JPS6041037A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent spotting by incorporating EDTA or a salt thereof and a specified compound or a salt thereof into a constituent layer formed on a support. CONSTITUTION:EDTA or a salt thereof and a compound represented by the formula or a salt thereof are incorporated into a constituent layer of a photosensitive material having a photosensitive silver halide emulsion layer on the support as the constituent layer. EDTA and salts thereof are superior to other chelating agent in spotting preventing effect and influence on photographic characteristics, so when EDTA or a salt thereof is used in the manufacture of a photosensitive material, spotting can be prevented. In the formula, each of A1-A5 is -COOH or -CH3OH, n is 0, 1 or 2, and when n is 0, at least one among A1-A4 is -CH3OH.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photosensitive material (A) "01", and relates to a halogenated photosensitive material that causes fewer spots on the tube.

During the manufacturing process of silver halide photographic materials, for example, during the manufacturing of the support, during the preparation of coating liquids such as silver halide emulsions, and at various process steps such as coating the support with a base liquid, etc. Subbeat,
It is well known that jJS color, gray or transparent spots appear on the photosensitive material when the photosensitive material is developed due to the inclusion or adhesion of totally fine powders such as aluminum and chromium. This spot is called "spot" in IIZ.

In order to prevent the occurrence of these spots, the greatest care and effort is usually taken to remove the fine dust floating in the air during the manufacturing process of silver halide photographic light-sensitive materials, but it is impossible to completely remove it. It is extremely difficult.

In addition, due to the scattering of fine metal powders caused by wear and rust on various metal coatings (4) and equipment used in the production of photographic light-sensitive materials, total bending fine powders may mix into or adhere to photographic light-sensitive materials. It is important to completely prevent this phenomenon.

Conventionally, it has been known to include various spot preventive agents in the light-sensitive emulsion layer or various non-light-sensitive layers of silver halide photographic materials in order to completely reduce the occurrence of such spots. In many cases, the preventive effect is insufficient, resulting in negative effects on photographic properties, such as beta drop, desensitization, and fog formation. These spot preventive agents are usually made up of chelating agents, but for example, ethylenediaminetetraacetic acid (EDTA) and its effects on the spot preventive effect and the four-layer properties are different from those of other chelates. In addition to being relatively superior to other drugs, it is also inexpensive, making it extremely useful. Therefore, when silver halide photographic light-sensitive materials are manufactured in an atmosphere where there are very few causes of spot generation, or even if substances that cause spot generation are mixed in or adhered to, halogenated materials are less likely to generate spots! = In the case of long photosensitive materials, EDT
By using A or its salt, it is possible to prevent the occurrence of spots in the river to such an extent that there is no quality problem. However, BDTA
When silver halide photographic light-sensitive materials are manufactured in an atmosphere where spots are likely to occur, the salts are used in silver halide photographs where spots are likely to occur due to contact with υ and the spot-causing substance 'Z4. This is insufficient for photosensitive materials.

The object of the invention is to provide a halogenated photosensitive material in which the generation of spots is effectively prevented.

Another object of the present invention is to provide a silver halide photographic light-sensitive material which has a small amount of carbon dioxide and which effectively prevents the occurrence of spots.

The purpose of the invention is to prepare ethylenediamine N1 or its salt, chemical compound represented by the following general formula, 71 or its salt, and 4
This can be achieved by using them together.

That is, the invention does not require at least one layer on the support as a constituent layer. 2, the photographic light-sensitive material has a non-photosensitive layer if necessary, and its +
? A silver halide photographic sensitizer containing at least one selected from ethylenediaminetetraacetic acid and its salts in the 7J stratification, and at least one selected from the compounds represented by the general formula below and salts thereof. It is the material.

General formula above General formula A, AI S person, , AI, person, and A,
are respectively -0 (J tJ Hl-U H, OH, n is o, i or 2 (11-, n is 00 and @ A I
, A @ , A @ and A4 represent -(IH, OH).

Ethylenediaminetetraacetic acid used in the present invention is represented by the following structural formula, and its salts include alkali metals such as sodium and potassium! 1 salt and ammonium salt are typical examples.

Representative examples of the compounds represented by the above general formula used in the present invention are listed below, but the compounds are not limited to these.

Typical salts of these compounds include alkali gold salts such as sodium and potassium + Qi salts, ammonium salts, etc.0 (1) 011, L100H Ethylenediaminetetraacetic acid or its salt used in the present invention, and The compound represented by the above general formula or its salt is usually used in an amount of 0.001 to 10 g, preferably 0.01 g, per square meter of silver halide photographic material.
In the production of the photosensitive material η of the present invention, which is used in an amount of 11 to 1 g, these spot inhibitors are usually dissolved in water, methanol, ethanol, flopanol, dimethylformamide, or a mixture thereof, and used in the photosensitive material. A photosensitive halogenated emulsion and/or a non-photosensitive liquid emulsion are added to these enemies and applied to the support before coating.

Photosensitive silver halide emulsion used in the invention A single layer of the silver halide emulsion may be prepared by any method such as an acidic method, a neutral method, or an ammonia method. Any method such as layer temperature self-determination, back mixing @ method, simultaneous mixing method, etc. may be used. Q Jr, IMk such as rhodium, iridium, cadmium, etc. may be added during the reaction with these soluble bone minerals or during physical ripening. The silver halide emulsion may be an emulsion that is not chemically sensitized, but it is usually chemically sensitized. A metal sensitizing agent such as a powder, amines, hydrazine derivatives, gold, metal sensitizers, iridium, palladium, etc. can be used alone or in combination of two or more. In addition, silver halide emulsions are sensitized with spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, multi-merocyanine dyes, etc.@Silver halide emulsions may be used as antifoggants or stabilizers as necessary. Various compounds (for example, benzothiazoles, compounds, benzimidazoles) 4, benzotriazoles and their mercapto compounds, mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles, triazaidans, tetrazaindenes, etc. may be used alone or in combination of two or more.

The non-photosensitive layers provided as necessary in the invention include an undercoat Jn (lower m layer), an intermediate layer, a protective layer, a filter layer, a halesh U prevention layer (t'FIIt prevention layer), a backing layer (curl prevention layer) (provided for the purpose of preventing halosin, preventing static electricity, etc.).

In the present invention, ethylenediaminetetraacetic acid or its salt and the compound represented by the above general formula or its salt may be used together in one layer of the silver halide photographic light-sensitive material k, rf9, or in separate layers. They may be contained one at a time, or they may be contained in combination in the 41η stratification of the photographic light-sensitive material as a whole. To explain a specific embodiment, as an embodiment in which they are used together in one layer, they may be included in either the silver halide emulsion layer or the previous He non-photosensitive layer, but if necessary, they may be included in the combination. Let's do it WI wo 2 I
e4 or more may be provided. In various embodiments of the present invention, the silver halide emulsion layer and the backing layer, the backing layer and the undercoat layer, the backing layer, the silver halide emulsion layer and the backing layer, the silver halide emulsion layer and the backing layer, and the silver halide emulsion layer and the backing layer, respectively, in various embodiments of the present invention. These compounds are preferably used in the non-photosensitive layer when the two types of spot inhibitors used in the invention tend to cause negative effects such as desensitization and capri formation. Moreover, it is effective to use these compounds in WIVC adjacent to the support.

Examples of hydrophilic colloids used in the silver halide emulsion layer and non-photosensitive layer according to the present invention include the following, but are not limited to these. Gelatin (including acid-treated gelatin, lime-treated gelatin, acylated gelatin, grafted gelatin, etc.), polyvinyl alcohol,
Polyvinylpyrrolidone, polyvinyl acrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl methyl ether, methyl vinyl ether/maleic anhydride copolymer, styrene/maleic anhydride copolymer, isobutylene/maleic anhydride copolymer, polyvinyl alcohol and styrene/ Condensate of maleic anhydride copolymer, polyvinyl alcohol and isobutylene/maleic anhydride copolymer (condensate of union, gum arabic, albumin, sodium alginate, etc., these natural or Ii
Autogenous polymers can be used alone or in combination for ages 2 and 11 and older.

Uninventively, the silver halide emulsion layer 2 has a non-uniform optical property #6, depending on necessity, an aldehyde hardening agent, an active halogen hardening agent, an ethylene ethylene hardening agent, and a vinyl sulfone hardening agent. curing agent, epoxy curing agent, isocyanate curing agent, acryloyl IP! A curing agent, its 110 dimethylol urea, ethylene urea side 11) i, mucohalogen, is explained by the hardening Mll of chromium, potash alum tatami.

An anionic, cationic, nonionic or betaine type surfactant is added to the halogenated emulsion 3, non-sensitive material and hydrophilic colloid solution according to the invention during coating.

Supports used for the uninvented silver halide photographic material include transparent or unclear synthetic resin films such as polyethylene terephthalate, polycarbonate, polystyrene, and polyglopylene, polyethylene-coated paper, baryta paper, etc. It cannot be limited to.

Next invention? Examples will be given for concrete explanation, but the invention is not limited thereto.

The compounds a according to the invention used in the Examples are the following compounds.

Compound 9 Compound -■ Compound-■ Compound-■ Compound-■ In addition, the iron dust, which is the substance that causes spot generation, used in the examples is mainly composed of fine iron powder, vl, and prefectural zinc powder, including tr.
i! Dust powder is coming out.

Example 1 Blocking and...
, the opposite side of the support (Table 1m) (corona radiation After printing, the substance that causes spots is sprinkled uniformly on the surface, and the compounds shown in Table 1 and formalin % (formula I-) V as a hardening agent are sprinkled on the surface.
C anionic surfactant A! An aqueous gelatin solution containing all of 1 was applied as an undercoat layer. Next, this lower fI'1 layer was subjected to total sulfur sensitization and gold sensitization to a silver iodobromide emulsion (silver iodide content 1.5 mol%) prepared by the ammonia method.
Spectral sensitization was achieved by adding a green-sensitive carbocyanine sensitizing dye, and 2-methyl-4-hydroxy-1,3,
A gelatin-silver halide emulsion containing 3M, 7-titrazaindene, formalin as a hardening agent, and an anionic surfactant as a wetting agent was coated.

The undercoating liquid and silver halide emulsion were both I"H 5.
．． It was adjusted to 0 and applied.

The halogenated sensitizer produced by the above method was completely printed on the entire surface of the monthly meeting, and the paper for black-and-white photographic paper was printed 1! After rinsing with R liquid Gutucol (Mitsubishi AU, Via), stop, soak, run water, and dry according to the usual method.The number of 1000 square centimeter roaring spots for each sample is shown in Table 4431. Indicated.

As shown in Table 1 and Table 1 KB, non-inventive samples 6.9.12 and 15 did not generate any spots and showed a remarkable effect in preventing spots.

Example 2 In Example 1, the compounds shown in Table 1? Fifteen types of silver halide photographic photosensitive materials were produced in exactly the same manner as in Jikkan i+'lJ 1, except that they were not contained in the undercoat layer but were contained in the silver halide emulsion layer in the same manner as in Table 1. When the development process was carried out, the occurrence of spots showed a similar tendency. Regarding 0 photographic sensitivity 4, for both Compound A and Compounds ■ to ■, when 0.1117 d was added alone, there was a tendency to desensitize from a small amount. However, Compound A of the present invention and Compounds ① to I
When using V'i0.05J'/I11'' in combination, there is a tendency for desensitization even though the total amount of shellfish contained in the compound is 0.III/haze? Didn't show it.

Example 3 In the silver halide photosensitive material Fl used in Example 1, was the compound ■, ■, ■, or ■ used in the undercoat layer? each individually 0
．． When the silver halide emulsion layers of Samples 4, 7, 10 and 13 containing 05#/j contained the θ compound A k O,0517s' gold, the entire development process was carried out in the same manner as in Example 1, and the spots were It did not occur at all and showed no tendency to desensitize.

Example 4 In sample 4.7.10 and 13 in Example 1,
When the backing layer contained O, 1 g/i of Compound 5 and was developed in the same manner as in Example 1, no spots were generated.

Claims (1)

[Claims] In a photographic photolithography system having at least one light-sensitive tin halide emulsion layer as a constituent layer on a support and optionally a non-light-sensitive layer, ethylenediaminetetraacetic acid is added to the layer. and at least one selected from salts thereof,
1. A silver halide photographic photosensitive material C containing at least one compound represented by the following general formula and a salt thereof. In the general formula, AI, A, , AI, A4 and A. are respectively −〇(J(Jll, −OH, υHSn represents 0°1 or 2, and when n is 0: at least one of A, , A, , A, and A is 100, @ representing LJH