JPH0413133A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration in antistatic ability and unequal rear discharge when humidity is high by forming antistatic layers consisting of a specific reaction product on a substrate and subjecting the rear of the surface coated with the antistatic layers to a treatment with UV light. CONSTITUTION:At least one layer of the antistatic layers consisting of the reaction product of a water-soluble conductive polymer, hydrophobic latex and epoxy hardener are provided on the substrate and the rear of the surface coated with the antistatic layers is subjected to the treatment with the UV light. The water-soluble conductive polymer is exemplified by a polymer having at least one conductive group selected from a sulfonic acid group, sulfate, etc. The unequal rear discharge and the deterioration in the antistatic ability when the humidity is high are prevented in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material having an antistatic layer, and particularly to a silver halide photographic material having excellent antistatic ability and film adhesion.

[Background of the invention]

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

For example, supports such as polyethylene terephthalate are generally used in silver halide photographic light-sensitive materials, but they 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 substances such as dust adhere to it, which causes pinholes and significantly degrades the quality. It will be. 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, fluorosurfactants are often used to adjust the charge series, or conductive polymers are used to improve conductivity.
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.

For this reason, for example, JP-A Nos. 55-84658 and 61-1
No. 74542 proposes an antistatic layer comprising a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group, and a polyfunctional aziridine. Although this method allows antistatic properties to remain after treatment, this antistatic layer has the disadvantage of poor adhesion to the silver halide emulsion layer, backing layer, etc. applied thereon. ing. This tendency becomes more noticeable at high temperatures, and at temperatures above 23° C. and 60% RH, it deteriorates to a level that makes it unusable. An effective method for improving the film adhesion of such a conductive layer is corona discharge to the surface on which the conductive layer is overlaid, and this treatment significantly improved the film adhesion.

However, a new problem has arisen: back discharge unevenness.

Back discharge unevenness is when corona discharge is applied on the support.
This is an unevenness that appears when the wettability of the back side changes partially, resulting in a coating failure of the emulsion layer and backing layer coated on top of it, and the higher the corona discharge voltage, the more severe the unevenness becomes. .

The shape of the unevenness varies, but the main one is a spot-shaped round unevenness. In order to suppress the occurrence of such unevenness, it is necessary to lower the corona discharge voltage, but from the viewpoint of improving film adhesion, it is impossible to lower the discharge voltage, and urgent measures are required.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver decagenide photographic material that does not deteriorate in antistatic ability even at high humidity and has excellent antistatic ability without uneven back discharge. It is.

[Structure of the invention]

The above-mentioned object of the present invention is to have an antistatic layer on a support, comprising at least one layer of a reaction product of a water-soluble conductive polymer, a hydrophobic latex, and an epoxy curing agent, and to coat the antistatic layer. This is achieved by using a silver halide photographic material whose back side is treated with ultraviolet light.

The details of the present invention will be explained below.

The water-soluble conductive polymer of the present invention has at least one group selected from sulfonic acid groups, sulfuric acid ester groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups.
Examples include polymers having two electrically conductive groups. The amount of conductive groups required is 5% by weight or more per polymer molecule. The water-soluble conductive polymer may contain a hydroxy group, an amine group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group.

The molecular weight of the polymer is 3000 to 100000,
Preferably it is 3500-50000.

Examples of water-soluble conductive polymer compounds used in the present invention are listed below, but the present invention is not limited thereto.

SO, Na CH3 CH.

SO, Na CH.

SO,K Dextran sulfate substitution degree 3.0 Mn-500000 So, Na Dextran sulfate substitution degree 2.0 Mn-100000 A-21 So, Na Mn=10000 In addition, in the above A-1-A-21, Mn is average molecular weight (in this specification, average molecular weight indicates number average molecular weight)
It is based on the measured value by GPC expressed in terms of polyethylene glycol.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are composed of so-called latex, which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, etc. in any combination. In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.

As the hexamer having an amide group to be included in the latex of the present invention, those represented by the following formula 1'l) are preferable.

General formula CI) CH2=C [In the formula, R represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. L represents a divalent group, and 3 represents 0 or l. RI+R
2 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms.

] Specific examples of the seven potions of the present invention will be given below.

l.

CH, -CH ONHZ CB, Tomi C ONH2 3.

C) I, =CH C0NHCHs There are two methods to make a hydrophobic polymer into latex form: emulsion polymerization, dissolving a solid polymer in a low-temperature solvent, finely dispersing it, and then using the solvent. Emulsion polymerization is preferred because it produces particles with fine and uniform particle sizes.

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

As a method for introducing a polyalkylene oxide chain into the hydrophobic polymer latex of the present invention, a method by copolymerizing a monomer having a polyalkylene oxide chain is preferred.

As the 7-mer, those represented by the following formula [M] are preferred.

General formula CM) RI CI, Maro C -X Here, R represents a hydrogen atom, a halogen atom, a lower alkyl group, -CH, -L-X, and L is -COO-R.

-CON-1 or an aryl group having 6 to 12 carbon atoms. R is a hydrogen atom, an aryl group, a lower alkyl group,
, and X represents fR2-Of nR3. R2 is -(J, CH2- CHzCHiCHzCl(z -C)IzCHCHz-
R1 represents a hydrogen atom, a lower alkyl group, an alkylsulfonic acid or a salt thereof, an alkylcarboxylic acid group or a salt thereof.

n is 2 or more It is an integer less than or equal to 70.

Ctl, -CH αphantom(CH,C)1.0)i-(CH,CICl0)-
Door CH3 CH.

CH.

■ CH.

C0N))(CH,CH,0)-ssO3N&CH.

M-26 CH.

CH.

CH.

CH3 Specific examples of the latex of the present invention are listed below.

CH.

CH.

CH.

B-13 B-17 Hr CHl Coo(CJmO)isO3Na Hs C.O.

=26 SO, Na The epoxy compound of the present invention includes: hydroxy Those containing groups or ether condensations are preferred.

Specific examples of the epoxy compound of the present invention will be given below.

α force CH.

C00C,H,OH α force (C1l(40)l.H HO E-5 The film surface pH of the conductive layer of the present invention is preferably 8.0 or less, but even if it is too low, it is preferable from the viewpoint of film stability. No. Particularly preferably 3.0 to 7.5.

The conductive layer of the present invention may be located closer to the support than the photosensitive layer, or may be located on the opposite side of the support to the photosensitive layer, ie, on the back surface.

In the present invention, a conductive layer is coated on a transparent support.

Any transparent support for photography can be used, but preferably,
Polyethylene terephthalate or cellulose triacetate made to transmit more than 90% of visible light.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a slight amount of dye may be added to give them a blue tint so as not to substantially inhibit light transmission. good.

The support of the present invention may be coated with a subbing layer containing a latex polymer after being subjected to a corona discharge treatment. Corona discharge treatment has an energy value of I W = l K
W/ (m"·■in) is particularly preferably applied. Also, it is particularly preferable to perform a corona discharge treatment again after coating the latex undercoat layer and before coating the rollable layer.

The energy value of the corona discharge treatment applied to the conductive layer is 5.
W=l KJ/(1·+nin) is particularly preferably applied.

Further, the ultraviolet light treatment applied to the back surface of the conductive layer overlapping surface is preferably applied with ultraviolet light having wavelength peaks of 185 na+ and 235 nm.

Incidentally, a low-pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. is preferably used for the ultraviolet light treatment, and the treatment time is preferably 1 second to 10 minutes, more preferably 5 seconds to 2 minutes.

The present invention can be applied to photosensitive materials formed on a support. For example, silver halide color photosensitive materials,
These include photosensitive materials for X-rays and photosensitive materials for plate making.

The silver halide emulsions used in the present invention are, for example, U.S. Pat.
No. 89.380, No. 2, No. 058,626, No. 2,
No. 118.411, Japanese Patent Publication No. 43-4133, U.S. Pat.
Compounds described in specifications or publications such as No. 825 and Japanese Patent Publication No. 49-13566, preferably, e.g.
．． 6-drimethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5.6-titramethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-5-triazolo(
1,5-8) Pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxyn-S-+-riazolone(1,5-a)pyrimidine, 5-methyl -6-promorph-hydroxy=S-)
Riazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (l-7enyl-5-mercaptotetrazole, 2-mercaptobenzthiazole) , benzotria 1-l!
(5-bromopenzitriazole, 5-methylbenzitriazole), benzimidazoles (6-nitropenzimidazole), etc. can be used for stabilization.

The silver halide photographic material and/or developer according to the present invention may contain an amino compound.

Further, in order to improve the developability, a developing agent such as phenidone or hydroquinone or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer can contain a developing agent or an inhibitor.

A hydrophilic colloid which is particularly advantageously used in the present invention is gelatin.

The gelatin used in the present invention can be treated with either alkali treatment or acid treatment, but when using ossein gelatin, it is preferable to remove calcium or iron. The preferred content of calcium is 1 to 9.
99 ppm, more preferably 1 to 500 ppm
m, and the iron content is preferably 0.01 to 50 ppm, more preferably (Ll - 10 ppm).The method for adjusting the amount of calcium and iron in this way is to pass an aqueous gelatin solution through an ion exchanger. can be achieved.

Developing agents used in developing the silver halide photographic material according to the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2
, 3-dibromohydroquinone, 2.5-diethylhydroquinone, catechol, 4-chlorocatechol, 4
-7enylcatechol, 3-methoxy-catechol,
Examples include 4-acetyl-pyrogallol and sodium ascorbic acid.

Further, as HO (CH=CH), NHw type developers, ortho and para aminophenols are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro -6-phenylphenol, N-methyl-p-aminophenyl, etc.

Further, examples of H,N-(CH-C11), -NH, type developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, and N-diethylaniline. -(4-amino-3-methylphenylindiamine, etc.).

Examples of the heterocyclic developer include l-phenyl-3-pyrazolidone, l-722-4,4-dimethyl-3-pyrazolidone, and l-7znyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. 3-pyrazolidones such as
Examples include l-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

T-H. The Theory of the Photographic Process, 4th Edition, by James.
of Photographic Process F
291-334 and Journal of the American Chemical Society.
Developers such as those described in Che+iical Society, Vol. 73, p. 3.100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. Hydroxylamine and hydrazide compounds can also be used as preservatives, and in this case, the amount used should be the same as that of the developer.
5 to 500 g per Q is preferred, more preferably 20
~200g.

Further, the developer may contain glycols as an organic solvent, and such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
Among them, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g per 1Q of developer solution. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material according to the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The pH value of the developer having the above composition is preferably 9 to 13.
However, from the viewpoint of storage stability and photographic properties, the pH value is 1O~1
A range of 2 is more preferred. Regarding cations in the developer, it is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.

The silver halide photographic material according to the present invention can be processed under various conditions. As for the processing temperature, for example, the development temperature is preferably 50°C or lower, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds. often has positive effects. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes include plate development,
It may be a so-called manual development process such as frame development, or a mechanical development process such as roller development or hanger development.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples.

Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example 1 After corona discharge, the undercoated polyethylene terephthalate was corona discharged again, and 10 cc/@2 of the epoxy curing agent (E) shown in Table 1 was added to the antistatic liquid having the following composition.
It was coated with an air knife coater at a speed of 50 m/+in so that

Water-soluble conductive polymer (A) Hydrophobic polymer particles (B) ammonium sulfate Hardening agent (E) The above composition is defined as lQ.

Note that E was added while coating.

Drying air temperature 90℃, overall heat transfer coefficient 25Kcal/(+n2
・hr・°C) under parallel flow drying conditions for 30 seconds.

Next, after performing corona discharge on the back side of the conductive column layer coating surface, subbing treatment, and corona discharge again, a gelatin solution having the following composition was applied under the same conditions as the conductive layer. Heat treatment was performed at 140°C for 90 seconds.

Ossein gelatin 9g/Q Dodecylbenzenesulfone 60g/Q 0gIQ 0, 5g/Q 12g/ff 200g/Q α) CH = CH 2 Finish to H2 with the above composition.

The support obtained in this way is divided into three parts, and the back side is untreated, the conductive layer is subjected to corona discharge, the back side is untreated, the conductive layer is subjected to corona discharge, and then the back side is treated with ultraviolet light. .

Three types of treatments were performed.

These samples were evaluated for back discharge unevenness by the following method, and the results are shown in Table 1.

Back discharge unevenness test When steam is applied to the gelatin layer coated surface of each support, unevenness can be seen due to differences in wettability. This number, thick hardening agent (H) 120mg#t Table-1 ◎: No back discharge unevenness. O: Appears but can be used △: Problematic level

Example 2 (Sample Preparation) Under the same conditions as Example 1, a support consisting of a 100μ-thick polyethylene terephthalate paste coated with a conductive layer and a gelatin layer was divided into 5 parts and subjected to the following treatment. .

Conductive layer overlapping side Back side 11 Untreated Untreated 2, Corona lOW Untreated 3, Corona 5
0W Untreated 4, Corona 101
Ultraviolet light treatment 5, Corona 50W
For ultraviolet light processing, the conductive layer was coated on the emulsion layer (EC) side and the backing layer (BC) side. O in Table 2 below represents this coating surface.

(Emulsion Preparation) Grains containing 10-' mol of rhodium per mol of silver were prepared by the controlled double jet method in an acidic atmosphere at pH 3.0. Particle growth was performed in a system containing 301 Ig of benzyladenine per 1 a of 1% aqueous gelatin solution. After mixing silver and halide, 6-methyl-4-hydroxy-1,3,3a,7tetrazaindene was added in an amount of 600+sg per mole of silver halide, followed by washing with water and desalting.

Next, 60 mg of 6-methyl-4-hydroxy-1,3,3a,7-titrazaindene was added per mole of silver halide, followed by sulfur sensitization. 6-methyl-4-hydroxy-1,3,3a as a stabilizer after sulfur sensitization;
7-Chitrazaindene was added.

(Silver Halide Emulsion Layer) Additives were added to each of the above emulsions in the amounts shown below, and coated onto the support.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0g/■2Tetraphenylphosphonium chloride 30mg/+"Saponin 200■g/lI2
Polyethylene glycol 100g / @
1 Sodium dodecylbenzenesulfonate 100mg/
i+”Hydroquinone 200mg/m”
Phenidone 100 Sou gets”
Sodium styrene sulfonate-maleic acid polymer (M
w=250,000) 200mg/+m" Gallic acid butyl ester 500mg/m" Hydrazine compound 20 mg/I@
25-methylbenzotriazole 30mg/
■22-mercaptobenzimidazole-sulfonic acid 30a+g/+a
“Inert ossein gelatin (isoelectric point 4.9) 1, 5
g/m" 1-(p-acetylamidophenyl)-5-mercaptotetrazole Silver amount Tetrazolium compound 30 + ag/m2 2.8 g/m" (Emulsion layer protective film) Prepared as an emulsion layer protective film to have the following amount. It was distributed.

Fluorinated dioctyl sulfosuccinate 3001g/
la'' Matting agent: Polymethyl methacrylate (average particle size 3.5 μm) 100 mg
/m” lithium nitrate salt 30+g/
m” acid-treated gelatin (isoelectric point 7-0) 1.2
g/ls” colloidal silica 50m
g/■2 Sodium styrene sulfonate-maleic acid copolymer 100 g/■2 (
Backing layer) A backing layer containing a backing dye having the following composition was coated on the support opposite to the emulsion layer.

The gelatin layer contains glyoxal and l-oxy-3,5-
It was hardened with dichloro-5-)riazine sodium salt and E-5, a hydroxy-containing epoxy compound.

(Backing layer composition) Hydroquinone 100mg/m"
Phenidone 30mg/+" Latex polymer: Butyl acrylate-styrene copolymer 0.5g/+*"Styrene-maleic acid 1 combination 100 gems" Citric acid
40g/s! Benzotriazole 100mg/■2 Styrenesulfonic acid-maleic acid copolymer 100mg/m”
Lithium nitrate salt 30mg/m" Backing dye (a) (b After the treated film test and back discharge unevenness, a surface resistivity test and evaluation were performed.

<Developer formulation> Hydroquinone 1-phenyl-4,4 dimethyl-3 Pyrazolidone Sodium bromide 5-Methylbenzotriazole 5-Nitroindazole Diethylaminopropane-1,2-diol Potassium sulfite 5-Sulfosalicylate Sodium ethylenediaminetetraacetate In water It was finished in la.

The pH was adjusted to 11.5 with caustic soda.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5w% aqueous solution) Sodium sulfite 5g 0.4g g 0.3g 0.05g 0g 0g 5g g 40mQ 7g Sodium acetate trihydrate 6.5g Boron I
! 6゜Sodium citrate dihydrate 2g acetic acid (
90w% aqueous solution) 13.6+Q (composition) Pure water (ion exchange water) 17■Q Sulfuric acid (50w% aqueous solution) 3.0g
20 g of aluminum sulfate (AQ20. aqueous solution with a converted content of 8.1 W%) When using the evaluator solution, it was dissolved in 500 l of water in the order of the above composition A1 and finished to lQ before use. The pH of this fixer
was about 5.6.

<Development processing conditions> (Process) (Temperature) (Time) Development
Fixing at 40°C for 8 seconds, washing with water at 35°C for 8 seconds, and room temperature for 10 seconds.The back surface specific resistance was measured to evaluate film attachment and back discharge unevenness, and the results are shown in Table 2.

The surface resistivity was measured using a terra ohmmeter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. at 23°O and 55%RH.

Evaluation of film attachment: Lightly scratch a sample that has been conditioned at 23°C and 80% RH.
Cellophane tape was attached from above, and when it was peeled off, evaluation was made based on the degree of peeling relative to the area of the cellophane tape.

A: No peeling B: Slight peeling C: Approximately half peeling D = Peeling over the entire surface (evaluation of back discharge unevenness) Emulsion layer (E C) coated surface: A sample with an average solid density of 0.7 was prepared and visually evaluated. did.

Backing layer (BC) coated surface: Difference in dye concentration was visually evaluated based on brightness.

Visual evaluation is m! It is expressed as the number of uneven hits.

a: Ob: 1-2 c: 3-10 d: 10 or more table-
From the results of 2, it can be seen that according to the method of the present invention, excellent antistatic ability is maintained even after development processing, and film formation and back discharge unevenness are also good.

In particular, the corona discharge voltage to the conductive layer is increased, and the back surface is treated with corona discharge.l-5,1-10,2-5,2-
It can be seen that 10,3-5,3-1O is excellent in both film formation and back discharge unevenness.

Furthermore, similar effects were obtained even when the tetrazolium compound in the emulsion layer was replaced with the following hydrazine compound.

Hydrazine Compound [Effects of the Invention] The present invention provides an excellent charging silver halide photographic light-sensitive material that exhibits excellent film-forming properties even at high humidity, does not cause back discharge unevenness failure, and does not deteriorate in antistatic ability even after development processing. A method for applying a preventive layer could be provided.

Claims (1)

[Claims] at least one layer of a water-soluble conductive polymer on the support;
1. A silver halide photographic material comprising an antistatic layer made of a reaction product of a hydrophobic latex and an epoxy curing agent, the back side of the surface on which the antistatic layer is coated being treated with ultraviolet light.