JP3146387B2 - Silver halide photographic materials for laser light sources - 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 light-sensitive material for a laser light source, which has reduced surface glossiness of a developed image and has improved diagnostic properties for medical use.

[0002]

2. Description of the Related Art In recent years, radiation diagnostic images such as MRI (magnetic resonance imaging), CT (computerized tomography), CR (computerized radiography), and computer-aided diagnosis have been converted into digital or analog (video) signals. 2. Description of the Related Art Means for taking in a processing device such as a computer, scanning the image with a laser beam, drawing the image on a silver halide photographic material, and providing the same as a transmission photographic image for medical diagnosis have become common.

As the silver halide photographic light-sensitive material, a laser printer film spectrally sensitized from a red light region to a near-infrared region, which is an oscillation wavelength of a laser beam, is used. Attempts have been made to reduce the size of silver halide grains or save silver.

[0004] However, the reduction in the size of silver halide grains and the saving of silver increase the processability, but also increase the surface gloss of the photosensitive material, and have the disadvantage of making characters difficult to see.

Conventionally, it has been known to use an inorganic substance such as silica, polymer beads, or the like to suppress the surface gloss of a photosensitive material. However, there is a problem that the transparency of a film after development processing is deteriorated. There was a need for a new response.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to eliminate the surface gloss of a film after development without deteriorating its transparency,
An object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source in which a character is easily seen and diagnostic performance is improved.

[0007]

The object of the present invention is to provide a single-sided photographic material having a silver halide emulsion layer having a silver content of 3.5 g / m ² or less on one side of a support, wherein the silver halide emulsion layer is Unchemically aged silver halide grains having an average grain size of 0.8 to 2.0 μm,
The chemically ripened silver halide grains having an average particle size of 0.1 to 0.6 μm are contained in a weight ratio of 30:70 to 5:95, and at least one polymer matting agent is contained on the emulsion surface side. This is achieved by a silver halide photographic light-sensitive material for a laser light source, characterized in that:

Hereinafter, the present invention will be described in detail.

The unchemically ripened silver halide grains according to the present invention are grains subjected to physical ripening only for grain formation, and generally second ripening (chemical ripening) after desalting excess salts. Means silver halide grains in which silver is omitted. In the present invention, the average particle size is 0.8 to 2.0 μm, more preferably 0.9 to 2.0 μm.
1.2 μm unchemically aged particles, with an average particle size of 0.1 to 0.6 μm,
More preferably, 0.15 to 0.40 µm of chemically aged particles are contained in a weight ratio of 30:70 to 5:95, and preferably 20:80 to 5:95.

The light-sensitive material of the present invention is a single-sided light-sensitive material in which light-sensitive silver halide is coated on only one side of a support, and the total amount of silver described above is 3.
5 g / m ² or less, more preferably 2.0 to 3.3 g / m ²
It is.

Further, the one side emulsion layer side contains a polymer matting agent. The polymer matting agent referred to in the present invention is not particularly limited and has, for example, an average particle size of 0.
Organic matting agents such as polyacrylate, polymethyl methacrylate, cellulose acetate propionate, and polystyrene having a size of 5 to 7.0 μm are exemplified.

The polymer matting agent is preferably contained in the silver halide photographic light-sensitive material of the present invention in an amount of 10 to 100 mg / m ² on the emulsion side. Preferable content positions on the emulsion surface side include an emulsion layer, a hydrophilic layer other than the emulsion layer, a protective layer, and the like, and preferably a protective layer on the emulsion layer.

In the present invention, an inorganic matting agent such as silica (silicon dioxide), which is a matting agent outside the present invention, may be used in combination. The silver halide photographic light-sensitive material for a laser light source according to the present invention is spectrally sensitized to an oscillation wavelength of laser light, for example, 600 nm or more. Any known method can be used for the spectral sensitization, and particularly preferably, the general formula [1] described in Japanese Patent Application No. 4-84132 by the same applicant as the present invention,
It is preferable to use the spectral sensitizing dyes represented by [2] and [3].

The silver halide photographic light-sensitive material according to the present invention can be used as an antistatic method described in (1) a water-soluble conductive polymer described in JP-A-4-80744 by the same applicant as the present invention. It may have an antistatic layer composed of a reaction product of a polymer and (3) a curing agent.

(1) Examples of specific compounds of the water-soluble conductive polymer include the following.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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(2) Specific examples of the hydrophobic polymer include the following.

[0025]

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[0026]

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(3) Specific examples of the reaction product of the curing agent include the following.

[0028]

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[0029]

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[0030]

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The above antistatic agent is applied directly onto the support or after subbing. Specifically, it is used by the method described in JP-A-4-80744.

The silver halide composition of the silver halide emulsion subjected to chemical ripening used in the present invention may be, for example, silver bromide,
Any silver halide such as silver iodobromide and silver chloroiodobromide may be used. Preferred silver halide compositions include silver iodobromide emulsions containing 30 mol% or less of silver iodide.

If the halogenated particles have the structure of the present invention,
It may be of any crystal type, for example, it may be a single crystal such as cubic, octahedral, or tetradecahedral, or may be multiple twin particles having various shapes.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention include, for example, those described in "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coating Photographic Emulsion "by Focal Press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The average grain size of the silver halide grains is 0.1 to 0.6 μm.
With m, a monodisperse emulsion having a narrow particle size distribution or a polydisperse emulsion having a wide particle size distribution may be used. Here, the monodisperse emulsion means a silver halide emulsion having a coefficient of variation of 0.20 or less with respect to the grain size defined in, for example, JP-A-60-162244.

Monodisperse emulsions include silver halide grains having an average grain size of more than 0.1 μm, wherein at least 95 wt% of the grains are within ± 40% of the average grain diameter. In addition, the average particle size is 0.25μm ~ 2μm, at least 9
Also included are silver halide emulsions in which 5 wt% or at least 95% of silver halide grains are in the range of an average grain size of ± 20%.

The average particle size referred to here is the diameter when spherical silver halide grains are used, or when the projected image is converted into a circular image of the same area for cubic or spherical particles other than spherical. When the diameters, each of which is ri and the number is ni, the average particle size is defined by the following equation:

Average particle size = Σniri / Σni The method for producing the above monodisperse emulsion is known, for example, J. Phot. Sci, 1
2.242-251, (1963), JP-A-48-36890, JP-A-52-16364
No. 55-142329, No. 58-49938, UK Patent 1,413,748
And U.S. Pat. Nos. 3,574,628 and 3,655,394.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is prepared by, for example, using a seed crystal as a method for obtaining the above-mentioned monodispersed emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. An emulsion that has been grown may be used. The silver halide composition of the unchemically ripened silver halide emulsion used in the present invention is, for example, silver bromide, silver iodobromide,
Any silver halide such as silver chloroiodobromide may be used. Preferred silver halide compositions include silver iodobromide emulsions containing 30 mol% or less of silver iodide.

The average grain size of unchemically ripened silver halide grains may be from 0.8 μm to 2.0 μm, and may be a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a broad grain size distribution.

The silver halide grains may be of any crystal type as long as they have the constitution of the present invention, and may be, for example, single crystals such as cubic, octahedral, and tetrahedral, and may have various shapes. May be a multiple twin particle having

The unchemically ripened silver halide grains can be prepared in the same manner as the above-mentioned chemically ripened grains according to the present invention. The crystal structures of the chemically ripened silver halide grains and the unchemically ripened silver halide grains of the emulsion according to the present invention may have different silver halide compositions on the inside and outside, and form a layered structure. May be. A particularly preferred embodiment of the emulsion is a silver halide grain having substantially two distinct layered structures (core / shell structure) comprising a high iodine core portion and a low iodine shell layer.

The high iodine core portion is silver iodide, and the silver iodide content is 20 to 40 mol%, preferably 20 to 30 mol%.

The silver halide composition other than silver iodide in the core may be either silver bromide or silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The outermost shell layer is a silver halide containing 5 mol% or less of silver iodide, preferably 2 mol%.
The layer contains the following silver iodide. The silver halide other than silver iodide in the outermost layer may be any of silver chloride, silver bromide and silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The method for producing the above-mentioned core / shell type emulsion is known, and is described, for example, in J. Phot. Sci, 24.198. (1976), US Pat.
Nos. 250, 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B No. 35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, the aforementioned (RD) No. 17643, (RD) No. 18716 and (RD) N
o.308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are shown in the following table.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 right 1005-6 XI Plasticizer 27 XII 650 right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the present invention Examples of the support used for the silver photographic light-sensitive material include those described in the above RD,
A suitable support may be a plastic film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The silver halide photographic light-sensitive material according to the present invention comprises a hydrophilic colloid such as a silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an ultraviolet absorbing layer, an antistatic layer, an antihalation layer and a backing layer. It may be composed of layers.

In these hydrophilic colloid layers, various synthetic high molecular compounds such as gelatin can be used as a binder or protective colloid.

As gelatin, lime-treated gelatin, acid-treated gelatin or gelatin derivative may be used. Examples of synthetic polymers other than gelatin include cellulose derivatives such as hydroxyethyl cellulose,
A homo- or copolymer such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polyacrylamide and the like can be used. The photographic processing of the light-sensitive material of the present invention can be performed, for example, by the methods described in RD-17643, XX to XXI, pp. 29 to 30, or 308119.
XX to XXI, pages 1011 to 1012, may be treated with a treatment solution. This processing may be either black-and-white photographic processing for forming a silver image or color photographic processing for forming a dye image. The processing temperature is usually in the range of 18 ° C to 50 ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0058]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of an unchemically ripened emulsion) A silver iodobromide emulsion (silver iodide content: 2 mol%) having an average grain size of 0.3 μm was used as a seed emulsion, and the average grain size was 0.7 to 2.2 by the ammonia method. A monodisperse silver iodobromide emulsion (silver iodide content: 3 mol%) was grown. Coefficient of variation (σ /
r) was in the range of 0.15 to 0.20.

[Preparation of Emulsions A and B] A having an average particle size of 0.1 μm
Using a gBrI (AgI content 2 mol%) seed emulsion, an aqueous solution of ammoniacal AgNO _{3 and an} aqueous solution of potassium bromide were added by a double jet method, and AgBr having an average particle size of 0.25 μm was used.
A cubic monodisperse emulsion of I (average AgI content 0.4 mol%) was grown. The coefficient of variation (σ / r) was 0.17.

After this emulsion was divided, one was dissolved just before chemical ripening and when the temperature became constant, the following dye (1) was added to obtain emulsion (A), and the other was the following dye (2) Was added to obtain an emulsion (B). The dye amounts were each 90 mg / mol silver halide. Next, ammonium thiocyanate, chloroauric acid and hypo were added and subjected to chemical sensitization,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

[0062]

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(Backing layer) Backing lower layer coating solution Gelatin 400 g i-amine-n-decylsulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Diethylene glycol 5.0 g Glyoxal 2.0 g Dye emulsified dispersion (the following) 33 g

[0064]

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Finish to 7 liters with water.

[Preparation method of dye emulsified dispersion] 10 kg of the following dye was mixed with 28 l of tricresyl phosphate and ethyl acetate.
Dissolved at 55 ° C. in 85 l of solvent. This is called an oil-based solution. On the other hand, anionic surfactant (AS) was added to 1.35
270 l of a 9.3% gelatin aqueous solution containing Kg was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. Phenol and 1,1'-dimethylol-1-bromo-
An appropriate amount of 1-nitromethane was added to make up to 240 kg with water.

[0067]

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Coating solution for backing upper layer Gelatin 400 g i-Amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polythimer methacrylate 12 g SAM-1 3.0 g SAM-2 0.75 g Phagent 100 (Neos Corporation) Made) 0.3g SMP 2.0g Griokizal 13.6g

[0069]

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Make up to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution The above emulsions A and B were mixed with the unchemically ripened emulsion at the weight ratios shown in Table 1, and the following were added per mole of silver halide by adding: A silver halide emulsion coating solution was prepared.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sodium sulfonate 10 mg 1,1-dimethylol-1-bromo- 1-nitromethane 10mg

[0073]

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Emulsion side protective layer coating solution A solution having the following composition was added in an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium i-amyl-n-decylsulfosuccinate 1.4 g Polymethyl methacrylate (particle size 4 μm) Amount shown in Table 1 Silicon dioxide particles (area average particle size 1.2 μm) 0.5 g Ludox AM (colloidal silica (manufactured by DuPont)) 30 g 2-4-Dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) 10 ml Formalin (35%) 2 ml Glyoxal (40%) 5 ml stringent _{100 60mg C 8 F 17 SO 3} K 180mg topside 300 (Permchem Asia Ltd. Ltd.) 45mg SAM-1 1.0g SAM -2 0.4g

[0076]

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Preparation of Support A polyethylene terephthalate support having a thickness of 180 μm was biaxially stretched and heat-set on both sides, and then subjected to a corona discharge treatment. An undercoat latex (Compound of Synthesis Example 1) described in Example 1 of JP-A-59-18945 was further applied thereon.

Next, on one surface of the upper layer, the following compound described in JP-A-4-80744 by the same applicant as the present invention was applied as an antistatic layer.

Water-soluble conductive polymer (Ex. P4) 0.6 g / m ² Hydrophobic polymer (Ex. HP1) 0.5 g / m ² Curing agent (Ex. AH5) 2 × 10 ⁻³ mol / dm ² Application is 30 m / min. After application at a speed by a roll-fit coating pan and an air knife, activation treatment by corona discharge was performed again in the same manner as described above to obtain a support.

Coating of Sample On the side of the obtained support on which the antistatic layer was not coated, the above-mentioned silver halide emulsions A and B according to the present invention and the coating solution for the emulsion surface protective layer were coated.

The backing lower layer and the upper layer described above were coated on the side on which the antistatic layer was coated.

The amount of gelatin in the backing layer was 3.0 g in the lower layer.
/ m ² and the upper layer was simultaneously coated by a slide hopper method at a speed of 90 m / min so that the upper layer became 1.2 g / m ² . The emulsion layer was coated so that the amount of gelatin was 2.4 g / m ² , the protective layer was 1.2 g / m ² , and the amount of silver was as shown in Table 1, to obtain a sample.

The following evaluation was performed on the obtained sample.

Sample Evaluation Method (1) Gloss The sample was exposed to tungsten light until the maximum density was reached, and SR was measured.
After processing for 45 seconds with X-501 (manufactured by Konica Corporation), the glossiness of the emulsion side was measured using a digital variable-angle gloss meter VG-ID type (manufactured by Nippon Denshoku Industries).
At a light incident angle of 20 °. It evaluated as follows from the obtained measured value.

Less than 20: very low gloss 20 or more and less than 25: low gloss 25 or more and less than 30: no problem in practical use 30 or more and less than 35: high gloss 35 or more: very high gloss (2) Character The visibility of the raw sample was evaluated in five steps as follows from the appearance of the numbers in the Konica Laser Imager LI-10 (manufactured by Konica Corporation) SMPT pattern.

1: Very poor 2: Poor 3: No problem in practical use 4: Good 5: Very good (3) Haze (evaluation of transparency) After the sample was treated with SRX-501 for 45 seconds with the final exposure The haze was measured with a turbidity meter (MODEL-T-2600DA) manufactured by Tokyo Denshoku Co., Ltd., and evaluated as follows.

15 to less than 20: inferior 10 to less than 15: no problem in practical use 5 to less than 10: good (4) Pressure failure (unexposed) Occurs in an unexposed sample developed by the same method as for haze. The liquid blackening pressure due to the automatic developing machine roller pressure was visually evaluated.

The evaluation was made in five steps as follows.

1: Very poor 2: Poor 3: No problem in practical use 4: Good 5: Very good (5) Fixability Poor fixing (residual silver halide) was evaluated visually with the same unexposed sample. .

The evaluation was made in four steps as follows.

1: very poor 2: poor 3: no practical problem 4: good The results obtained are shown in Table 1 below.

[0092]

[Table 1]

As is clear from the table, according to the method of the present invention, the glossiness is suppressed and the visibility of the character is improved. Further, it can be seen that there is no occurrence of liquid blackening pressure due to roller pressure during automatic development, and a silver halide photographic light-sensitive material excellent in transparency and free from fixing failure can be obtained.

Example 2 A sample was prepared in the same manner as in Example 1. However, the chemically ripened silver halide grains had a particle size of 0.3 μm, and the spectral sensitizing dye was exemplified in Example 2.

The writing of an SMPT pattern for character evaluation was performed in the same manner as in Example 1 except that a laser imager using a semiconductor laser of 820 nm was used, and the results were summarized in Table 2 below.

[0096]

[Table 2]

As can be seen from the table, even when the grain size of the chemically ripened emulsion is increased and the spectral sensitizing dye is changed, according to the present invention, a silver halide photographic light-sensitive material having an easily visible image can be obtained as in Example 1. Was.

[0098]

According to the present invention, the surface glossiness is suppressed and the visibility of the character is improved. Further, according to the present invention, it was possible to provide a silver halide photographic light-sensitive material excellent in transparency without occurrence of liquid blackening pressure due to roller pressure during automatic development and free from defective fixing.

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein one side of the support has a silver content of 3.5 g / m ^2.
In a single-sided light-sensitive material having the following silver halide emulsion layer, the silver halide emulsion layer has an unchemically ripened silver halide grain having an average grain size of 0.8 to 2.0 μm, and a chemically ripened halogen having an average grain size of 0.1 to 0.6 μm. 30: 70-5: 9 by weight ratio with silver halide particles
A silver halide photographic light-sensitive material for a laser light source, wherein the light-sensitive material contains at least one polymer matting agent on the emulsion surface side.