method is widely used. One of the reasons for this is that color negative film has a very wide exposure latitude, the probability of failure during shooting is very low, and even ordinary users without specialized knowledge can easily take color photos.

"Having a wide exposure latitude" means a wide exposure range from shadow areas with low exposure to highlight areas with high exposure in the so-called characteristic curve where the horizontal axis is the exposure and the vertical axis is the color density. This means that the gradation is good compared to the other. If this Ivllll is poor, the color reproducibility and tone reproducibility of the dye image will deteriorate.

Unlike Color Reversal Film and color paper, color negative film is a photosensitive material that requires strict control of gradation over a wider exposure range.
For this reason, in the currently commercially available color negative films for photography, each color-sensitive layer for blue, green, and red light is divided into a high-sensitivity layer containing silver halide grains with large grain sizes and a high-sensitivity layer containing silver halide grains with small grain sizes. A multilayer structure including a plurality of emulsion layers including a low-speed layer is used, and a so-called DIR compound is used which produces a development inhibitor as a result of reaction with an oxidized product of a developing agent.

This technology is unique to color negative film;
In particular, DIR compounds improve not only the gradation but also the sharpness, graininess, and color reproducibility of dye images, and are essential for color negative films.

On the other hand, photographic material packaging units with built-in silver halide color photographic materials and endowed with a photographing function, such as "Toreso-kun" manufactured by the applicant, have a film width of 110 or more. It is characterized by being large and compact, especially short and small in the length direction, making it easy to handle.

Since these packaging units are mainly sold at tourist spots, etc., their storage environment is particularly poor.

Normal color negative film improves the storage stability of photosensitive materials over time based on the environment such as temperature and humidity at film stores in urban areas, but when used as a packaging unit for photosensitive materials, the storage stability over time is even more improved. sexuality is required.

As mentioned above, a color negative film has a multilayer structure using multiple emulsion layers containing silver halide grains of different grain sizes.
Furthermore, since the gradation is strictly controlled using a DIR compound, when used as a photographic material packaging unit, the gradation deteriorates and the color deteriorates due to poor storage stability against external conditions such as temperature and humidity. It has the disadvantage that reproducibility and tone reproducibility deteriorate.

[Purpose of the invention]

The object of the present invention is to provide a photographic material packaging unit that has excellent stability against storage over time even under poor external conditions, has excellent gradation, color reproducibility, and tone reproducibility, and has a photographic function that is easy to handle. It is about providing.

[Structure of the invention]

As a result of intensive research to achieve the above-mentioned object of the present invention, we have discovered that this can be achieved by a photographic material packaging unit having the following configuration.

A photographic light-sensitive material package endowed with a photographing function, containing a silver halide color photographic light-sensitive material having at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. 1. A packaging unit for a photographic light-sensitive material, characterized in that the light-sensitive material contains a DIR compound, and at least one of the blue, green and red color-sensitive layers has a single layer structure.

The photographic material packaging unit provided with the photographing function of the present invention includes, for example, a first storage chamber in which unphotographed photographic material is wound and stored, a second storage chamber (for example, a patrone chamber) in which photographed photographic material is stored, and It has the functions necessary for photographing, such as a lens and a shutter.

The unphotographed photographic material is directly or indirectly (e.g. once stored in a cartridge)
Stored in the storage room.

The sizes of photosensitive materials are ilO size, 135 size,
Various sizes such as 126 size so-called disk type size can be taken.

The photographic material of the present invention will be explained in more detail below.

In the present invention, the DIR compound refers to a compound that releases a development inhibitor or a compound capable of releasing a development inhibitor upon reaction with an oxidized product of a color developing agent.

The compound capable of releasing the development inhibitor described above may be one that releases the development inhibitor imagewise or non-imagewise.

Examples of those that release imagewise include those that result from a reaction with an oxidized product of a developing agent, and examples of those that release non-imagewise include those that utilize the TIME group described below.

Representative structural formulas are shown below.

General formula (D-1) A-(Y)m A represents a coupler residue, y represents 1 or 2, and Y is bonded to the coupling position of the coupler residue A to form an oxidized product of the color developing agent. A group that leaves by reaction and represents a development inhibitor group or a group capable of releasing a development inhibitor.

In general formula (D-1), Y is typically represented by the following formulas (D-2) to (n-20).

-Formula (D-2) -Formula (D -3) -Formula (D -4) -Formula (D, -5) -Formula (D
-6) -Formula (D-7) -Formula (D-8)
- Formula (D -9) - Formula (D-2) ~ (D
-7), Rdl is a hydrogen atom, a halogen atom, or alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonylrubamoyl, N. Each layer of N-dialkylcarbamoylo, amino, N-alkylcarbamoyluoquine, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylaminokylthio, arylthio, aryl, heterocycle, cyano, alkylsulfonyl or aryloxycarbonylamino represent.

n represents 0, l or 2, and when n is 2, each Rd.

may be the same or different. The total number of carbon atoms contained in n Rdl is 0 to 10.

Furthermore, the number of carbon atoms contained in Rdl in formula (D-6) is 0 to 15.

X in the above formula (D-6) represents an oxygen atom or a sulfur atom.

In general formula (D-8), Rdl represents an alkyl group, an aryl group, or a heterocyclic group.

- In formula (D-9), Rds represents a hydrogen atom or each layer of alkyl, cycloalkyl, aryl, or heterocycle, and Rd4 represents a hydrogen atom, a halogen atom, or alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryl Represents each layer of oxycarbonylamino, alkanesulfonamide, cyano, heterocycle, alkylthio, or amino.

Rdl, Rdl, Rd, or Rd. When represents an alkyl group, this alkyl group may have a substituent and may be either a straight chain or a branched chain.

Rd. , Rdffi, Rd. When Rd represents an aryl group, the aryl group includes those having a substituent.

Rd, %Rd, , Rd, or Rd. represents a heterocyclic group, this heterocyclic group includes those having a substituent, and is a 5- or 6-membered ring containing at least one selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a heteroatom. A monocyclic ring or a condensed ring is preferable, and is selected from, for example, layers of pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, and oxazine.

- The number of carbon atoms contained in Rd in formula (D-8) is θ~15.

In the above formula (D-9), Rd, and Rd
The total number of carbon atoms contained in , is 0 to 15.

- Formula (D - 10) - (T I ME) n - I NH I B I T
In the formula, the TIME group is a group that is bonded to the coupling position of A and can be cleaved by reaction with an oxidized product of a color developing agent,
cleaved from the coupler; then sequentially cleaved, and finally I
It is a group that can release the NIIIBIT group in a moderately controlled manner. n is 1 to 3, and when n is 2 or 3, each TIME group may be the same or different.

The INHIBIT group is a group that becomes a development inhibitor upon release (for example, a group represented by the above-mentioned formulas (D-2) to (D-9)).

In general formula (D-10), the -TIME group is typically represented by the following formulas (D-11) to (D-19).

- Mathematical formula (D -11) General formula (D -16) General formula (D General formula (D -18) - Mathematical formula (D -19)
-Formula (D -12) -Formula (D -13)
-Formula (D-14) -Formula (D -15)-
Formulas (D -11) to (D -15) and (D -18
), Rdfi is a hydrogen atom, a halogen atom, or alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy,
Represents each layer of sulfo, hydroxy or alkanesulfonyl, - Formulas (D-11) to (D-13), (D
-15), (D -18), Rd may be combined with each other to form a condensed ring, and the formula (D -11)
, (D-14), (D-15) and (D-19)
In, Rd represents each layer of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl,
Rd represents a hydrogen atom or each layer of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl, -Rd in formula (D-19) and Rd
, respectively represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), - Formula (D-11)
, k in (D -15) to (D -18) is 0.1
or represents an integer of 2, - formula (D -11) ~ (D -
13), (D -15), (D -18) represents an integer of 1 to 4, - m in formula (D -16)
represents an integer of l or 2, and when Q and m are 2 or more, each Rd
,.

Rd? may be the same or different, -formula (D -19
), n represents an integer from 2 to 4, and n Rd and Rd may be the same or different, and - formula (D
-16) to (D-18), B is an oxygen atom or N
(Rd has the same meaning as already defined in table Rd.

vinegar. ), - represents that == in formula (D-16) may be a single bond or a double bond,
For a single bond, m is 2; for a double bond, m is l
It is.

General formula (D-20) 云T , qS R→T z piece I N HT B I 7
In the formula, T1 is 5R (T, a component that cleaves the tank INHIBIT, and SR is SR + T, a component that cleaves the tank INHIBIT.
The component that generates T is T, (T, the component that cleaves INN after INHIBIT is generated is INI(IBI
T represents a development inhibitor, and a and m each represent 0 or l.

The component represented by SR may be one that produces the above-mentioned component by reaction with the oxidized form of the developing agent, such as a coupler component that reacts with the oxidized form of the developing agent and a coupler component that reacts with the oxidized form of the developing agent. Examples include redox components that undergo redox reactions.

Coupler components include acylacetanilides, 5-
Pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, isidanones, carbamoylacetanilides, 2(5H)-imidacylones, 5-ynoxacilones, uracils, homophthalimides, oxacilones, 2 ,5-thiadiazoline-1
, 1-dioxides, triazolothiadiazines, indoles, etc., yellow solars, magenta couplers, cyan couplers, and other compounds that produce various dyes or those that do not produce dyes may be used.

It is preferable that the T1 SR→T and the old and new T are bonded to the active site of the component A of the general formula (D-1).

Also, if SR is a coupler component, SR is -1:T13
After being cleaved from -H, it is first combined with Tlq and six T2 in old BIT to function as a coupler.

For example, when the coupler component is 7 enols or naphthols, the oxygen atom of the hydroxyl group is the oxygen atom of the hydroxyl group at the 5-position of the tautomer, or the nitrogen atom at the 2-position when the coupler component is a 5-pyrazolone. However, also, aceto7enes/enes,
In Inter/7M, the oxygen atom of the hydroxyl group of the tautomer is bonded to -1-TlY.
Preferably, BIT is bound to the active site of the coupler.

When SR is a redox component, examples include hydroquinones, catechols, pyrogallols, aminophenols (e.g. (p-aminephenols,
0-aminophenols), naphthalene diols (e.g. 1,2-s7talediols, 1,4-s7talediols, 2,6-naphthalene diols), or aminonaphthols (e.g. .2-aminonaphthols, 1.4-aminonaphthols, 2.6-aminonaphthols), and the like. In addition, when SR is a redox component, SR is cleaved from +T, )- so that it functions as a redox component (T l← and (T ,
9-m I N1 Combines with old T.

Examples of the groups represented by T and T2 include those represented by the aforementioned general formulas (D-11) to (D-19).

Examples of the development inhibitor represented by INHIBIT include those represented by the aforementioned general formulas (D-2) to (D-9).

Among the DIR compounds, preferred are those in which Y has the general formula (D
-2), (D-3), (D-8) or (D-10)
or (D-20), (D-10
), (D-20), ! NHIBIT is the general formula (
D-2), (D-3), (D-6) (especially - formula (D
-6) when X is an oxygen atom) or (D-8) is preferred.

Examples of the coupler component represented by A in general formula (D-1) include yellow image-forming coupler residues, magenta image-forming coupler residues, cyan image-forming coupler residues, and colorless coupler residues. .

Preferred DIR compounds used in the present invention include, but are not limited to, the following compounds.

Exemplary compound Margin below R, -COCHCO-R* R1゜ in the table R8 and Y represent the following.

- C0NHCH2C82COOCH3/too2 ■ DI including these that can be used in the present invention
Specific examples of R compounds are U.S. Pat. Nos. 4,234,678, 3,227,554, 3,617,291, and
, 958,993, 4, 149, 886, 3,933,500, JP-A-57-56837, JP-A-51-13239, U.S. Patent No. 2,072,363,
No. 2,070,266, Research Disclosure (hereinafter abbreviated as RD), December 1981, No. 2122
It is written in No. 8 etc.

The DIR compound is 0.0001 per mole of silver halide.
-0.1 mol is preferably used, especially 0.001 mol
It is preferable to use ~0.05 mol.

The DIR compound may be added at any location that can affect the development of silver halide in the emulsion layer having a single layer structure.
Preferably it is a silver halide emulsion layer, more preferably a silver halide emulsion layer having a single layer structure and/or an emulsion layer having the same color sensitivity as the emulsion layer.

A single color-sensitive layer means that the color-sensitive layer is a single layer, which means that the emulsion layer contains multiple photosensitive layers having the same type of coupler, grain size of silver halide grains, halogen composition and crystal habit, and the same ratio of coupler and silver halide. It also includes a case where emulsion layers having the same color property are arranged as a continuous layer.

Here, "having the same color sensitivity" or "same color sensitivity" means that they are the same in terms of, for example, blue sensitivity, green sensitivity, and red sensitivity, but it is not necessary that the spectral sensitivity characteristics are exactly the same. There isn't.

In the present invention, it is preferable that the blue-sensitive layer is a single layer, and it is more preferable that both the blue-sensitive and green-sensitive silver halide emulsion layers are a single layer.
Preferably, all of the green-sensitive and red-sensitive silver halide emulsion layers are each a single layer.

When the color-sensitive layer has a single-layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional multi-layer structure, making it possible to form a thin film. Therefore, production efficiency, sharpness, and graininess are improved.

The film thickness after drying is preferably 20 to 3 pm, particularly preferably 15 to 5 μm.

Exposure latitude is the width of the amount of received light that produces significantly different exposure effects, and is the exposure range from highlights to deep shadows in the characteristic curve, as described in Photo Chemistry, page 393 (
Shashin Kogyo Shuppansha, 1982).

That is, it is the difference between Qog H at two points where the slope of the tangent line at the foot and shoulder of the characteristic curve, where the horizontal axis is (logH) and the vertical axis is the transmission density, is 0.2.

The light-sensitive material of the present invention preferably has an exposure latitude of 3.0 or more, and preferably 3.0 to 3.0 or more, as measured by the above method.
8.0 is particularly preferred.

As a means for widening the exposure latitude of a single silver halide emulsion layer to 3.0 or more, a method of mixing and using silver halide grains having different sensitivities can be used.

Specifically, examples include a method in which silver halide grains having different grain sizes are mixed and used, and a method in which a desensitizer is contained in at least a portion of the silver halide grains.

Silver halide grains with different grain sizes used in combination to obtain a wide exposure latitude have an average grain size of 0.2.
A combination of silver halide grains (having a maximum average grain size of 0.05 to 1.0 μm) and silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferable; One or more types of silver norogenide grains having an average grain size may be combined.

Further, the average grain size of the silver halide grains having the maximum average grain size is 1.5 to 4% of the average grain size of the silver halide grains having the minimum average grain size.
Preferably, it is 0 times.

In order to obtain a wide exposure latitude, it is possible to mix and use silver halide grains with different average grain sizes. If used, the difference in average grain size can be reduced without changing the sensitivity of silver halide grains, and furthermore, it is possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, a wide exposure latitude can be obtained even if the coefficient of variation of the entire grain is made small.

Therefore, these silver halide grains having a small coefficient of variation that are exposed to the same environment are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing.

Furthermore, from the viewpoint of production technology, it becomes possible to chemically sensitize a mixed system of silver decagenide grains having different sensitivities in the same batch.

In addition to metal ions, various desensitizers can be used, such as antifoggants, stabilizers, desensitizing dyes, and the like.

In the present invention, a metal ion doping method is preferred. Metal ions used for doping include Group Ib, Group ■b, and Group ■a in the periodic table of elements.

Examples include metal ions of group mb, group IVb, group Va, and group II. Preferred metal ions include ^u, Zn, and Cd.
.

T12. Sc, Y, Bi, Fe, Ru, Os, Rh,
Examples include metal ions of Ir, Pd, Pr, Ss, and Yb. Particularly preferred are Rh, Ru, and Os.

It is lr.

These metal ions can be used, for example, as halogen complex salts, and the pH of the AgX suspension system during doping is preferably 5 or less.

The amount of metal ion doping varies depending on the type of metal ion, the particle size of silver halide grains, the doping position of metal ions, the desired sensitivity, etc.
Morni vs. shite 1O-17~IO'''Molka preferred,
Furthermore, IQ-1j to 1O-3 mol is preferable, especially 10-
” to 1 O −6 mol is preferred.

Furthermore, by selecting the type of metal ion, doping position and doping amount, various different sensitivity qualities can be imparted to the silver halide grains.

If the doping amount is less than io-'' mol/AgX mol, it will not have a large effect on grain growth, so silver halide grains with a narrow grain size distribution are prepared under the same grain growth conditions and even under the same batch growth. be able to.

It is also possible to prepare silver halide grains with different doping conditions so that they can be put to practical use, then mix them in a predetermined ratio to form the same batch, and then chemically sensitize the grains. Each silver halide grain receives a sensitizing effect based on its properties, and an emulsion having a wide exposure latitude can be obtained depending on the sensitivity difference and mixture ratio.

The anti-capri agents or stabilizers include azoles (e.g., benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, etc.), peterocyclic mercapto compounds (e.g., mercaptotetrazoles, mercaptothiazoles, mercapto Thiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) Azaindenes (e.g., tetraazaindenes, pentaazaindenes, etc.) Nucleic acid decomposition products (e.g., adenine, guanine, etc.), benzenethiosulfonic acids, thioketo Examples include compounds.

Examples of desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

The location of the desensitizer is preferably mixed inside the silver halide grains from the viewpoint of storage stability of the photosensitive material, stagnation stability of the coating solution, etc., and even if its distribution is uniform, , even if it is localized at the center or intermediate position of the particle,
It may gradually decrease from the center of the particle toward the outside.

From the viewpoint of production efficiency, it is preferable that the seed particles be localized in the center of the particles, and if a method using seed particles with a small coefficient of variation is used, the steps after particle growth can be performed in the same batch.

In the light-sensitive material of the present invention, it is desirable that at least one color-sensitive layer (for example, a blue-sensitive layer) contains desensitizer-containing AgX particles. Preferably, the blue-sensitive layer contains desensitizer-containing AgX particles, more preferably the blue-sensitive layer and the green-sensitive layer, and most preferably all the color-sensitive layers contain desensitizer-containing AgX particles.

Further, the coefficient of variation defined by the ratio S/F of the standard deviation (S) of the grain size to the average grain size (〒) of the entire silver halide grains contained in each silver halide emulsion layer is 0.4 or less. It is preferably 0.33 or less, more preferably 0.25 or less, and particularly preferably 0.20 or less.

The average grain size (r') is the grain size (in the case of cubic silver halide grains, the length of the side thereof, or, in the case of grains with a shape other than a cube, converted to a cube having the same volume). When the number of particles of i is nl, it is defined by the following formula.

The relationship between particle size distribution is described in "Empirical relationship between sensitometric distribution and particle size distribution in photography," The 7 Otograph Journal, Vol. LXXIX (1949), 330-3.
In the method described in the paper by Tribel and Smith on page 38,
You can decide this.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any conventional silver halide emulsion can be used, but silver halides containing substantially iodine in the halogen composition (for example, silver iodobromide, silver iodochlorobromide) are preferred, especially silver iodobromide. is preferable in terms of sensitivity. The amount of iodine is preferably 1 to 20 mol%, particularly preferably 3.5 to 12 mol%.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Anticapri agents, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling with colored couplers, competing couplers, and oxidized forms of developing agents, which have the effect of color correction, developers, silver halide solvents, toning agents, hardeners, anti-capri agents, and chemical sensitizers can be obtained. Compounds that release photographically useful 7-ragments such as spectral sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, a Halley sheen prevention layer, and an irradiation prevention layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

For photosensitive materials, formalin scavenger-fluorescent brightener,
A matting agent, a lubricant, an image stabilizer, a surfactant, an anti-color capri agent, a development accelerator, a development retardant, a bleach accelerator, etc. can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The photosensitive material of the present invention is particularly useful as a negative photosensitive material.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Silver halide emulsions used in Examples were manufactured.

Preparation of seed emulsion Pour the aqueous gelatin solution into a reaction vessel, and add
) While controlling Ag and 9H, silver nitrate aqueous solution, potassium iodide aqueous solution and potassium bromide aqueous solution were added simultaneously while controlling the addition time, and then precipitation desalination was performed using pH coagulating gelatin and gelatin was added. A seed emulsion was prepared.

The obtained emulsion is called NE-1. Also, in the reaction pot, K3R
Seed emulsion N was prepared in the same manner as above except that hC12 was added.
E-2 was prepared.

The emulsion and its contents are shown in Table-1.

Table = 1 Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling pAg and pti in the reaction vessel,
An ammoniacal silver nitrate aqueous solution, a potassium iodide aqueous solution, and a potassium bromide aqueous solution were added in proportion to the surface area during grain growth, and at an appropriate particle size, the potassium bromide aqueous solution was changed and subsequently added. In the same manner as the seed emulsion, precipitation and desalting were performed, gelatin was added and redispersed, and the pA g7.8.
Add an emulsion with a pH of 6.0.

In this way, the inside of the grain is a silver iodobromide emulsion E with a moderately high content.
M-1-EM-4 was prepared.

Table 2 shows the emulsions and their contents.

Table 2 Preparation of Sample 101 (Comparison) A multilayer color photosensitive material 101 having an upper and lower layer structure having the following composition was prepared on a subbed cellulose acetate support.

The coating amount is expressed in units of g/la2 for silver halides and colloidal silver, and in g/la2 units for additives and gelatin.
Sensitizing dyes, couplers and DIR compounds are expressed in moles per mole of silver halide in the same layer.

The emulsions contained in each color-sensitive emulsion layer were optimally sensitized with sodium thiosulfate and chloroauric acid, and equimolar amounts of NE-IME-1 and NE-2 were used.

V- H V-2 C*H* C In addition to the above ingredients, each layer is coated with a surfactant M-1 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye V CH 0 ■ CH sensitizing dye■ (CH5SOs''' (C)It)ssOsH-N(CJIs)3S-1 υ S-1 Below, each layer of the above seven compositions is the above-mentioned HC, IL-1゜R
-1, R-2, IL-2, G-1, G-2, YC.

B-1, 8-2, Pro-1, Pro-2 (7)
The abbreviations shall be indicated.

Samples 102 to 103 (present invention) Except for B-2 and G-2 of sample 101, B-1 and G-
The emulsion contained in B-1 was replaced with an equimolar mixture of EM-1 and EM-2, and the emulsion contained in B-1, gelatin and TC
Sample 10 except that the amount of P used was increased by 15% and the amounts of emulsion, gelatin and TCP contained in Gl were increased by 30%.
Sample 102 was prepared in the same manner as in Example 1. (B-1 and G
(The amounts of the sensitizing dye, coupler, and DIR compound per mole of silver halide in sample 101 are the same as those in sample 101).
Sample 103 was prepared in the same manner as sample 102 except that M-3 was used.
was created.

Table 3 shows the contents of the sample thus prepared.

Table 3 B: Blue sensitive layer G: Green sensitive layer R: Red sensitive layer Each sample was cut into a 35 mm size and a length corresponding to 24 frames. It is wound so that the color-sensitive layer side is on the inside, and stored directly in the film storage chamber of the lens-equipped packaging unit described in JP-A-63-194255.
Attach it to a small size cartridge, store it in the cartridge chamber, and use the shooting function (Fixed focus F: 8°, shutter speed 1 /
A photographic material packaging unit was obtained.

1 of the unit containing each photosensitive material. [1 set was stored in a refrigerator (5°C) (standard), and the other set was stored at 37°C and 80% relative humidity for 1 month.

After photographing a continuous wedge object, it was processed through the following processing steps.

Treatment process (38℃) color development bleaching white Water washing fixed arrival Water washing Stabilization drying drying 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

Color developer 4-Amino-3-methyl-N-ethyl N-(β-hydroxyethyl) Aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine l/2 sulfate 2.0g Anhydrous potassium carbonate 37. 5 g potassium bromide
1.3 g nitrilotriacetic acid 3
Sodium salt (l water salt) 2.5 g Potassium hydroxide 1.0 g Add water to make lI2.

Bleach solution Ethylenediaminetetraacetic acid Iron (In) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and
ff and adjust the pH to 6.0 using aqueous ammonia.

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metasulfite 2.3g Add water
I2 and adjusted to pH 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.5+
++I2 Konidax (Konica Corporation m1) 7
．． Add 5 mQ water to make tc.

Samples 101 to 103 were evaluated for gradation preservation over time using the following evaluation method.

Good gradation preservation A method for evaluating gradation preservation will be explained using figures.

Figure wi1 shows a characteristic curve (broken line) serving as a reference and a characteristic curve (solid line) to be evaluated. Also, △Qog H is 3 from the exposure point that gives the minimum density of 10,1 in Fig. 1.
．． Each exposure point between 0 increasing exposure points (△f between each exposure point
The point gamma values of fogH-0,15) are shown in FIG.

From Figure 2, the absolute value Δ of the difference in point gamma at each exposure point between the reference characteristic curve and the characteristic curve to be evaluated.
Find γ. The standard deviation σ of Δγ was determined, and the gradation preservation property was expressed as 1000 times the value of σ (Σ).

That is, the larger the value of Σ, the less uniform the change in gradation, and the worse the gradation preservation.

Evaluation I: The results of the green sensitive layer are shown in Table 4.

Table 4 As is clear from Table 4, the photographic light-sensitive material packaging unit of the present invention has a small gradation shift from the highlight portion to the shadow portion of the characteristic curve during storage over time and has good tone reproducibility.

Furthermore, it was found that this effect was even greater in the case where all of the blue sensitivity, green sensitivity, and red sensitivity were configured in a single layer.

It can be seen that sample 103, which contains an emulsion in which grains were grown in a mixture of seed grains containing Rh ions and seed grains not containing Rh ions, has a particularly large improvement effect and is preferable. This emulsion allows grain growth and chemical sensitization to be performed in one operation,
It is also preferable in terms of production efficiency.

Ksghca, instead of Ru(, I13.0sCQz
, A seed emulsion prepared by adding Pb(NJ)2 to NE-
The emulsion prepared in place of EM-2 of sample 103 was
The effects of the present invention were also observed for each sample used in place of Sample No. 3.

Instead of (D-23) in G-1 of sample 102, (D-
6), (D-2), and (D-10), each sample using (D-2) and (D-2) in place of (o-23) and (D-42) of R-1 of sample 103. 17), also (D-19
) and (D-21) were also found to exhibit the effects of the present invention.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the characteristic curves of the standard (broken line) and evaluation target (solid line) photographic materials, and Figure 2 is the standard (broken line).
and a diagram showing the point gamma of the photographic light-sensitive material to be evaluated (solid line).

Claims (1)

[Claims] A photographic light-sensitive material package endowed with a photographing function, containing a silver halide color photographic light-sensitive material having at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. 1. A packaging unit for a photographic light-sensitive material, characterized in that the light-sensitive material contains a DIR compound, and at least one of the blue, green and red color-sensitive layers has a single layer structure.