JPH05107687A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which is improved in the transporting property in a scanner and facsimile plotter. CONSTITUTION:The silver halide photographic sensitive material having at least one layer of photosensitive silver halide emulsion layers on one side of a base and at least one layer of backing layers on the other side contains a matting agent having >=10mum average grain size in the uppermost layer on the backing layer side. In addition, a slipping agent is incorporated into the uppermost layer on the emulsion layer side and/or the uppermost layer on the backing layer side.

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 light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved transportability in scanners, facsimile plotters and the like.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have been increasingly used in photolithography. Also,
The market demands a shorter delivery time for product delivery. In order to shorten the delivery time, it is necessary to save the steps such as exposure and processing and perform these steps in a short time, and a scanner or a facsimile plotter is used for these steps. A problem when using these scanners and facsimile plotters is poor conveyance within the scanners and facsimile plotters. It is impossible to shorten the delivery time by causing defective transportation.

Generally, photographic light-sensitive materials use gelatin as a binder. Under high-humidity conditions, the photographic light-sensitive materials tend to stick to each other, resulting in poor conveyance in a scanner or a facsimile plotter.

In order to prevent conveyance defects in these scanners and facsimile plotters, a matting agent has been included in the outermost layer of the photographic light-sensitive material, but the conveyance property under high humidity conditions is improved. Wasn't enough. Further, when the amount of the matting agent is increased in order to improve the above-mentioned improvement effect, the transparency after the development processing is remarkably deteriorated, and the slip property is deteriorated, so that the transportability is deteriorated contrary to the intention. The problem arises.

It is known that a slipping agent is contained in a color photographic light-sensitive material to improve the running property in a photographing machine, a printer and a camera, in US Pat. Nos. 3,042,522 and 3,0.
No. 80,317, British Patent Nos. 1,466,304, 1,143,118, etc., the transportability in a scanner or a facsimile plotter is improved only by improving the slipperiness. However, these means are insufficient in improving the transportability in the scanner or the facsimile plotter.

Further, in JP-A-61-42653, a polymer matting agent having an average particle size of 3 μm or more, preferably 3.5 to 6.0 μm is used in combination with a silicone type slip agent, and the antistatic property and the slip property are improved. Although it is described that these techniques should be improved, these techniques were not effective enough to improve the transportability in a scanner or a facsimile plotter.

[0007]

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

[0008]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side and at least one backing layer on the other side of the support. A top layer on the backing layer side contains a matting agent having an average particle size of 10 μm or more, and
This is achieved by a silver halide photographic light-sensitive material characterized by containing a slipping agent in the uppermost layer on the emulsion layer side and / or the uppermost layer on the backing layer side.

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

The present invention will be described in detail below.

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

Specific examples of compounds of the slip agent used in the present invention are shown below.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4] These slip agents may be added in advance together with the dispersant used during 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 organic compounds include water-dispersible vinyl polymers such as polymethylmethacrylate, cellulose acetate propionate, starch and the like. Particularly, a spherical matting agent of a water-dispersible vinyl polymer such as a homopolymer of an acrylate ester such as methyl methacrylate, glycidyl acrylate, or glycidyl methacrylate, or a copolymer of these acrylate esters or a copolymer with other vinyl monomers is used. preferable. As the inorganic compound, silver halide strontium barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, boron nitride, hollow silica (manufactured by Nippon Philite Co.), ethylene tetrafluoride,
Titanium oxide and the like are preferably used. The addition amount is 1 mg /
m ² ~1,000mg / m ^2, preferably 50 mg / m ² to 500
It is mg / m ² . The average particle size is 10 μm or more, preferably 30 μm or less. When it is larger than 100 μm, the matting agent is easily peeled off from the film surface, which may cause a failure of the plotter, which is not preferable. The particle size can be measured by an electron micrograph or a Coulter counter.

It is preferable that the degree of swelling on the backing layer side expressed by the following formula 1 is 3 or less, particularly preferably 2 or less, because the intended purpose of the present invention can be achieved even in a high humidity atmosphere.

[0019]

[Equation 1] The silver halide emulsion used in the light-sensitive material of the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method, and the grain size is preferably 0.2 μm or more and 0.5 μm or less.

The silver halide grains used in the emulsion of the present invention can be incorporated inside the grain and / or on the grain surface by adding a water-soluble rhodium salt and a water-soluble iridium salt in the process of forming the grain. The addition amount is preferably 10 ⁻⁶ to 10 ⁻⁹ mol per mol of silver halide.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer, and a latent image May be particles mainly formed on the surface, or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,6.
66, JP-A-55-26589, JP-B-55-42
737, etc., and The Journal of Photographic Science (J. Photogr. Sci). Two
1 . It is also possible to prepare particles having a shape of octahedron, tetrahedron, dodecahedron, etc. by the method described in the literature such as No. 39 (1973) and use them. Further, grains having twin planes may be used.

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

Any grain size distribution may be used, an emulsion having a wide grain size distribution (referred to as polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (monodisperse emulsion). May be used alone or in combination of several kinds. Also, a polydisperse emulsion may be mixed.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the present invention, a monodisperse emulsion is preferred.
As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained in the 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 grain size referred to here is the diameter of spherical silver halide grains, or the projected image of grains having a shape other than spherical. It is the diameter when converted to a circular image of the same area.

The particle size can be obtained, for example, by enlarging the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the particle diameter on the print or the area at the time of projection. (It is assumed that the number of measured grains is 1000 or more indiscriminately.) The particularly preferred highly monodisperse emulsion of the present invention has a monodispersity degree of 20 or less defined by the formula 2, and more preferably 15 or less. belongs to.

[0029]

[Equation 2] Here, the average particle diameter and the particle diameter standard deviation are obtained from ri defined above. Monodisperse emulsion is disclosed in JP-A-54-485.
21, 58-49938 and 60-1229.
It can be obtained by referring to Japanese Patent Publication No. 35, etc.

The light-sensitive silver halide emulsion can be used as it is, as it is, as a so-called unprimed emulsion without chemical sensitization, but it is usually chemically sensitized.

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

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitizing method using a reducing substance, and a method using gold or other noble metal compound can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines and other compounds can be used, and specific examples thereof include US Pat. Nos. 1,574,944 and 2,410, 689
Issue 2, Issue 2,278,947, Issue 2,728,668
No. 3,656,955. Examples of the reduction sensitizer that can be used include primary tin salts, amines, hydrazine derivatives, formamidisulfinic acid, and silane compounds. Specific examples thereof include US Pat.
7,850, 2,419,974, 2,51
8,698, 2,983,609, 2,983
No. 610 and No. 2,694,637.

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

The conditions such as pH, pAg and temperature during chemical sensitization are not particularly limited, but the pH value is 4-9, especially 5-8.
Is preferable, and it is preferable to keep the pAg value at 5 to 11, especially at 7 to 9. The temperature is preferably 40 to 90 ° C, particularly preferably 45 to 75 ° C.

In the photographic emulsion used in the present invention, in addition to the above-mentioned sulfur sensitization, gold / sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound can be used in combination. ..

As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed and used.

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. Various stabilizers such as 2-mercaptobenzothiazole and the like can also be used. Further, if necessary, a silver halide solvent such as thioether, or a crystal habit controlling 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 may be contained therein. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material.

An example of a compound that can be used is described by K. Mees,
The Theory of the Photographic Process, No. 3
Ed., 1966) with reference to the original literature.

For more detailed specific examples of these and other uses, see US Pat. No. 3,954,47.
No. 4, No. 3,982, 947, No. 4, 021, 248
Reference can be made to the description in Japanese Patent Publication No. 52-28660.

The silver halide photographic light-sensitive material of the present invention has an alkyl acrylate described in US Pat. Nos. 3,411,911, 3,411,912 and JP-B-45-5331 in the photographic constituent layers. A system latex may be included.

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. Examples of thickeners or plasticizers include US Pat. No. 2,960,404 and 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, and Belgian Patent 588,143.
For example, styrene-sodium maleate copolymer, dextran sulfate, etc., as the hardener, aldehyde-based,
Epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based, isocyanate-based, sulfonate ester-based, carbodiimide-based, mucochloric acid-based, acryloyl-based various hardeners, ultraviolet absorbers, for example, U.S. Pat. 253,921, British Patent 1,309,349
Compounds described in each of the specifications, especially 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 a coating aid, an emulsifier, a permeability improver for a processing solution, a defoaming agent, or a surfactant used for controlling various physical properties of a light-sensitive material, British Patent No. 548,532, 1,216,389, U.S. Patents 2,026,202, 3,514,293,
Japanese Patent Publications No. 44-25580, No. 43-17922, No. 43-17926, No. 43-3166, and No. 48-2.
It is possible to use anionic, cationic, nonionic or amphoteric compounds described in 0785, French Patent 202,588, Belgian Patent 773,459, JP-A-48-101118 and the like. However, among these, anionic surfactants having a sulfone group, such as succinate sulfonates and alkylbenzene sulfonates, are particularly preferable. Further, as an antistatic agent, JP-B-46-24159 and JP-A-48-89979.
U.S. Pat. Nos. 2,882,157 and 2,972,5
No. 35, JP-A Nos. 48-20785 and 48-4313.
No. 0, 48-90391, Japanese Patent Publication No. 46-24159
No. 46-39312, No. 48-43809, and JP-A No. 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 prepared by mixing the coating liquids of the respective layers in the coating amount ratio is in the range of 5.3 to 7.5. If the pH is lower than 5.3, the dura mater progresses slowly, which is not preferable, and 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 depending on the purpose. These additives are
For more information, Research Disclosure (RD)
Volume 176, Item 17643 (December 1978) and Volume 187, Item 18716 (November 1979), are described in Table 1.

[0046]

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

The developing agent used in the black-and-white developing solution used in the present invention is likely to have good performance, and thus it has a dihydroxybenzene ring (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and amino. Phenols (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination.

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

Further, so-called "lith type" development processing can be performed. As a special form 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 treated with an alkaline aqueous solution to perform development. Hydrophobic developing agents can be incorporated in the emulsion layer by the method described in Research Disclosure 169 et al. Such a development process may be combined with a silver salt stabilization process using a thiocyanate.

As the fixing liquid, those having a generally used composition can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent.

The exposure to the photographic emulsion used in the present invention depends on the state of chemical sensitization, purpose of use, etc., but it is different from tungsten, fluorescent lamp, arc lamp, mercury lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser. Various light sources such as light, electron beams, X-rays, and fluorescent screens during X-ray imaging can be used as appropriate.

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

[0053]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of coating liquid for backing layer) 8 g of gelatin 500 g
After dissolving in 1 liter of water, 1 g of the following chemical formula 5 (dye) was added, 20 g of saponin as a surfactant, 20 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex, and styrene-as a thickening agent. It was adjusted by adding 2.5 g of maleic anhydride copolymer.

[0054]

[Chemical 5] (Preparation of coating solution for backing protective layer) Gelatin 400g
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 as a spreading agent was added.
An aqueous solution (3 g) was added, and a sliding agent was added as shown in Table 3 to adjust. (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 this solution at 6 × 10 ⁻⁷ mol per mol of silver halide. In addition, a mixed solution of potassium bromide and sodium chloride, in which hexabromorhodium salt was added so as to be 4 × 10 ⁻⁸ mol per mol of silver halide, was added by the double jet method to bromide. PH 3.0 of silver chlorobromide particles containing 35 mol% of silver (9% distribution, cubic crystal, particle size 0.25 μm),
After adjusting the pAg to 7.7 and returning the pH to 5.9, desalting was carried out by a conventional method, and 5 mg of the following mixture A was added per mol of silver halide.

This emulsion was sensitized with gold and sulfur, and 60 mg of the following sensitizing dye (a) was added to 1 mol of silver halide. 70 mg of 1-phenyl-5-mercaptotetrazole was added to 1 mol of silver halide. 4-hydroxy-6-methyl-
After 1.2 g of 1,3,3a, 7-tetrazaindene was added and gelatin was added to stop the 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 for adjustment.

[0056]

[Chemical 6]

[0057]

[Chemical 7] (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. Then, the matting agent and the slipping agent were added as shown in Table 2 to adjust.

A backing layer and a backing protective layer were coated on one side of a polyethylene terephthalate base having a thickness of 100 μm which had been subjected to an undercoating treatment with each of the above coating solutions, and the gelatin coating amount was 2 g / m ² and 1 g / m ² , respectively. 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 Simultaneous coating was performed so that the coating amount was 1.0 g / m ² .

In the emulsion protective layer, 8 mg of formalin per 1 g of gelatin was added to the total gelatin on the emulsion layer side, and in the backing protective layer, a hardener was added as shown in Table 4.

The sample thus obtained was processed into a sheet product, and the facsimile plotter FT201-RDA
Prototyped an automatic carrier with the same carrier mechanism as (NEC), automatically carried out in an atmosphere of 23 ° C. and 80% RH,
The transportability was evaluated.

The transportability was evaluated by the defect rate. 1.0%
The above defect occurrence rate is not practical.

In Table 4, the degree of swelling is the degree of swelling shown by the above-mentioned formula 1.

The results are shown in Table 4.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having improved transportability in a scanner or a facsimile plotter.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side and at least one backing layer on the other side of a support, and the uppermost layer on the backing layer side. Has an average particle size of 10 μm
A silver halide photographic light-sensitive material comprising the above matting agent and a slipping agent in the uppermost layer on the emulsion layer side and / or the uppermost layer on the backing layer side.