JPS581140A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To reduce the occurrence of desensitization, fogging, a reduction in the maximum density or staining in a photosensitive silver halide material contg. a precursor of a photographic reagent during storage by adding a photographic reagent blocked by a specified blocking group which is easily cleaved under alkaline conditions. CONSTITUTION:A precursor compound (blocked photographic reagent) represented by general formulaI(where PUG is a photographically useful residue), e.g., the compound of formula II or III has high stability during the storage of a photosensitive material and exerts no unfavorable influence on the material, and it cleaves easily the blocking group under conditions during processing. for example, a photosensitive material contg. a precursor compound of an aromatic primary amine color developing agent has high color developing density and undergoes slight fogging, and since the precursor is made colorless by treatment with an activator, the photosensitive material has no residual color after the treatment, and the untreated material has superior shelf stability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photosensitive material containing a precursor of a photographic reagent. A silver halide photosensitive material (hereinafter abbreviated as photosensitive material) containing a photographic sample IK) was used.

Such precursor compounds can be used in a variety of ways, from 0 to 1, which are blocked by groups that can be uniformly opened under %J611 conditions without releasing Kl during storage of the photographic material. There has been an example in which the compound is made into a precursor compound and incorporated into a photosensitive material.

For example, you can see an example of this in the 11KTh section of color photosensitive materials.

Generally, the process of processing a color photosensitive material containing a diffusion-resistant coupler in an exposure machine mainly consists of the following three steps.

(1) Process of coloring peach statue 1 (2) IIaJ6-1 (Group) In the process of factory coloring agent for winter clothing treatment, aromatic primary amine agent is dissolved in alkaline water 1IIl solution. Therefore, if this aromatic linker-based developer is included in the constituent layers of a photosensitive material like other additives, the color developer will basically be This can be done using only an alkaline aqueous solution.This not only reduces changes in the composition of the developer and makes it easier to manage, but also makes it easier to adjust the developer.In addition, the BOD of the waste solution is significantly lowered, making it easier to treat wastewater. It has many advantages, such as making it easier.

However, in general, the inclusion of an aromatic primary ein am active agent in a photosensitive material does not allow sufficient color development during printing or processing, which may result in desensitization, smearing, or contamination of the photosensitive material during storage. There are drawbacks such as not being able to obtain sufficient concentration.

Heretofore, several methods have been known for incorporating aromatic primary ein active agents into light-sensitive materials.

For example, US 1i141I permission IK3.342499-
In the book, Schiff base fjj1 with nalcylaldehyde
11 Nine examples of active drug precursors, U.S. Patent No. 3.719.49
In the Specification No. 2, an example of the combination with metal salts such as lead and cadmium is shown, and in the Specification of British Patent No. 1,069.061, phthalic acid ( Example of a do-type precursor, JP-A-853-1
No. 11729 describes an example of a combination of an aromatic primary aine developing agent and a complimentary β-dicarbonyl compound, and JP-A-53-135628 describes a combination of an aromatic primary aine developing agent and an unsubstituted (β-dicarbonyl compound). 0 Miscellaneous National Patent No. 1.159°758, Fl No. 1.20 disclosing an example of a precursor to which benzenesulfonyl)ethoxycarbonyl is bonded.
No. 0,679, U.S. min. s. 3.705,035, U.S. min. s. 4,060,468.
The method described in Publication No. 4-79035 is known.0 The photosensitive material contains photographic image-forming dyes, IA inhibitors,
II image accelerator, halogen/silver 3JtII agent, electronic flux agent 2 dye-forming Kabutsu, 11-coupler, DIR coupler) and its alpha compound, silver halide IS*, silver complex forming agent, fixing agent Photographic reagents such as antifoggants, fogging agents, and anticapri agents are used to prevent unwanted reactions between the reagents and constituent materials of the photosensitive material during storage of the photosensitive material, or to prevent decomposition of IIJ. In order to carry out the reaction, it is preferable that the photographic reagent be safely blocked from the outside before processing. Despite the great advantage of blocking this photographic reagent and incorporating it into a photosensitive material as a precursor compound, No practical blocking technology is known yet.The technology for blocking aromatic primary ein active agents and incorporating them into light-sensitive materials has been proposed in the patents mentioned above. , or %fh of 4 that fully satisfies the prevention of pollution.

Precursor compounds (blocked photographic reagents) that serve these purposes! , when storing photosensitive materials,
The precursor compound itself must have good stability, have no negative impact on the photosensitive material, and, on the other hand, must satisfy the following conditions: when exposed to Kll under processing conditions, it cleaves the ToK blocking group within the desired time. 0 There is no known blocking technique for photographic reagents that satisfies the contradictory conditions of storage stability and processability.

Therefore, the object of the present invention is to provide a photographic processing agent (V) containing a photographic reagent blocked with a protoxy group that is easily cleaved under alkaline conditions, and which prevents desensitization, fogging, and the like during storage.
It is an object of the present invention to provide a photosensitive material in which a decrease in the maximum density or the occurrence of contamination is significantly reduced. In the formula, X represents a hydrogen atom, an alkyl group, or a phenyl group, and Y represents a hydroxyl group or a hydrolyzable group that provides a hydroxyl group. represents the atomic age of forming a benzene ring which may have a substituent, and a naphthalene ilI which may have a substituent.
ta X in the naphthalene ring Olta PUG occupying the 1, 2 or 1, 4 positions is represented by O The alkyl groups and phenyl groups include alkyl groups and alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms, cyano groups, etc., halogen atoms,
Represents a phenyl group substituted with a nitro group or the like. The hydrolyzable group represented by Y that yields a hydroxyl group upon hydrolysis includes an acetoxy group, a trichloroacetoxy group, a trifluoroacetoxy group, a benzoyloxy group, etc. The group substituted with t + 7 talene group is preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an azilaquino group, an acyloxy group, an alkoxycarbonyl group, a carno(moyl group, a sulfonamido group) or a sulfamoyl group O as mentioned above σ) an alkyl group, an acyloxy group, an azila () group substituted on the benzene@t or naphthalene ring,
Alkoxycarbonyl groups and sulfonate groups have a vertical prime number of 1 to 30, and can be completely substituted with nitrogen atoms, cyano groups, etc. The nitrogen atom of a moyl group or a sulfamoyl group may be substituted with 211i1 of an alkyl group having 1 to 30 vertical primes or a phenyl group.

PUGs include aromatic primary color pigments such as color pigments and black and white 11 pigments, photographic pigments, development inhibitors, development accelerators, silver halide solvents, and electron transfer agents. Agent 1 dye-forming couplers, among the competitors, are particularly preferred examples are aromatic primary amino developing agents, a representative example being N,N-diethyl-p-phenylenethia(
Amino-5-diethylainotoluene, 2-a(no5
-(N”ethyl-N-lauryl)aminotoluene, 4-
(N-ethyl-N-(β-hydroxyethyl)aminocoaniline, 2-methyl-4-[N-ethyl-N-(β-
hydroxyethyl) ainocoaniline, U.S. Patent No. 2,
193.015 N-ethyl-N-(
/-methanesulfoahatethyl)-3-methyl-4-ainoaniline, N-(2-amino-5-dinithylainophenylethyl)methanesulfonaζ described in U.S. Pat. No. 2,592,364 Do, N, Ill methyl-p
-Phenylencia Jian, US AI Patent No. 3,656,95
No. 0, No. 3,698,525 as described in the specification bottle, etc.
-3-methyl-N-ethyl-N-methoxyethylaniline, 4-methyl-N-ethyl-N
-β-ethoxyetheraniline, and 4-amino-3
-N-ethyl-N-β-ptoxyethylaniline group in meth.

Precursor compounds, such as aromatic primary eins, are present.

0H- Dp-c to ---→Dp+CO.

When applied to the current aromatic primary drug,
The effect was not clearly recognized.

Examples of the blocked precursor compound represented by the general formula of the present invention are shown below, but the present invention is not limited thereto.

Compound 1゜ l1lO1 13° Next, typical European synthetic examples of the present invention will be shown.

Synthesis Example 1 (Compound 3) The chloroformic acid ester synthesized from p-acetoxypendyl alcohol 3.3 f tophosge/ was dissolved in acetonitrile 304, and 4-thiono-3-methykN,N-dief Rua Nilyy 3. 561 Pyridine 5oIRj
of dissolved WIK was added, and the mixture was stirred at room temperature for 2 hours. The target product was purified by column chromatography to obtain 3 tons of a yellowish brown solid having a pH of 83 to 86°C.

Synthesis Example 2 (Compound 5) Same procedure using N-ethel-N-(β-methanesulfonylaminoethyl)-3-methyl-4-aminoaniline in place of 4-aino-3-methyl N,N-diethylaniline. When reacted with 111p, a light brown solid with a temperature of 115 to 116°C was obtained.

-The structure of the compound obtained by synthesis was confirmed to be the desired structure by IR and NMR. Other blocked strawberry compounds according to the present invention can also be obtained by the same method. These compounds are added to and dispersed in the hydrophilic colloid solution using a hydrophilic organic solvent such as methyl alcohol, ethyl alcohol, or acetone. Other dispersion methods include those using latex and other polymers, and those used in oil-protected photosensitive materials.

For example, a method can be applied in which the metal compound is dispersed in a hydrophilic colloid III using a coupler fI# such as tri-0-cresyl phosphate and dibutyl phthalate. When dispersing these oil phases in an aqueous phase, generally known anionic, nonionic, cationic, or amphoteric surfactants may be used. Hydrophilic colloids include gelatin, photographic binders, etc. A wide range of materials can be used, including gelatin derivatives known as gelatin, graft polymers of gelatin, various cellulose derivatives, polyvinyl alcohol partial oxides, sodium alginate, and poly-N-vinylpyrrolidone. Known photographic antioxidants or stabilizers may be added to these emulsions. The content of the precursor compound of the color developing agent used in the present invention is 0 relative to the amount of gold and silver per unit area of the Fusho photosensitive material. .1~1
0 times molar, preferably 0.25 to 5 times molar 0 In the case of precursor compounds other than other color developing agents, 0.000
In addition, the coloring agent precursor may be used in a light-sensitive silver halide emulsion layer containing a diffusion-resistant coupler or in the emulsion layer. Although it can be contained in other layers on the side, it is preferably contained in a layer other than the light-sensitive silver halide emulsion layer, such as an intermediate layer. It is not necessary to use the conventional color developing solution, and instead, it is sufficient to use an alkaline activator solution, but the other processing steps S are completely the same as the conventional ones.

The activator liquid is basically a commonly used color liquid solution with the main system removed, and has a pH in the range of about 7 to 14, with a preferred PM of 8 to 13. It is @encircled. Treatment with activator solution [at ~°C]
The temperature is 70°C, and the most preferable temperature is 60°C. As a buffer for the activator solution, known metal compounds such as sodium hydroxide and sodium carbonate may be used alone.
Depending on the formulation, other additives such as anti-capri agents, development accelerators, water softeners, organic sludge agents, etc. can also be added to the Atateboehme solution.

The diffusion-resistant coupler incorporated in the photosensitive material of the present invention is a known coupler, and is disclosed in German patent 0L82.644,91.
Also included are black dye-forming couplers described in Japanese Patent Laid-Open No. 54-9924 and the like. In addition, a development inhibitor-releasing coupler or *@inhibitor-releasing compound may be added. The solvent for these couplers is preferably a known water-insoluble coupler solvent.

Further, halogenated* used in the photosensitive material of the present invention
These silver halide emulsions may be prepared by a conventional method and may be of any composition such as chloride steel, bromide steel, silver chlorobromide, iodobromide steel, silver chloroiodobromide, etc. can be chemically sensitized by conventional methods. Furthermore, the emulsion may contain commonly used additives such as KFi photosensitive dyes, antifoggants, hardeners, quenching agents, and surfactants.

As supports for the layers used in the light-sensitive material of the present invention, in addition to cellulose films and plastic films, glass, paper, Kti laminates, or paper laminated with polymers are useful.

As described above, the photosensitive material according to the present invention consists of a support and at least 41 layers of light-sensitive halogenated emulsions on the support, and at least one of the layers includes at least 41 layers of photosensitive halogenated emulsion. The layer contains a precursor compound represented by the above general formula.

In addition to the emulsion layer, the constituent layers include, for example, hydrophilic colloid layers such as a haze layer and an intermediate layer. A photosensitive material containing a precursor compound of an aromatic primary a(n) developing agent of the present invention. is an alkaline activator in the presence of so-called phosphorus oxidizing agents such as p-aminophenol derivatives, p-phenylenethiaine tliJ derivatives, and l-7enyl-3-pyrazolidone (phenidone) derivatives, which are well known outside the photo prefecture. Beta processing may also be carried out. Generally, these cross-oxidizers are black-and-white developing agents, which present the exposed silver I-resinide, but the resulting oxidation products are not cupped by the coupler. It is a substance that oxidizes the aromatic primary amine color developing agent without ringing and regains the moderating ability.◎Meanwhile, the acid-oxidized aromatic primary amine coloring agent **The main agent reacts with the coupler. The cross oxidizing agent is preferably incorporated into the color photosensitive material, but it may be added to the activator.The amount of the cross oxidizing agent used is as follows: When incorporated in a color photosensitive material, the amount is preferably in the range of 0.01 to 2 mol per 1 mol of total silver halide on the same area, and when Kl is added in the actepator, I (1'~IX
A range of 10" mol/l is preferred.

Preferred cross-oxidizing agents for use are Fi3-pyrazolidone derivatives, examples of which are shown below.

The characteristics of the light-sensitive material containing the precursor compound of the aromatic developing agent of the present invention are that it not only has a high color density but also has a low capri, and furthermore, the precursor is colorless after being treated with an activator. Photosensitive material K11 has many advantages such as no color generation after one processing and excellent storage stability of unprocessed photosensitive materials.

As a method for processing the photosensitive material of the present invention, other known methods such as bath processing, such as a spray method in which the processing liquid is made into a jet, may be used. Web method or viscous treatment 'IIMI
Various processing methods such as IK method % Formula % The present invention will be further explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.Example 1 Precursor of color-forming active agent Exemplary compound 504.3# was dissolved in 50 methanol and this solution was mixed with gelatin 5
- Mixed with aqueous solution 200 - and further added water, a coating aid, and a hardening agent to give 330 hair. The thus obtained anti-liquid was coated on a resin-coated paper support. The precursor used at this time The application amount for 100Qiffi is 4
, 01111 2-(2-(2°4-di-
t-Pentylphenoxy)butanead)-4,6-dichloro-5-methylphthalate was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then mixed with a red-sensitive silver chlorobromide emulsion. The amount of coating for 100 da of the 9 coupler used at this time is 30 ml.
, II ti21tptf.

Further, on this layer, a gelatin solution was coated to form a retaining layer.A coating aid and a hardening agent were added to each layer. The sample obtained in this way was designated as sample 1, and the precursor of the main agent for 0 color development 3J was used as a comparative compound u)4. represented by the following structural formula. B
Sample 2 was obtained in exactly the same manner as Sample 1 except that fK was changed, and it was used as a comparative sample for Sample 1. Similarly, comparative compound fB13 was used as a precursor of the color-forming agent.
．． The sample obtained by using 6ft was designated as sample 3. Similarly to sample 2, the O comparative compound was used as a comparative sample of sample 1.
Il! Compound (compound described in JP-A-53-135628) Comparative compound (B) (compound described in U.S. Pat. No. 3,342,599) Samples 1.2 and 3 were exposed to white light through a step wedge, and the following treatments were performed. 0 treatment process activator current g1145℃ 2 minutes bleach constant 9
40℃ 1 minute fraction second water wash
Heat for 3 minutes Activator liquid Benzyl alcohol 12 Potassium carbonate 201 Potassium bromide 0.1f Ethanol 100 Add water to make 1/2. (PH11,8) Bleach-fix solution Ethylenediaminetetraacetic acid iron ammonium 17m6.1f Ethylenecyinetetraacetic acid diammonium 5f Thio-i
Ammonium t-acid 133f Anhydrous sodium sulfite 2.7f Add aqueous ammonia and water to 11
(pH 7.0) The results obtained are shown in Table 1.

In addition, samples 1, 2 and 3 were stored for two days in an atmosphere of T [f degree son], and a forced deterioration test was carried out on each of them. Also listed below.

From Section 3, in the case of sample 3, the deblocking reaction occurred during processing and the maximum concentration was high, but after forced aging, the stain was significant and the maximum concentration decreased steadily, resulting in poor storage stability. In addition, in the case of sample 2, although the storage stability was favorable, a sufficient maximum concentration could not be obtained, indicating that the deblocking reaction was different. However, it can be seen that Sample 1 containing the precursor compound of the present invention fully satisfies these two requirements.

Example 2 The case where the precursor of the present invention is Ichirin dye will be described. The experimental method was based on the method described in JP-A-54-34731. A light-sensitive material was prepared by sequentially coating the following layers on a transparent cellulose triacetate film subbed with gelatin, and designated as sample 4.

(1) Yellow dye developer layer Exemplary compound (01 parts of 1 was dissolved in 1 part of N,N-diethyl lacrylide and 3 parts of ethyl acetate, and this was added to an aqueous gelatin solution containing dispersant alkanol B. In addition, it was emulsified and dispersed and applied.

The coating amount is shown below: Exemplary compound (1o) 14 fi#/1
00 csfN, N-diethyl lauryl ζdo 1
4 m/1 oo cdze5 ty
25 fiV'too cd (21 real emulsion layer silver iodobromide 18 ml/100 m gelatin) 281817100 csf
(3) Hoka layer p-) Rilhydrokinoy Z) ml/
100 a11 diptyl 7 talley) 22m1
/100a149f7 5tetl
/100ell image receiving elements were made by sequentially applying the following layers on baryta paper.

(a) Neutralization layer A 5-aryton solution of monobutyl ester of a copolymer of maleic anhydride and ethylene was coated with II. The dry film thickness was 2.
It was 0s.

(b) Timing layer An aqueous solution of hydroxypropylcellulose was applied.

The dry film thickness was 8JI.
- O poly-4-vinylpyridine prepared by dissolving phenyl-5-mercaptotetrazole in 1 water with a small amount of glacial acetic acid and applying it 30 da/100 m
-k 60M9/ 100 cdl-phenyl-
5-mercaptotetrazo-v xjw/1ooci Next, as a comparative sample, sample 5. was prepared using the following comparative metal material (C) in place of the exemplary compound (10) in the yellow dye developer layer of sample 4. Sample 6 was prepared using Comparative Compound (D) Comparative Compound 1 (C) Comparative Compound (Di Samples 4, 5, and 6 were wedge exposed with true color light from the emulsion layer side and from the base side, and then image-receiving Place the following alkaline processing liquid between the photosensitive elements and apply Gunsho'KIR.
K'! 90 alkaline treatment liquid composition water
oO, mz potassium hydroxide 11
2F carboxymethylcellulose sodium salt
3.5f-benzotriazole 2.
0f1-7 Enederu 2-picolinium bromide 2. Of samples and receiving gI
1 minute after superimposing the elements and spreading the alkaline processing liquid between them, the image receiving element T- is peeled off from the sample side, and the yellow color obtained on the tatami mat [D + aax and the minimum The density was measured using a true color filter.

The results obtained are shown in Table 2.

Samples 4.5 and 6 were heated to 28°C at a temperature of 80°C.
After being stored and subjected to a forced deterioration test, each sample was packed together and subjected to the above-mentioned exposure and processing, and the results are also shown.

Table 2 From Table 2, it can be seen that sample 6 (comparative compound (-) has a different storage stability Fi under forced deterioration, but the deblocking reaction (processability) during treatment is different. However, the compound of the present invention In sample 4, the maximum concentration was sufficiently high, indicating that the processability was good.

Furthermore, it can be seen that the storage stability is also favorable.

Agent Yoshimi Kuwabara Procedural Amendment 1980 101458 Haruki Shimada, Commissioner of the Patent Office 1 Indication of Matter A'1 Patent Application No. 99348 1988 2 Name of the invention Silver halide photosensitive material 3 Person making the amendment Relationship to the case Patent Applicant Address 26-2 Nishi-Shinjuku 1-chome, Shinjuku-ku, Tokyo Name (27) Konishiroku Photography Gyokugyo Co., Ltd. Address 1-5 Sakuracho, Hino-shi, Tokyo Date of Amendment Order Issue 6 7. Contents of the amendment The detailed description of the invention is amended as follows in the "Detailed Description of the Invention" of the specification to be amended.

Claims (1)

[Scope of Claims] A silver halide photosensitive material characterized by containing a compound represented by the following general formula. 5 [In the formula, X represents a hydrogen atom, an alkyl group or a phenyl group, Y represents a human W1dP syl group, and 9 represents a hydroscaly group providing a hydrosil group. t2 is a benzene ring which may have a substituent, or a group of atoms forming a nutmolenic ring which may have a substituent; 1,2 positions are 1,4
The @bot PUG that occupies the position represents a residue useful for photography◎]