JP2006215242A - Silver halide color photographic sensitive material for scanning exposure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material for scanning exposure which reproduces a gloss close to that of matte paper, excels in a white background in continuous processing, and also excels in the pressure resistance of a processed print sample. <P>SOLUTION: In the silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloidal layer disposed on a support by coating, a porous particulate fine powder ≥300 mg/m<SP>2</SP>and a liquid ultraviolet absorber which is liquid at ordinary temperature are contained in the at least one non-photosensitive hydrophilic colloidal layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a proof for confirming the finish of printed matter in advance. More specifically, it reproduces gloss similar to matte paper, is excellent in white background in continuous processing, and is excellent in pressure resistance of processed print samples. The present invention relates to a silver halide color photographic light-sensitive material.

  Silver halide color light-sensitive materials are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Because of these features, silver halide color photographic materials are widely used not only in the field of photography but also in the field of printing, so-called proofing for checking the state of the finished printed matter in the middle of printing. It is coming.

  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 matter is formed on color photographic paper, thereby determining the suitability of the layout and color of the final printed matter.

  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 was 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 color light-sensitive materials enables high-quality image formation, such as the ability to form accurate halftone images due to excellent sharpness, etc., while continuous processing is possible 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 color photosensitive materials have begun to be used advantageously in this field. In particular, a silver halide color photographic material for scanning exposure is useful.

  In a system that forms an area gradation image based on digital data, a halftone dot is divided into smaller units (herein, these are expressed as pixels), and this pixel is scanned and exposed at an appropriate exposure amount. It is possible to reproduce a halftone dot. For example, if a halftone dot is composed of 100 pixels, a halftone dot of 50% is formed by exposing 50 pixels so that they can be developed. I can do it.

  Conventionally, He-Ne lasers, semiconductor lasers, and the like have been used as scanning exposure light sources, but in recent years, LEDs that are inexpensive, have a long life, and are easily arrayed have come to be used.

  On the other hand, in recent years, the required quality for proof images is not limited to image reproducibility, and it has been required to approximate the gloss and texture thereof to printed matter.

  One means for adjusting the gloss level is to adjust the unevenness of the support. However, the difference mainly due to the surface roughness, such as the difference between the matte paper with large unevenness and the art paper with high smoothness, can be generally adjusted, but the difference in gloss mainly due to the difference in light scattering is also possible. It is difficult to make adjustments, and fine adjustment of gloss and texture is usually performed by appropriately using a matting agent.

  Matting agents used in silver halide color photographic light-sensitive materials for scanning exposure include inorganic particles such as silicon dioxide, titanium dioxide, magnesium oxide, aluminum oxide, and calcium carbonate, and organic materials such as polymethyl methacrylate, polymethyl acrylate, and polystyrene. In recent years, polyester latex particles, acrylic latex particles, spherical silica, and the like are also used (see, for example, Patent Documents 1 and 2).

  However, when the matting agent is used, when the surface of the developed sample is damaged by a sharp object, the halftone dot is broken and blurring occurs, which may cause a problem in image quality.

  On the other hand, the developed sample is placed in various environments. In particular, they are often exposed to light sources such as sunlight and fluorescent lamps for a long time. In this case, since the density is lowered, it is known that the silver halide photographic light-sensitive material contains an ultraviolet absorber (for example, see Patent Document 3).

However, the silver halide photographic light-sensitive material is continuously processed by adding a replenisher for the developed processing. However, the white background of the silver halide photographic light-sensitive material using the UV absorber is likely to fluctuate due to continuous processing. I understood. In the field of proofing, white background is an important performance and improvement was desired.
JP-A-10-104794 JP 2004-361550 A JP-A-5-303168

  The present invention has been made in view of the above problems, and its purpose is to reproduce a gloss similar to matte paper, excellent white background in continuous processing, and excellent pressure resistance of processed print samples. Silver halide for scanning exposure The object is to provide a color photographic light-sensitive material.

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

(Claim 1)
In a silver halide photographic light-sensitive material in which at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are coated on a support, at least one layer of the non-photosensitive hydrophilic colloid layer has a thickness of 1 m. ^A silver halide color photographic light-sensitive material for scanning exposure, comprising 300 mg or more of fine porous fine particles per ² and a liquid ultraviolet absorber that is liquid at room temperature.

(Claim 2)
In a silver halide photographic light-sensitive material in which at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are coated on a support, at least one layer of the non-photosensitive hydrophilic colloid layer has a thickness of 1 m. ^A silver halide color photographic light-sensitive material for scanning exposure, wherein 300 mg or more of fine porous fine particles per ² are simultaneously dispersed and contained using a liquid ultraviolet absorber which is liquid at room temperature.

(Claim 3)
3. The silver halide color photographic light-sensitive material for scanning exposure according to claim 1, wherein the fine porous fine powder is an inorganic compound.

(Claim 4)
4. The silver halide color photographic light-sensitive material for scanning exposure according to claim 3, wherein the porous fine particle powder is silica.

  According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material for scanning exposure that reproduces gloss similar to matte paper, is excellent in white background in continuous processing, and has excellent pressure resistance of processed print samples.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

In the silver halide color photographic light-sensitive material for scanning exposure according to the present invention, at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are coated on a support. At least one of the colloid layers contains 300 mg or more of porous fine particles per 1 m ² and a liquid ultraviolet absorber that is liquid at room temperature.

  As a result of intensive studies on the above problems, the present inventor has presented the present invention by simultaneously presenting at least one of the non-photosensitive hydrophilic colloid layers with fine porous fine particles and a liquid ultraviolet absorber that is liquid at room temperature. As soon as it has been found that the effect can be achieved, the present invention has been achieved.

  Furthermore, the present inventors have also found that the effect of the present invention can be further enhanced by simultaneously dispersing fine porous fine powder using a liquid ultraviolet absorbent that is liquid at room temperature.

  In particular, the pressure resistance of a processed print sample can be regarded as a phenomenon of bleeding, according to the study of the present inventor. Therefore, an oil component such as a liquid ultraviolet absorber is present in a layer other than the uppermost layer of the photosensitive material. Increasing the oil / gelatin ratio was found to increase and make bleeding more likely. On the other hand, when the matting agent such as porous fine particle powder is in the uppermost layer, the effect of tightening the surface of the photosensitive material due to the dispersing effect of the matting agent is recognized, and the liquid ultraviolet absorber and the porous fine particle powder are in the same layer. In addition, the present inventors have found that the phenomenon of bleeding can be greatly improved by dispersing a fine porous fine powder at the same time as the liquid ultraviolet absorber and adding it to the uppermost layer. Furthermore, it is possible to promote the diffusion of unnecessary developing agent oxide generated during development processing to the outside of the system by configuring the liquid ultraviolet absorber and porous fine particle powder in the same layer, or deterioration of the white background during continuous processing. It has also been found that the prevention is prevented.

(Porous fine particle fine powder)
The porous fine particle powder of the present invention may be used singly or in combination with other porous fine powders. Examples of the porous fine powder of the organic compound include natural and synthetic organic polymer compounds such as cellulose esters, polymethyl methacrylate, polystyrene, or polydivinylbenzene and copolymers thereof. In the present invention, inorganic compounds are used. The porous fine particle powder is preferably used. Specific examples of the inorganic compound include silica, alumina, aluminum hydroxide, titanium oxide, barium sulfate, calcium carbonate, magnesium sulfate, glass beads, and synthetic mica. Of these, silica is most preferred.

  The preferable average particle diameter of the porous fine particle powder of the present invention is 1.0 to 7.0 μm, particularly preferably 3.0 to 7.0 μm. If the particle diameter is smaller than 1.0 μm, it is difficult to obtain the effect of the present invention as a matting agent, and if it is larger than 7.0 μm, the amount of addition necessary for obtaining the same matting effect is increased, resulting in inefficiency in cost. In addition to this, pinholes are likely to occur due to dropout of particles. The average particle diameter is defined by numerical values measured by the laser diffraction / scattering method, and indicates the number average particle diameter measured by the same method. Specifically, a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by HORIBA) or the like is used.

The surface area of the porous fine particle powder of the present invention is 100 m ² / g or more, preferably 200 m ² / g or more. The pore size of the porous fine particles is preferably an average diameter of 30 nm or less, and preferably 25 nm or less. The surface area and pore diameter of the porous fine particle powder can be determined by a gas adsorption method.

  US Pat. Nos. 1,665,264; 1,935,196; 2,071,987; 2,459,903; 2,462 , 798, 2,469,314, 2,505,895, 2,685,69, 3,066,092, 4,070,286, etc. Can be made. The field using such a large surface area of the porous fine particle powder is wide, and since it is used for catalysts, chromatography, chemical sensors, filters, etc., it can be easily obtained in the market.

As apparent from the object of the present invention, the fine porous fine particle powder of the present invention is used not on the back surface but on the image layer side, and is contained in an amount of 300 mg or more per 1 m ² in the silver halide photographic light-sensitive material. 500-1500 mg is preferable, and 600-1200 mg is most preferable. The layer to be contained is a non-photosensitive hydrophilic colloid layer, and specifically, a protective layer that is the uppermost layer is particularly preferable.

  The porous fine particle powder of the present invention may be directly added as a powder to the coating solution for forming the non-photosensitive hydrophilic colloid layer to be added, but after being dispersed in water or an aqueous gelatin solution, the non-photosensitive hydrophilic colloid layer is added. And a method of adding to a coating solution for forming a non-photosensitive hydrophilic colloid layer after being dispersed in a high-boiling organic solvent or a liquid ultraviolet absorbent that is liquid at room temperature. The most preferred method is a method of adding a coating solution for forming a non-photosensitive hydrophilic colloid layer after being dispersed in a liquid ultraviolet absorbent that is liquid at room temperature.

  Means for dispersing the fine porous fine particles of the present invention in water, an aqueous gelatin solution, a high-boiling organic solvent, and a liquid ultraviolet absorber that is liquid at room temperature include a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic disperser. Can be used. It is also preferable to use a known surfactant.

  The liquid ultraviolet absorber that is liquid at room temperature according to the present invention, which will be described later, can be dispersed by a known method. When using an oil-in-water emulsion dispersion method, a water-insoluble high boiling point having a boiling point of 150 ° C. or higher is usually used. If necessary, the organic solvent is dissolved together 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 a 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 point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  In the present invention, it is preferable that the fine porous fine powder is previously mixed with a liquid ultraviolet absorbent that is liquid at room temperature and then simultaneously dispersed by the above-described process.

  As the high-boiling organic solvent that can be used for dissolving and dispersing the liquid ultraviolet absorber, phthalates such as dioctyl phthalate and dibutyl phthalate, and phosphates such as tricresyl phosphate and trioctyl phosphate are preferable. It is also possible to use two or more kinds of high-boiling organic solvents in combination. Most preferably, no high boiling point organic solvent is used.

  In the present invention, a liquid ultraviolet absorber that is liquid at room temperature is used. In the present invention, the “liquid ultraviolet absorber that is liquid at room temperature” has fluidity at 25 ° C. as defined in “Chemical Dictionary (1963) Kyoritsu Shuppan”, etc. Those having a substantially constant volume are shown. Therefore, the melting point is not particularly limited as long as it has the above properties, but a compound having a melting point of 30 ° C. or lower, particularly preferably 15 ° C. or lower is preferable.

  The liquid ultraviolet absorber of the present invention may be a single compound or a mixture, and as the mixture, those composed of a structural isomer group can be preferably used (for the structural isomer, US Pat. 587,346 etc.). The liquid ultraviolet absorber of the present invention can adopt any structure as long as the above is satisfied, but 2- (2-hydroxyphenyl) represented by the following general formula (A) from the viewpoint of light fastness of the ultraviolet absorber itself. ) A benzotriazole-based compound is preferred.

In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitrogen group or a hydroxyl group.

Examples of the halogen atom represented by R ₁ , R ₂ and R ₃ include a fluorine atom, a chlorine atom and a bromine atom, and a salt atom is particularly preferable.

The alkyl group and alkoxy group represented by R ₁ , R ₂ and R ₃ are preferably those having 1 to 30 carbon atoms, and the alkenyl group is preferably one having 2 to 30 carbon atoms. May be linear or parted. Further, these alkyl group, alkenyl group and alkoxy group may further have a substituent.

  Examples of alkyl groups, alkenyl groups, and alkoxy groups include, for example, methyl, ethyl, i-propyl, t-butyl, sec-butyl, butyl, pentyl, sec-pentyl, t-pentyl, octyl, nonyl, dodecyl, Examples include groups such as eicosyl, α, α-dimethylbenzyl, octyloxycarbonylethyl, methoxy, ethoxy, octyloxy and allyl.

As the aryl group and aryloxy group represented by R ₁ , R ₂ and R ₃ , for example, a phenyl group and a phenoxy group are particularly preferable and may have a substituent. Specific examples include phenyl, 4-t-butylphenyl, 2,4-di-t-pentylphenyl, and the like.

Of the groups represented by R ₁ and R ₂ , a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferable, and a hydrogen atom, an alkyl group and an alkoxy group are particularly preferable.

Among the groups represented by R ₃ , a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group are particularly preferable, but a hydrogen atom, an alkyl group, and an alkoxy group are more preferable from the point of bright fading.

Of the groups represented by R ₁ , R ₂ and R ₃ , at least one is preferably an alkyl group, and more preferably at least two are alkyl groups in order to become liquid at room temperature.

The alkyl group represented by R ₁ , R ₂ and R ₃ can take any alkyl group, but at least one is preferably a tertiary alkyl group or a secondary alkyl group. In particular, at least one of the alkyl groups represented by R ₁ and R ₂ is preferably a tertiary alkyl group or a secondary alkyl group.

  The following are typical examples of liquid ultraviolet absorbers according to the present invention, but the present invention is not limited thereto.

The liquid ultraviolet absorber according to the present invention can be added in any amount, but it is used in a range of 0.1 to 300% by mass with respect to the binder of the photographic composition layer containing the ultraviolet absorber. Preferably 1 to 200%, more preferably 5 to 100%. Further, preferably 0.01 - 100/100 cm ² as a coating amount, further 0.1 to 50 mg / 100 cm ^2, is preferably used, especially in 0.5 to 30 mg / 100 cm ^2.

  The layer containing the liquid ultraviolet absorber of the present invention is contained in the photographic constituent layer of the present invention in at least one of the non-photosensitive hydrophilic colloid layers together with the porous fine particle powder. A non-light-sensitive hydrophilic colloid layer in which at least 60% by weight, more preferably at least 80% by weight, of the total liquid ultraviolet absorber contained therein is located farther from the light-sensitive silver halide emulsion layer farthest from the support In particular, it is particularly preferable to be added to the protective layer.

  The maximum density of the silver halide color light-sensitive material for scanning exposure of the present invention is not particularly specified, but when each color of Yellow, Magenta, and Cyan is made to develop the maximum color, the scanning exposure in which any one of the reflection densities becomes 2.0 or more. When the present invention is used for a silver halide color light-sensitive material, a great effect is exhibited. The reflection density in this case refers to a numerical value measured by a densitometer capable of measuring the Status T reflection density. Specific examples of the densitometer capable of measuring the Status T reflection density include X-Rite 528 (manufactured by X-Rite).

  The glossiness in the present invention refers to that measured by a method according to the measurement method of incident angle / reflection angle = 60 ° / 60 ° described in JIS-Z8741 “Measurement method of specular gloss”. Even in art paper and coated paper, which are relatively high gloss printing papers, the glossiness is almost in the range of 1 to 15, and silver halide color photosensitive materials are subject to color calibration. When used as a proof image of many printed art papers and coated papers, the glossiness is preferably in the range of 1 to 15, and more preferably in the range of 1 to 6.

  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.

It is advantageous that the negative silver halide emulsion used in the present invention contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent 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, cobalt, and twelfth 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-described conditions, the heavy metal compound is dissolved together with the halide salt to completely or partly form the grain. In addition, it is also possible to prepare silver halide fine particles containing these heavy metal compounds in advance and add them to the silver halide. The amount added to the emulsion is preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, more preferably 1 × 10 ⁻⁸ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide. preferable.

  Any particle shape can be used in the present invention. 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, and JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  The 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 particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 when considering other photographic performances such as rapid processability and sensitivity. It is the range of -1.0 micrometer.

  This particle size can be measured using the projected area or approximate diameter of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a 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 0.1. 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 emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  In addition, 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 device disposed in a reaction mother liquor described in JP-A-57-92523, JP-A-57-92524, etc. The reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776, etc., which continuously adds the water-soluble silver salt and water-soluble halide salt aqueous solution described in No. 921,164, etc. Alternatively, an apparatus that forms grains while keeping the distance between silver halide grains constant by 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 at the time of forming silver halide grains or after the completion of grain formation.

  The negative 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 preferred to vary the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^- A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is 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 mol to 1 × 10 ⁻⁸ per mol of silver halide. Mole is preferred. More preferably 1 × 10 ^-5 mol to 1 × 10 ^-8 mol.

  As a chemical sensitization method for the negative 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 known for the purpose of preventing fogging during the preparation process of the silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development. Antifoggants and 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) The compound represented can be mentioned. 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 carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol 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 mol to 1 × 10 ⁻² mol per mol of silver halide, preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, an amount of about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol per mol of silver halide is preferable, and 1 × 10 ⁻⁵ mol 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 about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

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

The silver halide light-sensitive material used in the present invention has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. Is preferable, and the layer may contain a 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, and titanium dioxide is particularly preferred for various reasons. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / 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 such as an intermediate layer at an arbitrary position A layer can be provided.

  Addition of a fluorescent brightening agent to the silver halide light-sensitive material according to the present invention is preferred because the white background can be further improved. The optical brightener is not particularly limited as long as it is a compound that can absorb ultraviolet light and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the sensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  The silver halide light-sensitive material according to 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 spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, described in JP-A-3-251840, page 28. BS-1 to 8 can be preferably 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 a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 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 For example, 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. I can do it.

  Further, when using these dispersing apparatuses, 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 silver halide light-sensitive material according to 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. However, as typical examples, yellow dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, magenta dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical cyan dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm is representative.

  As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of its good spectral absorption characteristics. Specific examples of preferable compounds include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Still other specific examples include compounds M-1 to M-61 described on pages 6 to 21 of European Patent Publication 273,712 and compounds 1 to 223 described on pages 36 to 92 of 235,913. There are other than the above-described representative examples.

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

  The λmax of spectral absorption of the magenta image formed in the photosensitive material according to 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 silver halide light-sensitive material according to 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 of the present invention is a coupler represented by the general description [Y-Ia] described in JP-A-6-95283, page 12, right column. Among the couplers represented by the general formula [Y-1] of the same publication, particularly preferred are couplers represented by the combined [M-1] when combined with the 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 are not limited to these.

  As the cyan coupler contained in the cyan image forming layer in the light-sensitive material according to the present invention, known phenol-based, naphthol-based or imidazole-based, and azole-based couplers can be used. For example, phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, 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 the general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

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

  As the yellow coupler contained in the yellow image forming layer in the light-sensitive material according to the present invention, known acylacetanilide couplers can be preferably used.

  Specific examples of the yellow coupler include compounds described in pages 5 to 9 of JP-A-3-241345, compounds represented by YI-1 to Y-I-55, or JP-A-3-209466. The compounds described on pages 11 to 14 and the compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] 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 according to the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

  The spectral absorption λL0.2 of the yellow color image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24, and is a long wave in the spectral absorption characteristics of the yellow dye image. Indicates the size of unnecessary absorption on the side.

The yellow coupler can usually be used in the silver halide emulsion layer 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 exemplified.

  In the light-sensitive material according to 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 arranged as necessary.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent in order to prevent 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 an oil-in-water emulsion type dispersion method is used to add a stain inhibitor or other organic compound used in the silver halide light-sensitive material according to the present invention, it is usually a water-insoluble high-boiling organic material having a boiling point of 150 ° C. or higher. If necessary, the 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, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. 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 silver halide light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to a layer between the light-sensitive layer to prevent color turbidity, or it is added to the silver halide emulsion layer. It is preferable to improve fog and the like. 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 according to 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 according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  It is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination as a hardener for these binders. It is preferable to use compounds described in JP-A-61-249054 and JP-A-61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storage stability. In order to improve the physical properties of the surface of the light-sensitive material or processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

  As the support used for the photosensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white pigment. Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Among these, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is used further sheet of 70~120g / m ² is preferred.

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

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, 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 fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support 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 water-resistant resin layer of the paper support according to the present invention 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 resin layer of the paper support having water-resistant resin layers on both sides used in the present invention 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, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect that gloss is good is obtained.

  The photographic light-sensitive 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 (adhesion of the support surface, antistatic properties, dimensions). One or more subbing layers for improving the degree of stability, rub resistance, hardness, antihalation, friction properties and / or other properties.

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. 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, a material having an arbitrary width can be used according to the use, but a width of 400 mm or more is preferably used for the proof use. A photosensitive material having a width of 800 mm or more is also preferably used.

  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.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the 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 light source for exposure can be directly modulated by changing 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 as long as the photosensitive material has a sufficient sensitivity, but a wavelength region having a sufficient sensitivity difference with other photosensitive layers in order to prevent color turbidity. It is preferable to use it. 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 and operating conditions in which the light source is placed, it is theoretically preferable to match the peak wavelength of the spectral sensitivity. 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.

  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 photosensitive material may be selected by a method of setting with a switch or the like of the image forming apparatus, or may be selected based on setting information transmitted together with 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, making continuous unattended operation possible and advantageous. Can be used.

  In the present invention, the term area gradation image is used, but this does not represent the shading on the image by the shading of the colors of individual pixels, 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 developing colors of Y, M, C, and black. More preferably, 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. In printing, a specially colored plate may be used, but in order to reproduce this, it is preferable to use an exposure amount of 4 or more for different exposures.

  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 order to draw an image with such light, it is necessary to scan the light flux on the silver halide photosensitive material. The photosensitive material is wound around a cylindrical drum and rotated at a high speed in a direction perpendicular to the rotational direction. A cylindrical outer surface scanning method for moving a light beam may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical depression for exposure can also be preferably used. A planar scanning method may be employed in which the polyhedron mirror is rotated at a high speed to expose the silver halide photosensitive material conveyed by moving the light beam at right angles to the conveying direction. In order to obtain a high image quality and a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be brought into close contact with the cylindrical drum accurately. For this to be done accurately, it needs to be accurately aligned and transported. The silver halide photographic material used in the present invention can be preferably used because it can be more accurately aligned when the surface to be exposed is wound outward. From the same viewpoint, the support used for the silver halide 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 silver halide photosensitive material to be exposed. The number of revolutions of the drum can be arbitrarily set, but an appropriate number of revolutions can be selected depending on the beam diameter of the laser beam, the energy intensity, the writing pattern and the sensitivity of the photosensitive material. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher speed, but specifically 200 to 3000 rotations per minute are preferably used.

  The silver halide photosensitive material can be fixed to the drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material. It can also be adhered by suction. Adhering the photosensitive material to the drum as much as possible is important to prevent troubles such as image unevenness.

As the aromatic primary amine developing agent used in the present invention, 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 -Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, the above is optional in a color developer. However, 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 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C. or more and 60 ° C. or less.

  The color development time is generally 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, known developer component compounds 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 silver halide light-sensitive material of the present invention 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 of a washing process. The development processing apparatus used for the development processing of the silver halide photosensitive material of the present invention fixes 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. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank, and the photosensitive material is transported and the processing liquid is sprayed. Also, a web system by contact with a carrier impregnated with a treatment liquid, a system by a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, it is usual that the running processing is performed using an automatic processor. At this time, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technical report No. 94-16935 is most preferable.

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

Example 1
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having the layer structure shown in Tables 1 and 2 below is coated on the side of the polyethylene layer containing titanium oxide, and gelatin 6 on the back side. 00g / m ^2, a sample of amorphous silica (Silysia 350) silver halide color light-sensitive material for 0.65 g / m ² scanning exposure by coating the No. 1-41 were produced. The matting agent added to the eighth layer was added by ultrasonic dispersion in an aqueous gelatin solution.

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. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: disulfooxalate (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- Mixture SO having a mass ratio of 1: 1: 2 of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone Of 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 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 above (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. 0 was changed in the same manner as EMP-101 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-102 having a diameter of 64 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner except that EMP-102 was used instead of EMP-101 in the preparation of Em-B101, and a 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive silver halide emulsion. .

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

  The above EMP-102 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green photosensitive 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
Next, in the preparation of EMP-103, the average particle size was set to 0. 0 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 except that EMP-104 was used instead of EMP-103 in the preparation of Em-G101, and a 1: 1 mixture of Em-G101 and 102 was used as a green-sensitive silver halide 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
A 1: 1 mixture of Em-R101 and Em-R102 was used as the red-sensitive silver halide emulsion.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: p-Toluenethiosulfonic acid

  As the light source, 10 LEDs of B were arranged in the main scanning direction and the exposure timing was delayed little by little so that the same place could be exposed with 10 LEDs. Further, 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.

  At this time, exposure is performed by gradually changing the exposure energy amount of each light source so that a 100% image portion with a density of 0.10 is obtained from the minimum density to the maximum density of each density of Yellow, Magenta, and Cyan. The following development processing was performed.

Processing step Processing temperature Processing time Replenishment amount Color development 33.0 ± 0.3 ° C 120 seconds 80ml / m ²
Bleach fixing 33.0 ± 0.5 ° C 90 seconds 120ml / m ²
Stabilization 30-34 ° C 60 seconds 150ml / m ²
Drying 60-80 ° C 30 seconds Color developer tank solution and replenisher Tank solution Replenisher Pure water 800 ml 800 ml
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 2.9 g 4.8 g
N, N-diethylhydroxylamine 6.8 g 6.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid pentasodium 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.

Bleach-fixer tank solution and replenisher solution Diethylenetriaminepentaacetic acid ferric ammonium dihydrate 65g
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.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g
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
Bismuth chloride (45% aqueous solution) 0.65 g
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.

In addition, the same evaluation was performed using a new liquid prepared for evaluation using a new liquid prepared for evaluation and a running liquid obtained by treating a sample with 120 m ² with the new liquid and performing a predetermined replenishment.

[Evaluation of glossiness of image]
The glossiness was measured using HORIBA GLOSS CHECKER IG-310, and the matting effect by adding a matting agent was compared.

  The glossiness in the present invention refers to that measured by a method according to the measurement method of incident angle / reflection angle = 60 ° / 60 ° described in JIS-Z8741 “Measurement method of specular gloss”. Art paper and coated paper, which are relatively high gloss printing papers, have a gloss level almost in the range of 1 to 15 and are often subject to color proofing of silver halide color photosensitive materials. When used as a proof image of printed paper / coated paper, the glossiness is preferably in the range of 1 to 15, and more preferably in the range of 1 to 6.

[Evaluation of white background in continuous processing]
At the start and end of development, a spectrophotometer CM-2022 manufactured by Minolta Co., Ltd. was used, and the photometric measurement was performed using a geometric condition d-0 for illumination and light reception, and a xenon pulse light source ^. , A ^* and b ^* were measured, and the color difference of the sample when processed at the start and end of continuous processing was determined. The color difference ΔE is obtained by the following formula.

ΔE = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2
Note that ΔL ^* , Δa ^* , and Δb ^* represent the difference between processing at the start and end of continuous processing.

[Evaluation of pressure resistance]
The sample output so that the black net percentage is 50% is left at 25 ° C. and 55% RH for 2 hours, and then a ball point needle having a sphere diameter of 0.1 mm is set perpendicular to the sample surface, and the sample surface is 1 cm / second. At the same time, a weight of 50 g is applied to the ball point needle. Thereafter, the sample is allowed to stand at 25 ° C. and 70% RH for 24 hours, and then the mark scratched with the ball point needle is visually observed with a 50 × magnifier. The state of the black dots is judged visually.

1: No change 2: Halftone dots are broken slightly and bleeding occurs but no actual damage 3: Halftone dots are broken by about 50%, bleeding occurs, and there is a problem as an image 4: Halftone dots are broken by 80% or more, and bleeding occurs Table 3 shows the results obtained as described above.

As is clear from the results shown in Table 3, the sample of the present invention composed of the composition defined in the present invention reproduces gloss similar to matte paper, compared to the comparative example, and has white background variation and pressure resistance in continuous processing. It turns out that it is excellent.
Example 2
A sample was prepared in the same manner as in Example 1, but the matting agent used in the eighth layer (protective layer) was ultrasonically dispersed simultaneously with the ultraviolet absorber according to the following formulation and added as a dispersion. At that time, (SU-1) was used as a surfactant. The samples 51 to 74 obtained as described in Table 4 were evaluated in the same manner as in Example 1, and the results are shown in Table 4.

  The following dispersion prescription and dispersion conditions indicate the conditions for preparing the sample 55. In Table 4, the level at which the matting agent and the ultraviolet absorber are simultaneously dispersed was the same as these prescriptions and conditions.

<Dispersion prescription and dispersion conditions for sample 55>
The dispersion was dispersed at 70 ° C. for 30 minutes using an ultrasonic disperser (manufactured by ALEX Corporation: Ultrasonic Generator, frequency 25 kHz, 600 W) according to the following dispersion prescription.

Matting agent 15.0 g
UV-1 28.5g
Surfactant (SU-1) 1.2g
Gelatin 25.6g
120 ml of ethyl acetate
750 ml of water

  As is apparent from the results shown in Table 4, samples 62, 64, 69, and 74 in which silica, which is a fine porous powder according to the present invention, is dispersed using a liquid ultraviolet absorbent that is liquid at room temperature are matte papers. It can be seen that near gloss is reproduced, and further, the white background fluctuation and pressure resistance in continuous processing are remarkably excellent.

Claims (4)

In a silver halide photographic light-sensitive material in which at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are coated on a support, at least one layer of the non-photosensitive hydrophilic colloid layer has a thickness of 1 m. ^A silver halide color photographic light-sensitive material for scanning exposure, comprising 300 mg or more of fine porous fine particles per ² and a liquid ultraviolet absorber that is liquid at room temperature. In a silver halide photographic light-sensitive material in which at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are coated on a support, at least one layer of the non-photosensitive hydrophilic colloid layer has a thickness of 1 m. ^A silver halide color photographic light-sensitive material for scanning exposure, wherein 300 mg or more of fine porous fine particles per ² are simultaneously dispersed and contained using a liquid ultraviolet absorber which is liquid at room temperature. 3. The silver halide color photographic light-sensitive material for scanning exposure according to claim 1, wherein the fine porous fine powder is an inorganic compound. 4. The silver halide color photographic light-sensitive material for scanning exposure according to claim 3, wherein the porous fine particle powder is silica.