JP2006178297A - Area gradation image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an area gradation image forming method by which a high-quality proof image is stably obtained with neither displacement in exposure nor peeling from an external surface drum and with no problem on drying property and transportability in equipment. <P>SOLUTION: In the area gradation image forming method in which, after storage at ≤0°C for ≥100 days, a silver halide photosensitive material is wound on the external surface drum, exposed and developed to form an area gradation image, the silver halide photosensitive material has a gelatin-containing layer containing a vinylsulfone film hardening agent on a side opposite to a silver halide emulsion layer, drying is carried out after setting after coating, and the material is heat-treated after the storage at ≤0°C and before the exposure in such a way that tf value defined by the expression: tf=∫exp(-K/T)dt becomes ≥4×10<SP>-11</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a proof for confirming in advance the finish of a printed material, and more particularly to a method for forming an area gradation image of a proof image.

  Silver halide light-sensitive materials are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Because of these characteristics, silver halide photosensitive materials are widely used not only in the field of photography, but also in the field of printing, in the field of so-called proofs for checking the state of finished prints in the middle of printing. ing.

  In the field of proofing, each image of yellow (Y), magenta (M), and cyan (C) is output by outputting an image edited on a computer to a printing film and separating and exposing the developed film as appropriate. An image is formed, and an image of the final printed material is formed on color photographic paper, thereby determining the suitability of the layout and color of the final printed material.

  Recently, a method of directly outputting an image edited on a computer directly to a printing plate has been gradually spread. In such a case, it is desired to obtain a color image directly from the data on the computer without using a film. It is rare.

  For such purposes, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. There is a drawback, and the cost is low, and the method with excellent productivity has the disadvantage that the image quality is inferior. The system using silver halide light-sensitive material is capable of forming high-quality images, such as being able to form accurate halftone images due to excellent sharpness, etc., while being capable of continuous processing as described above. In addition, high productivity can be realized because images can be simultaneously written in a plurality of color image forming units.

  In recent years, so-called digitization has progressed in the field of printing, and the demand for obtaining an image directly from data in a computer has increased. For the reasons described above, silver halide photosensitive materials have begun to be used advantageously in this field.

  Recently, a proof has been presented to customers as an indication of the final printed product finish, and even the management of the printed product has begun to be aimed at this. In order to use it for such a purpose, stability higher than the stability of characteristics required in the conventional photographic field has been demanded.

  In order to stably produce silver halide light-sensitive materials, it is considered effective to expand production batches and store them at as low a temperature as possible for storage, but storage for 0.5 years or 1 year in a freezer It has been found that there are cases where the image cannot be formed due to positional displacement or peeling from the drum when the exposure is performed by wrapping around the outer drum.

In Patent Document 1, the thermal history after addition of a sensitizing dye is defined by a tf value in the method for preparing an infrared sensitized emulsion, and the fog is low when the tf value is 3.7 × 10 ⁻¹² or less. It describes that a silver halide photosensitive material can be provided. Patent Document 2 discloses that a silver halide photographic light-sensitive material in which a BC layer is cured with a vinylsulfone hardener and the pH of the film surface on the side having the BC layer is 6 or more improves the decrease in Dmax due to storage. Is disclosed. However, both publications do not disclose anything about the change in physical properties of the silver halide photosensitive material that occurs when the silver halide photosensitive material after frozen storage is wrapped around an outer drum and exposed.
JP 2000-199934 A JP 2000-267217 A

  An object of the present invention is an area gradation image forming method in which an area gradation image is formed by developing a silver halide photosensitive material that has been stored frozen and wrapped around an outer drum, and then the exposure position shift, from the outer drum. It is an object of the present invention to provide an area gradation image forming method in which a high-quality proof image can be obtained stably without causing problems of drying and without problems in dryness and transportability in equipment.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
The silver halide light-sensitive material having a paper support with a thickness of 150 μm or less, which is stored at 0 ° C. or lower for 100 days or more and coated on both sides with a synthetic resin layer, is wrapped around an outer drum and exposed, and then developed by an area gradation. In the area gradation image forming method for forming an image, the silver halide light-sensitive material has a gelatin-containing layer containing a vinylsulfone hardener on the opposite side of the silver halide emulsion layer, and is set after coating. After being stored at 0 ° C. or less after being dried and before being wound around the outer drum and exposed to light, heat treatment is performed so that the tf value defined by the following formula is 4 × 10 ⁻¹¹ or more. An area gradation image forming method.

tf = ∫exp (−K / T) · dt
(In the formula, t represents time (minutes), K represents a constant of 1.006 × 10 ^4, and T represents the temperature (K) of the environment in which the silver halide photosensitive material is placed.)
(Claim 2)
The area gradation image forming method according to claim 1, wherein the heat treatment is performed at 30 ° C. or more.

(Claim 3)
The area gradation image forming method according to claim 2, wherein the heat treatment is performed at 35 ° C. or more.

(Claim 4)
The area gradation image forming method according to claim 1, wherein the heat treatment is performed such that a tf value is 4 × 10 ⁻¹¹ to 2 × 10 ⁻¹⁰ .

(Claim 5)
The area gradation image forming method according to claim 1, wherein a base paper of the paper support is 70 to 120 g / m ² .

(Claim 6)
The area gradation image forming method according to claim 1, wherein the paper support has a thickness of 80 to 140 μm.

(Claim 7)
The area gradation image forming method according to claim 6, wherein the thickness of the paper support is 90 to 130 μm.

  According to the present invention, in an area gradation image forming method in which an area gradation image is formed by developing a silver halide light-sensitive material stored frozen and wound around an outer surface drum, the exposure position shifts, and the peeling from the outer surface drum. In addition, it is possible to provide an area gradation image forming method capable of stably obtaining a high-quality proof image without any problem in drying property and transportability in the apparatus.

As a result of diligent research, the present inventor has stored a silver halide photosensitive material having a paper support having a thickness of 150 μm or less, which is stored at 0 ° C. or lower for 100 days or longer and covered with a synthetic resin layer on both sides, and is exposed to light. Thereafter, in the area gradation image forming method of forming an area gradation image by development processing, the silver halide photosensitive material has a gelatin-containing layer containing a vinyl sulfone hardener on the opposite side of the silver halide emulsion layer. The heat treatment is such that the tf value becomes 4 × 10 ⁻¹¹ or more after being set after application, being dried, and after being stored at the temperature of 0 ° C. or lower and being wound around the outer drum and exposed. By the area gradation image forming method, the area gradation image forming method can be obtained in which a high-quality proof image can be stably obtained without displacement of the exposure position and separation from the outer drum. Heading, which has led to the completion of the present invention.

  Hereinafter, the present invention will be described in detail.

  One of the features of the present invention resides in that a silver halide photosensitive material (hereinafter also simply referred to as a photosensitive material) stored at a temperature of 0 ° C. or lower for 100 days or more is wrapped around an outer drum and exposed.

  In a system that forms an area gradation image based on digital data, a halftone dot is divided into smaller units (pixels), and the halftone dot is reproduced as an aggregate by exposing the pixel with an appropriate exposure amount. Is possible. To give a simple example, if one halftone dot is composed of 100 pixels, a halftone dot of 50% is formed by exposing 50 pixels so that they can be developed. Can do. In order to draw an image with such light, it is necessary to scan the photosensitive material with a light beam. The photosensitive material is wound around a cylindrical drum, and the light beam is moved in a direction perpendicular to the rotation direction while rotating at high speed. The exposure method (cylindrical outer surface scanning exposure method) is often used because it enables stable image formation up to the periphery. However, in this method, the photosensitive material must be closely attached to the cylindrical drum. In order for this to be performed accurately, it is necessary to accurately position and convey the material. To that end, it is very important that the slidability and curl of the photosensitive material have stable physical properties.

(Heat treatment)
One of the features of the present invention is that the photosensitive material is subjected to heat treatment after being stored at a temperature of 0 ° C. or lower, and the following tf value needs to be 4 × 10 ⁻¹¹ or more. The tf value is defined as follows.

tf = ∫exp (−K / T) · dt
Here, t represents time (minutes), and K represents a constant of 1.006 × 10 ⁴ . T represents the temperature (K) of the environment where the photosensitive material is placed.

The heat treatment applied after the frozen storage is preferably performed at 30 ° C. or higher, and more preferably 35 ° C. or higher. When it is lower than 30 ° C., the effect of improving the positional deviation and peeling from the drum is small, and it is not preferable because it takes time. The tf value during this heat treatment is more preferably 4 × 10 ⁻¹¹ to 2 × 10 ⁻¹⁰ .

(Vinyl sulfone hardener)
One of the features of the present invention is that it has a gelatin-containing layer containing a vinylsulfone hardener on the opposite surface (hereinafter also referred to as BC layer) of the emulsion layer.

  As the vinyl sulfone hardener used in the present invention, any known compound can be preferably used, but the following compounds are more preferably used.

  Furthermore, a chlorotriazine hardener can be used in combination as long as the effects of the present invention are not impaired.

  As a binder for the BC layer, a synthetic hydrophilic high polymer such as gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, mono- or copolymers can be used as long as the effects of the present invention are not impaired. A hydrophilic colloid such as a molecular substance can also be used in combination.

(Support)
One of the features of the present invention is that the support is a paper support having a thickness of 150 μm or less, coated on both sides with a synthetic resin layer. Examples of the synthetic resin layer include polyethylene, polypropylene, and polyethylene terephthalate. Can be mentioned.

For the purposes of obtaining a proof image, to approximate the sensation of handling the printing paper, 130 g / m ² or less of the base paper is preferably used, you are preferably used further 70~120g / m ² base paper. Similarly, the thickness of the support is preferably 80 to 140 μm, more preferably 90 to 130 μm. In the light-sensitive material using such a paper support, there was a phenomenon that when the heat treatment was performed after freezing, the physical properties such as curl were not a problem, but the drying property was deteriorated. The subject of the present invention can also be said to be a problem inherent to the proof photosensitive material.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  In the present invention, inorganic and / or organic white pigments can be used for the synthetic resin layers on both sides of the support, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as finely divided silicic acid, synthetic silicate, calcium silicate, alumina, alumina hydrate, Examples thereof include titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the synthetic resin layer can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  The synthetic resin layer may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, it is preferred that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less because of good gloss in photographic applications. In the proof use, those having a thickness of 0.8 to 2 μm are preferably used from the viewpoint of closeness to the printed matter.

  One of the features of the present invention is that a gelatin-containing layer provided on the opposite side of the silver halide emulsion layer is set after coating and dried. When the gelatin layer is dried, a method is adopted in which the gelatin is gelled by cooling immediately after coating, and then the water is gradually evaporated and the temperature is increased as the water is evaporated. The gelatin film formed by such a method is sometimes called a C film. In such a method, it is known that, when cooled, the collagen chain is coiled and oriented, so that high gloss and physical strength are increased.

  On the other hand, a method of drying under high temperature conditions without gelation is also known. In this case, gelatin forms a film in a dry sol state. This is sometimes called an H film. The gelatin layer opposite to the silver halide emulsion layer according to the present invention is characterized by comprising a C film. It has not been known that when this layer is an H film, the dryness remains at an insufficient level even by heat treatment after freezing storage.

(Silver halide emulsion)
The silver halide emulsion used in the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc. What has a composition is used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. Of the silver halide emulsion having a silver bromide-rich portion, the silver bromide-containing portion may be a so-called core-shell emulsion, or simply forming a complete layer without forming a complete layer. A so-called epitaxy-bonded region in which only a region having a partially different composition exists may be formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

The silver halide emulsion used in the present invention preferably contains heavy metal ions. This improves the so-called reciprocity failure, and is expected to prevent desensitization at high illumination exposure and softening on the shadow side. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and group 12 metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, water, pyridine, Pyrrol, pyrazole, imidazole, thiazole, 1,2,4-triazole, 2,2′-biimidazole, 2,2′-bipyridine or 2,2 ′: 6 ′, 2 ″ -terpyridine compound is preferably used. Cyanide ion, chloride ion, bromide ion, water, nitrosyl, 5-methylthiazole, 1,2,4-triazole, etc. In order to contain a heavy metal ion in a silver halide emulsion, the heavy metal compound is added. Before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains In order to obtain a silver halide emulsion satisfying the above conditions, the heavy metal compound is dissolved together with the halide salt to completely or partially add the grain. In addition, silver halide fine particles containing these heavy metal compounds can be formed in advance and added to the silver halide fine particles. 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol is more preferable, and 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol is more preferable per 1 mol of silver halide.

  The silver halide grains used in the present invention can have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973) and the like, particles having an octahedron, a tetrahedron, a dodecahedron, and the like can be made and used. Furthermore, particles having twin planes may be used.

  The silver halide grains used in the present invention are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions in the same layer.

  The grain size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0 in consideration of other photographic performances such as rapid processability and sensitivity. .2 to 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as diameter or projected area.

  The grain size distribution of the silver halide grains used in the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0. Two or more monodispersed emulsions of 15 or less are added to the same layer. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The silver halide grains may be grown at a time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing them may be the same or different.

  The form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and a reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus or the like that forms grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added and used at the time of forming silver halide grains or after completion of grain formation.

  The silver halide emulsion used in the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer, it is preferable to change the size of the applied silver halide emulsion types and expected effects, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^{- 5} mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol are preferable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol is more preferable.

  As a chemical sensitization method for the silver halide emulsion used in the present invention, a reduction sensitization method may be used.

  The silver halide emulsion used in the present invention is a known antifoggant for the purpose of preventing fogging during the preparation process of the light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development. Stabilizers can be used. Examples of preferable compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferable specific compounds. Are the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP 2000-267235, page 8, right column 32-36. The compound described in the row, a mercaptopyrimidine compound represented by general formula (I) in JP-A-9-152675, an adsorption promoting group and a substituted or unsubstituted group on silver halide represented by general formula (II) Compounds having a hydroxyl group or an amino group, specifically, (I-1), (I-2), (I-7), (I-9), (II-1), (II-3) Mention may be made of the compounds represented. In addition, compounds having sulfides and polysulfide groups shown in (A) to (D) of JP-A-10-31279 can be mentioned, and specifically, (C-1), (C-9), (C-14), (C-15), (C-16), (D-1), (D-6), α-sulfur, JP-A 2000-122204 (I-4), (I- 6).

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  In the photosensitive material used in the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, dyes AI-1 to 11 described in JP-A-3-251840, page 308 and JP-A-6 A dye described in No. 3770 is preferably used.

  The light-sensitive material used in the present invention comprises a hydrophilic colloid layer colored with at least one non-diffusible compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable to have. As the coloring substance, a dye or other organic or inorganic coloring substance or a white pigment can be used.

As the white pigment, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, among which titanium dioxide is preferable. The white pigment is dispersed in a hydrophilic colloid aqueous solution binder such as gelatin so that the treatment liquid can penetrate. The coating amount of the white pigment is preferably 0.1 to 50 g / m ² , more preferably 0.2 to 5 g / m ² .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, an undercoat layer as required, or a non-photosensitive hydrophilic colloid layer such as an intermediate layer at an arbitrary position Can be provided.

  Addition of a fluorescent brightening agent to the light-sensitive material used in the present invention is preferred because the white background can be further improved. The fluorescent brightening agent is not particularly limited as long as it is a compound capable of absorbing visible light and emitting visible light fluorescence, but is preferably a diaminostilbene compound having at least one sulfonic acid group in the molecule. These compounds are preferred because they have the effect of promoting the elution of the sensitizing dye to the outside of the photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  The light-sensitive material used in the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the sensitizing dye used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28 are used alone. Or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or the like. It may be added as a water miscible solvent solution, emulsion or suspension greater than 0.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. 58-105141 can be used. 8. A method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system under conditions of 60 to 80 ° C., and a surface tension described in JP-B-60-6496 of 3.8 × 10 ⁻² N / m or less A method of dispersing in the presence of a surfactant that suppresses to a minimum, dissolved in an acid that does not substantially contain water and that does not exceed pKa as described in JP-A-50-80826, and adds the solution to an aqueous solution A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include a high speed stirring type disperser described in FIG. 1 of JP-A-4-125561, a ball mill, a sand mill, an ultrasonic disperser, and the like. be able to.

  In using these dispersing devices, as described in JP-A-4-125632, a pre-treatment such as dry pulverization may be performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

  As the coupler used in the light-sensitive material used in the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Typical examples include yellow dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, magenta dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm, and wavelength range. A known cyan dye-forming coupler having a spectral absorption maximum wavelength at 600 to 750 nm is representative.

  As the magenta coupler used in the present invention, a compound represented by the general formula [M-1] described in JP-A-6-95283, page 7, right column is preferable because of good spectral absorption characteristics of the coloring dye. Specific examples of preferred compounds include compounds M-1 to M-19 described on pages 8 to 11 of the same. As other specific examples, compounds M-1 to M-61 described in European Patent No. 0273712, pages 6 to 21 and compounds 1 to 223 described in JP 0235913, pages 36 to 92 are described above. There are other than the typical examples.

The magenta coupler can be used in combination with other types of magenta couplers and is usually used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide. it can.

  The λmax of spectral absorption of the magenta image formed in the photosensitive material used in the present invention is preferably 530 to 560 nm, and λL0.2 is preferably 580 to 635 nm. λL0.2 is a wavelength on the spectral absorbance curve of the magenta image that is longer than the wavelength at which the maximum absorbance is 1.0 and the absorbance is 0.2.

  The magenta image forming layer of the light-sensitive material used in the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. A preferred yellow coupler to be contained in the magenta image forming layer is a coupler represented by the general formula [Y-Ia] described in JP-A-6-95283, page 12, right column. Of the couplers represented by the general formula [Y-1] of the same publication, a coupler represented by [M-1] is preferable when combined with a magenta coupler represented by the general formula [M-1]. The coupler has a pKa value not lower than 3 or lower than the pKa value not lower than 3 pKa.

  Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283, and compounds described on pages 13 to 17 of JP-A-2-139542 (Y -1) to (Y-58) can be preferably used, but of course not limited thereto.

  In the light-sensitive material used in the present invention, a known phenol-based, naphthol-based, imidazole-based, or azole-based coupler can be used as the cyan coupler contained in the cyan image forming layer. For example, phenol couplers substituted with an alkyl group, acylamino group, or ureido group, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group are representative. The Among these, preferred compounds include general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

The cyan coupler can usually be used in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  In the light-sensitive material used in the present invention, a known acylacetanilide coupler or the like can be preferably used as the yellow coupler contained in the yellow image forming layer.

  Specific examples of the yellow coupler include, for example, compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by YI-1 to Y-I-55, or 11 of JP-A-3-209466. The compounds described on pages 14 to 14 and the compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [YI] described on page 21 of JP-A-6-95283, compounds of general formulas (I) and (II) described in JP-A-2002-352023, and the like can also be mentioned. .

  The λmax of the spectral absorption of the yellow image formed by the photosensitive material used in the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

  ΛL0.2 of the spectral absorption of the yellow image is a value defined by the content described in JP-A-6-95283, page 21, right column, lines 1 to 24. Indicates the amount of unnecessary absorption.

The yellow coupler can usually be used in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, a phosphoric acid ester compound represented by the general formula [HBS-I] described in JP-A-6-95283, page 22 and a phosphine oxide compound represented by [HBS-II] are more preferable. A compound represented by the general formula [HBS-II] described on page 22 of the same number is preferred. Further, higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A-4-265975 can be mentioned.

  In the light-sensitive material used in the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenol compounds represented by general formula IIIB described in JP-A-3-174150, Particularly preferred for magenta dyes are amine compounds represented by the general formula A described in No. 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A No. 62-182741. Further, a compound represented by the general formula I ′ described in JP-A-1-196049 and a compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  When using an oil-in-water emulsion dispersion method to add a stain inhibitor or other organic compound in the light-sensitive material used in the present invention, it is usually necessary for a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. Depending on the conditions, the organic solvent is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. As high-boiling organic solvents that can be used to dissolve and disperse stain inhibitors and the like, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  Examples of the surfactant used for dispersing the photographic additive and adjusting the surface tension during coating include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. . Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time until the addition to the coating solution after dispersion and the time after the addition to the coating solution are short are better. Within hours, preferably within 3 hours and more preferably within 20 minutes.

  In the light-sensitive material used in the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, and is added to the silver halide emulsion layer to cause fogging. It is preferable to improve. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

  In the light-sensitive material used in the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and compounds represented by general formula III described in JP-A 64-66646. Compounds represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, general formula I described in JP-A No. 4-1633, general formula (I) described in JP-A No. 5-165144, The compound shown by (II) is mentioned.

  The light-sensitive material used in the present invention preferably contains an oil-soluble dye or pigment because the white background is improved. Representative examples of oil-soluble dyes include compounds 1-27 described on pages 8-9 of JP-A-2-842.

  In the emulsion layer of the light-sensitive material used in the present invention, it is advantageous to use gelatin as a binder. However, if necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin are used. Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used. As the binder hardener, it is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. In the light-sensitive material, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

  The photosensitive material used in the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesiveness of the support surface, antistatic properties, dimensions) It may be applied via one or more subbing layers to improve stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties.

  In applying the photosensitive material, a thickener may be used in order to improve applicability. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  As the width of the photosensitive material, those having an arbitrary width can be used depending on the application, but a width of 400 mm or more is preferably used in the proof application. A photosensitive material having a width of 800 mm or more is also preferably used.

  In the present invention, the term area gradation image is used, but this is not expressed by the shading of the color of each pixel, but by the size of the area of the color developed at a specific density. It can be considered synonymous with halftone dots.

  In the case of normal area gradation exposure, the purpose can be achieved by causing Y, M, C, and black to be colored. In order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  A laser light source having an SHG element is one in which light oscillated from an LD or YAG laser is converted into a half-wavelength light by the SHG element and emitted, and since visible light is obtained, there is no green light source. Used as light source for blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use. An edge-emitting diode that is a kind of a small area light-emitting diode as described in JP-A-2002-72367 can be preferably used.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of direct modulation, the amount of emitted light may be changed by adjusting the current value, or a pulse width modulation method in which light is emitted in pulses and the width of the pulse (light emission time) is changed may be used. A pulse number modulation method in which the number is changed may be adopted. In the case of LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, a device such as AOM or EOM (electro-optic modulator) is generally used.

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used if the amount of light is weak.

  The emission wavelength of the light source can be preferably used in any wavelength region where the photosensitive material has sufficient sensitivity, but it has a sufficient sensitivity difference with other photosensitive layers in order to prevent color turbidity. It is preferable to use a region. Although it depends on the contrast of the photosensitive material, it is preferable that the common logarithm of the exposure amount has a sensitivity difference of 0.6 or more, preferably 1.0 or more. In addition, when the emission wavelength varies depending on the environmental conditions, operating conditions, etc. where the light source is placed, it is theoretically preferable to match the peak wavelength of the spectral sensitivity, and the spectral absorption of the colored substances involved It is preferable to select the wavelength in consideration of the relationship. Examples thereof include JP-A-6-75342 and JP-A-2001-83663. Further, when not only the emission wavelength but also the emission intensity varies, it is preferable to select the emission wavelength in relation to the spectral sensitivity. Examples thereof include Japanese Patent Application Laid-Open No. 2002-72367 and Nikkei New Material September 1987. It is described on page 54 of the 14th of the month.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In the present invention, a cylindrical outer surface scanning method is used in which a photosensitive material is wound around a cylindrical drum and the light beam is moved in a direction perpendicular to the rotation direction while rotating at high speed. The rolled material can be more accurately aligned and can be preferably used. From the same viewpoint, the support used for the photosensitive material used in the present invention has an appropriate rigidity, and the Taber rigidity is preferably 0.8 to 4.0.

  The drum diameter can be arbitrarily set according to the size of the photosensitive material to be exposed. The number of rotations of the drum can be arbitrarily set, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The photosensitive material may be fixed to the drum by mechanical means, or a number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is sucked. It can also be adhered. In order to prevent troubles such as image unevenness, it is important to make the photosensitive material as close as possible to the drum.

  As an apparatus used for image formation, a method in which a plurality of photosensitive materials are set in advance and the photosensitive materials are appropriately selected and used can be preferably used. In this case, the two types of photosensitive materials can be, for example, photosensitive materials having different widths or photosensitive materials having different surface properties (unevenness of the support). The selection of the photosensitive material may be a method of setting with a switch or the like of the image forming apparatus, or may be selected based on the setting information transmitted together with the image data. It is also advantageous to automatically select the optimum photosensitive material size according to the size of the image data. In special cases, the same type of photosensitive material can be loaded, and when one photosensitive material is used up, the other photosensitive material can be automatically used. Can be used.

  As the aromatic primary amine developing agent used in the development processing, known compounds can be used. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β-methanesulfonamido) ethyl-aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N, N -Dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N-e Ru-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, the color developer is used in an arbitrary pH range. Although it can be used, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing.

  The processing temperature for color development according to the present invention is preferably 35 to 70 ° C. The higher the temperature, the shorter the treatment is possible and the better, but it is preferably not so high from the stability of the treatment liquid, and the treatment is preferably performed at 37 to 60 ° C.

  In general, the color development time is about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

  In addition to the above color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.

  The photosensitive material is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative to a washing process. The development processing device used for the development processing of the photosensitive material is an endless belt that fixes and conveys the photosensitive material to the belt even if it is a roller transport type that conveys the photosensitive material between rollers arranged in a processing tank. Although the method may be used, the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank and the photosensitive material is conveyed, the spraying method of spraying the processing liquid, and the processing liquid is impregnated. Further, a web system by contact with a carrier, a system using a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, a running process is usually carried out using an automatic processor. At this time, it is preferable that the replenishment amount of the replenisher is as small as possible. It is adding a processing agent in a form, and the method described in the open technical report 94-16935 is most preferable.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
[Preparation of photosensitive material 101]
Reflection of polyethylene laminated paper with a mass of 115 g / m ² and a thickness of 150 μm, in which high-density polyethylene is laminated on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide is dispersed on the other side On the support (Taber stiffness = 3.5, PY value = 2.7 μm), each layer having the layer structure shown in Table 1 below is coated on the side of the polyethylene layer containing titanium oxide, and further on the back side is gelatin. Photosensitive material coated with a gelatin layer containing 8.4 g / m ² , silica matting agent (manufactured by Fuji Silysia Chemical Co., Ltd., Silicia 430) 0.7 g / m ² and 0.17 g of Comparative Compound 1 as a hardener. 101 was produced. In forming the back layer, it was gelled through a 3 ° C. zone immediately after coating and then dried to form a C film.

The coupler was dissolved in a high boiling point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Moreover, (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: Exemplified Compound B8
H-2: Comparative compound 1
HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di- A mixture of sec-dodecyl hydroquinone, 2,5-di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2 SO-1: trioctylphosphine oxide SO-2 : Di (i-decyl) phthalate SO-3: oleyl alcohol SO-4: tricresyl phosphate PVP: polyvinylpyrrolidone (Preparation of blue-sensitive silver halide emulsion)
The following (A solution) and (B solution) were simultaneously added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) and (D liquid) was simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Liquid A)
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
(Liquid B)
Silver nitrate 10g
200ml with water
(C liquid)
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
600ml with water
(Liquid D)
300 g of silver nitrate
600ml with water
After completion of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm and a coefficient of variation in particle size distribution. A monodispersed cubic emulsion EMP-101 having 0.07 and a silver chloride content of 99.5 mol% was obtained.

  The monodispersed cubic emulsion (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B101).

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of EMP-101, the average particle size of 0 was obtained in the same manner as in EMP-101 except that the addition times of (A liquid) and (B liquid) and the addition times of (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a particle size distribution coefficient of 0.07 and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive emulsion.

(Preparation of green sensitive silver halide emulsion)
In the same manner as in the preparation of EMP-101, except that the addition time of (A liquid) and (B liquid), (C liquid) and (D liquid) was changed, the average particle diameter was 0.40 μm, the coefficient of variation was 0.08 A monodispersed cubic emulsion (EMP-103) having a silver chloride content of 99.5% was obtained.

  The EMP-102 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green sensitive silver halide emulsion (Em-G101).

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye GS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye GS-2 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Subsequently, in the preparation of EMP-103, the average particle size of 0 was obtained in the same manner as in EMP-103, except that the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-104 having a thickness of .50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained. Em-G102 was obtained in the same manner as in the preparation of Em-G101 except that EMP-104 was used instead of EMP-103, and a 1: 1 mixture of Em-G101 and 102 was used as a green-sensitive emulsion.

(Preparation of red-sensitive silver halide emulsion)
The EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R101).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-4 mol / mol AgX
Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer SS-1 2 × 10 ⁻⁴ mol / mol AgX
Next, in the preparation of (Em-R101), chemical sensitization was optimally performed at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R102).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-4 mol / mol AgX
Sensitizing dye RS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye RS-2 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer SS-1 2 × 10 ⁻⁴ mol / mol AgX
STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: A 1: 1 mixture of p-toluenethiosulfonic acid Em-R101 and Em-R102 was used as the red sensitive emulsion.

[Production of photosensitive materials 102 to 106]
In the preparation of the photosensitive material 101, the comparative compound 2, the comparative compound 3, the exemplary compound B2, the exemplary compound B5, and the exemplary compound B8 were used in place of the comparative compound 1 as the hardener of the back layer, and the others were the same in the same manner. Photosensitive materials 102, 103, 104, 105 and 106 were produced. The amount of the hardener in the back layer is the unit area after each photosensitive material is wrapped in a polyethylene light-shielding sheet, subjected to heat treatment at 35 ° C. for 6 days, and then subjected to the following development processing and stabilization processing. The hit mass was adjusted to be the same as that of the photosensitive material 101.

[Production of photosensitive materials 107 to 112]
In the production of the photosensitive materials 101, 102, 103, 104, 105, 106, the formation of the back layer was performed in the same manner except that the film was dried through a zone of 80 ° C. without gelation after coating, and an H film was formed. Photosensitive materials 107, 108, 109, 110, 111, and 112 were prepared.

[Evaluation]
The obtained photosensitive material 50 m was wound around a core having a diameter of 75 mm to obtain a roll-shaped sample. Light-shielding flanges were fitted to both ends of the roll-shaped sample, each sample and a polyethylene light-shielding sheet were put together and adhered with an adhesive tape, and the light-shielding sheet was stretched and wound about 3 times. After putting this sample in a cardboard box and placing it under the following storage conditions, it was exposed by wrapping around an outer drum using the exposure apparatus shown below, and the development process shown below was performed to form an area gradation image. . At this time, the tf value during the heat treatment was 5.6 × 10 ⁻¹¹ . The temperature and humidity during exposure were 25 ° C. and 20% RH, and after 10 sheets were automatically wound around the exposure drum, they were sucked from the inside of the drum and fixed, exposed and developed. The number of revolutions of the exposure drum was 1000 rpm. This was repeated three times while appropriately replacing the samples, and a total of 30 images were output.

Storage condition A: (−20 ° C., 150 days) and then (35 ° C., 6 days)
Storage condition B: (35 ° C., 6 days) and then (−20 ° C., 150 days)
The exposure apparatus was adjusted so that 10 LEDs could be exposed at the same location by arranging 10 B LEDs as the light source in the main scanning direction and delaying the exposure timing little by little. In addition, an exposure head was prepared in which 10 LEDs were arranged in the sub-scanning direction, and exposure for 10 adjacent pixels could be performed at once. Similarly, for G and R, exposure heads were prepared by combining LEDs. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 100 μm. The exposure time per pixel was about 100 nanoseconds.

  Development processing was performed as follows.

Processing step Processing temperature Time Replenishment amount Color development 33.0 ± 0.3 ° C 120 seconds 80ml
Bleach fixing 33.0 ± 0.5 ℃ 90 seconds 120ml
Stabilization 30-34 ° C 60 seconds 150ml
Drying 60-80 ° C 30 seconds (color developer tank solution and replenisher)
Tank liquid Replenisher Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β-hydroxyethyl) -4-aminoaniline sulfate
2.9g 4.8g
N, N-disulfoethylhydroxylamine
20.4g 18.0g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Add water to bring the total volume to 1 liter, adjust the tank solution to pH = 10.0, and the replenisher to pH = 10.6.

(Bleaching fixer tank solution and replenisher solution)
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Add water to bring the total volume to 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.

(Stabilizer liquid and replenisher)
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Zinc sulfate 0.5g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

(Number of drum peeling occurrence)
During the exposure, the number of peelings from the drum was counted.

(Drying)
The ninth and tenth samples that were continuously output were superposed and allowed to stand for 5 minutes, and the degree of sticking was observed, and the drying property was evaluated according to the following criteria.

○: There is no sticking. Δ: It is stuck weakly but can be easily peeled. ×: Sticking occurs and it cannot be peeled off.

  From Table 2, it can be seen that, under the storage condition B, any sample peeled off from the drum. The drying properties were all good.

  On the other hand, it is understood that those stored under the storage condition A have poor dryability except for the comparative compound 2 as a hardener in the H film. Regarding the peeling from the drum, the difference between the C film and the H film is not so great, but it varies greatly depending on the type of hardener and is greatly improved by using vinylsulfone hardener. I understand. Looking at the data in detail, it was found that the H membrane was slightly inferior when the vinylsulfone hardener was used. I don't know the exact reason, but curl seems to be mainly due to curl, but when gelatin's hardening reaction proceeds, the contribution of the gelatin film structure itself is fixed. It is presumed that a C film having a high structure and a dural reaction is advantageous.

Example 2
Using the photosensitive materials 101, 106, 107 and 112 produced in Example 1, after 150 days of freezing storage, the temperature and duration of the heat treatment were changed as shown in Table 3 below, and the same evaluation as in Example 1 was performed. went.

  The evaluation results are shown in Table 3 together with the tf value of the heat treatment.

  From Table 3, it can be seen that the samples using Comparative Compound 1 all have poor drying properties, and the peeling from the drum is large under any heat treatment conditions. On the other hand, when the vinyl sulfone hardener B8 is used, it can be seen that the drying property is good and the number of occurrences of peeling from the drum is very small. The temperature and the period are adjusted so as to have substantially the same tf value. However, when the temperature is low, the effect of improving peeling from the drum is small, and it is understood that the temperature range is preferably 30 to 40 ° C.

Example 3
Samples in which the tf value was changed by changing the temperature and the duration of the heat treatment as shown in Table 4 below after 150 days of freezing storage using the photosensitive materials 101, 106, 107, 112 produced in Example 1. The same evaluation as in Example 1 was performed.

  The results of evaluation are shown in Table 4 together with the tf value of the heat treatment.

From Table 4, the samples using Comparative Compound 1 all have poor drying properties, and the tendency to easily peel off from the drum is the same as before, and even if the tf value is increased, the effect of improving the drying properties. Is not seen. On the other hand, when the vinyl sulfone type hardener B8 is used, if the tf value is less than 4 × 10 ⁻¹¹ , the peeling from the drum and the drying property are insufficient. It can be seen that a sufficient improvement effect can be obtained in both properties and peeling from the drum.

Claims (7)

The silver halide light-sensitive material having a paper support with a thickness of 150 μm or less, which is stored at 0 ° C. or lower for 100 days or more and coated on both sides with a synthetic resin layer, is wrapped around an outer drum and exposed, and then developed by an area gradation. In the area gradation image forming method for forming an image, the silver halide light-sensitive material has a gelatin-containing layer containing a vinylsulfone hardener on the opposite side of the silver halide emulsion layer, and is set after coating. After being stored at 0 ° C. or less after being dried and before being wound around the outer drum and exposed to light, heat treatment is performed so that the tf value defined by the following formula is 4 × 10 ⁻¹¹ or more. An area gradation image forming method.
tf = ∫exp (−K / T) · dt
(In the formula, t represents time (minutes), K represents a constant of 1.006 × 10 ^4, and T represents the temperature (K) of the environment in which the silver halide photosensitive material is placed.) The area gradation image forming method according to claim 1, wherein the heat treatment is performed at 30 ° C. or more. The area gradation image forming method according to claim 2, wherein the heat treatment is performed at 35 ° C. or more. The area gradation image forming method according to claim 1, wherein the heat treatment is performed such that a tf value is 4 × 10 ⁻¹¹ to 2 × 10 ⁻¹⁰ . The area gradation image forming method according to claim 1, wherein a base paper of the paper support is 70 to 120 g / m ² . The area gradation image forming method according to claim 1, wherein the paper support has a thickness of 80 to 140 μm. The area gradation image forming method according to claim 6, wherein the thickness of the paper support is 90 to 130 μm.