JPS6019498B2 - Photographic materials for color diffusion transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material for color diffusion transfer, and more particularly to a photographic material for color diffusion transfer containing a novel development inhibitor precursor.

In particular, it relates to photographic materials for color diffusion transfer that contain novel development inhibitor precursors and which yield good dye images over a wide range of processing temperatures. A photographic material for color diffusion transfer containing a light-sensitive element having on a support at least one light-sensitive silver halide emulsion layer in combination with such a color image-forming substance, an image-receiving layer and a development inhibitor precursor can be prepared by e.g. Special Publication No. 38-112093, No. 41-
No. 10386, Tokukan Sho 47-38038, Tokukan Sho 47-3
No. 803y, No. 50-28823 and No. 50-89
It is known in each publication of No. 034.

In Japanese Patent Publications No. 38-12093 and No. 41-10386, by using a development inhibitor precursor,
A technique has been started in which the action of suppressing development by the development inhibitor released from the development inhibitor precursor is delayed for a certain period of time. However, in these conventional techniques, necessary development is excessively suppressed because the development inhibitory effect is insufficiently delayed, or conversely, the development inhibitory effect is excessively delayed, resulting in fog development. Color mixing of the dye image obtained on the layer, a decrease in maximum density, and an increase in maximum density occurred, making it impossible to obtain a good dye image.
Also, Mochikai Sho 47-38038 and Sho 47-3803
No. 9 discloses a technique for reducing fog formation over a wide range of processing temperatures, that is, increasing processing temperature latitude, by using a development inhibitor precursor that releases the development inhibitor more quickly as the temperature increases. has been done. However, even in these conventional technologies,
The temperature dependence of the rate at which the development inhibitor is released (hereinafter referred to as the development inhibitor release rate) is still insufficient.

In other words, a development inhibitor precursor that has an appropriate development inhibitor release rate at high temperatures will have a development inhibitor release rate that is too far compared to the development rate at low temperatures, resulting in excessive suppression of necessary development. Conversely, if the development inhibitor release rate is appropriate at low temperatures, the development inhibitor release rate is too slow compared to the development rate at high temperatures, resulting in excessive development. Therefore, even with these conventional technologies, it can be used over a wide temperature range (especially at high temperatures).
It was not possible to achieve adequate development inhibition and obtain a good dye image. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned drawbacks that could not be solved even with the prior art, and more particularly, it is an object of the present invention to solve the above-mentioned drawbacks that could not be solved even with the prior art. The purpose is to provide photographic materials. As a result of intensive research to achieve the above objectives, we have developed a phenomenon inhibitor precursor that has been highly desired, that is, has an appropriate development inhibitor release rate and has sufficient temperature dependence of the development inhibitor release rate. A large development inhibitor precursor was found here and released.

That is, a color diffusion transfer having at least one light-sensitive silver halide emulsion layer in combination with a color image-forming substance, a support for holding the emulsion layer, and an image-receiving layer, and containing a development inhibitor precursor. In the photographic material for use in photography, the development inhibitor precursor has the general formula: When n is 1, R represents an alkyl group or a phenyl group, and when n is 2, it represents an alkylene group or a phenylene group.

It was found that the above object could be achieved by using a compound represented by the following formula. The development inhibitor precursor represented by the general formula set forth in claim 1 will be described in detail below.

Z represents a group of metal atoms necessary to form a 5- to 6-membered heterocycle.

The heterocycle may be a monocyclic ring or a condensed ring, and may have a substituent. Examples of the heterocycle include tetrazole rings, such as tetrazole rings, phenyltetrazole rings,
Triazole rings, such as penzotriazole rings, 1.
2,4-triazole rings, diazole rings, such as penzimidazole rings, imidazole rings, pyrimidine rings,
Examples include a pyrimidine ring, monoazole rings, such as a penzothiazole ring and a benzoxazole ring. Preferred are double rings containing at least two heteroatoms, such as tetrazole rings, benzotriazole rings, benzothiazole rings, and more preferred are tetrazole rings, especially phenyl-substituted tetrazole rings. n is preferably 1. Among the alkyl groups represented by R, preferred alkyl groups are those having 1 to 25 carbon atoms, and particularly preferred alkyl groups are:
Alkyl groups having 1 to 3 carbon atoms (e.g. ethyl group, 2
-methoxyethyl group). The phenyl group represented by R may have a substituent, and preferable substituents include a nitro group, a cyano group, an alkoxyl group (preferably having 1 to 25 carbon atoms), an alkyl group (
(preferably having 1 to 25 carbon atoms), a sulfo group, an amide group (for example, an alkanamide having 1 to 25 carbon atoms), or a halogen atom (preferably a chlorine atom). Among R, preferred is an alkyl group or a phenyl group having no substituent or substituted with an electron-donating group (eg, an alkoxyl group), and the most preferred is a phenyl group having no substituent. Among the development inhibitor precursors according to the present invention detailed above, particularly preferred are those in which Z forms a 1,2,3,4-tetrazole ring or a 1-phenyl-1,2,3,4-tetrazole ring. represents a nonmetallic atom group necessary for the purpose of the present invention, and R is a phenyl group having no substituent, and the most preferred compound is Exemplified Compound 1, which will be explained later.

It is an object of the present invention that the development inhibitor precursor according to the present invention desorbs the development inhibitor at an appropriate time and at a remarkable rate over a wide temperature range in an alkaline medium during processing of photographic materials. It is assumed that this is achieved mainly by the protecting group moiety of the development inhibitor precursor, -CH2CH2
This is thought to be due to the R-S02- group in S○2nanR.

A protective group moiety CH3COCH containing a CH3CO- group is a compound very similar to the development inhibitor precursor according to the present invention.
Development inhibitor precursors having a 2C flower are known.

Both the R-S02- group and the R-CO- group fall within the scope of acyl groups, and the color diffusion transfer photograph containing the development inhibitor precursor having the R-S02- group according to the present invention It has become clear that better dye images can be obtained using the material, and particularly when processed at high temperatures, good dye images with lower minimum density and higher maximum density can be obtained. Next, the development inhibitor precursor according to the present invention will be illustrated, but the present invention is not limited to these compounds. Exemplary Compounds The development inhibitor precursor according to the present invention includes, for example, an alkali metal salt of a development inhibitor and an 8-halogenoethylsulfone compound (X-CH2-CH2S○2
NanR (where x represents a halogen atom, n and R
has the same meaning as above.

) can be easily synthesized by heating in a solvent such as acetone or methyl alcohol. A synthesis example is shown below.

Synthesis Example 1 Synthesis of Exemplified Compound 1 Phenyl-3-chloroethylsulfone 2.0 and 1
-Phenyl-5-mercapto 1,2,3,4-tetrazole sodium salt 2.0 g was added to 50% acetone, and after heating under reflux for 1 hour, the reaction solution was concentrated.

After extraction with 50 ml of ethyl acetate, the mixture was washed with water and further washed with an aqueous sodium bicarbonate solution. After drying over anhydrous sodium sulfate, it was concentrated and recrystallized from 30 ml of methyl alcohol.
The yield was 2.5 days, and the melting point was 110-111°C. As a result of mass spectrometry, a parent ion peak of I6 was confirmed. The results of elemental analysis are shown below.

Effort C Day N Theoretical value 52.01 4.07 16.17 Measured value 52.13 4.11 16.05 From the above elemental analysis and mass spectrometry results, the compound synthesized above has the structure of Exemplified Compound 1. was confirmed.

Synthesis Example 2 Synthesis of Exemplified Compound 2 - Synthesis except that p-methoxyphenyl-8-chloroethylsulfone 3.0 times was used instead of phenyl-8-chloroethylsulfone 2.0 times in Synthesis Example 1. It was synthesized in the same manner as in Example 1.

The yield was 2.0 mm, and the melting point was 87-88 mm. As a result of mass spectrometry, 376 parent ion peaks were confirmed. The results of elemental analysis are shown below.

Effort C Day N Theoretical value 51.05 4.28 14.88 Measured value 51.02 4.33 14.81 From the above elemental analysis and mass spectrometry results, the compound synthesized above has the structure of Exemplified Compound 2. was confirmed.

Synthesis Example 3 Synthesis of Exemplified Compound 3 Using 3.3 ml of phenyl-8-chloroethyl sulfone in place of 2.0 ml of phenyl-8-chloroethyl sulfone in Synthesis Example 1, recrystallization was performed using 30 ml of methyl alcohol. Synthesis was carried out in the same manner as in Synthesis Example 1, except that acetonitrile 50 was used instead of.

The yield was 3.2 days, and the melting point was 165-166 qC.
As a result of mass spectrometry, 391 parent ion peaks were confirmed. The results of elemental analysis are shown below.

Effort C Day N Theoretical value 46.03 3.35 17.89 Measured value 45.98 3.44 18.07 From the above elemental analysis and mass spectrometry results, the compound synthesized above has the structure of Exemplified Compound 3. was confirmed.

Synthesis Example 4 Synthesis of Exemplified Compound 9 Synthesis was carried out in the same manner as in Synthesis Example 1 except that 1.8 times of methyl-8-chloroethylsulfone was used instead of 2.0 times of phenyl-B-chloroethylsulfone in Synthesis Example 1. did.

The yield was 1.5 days, and the melting point was 138-139.5°C. As a result of mass spectrometry, 284 parent ion peaks were confirmed. The results of elemental analysis are shown below.

Release C Day N Theoretical value 42.24 4.25 19.70 Measured value 42.17 4.30 19.58
From the above elemental analysis and mass spectrometry results, it was confirmed that the compound synthesized above had the structure of Exemplary Compound 9.

The development inhibitor precursor represented by the general formula described in the claims is preferably used in the photographic material for color diffusion transfer according to the present invention, particularly in a layer into which a processing composition can penetrate during processing (hereinafter referred to as a processing composition). This is called the permeable layer.

). In the photographic material for color diffusion transfer of the present invention, in addition to the above-mentioned photosensitive silver halide emulsion layer and image-receiving layer, a neutralizing layer may be added as a processing composition permeable layer.
Mention may be made of timing layers, opacifying layers, light-reflecting layers, protective layers, interlayers, release layers, physical development nucleation layers, prefogged silver halide emulsion layers, dye image-forming material layers, and the like. Among the various processing composition permeable layers described above, the layers containing the development inhibitor precursor according to the present invention are preferably an intermediate layer, a protective layer, a dye image forming material layer, a photosensitive silver halide emulsion layer, and a timing layer. layers, a light reflecting layer, an opacifying layer, a physical development nucleus layer and a pre-fogged silver halide emulsion layer, and more preferably layers include an intermediate layer, a protective layer, a dye image forming material layer, a photosensitive halogenated A silver emulsion layer, a timing layer, and the most preferred is a timing layer.

A photographic material for color diffusion transfer having two timing layers as described in U.S. Pat. No. 4,061,496, i.e., having as essential layers in order a neutralizing layer, an activation energy for penetration by an aqueous alkaline solution of less than 1 cal per mole. timing layer with polymer latex and 1 per mole
The development inhibitor precursor according to the present invention is contained in the timing layer of a photographic material for color diffusion transfer having a support having a timing layer having a polymer latex having an activation energy of permeation by an aqueous alkaline solution of more than 100 yen cal. In this case, it is preferable to include the polymer latex in a timing layer having a polymer latex having an activation energy for penetration by an alkaline aqueous solution of not more than the primary cal per mole.

The amount of the development inhibitor precursor according to the present invention added when the treatment composition permeable layer is contained can vary depending on the type of development inhibitor precursor used, the place of addition, the method of addition, and the like.

Usually, it is added in an amount of 0.001 mol or more, preferably in the range of 0.005 mol to 1.0 mol, per 1 mol of photosensitive silver halide used in a photographic material for color diffusion transfer, and in particular, a development inhibitor precursor is added. The development inhibitor formed in an alkaline medium is 1-phenyl-5-mercapto-112.3.4
-Tetrazole is preferably added in an amount of 0.02 mol to 0.1 mol. The development inhibitor precursor according to the present invention can be added to the processing composition permeable layer by various conventionally known effective methods.
It is particularly preferred to dissolve it in a water-miscible organic solvent such as acetone, methanol or ethanol and add it to the coating composition of the treatment composition permeable layer.

Substantially non-diffusible color image-forming materials in alkaline media include, for example, U.S. Pat.
No. 443939, French Patent No. 228414, Tokusekki No. 53-46730, No. 53-50736, No. 5
1-1113624 and 53-3813, such as the so-called dye-releasing redox compounds described in Tokusekki No. 49-111628 and 51-63618.
A non-diffusible color image-forming material capable of releasing a diffusible dye in an alkaline medium, but whose rate of release is reduced if it reacts with the oxidation products of a silver halide developer before doing so. , for example, the so-called BE described in the publications of Bokan Sho No. 53-110827 and No. 53-110828.
Mention may be made of ND compounds, such as the so-called diffusible dye-releasing couplers described in US Pat. No. 3,227,550.

On the other hand, as color image-forming substances that are substantially diffusible in an alkaline medium, for example, U.S. Pat.
The so-called dye developer described in 3-needle rice cake can be mentioned. Particularly effective color image-forming substances in the present invention are the dye-releasing redox compounds and dye developers described above.

Further useful color image-forming materials are dye-releasing redox compounds. As the photosensitive silver halide emulsion used in the present invention, various conventionally known emulsions can be used as desired, and they may be of negative or positive type.

When a positive type photosensitive silver halide emulsion is used, a so-called internal latent image type direct positive silver halide emulsion is preferred. As the photographic material for color diffusion transfer, various conventionally known photographic materials for color diffusion transfer can be used.

Preferred photographic materials for color diffusion transfer include the following two types of photographic materials for color diffusion transfer. 1st
A photographic material for color diffusion transfer of the type consists of a support coated with at least one light-sensitive silver halide emulsion layer in combination with a color image-forming substance and a support coated with an image-receiving layer. A second type of photographic material for color diffusion transfer comprises a support coated on the same side with at least one light-sensitive silver halide emulsion layer and an image-receiving layer in combination with a color image-forming substance; This is a photographic material for color diffusion transfer consisting of a treated sheet. In addition, the first
In the type of photographic material for color diffusion transfer, it is sufficient that both supports are located outside the photosensitive silver halide emulsion layer and the image-receiving layer during processing with the processing composition; In the second type of photographic material for color diffusion transfer, the support and the processing sheet may be located outside with the light-sensitive silver halide emulsion layer and the image-receiving layer interposed therebetween. The neutralizing layer that may be used in the present invention increases the stability of the color image and increases the stability of the color image after substantial formation of the dye image on the image-receiving layer as a result of treatment with the alkaline processing composition. It is effective in effectively stopping the diffusion of the above-mentioned diffusible dyes and preventing discoloration and staining of images that occur at high pH.

Also used in the present invention, the timing layer functions to delay the pH drop until after the desired development and transfer has taken place.

That is, before silver halide development and formation of a diffusion transferred color image, the neutralization layer prevents an undesirable decrease in density of the transferred dye image due to a rapid decrease in pH. The neutralizing layer and the timing layer can be coated on the support on which the photosensitive silver halide emulsion layer and/or image-receiving layer described above are coated, and the neutralizing layer, the timing layer, the photosensitive layer are coated from the support side. It is preferable to coat the silver halide emulsion layer and/or the image-receiving layer in this order.

Further, the neutralizing layer and/or the timing layer can be coated on the above-mentioned treated sheet, and in that case, it is preferable to coat the neutralizing layer and the timing layer in this order on the support of the treated sheet. . When the processing sheet having this neutralizing layer and timing layer is used in the above-mentioned second type of photographic material for color diffusion transfer, both supports have a light-sensitive silver halide emulsion layer during processing with the processing composition. , the image receiving layer, the timing layer, and the neutralization layer, and may be located outside. The support used in the photographic material for color diffusion transfer according to the present invention may be transparent, opaque, or translucent depending on the purpose.

When the photographic material for color diffusion transfer according to the present invention is used as color print paper, a background for the formed image is required.

As a background for the formed image, a light reflecting layer with high whiteness is usually provided on the opposite side of the image receiving layer to the viewing direction. When the silver halide emulsion is developed in a bright place after exposure, it is preferable to provide an opaque layer to protect the silver halide emulsion from light. In some cases, the support functions as the light-reflecting layer and the opaque layer as described above, but the light-reflecting layer and/or the opaque layer may be provided in advance as a layer in the photographic material for color diffusion transfer, separately from the support. You can leave it there,
It may also be formed during processing.

When obtaining a multicolor dye image using the photographic material for color diffusion transfer according to the present invention, it is preferable to use two or more sets of combination units of a light-sensitive silver halide emulsion layer and a color image forming substance; If the color sensitivities differ, it is advantageous to use intermediate layers between the combined units.

The intermediate layer prevents undesirable interactions between the combined units and controls the diffusivity of the diffusible dye or its precursor and the alkaline processing composition. A protective layer can be provided at a position in contact with the processing composition in the photographic material for color diffusion transfer according to the present invention, if necessary. The color imaging material should be positioned so as not to reduce the sensitivity of the light-sensitive silver halide emulsion with which it is combined.

That is, if the absorption wavelength range of the color image-forming material used overlaps with the wavelength sensitivity range of the light-sensitive silver halide emulsion layer with which it is combined, the color image-forming material is exposed to the light-sensitive silver halide emulsion layer with which it is combined. It is desirable to contain it in a layer located on the opposite side of the direction. On the other hand, in color image-forming materials that do not have a dye structure upon exposure, such as ordinary color-forming couplers, color image-forming materials that have leuco-type dyes, and color image-forming materials that have short wavelength shift dyes, the emulsion Since it does not reduce the sensitivity, it can also be included in the photosensitive silver halide emulsion layer.
Furthermore, it can also be contained in a layer located in the exposure direction with respect to the silver halide emulsion layer. A photosensitive cyanide which is combined with a color image-forming substance in the photographic material for color diffusion transfer according to the present invention.

In addition to negative photosensitive silver halide emulsions,
Various types can be used. For example, when attempting to obtain a positive-working diffusion transfer dye image using a color image-forming material that, when simply combined with a negative-working light-sensitive silver halide emulsion, produces a negative-working diffusion transfer dye image, Various conventionally known inversion methods can be applied. For example, US Pat. No. 3,227,552, US Pat. No. 2,592,250, US Pat. No. 2,005,837, US Pat.
1276, British Patent No. 1011062, Japanese Patent Publication No. 41-17184, Hakama-Seki No. 50-8524, etc., or a method using a direct positive silver halide emulsion, or British Patent No. In this method, a negative photosensitive silver halide emulsion layer and an adjacent layer containing physical development nuclei are usually formed. use

Furthermore, Japanese Patent Publication No. 43-21778, U.S. Patent No. 32
As described in No. 27554 and No. 3632345, a color image forming substance is added to a fogged silver halide emulsion layer and reacts with an oxidized form of a silver halide developer as an adjacent layer to inhibit development. Methods such as using a negative-working light-sensitive silver halide emulsion layer containing a compound that releases the agent can be used. The photographic material for color diffusion transfer according to the present invention can be provided with a release layer if necessary.

The aforementioned neutralization layer, timing layer, light reflection layer, opacification layer,
Various conventionally known materials can be used for the intermediate layer, protective layer, and release layer.

In the present invention, a particularly preferred photographic material for color diffusion transfer includes an image-receiving layer, a light-reflecting layer, an opacifying layer, and a color image-forming layer as essential layers in order between two transparent supports during processing with a processing composition. a material layer, a photosensitive silver halide emulsion layer, a timing layer, a neutralization layer, preferably a processing composition;
A color image-forming material layer, a silver halide emulsion layer, which is distributable between the silver halide emulsion layer and the timing layer, or between the opaque support and the transparent support, as an essential layer from the opaque support side. , an image-receiving layer, a timing layer, a neutralizing layer, such that an alkaline processing composition preferably containing an opacifier and a light-reflecting agent can be distributed between the silver halide emulsion layer and the image-receiving layer. A photographic material for color diffusion transfer, which is particularly preferred for obtaining multicolor dye images, has an image-receiving layer, a light-reflecting layer, and an opacifying layer between two transparent supports as essential layers in order during processing. , cyan image-forming material layer, red-sensitive silver halide emulsion layer, interlayer, magenta image-forming material layer, green-sensitive silver halide emulsion layer, interlayer, yellow image-forming material layer, sound-sensitive silver halide emulsion layer, a protective layer, a timing layer, a neutralizing layer, the alkaline processing composition containing an opacifying agent being able to be distributed between said protective layer and said timing layer or, in order, necessary layers. The essential layers between the opaque support and the transparent support, in order from the opaque support side, are a cyan image-forming material layer, a red-sensitive silver halide emulsion layer, an intermediate layer, a magenta image-forming material layer, and a green-sensitive silver halide layer. An alkaline processing composition having an emulsion layer, an interlayer, a yellow image-forming material layer, a sound-sensitive silver halide emulsion layer, a protective layer, an image-receiving layer, a timing layer, a neutralizing layer, and containing an opacifying agent and a light reflecting agent. Materials can be distributed between the protective layer and the image-receiving layer.

The processing composition for processing the photographic material for color diffusion transfer according to the present invention is usually an alkaline processing composition,
It contains an alkaline agent and has a pH of about 10 or more at room temperature.

This processing composition provides alkaline conditions and forms a development inhibitor from the development inhibitor precursor according to the present invention.
The treatment composition preferably contains a viscosity agent and usually has a viscosity of about 100 to 300,000 centipoise. This allows uniform distribution of the processing composition during processing and also provides a non-flowing film during processing to prevent undesirable image changes after substantial dye image formation. are doing. When the color image-forming substance used itself does not have a silver halide developing function, a silver halide developing agent is used. Further, even when the color image forming substance itself has a silver halide developing action, it is preferable to use a silver halide developing agent as an auxiliary agent. these,
Silver halide developing agents are usually included in processing compositions and/or processing composition permeable layers in photographic materials. In addition, the processing composition may contain a silver halide solvent and the like, depending on the silver halide emulsion used, and may also contain various commonly used additives. As a means for applying the processing composition to the photographic material for color diffusion transfer according to the present invention, various conventionally known means can be used, but preferably a container that can be destroyed during processing is used. Preferably, it is stored in The superiority of the photographic material according to the present invention will be illustrated below with examples, but the present invention is not limited thereto. Example 1 A laminated three-color color diffusion transfer photographic material was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate film support having a thickness of 150 mm.

In addition, in each layer below, the numerical values written in parentheses are the coating amount of the material unless otherwise specified. Further, the chemical structural formulas of the crab optical brightener and DRR compounds A, B, and C used in the examples are described at the end of the examples. {1) Styrene and N・
Terpolymer of N-dimethyl-N-benzyl-N-p-(methacryloylaminophenyl)methylammonium chloride and divinylbenzene (molar ratio: 48/48/
4) (9/100 of 27), crab light brightener (9/9 of 0.4)
/100) and an image-receiving layer of gelatin (27 /100).

(2' Light reflective layer of titanium dioxide (9/100 of 230) and gelatin (9/100 of 22).'3} Carbon black (9/100 of 25) and gelatin (
9/100 of 17) opacifying layer.

'4' cyan DRR compound A (6 9/100c fins),
2-acetyl-5-Sec-octadecylhydroquinone (9/100 of 0.3), N-Nn diethyl lauramide (9/100 of 6) and gelatin (14.4/1)
00) cyan DRR compound-containing layer. {5) Red-sensitive internal latent image type direct positive silver bromide emulsion (11 females/silver equivalent)
100), 2-sec-ocdadecylhydroquinone-
Potassium 5-sulfonate (9/100c form of 1.3),
1-acetyl-2-{4-[5-amino-2-(2,4
-di-te-amylphenoxy)penzamide]phenyl}-hydrazine (9 of 100 per mole of silver), 1-
A light-sensitive silver halide emulsion layer of [4-(2-formylhydrazino)phenyl]-3-phenylthiourea (9/100 of 0.5 per mole of silver) and gelatin (9/100 of 17.5).

(6} 2-acetyl-5-SeC-octadecylhydroquinone (9/100 of 4.5), dibutyl phthalate (9/100 of 2.25), and gelatin (10.0
(9/100) middle class.

{7' Magenta DRR compound B (8.O/10 specific force) 2-acetyl-5-Sec-octadecylhydroquinone (9/100c of 0.4), N-N-diethyl lauramide (8.0 9/100), and gelatin (16
．． 9/100 of 0) magenta DRR compound-containing layer.

Legs Line-sensitive internal latent image type direct positive silver bromide emulsion (9/100 of 11 in terms of silver), potassium 2-sec-octadecylhydroquinone-5-sulfonate (1.3/10
0), 1-acetyl-2-{4-[5-amino-2-(2.4m-di-te-amylphenoxy)penzamide]phenyl}-hydrazine (300/9 per mole of silver
), 1-[4-(2-formylhydrazino)phenyl]
A light-sensitive silver halide emulsion layer of 1-3-phenylthiourea (Imp per mole of silver) and gelatin (17.5 mm/100 mm).

[9] Intermediate between 2-acetyl-5-SeC-octadecylhydroquinone (p/100 of 4.5), diptyl phthalate (9/100 of 2.25) and gelatin (9/100 of 10.0) layer.

Tsuyoshi Yellow DRR Compound C (10.rib o/100)
, 2-acetyl-5-Sec-octadecylhydroquinone (9/100 of 0.4), tricresyl phosphate (1
0.0 mo/100) and gelatin (20.0 mo/
10) Yellow DRR compound-containing layer.

(11) Acoustic internal cell-image type direct positive bromide emulsion (9/100 of 14 in terms of silver), potassium 2-sec-octadecylhydroquinone-5-sulfonate (9/100 of 1.6) .
00-9), 1-[4-(2-formylhydrazino)phenyl]-3-phenylthiourea (3-2 per mole of silver)
) and gelatin (9/loo average of 23) photosensitive silver halide emulsion layer.

(12) 2-acetyl-5-SeC-octadecylhydroquinone (9/100 of 4.5), dibutyl phthalate (9/100 of 2.25), 1,3,5-triacryloyl-hexahydro-s triazine ( 9/1 of 2
00c, a protective layer of N.N'-bis(1-aziridinecarponyl)-hexamethylenediamine (2 parts/100 parts) and gelatin (20 parts/100 parts).

The photographic material thus prepared was named photographic material 1 (control), and subsequently photographic materials 2 to 4 were prepared as described below.

Photographic material 2 (comparison); the above layers '61, '9' and (12)
) in each layer of 1-phenyl-5-captotetrazole at a concentration of 2 x 10-6 mol/100 (9/10 of 0.4).
Exactly the same as photographic material 1 except that 0) was added.

Photographic material 3 (comparison); 1-phenyl 5 of photographic material 2 above
- Exactly the same as photographic material 2 except that mercaptotetrazole was replaced with 5-(2-acetyl-ethylthio)-1-phenyltetrazole.

Photographic material 4 (invention): Same as photographic material 2 except that 1-phenyl-5-captotetrazole in photographic material 2 was replaced with 5-(2-phenylsulfonyl-ethylthio)-1-phenyltetrazole. Exactly the same.

The four kinds of photographic materials prepared in this way were exposed to prescribed light, and the following treated sheets were superimposed to produce a photographic material having the treated sheet, and a pot containing the following alkali treatment composition was attached between them, I made a film unit.

The pot is ruptured by passing the resulting film unit between a pair of pressurized juxtaposed loafs, and the contents are transferred between the protective layer (12) and the gelatin layer of the treated sheet below for treatment. The composition layer was developed to have a thickness of 80A. Treated sheet: Treated sheet with gelatin (45 mm/10 mm) and mucochloric acid (0.4 mm/100 mm) on a 100 mm thick transparent polyethylene tereftate film support. Treatment composition. Potassium hydroxide 67 points Sodium hydroxide 3.4 points 4-Hydroxymethyl-4-methyl-1-phenyl-3-hyrazolidone 12.6 points Sodium sulfite
2.0 5-methylbenzotriazole 3.4 rt-butylhydroquinone
0.3 2-methylhydroquinone
0.1 carboxymethyl cellulose sodium salt 60.0 carbon black
Add 171 ta distilled water and 10
The processed film unit was left for 10 minutes after processing.

After that, remove the pot and treatment sheet, and immediately remove the 5%
Soaked in acetic acid aqueous solution. After washing with water and drying, the reflection density (maximum density: Dmax and minimum density: Dmin) of the obtained dye image was measured. Each photographic material was evaluated at varying temperatures. Table 1 From Table 1, the photographic material according to the present invention is
It is easily understood that it has the excellent features of exhibiting a sufficiently high maximum concentration (Dmax) and having a sufficiently low minimum concentration even when processed at high temperatures.

Example 2 A sample similar to that in Example 1 was prepared.

However, in the photographic material according to the present invention, each DRR compound-containing layer (4},
{7;
It is the same as photographic material 1 of Example 1 except that 9/100 of 4 is contained. Treated in the same manner as in Example 1,
evaluated.

Results similar to those obtained in Example 1 were obtained. Example 3 A sample similar to Example 1 was prepared.

However, in the photographic material according to the present invention, instead of photographic material 4 described in Example 1, 5-(2 Example 1 except that 0.2 of 9/100c-phenylsulfonyl-ethylthio)-1-phenyltetrazole was contained.
This is the same as photographic material 1. It was processed and evaluated using the method described in Example 1.

Results similar to those obtained in Example 1 were obtained. Example 4 A three-color color diffusion transfer photographic material was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate film support having a thickness of 150 mm.

The chemical structural formulas of the halo brightener and DRR compound D used here are described at the end of the example. {1'Styrene and N・N
-dimethyl-N-benzyl-N-p-(methacryloylaminophenyl) terpolymer of methylammonium chloride and divinylbenzene (molar ratio 48/48/4)
) (9/100 of 26), crab light brightener (0.4 o/
100) and an image-receiving layer of gelatin (27/100).

[2} Light-reflecting layer of titanium dioxide (200 o/100 base) and gelatin (27 o/10 odor). '3l carbon black (17 females/Kita 00ji) and gelatin (11
9/100 of ) black opacifying layer.

[4} Cyan DRR compound D (9/100 of 6),
2-acetyl-5-Sec-octadecylhydroquine (9/100 of 0.3), tricresyl phosphate (9/9 of 6)
/100), and a cyan DRR compound-containing layer of gelatin (9/100 of 14.4). ■ Red-sensitive internal latent image type direct positive silver bromide emulsion (9/100 of 16 in terms of silver), 2-sec-octadecylhydroquinone-5-potassium sulfonate (9/100 of 1.8), 11 [4-
(2-formylhydrazino)phenyl]-3-phenylthiourea (9 of 0.6 per mole of silver) and gelatin (1
7.5 female/100c Hiiragi) photosensitive silver halide emulsion layer.

(6} Intermediate between 2-acetyl-5-SeC-octadecylhydroquinone (9/100 of 4.5), dibutyl phthalate (9/100 of 2.25) and gelatin (9/100 of 10.0) Layer.'7} Magenta DRR Compound B (9/100c flow of 8.0), 2-acetyl-5-
SeC-octadecylhydroquinone (9/10 of 0.3
0c), tricresyl phosphate (9/100 of 8.0)
and gelatin (3/100 of 16.0) magenta D
RR compound-containing layer.

'8] Green-sensitive internal latent image type direct positive silver bromide emulsion (16 female/100 c tiger in terms of silver), 2-Sec-octadecylhydroquinone-5-potassium sulfonate (1. & 9/
100), 1-[4-(2-formylhydrazino)phenyl]-3-phenylthiourea (0.5 per mole of silver
9) and a light-sensitive silver halide emulsion layer of gelatin (9/100 of 17.5).

■ 2-acetyl-5-sec-octadecylhydroquinone (9/100 of 4.5), diptyl phthalate (2
．． 9/100 of 25) and gelatin (9/9/10.0)
100 enemies) middle class.

00 Yellow DRR Compound C (9/100 of 10.0
), 2-acetyl-5-sec-octadecylhydroquinone (9/100 of 0.4), tricresyl phosphate (
10.0 female/100 ground) and gelatin (20.0/9/
100) yellow DRR compound-containing layer.

(11) Blue-sensitive internal latent image type direct positive silver bromide emulsion (18 o/100 in terms of silver), 2-sec-octadecylhydroquinone-5-potassium sulfonate (2.1 o/100)
/100), 11 [41 (2-formylhydrazino)
A light-sensitive silver halide emulsion layer of phenyl]-3-phenylthiourea (3 bars per mole of silver) and gelatin (2/100 of 23).

(12) 2-acetyl-5-sec-octadecylhydroquinone (9/100 of 4.5), dibutyl phthalate (9/100 of 2.25), tetrakis(vinylsulfonylmethyl)methane (4 9/100 of ) and a protective layer of gelatin (9/100 of 20).

Next, the following layers were sequentially coated on a transparent polyethylene terephthalate film support having a thickness of 100 mm to prepare a treated sheet A.

{a} Copolymer of acrylic acid and butyl acrylate (7
Neutralizing layer with a polymerization ratio of 0/30 (9/100 of 200).

{b- Cellulose diacetate (oxidation degree 55 mol%) (57
'c' copolymer of styrene and maleic anhydride (1:1) (4.5 female/100c bridge) 'c' terpolymer of vinylidene chloride, acrylonitrile and acrylic acid (79/15) /6 weight ratio) (9/100 of 21)
A timing layer with

Processing sheet B: 5 on timing layer {b} of processing sheet A
-(2-phenylsulfonyl-ethylthio)-1-phenyl-tetrazole at 9/100 of 3.4 (1 x 10
Same as treated sheet A except that -5 mol/100 c) was added. A photographic material is given a prescribed exposure through a silver wedge,
A photographic material having a treated sheet was prepared by superimposing the above two types of treated sheets, and a pod having the following alkaline IJ processing composition was attached thereto to prepare a film unit.

The pods are ruptured by passing each film unit between a pair of pressurized juxtaposed rollers, transferring the contents of the pod between the protective layer (12) of the photographic material and the timing layer (c) of the processing sheet. It was disseminated and processed. After processing, the reflection density of the transferred dye image was measured after being left at a constant temperature for 2 hours. The above two types of film units were evaluated by processing them at different temperatures (the 2 hours of standing was also carried out at the same temperature). Treatment composition Potassium hydroxide 67 Sodium polyhydroxide 3.4 4-Hydroxymethyl-4-methyl-1-phenyl-3-hyrazolidone 12.6 Sodium sulfite
2.0 days 5-methylbenzotriazole 3.4 days 2-1 rt-butylhydroquinone 0.3 days 2-methylhydroquinone
0.1 cyclobentanol
1.0 I carboxymethyl cellulose sodium salt 60.0 carbon black
Add 171 ta distilled water and 10
00' Table 2 shows the results of treatment at 1500, 23q0, and temperature.

Table 2 The results shown in Table 2 show that the film unit using the compound according to the present invention has a sufficiently low minimum density (Dmin) even in the integrated film unit after processing, and especially when processed at high temperatures. This indicates that it is significant when the

Example 5 In place of 5-(2-phenylsulfonyl-ethylthio)-1-phenyltetrazole in treated sheet B used in Example 4, 5-{2-(m-nitrophenyl)sulfonyl-ethylthio}- Evaluation was performed in exactly the same manner as described in Example 4, except that 1-phenyltetrazole was added in an equimolar amount.

Results similar to those obtained in Example 4 were obtained, indicating that the compound used in this example is useful as a development inhibitor precursor. Example 6 In place of 5-(2-phenylsulfonyl-ethylthio)-1-phenyltetrazole in treated sheet B used in Example 4, 5-{2-(p-methoxy)sulfonyl-ethylthio}-1 Evaluation was carried out in exactly the same manner as described in Example 4, except that -phenyltetrazole was added in an equimolar amount.

Results similar to those obtained in Example 4 were obtained, indicating that the compound used in this example is useful as a development inhibitor precursor. Example 7 5-(2-methanesulfonyl-ethylthio)-1 was used in place of 5-(2-phenylsulfonyl-ethylthio)-1-phenyltetrazole in treated sheet B used in Example 4.
Evaluation was conducted in exactly the same manner as described in Example 4, except that an equimolar amount of monophenyltetrazole was added.

Results similar to those obtained in Example 4 were obtained, indicating that the compound used in this example is useful as a development inhibitor precursor. Example 8 A three-color photographic material was prepared by sequentially applying the following layers onto a 100 mm thick opaque polyethylene terephthalate film support.

The chemical structural formulas of the dye developers E, F, and G used here are described at the end of Examples. '1' Cyan dye developer E (
11 9/100c mustache) and gelatin (17 9/10
cyan dye developer-containing layer.

(2) Red-sensitive silver iodobromide emulsion (1.6 mol % silver iodide) (14 o/100 in terms of silver) and gelatin (12 o/100) light-sensitive silver halide emulsion layer.

[3' Copolymer of butyl acrylate, diacetoacrylamide, methacrylic acid, and styrene (60:30:6:4
(polymerization ratio of 18 to 9/100) and an intermediate layer of polyacrylamide (0.5 to 9/100). (4) magenta dye developer F (8 to 9/100) and gelatin (12 to A magenta dye developer-containing layer containing a line-sensitive silver iodobromide emulsion (silver iodide 1.6 mol %) (9/100 of 10 in terms of silver) and gelatin (9/10 of 10).
100) photosensitive silver halide emulsion layer.

[English polymer used in 6' layer {3} (10 females/100)
and an intermediate layer of polyacrylamide (1.4/100). [7} Yellow dye developer-containing layer of yellow dye developer G (8 o/100 base) and gelatin (12 o/100).

[8} Blue-sensitive silver iodobromide emulsion (silver iodide 1.6 mol%) (
14/100 in terms of silver) and gelatin (14
A photosensitive silver halide emulsion layer of 9/100c treatment).

[9'4'-Methylphenylhydroquinone (5.0
(9/100 of), N.N-diethyl lauramide (2.
9/100 of 5), mucochloric acid (1.0 female/100
) and a protective layer of gelatin (9.5 c/10 flow).
Next, the following layers were sequentially coated on a transparent polyethylene terephthalate film support having a thickness of 100 mounds to prepare a support having an image-receiving layer. '1} Neutralization layer of partial butyl ester (270 female to 100 female) of copolymer of polyethylene and maleic anhydride.

(2) Copolymer of butyl acrylate, diacetone acrylamide, methacrylic acid, and styrene (60:30:6
:polymerization ratio of 4) (5 ridges 9/100) and a timing layer of polyacrylamide (9/100 of 1.4).

{3} Poly-4-vinylpyridine (9/100 of 11
) and polyvinyl alcohol (22/100)
image receiving layer.

A support having this image-receiving layer was superimposed on the photographic material to produce photographic material 5 (control).

Photographic material 6 (invention); 5-(2-phenylsulfonyl-ethylthio)-11-phenyltetrazole was added to each of the dye developer-containing layers 1', (4} and '7} of photographic material 5 in an amount of 0. 7 o/100 (2 x 10-6 mol/10 ratio)
Same as photographic material 5 except that it is included.

Photographic material 7 (comparison): Same as photographic material 6 except that 5-(2-phenylsulfonyl-ethylthio)-1-phenyltetrazole in photographic material 6 was replaced with 1-phenyl-5-mercaptotetrazole.

Photographic Materials 5-7 were given a defined exposure through a silver wedge and then pods containing the following alkaline processing compositions were deposited.

The film units thus prepared were treated in the same manner as in Example 4, but at different temperatures. After processing, each film unit was left in a room maintained at the same temperature as during processing for 2 hours, and then the reflection density of the transferred dye image was measured. The alkaline treatment composition used here is as follows.

Potassium hydroxide 46 Lithium hydroxide 2 N-phenethyl-Q-picolinium bromide 10 N-benzyl-Q-picolinium bromide 20 6-methyluracil 3 Benzotriazole
10 evening 61 benzylaminopurine
4 Tapolyethylene glycol (molecular weight 3000)
7. Carboxymethyl cellulose sodium salt 50. Titanium oxide 50 M. pH indicator dye a. 27. pH indicator dye B. Described.

Table 3 Table 3 shows that the control photographic material 5 has a significantly lower maximum density (Dmax) upon high temperature processing, and the comparative photographic material 7 has a sufficient maximum density but also a very high minimum density. , on the other hand, photographic material 6 of the present invention has been shown to have a sufficiently high maximum density and a sufficiently low minimum temperature at any of the temperatures shown in Table 3.

Therefore, from the results shown in Table 3, it is easily understood that the compounds of the present invention exhibit excellent effects as development inhibitor precursors even in color diffusion transfer methods using dye developers.

Example 9 A photographic material control similar to Example 8 was prepared by coating the following layers in sequence on a 100 rm thick opaque polyethylene terephthalate film support.

The chemical structural formulas of the dye developers 1, 1, and J used here are described at the end of the examples. (1} Red-sensitive silver iodobromide emulsion (
Ag: 9/100 of 12) A layer with cyan dye developer (9/100 of 7) and gelatin (9/100 of 20).

'2} Copolymer of butyl acrylate, diacetone acrylamide, methacrylic acid, and styrene (60:30:6
:polymerization ratio of 4) (20 to 9/100) and an intermediate layer of polyacrylamide (0.5 to 9/100).

{3' line sensitive silver iodobromide emulsion (Ag: 9/100 of 10) layer with magenta dye developer 1 (9/100 of 8) and gelatin (20/100). ■ Intermediate layer of the copolymer used in layer (■) (10 m 9/100) and polyacrylamide (1.0 m 9/100).

'5} Sound-sensitive silver iodobromide emulsion (Ag: 10 o/100
) Yellow dye developer J (9/100 of 8), 4'
-Methyl phenyl-hydroquinone (9/10 of 3.0
0), N-N-diethyl lauramide (9/1 of 1.5
00) and gelatin (9/100 of 22).

{6) Tetrakis(vinylphonylmethyl)methane (1.
c/100 of 2) and a protective layer of gelatin (9/100 of 10).

The photographic material obtained was exposed and processed as in Example 8.

The support having the image-receiving layer and the alkaline processing composition were exactly the same as those used in Example 8. 9/100 of the layers of photographic material 〔1', legs and 〔same each 0.5
5-(2-phenylsulfonyl-ethylthio)-1
A photographic material according to the invention having monophenyltetrazole and a photographic material control light-sensitive element were comparatively evaluated by the method described in Example 8.

Similar to that obtained in Example 8, it was confirmed that the photographic material of the invention exhibits excellent photographic performance over a wide processing temperature range. Crab photobrightener Cyan DRR compound A Magenta DRR compound B Yellow DRR compound C Cyan DRR compound D Cyan dye developer E Magenta dye developer F Yellow dye developer G pH indicator dye a pH indicator dye b Cyan dye developer Day mazen Evening dye developer I Yellow dye developer J

Claims (1)

[Scope of Claims] 1. A method comprising at least one light-sensitive silver halide emulsion layer combined with a dye image-forming substance, a support for holding the emulsion layer, and an image-receiving layer, and comprising a development inhibitor precursor. A photographic material for color diffusion transfer, characterized in that the development inhibitor precursor is a compound represented by the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, n is an integer of 1 or 2, and R When n is 1, it represents an alkyl group or phenyl group, and when n is 2, it represents an alkylene group or phenylene group.)