JPH01138553A - Silver halide photographic sensitive material with improved red safelight fogging - Google Patents

Abstract

PURPOSE:To suppress red safelight fogging by incorporating a copper phthalocyanine compd. into at least one layer. CONSTITUTION:A copper phthalocyanine compd. is incorporated into at least one layer of a sensitive material. The compd. is used by 10mg-10g, preferably 10mg-5g per 1mol. silver. Though the compd. may be incorporated into any of a silver halide emulsion layer and a hydrophilic colloidal layer, it is preferably incorporated into the emulsion layer. Two or more kinds of copper phthalocyanine compds. may be used and different compds. may be incorporated into the emulsion layer and the hydrophilic colloidal layer. Red safelight fogging can be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with reduced red safelight fog.

[Conventional technology]

In order to improve the efficiency of darkroom work, it is necessary to handle film under a safe light that is as bright as possible, but even with a safe light, prolonged exposure can cause fogging. Therefore,
Research on reducing safelight fog has been conducted for a long time. In particular, there is an urgent need to reduce red safelight fog in direct X-ray films for which the use of ORN sensitive materials has increased.

In order to solve the red safelight fog, for example, in US Pat. A method of providing is disclosed. However, this method has the disadvantage that it significantly deteriorates the thermal stability of the photosensitive material and causes frequent thermal coupling.

In addition, Japanese Patent Publication No. 45-8831 describes a method of chemical sensitization using gold mercaptide, but it also causes a large deterioration in thermal stability and may cause problems during long-term exposure at low illuminance.
This causes deterioration of so-called low-light reciprocity law failure characteristics, which reduces sensitivity.

Further, Japanese Patent Publication No. 56-24937 discloses a method of chemical sensitization using a thiosuccinimide compound, but this method also does not provide sufficient sensitivity.

Therefore, there is a need for the development of a technology that solves red safelight fog without deteriorating photographic characteristics.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that exhibits little desensitization, excellent storage stability, and significantly reduced red safelight fog.

[Structure of the invention]

As a result of extensive research into red light-absorbing compounds, the present inventors have discovered the outstanding effects of copper phthalocyanine compounds and have accomplished the present invention.

That is, an object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the at least one layer contains a copper phthalocyanine compound. This is accomplished using photographic materials.

The present invention will be explained in more detail below.

The copper phthalocyanine compound used in the present invention has the following general formula: Rl, Rx, Rs, Ra, Rs, R6, R,
and R8 are each a hydrogen atom or -OH.

-COOM, -303M, POsM, -POsMz(M
is a hydrogen atom, an alkali metal atom, or an ammonium group)
represents a group represented by These groups may be directly bonded to the benzene ring of copper phthalocyanine, or may be alkylene, oxyalkylene, -S-, -O-.

-5Q, -, -CO-, -NH-, -8O,NH-.

They may be bonded via a suitable linking group such as -CONH-. However, R4-R8 are never hydrogen atoms at the same time.

Next, typical examples of copper phthalocyanine compounds are shown.
The present invention is not limited to these.

Exemplary Compounds) +1UυniH, (,;H2C0OH These compounds can be synthesized according to the method described in US Pat. No. 3,498.784 and the like.

Copper 7-lysyanine compound is 10 mg to 10 per mole of silver.
g, more preferably in the range of 1011 g to 5 g, and even more preferably 50 m1P"ly. If too large an amount is added, desensitization will be large.

The additive layer may be either a silver halide emulsion layer or a hydrophilic colloid layer, but addition to the emulsion layer is more preferable.

Two or more types of copper phthalocyanine compounds may be used, and separate compounds may be added to the emulsion layer and the hydrophilic colloid layer.

In the present invention, other methods for improving red safelight fog, such as providing a dye filter layer or a layer in which a red-sensitive sensitizing dye is adsorbed to fine grain silver rhodanide that has substantially no photosensitivity, are proposed. You may also use methods such as providing a

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the silver halide emulsion are cubic, 8
It may have a regular crystal shape such as a hedron or a tetradecahedron, or it may have an irregular crystal shape such as a spherical shape, or it may have a crystal defect such as a twin plane. Or it may be a combination thereof.

The grain size of the silver halide may be fine grains of 0.01μ or less, or large grains with a projected area diameter of lθμ blades, monodisperse emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. good. The preferred grain size of photosensitive silver halide is 0.1 to 3 ura.

The silver halide emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure (R
esearch Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-2
3 pages, and the same magazine.

No. 18716 (November 1978), p. 648 can be followed.

The photographic emulsion used in the present invention is P.
(P, Glafkides) “Shimmy Knee 7”
Jisik Photographic (Chi+mie a
t PhysiquePhotographique)
J., published by Paul Montel (1967), G.F.

F. Duffin) Author: Odographic Emulsion Fist Chemistry
(Photographic Emulsio
'n Chemistry) J, The 7 Orcal
Published by The Focal Press (196
6 years), V. L. Zelikman et al.
kmanet al)r Making and Coating Photographic Emulsion (Mak
ing and coating photog
It can be prepared using the method described in ``Raphic E+++ulsion'', published by The 7 Orcal Press (1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used; however, the method for reacting the soluble silver salt and soluble halogen salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. You can. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase in which silver halide is produced constant, a so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pn during grain formation.

For more information, please see the Photographic Science and Engineering Link (Photo.

Sci, Eng-), 6 @, pp. 159-165 (1962), Journal of Photographic Science (J, Phot, Sci,), vol. 12,
242-251 (1964), U.S. Pat. No. 3,655.
No. 394 and British Patent No. 1,413,748.

A typical monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 0.1 μm, and at least 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average particle diameter is 0.25-2μ,
Emulsions in which at least 95% by weight or at least 95% by number of silver halide grains are within ±20% of the average grain diameter can be used in the present invention. Methods for producing such emulsions are described in U.S. Pat.
No. 5.394 and British Patent No. 1,413.748. Also, JP-A-48-8600, JP-A No. 51-
No. 39027, No. 51-83097, No. 53-137
Monodisperse emulsions such as those described in No. 133, No. 54-48521, No. 54-99419, No. 58-37635, and No. 58-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention.

Tabular grains are described in Gato 7, Phot, Sci, Eng-
(ibid.).

14, pp. 248-257 (1970), U.S. Patent 4
, 434.226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,112,157. When using tabular grains, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as reported in the above-cited U.S. Pat. No. 4,434.226, etc. It is detailed.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,14
No. 6, U.S. Pat. No. 3,505.068, U.S. Pat. No. 4,444.
No. 877 and Japanese Unexamined Patent Publication No. 14331/1984. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in U.S. Pat.
No. 094,684, No. 4.142.900, No. 4.4
No. 59.353, No. 4,349,622, No. 4,39
No. 5.478, old No. 4,433.5, No. 4,463.
No. 087, No. 3,656.962, No. 3,852.0
No. 67, British Patent No. 2,038.792, Japanese Unexamined Patent Publication No. 1983-
It is disclosed in No. 162540 and the like. Also, mixtures of particles of various crystal forms may be used.

It is also possible to use a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

When forming the silver halide grains used in the present invention, ammonia, thioether compounds (for example, U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574,628, No. 3,704,130, No. 4,297.439,
4,276.347, etc.), thione compounds (e.g., JP-A-53-144319, JP-A-53-82408,
55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.), etc. can be used.

Furthermore, the properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitate formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. U.S. Patent No. 2,448.060, U.S. Patent No. 2,628.167, U.S. Patent No. 3
, No. 737,313, No. 3,772,031 line j:
RD, No. 13452 (June 1975), 47-4
8 pages, U.S. Pat. No. 3,628.960, U.S. Pat. No. 4,183.
No. 756, No. 4,225.666, JP-A-61-10
3149 by the presence of compounds such as copper, iridium, lead, bismuth, cadmium, zinc, gold and Group II noble metal compounds or spectral sensitizing dyes during the silver halide precipitation process. You can control the properties of silver. Special Publication No. 58-1410,
Moiser et al., J. Phot, Sci. (ibid.), 25.
As described in Vol., pp. 19-27 (1977), silver halide emulsions can undergo reduction sensitization of the interior of the grains during the precipitation formation process.

The silver halide emulsions used in the method of the invention may be chemically sensitized, using conventional sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof.

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

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. In addition to the additives mentioned above, additives used in such a process include RD.

No. 17643 (December 1978), pp. 23-27 and No. 18716 (It., 1979),
Chemical sensitizers, spectral sensitizers, supersensitizers, brighteners, fog inhibitors, stabilizers, couplers, organic solvents, light absorbers, dyes, and ultraviolet absorbers described on pages 648 to 651 , stain inhibitors, color image stabilizers, hardeners, binders, plasticizers, smoothing agents, coating aids, antistatic agents, etc.

For 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 from 18°C to 50°C.
temperature selected between 18 °C or 50 °C
The temperature may be higher than 70°C, for example, 70'O.

The effect of the present invention is particularly remarkable in photographic black-and-white light-sensitive materials.
phenyl-3-pyrazolidone), amine phenols (
For example, known developing agents such as (f N-methyl-p-aminophenol) can be used alone or in combination.

For details, see "7 Otographic Processing Chemistry" by Mason, published by Calpress (L, F, A,
Mason, Photographic Processes
sing Chemistry, Focal Pres
s, 1975), RD, No. 18873 (December 1979), and RD, No. 2040 (April 1981).

〔Example〕

The present invention will be explained in more detail by showing specific examples below.

A silver iodobromide monodisperse cubic emulsion containing 1.5 mol% of silver iodide with an average grain size of 0.3 μm was produced by the double jet method at 60°C, pAg = 8.0, and pH -2.0. I got it. Observation of an electron micrograph of this emulsion revealed that the incidence of twin grains was 1% or less.

This seed crystal emulsion was dispersed in 8.4 g of a 2.5% gelatin aqueous solution kept at 40° C., and ammonia water equivalent to 0.2 N was added. After adjusting the pH to 9.0 using glacial acetic acid,
．． A 2N ammoniacal silver ion aqueous solution and a halide aqueous solution were added at the flow rate profile shown in FIG. 1 and mixed by stirring. As the halide aqueous solution, a potassium bromide-potassium iodide mixed solution containing iodide ions in an amount of 2% of the silver ion molecular weight used was used.

pH from 9.0 to 8.0 while maintaining pAg = 9.0
was changed in proportion to the amount of ammoniacal silver ion added.

The silver halide grains of the obtained emulsion have silver iodide distributed throughout the grains, with an average silver iodide content of 2 mol%, an average grain size (γ) of 1.21 μm, and a coefficient of variation (σ/γ). )0.
It was 12. Excess water-soluble salts were removed from the emulsion by a coagulation-sedimentation method, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added, and after chemical ripening, the following compound (A) was halogenated as a sensitizing dye for green light. An emulsion preparation solution was prepared by adding 300,119 mol per mol of silver and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene as a stabilizer at 2 x 10-'' mol per mol of silver halide. Various additives were added to the emulsion adjustment solution and the protective layer solution shown below.

Sensitizing dye (A) Next, on a polyethylene terephthalate support, the emulsion solution was coated simultaneously with a silver content of 60 mg/100 cm" and the protective layer solution was coated with a gelatin content of 10119/100 cm" by a conventional method, and dried. Sample 1 (comparison) was prepared.

Separately, Samples 2 to 13 were prepared by applying and drying the emulsion in the same manner using the above emulsion to which the compound according to the present invention was added as shown in Table 1.

Emulsion additives (per mole of silver halide) t-butylcatechol 400mg polyvinylpyrrolidone (molecular weight 10,000) 1.0g styrene-maleic anhydride copolymer 2.5g trimethylolpropane 10g diethylene glycol 5゜0g nitrophenyl tri Phenylphosphonium chloride 50n+g1.
Ammonium 3-dihydroxybenzene-4-sulfonate 4g Sodium 2-mercaptobenzimidazole-5-sulfonate 15mg・'
\\ It (1F, Nako 70tag 1.1-dimethylol-1-bromo-1-nitromethine 70+ag protective layer additive (per gelatin Ig) ■ 03Na (n is a mixture of 2 to 5) CJ + sO GHzCHzO) -rrCHzCHzOH
3mgC,F,5O1K
2 mg Matting agent consisting of polymethyl methacrylate with an average particle size of 7 μm
7mg sodium chloride
2mg colloidal silica with average particle size of 0.013μ- 70mg formaldehyde
3mg glyoxal
2mg 2-hydroxy-4,6-dichloro-1,
3,5-triazine sodium salt 3B
The sample thus obtained was exposed to l/100 seconds through an optical wedge using a light source with a color temperature of 5400°.
3,20M5), and then at 35℃ using the following developer.
, 30 seconds of development processing was performed.

Developer solution> Anhydrous potassium sulfite 50g Hydroquinone 10g Anhydrous boric acid
1g potassium carbonate l hydrate 1591-phenyl-3-pyrazolidone 0.5g potassium hydroxide
4g5-Methyl-bensylitriazole
0.05g potassium bromide
5g glutaraldehyde/sodium bisulfite adduct 159 glacial acetic acid
8mM 5-nitroindazole 0.109 Ethylenediaminetetraacetic acid, disodium salt 3g Add water to make IQ, and adjust to pH -10.20 with potassium hydroxide or glacial acetic acid.

After the sample was left for 3 days at 60° C. and 50% relative humidity, the same exposure and development process was performed to measure the increase in fog (open test).

Furthermore, the increase in fog was measured when the sample was irradiated with incandescent light for 30 minutes from 1.2 m above the sample through a red filter having the transmittance shown in FIG. These results are shown in Table 1.

The compound of the present invention was added to the protective layer.As is clear from the relative sensitivity table 1 when the sensitivity of the sample 1 was set as 100, the sample of the present invention suppressed the increase in red safelight fog and The increase in thermal fog is also reduced.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the profile of changes in the supply flow rate of silver ions and halide ions during the growth of silver halide grains in the emulsion preparation of the example, and FIG. 2 is a graph showing the red safelight fog evaluation in the example. This is the spectral distribution curve of a filter placed on the irradiated incandescent light bulb to achieve this.

Claims (1)

[Claims] A silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the at least one layer contains a copper phthalocyanine compound. material.