JPH01280750A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the title material having good absorption spectral characteristics, without giving an adverse effect to an emulsion by mounting an hydrophilic colloid layer contg. a cyanine dyestuff having a substituting group such as an acidic or a specified group in a dyestuff molecule, on the photosensitive material. CONSTITUTION:The hydrophilic colloid layer contains the cyanine dyestuff which has 3H-pyrrolopyridine, 4H-thienopyrol, 6H-thienopyrol, 4H-furopyrol or 6H-furopyrol as a mother nucleus, and to substituting groups having two acidic groups or one or more of -CH2CH2 OR groups in the molecule. The photosensitive material contains the hydrophilic colloid layer as mentioned above. The acidic group is composed of sulfonic acid or carboxylic acid group, etc., and the substituting group contg. the -CH2CH2OR group is exemplified by hydroxyethyl or hydroxyethoxy ethyl group, etc. The photosensitive material has the good absorption spectral characteristic and a less residual color stain, and is an inactive to the emulsion.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a dye, and particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. Related to silver photographic materials.

[Background of the invention]

In silver halide photographic materials (hereinafter referred to as "photosensitive materials"), dyes are added to the photographic material for the purpose of absorbing light of specific wavelengths for filters, anti-halation, anti-irradiation, or to adjust the sensitivity of photographic emulsions. It is well known that the hydrophilic colloid layer is colored with a dye.

A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and serves to convert incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, for the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back side of the support.
Harmful reflected light from the interface between the emulsion layer and the support, the back surface of the support, etc. is absorbed to prevent halation, and the emulsion layer is colored to absorb harmful reflected light and scattered light from silver halide grains, etc. It is common practice to prevent irradiation by absorbing

Dyes used for such purposes must have good absorption spectral characteristics depending on the purpose of use, be completely decolorized during photographic processing, be easily eluted from the photographic material,
There should be no residual color contamination caused by the dye after the development process, there should be no adverse effects such as fogging or desensitization on the photographic emulsion, there should be no diffusion from the dyed layer to other layers, and there should be no residual color contamination caused by the dye. It must satisfy various conditions such as having excellent stability over time in the material and not changing or fading.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, oxonol dyes described in British Patent No. 506°385, U.S. Patent No. 3,247,1.27, Japanese Patent Publication No. 39-22069 No. 43-131.68, etc.; Examples include styryl dyes as typified, merocyanine dyes as typified by US Pat. No. 2,493,747, and cyanine dyes as typified by US Pat. No. 2,843,486. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials.

[Purpose of the invention]

Therefore, the object of the present invention is to have good absorption spectrum characteristics, be decolorized during photographic processing, have extremely little residual color staining after processing due to elution from photographic materials, and be inert to photographic emulsions. An object of the present invention is to provide a silver halide photographic material containing a certain dye.

[Structure of the invention]

The above object of the present invention is to provide a cyanine dye having at least two acid groups in the dye molecule having 3H-pyrrolopyridine, 4H-thienovirol, 6H-chenopyrrole, 4H-furopyrrole, and 611-70pyrrole as a core, or This was achieved by a silver halide photographic material characterized by having a hydrophilic colloid layer containing at least one cyanine dye having at least two substituents having one or more -CH2CH20R groups.

R represents a hydrogen atom or an alkyl group.

The dye compound of the present invention has the following general formulas (I), (n) and general formula (I) general formula (If) general formula (III) where Rl, R2+R3+R, , R5 and R6 each represent an alkyl group. , Zl and Z2 are each pyrrolopyridine,
Represents a group of nonmetallic atoms necessary to form chenopyrrole and 70-pyrrole rings.

Y and Y2 represent a group of nonmetallic atoms necessary to form a pyrrolopyridine ring, and are included in the ring of Yl.

R l+R2, R8, R4, R6 in general formula (I)
+R6゜2,. 22, R r in general formula (II)
, R2, R3, R4.

Rs , Ra , Y + , Y 2 and the general formula (l
R , , R2+Rs , R* , Rs ,
Re, Y 1. Z2 is each a group that allows the dye molecule to have at least two acid groups or -CH2
Represents a group capable of having at least two substituents having one or more CH20R groups.

R represents a hydrogen atom or an alkyl group.

L represents a methine group, and Xe represents an anion.

m represents an integer of 1 to 5, and n represents an integer of 1 or 2.

When the dye forms an inner salt, n is 1.

The acid groups in the general formulas (I), (I[) and (I[[) include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, etc., and each of these acid groups includes salts thereof. do. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

The alkyl group represented by RI+R2, R3, R4, Rs and R6 is preferably a lower alkyl group having 1 to 8 carbon atoms (
For example, methyl, ethyl, propyl, i-brobyl, butyl group, etc.), and the above acid substituent or
It may have substituents other than the H7OR group.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

Examples of substituents containing a CH2CH20R group include hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethyl group, hydroxyethoxyethylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, hydroxy Examples include an ethylsulfamoylethyl group and a methoxyethoxyethoxycarbonylmethyl group.

z,,z 2. Other substituents that y and Y2 may have include sulfo groups (including salts), carboxyl groups (including salts), hydroxyl groups, cyano groups, and halogen atoms (e.g., fluorine, chlorine, bromine). atoms, etc.).

The methine group represented by L may also have a substituent, and examples of the substituent include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxypropyl, 2-sulfoethyl groups), halogen atoms (e.g.
Examples include fluorine, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). In addition, the substituents of the methine group are bonded to each other to form a 6-membered ring containing three methine groups (e.g., 4,4-
dimethylcyclohexene ring).

The anion represented by Xo is not particularly limited, but specific examples include halogen ions, p-toluenesulfonic acid ions, and ethyl sulfate ions.

The above formulas (I), (II) and (
Dye represented by III) (hereinafter referred to as the dye of the present invention)
Specific examples are shown below, but the present invention is not limited thereto.

Specific compound 18 = CH2COOHCH□C00H 1l- CHzCONt(CH2CH20HCH□C0NHCH
2CH20HI.ヮ・CH、C0NH(C1(2CH20)・I(CH
・C0NH(CH・0H・0)・0(CH2)3P03
H2(CH2)3PO3H2(Ct(2)3sO8゜(
CH2)3SO3Na(CH2)3SO3. (Ct(□
) 3SOJ The dye of the present invention is published in Journal of the Chemical Society (J, Chem, Soc, ) 18
9 (1933), U.S. Pat. No. 2,895,955, and Japanese Patent Application Laid-Open No. 62-123454.

Examples of the mother nucleus of the dye of the present invention include the following compounds.

Compound (A) is described in J, Chem, Soc, 3202 (1
959) and British Patent No. 870,753.

Compound (B) is described in J, Chem, Soc, 584 (1
961).

Compound (C) is disclosed in British Patent No. 841. ．． It can be synthesized by the method described in No. 588.

Compound (D) was manufactured by Chemical Abstracts (CA) 62.

10438c and CA″71, 22045m.

Compound (E) can be synthesized by the method described in CA 71.22045m.

Compounds (F) and (G) can also be synthesized in a similar manner.

Using these cores, quaternization, sulfonation, etc. can be performed as necessary. Or J, Chem.

Soc, 3202 (1959) and J. Chem.
N-alkyl-N-pyridylhydrazine was synthesized according to the synthesis method described in Soc, , 584 (1961), a cyclization reaction was performed via hydrazone, and if necessary, acid treatment was performed to obtain 1-alkyl-substituted -3H- It is also possible to obtain a pyrrolopyridine derivative and use it as a starting material.

The compound of the present invention can be easily obtained by reacting a suitable methine chain donor with these quaternized and optionally sulfonated mother compounds.

If glutaconaldehyde cyanyl hydrochloride is used as a methine chain donor, a heptamethine dye can be obtained, and if propendianil hydrochloride is used, a pentamethine dye can be obtained.

In the case of trimethine dye, diphenylformamidine hydrochloride may be used.

In the case of a monomethine dye, it can be synthesized in the same manner by using a core compound having an alkylthio group in the active moiety according to a conventional method. In the case of nonamethine dyes, the methine chain donor is, for example, described in "The Cyanine Soy and Related Compounds J (F, M, Hamer" T.
he cyanine dies and relat
edcompounds”1964.Intersci
Compounds such as those described on pages 249-251 of ence Publishers) can be used.

In the photosensitive material of the present invention, the formula (I), (II
) and (III) can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or can be incorporated into a non-photosensitive hydrophilic colloid layer to form a filter. It can also be used as a dye or an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye of the present invention can be easily incorporated into a silver halide emulsion layer or other hydrophilic colloid layer by a conventional method. In general, a dye or an organic or inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. I can do it. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1 to 800 mg per square meter of area on the photographic material.

The light-sensitive materials to which the present invention is applied include not only black-and-white photographic materials but also color photographic materials. Examples of the former include photosensitive materials for printing. At this time, two or more silver decagenide emulsion layers may be provided. The amount of coated silver is preferably in the range of 1 to 8 g/m2.

The silver halide used in the present invention may be, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), Volume 176, No. 17643 (1978
(December).

The method described in p. 22-23, No. 18716 (November 1978), p. 648 can be followed.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, thiosulfate, thioether and cystine; noble metal sensitizers such as potassium chlorooleate, aurous thiosulfate and potassium chloroparadate. ; Examples include reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitizing dye used is Research Disclosure (cited above) No. 17643. Those described in Section (2) can be used.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.

These compounds include many heterocyclic compounds, including nitrobenzimidazole, ammonium chloroplatinite, 4-hydroxy-6-methyl-1,3,3a, 7-titraazidene, and -7enyl-5-mercaptotetrazole. A large number of compounds such as mercury compounds, mercapto compounds, and metal salts have been known for a long time.

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used.

In addition to the above-mentioned materials, the photosensitive material of the present invention includes a desensitizer, a brightener, a coupler, a hardening agent, a coating aid, a plasticizer, a slippery agent, a matting agent, a high-boiling organic solvent, a stabilizer, and a developer. Accelerators, antistatic agents, anti-stain agents, etc. can be used.

As for these additives, those described in Research Disclosure (supra) No. 17643, Items I to XVI can be used.

-23= For the photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. In addition, the processing temperature is usually 18°C to 50°C.
temperature chosen between 18 °C or 5 °C
The temperature may exceed 0°C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process consisting of a development process for forming a dye image can be applied.

〔Effect of the invention〕

The silver halide photographic material of the present invention has good image quality, does not impair sensitivity, and has little residual color after development.

Moreover, the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is colored with a water-soluble dye, has good storage stability without adversely affecting the photographic properties of the photographic emulsion, and is easily processed through photographic processing. It is extremely excellent in terms of decolorization.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 3.5 g of gelatin was added and dissolved in 35 m4 of distilled water, and 2.5 g of exemplified dyes (1), (2) and (3) of the present invention were added thereto, respectively. Add 5 m12 of an aqueous solution containing 10-' moles of OX, and add 1.25 m12 of a 10% saponin aqueous solution.
and 0.75 mQ of 1% formalin solution were added, and water was added to bring the total volume to 50 m12. This dye solution was coated on an acetylcellulose film support, dried, and sample 1
．． 2 and 3. Comparative samples 4 and 5 were also created in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Comparative Dye (A) Each of these samples was immersed in a developer having the following composition at 25°C for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Mail 1.
3.0g sodium sulfite (anhydrous) 45.0g hydroquinone 12.0g sodium carbonate (monohydrate) 80.0g potassium bromide
Add 2.0g water and 10. shall be.

The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 11 below.

(E+ is the absorbance before being immersed in the developer, and E2 is the absorbance before being immersed in the developer.
As is clear from Table 1, the dyes of the present invention were found to exhibit superior decolorizing properties compared to the comparative dyes.

Example 2 Consists of 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 mol% of silver iodide, with an average grain size of 0.32 μm
A silver chloroiodobromide gelatin emulsion was prepared. 2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) 3'5 m Q per 1 kg of this gelatin emulsion (containing 48 g of silver and 75 g of gelatin)
After adding 50m+2 of saponin (10% aqueous solution),
It was coated on a subbed-treated polyethylene terephthalate film support so that 501 Rg of silver was contained per 100 cm 2 and dried.

Further, on this emulsion layer, the exemplary dye (4) of the present invention was applied = 27
- A protective layer having the following composition was coated to have a dry film thickness of 2 μm. (Same as sample 6) (Protective layer composition) Gelatin 407 water

850+++ff Exemplary dye of the present invention (4) (2% aqueous solution) 100m12
．． 4-dichloro-6-hydroxy-1,3,5-1-riazine sodium salt (1% aqueous solution)
20mQ saponin (10% aqueous solution) 30m (Similarly to 2, instead of exemplified dye (4) of the present invention, exemplified dye (5) and (6)
) and comparative dyes (A) and (B) used in Example 1
), respectively, and sample 7.8.
．． 9 and IO.

Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using developer and fixer solutions having the following compositions.

Development was carried out at 20°C for 1.5 minutes, fixation was carried out at 20°C for 2 minutes, water washing was carried out at 20°C for 5 minutes, and then dried.

=28- (Developer composition) Hydroquinone 15g Formaldehyde sodium bisulfite adduct 55g Anhydrous sodium sulfite 3g Sodium carbonate (-
hydrate) 80 g Boric acid 5 g Potassium bromide 2.5 g Disodium ethylenediaminetetraacetate 2 g Add water 1,000 mα (Fixer composition) Sodium thiosulfate 160 g Anhydrous sodium sulfite 149 Glacial acetic acid
12mQ borax
12g potash alum
Add 5g water
Ten sheets of each sample that had been subjected to a 1,000 mff development process were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 2 below.

In the samples using the comparative dyes in Table 2, colored stains were observed in the samples, but with the dyes of the present invention, there was no colored staining at all due to excellent run-off and decoloring properties.

Example 3 A silver chlorobromide emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having an average grain size of 0.311 m was prepared.

After adding 20 ml of formalin (1% aqueous solution) and 50 mQ of saponin (10% aqueous solution) per kg of this emulsion (containing 48 g of silver and 75 g of gelatin), it was coated on a subbed-treated polyethylene terephthalate film support. Further, a protective layer having the composition shown below was coated on the second side of this emulsion layer.

(Protective layer composition) Gelatin 40g water

960m12 Formalin (1% aqueous solution) 12mα Saponin (10% aqueous solution) 30mQ
Next, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye with the following composition was applied to a dry film thickness of 3 μm.
It was applied so that the thickness was m. (Same as sample 11) (Gelatin layer composition) Gelatin 50g water

835m (1 Exemplary dye according to the present invention (7) (2% aqueous solution) 100mQ formalin (1% aqueous solution) 15m0°Saponin (10% aqueous solution) 50mff
Similarly, a sample comparison dye (C) was developed in the same manner as in Example 2 using the exemplary dye (9) and the following dye (C) instead of the exemplary dye (7) of the present invention. , each sample 10
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 3 below.

As shown in the above clothing in Table 3, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes of the present invention. Furthermore, it has been found that the dye of the present invention can produce a photographic material having an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on photographic emulsions.

Example 4 A color photographic material was prepared by sequentially depositing the following layers on a support made of polyethylene-coated paper from the support side (
Sample 14).

1st layer...Yellow coupler: α-pivalyl α-(1-
benzyl-2-phenyl-3,5-dioxotriasilidin-4-yl)-2'-chloro-5'-[γ-(2,
A blue-sensitive silver halide emulsion layer containing 4-di-t-amylphenoxy)butyramide]acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin) (chlorobromide containing 90 mol% silver bromide) A silver emulsion sensitized using a sensitizing dye) was coated with a silver amount of 3.5 mg/10
It was set so that the distance was 0 cm2.

Second layer: A gelatin layer (intermediate layer) was provided.

3rd layer...magenta coupler; 1-(2,4,6
-trichlorophenyl) -3-C3-(2,4-di-
Green-sensitive silver halide emulsion layer containing t-amylphenoxyacetamide) benzamide 5-pyrazolone, hardener (dichlorotriazine) and surfactant (saponin) (silver chlorobromide containing 80 mol% silver bromide) An emulsion sensitized using a sensitizing dye) with a coated silver amount of 4.5y.
It was provided so that it was 1g/100cm2.

Fourth layer: A gelatin layer (intermediate layer) was provided.

5th layer... Cyan coupler: 2,4-dichloro-3-methyl-6-(2,4-di-t-amylphenoxyacetamide)phenol, hardener (dichloro] riazine)
A red-sensitive silver halide emulsion layer (silver chlorobromide emulsion containing 75 mol% silver bromide, sensitized using a sensitizing dye) containing a surfactant (saponin) is applied to the coating amount of silver. is 2
．． The amount was set at 0 mg/100 cm2.

Sixth layer: A gelatin layer (protective layer) was provided.

Furthermore, the exemplary dye (43) of the present invention or the comparative dye (D
) A green-sensitive emulsion (third layer coating solution) was prepared by adding 200 + 1112 2% aqueous solution of (200 + 1112) per kg of emulsion, and Samples 15 and 16 were prepared in the same manner as Sample 14. Comparative Dye (D) These Samples 14 After exposure of .15 and 16, the following processing steps were followed.

[Processing step (3100)] Processing time 1, color development 3 minutes 2, bleach-fixing 1 minute 3, water washing 2 minutes 4, stabilization 1 minute 5, water washing 2 minutes The processing liquid composition used in each processing step is as follows: It is as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8 g = 35- Anhydrous sodium sulfite 4.0 g hydroxyamine 1/2 sulfur Wf! Salt' 2.0g Anhydrous potassium carbonate 28.0g Potassium bromide 1.5g Potassium hydroxide 1.0g Add water and 10. shall be.

[Bleach-fix solution composition]

Ethylenediaminetetraacetic acid ferric salt 65. Og Ethylenediaminetetraacetic acid disodium salt 3.0g Anhydrous sodium sulfite 9.5g Ammonium thiosulfate 77.5g Anhydrous sodium carbonate 4.0g Add water to make IQ.

[Fixer composition]

Glacial acetic acid 9mα Sodium acetate 3g Add water to make ia.

Table 4 shows the density of the unexposed area of each sample after treatment.

Table 4 As is clear from Table 4, in the samples containing the dye of the present invention, color staining due to residual color of the dye was not observed as in the samples containing the comparative sample. Furthermore, when the sensitivity of each sample was compared, it was found that the dye of the present invention had extremely little adverse effect on the emulsion.

Claims (1)

[Claims] 3H-pyrrolopyridine, 4H-thienopyrrole, 6H-
A cyanine dye having thienopyrrole, 4H-furopyrrole and 6H-furopyrrole as its core has at least two acid groups in the dye molecule, or -CH_2CH_2OR
A silver halide photographic material comprising a hydrophilic colloid layer containing at least one cyanine dye having at least two substituents having one or more groups. R represents a hydrogen atom or an alkyl group.