JPH03259143A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make improvement in antistatic characteristic and preservable property with lapse of time by providing at least one layer of layers contg. a water-soluble conductive polymer, hydrophobic polymer particles and epoxy hardener. CONSTITUTION:At least one layer of the layers contg. the water-soluble conductive polymer, hydrophobic polymer particles and epoxy hardener are provided. The water-soluble conductive polymer is exemplified by polymers having at least one conductive group selected from a sulfonic acid group, sulfonate group, quanternary ammonium salt, ternary ammonium salt, carboxyl group, and polyethylene oxide group, among which the sulfonic acid group, sulfate group and quanternary ammonium group are more preferable. The antistatic characteristic and the preservable stability with lapse of time are improved 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 and long-term storage stability.

[Background of the invention]

Generally, plastic films have strong electrostatic properties, and this often imposes many restrictions on their use.

For example, in silver halide photographic light-sensitive materials, supports such as polyethylene derephthalate (1) are generally used, and are easily charged, especially at low temperatures such as in winter. Antistatic measures are particularly important when high-sensitivity photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed through 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, which causes pinholes and significantly deteriorates the quality. I'll put it down. For this reason, photosensitive materials generally use an antistatic agent or are provided with an antistatic layer. For example, French patent 2,318
．． No. 442, British Patent No. 9Q8,642, US Patent No. 4,
No. 078,935, No. 3,801,325, No. 4,7
No. 01.403, No. 4,585,730, etc., these techniques are applied to gold-sensitized silver chloride at 50%
When silver chlorobromide or silver chloroiodobromide having a mole % or more is used, there are drawbacks such as fogging and sensitivity fluctuations during long-term storage or under high temperature and high humidity conditions.

[Purpose of the invention]

In order to solve the above-mentioned problems, the object of the present invention is to first provide a silver halide photographic material that has excellent antistatic properties, good storage stability over time, and low sensitivity fluctuations and fogging at high temperatures. Another object of the present invention is to provide a silver halide photographic material free from pinholes.

[Structure of the invention]

The above object of the present invention is to provide a halogen halogen compound having at least one gold-sensitized silver halide emulsion layer containing silver chlorobromide or silver chloroiodobromide containing at least 50 mol% of silver chloride on a support. This is achieved by a silver halide photographic material characterized by having at least one layer containing (1) a water-soluble conductive polymer, (2) hydrophobic polymer particles, and (2) an epoxy curing agent.

The details of the present invention will be specifically explained below.

Examples of the water-soluble conductive polymer of the present invention include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, and a polyethylene oxide group. . Among these groups, sulfonic acid groups, sulfuric acid ester groups, and quaternary ammonium bases are preferred. The amount of conductive groups required is 5% by weight or more per polymer molecule. Carboxy groups, hydroxy groups, amino groups among the carboxyl groups, hydroxy groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, and vinyl sulfone groups contained in water-soluble conductive polymers. , an epoxy group, an aziridine group, and an aldehyde group are preferred. These groups are required in an amount of 5% by weight or more per polymer molecule. The molecular weight of the polymer is 3000-10000
0, preferably 3,500 to 50,000.

Examples of the water-soluble conductive polymer used in the present invention are listed below, but are not limited thereto.-1 Homopolymer-2 Homopolymer-6 SO, Na CH.

-7 So, Na -8 ≧L1. Na 5038a 9 OJa 0 CH.

03Na H Q SO3Na 2 So3Na 7 CH8 0 C.B.

3 CH3 So, K 4 O3Na Mmasu, bka 1 2 3 Degistran Sulfate Degree of substitution 2.0 M - 100,000 4 x:y+z-85:10:5 M#10,000 -26 7 -28 9 SO, Na 4 SO, Na 35 36 -37 0 -31 32 -33 So, Na -38 -39 0 CH.

-41 To41,000 45 Enemy! -i50,000 l] 4 [; 7- Molecular weight (in this specification, average molecular weight means number average molecular weight).

These polymers are commercially available or obtained by conventional methods ()
-! It can be synthesized by polymerizing -. The amount of these compounds added is 0.01g-10g-4
9-50 In the above 1"l-P-50, W represents the mole % of the monomer component, x, )', z.

Also, M is preferably average/ra2, particularly preferably 0.1g-5g/ra2.
m”.

These compounds can be used alone or mixed with various hydrophilic binders or hydrophobic binders to form a layer. Gelatin or polyacrylamide is particularly advantageously used as the hydrophilic binder. , and others include colloidal albumin, cellulose acetate, cello-snitole+-, polyhydric alcohol, hydrolyzed polyhinyl acede-], and heptadated geladine. Hydrophobic binders include Polymers with a molecular weight of 20,000 to 1,000,000 or more are included, including styrene-butyl acrylate-1/-acrylic acid ternary copolymer, butyl acrylate-1---acrylodiF/lyluacrylic acid ternary copolymer, methyl methacrylate-ethyl acrylate - Acrylic acid ternary copolymer polymers may be mentioned.

Next, the hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are contained in a so-called latex form that is substantially insoluble in water. This hydrophobic polymer is selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, acrylamide derivatives, methacrylamide derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination; Obtained by polymerizing. In particular, at least 30 mol% of styrene derivatives, alkyl acrylates, alkyl methacrylates
It is preferable that it be contained. Particularly preferred is 50 mol% or more.

There are two methods to make a hydrophobic polymer into a latex: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then distilling off the solvent. Emulsion polymerization is preferable because it can produce a product.

As the surfactant used during emulsion polymerization, it is preferable to use an anionic or nonionic surfactant.
It is preferably 0% by weight or less. A large amount of surfactant causes clouding of the conductive layer.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

100 Specific examples of the hydrophobic polymer of the present invention will be given below.

-1 -5 CH.

-2 -5 -3 -7 CH.

-8 CH.

-4 9 10 1 -12 CH3 0OCH3 C00C,H,-n OOH 7 113 8 9 CH.

−20 3 B)1. C-pan.

ICH2C assistant b ICH, C-pan 0OCR3 COOC2H,0H COOII 4 CH.

ICH2C□ (CH2Clten C00C,,tl.

OOH 5 CH.

CH.

N C00C4II　m OOH 6 CHl 1 2 3 L-24 L-25 -26 L-2F iCHHzCH%.

=32 C.I.

BeCH,C)li.

-(CHzCH+3 113 8 -29 -30 CH3 CH3 CD Yu So, Na 5o, Na Next, as the Evoquin curing agent used in the present invention, an epoxy curing agent containing Hashidroxy is preferable. The reaction product of tolled shrimp halohydrin is preferred.This is considered to be a mixture of synthesis method 1, but the effect and performance of the present invention is improved by suppressing the number of hydrochloride groups and the number of epoxy groups. As determined, it may be isolated or a mixture.

Preferred examples of the isolated hydroxy-containing epoxy curing agent of the present invention include compounds represented by the following general formula [E].

General formula [E] Then the general formula () Here is a specific example of 1.

X, Y, Z, II: may be integers from 0 to 50 or different -].

8”/% Oy 7*+・1・・1・“11・−C8z
Y2] -8 -10 -7 12 -13 -14 The compound represented by the formula [E] above may be dissolved in water or an organic solvent such as alcohol or acetone and added as is, or it may be added as is by dissolving it in water or an organic solvent such as alcohol or acetone. It may be added after being dispersed using a salt or a surfactant such as nonylphenoxyalkylene oxide. The preferred addition amount is 1 to 1000 mg/Ill! It is.

In the silver halide emulsion used in the light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver chloroiodobromide, etc. can be used as the silver halide, but preferably, substantially no silver iodide is used. It is silver chlorobromide that does not contain (silver iodide content o, 1 mol % or less) and contains 50 mol % or more of silver chloride. The silver halide grains may be 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 preferable example is a cube having (1001 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 7 Autographic Science (J, Photogr, S
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literatures such as Ci), 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.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used.11 Emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used alone. Alternatively, several types may be mixed. 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 primitive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, Glafkides or Zel
Ikman et al. or H. Frleser (ed.)
Die
Grundlage-under Photography
iscben Prozesse with Silbe
rha-1ogeniden, Akademich
e Verlagsgesellschaft, 19
68) 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, 7-7′-h 〉Zai>fn, 5-Mercap[・
Various stabilizers can also be used, including -17enyltetrazole, 2-mercametopenzothiazole, and the like.

In addition, if necessary, use \17 Silver Genide Solvent (such as Thioable) or Mercap! - Crystal habit control agents such as group-containing compounds and sensitizing dyes 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. If you want to remove the salts, please use the Research Disk! - It can be carried out based on the method described in Codger 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 No. 176@Ite
m17643 (December 1978) and Volume 187 I
tem18716 (November 1979), and the relevant parts are summarized in the table below.

The following is the rest: Q...＼ +ξ C' Additive type RD 17643 RD 18716 ■, Chemical sensitizer page 23, page 648, right column 2, Sensitivity 1 - increasing agent 4° Brightener 4Q 7, Sudein inhibitor page 25 Right column 650
Page left-right column 8, dye image stabilizer page 25 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 2
Pages 6-27 Same as above 13, anti-static agent
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 may be constructed by coating on one or both sides of a flexible support commonly used in photographic sensitizers. can. Pressurized flexible supports include semi-synthetic or semi-synthetic materials such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyhinyl chloride, polyethylene terephthalate, and polycarbonate. A film made of a synthetic polymer, a baryta layer, or an α-olefin polymer (for example, polyethylene, polypropyleno, ethylene 7/butene copolymer) coated or unlaminated paper may be used. 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 treatment is preferably the treatment described in JP-A-52-104913, JP-A-59-18949, JP-A-59-19940, and JP-A-59-18949.

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 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 used5. Processing such as second development is a method commonly used in the art for processing silver halide photographic materials. Various known methods can be used.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited thereto.

Example 1 Serazane, sodium chloride, and water - In a container heated to 40°C, an aqueous silver nitrate solution, 1 mol of silver halide, 2 x 10-6 mol of potassium hexachloroiridate salt, and 1 mol of silver halide were added. Adding a mixed aqueous solution of potassium bromide and thorium chloride to which 4XlO'-' moles of l\xabromorodic acid potassium salt was added by a double jet method,
Silver chlorobromide grains were prepared, and this emulsion was adjusted to pH 3,0 pAg7.
．． After adjusting the pH while maintaining the pH at 5.7 and returning it to pH 5.9, it was desalted using a conventional method.

The silver chloride bromide particles have a silver chloride composition of 50.60°7.
0,. Four types of 80 mol% were prepared.

This emulsion was gold sensitized and sulfur sensitized 1, and the following sensitizing dye (a
, ) was added at 40@g per mole of silver halide, and further 70 mg of l-phenyl-5-mercaptotetrazole per mole of silver halide, 4-hydroxy-6-methyl-1,3,3a, 7 -Tetrazaindene 1.2
g, potassium bromide 0.7 g, and gelatin were added to stop the ripening.

Sensitizing dye (a) Additives were added to the emulsion in the amounts shown below, and a latex-subbed polyethylene terephthalate support (thickness: ciooμm) was coated on the support after corona discharge. .

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer 1.0 g/m2 Tetraphenylphosphonium chloride 30 mg/m" Potassium bromide 30 +ng/m
“Saponin 200 mg/m
2 Polyethylene glycol 100 ff1g
/m” Sodium dodecylbenzenesulfonate 1.00
mg/m2 Hydroquinone 200 B/m2 Phenidone 10 B/a+2 Sodium styrene sulfonate-maleic acid polymer (Mw
= 250,000) 200 B/m2 Gallic acid butyl ester 500 B/m'5-methylbenzotriazole 30 mg/m''2-mercaptobenzimidazole-5-sulfonic acid
30 mg/m' Inatoossein gelatin (isoelectric point 4,9) 1.5 g/m" 1-(p-acetylamidophenyl)-5 mercaptotetrazole 30 mg/II+2
Silver amount 4. Ogem2 (emulsion layer protective film) An emulsion layer protective film was prepared and coated in the following amount.

Fluorinated dioctyl sulfosuccinate 300mg/
m2 Matting agent: polymethyl methacrylate (average particle size 5.5 p m) 50 mg
/m2 Silica (average particle size 3.5μm) 200
mg/m” lithium nitrate salt 30
mg/m” Potassium Bromide 25
mg/m' acid-treated gelatin (isoelectric point 7.0)
0.8 g/m2 colloidal silica 5
0 mg/m' Sodium styrene sulfonate-maleic acid copolymer 100 mg
/m2 1-Hydroxy-3,5-dichloro-5-triazine sodium salt 35 mg/m2 (antistatic layer) 30 W/m2 was applied to the support opposite to the emulsion layer in advance.
After corona discharge with a power of m1n, poly(styrene-
Butyl acrylate-glycidyl methacrylate) latex polymer was applied in the presence of hexamethylene aziridine hardener, and after corona discharge, an antistatic liquid having the following composition was applied at a speed of 33 m/min in the following amount. Apply using a roll-fit coating pan and air knife.

Water-soluble conductive polymer CP of the present invention) It is shown in Table 1.

Latex (L) Shown in Table 1.

Curing agent (E) Table II shows.

It was dried at 90°C for 2 minutes and heat-treated at 140°C for 90 seconds. A backing layer containing a backing dye having the following composition and a protective layer were then applied onto this layer.

(Backing layer) Hydroquinone 100 mg/m”
Phenidone 30 mg/m
"Latex polymer: Butyl acrylate-styrene copolymer 0.5 g/m" Styrene-maleic acid copolymer 100 mg/m" Citric acid
40 mg/m" Glyoxal 30 a+g/glum 2 benzotriazole 100 tag/a+" Styrene sulfonic acid sorta copolymer Lithium nitrate salt Bagging dye (a), (b) Ossein gelatin Maleic acid 200 mg/m2 30 +ng/m+2 (e) 2.0 g/m2 (b) 03K SO3 at 40 + mg/m2 The sample obtained as above was exposed and developed using the developer and fixer shown below, followed by post-evaluation. <Developer formula Hydroquinone 25 g
-71yl-4,4dimethyl-3pyrazolidone 0.4
G bromide,
3g 5-methylbenzotriazole 0.3g 5-=trointazole 5g diethylaminopropane-2-diol lo
g Potassium sulfite 90 g5-
Sodium sulposalilate 5 It was finished to IQ with aqueous sodium diaminetetraacetate.

p[( was adjusted to 10.8 with caustic soda.

<Fixer prescription. 1'2 (Composition A) Ammonium 1,000 sulfate (72.5w% aqueous solution) 240 mQ 1, 7 g 6, 5 g g g 13, , 6 m Q Tenthorium sulfite Sothorium acetate trihydrate Octacid Citric acid Acetic acid ( 90w% (Composition) Condensed water (ion exchange water) Sulfuric acid (50w% aqueous solution) Aluminum sulfate (AQ203 equivalent content is 8, 1w%)
aqueous solution) 20 of the above composition in 500 I of water when using a fixer.
mU 3.0 g aqueous solution) Dissolved in thorium dihydrate in the order of composition and heated with lQI at 1°C. The pH of this fixer was about 4.6.

<Development processing conditions> ( ] degree) (temperature) (time) development
34°C 15 seconds fixation 33°C
Rinse with water for 10 seconds at room temperature 1.0 The evaluation value was determined as follows (・The results are shown in Table 1).

Performance evaluation was conducted using the following method.

A net film is placed on the base for pasting the vinyl pole evaluation, and the periphery of the net film is further fixed with a transparent sconti tape for plate making, and after exposure and development processing, the time when no vinyl poles occur is rated as 5. The highest and worst level was set as 1.

Incidentally, if it is 3 or less, there is a practical problem.

Stability over time Divide each sample into two halves and store the -half at 23°C, 548% RH't.
'After controlling the humidity, it was sealed and packaged with a moisture-proof material laminated with polyvinyl acetate (thickness 100 μm) at 40°C 150%.
Table 1 shows the difference in sensitivity from the same day after heat treatment for 5 seconds in a RH humidifier.
From the results, it is clear that the samples of the present invention have higher storage stability over time and fewer pinholes than the comparative samples. In addition, the surface resistivity of the sample was adjusted to 25°Cl2O%RH.
As a result of IM measurement, Sample No. 1 was on the order of 10''070 m, and Sample No. 2-14 was on the order of 1010 Ω/am.

[Effects of the Invention] According to the present invention, it is possible to provide a silver halide photographic material that has excellent storage stability over time, has less sensitivity fluctuations and fogging under high temperature and high humidity, and has less pinholes. Ta.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having, on a support, at least one gold-sensitized silver halide emulsion layer containing silver chlorobromide or silver chloroiodobromide containing at least 50 mol % of silver chloride, [1] Water-soluble conductive polymer, [2]
A silver halide photographic material comprising at least one layer containing hydrophobic polymer particles and [3] an epoxy curing agent.