WO2004068236A1

WO2004068236A1 - Silver halide color photography photosensitive material

Info

Publication number: WO2004068236A1
Application number: PCT/JP2003/000987
Authority: WO
Inventors: Toyoki Nishijima
Original assignee: Konica Corporation
Priority date: 2003-01-31
Filing date: 2003-01-31
Publication date: 2004-08-12

Abstract

A silver halide color photography photosensitive material having a support and, applied thereon, at least one photosensitive emulsion layer and non-photosensitive emulsion layer, characterized in that at least one selected from the photosensitive emulsion layer, the non-photosensitive emulsion layer and the support contains a brightening agent, and a blue-sensitive silver halide emulsion has an average particle diameter of 0.7 μm or less. The silver halide color photography photosensitive material has good white ground characteristics, is reduced in the fluctuation of gradation in the case of multiple exposure and further is reduced in variations in densities of a white ground portion and an image portion, even after the continuous printing with a high speed digital printer.

Description

Silver halide photographic materials Technical field ''

The present invention relates to a silver halide color photographic light-sensitive material which is excellent in white background and has improved dispersion in white background and image density portion in high-speed digital printing.

Background art

In recent years, the opportunities for handling images as digital data have been rapidly increasing in accordance with the improvement in computing power of computers and network technology. Image information captured by a digital camera or image information that has been converted into digital data from a film or print using a scanner, etc., can be edited and processed on a computer, and data such as character first can be added. Can be done relatively easily. Hard copy materials that make hard copies based on such digitized image information include, for example, sublimation thermal transfer prints, melt-type thermal transfer prints, ink jet prints, and electrostatic transfer prints. , Thermochromic prints, silver halide color photographic materials, etc. Among them, silver halide color photographic materials (hereinafter also referred to as color prints or photographic materials) must have high sensitivity. It has excellent properties compared to other printing materials, such as excellent gradation properties, excellent image storability, and low cost. It is used extensively today, especially for producing high-quality hard copies. Digitally converted image information can be edited and edited on a computer relatively easily.For example, an image based on photographic data of people, landscapes, still life, etc. More opportunities to handle.

In addition, many types of digital exposure devices are currently sold as digital exposure devices that perform exposure based on digitally converted image information, and many new digital exposure devices have been combined with advances in exposure light sources and control devices. Research and development. Among these digital exposure apparatuses, apparatuses using a sharp light source wavelength distribution such as a laser or an LED as an exposure light source are becoming mainstream.

On the other hand, various characteristics are required in recent silver halide color photographic light-sensitive materials. Among them, the color reproducibility and whiteness of image dyes are important as basic characteristics, and their commercial value is important. Depends. Various methods have been proposed to improve the whiteness. In this case, it is a minimum condition that the color development in the unexposed area is small. Therefore, the color development (capri) in the unexposed area of the silver halide emulsion is proposed. It is known that the compounds described in, for example, JP-A-2-14636 have an effect of preventing force fray in order to minimize the amount of odor. It is widely known that capri changes depending on the temperature of the processing solution, the halogen ion concentration, the type and concentration of the developing agent, and the staining of the coloring components in the processing solution, and it is necessary to adjust these. However, suppressing capri is the minimum condition, and even in ideal conditions, it is the limit up to zero color development and coloring. In order to satisfy the strict requirements of white background on color prints, it is necessary to devise ways to improve the white background in addition to suppressing the coloring and coloring of the white background. As one method for this, a method of applying an oil-soluble fluorescent whitening agent to a color print has been proposed (for example, see Patent Document 1).

However, a silver halide lamp containing an oil-soluble optical brightener as described above. -When photographic photosensitive materials are printed using a digital high-speed printer as described above, variations in white areas are likely to occur, especially when a large number of prints are made. In addition, it has been found that exposure unevenness easily occurs during scanning exposure using a laser.

(Patent Document 1)

Patent No. 304932 22 Disclosure of the Invention

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

(1) In a silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and at least one non-light-sensitive emulsion layer on a support, the material is selected from a light-sensitive emulsion layer, a non-light-sensitive emulsion layer, and a support. Wherein at least one of the silver halide emulsions contains an oil-soluble fluorescent whitening agent, and the blue-sensitive silver halide emulsion has an average particle size of 0.7 ^ ππ or less. .

(2) Horizontal axis: exposure amount (L _{0 g} E) obtained by performing exposure and color development processing with an exposure time of 10 to ⁶ seconds or less, vertical axis: density 0 on a characteristic curve composed of color density The variation of the average gradient of a straight line passing through the point giving .5 and the point giving density 1.5 is within 10% in multiple exposure, and the silver halide color described in (1) is one photograph. Photosensitive material.

(3) 2 3. The silver halide color photographic light-sensitive material according to (1) or (2), wherein the curl degree at C ヽ 20% RH is +15 or less. BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a silver halide light-sensitive material having at least one light-sensitive emulsion layer and at least one non-light-sensitive emulsion layer on a support. At least one selected from a photosensitive emulsion layer, a non-photosensitive emulsion layer, and a support contains an oil-soluble fluorescent whitening agent, and the blue-sensitive silver halide emulsion has an average particle size of 0.7. The silver halide color photographic light-sensitive material of less than m gives good white background and even if a large number of prints are made with a high-speed printer with very short exposure using a laser, the white background and the density will vary. It has been found that an image having few images can be stably obtained, and this has led to the present invention.

In addition to the above configuration, the horizontal axis: exposure amount (Log E) obtained by performing exposure and color development processing with an exposure time of 10 to ⁸ seconds or less, and the vertical axis: on a characteristic curve composed of color density. The variation of the average gradient of the straight line passing through the point giving the density 0.5 and the point giving the density 1.5 should be within 10% in multiple exposure, or at 23 ° C and 20% RH. It has been found that by setting the curl degree to +15 or less, the above-mentioned effect is further exhibited.

Hereinafter, details of the present invention will be described.

The silver halide color photographic light-sensitive material of the present invention comprises a silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and a non-light-sensitive emulsion layer on a support. At least one selected from the photosensitive emulsion layer and the support contains an oil-soluble fluorescent whitening agent, and the average particle size of the blue-sensitive silver halide emulsion is 0.7 βm or less. .

First, the oil-soluble fluorescent whitening agent according to the present invention will be described.

The oil-soluble fluorescent whitening agent that can be used in the present invention is not particularly limited. For example, the following compounds can be used.

CH ₃ CHg— C-CH ₃

L86000 / £ 00Zd £ / 13d 9CZ890 / 00i OAV

These oil-soluble fluorescent whitening agents may be added to any of the support, the photosensitive layer, and the non-light-sensitive emulsion layers such as the intermediate layer and the protective layer, which constitute the silver halide color photographic light-sensitive material of the present invention. However, it is preferably a support. The addition amount is preferably in the range of 1 mg / dm ^{2 to} 500 mg / dm ² .

The support that can be used in the present invention is preferably a paper support in which a resin coating layer is applied to both surfaces of a substrate.

As the paper support having a resin coating layer coated on both sides of the base paper, a paper support in which the rain surface of the base paper is laminated with a polyolefin is preferable, and a paper support laminated with polyethylene is particularly preferable. It is.

The base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fiber such as Nyopen® polyester in addition to wood pulp. . As wood pulp, any of L BKP, LBSP, NBKP, NBS P, LDP, NDP, LUKP, and NUKP can be used, but L BKP, NB SP, LBSP, NDP, and LDP, which are rich in short fibers, can be used. It is preferable to use more. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less. As the pulp, a chemical pulp (sulfate pulp or sulfite pulp) having a small amount of impurities is preferably used, and pulp having improved whiteness by a bleaching treatment is also useful. Base paper contains sizing agents such as higher fatty acids, alkyl ketene dimer, etc., white pigments such as calcium carbonate, talc, titanium oxide, paper strength agents such as starch, polyacrylamide, polyvinyl alcohol, polyethylene glycols, etc. A water retention agent, a dispersant, and a softening agent such as quaternary ammonium can be added as appropriate. Further, the oil-soluble fluorescent whitening agent according to the present invention can also be used.

The freeness of pulp used for papermaking is preferably 200 to 500 m1 according to the CSF regulations, and the fiber length after beating is specified in JIS-P-8207. It is preferable that the sum of the mass% and the residual amount of 42 mesh is 30 to 70%. In addition, the mass% of the 4-mesh residue is preferably 20% by mass or less. The basis weight of the base paper is preferably 30 to 250 gZm ² , particularly preferably 50 to 200 gZm ² . The thickness of the base paper is preferably from 40 to 250 m. The base paper can also be subjected to power rendering at the papermaking stage or after papermaking to provide high smoothness. The base paper density is generally 0.7 to 1.2 g "cm ³ (JIS-P-8118). The base paper stiffness is 20 to 200 g under the conditions specified in JIS-P-8143. A surface sizing agent may be applied to the surface of the base paper, and a sizing agent similar to the size that can be added to the base paper can be used as the surface sizing agent. It is preferably 5 to 9 when measured by the hot water extraction method specified in P-8113.

The polyethylene that covers the front and back of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE). In addition, LLDP E (Linear density—polyethylene) ゃ polypropylene etc. can be partially used. In particular, as the polyethylene layer on the photosensitive layer side, as is widely used in photographic paper, rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness. preferable. The content of titanium oxide is usually 3 to 20% by mass, preferably 4 to 13% by mass based on polyethylene.

Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melt-extruded onto the base paper surface and coated, a so-called molding process is performed to obtain a matte surface that can be obtained with ordinary photographic printing paper.物 Those having a silk surface can also be used in the present invention.

The amount of polyethylene used on the front and back sides of the base paper is usually in the range of 20 to 40 m for the polyethylene layer on the side where the photosensitive layer is provided, and 10 to 30 m for the back layer side.

Further, the polyethylene-coated paper support preferably has the following characteristics.

1. Tensile strength: The strength specified by JIS-P- 8113, preferably 20-30 ON in the vertical direction and 10-20 ON in the horizontal direction.

2. Tear strength: According to the method specified in JIS-P-816, preferably 0.1 to 20 N in the vertical direction and 2 to 2 ON in the horizontal direction

3. Compression modulus 98. IMP a

4. Surface Beck smoothness: Under the conditions specified in JIS-P-819, 20 seconds or more is preferable for the glossy surface, but it may be less for so-called molded products.

5.Surface roughness: The surface roughness specified in JI SB-060 1 is the standard length 2. The maximum height is preferably less than 10 m per 5 mm

6. Opacity:: 以上 80% or more, particularly preferably 85 to 98%, as measured by the method specified in IS-P-81 38

7. Whiteness: L * and ab * specified by JIS—Z—8729 are L * = 80 to 95, a * = 3 to 10 and b * =-6 to 10 2 Is preferably

8. Surface glossiness: The 60-degree specular glossiness specified in JIS-Z-8741 is preferably from 10 to 95%.

9. Clark stiffness: A support having a Clark stiffness of 50 to 300 cm10 in the transport direction of the recording medium is preferable.

100. Water content of middle paper: usually 2 to 100% by mass, preferably 2 to 6% by mass with respect to the middle paper

In the silver halide color photographic light-sensitive material of the present invention, the photosensitive emulsion layer contains a silver halide emulsion.

The silver halide emulsion used in the present invention is preferably a high silver chloride emulsion having a silver chloride content of at least 90 mol% or more. The balance is preferably made of silver bromide containing substantially no silver iodide. The silver bromide content is more preferably from 0.03 to 3 mol%, particularly preferably from 0.05 to 2 mol%.

Arbitrary silver halide grains can be used. In addition to a cube having a (100) plane as a crystal surface, U.S. Pat. Nos. 4,183,756 and 4,225,666, Japanese Patent Application Laid-Open No. 55-26658 9, No. 55-4273, and The Journal of Photographic Science (J. P hotogr. Sci.) 21: 39, 1973 Octahedron, tetradecahedron, dodecahedron, etc. are produced and used by the method described in the literature You can also. Further, grains having twin planes and tabular silver halide grains may be used, but in the present invention, cubic silver halide grains having a (100) plane as a crystal surface are excellent in productivity and production stability. It is preferable that

As the silver halide grains, grains having a single shape are preferably used, but two or more monodisperse silver halide emulsions can be added to the same layer.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 5.0 m, more preferably 0.2 to 3.3 in consideration of other photographic properties such as rapid processing property and sensitivity. In particular, when a cube is used, the thickness is preferably in the range of 0.1 to 1.2 μm, and more preferably in the range of 0.2 to 1,0 μm. One feature is that the silver halide emulsion used has an average grain size of 0.3 or less, more preferably 0.35 to 0.65 m, and still more preferably 0.35 to 0.3 mm. 60 m. By setting the average particle size of the silver halide emulsion used in the blue-sensitive layer under the conditions specified in the present invention, it is possible to improve the object effect of the present invention, particularly, to improve the white background property or to reduce the variation in the white background. New

This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The grain size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15, and particularly preferably 0 to 0. 0.05 to 0.15 monodispersed emulsions are added to two or more layers in the same layer. Here, the coefficient of variation is a coefficient that indicates the breadth of the particle size distribution, and is defined by the following equation. Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide grain, In the case of particles having a shape other than a spherical shape, it represents the diameter when the projected image is converted into a circular image having the same area.

Various methods known in the art can be used as a device and method for preparing a silver halide emulsion.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been produced. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt is reacted with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble haeogenide from an addition device disposed in a reaction mother liquor, Apparatus for continuously changing the concentration of a water-soluble silver salt and water-soluble halide aqueous solution described in Japanese Patent No. 2,921,164, etc., and a reactor described in Japanese Patent Publication No. The reaction mother liquor may be taken out and concentrated by an ultrafiltration method to form a grain while keeping the distance between the silver halide grains constant. Further, if necessary, a silver halide solvent such as thioether may be used. The silver halide grains of the present invention can contain various polyvalent metal ions alone or in combination during the grain formation or physical ripening. For example, salts such as potassium, zinc, copper, thallium, and gallium, or salts or complex salts of group VIII transition metal ions, such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum, may be mentioned. it can.

The silver halide grains of the present invention preferably have a chemical sensation. As the chemical sensitization method, gold sensitization method using a gold compound (for example, US Pat. Nos. 2,448,060 and 3,320,069) or sensitization method using a metal such as iridium, platinum, palladium, etc. (Eg, US Pat. Nos. 2,448,060, 2,566,245, and 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 264) or a combination of two or more of these.

In the present invention, a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity. The spectral sensitizing dye used at this time is described in, for example, Hemocyc 1—icco mp ounds—Cyaninedyesandrelated com mp ounds attached to FM Hamer (John Wiley and Sons; New York, 1964). Compounds. Examples of the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye. In addition, there are complex cyanine dyes, horopora-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. As the cyanine dye, simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used. In the silver halide color photographic light-sensitive material of the present invention, components other than those described above, for example, other silver halide photographic emulsions, emulsion additives, sensitizing methods, anti-capri agents, stabilizers, anti-irradiation dyes Yellow coupler, magenta coupler, cyan coupler, spectral sensitizing dye, emulsification dispersion method, surfactant, anti-turbidity agent, binder, hardener, slipping agent and matting agent, support, bluish Agents, red tinting agents, coating methods, color developing agents, processing methods, development processing equipment, processing agents, etc. are described in JP-A-11-3147615, page 9, left, 22nd line, paragraph numbers 0044 to 14 Each compound and the method described in paragraph No. 0106 on the 17th line on the left of the page can be used. No. 17643, No. 1 8716 and No. 3081 19 (hereinafter abbreviated as RD 17643, RD 1871 6 and RD3081 19, respectively) Each component can be appropriately selected and used.

Next, a digital exposure method using the silver halide color photographic light-sensitive material of the present invention will be described.

To form a photographic image using the silver halide color photographic light-sensitive material of the present invention or to form a copy image using the color print of the present invention, the image recorded on the negative must be printed. The image may be formed optically on a silver halide color photographic light-sensitive material and printed. Alternatively, the image is once converted into digital information, and then the image is formed on a CRT (cathode ray tube). The image may be printed on a silver halide color photographic light-sensitive material to be printed, or may be printed by changing the intensity of a laser beam based on digital information and scanning. It is preferable to perform exposure based on digital information using a digital exposure machine. When exposure is performed using one laser beam, the exposure time per pixel is not particularly limited, but is often in the range of 100 nanoseconds to 100 microseconds. The exposure time per pixel is defined as the outer edge of the light beam when the light intensity becomes 1/2 of the maximum value in the spatial change of the light beam intensity, and it is parallel to the scanning line and the light intensity is When the distance between the two points where the line passing through the maximum point and the outer edge of the light beam intersect is the diameter of the light beam, the (exposure time per pixel) is (light beam diameter) / (scanning speed). Examples of laser printers that can be applied to such systems include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-197794, JP-A-74942, and JP-A-74942. 2-236538, JP-B-56-14963, JP-B-56-40822, European wide-area patent 7710, Electronic Communication Science Technical Report 80, 244, and Movie and TV Technology Magazine 1984Z6 (382) , Pages 34-36.

In the silver halide color one photographic light-sensitive material of the present invention, the horizontal axis is obtained by performing exposure and color development processing in ^10-6 seconds or less exposure time: exposure (L ₀ g E), vertical axis: coloring It is preferable that the variation of the average gradient of a straight line passing through the point giving the density 0.5 and the point giving the density 1.5 on the characteristic curve composed of the density be within 10% in the multiple exposure.

The characteristic curve in the present invention, was subjected to high-intensity exposure below 10- ⁶ seconds, the image obtained by performing the color development of the standards, the horizontal axis L og E a (E is the exposure amount), This is a curve plotted by taking D (color density) on the vertical axis. Multiple exposure means that the same pixel is exposed twice or more during high-illuminance exposure for ¹⁶ seconds or less. The variation of the average gradient at that time is defined as the point at which density 0.5 is given on the characteristic curve obtained by color development after one exposure and the density 1.5 Means the variation of the slope (tan) when a straight line is drawn through the point.

Fluctuations in the density gradient due to multiple exposures mean color fluctuations in the print, and ideally no average gradient fluctuations.

As a light source for exposing the silver halide color photographic light-sensitive material of the present invention, in addition to a Xe flash light, a light emitting diode gas laser, a solid-state laser, a semiconductor laser, HeNe Laser, Ar laser, dye laser, and the like. In addition, it can be used in either vertical single mode or horizontal multi mode, and it is also possible to use a light source modulated by electrical modulation by superposition of high frequency and SHG (second harmonic element). In particular, in order to design a compact, inexpensive, long-life, and highly stable apparatus, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

The exposure time in such a scanning exposure is defined as the time for exposing a pixel size in the case of the pixel density 400 dpi, preferably 1 0 one ³ sec or less as an exposure time, and more preferably 1 0 ⁶ seconds or less is there. In the present invention, dpi refers to the number of dots per 2.54 cm.

Further, in the silver halide color photographic light-sensitive material of the present invention, the curl degree at 23 ° C. and 20% RH is +15 or less from the viewpoint of reducing the density variation and density unevenness during short-time exposure. And more preferably 0 to 10 15

The curl degree in the present invention can be determined according to the following procedure.

23. The silver halide color photographic light-sensitive material of the present invention was cut into 10 cm × 10 cm, and left at 23 in a 20% RH environment for 24 hours. (: In an environment of 20% RH, find the reciprocal of curvature radius R (1 / R unit m) Is defined. A curl degree of + indicates that the image recording surface is concave and warped.

In the present invention, the method for adjusting the curl degree of the silver halide color photographic light-sensitive material to +15 or less is not particularly limited. For example, coating of a hydrophilic binder in a constituent layer provided on both sides of a support A desired degree of curl can be obtained by appropriately adjusting the amount, the pulp density and mass of the substrate in the support, or the amount of lamination of the polyethylene resin coating the surface of the substrate.

In the present invention, the above-described configuration according to the present invention can reduce the density variation in a white background portion and the density variation in an image portion even when a large amount of printing is performed by a high-speed printer. A high-speed printer capable of outputting at least 100 L-hour prints per hour, capable of fully exhibiting the effects of the present invention, and more preferably a high-speed printer capable of printing over 150 ZL plates / hour. It is particularly preferable to use a high-speed printer with a printing speed of 2000 sheets or more.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.

<< Preparation of silver halide emulsion >>

Each silver halide emulsion was prepared by the following method.

(Preparation of red-sensitive / silver silver halide emulsion)

In 1 liter of a 2% aqueous solution of gelatin maintained at 40 ° C, apply the following (Solution A) and (Solution B) over 30 minutes while controlling pAg to 7.3 and pH to 3.0. The following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling the pAg at 8.0 and the pH at 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by sulfuric acid or aqueous sodium hydroxide. Liquid <

(A liquid)

Sodium chloride 3 • 4 2 g bromide power 0 • 0 3 g Add water to 200 m 1 (Solution B)

1 0 g Add water 2 0 0 m 1

(C solution)

Sodium chloride _{102. 7 g K 2 I r C} 1 e Monore / mol _{A g K 4 F e (CN} ) mol / mol A g Nioikaryoku Riumu 1. 600 ml by adding 0 g water

(D solution)

After adding 300 g of water and adding 600 ml of the above solution, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate. The emulsion EMP-1 was a monodisperse cubic emulsion having an average particle size of 0.40 m, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.

Next, the average particle size was 0.38 in the same manner as in Emulsion EMP-1 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a m of 0.07, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.

The above emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. In the same manner, the emulsion EMP-1B was also optimally chemically sensitized, and then the emulsion EMP-1 and the emulsion EMP-1B were mixed at a silver ratio of 1: 1. A red-sensitive silver halide emulsion (101 R) was obtained.

Chio sodium sulfate 1 X 1 0- ⁴ mol / mol A g X chloroauric acid 1. 2 X 1 (T ⁴ mol / mol A g X Stabilizer: STAB- 1 3 X 1 CT ⁴ mol / mol A g X stabilizer: STAB- 2 3 X 1 0- ⁴ mol Z moles A g X stabilizer: STAB- 3 3 X 1 0- ⁴ mol Z moles A g X sensitizing dyes: RS- 1 1 X 1 0- ⁴ mol Z moles A g X sensitizing dye: RS- 2 1 X 1 0- ⁴ mol / mol A g X

STAB—1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

S T A B—2: 1 _phenyl-5-mercaptotetrazole

STAB—3: 1- (4-ethoxyphenyl) -1-5-mercaptotetrazo

Also the red-sensitive emulsion, SS- 1 was per mol of silver halide 2. 0 X 1 0 one ³ addition.

(Preparation of green photosensitive silver halide emulsion)

In the preparation of the emulsion EMP-1, the average particle size was 0.40 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a m of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%. Next, in the preparation of the emulsion EMP-1, the average particle size was reduced in the same manner except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed. An emulsion was prepared as a monodisperse cubic emulsion having a dispersion of 50 μιη, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol%.

The emulsion II prepared above was optimally subjected to chemical sensation at 55 using the following compound. Similarly, after optimal chemical sensitization of Emulsion ΕΜΡ-2Β, sensitized Emulsion ΕΜΡ-2 and Emulsion EMP—2Β were mixed at a silver ratio of 1: 1. Thus, a green light-sensitive silver halide emulsion (101 G) was obtained.

Sodium thiosulfate 1 X 10— ' ¹ mol / mol A g Chloroauric acid 1.2 X 10—' mol / mol A gx Stabilizer: STAB— 1 2.5 X 10— 'mol / mol A g stabilizers: S tAB- 2 3. 1 X 1 0- '4 mol / mol A gx stabilizer: S tAB- 3 3. 1 X 10- ' 4 mol / mol A g X增感dye: GS- 1 X 1 0 " ⁴ mol / mol A g X

(Preparation of blue-sensitive silver halide silver halide emulsion)

In the preparation of the emulsion EPM-1, the average particle diameter was 0.7 in the same manner except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed. Emulsion EMP-3 was obtained as a monodisperse cubic emulsion having 1 βm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol%.

The above EMP-3 was optimally chemically sensitized at 60 ° C using the following compound to obtain a blue-sensitive silver halide emulsion (101B).

Chio sodium sulfate 1 X 10- ⁴ mol / mol A g X 22 chloroauric acid 1, 2 X 1 0 ^"4 mol / mol A g X Stabilizer: STAB- 1 2 X 1 0 one ⁴ mol / mol A g X Stabilizer: STAB- 2 2. 4 X 1 0 one ⁴ mol / mol A g X stabilizer:. STAB- 3 2 1 X 1 0 one ⁴ mol / mol A g X增感dye: BS one 1 ⁴ X 1 0 _ 4 mol / mol A g X sensitizing dyes: BS one 2 1 X 1 0 one ⁴ mol / mol A g X

Then, in the preparation of the blue-sensitive silver halide emulsion (101B), (Solution A) and (Solution B) were added in place of Emulsion EMP-3 (average particle size 0.71〃m). Blue-sensitive silver halide emulsion (102 B: average particle size 0.66 m), blue-sensitive using each emulsion with the time and addition time of (Solution C) and (Solution D) appropriately changed Silver halide emulsion (103B: average grain size 0.63 ^ m), blue-sensitive silver halide emulsion (104B: average grain size 0.58 ^ m), blue-sensitive silver halide emulsion A silver emulsion (105B: average particle size of 0.57〃m) and a blue-sensitive silver halide emulsion (106B: average particle size of 0.1μχα) were prepared.

(Preparation of photosensitive silver halide emulsion 異なる with different suitability for multiple exposure)

In the preparation of the above photosensitive silver halide emulsions (101R, 101G, 105B), stable with chemical sensitizers (sodium sodium thiosulfate, chloroauric acid) during chemical sensitization. Silver halide emulsions (102R, 1R) with different multi-exposure suitability by appropriately changing the addition amounts of the agents (STAB-1 to STAB-3) and the chemical sensitivity conditions (temperature and time). 02 G, 107 B) was prepared. << Production of silver halide photographic light-sensitive material >>

[Preparation of Sample 101]

A reflective support 1 was prepared by laminating high-density polyethylene on one side of a paper pulp having a basis weight of 180 gZm ² . However, on the side to which the photosensitive layer was applied, molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated.

After the reflective support 1 was subjected to a corona discharge treatment, a gelatin undercoat layer was provided thereon, and further, each layer having the following constitution was provided thereon, to thereby prepare a sample 101 as a silver halide color photographic light-sensitive material. The coating solution was prepared as described below.

(Preparation of first layer coating solution)

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stin prevention 0.34 g of agent (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP) and 60 ml of ethyl acetate This solution was added and dissolved, and this solution was emulsified and dispersed in a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. did. The yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101 B) prepared above to prepare a first layer coating solution.

(Preparation of coating solution for 2nd to 7th layers)

The coating liquids for the second layer to the fifth layer were prepared using the following additives in the same manner as in the preparation method of the first layer coating liquid. -(Structure of sample 101) 7th layer: protective layer>, m gelatin 1.00 DIDP 0.005 silicon dioxide 0.003 6th layer: ultraviolet absorbing layer>

Gelatin 0.40 UV absorber (UV-1) 0.12 UV absorber (ϋV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0.04

PV P (Polyvinyl pyridone, 0.03 Anti-irradiation dye (AI 2) 0,01 1st layer: Red photosensitive layer)

Gelatin 1, 30 Red-sensitive silver halide emulsion (10 1 R) 0.2 1 Cyan coupler (C-1) 0, 25 Cyankabra (C-2) 0, 08 Dye image stabilizer (ST— 1) 0,10 Sting inhibitor (HQ-1) 0,004 D 0 P 0,34

<4th layer: UV absorbing layer>

Gelatin 0 94 UV absorber (ϋV—1) 0 28 UV absorber (UV-2) 0.09 UV absorber (ϋV-3) 0.38 Sting inhibitor (HQ-3) 0.10 Anti-irradiation dye (AI-2) 0.02 3rd layer: green photosensitive layer>

Gelatin 1.30 Green photosensitive silver halide emulsion (101G) 0.14 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17

D I D P 0.1 3

D B P 0.13 Anti-irradiation dye (AI-1) 0.01 Second layer: middle layer

Gelatin 1.20 Stin inhibitor (HQ-2) 0.03 Stin inhibitor (HQ-3) 0.03 Stin inhibitor (HQ-4) 0.05 Stin inhibitor (HQ-5) 0 . twenty three

DIDP 0.06 Optical brightener (W-1) 0.10 Anti-irradiation dye (AI-3) 0.01

<First layer: blue-sensitive layer> Gelatin 1.2 b Blue-sensitive silver halide emulsion (101 B) 0.26 Yellow Ichizoku puller (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer ( ST—2) 0.10 Sting inhibitor (HQ-1) 0.1 0 Dye image stabilizer (ST-5) 0.10 Image stabilizer A 0.15

DN P 0. 05

DBP 0.10 Support: Reflective support 1 Polyethylene laminated paper (containing a trace amount of colorant) The amount of each silver halide emulsion described above was expressed in terms of silver. Further, (H-1) and (H-2) are added to each of the above coating solutions as a hardening agent, and surfactants (SXJ-2) and (SU-3) are used as coating aids. ) Was added to adjust the surface tension. Preservative F-1 was added as appropriate.

S U-1: Tree i-propylnaphthalenesulfonic acid sodium

S U-2: Di (2-ethylhexyl) sulfosuccinate 'Nadium salt

S U-3: Di-sulfosuccinate (2,2,3,3,4,4,5,5-taktoropentyl) 'Natrium salt

DBP: dibutyl phthalate

DNP: dinonyl phthalate

DOP: Dioctyl phthalate

DIDP: di-i-decyl phthalate H—1: Tetrakis (vinylsulfonylmethyl) methane

H-2: 2,4-dichloro-6-hydroxy-1-s-triazine 'sodium Image stabilizer A: P-t-octylphenol

Y

C-1

C-2

ー丄 s οτ

(!) "Η ^ει ΌΟ-

S-.

Ζ— 丄 S

ー丄 s

6Ζ .86000 / fOOZdf / X3d 91X890 ΟΟΖ ΟΛ \

1-Ή

οε

Z, 86000 / e00Idf / 13d 9 £ Z890 / t00∑; OW W-1

F— 1

CI

(50%) (46%) (4%) molar ratio

[Preparation of sample 102 104]

In the preparation of Sample 101 above, the blue-sensitive silver halide emulsion (102B) (102B) was replaced with the blue-sensitive silver halide emulsion (101B) of the first layer (blue-sensitive layer). Sample 10210 was prepared in the same manner except that 104B) was used.

[Preparation of Sample 105]

In the preparation of the above sample 101, the same procedure was carried out except that the reflective support 2 was prepared by adding 5 mg / m ² of an oil-soluble fluorescent whitening agent (exemplified compound 6) to the polyethylene laminate layer of the reflective support 1. Thus, Sample 105 was prepared.

[Preparation of sample 106 1 09]

In the preparation of Sample 105 above, a blue-sensitive silver halide emulsion (102B) was used instead of the blue-sensitive silver halide emulsion (101B) of the first layer (blue-sensitive layer). Blue-sensitive silver halide emulsion (103 B), silver-sensitive silver halide emulsion (105 B), Samples 106 to 109 were prepared in the same manner except that the blue-sensitive silver halide emulsion (106 B.) was used.

[Preparation of Sample 110]

In the preparation of Sample 105, the photosensitive silver halide emulsions of the first layer (blue-sensitive layer), the third layer (green-sensitive layer), and the fifth layer (red-sensitive layer) were respectively The same except that the photosensitive silver halide emulsion (107B), green photosensitive silver halide emulsion (102G), and red photosensitive silver halide emulsion (102R) were changed to In this way, a sample 110 was prepared.

[Preparation of samples 1 1 1 and 1 1 2]

In the preparation of Sample 110 above, a sample was prepared in the same manner except that a gelatin layer was coated on the surface of the reflective support 2 opposite to the surface on which the photosensitive layer was coated so that the curl degree was as shown in the following table. 1 1 1 and 1 1 2 were produced.

Sample Oil-soluble blue-sensitive layer silver halide in the support Support Remark No.Presence or absence of fluorescent whitening agent Emulsion Average particle size (m) Force

10 1 10 1 B 0.77 26 Comparative example

5 102 102 B 0.666 26 Comparative example

103 None 103 B 0.63 26 Comparative example

104 None 104 B 0.58 25 Comparative example

105 Yes 10 1 B 0.7 0.7 26 Comparative example

106 Yes 102 B 0.66 26 The present invention

10 107 Yes 103 B 0.63 23 The present invention

1 08 Yes 105 B 0.57 24 Honkiaki

1 09 Yes 106 B 0.51 24 The present invention

1 10 Yes 107 B 0.57 24 The present invention

1 1 1 Yes 107 B 0.57 18 Present invention

15 1 12 Yes 107 B 0.57 13 The present invention

《Evaluation of silver halide photographic light-sensitive material》

(Exposure)

For each sample prepared as described above: About the blue light source, the helium-force dome

20 lasers — (approximately 422 nm), a green light source

44 nm), red light source: luminous: arsenic semiconductor laser-(about 7

In 80 eta m) optical system using, bi - - beam diameter of about 80, a polygon $ la - the use scanning speed 16 OMZ seconds, an exposure time per pixel in the conditions of 5 X 10_ ⁷ seconds The following two types of exposure were performed.

1: A sample that has been subjected to gray-scale exposure once and a sample that has been subjected twice by controlling the exposure amount using an external modulator.

2: Sample subjected to uniform scanning exposure to obtain a patch with a density of 1.0 [Development processing]

Each of the exposed samples was subjected to the following development processing.

Development process>

Process treatment temperature Time replenishment rate color developing 38. 0 ± 0. 3 ° C 45 sec 80 ml / m ² blix 35. 0 ± 0. 5 ° C 45 sec 1 20m l / m ² Stabilization of 30 to 34C ° C 60 sec 150m l / m ² drying 60 to 80 ° C 30 sec

The composition of each developing solution used in the developing step is shown below.

Color developing solution>

Tank liquid Replenisher Pure water 800 ml 800 ml Triethylene diamine 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.0 1 g Potassium monochloride 3.5 g ― Potassium sulfite 0.25 g 0. 5 g

N-ethyl-N-(/ 3 methanesulfonamidoethyl) 13-methyl-14-aminoaniline sulfate 6.0 g 10.0 g N, N-Jetylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 Og 1 0.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2. Og 2. Og Fluorescent white (4, 4'-Diaminostilbene disulfonic acid derivative)

2.0 g 2.5 g Carbonium carbonate 30 g 30 g Add water to make 1 liter, adjust pH to 10.10 for tank fluid and 10.60 for replenisher It was adjusted.

Bleach-fixer: tank solution and replenisher>

Diethylene triamine pentaacetate ammonium dihydrate 65 5 g Dethylene triamine pentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazol 2 0.0 g ammonium sulfite (40% aqueous solution) 27.5 ml water was added to make up the whole volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

0—Pheninolephenol l. O g 5—Cross-2-methyl-14-isothiazolin-3-one 0.0 2 g 2-Methyl-4-isothiazolin-3-one 0.0 2 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g

1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution)

Magnesium sulfate7-hydrate

P V P

Ammonia water (25% aqueous ammonium hydroxide solution)

Tri-acetate trisodium salt

Add water to make 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

(Evaluation of suitability for multiple exposure)

For each sample subjected to the exposure and color development, the gradation image obtained was measured by the reflection densitometer (XR ite Co. XR ite 938), horizontal axis: exposure (L ₀ g E ), Vertical axis: After creating a characteristic curve consisting of the color density (D), the gradient of the density change with respect to the exposure amount between 0.5 and 1.5 for each of the yellow, magenta, and cyan images ry, rm, About the tilt at l exposures? The absolute value of the change rate of the slope a2 in the _second exposure with respect to ^ i was determined as a gradation change rate Δry, Arm, and Arc according to the following formula, and this was used as a measure of the suitability for multiple exposure.

Gradation fluctuation rate (%) = {| 2-r i l / r i} xi oo

(Evaluation on white background)

The white background of each of the samples prepared above was visually observed by 10 people, and a score of 6 or more was judged to be a bright white background or a preferable white background, and a score of X was determined to be 5 or less.

(Evaluation of suitability for high-speed digital printing)

Using each sample, a high-speed laser printer (Noritsu QSS 3101 digital printer manufactured by Norritsu Co., Ltd.) was used to obtain a density of 1.350 sheets per hour under conditions of 2350 sheets per hour. After continuously printing the image obtained by uniform scanning exposure for 5 hours so that a gray patch of 0 was obtained, the following evaluation was performed for the final print.

For the white background part of the final print, the yellow reflection density was measured using a reflection densitometer at the 100th point, and the difference between the maximum density and the minimum density (AD „ _IN ) was calculated. It was a measure of variation.

Evaluation of variation in image density area>

Using a reflection densitometer for the gray patch portion of density 1.0 in the final print, measure the yellow reflection density at 100 points, find the difference between the maximum density and the minimum density (ADL.), And use this as the image. It was a measure of the variation in the density part.

The results obtained above are shown in the table below.

Sample Multiple exposure suitability White background High-speed digital print suitability Remarks

Δ r y A m Α. Γ c Evaluation Δ D m i n Δ D i. O

10 1 22 17 18 X 0 .005 0 .0 1 7 Comparative example

5 102 22 17 18 X 0.0008 0.018 Comparative example

103 20 15 16 X 0.006 0.01 6 Comparative example

1 04 17 15 14 X 0.005 0.017 Comparative example

1 05 22 1 7 18 〇 0.018 0.01 7 Comparative example

106 22 17 18 〇 0.0008 0.0016

10 107 18 16 15 〇 0.007 0.

1 08 18 1 6 15 〇 0.006 0.015 The present invention

109 18 16 15 〇 0.005 0.015

1 10 9 9 8 〇 0.004 0.

1 1 1 9 9 8 〇 0.004 0.007 The present invention

15 1 12 9 9 8 〇 0.003 0.004 The present invention As is clear from the above results, the sample having the configuration defined by the present invention has better white background characteristics than the comparative example, Low gradation fluctuation of white area and image density even after continuous printing with a high-speed digital printer

It can be seen that a stable image can be obtained with less variation of 20. Industrial potential

As described above, according to the configuration of the present invention, it has good white background characteristics, It is possible to provide a silver halide photographic light-sensitive material having a small gradation variation and a small variation in the density of a white background and an image area even after continuous printing with a high-speed digital printer.

Claims

The scope of the claims

1. a silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and at least one light-insensitive emulsion layer on a support, selected from a light-sensitive emulsion layer, a light-insensitive emulsion layer, and a support A silver halide color photographic material comprising at least one oil-soluble fluorescent whitening agent and a blue-sensitive silver halide emulsion having an average particle size of 0.7 m or less.

2. The horizontal axis is obtained by performing exposure and color development processing in ^10-6 seconds or less exposure time: exposure (L 0 g E), vertical axis: on the characteristic curve consisting of color density, density 0.5 2. The silver halide according to claim 1, wherein the variation of the average gradient of a straight line passing through the point giving the density and the point giving the density of 1.5 is within 10% in the multiple exposure. Color photographic light-sensitive material.

3.23. The silver halide photographic material according to claim 1 or 2, wherein the curl degree at C ヽ 20% RH is +15 or less.