JP2799582B2 - Developing method of silver halide photographic material - Google Patents

Description

The present invention relates to a method for developing a silver halide photographic light-sensitive material, and more particularly, to a method for developing a silver halide photographic light-sensitive material having excellent antistatic ability.

[Background of the Invention]

The silver halide photographic light-sensitive material tends to be charged particularly at low humidity such as in winter. In recent years, when a high-sensitivity photographic emulsion is coated at a high speed, or when a high-sensitivity photosensitive material is exposed through an automatic printer, antistatic measures are particularly important.

When the photosensitive material is charged, the discharge produces a static mark or adheres foreign matter such as dust, thereby causing pinholes and significantly deteriorating the quality.
Because of the correction, workability is greatly reduced. For this reason, photosensitive materials generally use an antistatic agent, and recently, a fluorinated surfactant, a cationic surfactant, an amphoteric surfactant, a surfactant or polymer containing a polyethylene oxide group, a sulfonic acid or Polymers having a phosphate group in the molecule are used.

In particular, charge train adjustment with a fluorine-based surfactant or improvement in conductivity with a conductive polymer has been frequently used. For example, JP-A-49-91165 and JP-A-49-121523 disclose a dissociative group in the polymer main chain. An example in which an ionic polymer having the following formula is applied is disclosed.

However, in these conventional techniques, the antistatic ability is greatly deteriorated by the development processing. This is presumably because the antistatic ability is lost due to the steps of developing with an alkali, fixing with an acid, washing with water, and the like.
Therefore, when printing is further performed using a processed film, such as a printing photosensitive material, a problem such as generation of pinholes due to adhesion of dust occurs.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a method for developing a silver halide photographic light-sensitive material in which the antistatic ability does not deteriorate even after the development processing.

[Configuration of the invention]

The object of the present invention is to provide a conductive layer containing a water-soluble polymer represented by the following general formula [I] on the opposite side of a support provided with a photosensitive emulsion layer, and then substantially converting the conductive layer from gelatin and a derivative thereof. In a method for rapidly developing a photographic light-sensitive material provided with an antihalation layer by using an automatic processor, the fixing solution has an effect of substantially hardening the antihalation layer and / or the conductive layer. A silver halide photographic light-sensitive material, [Wherein, R represents a hydrogen atom, a halogen atom, or an alkyl group, and A, B, and C each represent a copolymerizable carboxy group or an ester derivative thereof or an ethylenically unsaturated monomer containing a halogen atom. Represents different monomer units. x is 10 to 100 mol%, y is 0 to 90
Mol%, z is 0 to 20 mol%, w is 0 to 10 mol%.

D represents a simple bonding group or a divalent bonding group composed of carbon, nitrogen, sulfur, oxygen and phosphorus atoms. L represents a benzene ring or a hetero ring, and M represents a hydrogen atom, an ammonium cation or an alkali metal ion. n is 1
Or 2. Hereinafter, the details of the present invention will be described. Examples of the compound of the general formula [I] used in the present invention will be given.

In the above (1) to (38), x, y, and w each represent mol% of the monomer component or an average molecular weight (in the present specification, the average molecular weight indicates a number average molecular weight). .

These polymers can be synthesized by polymerizing commercially available or conventional monomers. The addition amount of these compounds is preferably 0.01g~10g / m ^2, particularly preferably 0.1g~5g / m ^2.

 Next, the fixing solution used in the present invention will be described.

The fixing solution of the present invention is characterized by containing a compound acting as a hardener for the antihalation layer and / or the conductive layer. As the hardener, a water-soluble aluminum salt is preferable. , Aluminum sulfate, potassium alum and the like. The amount of the water-soluble aluminum salt used is 0.1 to 50 g, particularly 1 to 50 g in the fixing solution 1.
It is preferably 40 g, more preferably 5 to 30 g.

The fixing solution is an aqueous solution containing a thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 6.0. More preferably pH 4.
3 to 5.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. Thiosulfuric acid ions and ammonium ions are essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to about 6 mol /.

Tartaric acid, citric acid, gluconic acid, sulfosalicylic acid or a derivative thereof can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain at least 0.005 mol per fixing solution.
0.01 mol / -0.03 mol / is particularly effective.

Specific examples include tartar wire, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, and sodium sulfosalicylate.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent having a water softening property, The compounds described in JP-A-60-218562 can be included.

Fixing temperature and time are the same as for development, about 20 ° C
6 seconds to 2 minutes at about 50 ° C, preferably 6 seconds to 90 at 30 ° C to 40 ° C
Second is more preferable, and more preferably 8 seconds at 30 ° C. to 40 ° C.
It takes 60 seconds to settle.

Next, in the present invention, a tetrazolium compound can be preferably used.

The tetrazolium compound can be represented by the following general formula.

In the present invention, the substituent R ₁ of the phenyl group of the triphenyltetrazolium compound represented by the general formula (II),
R ₂ and R ₃ are preferably a hydrogen atom or a compound having a Hammett sigma value (σP) indicating a degree of electron withdrawing property of negative or positive. Particularly, a negative one is preferable.

Hammett's sigma values for phenyl substitution are described in many publications, for example, Journal of Medical Chemistry 20, 304, 197.
For example, a group having a preferable negative sigma value is, for example, a methyl group ([sigma] P = -0.17 or less, all of which have a negative sigma value).
P value) ethyl group (-0.15), cyclopropyl group (-0.2
1), n-propyl group (-0.13), isopropyl group (-0.
15), cyclobutyl group (-0.15), n-butyl group (-0.
16), iso-butyl group (-0.20), n-pentyl group (-
0.15), a cyclohexyl group (-0.22), an amino group (-0.
66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.07).
24), propoxy group (-0.25), butoxy group (-0.3
2), a pentoxy group (-0.34) and the like, all of which are useful as substituents of the compound of the general formula [II] of the present invention.

Hereinafter, specific examples of the compound of the general formula [II] used in the present invention will be shown, but the compound of the present invention is not limited thereto.

The tetrazolium compound used in the present invention is described, for example, in Chemical Reviews, Vol. 55, No. 33.
It can be easily synthesized according to the method described on pages 5 to 483.

The tetrazolium compound of the present invention is preferably used in an amount of about 1 mg to 10 g, more preferably about 10 mg to about 2 g, per 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention.

The tetrazolium compound used in the present invention can obtain preferable characteristics by using it alone.
Even if a plurality of them are combined in any ratio, preferable characteristics are not deteriorated.

One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the present invention, the compound is added to the hydrophilic colloid layer directly adjacent to the silver halide emulsion layer or to the hydrophilic colloid layer adjacent via the intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters and the like, and the silver halide photographic light-sensitive material is prepared by overcoating or the like. The composition may be directly applied to the outermost layer on the side of the silver halide emulsion layer to be incorporated in the silver halide photographic material.

The silver halide emulsion used in the light-sensitive material of the present invention may be a silver halide emulsion such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or silver chloroiodobromide. Any used silver halide grains can be used.
Any of the acidic method, neutral method and ammonia method may be used.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be particles formed mainly in the particles or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patent 4,
183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, etc., and the Journal of
Photographic Science (J.Photgr.Sci). Two
By the method described in 1.39 (1973) documents, such as octahedral, tetradecahedral, create a particle having a shape such as dodecahedral, it can also be used this. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

Emulsions having any grain size distribution may be used, and emulsions having a wide grain size distribution (referred to as polydisperse emulsions)
May be used, or an emulsion having a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or as a mixture of several kinds.
Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

The photosensitive silver halide emulsion is not subjected to chemical sensitization,
A so-called unripened (Primitive) emulsion can be used as it is, but usually it is chemically sensitized. For chemical sensitization, Glafkides or Zelikman et al., Or H. Fries
er ed. de Grundlagen del Photography Schen Protzese Mito Silberhalogeneden (Die
Grundlagender Photographischen Prozesse mit Silber
halogeniden, Akademicche Verlagsgesellschaft, 196
The method described in 8) can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, gold or another noble metal compound can be used or used in combination.

As the photosensitive emulsion, the above-mentioned emulsions may be used alone, or two or more kinds of emulsions may be mixed.

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3
Various stabilizers such as a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole and the like can also be used.

If necessary, a silver halide solvent such as thioether or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. The removal of the salts can be carried out based on the method described in Research Disclosure No. 17643.

In the light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item 17643.
(December 1978) and Volume 187, Item 18716 (November 1979)
The relevant locations are summarized in the table below.

In the implementation of the silver halide photographic light-sensitive material of the present invention,
For example, the emulsion layer and other layers can be formed by coating one or both sides of a flexible support generally used for photographic light-sensitive materials. Useful as a flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like coated or laminated. The support may be colored using a dye or a pigment.
It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with an emulsion layer or the like. Undercoating treatment is described in JP-A-52-104913 and JP-A-59-1894.
No. 9, No. 59-19940, and No. 59-11941 are preferred.

In the silver halide photographic light-sensitive material according to the present invention, a photographic emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used.

For processing such as development, various methods known in the art that are generally used for processing silver halide photographic light-sensitive materials can be used other than incorporating the compound of the present invention into a fixing solution.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of Emulsion) Rhodium salt containing 10 ^-5 mol per mol of silver, average grain size 0.20 μm, monodispersity of silver halide composition by controlled double jet method under acidic atmosphere of pH 3.0 20,
Silver chlorobromide particles containing 2 mol% of silver bromide were prepared. Particles were grown by adding benzyladenine to a 1% aqueous gelatin solution.
Per system. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added per mol of silver halide, and then washed with water and desalted.

Then, after adding 60 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene per mol of silver halide, 15 mg of sodium thiosulfate per mol of silver halide was added, and the mixture was added at 60 ° C. For sulfur sensitization. After sulfur sensitization, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer per mole of silver halide.

Additives were added to the obtained emulsion so as to be in the following amounts, and one side of a 100 μm-thick polyethylene terephthalate support, which was subjected to latex subbing treatment on both sides according to Example 1 of JP-A-59-19941, was used. Coated on top.

Latex polymer: styrene-butyl acrylate acrylic acid terpolymer 1.0 g / m ² phenol 1 mg / m ² saponin 200 mg / m ² sodium dodecylbenzenesulfonate 50 mg / m ² tetrazolium compound (I-7) 40 mg / m ² compound (N) 40 mg / m ² Compound (O) 50 mg / m ² Styrene-maleic acid copolymer 20 mg / m ² Alkali-treated gelatin (isoelectric point 4.9) 2.0 g / m ² Silver amount 3.5 g / m ² Formalin 10 mg / m ² The coating solution was adjusted to pH 6.5 with sodium hydroxide before application. As an emulsion protective film, an additive was prepared so as to have the following amount, and was simultaneously coated with an emulsion coating solution.

Fluorinated dioctyl sulfosuccinate 100 mg / m ² Dioctyl sulfosuccinate 100 mg / m ² Matting agent: amorphous silica 50 mg / m ² compound (O) 30 mg / m ² 5-methylbenzotriazole 20 mg / m ² compound (P) 500 mg / m ² propyl gallate ester 300 mg / m ² styrene - maleic acid copolymer 100 mg / m ² alkali-treated gelatin (isoelectric point 4.9) 1.0 g / m ² formalin 10 mg / m ² in advance citrate pH5.4 And then applied.

Next, a conductive layer, an antihalation layer and an antihalation protective layer having the contents shown below were coated and dried in this order on the support opposite to the emulsion layer to prepare a sample.

Antihalation layer Styrene-maleic acid copolymer 100 mg / m ² Citric acid (adjusted to pH 5.4 after coating) 40 mg / m ² Saponin 200 mg / m ² Lithium sulfate 30 mg / m ² (Antihalation Layer Protective Film) An additive was prepared so as to have the following amount, and was applied on the packing layer.

Dioctyl sulfosuccinate 200 mg / m ² Matting agent: polymethyl methacrylate (average particle size 4.0μ
m) 50 mg / m ² Fluorinated sodium dodecylbenzenesulfonate 50 mg / m ² Alkali-treated gelatin 1.0 g / m ² Formalin 10 mg / m ² The thus obtained sample was prepared using a developing solution and a fixing solution having the following formulation. The film was processed by an automatic processor under the following processing conditions. Incidentally, ordinary tap water was used for preparing processing solutions such as a developing solution and a fixing solution.

(Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 1-phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide used Amount to bring the pH of the solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 mg Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 1-phenyl-3-pyrazolidone 500 mg At the time of use of the developer, the composition A and the composition B were dissolved in 500 ml of water in this order, and finished to 1 before use.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% aqueous solution) 240 ml Sodium sulfite 17 g sodium acetate trihydrate 6.5 g boric acid 6 g sodium citrate dihydrate 2 g acetic acid (90% aqueous solution) 13.6 ml ( Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an equivalent content of 8.1 w% in terms of Al ₂ O ₃ ) The composition A and the composition B were melted in this order and finished to 1 for use. The pH of the fixing solution was about 4.3.

<Development conditions> (Step) (Temperature) (Time) Development 40 ° C for 15 seconds Fixing 35 ° C for 10 seconds Rinse at room temperature 10 seconds The results obtained are shown in Table 1.

From the results shown in Table 1, it can be seen that the sample according to the present invention has little deterioration of the antistatic ability after the development processing and is remarkably improved as compared with the comparison.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material that does not deteriorate in antistatic performance even after processing such as development can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 5/38 G03C 1/89 G03C 1/825

Claims (1)

(57) [Claims] (1) On the opposite side of a support provided with a photosensitive emulsion layer,
After providing a conductive layer containing a water-soluble polymer represented by the following general formula (I), a photographic light-sensitive material provided with an antihalation layer substantially consisting of gelatin and its derivatives, using an automatic processor, In the method of rapid development processing,
A method for developing a silver halide photographic light-sensitive material, wherein a fixing solution has a function of substantially hardening the antihalation layer and / or the conductive layer. [Wherein, R represents a hydrogen atom, a halogen atom, or an alkyl group, and A, B, and C each represent a copolymerizable carboxy group or an ester derivative thereof or an ethylenically unsaturated monomer containing a halogen atom. Represents different monomer units. x is 10 to 100 mol%, y is 0 to 90
Mol%, z is 0 to 20 mol%, w is 0 to 10 mol%. D represents a simple bonding group or a divalent bonding group composed of carbon, nitrogen, sulfur, oxygen and phosphorus atoms. L represents a benzene ring or a hetero ring, and M represents a hydrogen atom, an ammonium cation or an alkali metal ion. n is 1 or 2. ]