JP3124082B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having improved transportability in a scanner, a facsimile plotter or the like.

[0002]

2. Description of the Related Art In recent years, the use of silver halide photographic materials has been increasing in photolithography. Also,
The market demands a shorter delivery time for product delivery. In order to shorten the delivery time, it is necessary to reduce the labor of the exposure and processing steps and to perform these steps in a short time. For these steps, a scanner or a facsimile plotter is used. When using such a scanner or facsimile plotter, a problem is a transport failure in the scanner or facsimile plotter. Delivery failures cannot be shortened due to defective transport.

[0003] Generally, gelatin is used as a binder in a photographic light-sensitive material. Under high-humidity conditions, the photographic light-sensitive materials are liable to stick to each other, resulting in poor conveyance in a scanner or a facsimile plotter.

In order to prevent transport failures in these scanners and facsimile plotters, a matting agent has been added to the outermost layer of the photographic light-sensitive material. However, transportability under high humidity conditions has been improved. Was not enough. In addition, when the amount of the matting agent is increased in order to improve the above-described improvement effect, the transparency after the development processing is significantly deteriorated, and the slipperiness is deteriorated, which contradicts the intention, thereby deteriorating the transportability. The problem arises.

It is disclosed in US Pat. Nos. 3,042,522 and 3,055 that a sliding agent is incorporated into a color photographic light-sensitive material to improve the running property in a photographing machine, a printer, and a camera.
No. 80,317, British Patent Nos. 1,466,304 and 1,143,118, etc., but the transportability in a scanner or facsimile plotter is improved only by improving the slipperiness. However, these means were insufficiently effective for improving the transportability in a scanner or a facsimile plotter.

Further, JP-A-61-42653 discloses that a polymer matting agent having an average particle diameter of 3 μm or more, preferably 3.5 to 6.0 μm, and a silicone-based slipping agent are used in combination to provide an antistatic property and a slipping property. Although improvements are described, these techniques were also insufficiently effective in improving transportability in scanners and facsimile plotters.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having improved transportability in a scanner or a facsimile plotter.

[0008]

The object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and at least one backing layer on the other side. The uppermost layer only on the backing layer side contains a matting agent having an average particle size of 10 μm or more, and the degree of swelling on the backing layer side is 3 or less, and the uppermost layer on the emulsion layer side and / or the uppermost layer on the backing layer side And a silver halide photographic light-sensitive material characterized by containing a sliding agent.

When a large particle size matting agent is used in a photographic light-sensitive material, it is expected that the surface roughness will increase, the slip property will deteriorate, and the transportability will deteriorate. In the present invention, contrary to this prediction, by using a matting agent having an average particle size of 10 μm or more and adopting the constitution of the present invention, the transportability in a scanner or a facsimile plotter could be improved.

Hereinafter, the present invention will be described in detail.

Representative examples of the sliding agent used in the present invention include, for example, US Pat. No. 3,042,522,
UK Patent No. 955,061, US Patent No. 3,080,
No. 317, 4,004,927, 4,047,9
Nos. 58 and 3,489,567; British Patent No. 1,14
3,118, JP-A-60-140341 and the like, silicone-based sliding agents, U.S. Pat. No. 2,454,043
No. 2,732,305, No. 2,976,148
No. 3,206,311; German Patent No. 1,284,
No. 295, 1,284,294, etc., higher fatty acid-based, alcohol-based, acid amide-based sliding agents, British Patent No. 1,263,722, US Pat. No. 3,933,516.
No. 2,588,76
No. 5,3,121,060, British Patent No. 1,19
No. 8,387, etc., ester-based and ether-based sliding agents, U.S. Pat. Nos. 3,502,473 and 3,042.
No. 222, a taurine-based slip agent and the like.

The following are specific examples of the sliding agent used in the present invention.

[0013]

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[0014]

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[0015]

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[0016]

Embedded image These sliding agents may be added in advance together with the dispersant used in the synthesis of the organic matting agent.

The matting agent contained in the uppermost layer on the backing layer side in the present invention is a powder of an organic or inorganic compound. Specific examples of the organic compound include a water-dispersible vinyl polymer such as polymethyl methacrylate, cellulose acetate propionate, and starch. Particularly, methyl methacrylate, glycidyl acrylate, spherical matting agents of water-dispersible vinyl polymers such as homopolymers of acrylates such as glycidyl methacrylate, or copolymers of these acrylates or other vinyl monomers. preferable. Examples of the inorganic compound include silver strontium barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, boron nitride, hollow silica (manufactured by Nippon Philite), ethylene tetrafluoride,
Titanium oxide and the like are preferably used. The addition amount is 1mg /
m ² ~1,000mg / m ^2, preferably 50 mg / m ² to 500
mg / m ² . The average particle size is 10 μm or more, preferably 30 μm or less. If it is larger than 100 μm, the matting agent tends to peel off from the film surface, which may cause a failure of the plotter or the like, which is not preferable. The particle size can be measured by an electron micrograph or a Coulter counter.

The degree of swelling on the backing layer side is 3 or less.
However, it is particularly preferably 2 or less. The degree of swelling is given by
Is shown.

[0019]

(Equation 1) The silver halide emulsion used in the light-sensitive material of the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method, and preferably has a particle size of 0.2 μm or more and 0.5 μm or less.

In the silver halide grains used in the emulsion of the present invention, a water-soluble rhodium salt and a water-soluble iridium salt can be added in the course of forming the grains, and can be contained inside the grains and / or on the grain surfaces. The addition amount is preferably from 10 ^-6 to 10 ^-9 mol per mol of silver halide.

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 and the surface layer of the grains. May be particles formed mainly on the surface, or particles formed mainly inside the particle.

The shape of the silver halide grains according to the present invention is arbitrary.
Anything can be used. One preferred example is
It is a cube having a {100} plane as a crystal surface. Ma
U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737, etc., The Journal of Photography
J. Photoscience (J. Photogr. Sci).2
1. 39 (1973).
Particles having a shape such as octahedral, tetrahedral, dodecahedral, etc.
Can also be used. Furthermore, the 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, emulsions having a wide grain size distribution (referred to as polydispersed emulsions), and emulsions having a narrow grain size distribution (monodispersed emulsions). ) May be used alone or in combination. Further, a polydisperse emulsion may be mixed.

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

In the present invention, a monodisperse emulsion is preferred.
As the monodispersed silver halide grains in the monodispersed emulsion, the weight of silver halide contained within a grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. It is preferably 70% or more, more preferably 80% or more.

Here, the average particle size defines the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri becomes maximum. (Three significant digits and the least significant digit are rounded off.) The particle size referred to here is the diameter of spherical silver halide grains, or the projected image of grains other than spherical. This is the diameter when converted to a circular image of the same area.

The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter or the projected area on the print. (The number of particles to be measured is 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention have a monodispersity of 20 or less, more preferably 15 or less, as defined by Formula 2. belongs to.

[0029]

(Equation 2) Here, the average particle diameter and the particle diameter standard deviation are determined from ri defined above. Monodispersed emulsions are described in JP-A-54-485.
Nos. 21, 58-49938 and 60-1229
It can be obtained with reference to JP-A-35-35 and the like.

The photosensitive silver halide emulsion can be used as it is, without chemical sensitization, as it is, a so-called "primitive" emulsion, but is usually chemically sensitized.

For chemical sensitization, the above-mentioned book by Glafkides or Zelikman et al. Or edited by H. Frieser
Die Grundla
gen der PhotographischenProzesse mit Silberhalogen
iden, Akademische Verlagsgesellschaft, 1968).

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, and a method using gold or another noble metal compound can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines and other compounds can be used, and specific examples thereof are described in U.S. Pat. Nos. 1,574,944 and 2,410, 689
No. 2,278,947 and No. 2,728,668
No. 3,656,955. Examples of the reduction sensitizer include stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, and silane compounds. Specific examples thereof are described in US Pat.
7,850, 2,419,974, 2,51
No. 8,698, No. 2,983,609, No. 2,983,
610 and 2,694,637.

In order to sensitize noble metals, complex salts of metals of Group VII of the periodic table such as platinum, iridium and palladium can be used in addition to the gold complex salts, and specific examples thereof are described in US Pat. No. 2,399,083. No. 2,448,060 and British Patent No. 618,061.

The conditions such as pH, pAg and temperature at the time of chemical sensitization are not particularly limited, but the pH value is 4 to 9, especially 5 to 8
The pAg value is preferably maintained at 5 to 11, particularly preferably 7 to 9. Further, the temperature is preferably from 40 to 90C, particularly preferably from 45 to 75C.

The photographic emulsion used in the present invention can be used in combination with the above-described sulfur sensitization and gold / sulfur sensitization, as well as a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound. .

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

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole And various stabilizers such as 2-mercaptobenzothiazole and the like. If necessary, a silver halide solvent such as thioether, or 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 the silver halide grains is completed, or may be kept contained. The removal of the salts can be performed based on the method described in Research Disclosure 17643.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a reduction in sensitivity and generation of fogging during the production process, storage or processing of the silver halide photographic material.

An example of a compound that can be used is described by K. Mees,
The Theory of the Photographic Process, 3
Edition, 1966).

For more detailed examples and other uses thereof, see, for example, US Pat. No. 3,954,47.
No. 4, 3,982,947, 4,021,248
Or JP-B-52-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention contains an alkyl acrylate described in US Pat. Nos. 3,411,911 and 3,411,912 and JP-B-45-5331 in a photographic constituting layer. A system latex can be included.

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, US Pat. No. 2,960,404, JP-B-43
-4939, West German Application Publication No. 1,904,604,
JP-A-48-63715, Belgian patent 762,8
33, U.S. Pat. No. 3,767,410, Belgian Patent 588,143,
For example, aldehyde-based hardening agents such as styrene-sodium maleate copolymer and dextran sulfate,
Various hardeners such as epoxy type, ethyleneimine type, active halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, and acyloyl type, and ultraviolet absorbers include, for example, US Pat. No. 253,921, British Patent 1,309,349
The compounds described in each of the specifications, particularly 2- (2 '
-Hydroxy-5-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t
-Butylphenyl) benzotriazole, 2- (2-hydroxy-3'-t-butyl-5'-butylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and the like can be mentioned. Further, as coating aids, emulsifiers, improvers of permeability to processing solutions, etc., defoamers and surfactants used for controlling various physical properties of photosensitive materials, British Patent No. 548,532, and the like. No. 1,216,389, U.S. Pat. Nos. 2,026,202 and 3,514,293,
JP-B Nos. 44-26580, 43-17922, 43-17926, 43-3166, 48-2
No. 0785, French Patent No. 202,588, Belgian Patent No. 773,459, JP-A-48-101118 and the like can be used as anionic, cationic, nonionic or amphoteric compounds. Of these, anionic surfactants having a sulfone group, such as succinate sulfonates and alkylbenzene sulfonates, are particularly preferred. Examples of antistatic agents include JP-B-46-24159 and JP-A-48-89979.
Nos. 2,882,157 and 2,972,5
No. 35, JP-A-48-20785 and JP-A-48-4313.
No. 0, No. 48-90391, JP-B-46-24159
And JP-A-46-39312, JP-A-48-43809, and JP-A-47-33627.

The pH of the photographic emulsion coating solution is preferably in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that the pH of the coating liquid obtained by mixing the coating liquids of the respective layers at a coating amount ratio is in the range of 5.3 to 7.5. If the pH is lower than 5.3, the hardening progresses slowly, which is not preferable. If the pH is higher than 7.5, photographic performance may be adversely affected, which is not preferable.

Various additives can be further used in the light-sensitive material of the present invention according to the purpose. These additives are
For more details, Research Disclosure (RD)
It is described in Vol. 176, Item 17643 (December, 1978) and Vol. 187, Item 18716 (November, 1979).

[0046]

[Table 1] The photographic processing of the silver halide photographic light-sensitive material according to the present invention comprises:
There is no particular limitation, and various methods can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The developing agent used in the black-and-white developer used in the present invention is preferably a dihydroxybenzene ring (for example, hydroquinone), a 3-pyrazolidone (for example, 1-phenyl-3-pyrazolidone), Phenols (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination.

The silver halide photographic material of the present invention can be processed with a developer containing imidazoles as a silver halide solvent. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, etc., and further, if necessary, a dissolution aid, a color tone agent, a development accelerator,
It may contain a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent and the like.

Also, a so-called "lith type" developing process can be performed. As a special type of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion, and the light-sensitive material is processed with an aqueous alkali solution to perform development. Hydrophobic developing agents can be included in the emulsion layer by the method described in Research Disclosure No. 169 or the like. Such a development process may be combined with a silver salt stabilization process using a thiocyanate.

As the fixing solution, those having a commonly used composition can be used. The fixer may contain a water-soluble aluminum salt as a hardener.

Exposure to the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, purpose of use, and the like. Tungsten, fluorescent lamp, arc lamp, mercury lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser Various types of light sources such as light, electron beams, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

As for the exposure time, in addition to normal exposure of ^1/1000 to 100 seconds, short-time exposure of 1/10 ^-4 to 1/10 ^-9 seconds can be applied to xenon flash, a cathode ray tube, and laser light.

[0053]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of coating solution for backing layer)
After dissolving in 1 liter of water, 1 g of the following formula (dye) was added, 20 g of saponin was used as a surfactant, 20 g of a copolymer of butyl acrylate and vinylidene chloride was used as a polymer latex, and styrene was used as a thickener. It adjusted by adding 2.5 g of maleic anhydride copolymers.

[0054]

Embedded image (Preparation of coating solution for backing protective layer) Gelatin 400 g
Was dissolved in 600 ml of water, a matting agent was added as shown in Table 3, and 1% of 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate was used as a spreading agent.
3 g of the aqueous solution was added, and a slipping agent was further added as shown in Table 3 for adjustment. (Preparation of Coating Solution for Emulsion Layer) An aqueous solution in which gelatin and sodium chloride were dissolved was kept at 40 ° C., and an aqueous solution of silver nitrate and potassium hexachloroiridate were added to the aqueous solution at a concentration of 6 × 10 ⁻⁷ mol per mol of silver halide. And a mixed aqueous solution of potassium bromide and sodium chloride to which a hexabromorhodium salt is added in an amount of 4 × 10 ⁻⁸ mol per mol of silver halide is added by a double jet method. Silver chlorobromide particles containing 35 mol% of silver (distribution area: 9%, cubic, particle size: 0.25 μm) were adjusted to pH 3.0,
The pH was adjusted while maintaining the pAg at 7.7, and after the pH was returned to 5.9, desalting was carried out by a conventional method, and 5 mg of the following mixture A was added per 1 mol of silver halide.

This emulsion was sensitized with gold and sulfur, and the following sensitizing dye (a) was added in an amount of 60 mg per mol of silver halide, and 70 mg of 1-phenyl-5-mercaptotetrazole was added per mol of silver halide. 4-hydroxy-6-methyl-
After adding 1.2 g of 1,3,3a, 7-tetrazaindene and further adding gelatin to stop ripening, 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin,
As a thickener, 2 g of a styrene-maleic acid copolymer and 3 g of a polymer latex of ethyl acrylate were added and adjusted.

[0056]

Embedded image

[0057]

Embedded image (Preparation of Coating Solution for Emulsion Protective Layer) 10 g of potassium bromide was added to an aqueous solution of 500 g of gelatin, and 4 g of a 1% aqueous solution of 1-decyl-2- (3-isopentyl) succinate-2-sulfonate as a spreading agent was added. The matting agent and the slipping agent were added and adjusted as shown in Table 2.

Using a backing layer and a backing protective layer on one side of a 100 μm-thick polyethylene terephthalate base which had been subjected to a subbing process using each of the above coating solutions, the respective gelatin coating amounts were 2 g / m ² and 1 g / m ² . ² so as to be simultaneously coated, followed emulsion layer on the other, the emulsion protective layer, the silver amount of 3.8 g / m ² of the emulsion layer, the amount with gelatin 1.5 g / m ^2, the emulsion protective layer gelatin Co-application was performed so that the coating weight was 1.0 g / m ² .

The emulsion protective layer was added with 8 mg of formalin per gram of gelatin relative to the total gelatin on the emulsion layer side, and the backing protective layer was added with a hardener as shown in Table 4.

The sample thus obtained was processed into a sheet product, and the facsimile plotter FT201-RDA was used.
A prototype of an automatic transfer machine having the same transfer mechanism as that manufactured by NEC Corporation was manufactured, and was automatically transferred under an atmosphere of 23 ° C. and 80% RH.
The transportability was evaluated.

The transportability was evaluated based on the rate of occurrence of defects. 1.0%
The above failure rate is not practical.

In Table 4, the degree of swelling is the degree of swelling represented by the above equation (1).

Table 4 shows the results.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

According to the present invention, a silver halide photographic light-sensitive material having improved transportability in a scanner or a facsimile plotter can be provided.

Continuation of the front page (56) References JP-A-3-168637 (JP, A) JP-A-3-137635 (JP, A) JP-A-4-127142 (JP, A) JP-A-60-80845 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/76 502 G03C 1/32 G03C 1/95 G03C 1/30

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on one side of a support and at least one backing layer on the other side. Average particle size of 10 in upper layer
a halogen containing a matting agent of at least 3 μm, a swelling degree on the backing layer side of 3 or less, and a slipping agent contained in the uppermost layer on the emulsion layer side and / or the uppermost layer on the backing layer side. Silver halide photographic material.