JPH02208651A - Silver halide photographic sensitive material having improved electrostatic chargeability - Google Patents

Abstract

PURPOSE:To prevent the deterioration of antistatic performance even after a development processing by providing a specific conductive layer, then providing a halation preventive layer substantially consisting of gelatin and its deriv., holding the swelling rate is 50-250pts. CONSTITUTION:The conductive layer contg. a water soluble polymer having the repeating unit expressed by formula I is provided and thereafter, the halation preventive layer essentially consisting of the gelatin and its deriv. is provided. The halation preventive layer is so provided as to attain 50 to 250% swelling rate. In formula I, R denotes a hydrogen atom. halogen atom, etc.; A to C respectively denote monomer units, which are copolymerized with respectively copolymerizable ethylenic unsatd. monomers contg. carboxyl groups or the ester deriv. thereof, etc., and are different from each other; x is 10 to 100mol%; y is 0 to 90mol%,; z is 0 to 20mol%; w is 0 to 10mol%. D is a mere bond group or a bivalent bond group constituted of carbon, nitrogen, etc., and phosphorus; L is a benzene ring or heterocycle; M denotes a hydrogen atom, ammonium cation or alkaline metal ion; n is 1 or 2. The deterioration in the antistatic performance is obviated in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent antistatic properties.

[Background of the invention]

Silver halide photographic materials are easily charged, especially at low humidity such as in winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.

When a photosensitive material is charged, static marks appear due to the discharge, or foreign matter such as dust adheres to it, which causes pinholes and significantly degrades the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfonic acid Alternatively, a polymer having a phosphoric acid group in the molecule is used.

In particular, adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers has been widely used, for example, in JP-A-49-91165 and JP-A-49-1.
No. 21523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.

This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.

[Purpose of the invention]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic material whose antistatic ability does not deteriorate even after development.

[Structure of the invention]

The above object of the present invention is to provide gelatin and An antihalation layer consisting essentially of the derivative is provided, and the antihalation layer has a swelling ratio of 50% to 2.
This is achieved by using a silver halide photographic material characterized by a silver halide of 50%.

It is preferable that the antihalation layer of the silver halide photographic material contains a compound that binds to calcium ions and/or magnesium ions.

General formula [I] L represents a benzene ring or a heterocycle, and M represents a hydrogen atom, an ammonium cation, or an alkali metal ion. n is 1 or 2. ] The details of the present invention will be explained below.

Examples of the compound of general formula [I] used in the present invention are listed below (SO
sM)n [In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group, and A%B and C each represent a copolymerizable carboxy group or its ester derivative, or an ethylenically unsaturated 7-mer containing a halogen atom. Represents mutually different monomer units copolymerized.

X is 10 to 100 mol%, y is 0 to 90 mol%, 2 is 0
-20 mol%, W is 0-10 mol%.

The preferred molecular weight is 2 million to 2 million.

D is a simple bonding group or a divalent bonding group composed of carbon, nitrogen, sulfur, oxygen, and phosphorus atoms. 10 M'-FIO million■! ■ ■ 0xNa SO, Na O3Na ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ! ■ x:y:z:w=50:30:10:10M1=t50,000■ -37 ■ -34 x:y=z:w-40:30:20: 10t 40,000■ -38 ■ -35 ikqs -36 M#3 In (1) to (38) above, X, y+W each represent the mole percent of the monomer component, and M represents the average molecular weight (in this specification, average molecular weight refers to the number represents the average molecular weight).

These polymers can be synthesized by polymerizing monomers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably 0.01g/10g/8, particularly preferably 0.1g to 5g/1.

These compounds can be used alone or in combination with various hydrophilic binders or hydrophobic binders to form a layer. Particularly advantageously used as hydrophilic binders are gelatin or polyacrylamide, but others include colloidal albumin, cellulose acetate, cellulose nitrate, polyvinyl alcohol, hydrolyzed polyvinyl acetate, phthalated gelatin. can be mentioned. Hydrophobic binders include polymers with a molecular weight of 20,000 to 1,000,000 or more, such as styrene-butyl acrylate-acrylic acid ternary copolymer, butyl acrylate-acrylonitrile-acrylic acid ternary copolymer, methyl methacrylate-ethyl acrylate-acrylic acid Examples include tertiary copolymer polymers.

The photosensitive material of the present invention is characterized in that its antihalation layer has an expansion coefficient of 50% to 250%. Here, the anti-halicin layer includes all layers provided on the conductive layer and consisting essentially of gelatin and derivatives thereof. Further, the expansion coefficient is measured as described below in the same manner as described in US Pat. No. 4,414,304.

That is, the photosensitive material was stored at 38° C. and 50% RH for 3 days, the thickness of the anti-silica layer was measured, and then the photosensitive material was immersed in 21"O distilled water for 3 minutes, and then expanded. The film thickness of the Halesh blind prevention layer is measured. Both film thicknesses are measured. The expansion rate is expressed as a percentage of the change in both thicknesses.

As a method for controlling the expansion rate of the photosensitive material in the present invention, methods well known in the art can be used by selecting the amount and type of cured gelatin film.

Next, the compound that binds to calcium ions and/or magnesium ions in the present invention is not particularly limited as long as it is a compound that rusts with calcium ions and/or magnesium ions; Contains all complexing agents. Particularly preferred are those that are difficult to elute during treatment, and are
Polymers of hydrolyzed maleic anhydride as described in JP-A-165057 and JP-A-63-2760.
Examples include cyclodextrin polymers described in No. 50. The preferred addition amount of these compounds is lO-!
~109/DI'', particularly preferably 10-''5
91m".

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr,
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in the literature such as Sci. Sci., 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Further, any grain size distribution may be used, and an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

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

Although the photosensitive silver halide emulsion can be used as a so-called Pri+5ative emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, Glafkides or Zel
ikman et al., or edited by H. Frleser, Die G.
rundlagender PhoLographis
chen Prozesse with 5ilberh
al.

geniden%Akademiche Vsrla
gsgasellschaft.

(1968) can be used.

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

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
3a, 7-chitrazaindene, 5-mercapto-1-7
Various stabilizers can also be used, including enyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control 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 silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 1 te+
117643 (December 1978) and Volume 187 I
rem18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type 1. Chemical sensitizer 2, sensitivity enhancer RD 17643 page 23 RD 18716 page 648 right side same as above 4, brightener 24 page 7, stain inhibitor page 25 right column 650
Page left to right column 8, Dye image stabilizer 25 page 9,
Hardener page 26, page 651 left column 10, binder page 26
Same as above 11, plasticizer/lubricant page 27
650 right column 12, coating aid/surfactant 26~
Page 27 Same as above 13, Static inhibitor
Page 27 Same as above In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. . Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or a
- Paper coated or laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating process is based on JP-A-52
・No. 104913, No. 59-18949, No. 59-1
The treatments described in Publications No. 9940 and No. 59-18949 are preferred.

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

Further, for processing such as development, various methods known in the art that are normally used for processing silver halide photographic materials can be used.

〔Example〕

Hereinafter, the effects of the present invention will be illustrated by examples.

Example 1 The opposite side of a polyethylene terephthalate support coated with a silver halide photographic emulsion prepared according to a conventional method was subjected to latex subbing treatment according to Example 1 of JP-A-59-19941. A polymer layer, an antihalation layer, and an antihalation protective layer having the contents shown below were applied in this order and dried to prepare a sample.

Polymer layer latex polymer: Butyl acrylate - styrene -
Acrylic acid ternary polymer polymer 0.29/■2 Polymer of the present invention Hardener shown in Table 1 (H
) Antihalation layer Styrene-maleic acid copolymer 100 citric acid (pH 5,4i after coating: preparation) 40 saponin
200 Lithium nitrate salt 3
0 Bucking dye mg/m" ll1g81 1g/m" 1μm2 SO, Na Alkali-treated gelatin 2.0g/m"Glyoxal Amounts shown in Table 1 (Halesh carp prevention layer ff1l [I[) Additives as shown below The amount was adjusted to the desired amount and applied to the top of the backing layer.

Dioctylsulfosuccinate ester 200 g/- Matting agent: Polymethyl methacrylate (average particle size 4.0 μm) 50 g
/va” fluorinated dodecylbenzenesulfonic acid thorium
50 wag/Compound of the Present Invention Compound that binds to nesium ions and/or calcium ions The amount shown in Table 1 Alkali-treated gelatin 1.09/II" Glyoxal The amount shown in Table 1 The sample thus obtained was Processing was carried out using an automatic processor under the following processing conditions using a developing solution and a fixing solution having the following formulations.Ordinary tap water was used to prepare processing solutions such as the developing solution and fixing solution.

Developer formulation Hydroquinone 25 gl-
7enyl-4.4dimethyl-3-pyrazolidone 0.4g Sodium Bromide 3g 5-Methylbenzotriazole 0.3g 5-Nitroindazole
0.05g diethylaminopropane-1,
2-diol 0 g Potassium sulfite 90 g Sodium 5-sulfosalicylate 75 g Sodium ethylenediaminetetraacetate 2 g Finished to 1a with water.

The pH was adjusted to 11.5 with caustic soda.

Fixer formulation (composition A) Ammonium thiosulfate (72.5W% aqueous solution) 240
mQ Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate dihydrate 2g acetic acid (901% aqueous solution)
13, 6mQ (composition) Pure water (ion exchange water) 17 ■Q
Sulfuric acid (501% aqueous solution) 4.7 g Aluminum sulfate (A Q! 0 m equivalent content is 8.1
1% aqueous solution) When using 26.5 g of fixer, the above compositions were dissolved in 500+ sil of water in the order of composition A1 and finished to IQ. The pH of this fixer was about 4.3.

<Development processing conditions> (Process) (Temperature) (Time) Development
Fixing at 40°C for 15 seconds 35°C Washing for 10 seconds Regular @ 10 seconds In the table, the compound refers to a compound that binds to magnesium ions and/or calcium ions.

A is a hydrolyzed maleic anhydride polymer and B is a cyclodextrin polymer.

From the results in Table 1, it can be seen that the samples according to the present invention showed little deterioration in antistatic ability after development, and were significantly improved compared to the comparison.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material whose antistatic performance does not deteriorate even after processing such as development.

Claims (2)

[Claims] (1) After providing a conductive layer containing a water-soluble polymer having a repeating unit represented by the following general formula [I] on the opposite side of the support provided with the photosensitive emulsion layer, a conductive layer containing a water-soluble polymer having a repeating unit represented by the following general formula 1. A silver halide photographic light-sensitive material, comprising an antihalation layer having a swelling ratio of 50% to 250%. (2) Calcium ions and/or
2. The silver halide photographic material according to claim 1, further comprising a compound that binds to magnesium ions. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Alternatively, it represents a mutually different monomer or unit copolymerized with an ethylenically unsaturated monomer containing a halogen atom. x is 10 to 100 mol%, y is 0 to 90 mol%, z is 0
-20 mol%, w is 0-10 mol%. The preferred molecular weight is 2 million to 2 million. 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 heterocycle, and M represents a hydrogen atom, an ammonium cation, or an alkali metal ion. n is 1 or 2. ]