JPH06130527A - Silver halide photographic sensitive material using laser beam - Google Patents

Abstract

PURPOSE:To provide the laser beam-using silver halide photographic sensitive material grayed on the surface of a film without deteriorating its transparency after development processing, facilitated in discrimination of characters, and enhanced in diagnostic precision. CONSTITUTION:The laser beam-using silver halide photographic sensitive material is characterized by having a silver halide emulsion layer containing silver halide in <=3.5g/m<2> in terms of silver on one side of a support, comprising silver halide grains not subjected to chemical ripening and having an average grain diameter of 0.8-2.0mum and those subjected chemical ripening and having an average grain diameter of 0.1-0.6 in a proportion of 30:70 to 5:95, and by containing at least one kind of polymer matting agent on the emulsion 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 for a laser light source, which suppresses surface glossiness of an image after development processing and has improved diagnostic properties for medical use.

[0002]

BACKGROUND OF THE INVENTION In recent years, images for radiation diagnosis such as MRI (Magnetic Resonance Imaging), CT (Computed Tomography), CR (Computed Radiography) and Computer Assisted Diagnosis are converted into digital or analog (video) signals. A means for taking in a processing device such as a computer and processing the image, scanning it with a laser beam to draw it on a silver halide photographic light-sensitive material, and providing it as a transmission photographic image for medical diagnosis is generalized.

As the silver halide photographic light-sensitive material, a film for a laser printer which is spectrally sensitized from a red light region which is an oscillation wavelength of a laser beam to a near infrared region is used, and recently, with the rapid processing, It is attempted to reduce the size of silver halide grains or save silver.

However, while reducing the size of silver halide grains and reducing silver consumption improve the processability, they result in enhancing the surface gloss of the light-sensitive material, which leads to a demerit of making characters difficult to see.

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

[0006]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to eliminate the surface gloss of a film after development without deteriorating the transparency,
It is an object of the present invention to provide a silver halide photographic light-sensitive material for a laser light source that makes characters easy to see and has improved diagnostic ability.

[0007]

The above object of the present invention is to provide a single-sided light-sensitive material having a silver halide emulsion layer having a silver amount of 3.5 g / m ² or less on one side of a support, wherein the silver halide emulsion layer is Unchemically ripened silver halide grains having an average grain size of 0.8 to 2.0 μm,
Chemically ripened silver halide grains having an average grain 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. And a silver halide photographic light-sensitive material for a laser light source.

The present invention will be described in detail below.

The unchemically-ripened silver halide grain according to the present invention refers to a grain which has been subjected to only physical ripening for grain formation, and generally, the second ripening (chemical ripening) after desalting excess salts. Refers to silver halide grains without. In the present invention, the average particle size is 0.8 ~ 2.0 μm, more preferably 0.9 ~
Unchemically aged particles of 1.2 μm and average particle size of 0.1 to 0.6 μm,
More preferably, the chemically aged particles of 0.15 to 0.40 μm are contained at a weight ratio of 30:70 to 5:95, and preferably at a ratio of 20:80 to 5:95.

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

Further, a polymer matting agent is contained on the side of the one-sided emulsion layer. The polymer matting agent referred to in the present invention is not particularly limited, for example, the average particle size is 0.
Organic matting agents such as polyacrylate, polymethylmethacrylate, cellulose acetate propionate and polystyrene having a thickness of 5 to 7.0 μm can be mentioned.

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

In the present invention, an inorganic matting agent such as silica (silicon dioxide) which is a matting agent other than 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 of, for example, 600 nm or more. Any known method can be used for the spectral sensitization, but 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 is (1) a water-soluble conductive polymer (2) hydrophobic as described in JP-A-4-80744 by the same applicant as the present invention as an antistatic method. You may have the antistatic layer which consists of a reaction product of a polymer and (3) hardening | curing agent.

(1) Specific examples of the water-soluble conductive polymer include those shown below.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

(2) Specific examples of the hydrophobic polymer include those shown below.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

(3) Specific examples of the reaction product of the curing agent include those shown below.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

The above-mentioned antistatic agent is applied to the support directly or after subbing. Specifically, it is used by the method described in JP-A No. 4-80744.

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

If the halogenated particles have the constitution of the present invention,
It may be of any crystal type, for example, a single crystal such as a cube, octahedron, or tetrahedron, or multiple twin grains 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
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

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

The average grain size of silver halide grains is 0.1 to 0.6 μm.
It may be a monodisperse emulsion having a narrow particle size distribution and a polydisperse emulsion having a wide particle size distribution. The monodisperse emulsion referred to herein means a silver halide emulsion having a grain size variation coefficient of 0.20 or less as defined in JP-A-60-162244.

Examples of monodisperse emulsions include silver halide grains having an average grain size of greater than 0.1 μm, at least 95 wt% of which are within ± 40% of the average grain diameter. Also, the average particle size is 0.25 μm to 2 μm and at least 9
Also included are silver halide emulsions in which 5 wt% or at least 95% of silver halide grains are contained within the range of average grain size ± 20%.

The term "average grain size" as used herein means the diameter of spherical silver halide grains, and the projected image of a cubic or non-spherical spherical grain converted into a circular image of the same area. When the diameter is that of each individual particle size r i and its number is n i, the average particle size is defined by the following equation.

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

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, for example, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion 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. A preferable silver halide composition is a silver iodobromide emulsion containing 30 mol% or less of silver iodide.

The non-chemically ripened silver halide grains may have an average grain size of 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, for example, a single crystal such as a cube, octahedron or tetrahedron, and various shapes. It may be a multi-twin crystal grain having.

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

The high-iodity 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 portion 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%.
It is a layer containing the following silver iodide. 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.

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

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. Preferred water washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

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

Examples of the compound used in such a step include (RD) No. 17643, (RD) No. 18716 and (RD) N described above.
Various compounds described in o.308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are listed 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 Whitening agent 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 Invention Examples of the support used for the silver photographic light-sensitive material include those described in RD above,
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or 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.

For these hydrophilic colloid layers, various synthetic polymer compounds such as gelatin can be used as a binder or protective colloid.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or gelatin derivative may be used. Examples of synthetic high molecular substances other than gelatin include cellulose derivatives such as hydroxyethyl cellulose,
A single or copolymer of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide and the like can be used. Photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX-XXI, pages 29-30 or 308119.
Treatment with a treatment liquid as described in XX to XXI, pages 1011-1010 may be performed. This process may be either a black and white photographic process for forming a silver image or a color photographic process for forming a dye image. The treatment temperature is usually in the range of 18 ° C to 50 ° C.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants,
A defoaming agent, a toning agent, a water softening agent, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution 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]

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

Example 1 (Preparation of unchemically ripened emulsion) A silver iodobromide emulsion having an average grain size of 0.3 μm (silver iodide content: 2 mol%) was used as a seed emulsion, and the average grain size was 0.7 to 2.2 by the ammonia method. A monodisperse emulsion of a silver iodobromide emulsion having a grain size of 3 μm (silver iodide content: 3 mol%) was grown. Coefficient of variation (σ /
r) was within 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 ammoniacal AgNO ₃ aqueous solution and a potassium bromide aqueous solution were added by a double jet method to obtain an AgBr having an average particle size of 0.25 μm.
A cubic monodisperse emulsion of I (average AgI content 0.4 mol%) was grown. The coefficient of variation (σ / r) was 0.17.

After the emulsion was divided, one was dissolved just before chemical ripening and when the temperature became constant, the dye (1) below was added to form an emulsion (A), and the other was the dye (2) below. Was added to give an emulsion (B). The amount of dye was 90 mg / mole silver halide. Next, after ammonium thiocyanate, chloroauric acid and hypo were added for chemical sensitization,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

[0062]

[Chemical 14]

(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 emulsion dispersion (with the following contents) 33 g

[0064]

[Chemical 15]

Make up to 7 liters with water.

[Preparation Method of Dye Emulsion Dispersion] 10 kg of the following dye was mixed with 28 l of tricresyl phosphate and ethyl acetate.
It was dissolved in a solvent consisting of 85 l at 55 ° C. This is called an oil-based solution. On the other hand, the anionic surfactant (AS) was 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 solution were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C. Phenol and 1,1'-dimethylol-1-bromo- were added to the resulting dispersion.
An appropriate amount of 1-nitromethane was added and the weight was adjusted to 240 Kg with water.

[0067]

[Chemical 16]

Backing upper layer coating liquid Gelatin 400 g i-amyl-n-decyl sulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polythymer methacrylate 12 g SAM-1 3.0 g SAM-2 0.75 g Futgent 100 (Neos Co.) Made) 0.3g SMP 2.0g Glyoxal 13.6g

[0069]

[Chemical 17]

Make up to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution The above emulsions A and B and unchemically ripened emulsion were mixed in the weight ratio shown in Table 1, and the following was added per mole of silver halide to give a red-sensitive emulsion. A silver halide emulsion coating solution was prepared.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-nitromethane 10mg

[0073]

[Chemical 18]

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

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g i-amyl-n-decylsulfosuccinate sodium 1.4 g Polymethylmethacrylate (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 [made by DuPont]) 30g 2-4-dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) 10ml formalin (35%) 2ml glyoxal (40%) 5ml footer Gent 100 60mg C ₈ F ₁₇ SO ₃ K 180mg Topside 300 (manufactured by Permchem Asia Ltd.) 45mg SAM-1 1.0g SAM-2 0.4g

[0076]

[Chemical 19]

Preparation of Support After a biaxially stretched heat set on both surfaces of a polyethylene terephthalate support having a thickness of 180 μm, corona discharge treatment was performed. A subbing latex (Synthesis Example 1 compound) described in Example 1 of JP-A-59-18945 was applied thereon.

Then, on one surface of the upper layer, the following compounds described in JP-A-4-80744 by the same applicant as the present invention were coated 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 Coating is 30 m / min After coating with a roll-fit coating pan and an air knife at a speed, the activation treatment by corona discharge was performed again in the same manner as above to obtain a support.

Coating of Samples The silver halide emulsions A and B according to the present invention and the emulsion surface protective layer coating solution were coated on the side of the support thus obtained which was not coated with the antistatic layer.

The backing lower layer and the upper layer were coated on the surface side coated with the antistatic layer.

The amount of gelatin in the backing layer was 3.0 g in the lower layer.
/ m ² and the upper layer was 1.2 g / m ² at the same time by the slide hopper method at a speed of 90 m / min. A sample was obtained by coating the emulsion layer 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.

The following evaluations were performed on the obtained samples.

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

Less than 20: Very weak gloss 20 or more and less than 25: Weak gloss 25 or more and less than 30: Gloss that does not pose any practical problems 30 or more and less than 35: Strong gloss 35 or more: Very glossy (2) Character The visibility of the Konica laser imager LI-10 (manufactured by Konica Corporation) SMPT pattern on the raw sample was evaluated according to the following 5 grades according to the appearance of the numbers.

1: Very inferior 2: Inferior 3: No problem in practical use 4: Good 5: Very good (3) Haze (Evaluation of transparency) After the sample was exposed to SRX-501 for 45 seconds without being exposed. Haze was measured with a turbidimeter (MODEL-T-2600DA) manufactured by Tokyo Denshoku Co., Ltd., and evaluated as follows.

15 or more and less than 20: inferior 10 or more and less than 15: practically no problem 5 or more and less than 10: good (4) Pressure failure (unexposed) Occurrence in unexposed sample developed by the same method as haze. The liquid blackening pressure due to the automatic processor roller pressure was visually evaluated.

The evaluation was made in the following five grades.

1: Very inferior 2: Inferior 3: No problem in practical use 4: Good 5: Very good (5) Fixability Poor fixation (remaining silver halide) was visually evaluated in the above unexposed sample. .

The evaluation was carried out in the following four grades.

1: Very poor 2: Poor 3: No problem in practical use 4: Good The obtained results are shown in Table 1 below.

[0092]

[Table 1]

As is apparent from the table, the method of the present invention suppresses the glossiness and improves the legibility of the character. Further, it can be seen that a silver halide photographic light-sensitive material excellent in transparency without generation of liquid blackening pressure due to roller pressure at the time of automatic development and without fixing failure can be obtained.

Example 2 A sample was prepared in the same manner as in Example 1. However, the grain size of chemically ripened silver halide grains was set to 0.3 μm, and the spectral sensitizing dye was set to Ex.

For writing the SMPT pattern for character evaluation, the same sample preparation and evaluation as in Example 1 were carried out except that a laser imager using a 820 nm semiconductor laser was used, and the results are summarized in Table 2 below.

[0096]

[Table 2]

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

[0098]

According to the present invention, the surface glossiness is suppressed and the legibility of characters is improved. Further, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is free from liquid blackening pressure due to the roller pressure at the time of automatic development, has no fixing failure, and has excellent transparency.

Claims (1)

[Claims] 1. The amount of silver on one side of the support is 3.5 g / m ²
In a single-sided light-sensitive material having the following silver halide emulsion layer, the silver halide emulsion layer comprises unchemically ripened silver halide grains having an average grain size of 0.8 to 2.0 μm and chemically ripened halogen having an average grain size of 0.1 to 0.6 μm. 30: 70-5: 9 by weight with silver halide grains
A silver halide photographic light-sensitive material for a laser light source, characterized in that it is contained in a ratio of 5 and contains at least one polymer matting agent on the emulsion surface side.