JPH0284637A - Reflection type color photosensitive material and method for forming color image thereon - Google Patents

Abstract

PURPOSE:To improve the image quality of a CG image, a line drawing or a character image without lowering effective sensitivity by allowing a silver halide photosensitive layer to include chlorobromide emulsion whose average content rate of silver chloride is >=50mol% and in which the surface of particle is gold-sensitized and providing a colored layer where decolorization can be performed between the photosensitive layer and a reflective supporting body. CONSTITUTION:The silver halide photosensitive layer including a color coupler provided on the reflective supporting body is allowed to include the chlorobromide emulsion whose average content rate of silver chloride is >=50mol% and which has a silver bromide containing localized phase inside the particle or on the surface of the particle, which is gold-sensitized, and the colored layer where the decolorization can be performed by color developing processing is provided between the above-mentioned photosensitive layer and the reflective supporting body. Thus, not only a photographic image excellent in the sharpness of image but also a color in which edge contrast is high such as the line drawing and the character image can be rapidly and easily obtained. Especially, by using what is called a mini-lab system, not only the photographic image but also the print obtained by combining the CG image, the line drawing and the character image excellent in the sharpness of image can be easily obtained in a short time.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a reflective color photosensitive material that has excellent image sharpness and can quickly and easily obtain color images. In particular, it uses a scanning exposure method and has excellent image sharpness and edge contrast. The present invention relates to a reflective color photosensitive material that can quickly and easily obtain CG images, line drawings, or character images together with photographs. (Prior art) Color prints are usually obtained by printing an original obtained from a color-sensitive photographic material (for example, color negative film, color positive film, or reversal color film) onto color photographic paper, and then performing color development. It will be done. Recently, due to improvements in the performance of color photosensitive materials for photography, the image quality of color photographic paper has been improved, without sacrificing the conventional performance such as sensitivity, gradation, whiteness, etc. In particular, image sharpness and contrast of microscopic images of line drawings have been improved. The need for improvement has increased. Also, with the spread of color printing, in addition to regular photographic images, CG (Computer Graph)
Color photographic paper is often used to print icsJ images, line drawings, or character images.For example,
Conventionally, to print line drawings and character images from color photographic paper to obtain various cards, postcards, sticker prints, etc., an enlarger or printer similar to that used for printing photographs was used, and a separate lithographic film was used. The method used was to create a block film for printing line drawings and character images, and then print this as the original. Although this method produces shunga and character images of excellent image quality, it is artificial and time consuming. In place of the above-mentioned printing plate film, it is also possible to print on translucent base paper using a word processor, but the image quality is inferior. Tube) or tlFOT (Fib
A method is also known in which the displayed image is output to a computer (Eroptics Tube) and then printed. So-called"
Examples of printers using the "cRTil optical system" include Japanese Patent Application Laid-Open No. 2003-120032-4! !
No. 4, No. 4.2-295037, No. 62-Kota 5
It is described in numerous specifications such as JP OIR No. 62-2-6032, and printers with the FOT exposure method are described in, for example, JP-A-Sho + Are listed. But regular color photographic paper?
However, the obtained image quality, sensitivity, and speed of processing were insufficient. Printers using laser light controlled from similar storage means are also known, but are insufficient in cost and simplicity. JP-A No. 63-63036 discloses that a reversal type silver halide emulsion'& [in the light-sensitive material used, the support is made thin It is described that the sharpness can be improved by providing a layer to prevent deterioration of sharpness. However, it does not suggest any improvements in surface latent image type silver halide emulsions or supports used in general color photographic paper, or improvements in scanning exposure, particularly character reproducibility. (Problems to be Solved by the Present Invention) The image quality of ordinary photographic prints has improved due to improvements in color photosensitive materials and color photographic paper. (FOT) The image quality printed by the exposure method is insufficient, and especially in images in which line drawings and character images are printed together with photographic images, the quality of the line drawings and character images is very noticeable. Japanese characters are especially difficult to reproduce compared to alphabetical characters, and the thicker the thin lines, the more noticeable the blurring becomes. To speed up and simplify the color development process for color photographic paper,
When a silver halide emulsion with a high silver chloride content (for example, 50 moles or more of total silver halide) is used in at least one layer of the color light-sensitive material of the present invention, a conventional silver chlorobromide emulsion (for example, a silver chloride content of 20 moles or more) is used. Compared to silver halide emulsions (less than silver halide emulsions), the sensitivity can be increased, and the sensitivity and stability of latent images are inferior. If a large amount of dye is used to prevent irradiation or halation, the effective sensitivity will further decrease, and the spectral sensitivity in particular will decrease due to gray sensitization and desorption of the sensitizing dye used. Silver halide emulsions with a high silver chloride content absorb almost no light in the visible range (≠00 to 700 nm), and this problem of spectral sensitivity is particularly important because sensitivity is obtained by spectral sensitization. The scanning exposure method uses laser light, fluorescent light, LED light, liquid crystal light, etc., which have different intensities in at least three different wavelength ranges, and is used in combination with color separation filters if necessary.Especially fluorescent light. In scanning exposure systems that use body luminescence, such as CRT and F'OTW systems, it is necessary to adapt the luminous intensity and efficiency of the phosphor and the spectral sensitivity of each photosensitive layer of color photographic paper. This is necessary for stabilization. Normally, photographic exposure methods use stable tungsten light, halogen lamp, or xenon lamp light, and the sensitivity of each photosensitive layer of color photographic paper is determined according to this light. The sensitivity ratio of each photosensitive layer of ordinary color photographic paper is
? It is not compatible with the FOT exposure method at all. Many of them have a relative lack of sensitivity to longer wavelength light (and red sensitivity).The object of the present invention is to remedy these deficiencies.The first object of the invention is to improve the effectiveness [ The object of the present invention is to provide a color photosensitive material that has excellent image quality, especially for CG images, line drawings, or text images, without deteriorating the image quality.Second, the object of the present invention is to provide a color photosensitive material that has excellent image quality, especially for CG images, line drawings, or character images.
An object of the present invention is to provide a color photosensitive material and a color image forming method that can quickly and easily form images, line drawings, and character images, particularly by shortening the exposure time using three types of light sources in the exposure step and the color development processing time. Third, the reflective support is 200
It is an object of the present invention to provide color photographic paper that can be used to make various cards or postcards using the color photographic paper that is thinner than μm. (Means for Solving the Problems) As a result of examining factors such as the exposure means to be used and the sensitivity of color photographic paper, and the adaptation of the exposure means, the present inventors have achieved the object of the present invention as follows. I found out what I can do. (11) In a color photosensitive material comprising at least one silver halide photosensitive layer containing a color coupler on a reflective support, the silver halide photosensitive layer has an average silver chloride content of jOmolti or more. and a silver bromide-containing localized phase inside or on the surface of the grain, the grain surface contains a gold-sensitized silver chlorobromide emulsion, and a color development process is performed between the photosensitive layer and the reflective support. Did you provide a colored layer that can be decolored?
A reflective color photosensitive material with special features. (2) The reflective support described above is contained in a water-resistant resin containing 12M
Projected occupied area ratio per unit area containing all white pigment particles with a size of 1 or more, and in which the dispersion and hiding of the white pigment particles is specified (
%” coefficient of variation S/and (For example, if white pigment particles are 70
It is contained at a density of 2 μmXAμ or more by weight%.
The fluctuation coefficient s/R of the occupied area ratio of the white pigment particles per m (unit surface area) is 0.20 or less, and furthermore, there is N between the support and the silver halide photosensitive layer that can be decolorized by photographic processing. A silver halide photographic material having a color L. (4) In the colored layer that can be decolorized by photographic processing, pi″i7
．． It is substantially insoluble in water of 0, pl(ri, θ), and is a silver oxide photographic light-sensitive material. 750 gen according to any one of claims 1 to 2, characterized in that it comprises a solid 98 particle dispersion of a dye selected from among the compounds coated by X11), (Xffl) and (XIVI). Silveride photographic light-sensitive material. General formula (Me) General formula (x1) General formula (%I+) A2=L1 (L2°L3snA2 General formula (Xll
l) Az+Lt-L2? r? 7rIB2 general formula (XIV
) (In the formula, A2 is an acidic nucleus having one substituent (the substituent is an acidic nucleus selected from carboxyphenyl group, sulfamoylphenyl group, sulfonamidophenyl group, carboxyalkyl group, and hydroxyphenyl group) The acidic nucleus may include 2-vilasorin-!-one, rhodanine, hydantoin, thiohydantoin, ko, Hiro-oxazolidi/dione, inoxazolidinone, barbituric acid, naoparbituric acid, indantoin, etc. selected from the group consisting of diones and human pyridones.B2 is a basic nucleus having at least one substituent selected from carboxyl group, sulfamoyl group, and sulfonamide group (substituents include groups other than those listed above). and the basic nucleus is selected from the group consisting of pyridi/, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, and pyrrole. Each substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group,
It represents an acyl group or a sulfonyl group, and R41 and R42 are connected! Alternatively, a 6-membered ring may be formed. R43 and R4
6 each represents a hydrogen atom, a hydroxy group, a carnexy group, an alkyl group, an alkoxy group, or a halogen atom, and R4
4 and R45 are each a hydrogen atom, or R41 and R44 or R42 and R45 are connected! Or, it represents a group of nonmetallic atoms necessary to form a 6-membered ring. Ll, B2, and B3 each represent a substituted or unsubstituted methine group, and X3%Y3
each represents an electron-withdrawing group;
It has a boxyalkyl group or a hydroxyphenyl group. m represents O or l, mouth represents O1/or 2. p
represents O or /, and when p is O, R43 represents a hydroxy group or a carboxy group, and R44 and R45 represent a hydrogen atom. ) (6) A color image forming method characterized in that the reflective color photosensitive material according to any one of items (1) to (3) above is printed by a scanning exposure method and then subjected to color development processing. The present invention The scanning exposure method is a scanning method in which the pixels are
On the contrary, it is a method of assembling things in chronological order according to certain rules. For more details, for example, the Image Electronic Handbook (
It is described on page 5 of Chapter 3, 4A, Basic Edition (edited by the Institute of Image Electronics Engineers). For image exposure, laser light, CRT, LE
In the present invention, a scanning exposure method using Cr1T is preferred. In addition, a preferred color photographic paper according to the present invention has at least three kinds of silver halide photosensitive layers on a support. The maximum wavelength of the different spectral sensitivities of these silver halides is matched with the wavelength of the CRT's emission and maximum intensity.In the case of laser light, at least three types of laser light, such as He- Cd laser, Ar-gas laser, He-Ne
Gas laser, GaAs system, GaAsxPrx system and In
It is preferable to use a laser beam selected from a P-based semiconductor laser or the like. In scanning exposure, each pixel emits light repeatedly for several milliseconds to several microseconds, so a sufficiently high amount of light can be obtained using relatively low-output CI (T7fr).The device is also compact and It is inexpensive.The present invention uses color CRTs.Black and white CRTs, especially those called high-performance tubes, have high resolution, are distortion-free, can display images over the entire fluorescent surface, and have fewer spots and halos. A particularly preferred CRT'IIr optical system according to the present invention uses a black and white CRT using a phosphor that emits light in the blue, green, and red wavelength ranges in order to increase the pixel density. From digital information storage means, such as floppy disks,
Alternatively, a photo or CG image, line drawing, or text image can be directly input and displayed on a black and white CRT, and then passed through blue, green, and red filters to an optical lens and shutter, and then sequentially displayed on the photosensitive layer of color photographic paper. This method involves forming an image and exposing it to light. The exposure time of each blue image, green image, and red image obtained through the blue, green, and red filters is taken in inverse proportion to the spectral sensitivity of each photosensitive 1 of the color photographic paper due to multiple high-intensity, short-time exposures. The CRT used in the present invention has a large number of pixels! 00 to 7000 x! The light emitting time of the seven pixels is about l x 50 to / x 50-7 seconds, and /θ for seven exposures to each photosensitive layer.
It will emit light up to 500 times. The boom diameter of 1 pixel emission is 2
It is about 0 to 500μ. Further, the above-mentioned F, O, T, and CRT can also be used for exposure. In this case, contact exposure can be carried out by using a special device such as a liquid crystal filter to separate blue, green and red colors. FIG. 1 shows an example of the print production process using the CRT exposure method according to the present invention. The character image input section/λ consists of a console consisting of a CRT and a keyboard, and character information is input by operating the keyboard while looking at the CRT. It is also possible to store already input character information in a storage medium (for example, a floppy disk). It is possible to instruct the start of CRT dimming. The graphic image input unit 13 is composed of a digitizer, and can input line drawings and combiator graphics (CGI images), and can store the data of the input graphic images on the H170 disk. The human image input section IO can input n light using a separate photographic image exposure system, but can also input information or a photographic image inputted from, for example, an electronic still camera using a digitizer. The image synthesis section/l is composed of a microcomputer, and reads out data in a certain order from the human image input section IO1 character image input section 12 or the figure image input section 13'' as necessary, and stores them at a predetermined position. The CRT controller controls the color monitor and the black and white CRT for exposure.Before the start of exposure, the composite image data is sent only to the color monitor. The composite image is output and a positive image is displayed on the display screen.During exposure, the composite image is inverted to a negative image, output to a black and white CRT/4, the electron beam is swayed in the opposite direction, and the composite image is moved left and right. Also invert. Optical lens 1ry2 (through, optical filter B%G, R
A black and white CTtT image is inserted in synchronization with the light emission of the black and white CRT display surface, and is also synchronized with the shutter/7 to print on the color photographic paper for each predetermined time using a three-color surface sequential exposure method. A predetermined color development process can then be performed through photoprocessing apparatus 20. The phosphors used in black and white CRTs are the same as the color photographic paper used.
It is preferable to use a phosphor having a wavelength of maximum brightness that matches the dominant wavelength of spectral sensitivity of the photosensitive layer of the species. It is preferable that the afterimage time is short, there is no afterimage, and there is little flare on the display surface. Furthermore, since short-time exposure is required, a phosphor is used that emits strong light at high voltage and high current density and has excellent current saturation characteristics and temperature stability. The phosphor can be selected from phosphors for projection tubes. Red fluorescent materials that can be stably obtained industrially include Y2O3:Eu, Y2O2S:Eu,
In green, Zn2SiO4:Mn, Gd2O2S:Tb
, among which %Y2S i GeO5: Tb and Y3Als
otz'Tb for blue ZnS:Ag, CJ or ZnS
: There are Ag, Al, etc. The red sensitivity (Srl), green sensitivity (S, ) and blue sensitivity (SB) of ordinary color photographic paper,
SB s S (lower than 3 and 11 of SR. In particular, the emission wavelength of the red phosphor is too to 630 nm and 70 nm.
It is in the vicinity of 0 nm, and has poor compatibility with the red sensitivity wavelength of color photographic paper. In the present invention, it is particularly important to increase the spectral sensitivity of the color photosensitive material and to optimize the wavelength distribution. 7. The color light-sensitive material of the present invention is characterized primarily by the use of a silver chlorobromide emulsion having a high silver chloride content in order to obtain rapid processability. The second method is chemical sensitization and spectral sensitization using dyes that are used to effectively suppress the spread of the exposure light flux. Thirdly, the newly devised support
The purpose is to apply an antihalation layer. The silver chlorobromide emulsion having a high silver chloride content used in the present invention is preferably of a type that mainly forms a latent image on the surface of the silver chlorobromide grains. The silver chlorobromide emulsion according to the present invention is essentially a silver chloride or silver chlorobromide emulsion, and the silver iodide content is 2 moles or less, preferably 1 mole or less, particularly preferably 0.1 mole or less. These are as follows. Further, the silver chloride bromide emulsion according to the present invention has a silver chloride content of at least JO mole or more, preferably tO mole or more, and more preferably θ mole or more, particularly preferably H!
It is more than a large number of moles. The remaining components include silver bromide, silver iodide, and silver rodan. These halogen components are preferably different within or on the surface of the silver halide grains in a layered manner or discontinuously isolated. Particularly preferably, a localized phase having a higher silver bromide content than the surrounding phases exists in the vicinity of the surface of the grain, either in a layered manner or discontinuously. The silver bromide content of the localized phase is at least the Tamor coefficient, preferably more than 50 mmol, particularly preferably more than 20 mmol and more than 70 mmol. The silver halide grains contained in the silver halide emulsion according to the present invention may be grains of any crystal habit, but include spherical and polymorphic grains, particularly normal crystal grains such as cubes, /II-hedrons, and r-hedrons, and tabular grains. particles are preferred. The silver halide grains preferably have a multilayer structure in which the crystal structure differs inside or near the surface. Grains with a layered structure having different halogen compositions or grains having a localized phase near the surface of the grain with a silver bromide content different from the surrounding phases are preferred. In the case of core-shell type particles, it is preferable that the silver chloride content in the core part is higher than that in the shell part. No-rodanized silver grains with high silver chloride content according to the present invention (
(hereinafter referred to as "high silver chloride grains") are generally <1oo)
Although only cubic grains consisting of faces can be obtained, by devising a method, it is possible to obtain grains such as octahedrons and tabular grains having (IIT) faces. The manufacturing method of t-hedral particles consisting of (II/) planes is disclosed in the patent application filed in 1973.
-4!72 Kota issue, JP-A Show JT-2/6ZR specification, C1aes', etc. [Journal of Photography Science (Journal of Photography Science)
tographic 5science month, volume 21, 3
R (1973) and Wyrsh [International
Combres Op Photographic Science (
International Congress of
Photographic 5science), [1
-/J, l here (l 7r), etc. Preferably, the method described in the specification of Japanese Patent Application No. 722/1988 is preferred. Normal crystal grains with (///) faces are as described in the above-mentioned patent application No. 42-1.
Compounds represented by general formula (1) or general formula (II) described in JP-A No. 47221, and JP-A-Sho JJ-
24-A4! J specification, consisting of 3 to 1 nitrogen atoms, oxygen atoms or sulfur atoms, together with sulfur atoms
During particle formation, preferably in the particle growth process after forming a core particle It is best to control crystal habit by using The tabular grains according to the present invention include the above-mentioned compound having a sulfur-containing heterocycle and the JP-A-63-4! /rψY compound described in the specification: RIS (X)m Y-R2 (X is a divalent organic group, alkylene, arylene, alchemolene, -8O2--8o --0--S--C --to-, etc., R1 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, R2i a hydroxyl group, an alkyl group, an aryl group, a heterocyclic residue, an amino group, an alkoxy group, an aryloxy group, etc., and Y is -co--5o2-, m is O or l; R3 represents a hydrogen atom, an alkyl group, an aryl group, etc. (substituents may be introduced into each group), etc. is preferably used in the process of grain formation to control crystal habit. In particular, for the formation of high silver chloride tabular grains, the chloride concentration in the aqueous gelatin solution added during the formation of the core grains is approximately O1/! Advantageously, the concentration is low, below mol/l. Also, the chloride concentration of the grain growth is below the concentration of t mol/l, especially between 3 and 0.07 mol/l! ! degree is preferred. The silver chlorobromide grains of the present invention are produced by mixing silver ions with chloride or bromide, or a mixture thereof, preferably in the presence of the compound for controlling crystal habit, after forming the core grains. Near Ir], particles can be grown rapidly. Preferably, fine silver halide grains, such as silver bromide, silver chloride, or a mixed silver halide thereof, can be mixed with a silver chloride, silver bromide, or silver chlorobromide emulsion to form grains. layered by recrystallization of silver rhodide or halogen conversion,
Alternatively, an isolated localized phase can be provided on the particle surface. The particle formation is between 50 and 50°C, especially ≠θ°
It is preferable to use Naishiri OoC. Examples of silver rhodanide solvents that can be used during grain formation include thiocyanates, thioethers, and thioureas, and ammonia can also be used in combination without causing any adverse effects. For example, thioneanate (U.S. Pat. No. 2,222゜2t≠
No. 2, 1, 63 Hiroshi, 3゜320, Di,
L? ), thioether compounds (e.g., U.S. Pat. No. 3,27/, U.S. Pat.
3.70'A, No. 130, Kota No. 7, Kota 7. ≠No. 3, Hiroshi 276゜3≠7, etc.), thione compounds (
For example, WIJ, JP-A-53-11711319, J-J
-421401, JJ-77737, etc.), amine compounds (e.g., JP-A No. 2003-007/007/7, etc.), etc. can be used. In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an indium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together. In particular, it is preferable to use iridium salts, rhodium salts, iron salts, or complex salts thereof. When producing the silver halide grains of the present invention, a silver salt solution (for example, AgNO3) is added to accelerate grain growth.
aqueous solution) and halide solution (e.g. NaCl aqueous solution)
A method of increasing the addition rate, amount, and concentration of addition is preferably used. Regarding these methods, see, for example, British Patent No. 7.33.
No. 225, U.S. Patent No. 3.672. ri No. 00, same No. 3.
4!0.717 issue, same number G, 2≠2, +≠j number, JP-A-J Yoichi 7≠23.22 number, same jr-/6112IL1 number, same jJ'-//3 octopus 7 number , same 5♂-//3ri 2I!
' No., same ta r-///? 3≠ issue, same jf-///ri3z
You can refer to the description of the number etc. The structure of the surface and vicinity of the high silver chloride grains according to the present invention is as follows:
In particular, the sensitivity and stability of the present invention, the reciprocity law characteristics,
This is important for the stability of the latent image. The final stage of grain formation, e.g. rj of all silver halide grains
When the growth is more than a mulch, Japanese Patent Application No. 62-r62-2, Japanese Patent Application No. 2-32221j, A2-/
Particle formation method described in J2330 specification and CR-
Compounds (), inhibitors of Rodan conversion and chemical sensitization) may be used. When a halide is added to silver halide grains after adsorbing the CR-compound, the halide may be a rhodane donor that can control the supply rate and amount of chlorine ions or bromide ions. is desirable. This method is advantageous in that a localized phase having a silver bromide content different from that of the surrounding phases can be formed on or near the surface of the silver halide grain. It is preferable that the localized phase or other substrate of the silver halide grains of the present invention contains a metal ion selected from Group ♂ metal ions or a complex salt thereof. For example, iridium ions are mainly used in the localized phase, and metal ions selected from osmium ions, iridium ions, rhodium ions, ruthenium ions, radium ions, iron ions, cobalt ions, nickel ions, etc. are mainly used as substrates. It is better to use different types and concentrations of metal ions in the localized phase and the substrate, such as by using a combination of these complex ions.Also, use metal ions such as cadmium ions, zinc ions, lead ions, mercury ions, and thallium ions. The amount of these metal ions or their complex ions added is about IO to 50 mol based on silver halide. The presence of the localized phase and its silver bromide content in the present invention are Diffraction method (for example, edited by the Chemical Society of Japan [New Experimental Chemistry Structure J
A. It is described in Structural Analysis published by Maruzen. ) or XPS method (for example, surface analysis; application of rI MA, Auger electron, photoelectron spectroscopy, published by Kyudokusha).
In particular, the silver bromide content of localized phases that are uneven or isolated at edges and corners can be determined using the EDX method (Energy Di).
supersive X-ray analysis
) (For example, "Electron Beam Microanalysis" by Hiroyoshi Soejima
EDX equipped with a transmission electron microscope (as described in Nikkan Kogyo Shimbun, 7917, etc.) was used to obtain a MW of about JM in an aperture with a diameter of about 6 to 0.2 μm using a chromator. It can be measured by In the high silver chloride emulsion used in the present invention, 0% or more of the total grains in terms of projected area have a diameter equivalent to a circle of the projected area of 0.0%. / to 3μ, and in the case of tabular grains, the ratio of the equivalent circle diameter to the grain thickness (referred to as the equivalent ratio) is 2 or more, preferably 3 to 50, particularly preferably 3μ to 3μ. It is. The high silver chloride emulsion is preferably a monodisperse emulsion, and preferably has a dispersion coefficient of equivalent circle diameter (ratio ν of standard deviation of equivalent circle diameter to average grain size of 0./or less. Other features of the present invention Chemical sensitization according to the present invention preferably involves gold sensitization, particularly sulfur sensitization, of emulsions containing high silver chloride grains with localized phases in the presence of chemical sensitization controlling compounds. High silver chloride emulsions that require gold sensitization are green-sensitive emulsions and red-sensitive emulsions. The conditions for gold sensitization (pH, pAg, temperature, time i are not particularly limited, but for example, the pH value is 3° o-r, r
,especially! , θ~7.5 is preferable, and the pAg value is r
, o~ri, 01, especially j, j~7, j are preferred, the temperature is preferably Hiroo~rs0c, especially 4t~7~0C, and the time is 10~200 minutes, especially 30~/koo minutes. preferable. Preferred gold sensitizers include US Pat.
No. 2jli00r6, λzuoo. Examples include compounds described in No. 26 or No. 71RJT, and specific examples include chloroauric acid and its salts, potassium gold cyanide, potassium gold thiocyanide, gold sulfide, and the like. Intensifying gold sensitization by using thiocyanate in combination, and Tokkosho! It is also useful to use a thiourea compound in combination as described in Ter//Iri No. 2. Examples of sulfur sensitizers that can be used in combination in the present invention include US Pat.
Examples include thiosulfates, sulfinates, thioureas, thiazoles, rhodanines, and other compounds described in No. TTR, No. 3656-J. Also, U.S. Patent No. 3l-17711, No. 2460/r and
Sulfur-containing compounds described in No. j≠gji can also be used. The amount of the gold sensitizer used is selected to be about lo-8 mol to 50-5 mol to increase the sensitivity/fuzz ratio. Due to the combination of chemical sensitization inhibitors, fogging can be minimized (
High sensitivity can be detected. It is preferred to use relatively small amounts depending on the target sensitivity. The amount of sulfur sensitizer that can be used in combination with this is determined depending on the conditions such as particle size, chemical sensitization temperature, pAg, and pH.
You can choose fi. per mole of silver halide,
50 to 50 mol, preferably Xl0-7 to 50
-'More preferably jX/0 to 50 mol is used. When both gold and sulfur sensitization are used together, it is preferable to carry out chemical sensitization by coexisting the sulfur sensitizer and the gold sensitizer in an amount of 250 molar or more. The silver halide emulsion of the present invention can be treated with an oxidizing agent after grain formation. This method is used in
J iG No. 774, for example, hydrogen peroxide is used. By adding at least seven compounds represented by any of the following general formulas (N to 1ll) to the high silver chloride emulsion used in the present invention, fog increases, especially when a gold sensitizer is used. It is extremely effective in preventing It can be added at the particle formation step, desalination step, chemical ripening step, or just before coating, but it is preferably added during the particle formation, desalination, and chemical ripening steps, especially before the addition of the gold sensitizer. . General formula (1), (II)-ztake (I
The compound having a thiosulfonyl group represented by IIJ will be explained. General formula (1) Z 5O28M General formula (1ll General formula CIII) In the formula, Z represents an alkyl group, an aryl group, or a heterocyclic group, and these may be further substituted. Y is necessary to form an aromatic ring or a heterocycle4

[represents a group of atoms]
However, these rings may be further substituted. M is metal
Ding represents an atom or an organic cation. nμλ~50o integer
It represents Ding. Placed on the above alkyl group, aryl group, aromatic ring or hetero ring
Examples of substituents that can be replaced include methyl group, ethyl group, etc.
lower alkyl group, 71J-l group such as phenyl group, carbon
number/~r of alkoxyl groups, halogen atoms such as chlorine,
Examples include tro groups, amino groups, carboxyl groups, etc.
I can do it. The number of carbon atoms in the alkyl group represented by Z is /~/r,
The number of carbon atoms in the aryl group and aromatic ring represented by Z and Y is 6.
~/r. The heterocycle represented by Z and Y includes thiazole,
Benzthiazole, imidazole, benzimidazole
, oxazole ring, etc. The metal cation represented by M includes sodium ion.
Alkali metal cations such as ions, potassium ions,
Examples of organic cations include ammonium ions and guanidinium ions.
Preferred are um ions and the like. Represented by the general formula (II, [11], or (IIIJ)
Examples of such compounds are listed below. 6 H3C-8O2・SNa kL-cystine-disulfoxide l H5C2・S02・S-K m Hl 7CB -802・5NB General formula (1),
The compound represented by (If) and (nl) is
Sulfites, alkyl sulfinates, arylsulfites
sulfinates such as phosphates, heterocyclic sulfinates, etc.
Can be used in conjunction with Methine dye commonly used for spectral sensitization in the present invention
type is used. In the present invention, in particular,
1'62j No. 2, No. 12330, No. 12330, No. 12330, No. 12330 and No. 12330
-Specific monomethods as described in Specification No. 32-261
Trimethine, pentamethine dyes, and merocyanine
Dyes can be used as chemical sensitization control agents to control high silver chloride grain growth.
adsorbed to silver halide grains during process or chemical sensitization process
It is better to leave it alone. When the silver chlorobromide emulsion used in the present invention is a high silver chloride tabular grain
The selection of the time of addition of the dye is extremely important.
It is necessary to carry out this process before the silver generide precipitate formation is completed.
However, the addition method described below can also be used in combination. most
This is usually done after the completion of chemical sensitization and before application.
However, U.S. Pat. No. 3,421. No. 62, and No.
V, λj, t6 were chemically sensitized as described in the issue.
Add at the same time as the agent, and perform spectral sensitization at the same time as chemical sensitization.
Also, JP-A-5R-II3. It is listed in the 2r issue.
It can also be carried out prior to chemical sensitization. Further more
As taught in U.S. Patent No. 226.6At.
Adding these compounds separately, i.e.
Some of these compounds are added prior to chemical sensitization, and the remaining
It is also possible to add after chemical sensitization, and the U.S. patent
Starting with the method taught in No. 4Z, /13.7jA
For example, at any stage during silver halide grain formation.
good. used for spectrally sensitizing the silver chlorobromide emulsion used in the present invention.
The pigments used include cyanine pigment, merocyanine color
Synthetic cyanine dye, composite merocyanine dye, holopolar
Cyanine dyes, hemicyanine dyes, styryl dyes and
Included are hemioxonol dyes. Particularly useful dyes are
, cyanine pigment, melonanine pigment, and complex melon
It is a pigment belonging to anine pigments. These pigments include
Usually used in cyanine pigments as a basic heterocyclic nucleus
Any nuclear can be applied. In other words, pyrroline nucleus,
xazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazo
le nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus
, tetrazole nucleus, pyridine nucleus, etc.; alicyclic nucleus in these nuclei
Nuclei in which the formula hydrocarbon rings are fused; and aromatic carbon in these nuclei
Nuclei with fused hydrogen rings, i.e., indolenine nucleus, benz
Indolenine nucleus, indole nucleus, benzoxadol nucleus
, naphthoxazole nucleus, benzothiazole nucleus, naphtho
Thiazole nucleus, benzoselenazole nucleus, benzimidazo
Can be applied to core nuclei, quinoline nuclei, etc. These cores are charcoal
It may be substituted on an elementary atom. Keto for merocyanine dyes or complex merocyanine dyes
Pyrazoline-ion nucleus as a nucleus with methylene structure
, thiohydantoin core, 2-thioxazolidine-2,
Hiro-dione nucleus, thiazolidine-, 2,4cm dione nucleus,
J-A member differences such as rhodanine nucleus and thiobarbyl acid group
Nodal ring nuclei can be applied. These spectral sensitizing dyes
As described in Japanese Patent Application Sho tco, No. 22733r,
Formulas (111a), (lllb) and (IIIC) are expressed as
Examples include sattl compounds. The amount of JJO added is per mole of silver halide, / X 50
-6 to rX/0 mol can be used, but
A preferred silver halide grain size is 0.2 to 1. In the case of Copm, about jX50-5 to 2
It is effective. Tabular silver halide emulsions are spectrally sensitized in the blue region to produce blue-sensitive emulsions.
It is preferably used in the agent layer. Here, it is divided into the blue region.
Photosensitized means that when adsorbed to the emulsion grains of the present invention,
From ≠00, more preferably to roomm f714
tl On m to 0 m, more preferably
At least one absorption peak from 4t~nm to '190nm
The method is to use a spectral sensitizing dye that contains blue
As a specific example of a spectral sensitizing dye, the general formula (
lla) and general formula (ill C) with n3t = 0
A compound having the structure can be used. specific compound
For example, from 1ll-/ to ■'' stated in the application specification.
-g compound and Hlit -, 2 to l1l-32
2 can be mentioned, and the particle formation in the presence of these
? Tabular high silver chloride grains can be preferably used. High silver chloride tabular grains are formed in the presence of dye.
can be determined from the spectral sensitivity distribution. That is, high silver chloride emulsion
In general, a spectral sensitivity distribution of 7 yap is formed and it is painful.
. When particles are formed in the presence of a dye as in the present invention,
represented by the general formulas (Illa) and (III b J)
In the case of methine dye, a sharp J-band is formed.
and the merocyanine color represented by the general formula (IItCJ)
In the case of element, sharp monomer band (M-band)
In both cases, a sharp spectral sensitivity distribution is obtained.
give. Therefore, identification of peak wavelength, spectral sensitivity distribution, and pigment-like
It can be determined that particle formation took place in the presence of the dye.
Ru. For J-band and M-band, HT,
H. James, “Theory of the Photographic Process”, Chapter 1, Macmilla
Konsha (1977) K explanation is given. Spectral sensitizing dyes can be used alone or in combination.
Ru. It is recommended to use it in combination with a supersensitizer. For example, amine-stilbene compounds (e.g., U.S. Patent No.
2. 33, 3 0, 363-721, 3
6/J, No. 6l3, No. 367, No. 6μ/, No. 341
72F! No. 3635?2/No. 3635?2/Special Application Showa A/-30
J, aromatic ring or hetero ring described in the specification of No. 6030 etc.
Mercapto compounds etc. are added to high silver chloride emulsions as supersensitizers.
It is best to use it as Particularly red spectral sensitization, i.e. wavelengths between jlo and 7j□nm.
For sensitization in the range, the ring potential has a value of −7.27 (V vs. SCE) f or less.
Sensitizing dye has excellent sensitivity and stability of sensitivity and latent image.
Excellent. The chemical structure is a conjugated metal between he atoms.
It has a structure in which 7 or 2 of the chin chains are fused together.
Pentamethine cyanine dye molecule,
Limethine cyanine pigment, tetramethine merocyanine color
Dimethine merocyanine with Moto or Hiro-quinoline nucleus
I like the pigment. The reduction potential is measured using phase-discriminative second harmonic AC polar log.
It can be done with roughy. Add mercury to the working electrode, and add the reference electrode to the working electrode.
A Sho calomel electrode is used as the pole, and platinum is used as the counter electrode.
conduct. These sensitizing dyes, hydroquinone, catechol,
Adsorption formyl to amine phenol, halogen (t[
Concomitant use of hydrazine compounds or their derivatives
Good. For details on the formylhydrazine compound mentioned above,
It is stated in the specification of Japanese Patent Application No. 1983-7-OJ'.
There is. The high silver chloride emulsion used in the present invention has an inherent sensitivity in the visible wavelength range that is higher than that of a high silver bromide emulsion.
(substantially low when the silver chloride content is 50 molt or more)
The sensitivity can be increased by spectral sensitization. On the other hand, green
Silver halide according to the present invention for spectral sensitivity and red spectral sensitivity
The spectral sensitivities of the emulsions in the blue wavelength range do not mix.
, increasing the sensitivity of the silver halide emulsion to substantially improve separation.
The trick is to find a way to increase light sensitivity. Therefore, in addition to the above-mentioned spectral sensitization technology, silver halide emulsion
Applying gold sensitization technology to increase the intrinsic sensitivity of
, B, G, and R photosensitive layers to balance the spectral sensitivities.
It is extremely effective. The silver halide emulsion used in the present invention contains a mercapto group.
Fogging of photosensitive materials can be reduced by adding compounds with
It can be used to reduce the amount of milk used in the production of photosensitive materials and to improve raw shelf life.
The stability of the agent coating liquid over time can be improved. Tetrazaindenes are usually used for these purposes.
mercapto-containing compounds are particularly suited for these purposes.
It should be used in small quantities (limited quantities) and should be used within the optimal range.
Below this range, it becomes ineffective, and above it, there are negative effects such as desensitization.
was thought to be large. This is unexpected, but
The emulsion of the present invention contains mercaptotin, which is considered to have a strong inhibitory effect.
It is preferable for the above purpose to add a desensitizing compound,
There are fewer adverse effects such as development inhibition. In the case of high silver chloride emulsions,
May exhibit supersensitizing effect when used with sensitizing dyes.
Ru. The mercapto-containing compounds preferably used in the present invention are as follows:
It can be expressed by the general formula (S). General formula (S) In the formula, Ml is cleaved by a hydrogen atom, a cation, or an alkali.
represents a protecting group for a mercapto group, and Zl is a member or t
Represents the group of atoms required to form a member heterocycle. this
Heterocycles may have an @ group and may also be fused.
It's okay. To explain in more detail, Ml is a hydrogen atom, an positive
ions (e.g. sodium ions, potassium ions,
ammonium ion, etc.) or alkali.
Protecting groups for capto groups (e.g. -cort'-COOH'
-CH2CH2COR' etc. However, R' is a hydrogen field
children, alkyl groups, aralkyl groups, aryl groups, etc.
). Zl is an atom necessary to form a j-membered to t-membered heterocycle
The child group is the front child. This heterocycle has a sulfur atom as a hetero atom,
It contains ren atoms, nitrogen atoms, oxygen atoms, etc.
May be fused, or on a heterocyclic ring or on a fused ring
may have a substituent. Examples of zl include tetrazole, triazole, immi
dazole, oxazole, thiadiazole, pyridine,
pyrimidines, triazines, azabenzimidazoles,
Phosphorus, tetraazaindene, triazaindene, inter
Azaindene, benztriazole, benzimidazole
benzoxazole, benzthiazole, benzuse
These include renazole and naphthoimidazole. This again
# substituents for the rings include alkyl groups, (for example
Methyl, ethyl, n-hexyl, hydroxyethyl, carbon
ruboxyethyl), alkenyl M (fJ is allyl)
, aralkyl groups (e.g. benzyl, phenethyl), aralkyl groups (e.g. benzyl, phenethyl),
group (e.g. phenyl, naphthyl, p-acetamide)
phenyl, p-carboxy, diphenyl, m-hydroxy
phenyl, p-sulfamoylphenyl, p-acetyl
Phenyl, 0-methoxyphenyl, co, ≠-diethyl a
minophenyl, 28 μm dichlorophenyl), alkyl
Thio groups (e.g. methylthio, ethylthio, n-butyl
thio), arylthio groups (e.g. phenylthio, naphthio)
ruthio], aralkylthio group, (eg benzylthio)
, a mercapto group, etc. may be substituted. Toku again
In addition to the above substituents, there are also nitro groups and amino groups on the condensed ring.
group, halogen atom, carboxyl group, sulfo group, etc.
May be replaced. The use of these mercapto-containing compounds @ halogenated
It is preferably lo-3 moles or less per mole of silver. Specific formulation of nitrogen-containing heterocyclic compounds having mercapto groups
Examples of compounds are disclosed in JP-A-42-. No. r of Specification No. 2/Ta 27λ
Compounds A-3717 to A-J' described on pages i to 6,
27 etc. can be applied. The color coupler used in the present invention will be explained.
. General requirements such as its various colored phases and its high extinction coefficient
In addition, the development progress of the emulsion used in the present invention is particularly fast.
, color developing agent such as rough enylene diamine conductor
so that the coupling color reaction with the oxidized form of
Highly active color couplers are required. From this point of view
In the following formula (IV), (V), (fJ, [■] or [■]
Preference is given to using the couplers shown. Formula (f'/) [■] Ct13 Y. Formula (V) Formula (MJ Formula [■1] In the formula, R1s R4 and R5 are an aliphatic group and an aromatic group, respectively.
Aromatic group, heterocyclic group, aromatic amino group or heterocyclic amino group
, R2 represents an aliphatic group, and R3 and R6 are
hydrogen atom, halogen atom, aliphatic group, aliphatic oxygen atom, respectively.
represents an oxy group or an acylamino group, and R7 and R9 represent a substituted or unsubstituted phenyl group.
R8 is a hydrogen atom, an aliphatic or aromatic acyl group, a fatty acid
represents an aliphatic or aromatic sulfonyl group, RIO represents a hydrogen atom or a substituent, and Q represents a substituted or
represents an unsubstituted hephenyl group, and Za and zb are methine, substituted methine, or diN-?
In the expression, Yl, Yl and Y4 are halogen atoms or developing agents.
A group that can be separated during a coupling reaction with an oxidant (hereinafter referred to as
, leaving group and lattice)′? : Representation, Y3 is a hydrogen atom or
In the general formula (IV) and the general formula (Vl, R2 and R3
and R5 and R6 combine to form j or 7-membered
It may form a ring. Further RI s R2, R3 or Y 1 : R4,
R5, R6 or Yl; R7, R8, R9 or Y3: RI
OlZa, Zb or 1cY4; Q or Y5 with dimer or more 1
7) May form a multimer. R5 and R6 combine
to form a J-membered ring, oxindole or indazoli
It is preferable to form a cyan coupler with a cyan on-on yarn.
Yes. The above formulas (IV), (V), [■], [■] and [V
R1, R2, R3, R4, R5, [(6,
R7, R8, R9, R+ as Z a % Z! ]
, Ql, Yl, Yl, Y3 and Y4 details,
From page V to page 2 of the specification of JP-A-J 3-//ri 3
The general formula (11, (1), (III),
Same as that of (IV) and (V). A specific example of a glossy color coupler is the above-mentioned JP-A
Written on page 1 to cog page of specification No. 1.3-11932.
(C-/7~(C-guO), (M-/)~(M
-Hiroshi2), (Y-/) ~ (Y-≠6) can be listed.
Wear. The standard amount of color coupler used is photosensitive
ranging from o, ooi to 7 moles per mole of silveride.
preferably a yellow coupler with IflO, 0/no
O1θ03 to magenta coupler
0.3 mol, also cyan coupler tl-50,002
0.3 mole. The general formula (IVJ, [V), ('tL), [■] or
or CMll) is used.
In the photographic material, the preferred silver halide coating a'
D, / , 697 m2-0, 7 g 7-2
. These couplers can be used in combination with a small number of high-boiling organic solvents.
It can be contained in the dispersed emulsion layer. Like
Or with a high boiling point represented by the following formula (A) or E)
A solvent is used. Formula (A) Formula% Formula% Formula (D) Formula% Formula% (In the formula, wl, w2 and W3 are each substituted or
Unsubstituted alkyl group, cycloalkyl group, alkenyl group
, represents an aryl group or a heterocyclic group, w4 Hw,
,OW1'! lds Wt l: table bL, n is 1
W4 is an integer of 1 and 2, and when n is 2 or more, W4 is the same.
They may be the same or different, and in the general formula (EJ, W
1 and W2 may form a condensed ring. The photosensitive material produced using the present invention also contains a color antifoggant.
or as a color mixing prevention agent, hydroquinone derivatives, amino
Nophenol derivatives, amines, gallic acid derivatives, categorical
Cole derivatives, ascorbic acid derivatives, colorless couplers
, sulfonamide phenol derivatives, etc.
stomach. A known anti-fading agent may be used in the photosensitive material of the present invention.
Can be done. High as an organic anti-fading agent)”oki/yl
i, A-hydroxychroman Lj-hydroxykuma
orchids, spirochroman m, p-alkoxyphenol
Hindered phenols, mainly bisphenols
gallic acid derivatives, methylene dioxybenzenes,
minphenols, hindered amines, and their respective
Silylates and alkylates the phenolic hydroxyl groups of compounds.
Typical examples include ether or ester derivatives.
It will be done. Also, (bissalicylaldoximad) nickel
complex and (bis-N,N-dialkyldithiocarba
Metal complexes such as nickel complexes can also be used.
Wear. Used to prevent yellow dye images from deteriorating due to heat, humidity, and light.
As described in National Patent No. 4', JAF, Ri No. 23,
Partial structures of hindered amines and hindered phenols
Compounds having in the same molecule give good results. Also
To prevent deterioration of magenta dye images, especially deterioration caused by light,
For this purpose, spiroi described in JP-A-5A-IJYTAA
and those described in JP-A-1J-119136.
Hydroquinone diether or monoether ota
chromans give favorable results. Also, the image stabilization described in Japanese Patent Application Laid-Open No. 2002-1732
using a pyrazolotriazole type magenta coupler.
, is particularly advantageous for stabilizing the formed magenta image. To improve the storage stability of cyan images, especially the light fastness.
, benzotriazole UV absorbers can be used together.
preferable. This UV absorber is co-emulsified with cyan coupler.
You may. The amount of UV absorber applied adds photostability to the cyan dye image.
It is fine as long as the amount is sufficient to
Yellowing in the unexposed areas (white areas) of color photographic materials.
Usually, /x/ 0″′″
4mol/m2 to JXto-3mol/m2, especially 1x/m2
0-'mol/rn2~l. It is set in the range of jXlo mol/m 2 . In the photosensitive material layer structure of normal color paper, cyan coupler
- Either one of the layers on both sides adjacent to the red-sensitive emulsion layer containing
Preferably, both layers contain an ultraviolet absorber. green
Adding a UV absorber to the intermediate layer between the sensitive layer and the red sensitive layer
It may also be co-emulsified with a color mixing inhibitor. UV absorber
When added to a protective layer, another layer is added as the outermost layer.
A protective layer may also be applied. This protective layer contains any grains.
Contains a mixture of matting agents with different diameters and latex with different particle diameters.
You can force it. In the photosensitive material of the present invention, ultraviolet light is present in the hydrophilic colloid layer.
Line absorbers can be added. In addition to the above-mentioned additives, the photosensitive material of the present invention further contains
stabilizers, anti-fouling agents, developing agents or
, development accelerator or its precursor, lubricant, mordant, magenta.
antistatic agents, antistatic agents, plasticizers, and other photographic sensitizers.
Various additives useful to the material may be added. these
Typical examples of additives are Research Disclosure/7
6143 (/7g/72) and the same/17/l, (
/7 years//month]. The photographic emulsion layer or other hydrophilic layer of the light-sensitive material of the present invention
In the roid layer, stilbene, triazine, oxazole
The whitening agent may also contain a brightening agent such as a coumarin-based or a coumarin-based brightener. Water-soluble brighteners may be used; water-insoluble brighteners may also be used.
It may also be used in the form of a dispersion. Reflection support used in silver halide photographic light-sensitive material according to the present invention
The support shall be provided with a water-resistant resin layer on the substrate.
Can be done. Substrates include natural pulp, synthetic pulp or
are base paper and polyethylene paper obtained from those mixtures.
Polyesters such as phthalate and polybutylene terephthalate
Stell film, cellulose triacetate film, polystyrene film
Len film, polypropylene film, and polyolef
Using plastic film such as fin film
I can do it. The base paper used in the present invention is commonly used for photographic paper.
Selected from materials. In other words, you can choose from conifers, hardwoods, etc.
The main raw material is naturally occurring rubber, and if necessary, clay,
Fillers such as Merck, calcium carbonate, urea resin fine particles, etc.
Gin, alkyl ketene dimer, higher fatty acid, paraffin
wax, sizing agents such as alkenyl succinic acid, polyamide
Paper strength agents such as crylamide, sulfuric acid, cationic
A material to which a fixing agent such as a polymer is added is used. Especially alkyl ketene dimer, alkenyl succinic acid, etc.
Using a reactive sizing agent, pHj ~ 7 (Toa Electric Co., Ltd.
I used flat GST-Yo373F manufactured by Han Kogyo Co., Ltd.
It is preferable to use neutral paper (measured with a pH meter). Furthermore, instead of the natural T-lube mentioned above, the synthetic valve Meigetsu is used.
Any ratio of natural pulp and synthetic pulp can be used.
It may also be mixed with. In addition, gelatin, starch, and carboxylic acid are added to the surface of this pulp.
dimethylcellulose, polyacrylamide, polyvinyl
Film forms of alcohol, modified products of polyvinyl alcohol, etc.
The surface size can also be treated with synthetic polymers. child
In this case, the polyvinyl alcohol modified product is carboxyl alcohol.
With xyl group modified products, silanol modified products and acrylamide
Examples include copolymers of. Also film-forming polymers
Application of film-forming polymers for more surface sizing
The machine is o, ir, og7m2, preferably 00j-
It is adjusted to 2,09/rA. Furthermore, the film shape at this time
For synthetic polymers, antistatic agents and fluorescent whitening agents are added as necessary.
Agents, pigments, antifoaming agents, etc. can be added. In addition, the base paper is
Contains additives such as fillers, sizing agents, paper strength reinforcing agents, and fixing agents.
The valve slurry is made into paper using a paper machine such as a Fourdrinier paper machine.
, dried and rolled up. Before and after this drying
The above-mentioned surface size treatment is carried out in one of the methods, and after drying
Calendaring is performed between winding and winding. This boyfriend
Under treatment is performed when surface size treatment is performed after drying.
, to be carried out either before or after surface size treatment.
Can be done. Whether or not the base paper used for the support substrate of the present invention is neutral paper is an example.
For example, the electrode is manufactured by Toa Denpa Kogyo ■ GST-13/3F for flat surfaces.
This can be determined by measuring the pH value using a . Neutral paper is p
) 1 value! The above is preferably as shown below.
Ru. The water-resistant resin layer according to the present invention is made of a material such as vinyl chloride resin.
The sea urchin itself may constitute a support. The water-resistant resin used in the present invention refers to the water absorption rate (weight%).
is o, r, preferably o, i or less, for example, poly
Alkylene (polyethylene, polypropylene, carbon dioxide)
polymers), vinyl polymers and their copolymers (polymers), vinyl polymers and their copolymers (polymers)
listyrene, polyacrylate and its copolymers) and polymers.
These include polyesters and their copolymers. Preferably,
Polyalkylene resin, low density polyethylene, high density polyethylene
Polyethylene, polypropylene and their blends are used.
It will be done. Fluorescent brightener, antioxidant, antistatic agent as required
A blocking agent, a release agent, etc. are added. In this case, the thickness of the resin layer is approximately 1 to 200 μm, particularly
Preferably, the IO depth is 0 μm, and a white pigment is usually used.
The pigment is kneaded using a melt mixing method etc. and then passed through a melt extruder.
and melt extrusion lamination. Also, if you look back, you will see JP-A-7-272J-7 and Sho-J7-Rita.
As described in Tag No. 6 and Specification No. 61-λ62731
Sea urchin has one polymerizable carbon-carbon 21 bond in each molecule.
unsaturated organic compounds with more than
Tel-based compounds, JP-A/-2t2731 per 2t car
Gintri-tetra-acrylic acid represented by the general formula
Ester etc. can be used. In this case, on the substrate
After coating, it is cured by electron beam irradiation to create a water-resistant resin.
Make it a fat layer. White pigments are contained in these unsaturated organic compounds.
Spread. It is also possible to mix and disperse other resins.
Ru. The method for coating the water-resistant resin layer of the present invention includes, for example, processing techniques.
Laminate described in "New Laminating Processing Handbook" edited by Jigaku Kenkyukai, etc.
lamination methods, e.g. dry lamination, solvent-free
Mold dry lamination etc. are used, and for application
Gravure roll type, fee 2-bar type, doctor blade
do type, reverse roll type, dip type, air knife type
, calendar type, kiss type, skies type, fanchin type
It is selected from methods such as The water-resistant resin contains white pigments, such as rutile.
Cloth, titanium oxide, anatase titanium oxide, barium sulfate
calcium sulfate, silicon oxide, zinc oxide, phosphoric acid
Titanium oxide, aluminum oxide, etc. are used, and titanium oxide face
The surface of the fine particles of the material is made of silica, aluminum oxide, etc.
Co or μ value alcohols together with or separately from inorganic oxides.
For example, 2 described in Japanese Patent Application Laid-Open No. 2003-111007/7/J/, etc.
゜Gudihydroxy-2-methyl is Ntanyatrimethyl
It is preferable to use it after surface treatment with ethane or the like. The surface of the support is preferably subjected to corona discharge treatment, glow radiation treatment, etc.
Silver halide photosensitive materials are processed by electrical treatment, flame treatment, etc.
A protective colloid layer group is provided. The total thickness of the support is 30 to 3jO! l/m2 (approx.
30 to 4! ooμm) is preferable, more preferably
approximately 2009 jo to 2009/m2, of which water-resistant trees
The fat layer preferably has a thickness of about 1 to 200 μm, more preferably
or about io to UO μm. The characteristics of the support in the present invention are that it is preferable for white pigments (and
or titanium oxide], preferably by weight of 1
% or more, and izML amount Chi or more and 50 debt debts or less
Disperse it in the water-resistant resin layer so that it has a certain density.
It is in. In particular, fine particles of white pigment are
Densely on the surface or at a thickness of 50 μm 8 degrees from the surface
And it is important to disperse it evenly (so that there are no rough spots).
good. The dispersibility of white pigment fine particles in the resin layer depends on the surface of the resin.
The thickness of the groove is about 0.1μm, preferably about 600A.
- Surface trees are removed by ion sputtering method using electric discharge.
The fat is scattered and the exposed pigment particles are exposed to an electron microscope.
Observe more closely, find the area occupied by the photograph, and calculate the occupied area ratio (
It can be evaluated by the coefficient of variation (%). Ion sputtering
The ring method is based on Hiroshi Murayama-1 Kunihiro Aiki's ``Plasma-based
"Surface Treatment Technology", Mechanical Research Vol. 33, No. 6 (1971)
) etc. are described in detail. The coefficient of variation of white pigment particles is 0.7! To control below
, thoroughly kneading the white pigment in the presence of a surfactant is
Often, the surface of the pigment particles is
It is preferable to use one treated with alcohol. Occupancy area ratio per specified unit area of white pigment fine particles
(%), most typically the observed area,
divided into unit areas of 6 μm x + μm, and
Occupied area ratio (%) of projected fine particles (Ri) Y measurement
It can be found by Change in occupied area ratio (%)
In the number, the standard deviation S of R1 with respect to the average value (R) of R,
It can be determined by the ratio S/[t. target unit
The number of position areas (n) is preferably 6 or more. Therefore, the coefficient of variation
s/lt can be calculated. In the present invention, the occupied area ratio (%) of pigment fine particles is
The coefficient of variation is preferably 0./2 or less.
stomach. o, or less, the dispersibility of the particles is substantially "uniform".
It can be said that there is one. Generally, such white pigments are used in silver rhodanide photosensitive materials.
When it is contained in a support, a white color appears when viewing a photograph.
Provides a background (white background) and reduces the sharpness of the image.
It can also cause it to change. In contrast, white in the present invention
Satisfies the density and dispersibility conditions of color pigments, and
The intensity of the first type diffuse reflected light is increased, and the spread of the diffused light is also increased.
It is possible to reduce the This improvement effect due to the support
The result is not only the incident light at the time of exposure, but also when viewing the photograph.
It has the characteristic that it is remarkable when the incident light is high. Other features of the silver halide photographic material in the present invention are
, between the support and the silver halide photosensitive layer, photographic processing (
After development, bleaching, fixing, water washing, stabilization, etc.)
The purpose is to provide a colored layer that can be colored. By fixing the light absorber in the colored layer, silver halide
The halation prevention effect on the photosensitive layer can be improved by inhibiting spectral sensitivity and
This allows for effective performance while avoiding fogging.
Wear. Light absorbers include colloidal silver (black to yellow) and dyes.
is used. By providing this colored layer, the support
Image sharpness due to scattering of diffused light from t111
This further effectively prevents deterioration of the battery. Colloidal silver emulsion is used as a light absorber in the colored layer of the present invention.
It is preferable to be there. Colloidal silver emulsions are usually
Those used for color-sensitive materials can be used. Colloidal silver is used, for example, in U.S. Patent No. 2650tO1;
3μ! 11.3 and Belgian Patent No. 622 Butata
It can be manufactured according to the method described in the specifications. Main departure
The colloidal silver used for light is the tone! After R, electrical conductivity/ro
It is preferable to use it after sufficiently desalting it to less than opscm-'. The usefulness of the colloidal silver-containing layer is 0.0/m/m of silver.
to θ, jy1 preferably o, or to 0.2f
l is preferred. It also prevents irradiation, stabilizes sensitivity, and protects
Other objectives such as improved light safety and improved spectral sensitivity distribution
A dye can also be used as a target. In another preferred embodiment, the colored layer of the present invention contains a dye and
The mordanting cationic polymer can be used. Cationic polymers that can be preferably used in the present invention
is a cation exchange polymer that functions as an anion exchange polymer.
Ammonium with at least one hydrogen atom in the site
It is a non-color-forming polymer with a base thread. General formula (■) In the formula, AI-r has a small number of copolymerizable ethylenically unsaturated groups.
have at least two of them, and at least seven of them are included in the side chain.
The monomer units copolymerized with copolymerizable monomers are shown below.
Child. B is a copolymerizable ethylenically unsaturated monomer.
represents the combined monomer unit. 1141 is a hydrogen atom, low
A represents an alkyl group or an aralkyl group. Q is a single bond or
is an alkylene group, an arylene group, an aralkylene &, -c
-o-L- may be used. It represents the group that will be used. Here, L is an alkylene group, arylene
Di(or aralkylene group, R is an alkyl group)
Waching. lL125I'L13\RL4s R15%
R16% R17% R1B% R19 is a hydrogen atom, an alkyl
represents a halalkyl group, an aryl group, or a halalkyl group;
may be the same or different. Also mentioned above
Any of the above groups also includes substituted groups. Xe is an anion
Na Omote Wa Ding. Also, Qs R12, R13, RI4 and t! Q, R1
5,tt, 6,R17,Rm,, any of FLts
λ or more groups are bonded to each other to form a ring structure with a nitrogen atom.
At least one of R14 forming the structure is a hydrogen atom. X% Y% and ztrl represent molar percentage, xhO
From to to, y is from O to 60%, 2 is from 30 to
Displays values up to 00. To explain the above general formula (DC) in more detail, A
Examples of monomers that can be used include divinylbenzene and ethylene glycol.
Cold dimethacrylate, diethylene glycol dimethacrylate
Acrylate, triethylene glycol dimethacrylate
, ethylene glycol diacrylate, diethylene glycol
Cold diacrylate, /, 4-hexanedioldia
Acrylate, neoantyl glycol dimethacrylate
, tetramethylene dimethacrylate, etc., of which 1.
Divinyl dimethacrylate, ethylene glycol dimethacrylate
Particularly preferred. An example of an ethylenically unsaturated monomer in B is ethylene
, propylene, y ten, isobutyne, styrene, α
- Methylstyrene, vinyl ketone, monoethylene of aliphatic acids
Renically unsaturated esters (e.g. vinyl acetate, I!lr[
allyl acid), ethylenically unsaturated monocarboxylic acid or
is an ester of dicarboxylic acid (e.g. methyl methacrylate)
ethyl methacrylate, n-butyl methacrylate
, n-hexyl methacrylate, cyclohexyl methacrylate
rylate, benzyl methacrylate, n-butyl acrylate
rate, n-hexyl acrylate, coethylhexylate
acrylate) monoethylenically unsaturated compounds (e.g.
acrylonitrile) or dienes (e.g. butadiene)
, isoprene], among which styrene,
methacrylate, cyclohexyl methacrylate, etc.
is particularly preferred. B contains two or more of the above monomer units.
You can stay there. RIIJ hydrogen atom or lower alkyl having carbon number/-j
group (e.g. methyl, ethyl, lopropyl, n-glyph)
n-amyl, n-hexyl) aralkyl group (e.g.
For example, benzyl 1 is preferable, and among these, hydrogen atom or metal
A chill group is particularly preferred. Q is preferably a divalent substituted compound having carbon number /-/λ.
alkylene groups (e.g. methylene group or -(CH
2) a group represented by 6-), an optionally substituted phenyl group
Ren group or an optionally substituted aram having 7 to 12 carbon atoms
A lekylene group (for example, a group to be used) is preferable, and the following formula
A group represented by where L is substituted with carbon number l to
optional alkylene group or optionally substituted aryle group
or an optionally substituted aramyl group having 7 to 2 carbon atoms
A lekylene group is preferred, and is substituted with carbon number/-4.
A good alkylene group is more preferred. An alkyl group having Rfl carbon number/~t is preferred. 112% R13% R14% R15% R
16S R11R18%Th9 is a hydrogen atom or /-2
Alkyl group with 0 carbon atoms or 6 to 20@
an aryl group having carbon atoms or 7 to λO carbon atoms
Aralkyl groups containing elementary atoms are preferable, and each has the same
may be different. This alkyl group ary
Substituted alkyl groups and substituted aralkyl groups include substituted alkyl groups and aralkyl groups.
Contains lyl groups and substituted aralkyl groups. The alkyl group is an unsubstituted alkyl group (for example, methyl,
Ethyl, lopropyl, isopropyl, lopropyl, i
butyl, t-butyl, n-amyl, isoamyl, n-
hexyl, cyclohexyl, n-heptel, n-octyl
2-ethylhexyl, n-nonyl, n-decyl, n
-dodecyl); The carbon atoms of the alkyl group are preferably 7 to
There are 12 pieces. More preferably, it has 4 to 50 carbon atoms.
be. Examples of substituted alkyl groups include alkoxyal
Kill groups (e.g. methoxymethyl, methoxyethyl, meth)
xybutyl, ethoxyethyl, ethoxypropyl, meth
xybutyl, butoxyethyl, butoxyethyl, butoki
Sibutyl, vinyloxyethyl), cyanoalkyl groups (e.g.
For example, λ-anoethyl, 3-cyanopropyl,
abutyl), halogenated alkyl groups (e.g. 2-fluor
oroethyl, cochloroether, 3-fluoropropyl
), alkoxycarbonylalkyl groups (e.g. ethoxy
carbonylmethyl), allyl group, 2-butenyl group, pro-
Examples include pagil group. The aryl group is an unsubstituted aryl group (for example, phenyl
, cafthyl), substituted aryl groups include, for example, alkyl
ruaryl group (e.g. λ-methylphenyl, 3-methyl
Phenyl, 4Z-methylphenyl, μ-ethylphenyl
, Hiro-isopropylphenyl, ≠-tert-if
phenyl 1, a flukoxyaryl group (e.g. goumethoxy
Phenyl, 3-methoxyphenyl, goomethoxyphenyl
), aryloxyaryl group (for example gAI≠-pheno
Examples include xyphenylon. Carbon atom of aryl group
The number of children is preferably 6 to /4Z, more preferably 6
~50 pieces. Particularly preferred is a phenyl group. Examples of aralkyl groups include unsubstituted aralkyl groups (e.g.
benzyl, phenethyl, diphenylmethyl, naphthyl
methyl); substituted aralkyl group, e.g. alkylaralkyl
group, (e.g. hi-methylbenzyl, λ, yo-dimethyl
benzyl, gooisozolobylbenzyl), alkoxy
ralkyl group, (e.g. Hiro-methylbenzyl, l-ethoxy
siethylin, cyanoaralkyl group, (e.g. Hiro-cyano
benzyl), per70-roalkoxyaralkyl group, lJ
tbahiro-pentafluoropropoxybencyl i, 44-
177 decafluorohequinyloxybenzyl group, etc.),
rogenated aralkyl group, (e.g. th, ≠-chlorobenzyl
group, ≠-bromobenzyl group, 3-chloroindyl group, etc.
) can be given. The number of carbon atoms in the aralkyl group is preferably 7 to /! individual,
Preferably it is 7-71 pieces. Among these, benzyl group,
A phenethyl group is particularly preferred. Xe represents an anion, such as a halogen ion (e.g.
chloride ion, bromine ion), alkyl or flavor ally
sulfonic acid ion (e.g. methanesulfonic acid, ethane
Sulfonic acid, be/ynesulfonic acid, p-1 luene sulfonate
), acetate ions, sulfate ions, nitrate ions, etc.
Among them, chloride ion, myacetate ion, and sulfate ion are particularly preferred.
stomach. Also, any two or more groups of QSR12, R13, R14
combine with each other to form a cyclic structure with nitrogen atoms
It is also preferable to do so. The cyclic structure formed is pyro.
Lysine ring, piperidine ring, morpholine ring, pyridine ring,
An imidazole ring, a quinuclidine ring, etc. are preferred. Especially good
Preferred are pyrrolidine ring, morpholine ring, and toba-lysine ring.
, imidazole ring, and pyridine ring. Also, Qs R+s, R16, R17, T't18, R1
Any two or more groups of 9 bond to each other and form a nitrogen atom.
Both may form a cyclic structure, and the cyclic structure formed
A t-membered ring or a j-membered ring is particularly preferred. x Its O up to 60 mol%, preferably
is O or Hiroθmolti, more preferably O or
It is 30 morti. y is from Q to 60 mol%
, preferably O to aO morti, more preferably
is O to 30 mol. z ir, 30 to 500 molar, preferably
, ≠ 0 or less, more preferably SO
or rr morti. G in the general formula (■) has a pKa value of 4 in an aqueous solution.
Z is preferably a basic residue of 5 or more, especially 7 or more. ICfx as a cationic polymer of general formula (K)
Polymer latex is particularly preferred in terms of film quality. Specific examples of compounds represented by the general formula [■] are listed below.
do. x:z=50:'? 0 x:z =20: ro :z=jO:50 x:y:z-40:50:≠Q +-C-CI-12CH3 x:y:z=30:3Evening:3j CH3 x: z=20:50 C=0 (-CH2Cx:y:z=lI0 2 50:60H3 x:y=30near 0 y:z=30near0 z=jO: jo CH3 (-CCHzsux:y :z=20:50 near 0 CH3 CH3 x:y:z=/yo: / j: 70H3 CH3 CH3 exposure (CH3 in l ↓ CH3 x:y:z=/j:j:50 CH3 C=0 CH3 CH3 1/2SO4e x:y:z=20:50 near 0 CH3 (-C-CH2suCH3 x:y:z=uO:50: IQ deviceC=0 +CH2CsuCH3 x: y: z=koj: 2j : Yo0CH3co
When making a fine particle dispersion of CP cationic polymer,
Generally, crosslinking monomers such as divinylbenzene are used.
Depending on the monomer used,
The use of crosslinking monomers is not essential. Regarding the carcinogenicity of the compound represented by the general formula (IXI) of the present invention,
This will be explained below. The polymer of the present invention represented by the general formula ([1()) is
A covalent compound containing at least two of the above ethylenically unsaturated groups in
Polymerizable monomers, ethylenically unsaturated monomers, and
and general formula [111% formula% (however, R11, R12, R13, Q are as shown above)
unsaturated monomers (e.g. N,
N-dimethylamine ethyl methacrylate, N, N+,
Diethylaminoethyl methacrylate, NN-dimethyl
Aminoethyl acrylate, N. ~-diethylaminoethyl acrylate-1-1N-(N,
N-dimethylaminopropyl) acrylamide, N-(
N,N-dihexylaminomethyl)acrylamide,!
-(44-pyridylsinprobyl acrylate, N,N
-dimethylaminomethylstyrene, N,N-diethyl acetate
Minomethylstyrene, NN-diethylaminomethylstyrene
Ren, 2-vinylpyridine, or ≠-vinylpyridine
etc., particularly preferably 1''[N,N-diethylaminoethyl
methacrylate, matafiN, N-dimethylaminomethyl
methylstyrene, ~-diethylamine methylstyrene
), a compound having the structure nh4-
(In the formula, fh4, X are the same as shown above) (Example
Hydrochloric acid, nitric acid, sulfuric acid, acetic acid, p-toluenesulfone
Obtained by converting it into ammonium salt with acid etc.)
I can do things. In addition, the polymer represented by the general formula (■) of the present invention is
Copolymerizable with at least two ethylenically unsaturated groups of
monomers, ethylenically unsaturated monomers, and unsaturated monomers with the general formula % same as shown above]
(For example, N,N-dimethylamine ethyl methacrylate 1/-
hydrochloride, N,N-diethylaminoethyl methacrylate
sulfate, N,N-dimethylaminoethyl acrylate
Hydrochloric acid ring, N,N-diethylaminoethyl acrylate vinegar
acid salt, N,N-dimethylaminostyrene hydrochloride, N,N
-diethylaminomethylstyrene sulfate, λ-vinylpylene
With lysine hydrochloride or ≠-vinylpyridine hydrochloride, etc.
It can be obtained by polymerization. In addition, the polymer represented by the general formula NX) of the present invention is
Copolymerizable with at least λ ethylenically unsaturated groups
monomer, ethylenically unsaturated monomer, and general formula (where X is a halogen atom (e.g. chlorine atom, bromine atom
), sulfonic acid esters (e.g. p-toluenesulfonyl
Luoquine group l kTable b L, , R11, Q are shown above
unsaturated monomers (e.g.
β-chloroethyl methacrylate, β-p-toluene
sulfonyloxyethyl methacrylate, chloromethyls
After polymerization, the structure of RI2-N-n+3 is
(However, R12, R13, R14 are
(e.g. dimethylamine, dimethylamine)
Ethylamine, Moro-propylamine, Moro-Butylamine
ammonium, morpholine, biiridine, etc.)
It can also be obtained by turning it into salt. A method for synthesizing a compound represented by the general formula (IX) of the present invention, where G is a compound, will be explained below. The polymer represented by the general formula of the present invention has the above-mentioned ethylene
Polymerizable monocontaining at least two unsaturated groups
mer, ethylenically unsaturated monomer and general formula (where R11% RI5, Q are as shown above)
unsaturated monomers (e.g., methyl
vinyl ketone, methyl-(/-methylvinyl)ketone,
Ethyl vinyl ketone, ethyl-(/-methylvinyl)ketone
ton, low propyl vinyl ketone, diacetone acrylic
Particularly preferred are amides, diacetone acrylate, etc.
Methyl vinyl ketone, ethyl vinyl ketone, diacetone
Polymerized with acrylamide, diacetone acrylate)
After that, the general formula (however, formulas R16, R1?, R18, RI9 are as above)
(same as shown) (e.g. heavy
Aminoguanidine carbonate, N-amino-he'-methybicarbonate
Luguanidine, N-amino-N'-methylguanibicarbonate
gin, particularly preferably aminoguanidine bicarbonate).
react, and then add H-X (where H-X is shown above)
(same) (e.g. hydrogen chloride, hydrogen bromide)
, sulfuric acid, acetic acid, nitric acid) to form a guanidinium salt.
You can get it by doing things. The above polymerization reaction is generally known as solution polymerization or emulsification.
Polymerization, suspension polymerization, precipitation polymerization, dispersion polymerization
You can have it too. Preferably solution polymerization and emulsion polymerization
. Among the above polymerization reactions, for example, emulsion polymerization is generally anionic.
surfactants (e.g. sodium dodecyl sulfate,
Triton 770 (commercially available from Rohm & Novus),
Thione surfactants (e.g. octadecyltrimethylan
monium chloride), nonionic surfactants (e.g.
Marex NP-20 (commercially available from Nippon 2F Emulsion)
), gelatin, polyvinyl alcohol, etc.
At least one emulsifier and a radical polymerization initiator (e.g.
Combination of potassium persulfate and sodium bisulfite, Wako
In the presence of j, which is commercially available from Tsumugi Yaku under the name V-jo
and generally 300C to about 1oo0C, preferably ≠
It is carried out at a temperature of 00C to about rθ0C. The reaction to form the above ammonium salt is generally carried out at -50'C
It is carried out at a temperature of ≠00C to about ≠00C, but especially at a temperature of 00C~
3o0c is preferred. The polymer of the present invention allows the entire manufacturing process to be carried out in one container.
It can be produced very easily. Hydrophilicity used in the dispersion of cationic polymers according to the invention
Examples of protective colloids include gelatin and modified gelatin.
, graphs of gelatin derivatives and gelatin and other polymers
polymers, etc. are used, and these are combined with albumin and carbon.
Proteins such as zein; hydroxyethylcellulose, calcium
Ruboxymethyl cellulose and cellulose sulfate esters
cellulose derivatives such as; dex1ran, alginic acid
Soda and starch derivatives 7: [Which sugar derivatives; vorivinyl
Alcohol, partially acetalized polyvinyl alcohol
, poly-N-vinylpyrrolidone, polyacrylamide,
Acrylic acid or methacrylic acid copolymer or polyvinyl
By combining homopolymers and copolymers such as pyrazole
Can be used. Especially preferably, gelatin is used as a hydrophilic colloid,
Gelatin is so-called lime-processed gelatin or acid-processed gelatin.
and enzyme-treated gelatin. Particularly preferred for rapid processing are those with a narrow molecular weight distribution.
It is. The molecular microdistribution of gelatin can be determined using the GPC method (gel/mimie
can be measured by
Wear. The ratio of high molecular weight components is 72 or more, preferably
Preferably, gelatin contains at least 100% of the total amount of 100% or more. G
Regarding the PC method, see JP-A-Sho, gJ-f7 Riyo No. 2 specification.
It is described in the main text and Example-1. Cationic polymer Old/if used in the present invention
Alternatively, other hydrophilic colloid layers may be inorganic or organic @!
Hardened with a coating agent. As a hardening agent, for example, chlorine
salts, aldehydes (formaldehyde, glitter
(e.g. aldehyde), hemethylol compounds (dimethylol
urea etc., activated vinyl compounds (1,3,j-1-rea
Kryloyl-hexahydro-s-)') azine, bicarbonate
(vinylsulfonyl)methyl ether, N, N'-
Methylenebis-[β-vinylsulfonyl]propionia
3,323-, )! 1
Active halogen compounds (2,q-dichloro) described in No. 7 etc.
/L/-7r-hi)" Roxy S-) Reazin ft.
, mucohalogen acids (mucocumylic acid),
Moylpyridinium salt M (/-morpholinocarbonyl-
3-pyridinio) methanesulfocate, etc.), heloamide
Zinium salt ff1(/-(/-chloro-/-pyridinome)
tyrene) pyrrolidinium, conaphthalene sulfonate
etc.) can be used alone or in combination. Main departure
In the Ming Dynasty, hardeners with two or more vinylsulfonyl groups are used.
(For example, Tokuko Akihiro 7-2 Hiro, 2j Rigo, Dosho≠2-/
No. 3663, No. 57-Co V2O2, etc.
(compounds listed above), hardeners having λ or more active vinyl groups (
For example, JP-A No. 3-1/-20, JP-A No. 53-J723
No. 7, No. 6 from Showa J Tar/6ko, No. 6 from Showa 60-♂ort
Compounds described in specifications such as No. tt), others, JP-A-Sho
t2-2222≠No. 2, 1986-24tr21. /issue
, Sho 62-509OJrO and special application Sho t/-/J5'
The compounds described in the specifications such as No. 7/J can be stably used in the present invention.
damage to the cation sites of polymers used in
It can be used in any way. Acid dyes for use with cationic polymers according to the invention
The material is the spectral sensitivity wave possessed by the photosensitive layer of the color photosensitive material of the present invention.
There is a selected optical absorption in the long range, and the molar absorption coefficient is expressed in %.
The number is 50 1-moI・cm-1 or more (mi;
Especially in color photosensitive materials using reflective supports,
Dyes that leave no residual color when decolored or eluted after image processing are preferred.
Delicious. Insoluble dyes are solidified in colloids with dispersion aids.
It is preferable to use it by dispersing it in the form of fine particles. “In the form of solid fine particles” refers to the average particle size (projection, circular approximation)
similar) is 78m or less, preferably 0.5μm to 0.01
μm, substantially resistant to expansion with respect to other adjacent layers in the colloidal layer.
Dispersed, not coarsely aggregated and dispersed to a size of 3 μm or more
means. Fractional auxiliaries include ordinary nonionic surfactants, anionic surfactants,
Surfactants and amphoteric surfactants, such as JP-A-Sho tλ-27
Ta 272's 6 Hiroranai 4A? Cited patents listed on page
Detailed description and specific compound @W-/ to W-Tata
The compound represented by this, Special Publication No. 54-36 Hiro/Ta,
Ya Tokkosho, No. t9-3/611 and Tokusho 42-//
r evening/ri issue BA @ general ceremony of oath [■], CMj ), [■
]Choose from among the surfactants expressed by the formula
It can be used. For example (1)C11H23CON-C)42-CH2COON
aH3 0H 0-(CH2)3-8O3~a (x: y=r: j, x: 6 in y) Also a dispersion aid
, a water-soluble organic solvent such as dimethylformamide,
Methyl alcohol, ethyl alcohol, dimethyl sulfo
Nylamide etc. can be used. Also, it is friendly to dispersion media.
Aqueous colloids such as gelatin, casein, hydroxy
Le ethylcellulose, polyhevinylpyrrolidone,
Polyacrylic acid, gelatin derivatives, etc., and alkaline
of water can be used. Solid microplatelet dispersions are made by dispersing dye solids in a water-soluble V-organic solvent.
However, when dispersed in a colloidal aqueous solution with a neutral or acidic pH,
It is particularly preferred that the dye solid be dissolved in water or an insoluble solution.
It gets wet with the liquid, mixes with the dispersion aid, and becomes fine particles in the mill.
A method of colloidalization and dispersion in a water bath solution, using ultrasound.
After the dye solid is made into a fine powder, a surfactant, which is a dispersion aid, is added.
A method of dispersing the colloid in a water bath using a sex agent, etc.
Dissolve the dye in an alkaline solution and add it to an acidic colloid bath solution.
It can be produced by a method such as dispersion into. Dye or colloid aqueous solutions contain organic acids, such as citric acid.
It is best to use oxalic acid, vinegared rice, tartaric acid, etc. The solid particles used in the invention may be dye microcrystals,
Even if the collector has a micellar structure, it is a micro-agglomerated particle.
Good too. The particle size of solid fine particles is determined by the colloid containing them.
Observation of the cross section of the id layer using a transmission electron microscope
, 1ffllll can be determined. The solid particulate dispersion method involves dispersing pl (substantially
It is insoluble and contains hydroxyl and carboxyl in the molecule.
Group: amino group, sulfomoyl group, etc. p) In L7, substantially
Hydrophilic groups that do not dissociate protons and dissociate above pH level.
The dye contained is M-rich. What does “substantially insoluble in water” mean?
, a hydrophilic colloid 'P with a fine particle dispersion state of pb7 or less
For example, it is insoluble to the extent that it can be retained in an aqueous gelatin solution.
It means that. Bath dissolution at room temperature (26o(') for water with pH 7)
is less than a lot%, and even less than 5% by weight.
dyes, butadiene dyes, oxonol dyes, cyanine
dyes, melon aniline dyes, hexianine dyes,
Arylmethane dyes, triaryl dyes, azomethylene
dyes, azo dyes, metal chelate dyes, anthraquino dyes
chalcone dyes, chalcone dyes, chalcone dyes, indofu
You can choose from a group of phenolic dyes. Also, for example
, U.S. Patent No. I, RRO, TRY, 3rd Edition,
/4 (4<, 3.932.350, 3, ri 3
λ, 3t/issue, same 3. Tagco, ri, r7 gei 7a
Fabian, H. Hartmann (written by J. Fabian, H. Hartmann, 1 rai) -
Absorption of Organic Kararan
(Light Absorption of O
rganicColorantsJ, (Schbringer
・Verlag (published by Springer-VerlagJ)
) (or diffusion-resistant relatives)
body). The dye used in the present invention is disclosed in Japanese patent application No. 62-50tr92.
Functional dyed peach patent application No. 6-2-Co/J Core No.
Specification, patent application Sho t Kokota 32 Ko No. 3 specification 11 or no
[Page 117] Yamata Patent Application No. 1982-41370'1 and
Gansho J, 2-/! According to the general formula (1) of the specification of 3/32
Dye represented by, opening and closing 1r2-22t/3/specification
General formula (in dyes etc. represented by IN)
It matches the spectral absorption characteristics and has no residual color after processing.
I can choose things. To prevent halation
is a photosensitive layer provided on a cationic polymer dispersion layer.
A dye that has light absorption in the spectral sensitivity wavelength range also has a spectral sensitivity of
In order to modify the distribution, a corrector is used to adjust the optical absorption in the sensitivity wavelength range.
Dyes with Dyes used in photographic emulsion layers or other constituent layers of sensitive materials
More than 50% of the amount is contained in the cationic polymer-containing layer.
Good. Also, the amount of dye added is proportional to the number of cation sites.
and the number of anionic groups in the dye is from 0.0 to 50, preferably
Advantageously, it is preferably between 0.2 and 1. Preferred dyes used in the present invention include ), lacy
Patent application number 7.22j,
Otsu/-37 Gugu No. 2g, same tλ-72 Hiro r No. 3, same 1j
-/No. 50333, A, No. 2-22613/, Otsu 2
-277A69, 1.2-211117 Hiroshi, etc.
For dyes described in , and also for correction of spectral sensitivity, a patent application filed in 1983 was applied.
2-3μ26μ, same t2-237032, same 1.2
-21,113 Rino No., same Otsu 2-2t50!2, same 6
Kiichii's dyes are listed in λ-, 2μ7≠77, etc.
. Particularly preferred as the dye is Japanese Patent Application No. A/-217λ 3
, same Otsu 2-7 Hari No. 3, same 62-7 Yo J/7.2, same
t2-226/3/No. 62-2114 Hiroμg, Special
Kaisho 42-/23! Examples include dyes described in Yuhiro issue. Next, specific examples of dyes used in the present invention will be shown. However, it is not limited. Dye-1 03K SO3 to 8031'tl a 03Na 03Na S O3N a (CH2)2SO3 to (CH2)2SO3K CH3 (CH2)2 SOa K (CH2)2SO3 to 03Na S O3N a 03Na 03Na S O3K SO3 to H O 3Na N( CH3)2 (C1-12) 2 So 3 K (CH212SO3 to SO3 (C)12 ) 4803e (C1-12)4sO3Na 03K (CH2)2SO3Na Cl-12cl (zsOaK CH2C) 12 S Oa K Suitable for child dispersion And dye-gu! For solid fine particle dispersion
It can also be used. General formulas (x), (x1), (7e, 11
), (%jll ) and (XIV)
These dyes are particularly suitable for solid fine particle dispersion. and(ni, arrival)
Using colloidal silver as a color layer (for example, using colloidal silver)
A cationic polymer that provides cationic sites is used as a mordant
(Compared to the method of use, etc.) The following features appear
. (1) Purpose of use, e.g. filter layer, Halley/Co
Easily select appropriate spectral absorption characteristics according to
You can choose. (2) Photochemically inert. Adjacent silver halide feeling
Chemically desensitize the optical layer, fog it, or create a latent image.
I won't let you regress. (3) Easily eluted, bleached, and leftover color during the development process.
Don't leave Stin behind. (4) Solid fine particles do not diffuse into other layers. Also stable over time
It has good durability and does not change color or fade. These features are especially useful for printing with reflective supports.
Color photogenic materials, for details, color photographic paper, direct positive
anti-halation layer of color photographic paper and color reversal photographic paper,
Spectral sensitivity summer distribution (useful for ψ pressure filter layer, etc.)
Ru. When used for filter 1, it constitutes a color photosensitive material.
The photorepellent layer is the blue-sensitive layer (BL), the green-sensitive layer (GL), and
Or change the 1s composition of the red sensitive layer (RL) and apply a filter layer.
It is better to set it up properly. In the normal intermediate layer, dye solid fine particles
It is also possible to form a filter layer by containing the following. Dye hardness
It is preferable to use a combination of body particulates and the above-mentioned acid dye.
Delicious. General formula (x), (xl), (%50, (XIIIJ and
Six groups in (XIV) will be explained in detail. Acidic nucleus represented by A2 and represented by ×3 or Y3
Electron-withdrawing/specific crystals have one carboxyphenyl group
as well as phenyl with 2 or 3 carboxy groups
Also includes sulfamoylphenyl groups, sulfamoylphenyl groups, and sulfamoylphenyl groups.
The amidophenyl group and hydroxyphenyl group are also
sulfamoyl group, sulfonamide group and hydroxy
Phenyl having not only one but also two or three groups each
It also includes carboxyne groups, sulfamoyl groups, sulfamoyl groups, etc.
Substituents other than amide group and hydroxyl group (as a substituent)
In a solution with a volume ratio of water and ethanol of /vs/
Dissociative #mata group with pKa (acid dissociation constant) or more
There are no particular restrictions as long as it is a non-dissociable substituent. ) has
You can leave it there. Specifically, Hiroki lupoxyphenyl,
3. Tardical terminal xyphenyl, 2,1l--dicarbo
xyphenyl, 3-carboxyphenyl, λ-methyl-
3-carpoki/phenyl, 3-ethersulfamoyl
phenyl, Hiro-phenylsulfamoylphenyl, l-carpyl
ruboxyphenyl 1.2. j'-dicarboxyphenyl
, 2,4c, t-trihydroxyphenyl, 3-benze
sulfonamidophenyl, ≠-(p-cyanobenzene
sulfonamido) phenyl, 3-hydroxyphenyl,
λ-hydroxyphenyl, Hiro-hydroxyphenyl, λ
, Hiro-dihydroxyphenyl, 3 + 4' + !
-trihydroxyphenyl, λ-hydroxy-Hirocal
Poxyphenyl, 3-medoxyhiro-carboxyphenylene
2-methyl-≠-phenylsulfamoylphenyl
The so group can be mentioned, and these groups directly attach to the acidic nucleus.
(, methylene group, ethylene group or propylene group)
They may be connected via. Acidic nucleus represented by A2 and represented by X3 or Y3
The carboxyalkyl group on which the electron-withdrawing group is attached is /~50
It is preferable that the carbon atoms of
Fer, 2-carboxyethyl, 3-carboxypropyl
ru, cocarboxypropyl, q-carboxybutyl,
? -carboxyoctyl and the like. The alkyl group represented by R40, R43 or R46 is carbon
An alkyl group having a prime number of 1 to 50 is preferable, such as methyl,
Ethyl, n-propyl, isoamyl, n-octyl, etc.
The following groups can be mentioned. The alkyl group represented by R41 and R42 has carbon number/~2
0 alkyl groups (e.g. methyl, ethyl, n-propylene)
n-butyl, n-octyl, n-octadecyl, i
butyl, impropyl) are preferred, and substituents [e.g.
, halogen atoms such as chlorine bromine, nitro groups, cyano groups,
droxy group, carboxy group, alkoxy group (e.g.
toxy, ethoxy), alkoxycarbonyl groups (e.g.
, methoxycarbonyl, i-propoxycarbonyl),
Aryloxy group (e.g. phenoxy group), phenyl
groups, amide groups (e.g. acetylamino, methanesulfonate)
carbamoyl group (e.g. methylcarbamo), carbamoyl group (e.g.
yl, ethylcarbamoyl), sulfamoyl group (e.g.
methylcarbamoyl, phenylsulfamoyl)]
You may have one. R41s The aryl group represented by R42 is a phenyl group
, a naphthyl group is preferable, and the substituents include the above-mentioned substituents.
The alkyl group represented by R41 and R42 of
The groups listed as substituents and alkyl groups (e.g. methyl, ether)
Chill) is included. ]. The acyl group represented by R41 and R42 has 2 to IO carbon atoms.
Preferred are acyl groups such as acetyl, propionyl,
n-octanoyl, n-decanoyl, imbutanoyl
and benzoyl. R4R4
an alkyl or arylsulfonyl group represented by
is methanesulfonyl, ethanesulfonyl, n-7
'ta/sulfonyl, n-octanesulfonyl, benzene
Sulfonyl, p-1rue/sulfonyl, 〇-calhoki
Flea such as cybenzenesulfonyl can be mentioned. The alkoxy group represented by R43 and R46 has carbon number/~
Preferably the alkoxy group of IQ is methoxy or ethoxy group.
cy, n-butoxy, n-octoxy, 2-ethylhexy
Examples include groups such as fluoroxy, imbutoxy, and impropoxy.
can be done. Halogen represented by R43, R46
Atoms include chlorine, bromine, and fluorine
. Formed by connecting R41 and R44 or R42 and R45
An example of such a ring is a julolidine ring.
Wear. It is formed by connecting R41 and R42! Or as a t-membered ring
For example, P is a lysine ring, a morpholine ring, and a hylolysine ring.
Rings can be mentioned. The methine groups represented by Ll, L2, and L3 are substituted! (example
For example, methyl, ethyl, cyanide, phenyl, chlorine atoms,
(Droxypropyl). The electron-withdrawing groups represented by X 3 % Y 3 are the same.
4 may be different, cyan group, carboxy group, alkyl group
carbonyl group (alkylcarbonyl group that may be substituted)
For example, acetyl, propionyl, heptanoyl
L, dodecanoyl, hexadecanoyl, l-okine-7
-chloroheptel group], arylcarbonyl group (
An arylcarbonyl group that may be substituted, for example,
Benzoyl, Hiro-ethoxycarbonylbenzoyl, 3-k
lolobenzoyl group), alkoxycarbonyl group (alkoxycarbonyl group, etc.),
an alkoxycarbonyl group which may be substituted with, for example,
Methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl
Rubonyl, t-amyloxycarbonyl, hexyloxycarbonyl
Cycarbonyl, λ-ethylhexyloxycarbonyl
, octyloxycarbonyl, decyloxycarbonyl
, dodecyloxycarbonyl, hexadecyloxycarbonyl
Bonyl, octadecyloxycarbonyl, λ-butoxy
etquincanohyphonyl, λ-methylsulfonyl ethoxy
carbonyl, 2-cyanoethoxycarbonyl, 2-(2
-chloroethoxy)ethoxycarbonyl, 2-[λ-(
2-chloroethoxy)ethoxy]ethoxycarbonyl 1
ift), aryloxycarbonyl group (substituted
It is a good aryloxycarbonyl group, for example,
noxycarbonyl, 3-ethelphenoxycarbonyl,
Hiro-ethylphenoquine carbonyl, ≠-fluorofeno
xycarfonyl, hiro-nitrophenoxycarlnyl, ≠
-methoxyphenoxycarbonyl, λ, Hongi (t-
amyl)phenoquine carbonyl group), carbamoyl
group (a carbamoyl group that may be substituted, e.g.
Rubamoyl group, ethercarbamoyl, dodenlupamoyl group
il, phenylcarbamoyl, goomethoxyphenylka
Rubamoyl, λ-Fromophenylcarbamoyl, Hiroku
Lorophenylcarbamoyl, Hiro-ethoxycarbonylph
Rubamoyl, <2-furobylsulfonylphenyl
lucarbamoyl, ≠-cyanophenylcarbamoyl, 3
-Methylphenylcarbamoyl, Hiro-hexyloxyf
Enylcarpamoyl, Ko, Hiroji (t-T Milnfe)
Nylcarbamoyl, λ-chloro-3-(dodecyloxy
carbonyl) phenylcarbamoyl, 3-(hexyl)
(xycarbonyl) phenylcarbamoyl group, etc.),
sulfonyl group, methylsulfonyl, phenylsulfonyl
(honyl group), sulfamoyl group (optionally substituted sulfamoyl group),
sulfamoyl group, e.g. sulfamoyl, methyl
(such as rusulfamoyl group). Next, we will discuss the methods used in the present invention that are particularly suitable for solid fraction dispersion.
Specific examples of dyes will be given, but the present invention is limited to these.
It's not a thing. %-/ ×-! ×-! -A ×-3 X-Hiroshi-r C)13 ri×−10X−J/ −JJ 0OH COOC2−i5 ×−25 X−, 2A M I−1 ×1−3 ×1−≠ ×1−! Hari-1 Xll-ta×I+'-50 ~H802CH3 X11-// ' H3 Deposit 1l-6 Xll+ -7 21″15 Kari-2yo 0OH W-3 AV-ψ UIJIJI-1 ×l1t-/ Ko2t-t5 Marugame-/!'IJUl-/ 2Hs ×IV-z XIV-J X\V-7 The dye used in the present invention is covered by the international patent worr704!7
European % permission EP oλ7 ≠ 7 ko JA / number
, JP-A Akita λ-Taco 7/A, same! ! -/No. 11350
,same! Tar/113j/issue, direction 6/-20! '934!
No. 4J'-4r423, U.S. Patent No. 2. ! 27.
r♂No.3, same 3. Hiroj. rri No. 7, 3,7tLL4. J'j issue, same 3. ri3
3.79r, same 1t, /30. ! A2 number, waiter. The method described in 0 Hiroo, r Hiro/No., etc. and the method
It can be easily synthesized according to the same method. The hydrophilic protective colloid used in the colored layer in the present invention includes:
, such as gelatin, modified gelatin, derivatives of gelatin,
Graft polymers of these and other polymers, albumin
Proteins such as cellulose and casein; hydro, xycellulose,
Carboxymethyl cellulose and cellulose sulfuric acid ester
Kinds like seven-leaf “F 乍台rose derivatives; dextran, sodium alginate and starch
Sugar derivatives such as derivatives; polyvinyl alcohol, partially
Cetalization, telJ hinyl alcohol, poly-N-vinyl alcohol
Nylpyrrolidone, polyacrylamide, acrylic acid or
are methacrylic acid copolymers, bolibimol pyrazole, etc.
homopolymers and copolymers can be used in combination.
Wear. Particularly preferably gelatin is used as hydrophilic colloid.
The gelatin used is so-called lime-processed gelatin or acid-processed gelatin.
These include latin and enzyme-treated gelatin. On quick processing
Particularly preferred is one whose molecular weight distribution is narrow. The molecular weight distribution of gelatin can be determined using the GPC method (gelatin chemistry).
can be measured by
Wear. The proportion of high molecular weight components is 72 or more, preferably
Preferably, gelatin contains 77% by weight or more. Regarding the GPC method, see Japanese Patent Application Laid-open No. 172-172-2
It is described in the main text and Example-1. The cationic polymer used in the present invention is water-soluble.
It is also dispersed in hydrophilic colloids as latex.
Ru. In the case of water-soluble cationic polymers, additional dyes
It is possible to obtain a colored layer coating solution by adding 7JD. Click
For on-based latex, use a pre-dyed master.
The coating solution is further diluted and dispersed in a hydrophilic colloid to form a coating solution.
It is better to Dispersion of water-soluble cationic polymer is
゛, relatively agglomeration occurs, and for cationic polymers
and use a relatively small amount of dye. Cationic according to the invention
The polymer may vary depending on the conditions of use, but it may be a hydrophilic protective colloid.
It is preferable to use about 5,009 to 700g.
more preferably / to 30g, furthermore / to
It is preferable to use about 20g/20g. Also, for example,
Used for anionic groups/units of anionic compounds such as dyes.
On the other hand, the cationic polymer has 0.1 or more cationic sites.
Above, preferably 0.3 to 50 and <vc/ to 30
The amount equivalent to 1 is used. Water-soluble cationic polymer
- per hydrophilic protective colloid layer oo, g, preferably /
to 2o9, and the carbon per anion group of the acidic dye.
A world in which there are at least 30 thione sites is preferable. Furthermore, the coating liquid for the colored layer may be nonionic, amphoteric or anionic.
Ionic surfactants are used, especially cationic surfactants.
It is better to use sex drugs. Place of water-soluble cationic polymer
In such cases, a polymer latex dispersion may also be used.
, especially when used in conjunction with cationic polymer latex dispersions.
It is better to Colored layer or other hydrophilic colloid used in the present invention
The layers are hardened with inorganic or organic hardeners. hard
Examples of membrane agents include chromium salts, aldehydes (form
aldehydes, glitaraldehydes, etc.), hemethylo
compound (such as dimethylol urea), activated vinyl compound
Thing (/, J. !-triacryloyl-\xahydro-5-) riazi
N, bis(vinylsulfonyl) methyl ether, N, N
'-methylenebis-[β-vinylsulfonyl]propio
), for example, U.S. Pat. No. 3.32, 21
7, etc. (2, Hiro-jiku)
Rol-Otsu-Pidroxy S-Triazine, etc.), Muco
Halogen acids (Yol Ml, etc.), N-carbamo
Ilpyridinium salt a<i-morpholinocarbonyl-3
-pyridinio) methanesulfonate, etc.), haloamide
salts (/-(/-chloro-1-piIJ dinoyt
-y-vn) Hiro IJ Zinium, Cornaphthalene Sulfur
Honert, etc.) can be used alone or in combination.
Ru. In the present invention, in particular, vinylsulfonyl groups having λ or more
hardening agents (for example, Tokuko Akihiro 7-2 Hiro, 2! Ri No.,
Tar/No. 311.3, opening! 7-211θ202 etc.
(compounds described in the specification), having two or more active vinyl groups.
hardening agents (e.g., JP-A-Shoyo 3-Horiru Koko-O, Kai-Kai J
3-Evening 72-7, 19-/1, 26171,
Open to-t. Compounds described in specifications such as rμ No. 6), others, and JP-A
No. 1982-22.2.2112, No. 1982-2μj2t
/ issue, Kaikai No. 62-509050 and patent application Sho t/-/3ri
The compounds described in the specifications such as No. 7l3 can be stably used in the present invention.
The cationic sites of polymers used in
It can be used in any way. Cationic polymer latex fine particles used in the present invention
The average particle diameter of the particles is 1 μm or less, preferably 1 to 0.
．． 0θ/μm, particularly preferably 0.2 to o, oiμm
, the particle size distribution is preferably narrow. Also, in the photographic composition layer
So, U.S. Patent No. 3. ll1l, ri No. 11, same 3. Hiroshi／／
, Ri/, No. 2 and Special Publication No. 4'j-ll3l, etc.
Can be used in conjunction with other polymer latex
. For example, adsorbs anionic compounds such as acid dyes.
When dispersing the polymer in advance,
The anionic compound is adsorbed onto the surface and then dispersed.
good. Using this dispersion method, the hydrophilic colloid layer
Anionic surfactants and hydrophilic colloids that coexist in
Can prevent desorption due to body anion groups, etc.
. The colored layer according to the present invention is formed on the white pigment-containing water-resistant resin layer.
Alternatively, it can be applied directly and dried. Also halogen
It can also be provided directly on the support side of the silveride photosensitive layer. Ma
An intermediate layer may be provided between the first two layers. Also other halogen
It is also possible to insert a photosensitive layer of silver oxide. Support for colored layer
Provided on the side...The spectral sensitivity distribution of the silver rodanide photosensitive layer is
A colored layer should be provided to correct the problem. The colored layer of the present invention has a film layer of Q, I to ioμm, preferably
A good value is 0.2 μm. Its maximum spectral reflection density is
, 0.2 or more is preferable, and 0°3 to /, j is particularly preferable.
Delicious. The color photosensitive material according to the present invention is prepared by disposing a yellow photosensitive material on a support.
A blue-sensitive silver halide photosensitive layer containing a coupler;
Green-sensitive silver halide photosensitive layer containing Zenta coupler
and red-sensitive silver halide containing cyan coupler
It is preferable to provide a photosensitive layer, but the order of the layers depends on the purpose.
You can change it accordingly. Especially high silver chloride rodan
Silver oxide is unique to the blue sensitive wavelength range (Hiro00 to jOOnm)
It has little sensitivity and the order of layers can be easily changed.
I can do it. For example, from the support side, red sensitivity, green sensitivity, blue sensitivity
Sensitive photosensitive layer, or blue-sensitive, red-sensitive, edge-sensitive photosensitive layer, etc.
The order is The color sensitivity of each photosensitive layer of the color photosensitive material according to the present invention is
Select a color separation filter according to the scanning exposure light source used.
It is best to use it in conjunction with a tar. For example, blue sensitivity, green sensitivity,
and red-sensitive layers, or a combination of green-sensitive, red-sensitive and
It is a combination of infrared-sensitive layers. Next, the color development process applied to the color sensitive material of the present invention
explain about. The color photosensitive material of the present invention is preferably
Following scanning exposure, a color development process is performed. The color developing solution used in the development of the photosensitive material of the present invention is preferably
Preferably, the main ingredient is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution. As this color developing agent
Aminophenol thread compounds are also useful, but p-fiber compounds are also useful.
Preferably, phenylenediamine compounds are used;
As a table example, 3-methyl-guamino-N,N-diethyl
Laniline, 3-methyl-μm amino-he-ether-he
-β-hydroxyethylaniline, 3-methyl-V-a
Mino-N-ethylhe β-methanesulfonamidoethyl
Ruaniline, 3-methyl-7-amino-N-ethylhe
-β-methoxyethylaniline and their sulfates and salts
Examples include acid salts or ip-toluenesulfonate salts.
. Two or more of these compounds may be used in combination depending on the purpose.
can. The color developer is an alkali metal carbonate, borate or
are pH buffering agents such as phosphates, bromide salts, iodide salts,
Benzimidazoles, benzothiazoles or medicinal
Development inhibitors or antifoggants such as lucapto compounds
Generally, it includes such things as Also, if necessary,
Roxylamine, diethylhydroxylamine, sulfite
Salt hydrazines, hydrazides, phenyl semicarbazi
compounds, triethanolamine, catechol sulfonic acids
, triethylenediamine (/, 4t-diazabicyclo(
X, 2. X) Add various preservatives such as octane)
is preferable. Among them, hydrazines and hydrazides
These compounds are preferably used for
/, Compound represented by general formula (It) of Specification No. 5 of 2
A specific example thereof is shown in Article 27 of the application specification.
These are the compounds listed on pages 7 to 7. these compounds
The amount of addition is preferably 0.0/~soy per liter of developer.
, more preferably fly, /~3θy. Also, hydro
The amount of xylamine added is o9 to 509 per liter of developer.
is preferable, more preferably (J-sfl.
- If the stability of the developer is maintained, the role of additive 71 [] is small.
It is preferable. Other additives to color developers include ethylene glycerin.
Coal, organic solvents such as diethylene glycol, benzene
dial alcohol, polyethylene glycol, quaternary ammonium
development accelerators such as nium salts, amines, and dye-forming caps.
The competitive coupler sodium boron hydride.
Fogging agents such as l-phenyl-3-pyrazolidone
Auxiliary developing agent, viscosity imparting agent, aminopolycarboxylic acid
, aminopolyphosphonic acid, alkylphosphonic acid, phosphonic acid
Various chelating agents such as nocarboxylic acids, e.g.
Examples: ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethyl
Lentriaminepentaacetic acid, cyclohexanediaminetetraacetic acid
, hydroxyethyliminodiacetic acid, l-hydroxyethyl
Lyden-7, l-diphosphonic acid, nitrilo-N, N, N
-) Rimethylenephosphonic acid, ethylenediamine-N, N
, N'to'-tetramethylenephosphonic acid, ethylene glycol
Cole (0-hydroxyphenylacetic acid) and their salts
can be cited as a representative example. The processing temperature of the color developer in the present invention is 3o'c-
zo'c is preferred, more preferably 33°C-μ2°
It is C. The replenishment amount is 2000ml or more per 1m2 of photosensitive material.
It is preferably 7,500 m1 or less. View of waste liquid reduction
In this respect, it is preferable that these supplementary charges be small. In the color developing solution of the present invention, environmental pollution or
Ventilation is disadvantageous due to the storage stability of color images and the occurrence of stains.
Rapid development with color developer that is virtually free of alcohol
It is preferable to
Restorer and restorer for oxidized color developing agent described in No.
A color development system is constructed that uses a capture agent for the oxidized form of the base material.
It is better to Furthermore, the color developing agent in the present invention substantially contains iodine ions.
It is preferable that it not be included. Execute iodine ions here.
Qualitatively does not contain / m9 / less than 1 iodine
This means that it includes In addition, the color developing solution in the present invention is
Preferably, it does not substantially contain sulfite ions;
Substantially free of sulfite ions means subsulfite ions.
This means that the content is 0.02 mol/l or less. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be carried out simultaneously with fixing treatment.
(fixing process) may be performed separately. Even faster processing
In order to achieve
Good too. Furthermore, it can be processed in two continuous bleach-fix baths.
and fixing before bleach-fixing or bleach-fixing.
Bleaching treatment can also be carried out after the dyeing treatment depending on the purpose.
Ru. Examples of Rinhakuge include iron (11) and cobalt (I).
of polyvalent metals such as ll +, chromium (■), copper (II), etc.
Compounds, peracids, quinone lamps 1, nitro compounds, etc. are used.
It will be done. Typical pond shavings include ferricyanide; dichromate
; Presence of iron (Ill 3 or cobalt < lit)
organic complex salts, e.g. ethylenediaminetetraacetic acid, diethylenetetraacetic acid
lyaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyl
luminodiacetic acid, l,3-diaminopropanetetraacetic acid, glycol
Aminopolymers such as recall ether diamine tetraHF acid, etc.
Carboxylic acids or citric acid, tartaric acid, malic acid, etc.
complex salts; persulfates; bromates; permanganates; nitro
Benzenes and the like can be used. Of these,
Including ethylenediamine tetra^゛I; acid iron (Ill) complex salts
Aminopolycarboxylic acid iron (01) complex salt and persulfuric acid
Salt is preferable from the viewpoint of rapid processing and prevention of environmental pollution. Sara
iron aminopolycarboxylate (0 complex salt is in the original text)
are also particularly useful in bleach-fix solutions. Using these aminopolycarboxylic acid iron (Ill) complex salts,
p)lFX of bleaching solution or bleach-fixing solution, usually r, t~
g, but for faster processing, an even lower p)1
It can also be processed with. Bleach solution, bleach-fix solution, and their pre-baths may contain
bleach accelerators can be used. A specific list of useful annotation promoters is described in the following specification:
US Patent No. 3. r93,1611, West German patent no.
No. 1,220.112, Japanese Patent Application Publication No. 13-197-JT & No. 30,
Research Disclosure Waterfall/7. /2 issue (lri)
Mercapto group or disulfide described in Jul. 7r) etc.
Compounds with a do bond; JP-A-Sho! rO-/Hiro0. /2
Thiazolidine visiting conductor described in No. 3; U.S. Patent No. 3,70
1. ．． Thiourea derivatives described in No. 161; JP-A-Sho JK-
/A. Iodide salt described in No. 235; West German Patent No. λ, 7 Hir, 1
Polyoxyethylene compound described in No. 130;
Hiroyo - polyamine compound described in rrJt issue; bika silver io
etc. can be used. Among them, mercaptoya or jisuru
Compounds with a fido group are preferred because they have a large promoting effect.
especially U.S. Patent No. 3.193.161, West German Patent No.
No. 7.290.272, JP-A-13-91, 1b30
The compounds described in No. 1 are preferred. Additionally, U.S. Pat.
j2. Also preferred are the compounds described in No. 131I. these
A bleach accelerator may be added to the photosensitive material. color for photography
These bleach accelerators are especially useful when bleach-fixing photosensitive materials.
It is effective for As a fixing agent, thiosulfate, thiocyanate, thioether
Examples include tel-based compounds, thioureas, large amounts of iodide salts, etc.
However, the use of thiosulfates is common and
Ammonium thiosulfate is the most widely used. bleaching
Fixer preservatives include sulfites, bisulfites, and sulfites.
Phinic acids or carbonyl biwaxic acid adducts are preferred.
stomach. The uninvented silver halide color photographic material is subjected to desilvering treatment.
After that, it is common to undergo a water washing and/or stabilization process. The washing water 1d in the washing process is based on the characteristics of the photosensitive material (for example,
(depending on the material used such as puller), usage, washing water temperature, water
The number of washing tanks (number of stages), replenishment methods such as counterflow, forward flow, etc.
It can be set in a wide range depending on the conditions of other companies. Kono),
The relationship between the number of washing tanks and water m in the multistage countercurrent method is J
our own of the 5ociety o
r ~1tion Picture and Te
1evision Engineers %A Volume 17
, P, λtIg-koj3 (/Riyoj Monthly issue)
You can find out how. According to the multistage countercurrent method described in the above-mentioned document, the washing water M is
The amount of time the water remains in the tank increases.
As a result, bacteria proliferate and the resulting suspended matter becomes photosensitive.
Problems such as adhesion to the material may occur. Color feeling of the present invention
As a solution to such problems in processing optical materials,
, Patent Application No. 632, No. 4/-/3/1973.
On, there is an extremely effective way to reduce magnesium ions.
It can be used effectively. Also, Unexamined Japanese Patent Publication No. 7-F, J-RI
Inchiazolone compounds and thiabendazole described in No. 2
chlorine-based disinfectants such as chlorinated sodium incyanurate, etc.
Bacterial agents, other benzotriazole, etc., written by Hiroshi Horiguchi,
"Chemistry of fungicidal agents", Hygiene Technology Kanawa "Sterilization, sterilization, and prevention of microorganisms"
"MildewTechnique" in the Japan Antibacterial and Antifungal Science Kanawa "Encyclopedia of Antibacterial and Antifungal Agents"
The fungicides mentioned can also be used. Day 0 of milky water in the processing of the photosensitive material of the present invention is
j-r, preferably j-r. Washing water temperature, during washing
Although the time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.,
Generally /j-#t'C for 20 seconds-7C minutes, preferably
2yo1dao 0C for 30 seconds - j minutes ll [j circle is selected
It will be done. Furthermore, the photosensitive material of the present invention can be directly washed instead of washing with water.
It can also be handled by a contact antinode. Like this

[
In the stabilization treatment, Japanese Patent Application Laid-Open No. 7-7-. 1', Tag No. 3, j♂-/Hiroshi, No. 1311, No. 60-220, and No. 3 μ can be used in combination. Further, following the water washing treatment, a further stabilization treatment may be carried out. For example, a stabilization bath made of formalin and interface method 141, which is used as the final bath for photographic color light-sensitive materials, is used. can be mentioned. A chelating agent or a fungicide can also be added to this stabilizing bath. The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process. The silver rodanide color light-sensitive material of the present invention has a simple processing method.
For the purpose of simplifying and speeding up, a color developing main system may be incorporated. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,3gλ,
Indoaniline compounds described in No. 527, No. 3.3, No. 2,672, Research Disclosure I Hiro, r
ro issue and same/! ;,/! Schiff base-type compound of No. 3, aldol compound described in No. 3,72, metal salt complex of U.S. Patent No. 3,7/22, JP-A-1
3-/36, A, 2. Urethane compound described in No. l'? can be mentioned. The silver halide color light-sensitive material of the present invention may be manufactured by various companies' 7-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are JP-A-Sho jt-t4t, No. 337, j7-/≠, ≠! No. 7, and No. j♂-//j, No. ll3r, etc. are described. /o'C-s, ooc for each yuzu treatment solution in the present invention
The oil phase is added to the oil phase. Normally, the standard temperature is between 33°C and 300°C, but higher temperatures can be used to accelerate processing and shorten the processing time, or conversely, lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. In addition, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2.2.2t, 770 or US Pat. It's okay. In this development process, from color development to desilvering, water washing, and drying? : Can be done within 120 seconds. (Preferred Embodiment of the Present Invention) (11) The reflective support contains white pigment particles of isN@1 or more in a water-resistant resin, and the degree of dispersion of the white pigment particles is expressed by the coefficient of variation (s/rtl). 0.12 or less, and a photosensitive layer containing a silver chlorobromide emulsion chemically sensitized in the presence of a CR compound and an antihalation layer are provided on the support. Reflective color photosensitive material. (2) In the embodiment section H above, general formula [1], (f
A salt having a silver bromide-containing localized phase on the grain surface and having an average silver chloride content of 0 molar or more, which is gold-sensitized in the presence of a compound containing a thiosulfonyl group represented by lJ or uCIII). A reflective color photosensitive material having a photosensitive layer containing a silver bromide emulsion. (3) A color image forming method in which the color photosensitive material of the present invention is printed using a printer having a CRTli light system and then subjected to digital processing. (4) The color image forming method according to the embodiment (3), using a printer having a black and white CTtT light system. Example 1-1 Production of support LBKP for photographic printing paper (Bleached hardwood, i: Acid pulp) 700% (Weighing scale L/7 r&/m 1 Thickness approx./50
μ): A white pigment-containing pattern fat layer made of water-resistant titanium oxide having the composition shown below was provided on the surface of a white base paper to obtain Support 1. Support I: Polyethylene composition (density 0.2λog7cc, melt index (MI J r , oJ (ylo min) of 2
0 TLf fit part, IO subbt part of titanium oxide white pigment whose surface was treated with silicon oxide and aluminum oxide.
A water-resistant resin layer of μm was obtained. On the other hand, another polyethylene composition (density 0.2RO17cc, Mx
A water-resistant resin layer with a thickness of 20 μm was obtained by coating only 20 μm of water-resistant resin. Support n: rr2 weight of the polyethylene composition used in support 1,
After adding 72 parts by weight of the following surface-treated anatase type titanium oxide white pigment and kneading in the same manner, a 30 μm water-resistant resin layer was obtained by melt extrusion coating. Support! The same titanium oxide powder used in was immersed in an ethanol solution of trimethylolethane and heated to evaporate the ethanol to produce a surface treated titanium oxide white t = SS family? Obtained. The alcohol has a weight of about 1/h based on titanium oxide.
; coated on the surface of the corresponding particle. The surface of the blank base paper is made of a polyethylene composition similar to that of the support A, and a water-resistant resin N is used.
has been established. Support 111: Support 1 except that instead of the anatase-type titanium oxide white pigment in Support H, titanium oxide containing 1% zinc oxide was used in an amount of 1/2 weight part based on the polyethylene composition.
It is similar to Support sample ■ 5011 parts of hexaacrylate ester of nidipentaerythritol propylene oxide adduct equivalent to 7172 moles and a composition of SO heavy poisonous part of rutile titanium oxide were mixed and dispersed in a ball mill for more than 2 hours, and then the dry film thickness was determined. It was coated and dried on the following base paper so that it had a thickness of 20 μm. The base paper used was a 20-μm-thick layer of a polyethylene composition on the white base paper used in Support A, and a layer of polyethylene composition (KO0riAo, 9/cc, MIλyo1750) on the back side.
This was obtained by providing a 20 μm layer of 20 μm. The coated layer was irradiated with an electron beam under a nitrogen atmosphere at an accelerating voltage of 200 kV and an absorbed dose of j equivalent to a megarad to obtain a support sample (2). Support 1. In the case of support 1, about 0-3 nfffl, % of ultramarine blue was impregnated with respect to the sum of the polyethylene and white pigment particles, and in the case of support 1, about 0./5 weight-% of ultramarine was contained. The dispersibility of the white pigment particles in the surface part of the water-resistant resin layer of the support according to the present invention was determined by etching the resin about 0,000 μm from the surface by ion sputtering method, and dispersing the white pigment particles by electron microscopy at Oi1. Continuous tμ observed with a mirror
The projected area ratio Ri of each particle was determined for six unit areas of m x j μm, and its standard deviation and average particle projected area ratio (%) R were determined. The results are shown in Table 1. Compared to Support Sample I, the dispersibility of the white pigment was excellent in support sample opening to (1). In particular, sample nl workpiece (2) was substantially uniformly dispersed. Example 2 Silver halide holes -7 and 6 were produced as follows. (L liquid) Water g0
0mlNaQ! g, jg Gelatin 219 (2 liquids) The following compound (7% aqueous solution) 3 ml H3 3 liquids] (Hiroshi liquid) act Add water and add water /, 79 7 re omt Evening, Og l g Oml ( J liquid) NaCe u/
, 39 Add water to make 320 m1 (,4
7fiJ AgNO3/71 sips of 20fl water
Heat 320ml (/liquid) in a jroc, (
After adding 2 liquids, 3 liquids and ≠ liquids were added simultaneously for 50 minutes. After a further 70 minutes, (Liquid 1) and (Liquid 6) were added simultaneously over a period of 3 evenings. 5 minutes after the addition is complete,
Desalination was performed by lowering the temperature. Add 7JO of water and gelatin for dispersion and adjust the pH to 6.2 to obtain a 38-uniform monodisperse cubic chlorobromide with a particle size of 0.70μ and a coefficient of variation (standard deviation divided by the average particle size) of 0.73. An emulsion (il) was obtained. Next, emulsion (1) was mixed with Ex DyeB f as a CR-compound at 1.rr'C and 2°3x per mole of silver halide.
After adding 50' mol, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, and after chemical sensitization was performed, which was optimal for obtaining a surface latent image type emulsion, ≠-- was added as a stabilizer.
An emulsion to which hydroxy-t-methyl-/, 3.3a, 7-titraazaindene was added was designated as emulsion (1). As shown in Table 2, when the particle formation rate and CR-compound were changed, and when bromide *' was added, the y1 of chloroauric acid
? : Emulsions U and O were obtained in the same manner except that the amount was reduced by half and the optimum chemical sensitization was performed. Table 2 Emulsion Grain formation Bromide grain size used / tar 0COx, z x 50-' 77
．． 7 moles 1 mole Ag Yu! 500 No Same as above 0.7 Ex DyeG Hiro2°CO HiroX/(1)-' 0. Hiromol 1 mole Ag ≠ ≠2°C2 Same as above O8 Hiro! xDyeR Hiro 2° (:Q/, yoX/(1)-40, Hiro 1 mol A
g Hiro2°C2 Same as above O3 Hiro coefficient of variation / 3 / 2 / 2 / 2 *However, in emulsions 2, t, and O, the addition of the CR-compound was also due to the odor relative to the total silver halide shown in Table 1. A fine-grain beautified silver emulsion (grain average O, OSμ) corresponding to the silver bromide content @ (mol %) was added to give a silver bromide-containing localized phase to the grain surface. Paper laminated on both sides with polyethylene (support sample f-
A multilayer color photographic paper having the layer structure shown below was prepared on In+. Blood is prepared by mixing and dissolving an emulsion, each component, and an emulsified dispersion of couplers, and the respective preparation methods are shown below. Preparation of coupler emulsion Yellow coupler (Ex Y) / 7 g and color image stability 11NCpd-/) Hiro, Gy and ethyl acetate 27.2
Add and dissolve CQ and solvent (Solv-/) 7.7CC)
Cry and add this solution to a 70% ceftin water bath containing IO sodium tidedecylbenzenesulfonate rCC.
It was emulsified and dispersed. Thereafter, emulsions for magenta, cyan, and intermediate layers were prepared in the same manner. In the blue-sensitive emulsion layer, the stabilizer Ex-3d was added to λ,!, per mole of silver rodanide. r×50 moles were added. As a gelatin hardening agent for each layer, /-Okin-3,j-
Dichloro-s-triazine sodium salt was used. Dye Ex-j is added to the emulsion layer to prevent irradiation.
a.Ex-Jb is attached 7JDL. For the red-sensitive emulsion layer, the compound Ex-3c was added at 2.0% per mole of silver halide. A×/Q moles were added. As shown in Table 3, sample l, 2.3
I got this. (Layer structure) The composition of each layer in sample/~Hiro is shown below. The numbers are coating ftl: (9/m2). The amount of coating applied in terms of silver is shown in the table for silver rodanide emulsion. Support polyethylene laminate paper (Support sample ■) [However, the polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] -th layer (colored layer) Sensitive material sample -/: (A+ Gelatin ---O, SO Sample-2, 3: (B) Gelatin ---0,50 Black colloidal silver --0,20 Ex-3e ---0,002 Sample-Hiroshi: (C) Gelatin --- -o, t. Cationic polymer (1) ---o, t. Dye (J) ---r, j (da/m ) (31r)
---j. 2nd layer (blue sensitive layer) Silver halide emulsion gelatin yellow coupler (Ex YJ Color image stabilizer (Cpd-/) Moring medium (SOIV-/) Keisan Al (color mixing prevention layer) Gelatin color mixing prevention agent (cpa-2 ) Fourth layer (green-sensitive layer) Silver halide emulsion gelatin magenta coupler (Ex M/ Color image stabilizer (CPCI-, ?1 Color image stabilizer (CPA-Hiro) Solvent (Solv-λ) Fifth layer (Ultraviolet light) Absorption layer) Gelatin OC'R97m), 30, tt, r2, l, 3! Q, Tata0, or] 0.36 /,, 24C 0,31 0,2! 0, / KoO, li 2 i, jr Ultraviolet absorber (UV-/) Color mixing inhibitor (Cpd-5) Solvent (Solv-J) Sixth layer (red-sensitive layer) Silver halide emulsion 0.23 gelatin
/, 3 Gusian Cabler (Ex
Blend of C/ and Ex C co, /:l)
0.3 color image stabilizer (cpa-x)
0. /7 Polymer (Cpd-730, Hiro0 Solvent (Solv-<<) 0.23 Seventh layer (UV absorbing layer) Gelatin Ultraviolet absorber (UV-/ Solvent (Solv-3) Eighth layer (protective layer) Gelatin /, 33 Acrylic modified copolymer of polyvinyl alcohol (17% modified)
0. /7 Flow/ξ Rough-in
0.030,! 3 0 , 21 0, or 0.62 o, or O, +2 ≠ ] The following experiment was conducted to investigate the photographic properties of these coated samples. First, a photosensitive layer (for Fuji Photo phytometry) was applied to the coated sample.The exposure at this time was 777
The exposure time was 0 seconds and the exposure time was 2joCMS 7. The bales were subjected to the color development treatment shown below. (Processing process) (@ degrees) (time) Color development
3j0c p second bleach fixing 3s
0c ≠ Wash with water for 5 seconds 2g~3j
0 C Ta O second color developing solution Triethanolamine ♂, 72 g NN-Dietherhydroquine Luaminda, 93 g Fluorescent bleach (Ciba Geigy #UVITEXCKI
a, rop≠-amino-3-methyl-~-ethyl-N-[β-(methanesulfonami-p-]22-reuniamine sulfate Sodium sulfite Potassium carbonate Potassium bicarbonate EDTA, 2Na-2H20 Add sodium chloride water pH Do) Ethyl A9 0, /39 /f, Google ≠, Ijri λ, 209 /, 36g 000ml io, or Hereinafter Bleach-fix solution Water Ammonium thiosulfate (70%) Sodium sulfite Ethylenediamine Tetraacetate Iron (■) Add ammonium ethylenediaminetetraacetic acid disodium water and adjust the pH (λ = 0C) ≠ ooml zome /Iji! t, fy y 5000 rnet t, 70 For the sensitive material samples treated in this manner, the density was measured using red light, green light, or blue light to determine the relative sensitivity and fog of each photosensitive layer. The results are shown in Table ≠. As is clear from the results in Table ψ, the relative sensitivity of Sample 2 was lower than that of Sample -/ due to the provision of the antihalation colored layer on the support. In particular, the B and G sensitivities decreased relatively significantly. In sample 3, the sensitivity of the emulsion used increased and fog was suppressed, so that the sensitivity FL'1 was adjusted to the same level as sample -/, and fog was suppressed to 1B.
I was able to do IT. It can be seen that sample q has a well-balanced blue, edge, and red sensitivity at a higher level than sample /, and fog is strongly suppressed. In order to measure resolution, a rectangular wave pattern for CTF measurement was brought into close contact with each sample surface, and exposed using the photosensitive needle. Subsequently, the color development process described above was carried out, and the density was measured using a micro-a meter, and the results shown in Table J were obtained. Instead of the mixture in Table C2, ExCj, ExC4(, ExC!
Similar performance can be obtained by using both. In addition, in the above emulsion B, E
Similar performance can be obtained using xDyeR-/. Yellow coupler (ExY) As is clear from the results in Table J, Samples 3 and Hiro are superior in solution strength compared to Sample I. is used in the fourth layer instead of ExMl, ExMJ, ExMJ, ExM
ExC/ and Ex magenta coupler (ExMJl (ExM≠) I ExMJ ) α cyan coupler (ExC/1 C8 day 17 (t) (ExCJl α (ExCII) α (ExCj 1 CH ( Cp (1-6) Color image stabilizer C4H9 (t) j: Remixture (weight 11 ratio) (Cpd-7) Polymer (C1l 2-CH) n C0NI-IC4119 (t) Average molecular size 0 Oθ Q (cpa-/) Color image stabilizer (Cpd-2l Color mixing prevention agent CH l-1 (Cpd-jl Color mixing prevention cutting CH (UV-/ Ultraviolet absorption cutting C) + 2012 COOC8H, 7. C4Hg (t) No. 2: ? = r l#, compound (N t'+i, ratio) (S. V-/j bath medium C4C41-l+) (SolV-31 solvent (Solv-da) solvent compound x-ja compound E x -3d compound E x 3 e Compound x-Jf x ye O3K Compound x-jb Compound x-Jc x ye x ye x ye [(-/ (Cpd-3 (cpa-≠) Color image stabilizer) Color image stabilizer implementation r2 Lee 3 Color photographic paper samples j and i were prepared in the same manner as sensitive material sample 3 obtained in Example 2, using supports I, Ill and ■ instead of support sample H obtained in Example-1.
G and 7 were obtained. Sensitometry was performed in the same manner as in Example Row-2. Furthermore, in the same manner as in Example 2, CT F fil
The resolving power was measured by contact exposure to a fixed rectangular wave pattern, and the results shown in Table 6 were obtained. Table 6 (S. lv-,2) The l/mixture (volume ratio j) of the solvent is clear from the results of Table 6, as compared to support sample I, sample 11, l used color markings 1 It can be seen that the surface papers (Samples t and 7) have high sensitivity and resolution.Example 4 Emulsions G and G were prepared as follows.The emulsion of Example 2 (
i) was prepared similarly and the above ExDyeR-// as CR- compound at ≠2°C. After adding 17 moles of fine grain silver halide I as in Emulsion 6 of Example 2 and heating, cadmium thiosulfate, auric acid chloride, and ammonium rhodan were added. 501497 mol Ag of the aforementioned compound g having a thiosulfonyl group or compound I/
After adding 91 mol of Ag and carrying out optimal chemical sensitization to obtain a surface latent image type emulsion, it was processed as a stable 1st cut.
Hydroquine-Otsu-Methyl-/. Emulsions 7 and t were obtained by adding J+Ja, 7-chitrazaindene and the compound Ex-31 described in Example 3. In Example 2, when sample ≠, emulsion 7-j near': was replaced with emulsion 7-j and emulsion-r was used instead of emulsion 7-j, and samples t and ? were used, respectively. 2
Obtained. In the same manner as in Example 2, sensitometry was performed on sample r, and the results shown in Table 7 were obtained. In Table 7, sensitive material samples r and 2 had the same resolution as sample ≠. As is clear from the results in Table 7, compounds with a thiosulfonyl group? In the emulsions 7 and 1 (RL) used,
Both can significantly increase the sensitivity, and the Cub I
J = i can be lowered even further. Actual 11+ai row 5 A practical test was conducted on the sensitive material samples 1 to μ obtained in Example 2 and samples t and 2 obtained in Example 4 as described below. Each of the six types of samples described above was loaded into a video printer FVP500 manufactured by Fuji Photo Film ■, and a color business card consisting of a person image, a C0 image, and a character image was produced. FVPjo
o has a built-in mechanism shown in FIG. The human image is displayed on a color monitor and a black and white CRT through a CRT controller by combining a portrait as digital information and a C0 image and a character image by an image composition section. In synchronization with the yellow, green, and red images displayed on this black-and-white CRT, three color filters with the spectral transmittances shown in Figure 2: B+Y filter, G filter, and R filter are applied to the lens. The sample was baked through the system. The black and white CRTK used a mixture of phosphors (P-J, 21 (and P-1j series)) that gave the spectral emission intensity as shown in Figure 3. Each was printed with blue, green, and red light. The baking time is set in advance in accordance with the spectral sensitivity of each BL, GL, and RL of the sample.The baking time is shown in Table 1. The printing time can be shortened by 0.3 to 0.7 times compared to that of samples 1 to ≠ and r. In addition, the character image quality obtained from samples 1 to ≠ and r is better than that of sample 1. It was sharp and the edge contrast was high and excellent. Sample 3 was cut into rolls with a width of The portrait photographic image was printed using the photographic fog light method, and the character image was printed using the CRT & light method. By doing this, I obtained a photographic print with letters written on it.I cut this into J'mm As described in JP-A No. 70111, a postcard could be obtained by gluing it onto a postcard mount with a lottery number. Example 6 Solid fine particles of dye Dispersion method〉 Dispersion corporation〉 Dye crystals with the following composition were kneaded and made into fine particles using a sand mill. Dye - Hiroyo...0.Jf -37...0.7F -≠3...・o,ry 3% aqueous solution of the surfactant (5)... 5ml Furthermore, disperse in 2jd of an io% lime-treated gelatin aqueous solution prepared by dissolving citric acid ly, and filter the used sand using a glass filter. Wash off the dye adsorbed on the sand on the glass filter using hot water and add 7% gelatin solution.
ootttl (solid fine particle dispersion of dye) was obtained. After carrying out corona discharge treatment using support sample (1) to provide nine layers of gelatin undercoat, a colored layer was provided in accordance with the first layer of Example-2. 2. To the hardening agent. lA-dichloro-y-hydroxy-l, 3. ≠− Sodium triazine was used. Layer gelatin......o, roy/m2 Dye-hiroj.../Ida/rn2 By observation with a transmission electron microscope, the average solid fine particles of the dye Particle size is approximately O
1λjμm, and no aggregates larger than 3μm were observed. When this sample was immersed in the color developing solution shown in Example-2, it was decolored in about 71 seconds. Decolorization of Kanashi was observed even when immersed in bleach-fix solution in the same way. Furthermore, according to Example 2, second to eighth layers were provided to obtain Sample 50. In Example 2, sensitometry and CTF measurements were carried out in the same manner as Sample/Hiroshi, and the results shown in Table 1 were obtained. Table 1 Hiro table and section! In comparison with the results shown in the table, it can be seen that higher resolution and lower fog can be obtained by applying the solid fine particle dispersion method. Example 7 According to the dispersion company shown in Example 6, the dye crystals and dispersion aid shown in Table 1O were kneaded, ground in a ball mill, and treated with 50% lime by dissolving citric acid IP. Bone gelatin aqueous solution 2! The beads were removed by a filter, and the dye adsorbed on the filter and beads was washed away with hot water and added to obtain 500 ml of a 7tisgelatin solution (solid fine particle dispersion of dye). Using support samples ① and ②, dye solid fine particles (
A microcrystalline dispersion was used. Furthermore, the second layer and the eighth layer shown in Example-2 were coated on top of it in the same manner as Samples 6 and 7 of Example-3, and Samples // to l! I got it. Sensitometry similar to that shown in Example-2 was performed on these samples. CTF measurement was also performed in the same manner. The results obtained are shown in Table 70. As is clear from comparing the terminology in Table 1Q with the results in Tables ≠ and 5 of Example 2, the sample using the solid fine particle dispersion of dye has a colored layer using black colloidal silver. It can be seen that there is less desensitization than the samples (Samples 2 and 3), and that it provides sufficiently high resolution. In particular, flavoring agent/j was found to improve color separation between the green and red sensitive layers and to improve resistance to safelight light. Sections of samples // to /j were observed under a transmission electron microscope (200 Kv). Colored layer (first layer)
Also, the microcrystalline dispersion of the dye contained in the eighth layer did not diffuse into other adjacent layers, and no aggregates of 3 μm or more were observed. Example-r Using the support ① and the second layer (colored layer) used for the sample in Example-7, and the second to eighth layers used for preparing the sample in Example-Hiro Sample 16 was obtained. Sensitometry was performed on this sample lB in the same manner as that performed in Example-Hiro and Example-J using the sample sample, and back-colored light, green light and Burning in red light was timed. The results are shown in Table 1. From the results in Table 11, it can be seen that Sample No. 6 can be baked at the same rate or faster than Sample No. 1. In addition, the fog of sample l O is o for both BL and GL%RL.
Or, there weren't many. (Effects of the Invention) By using the color photosensitive material of the present invention, it is possible to quickly and easily obtain color prints that are not just photographic images with excellent image sharpness, but also have particularly high edge contrast of line drawings and character images. In particular, we use a so-called minilab system that includes a printer using a CRT exposure method and a photo processing device to produce not only photographic images but also images.
Prints that combine CG images, line drawings, and character images with excellent sharpness can be easily obtained in a short time of about μ minutes or less. (This is useful for creating postcards.

[Brief explanation of the drawing]

FIG. 7 shows a print making process 8 using the CRT exposure method. FIG. 2 shows the spectral transmittance curves of the B, G, R and Y filters. The vertical axis is the transmittance, and the horizontal axis is the wavelength (in nml). Figure 3 shows the relative luminescence intensity distribution of P-22R and P-≠N-type fluorophore mixture. The vertical axis is the relative light intensity, The horizontal axis represents wavelength (nm) 'a'. Patent bleeding person Fuji Photo Film Co., Ltd. Figure 2 Figure 1, & Length (nm) Figure 3 Growth (n+nl)

Claims (6)

[Claims] (1) In a color photosensitive material comprising at least one silver halide photosensitive layer containing a color coupler provided on a reflective support, the silver halide photosensitive layer has an average silver chloride content of 50 mol%. and a silver bromide-containing localized phase inside or on the grain surface, the grain surface contains a gold-sensitized silver chlorobromide emulsion, and a color layer is provided between the photosensitive layer and the reflective support. A reflective color photosensitive material characterized by having a colored layer that can be decolorized by development. (2) The reflective support is 12% by weight in the water-resistant resin.
Projected occupied area ratio (%) per unit area that contains the above white pigment particles and has a defined degree of dispersion of the white pigment particles.
A claim characterized in that the coefficient of variation s/@R@ (where @R@ is the average occupied area ratio per unit area, and s represents the standard deviation of the occupied area ratio) is 0.15 or less. The reflective color photosensitive material described in item (1). (3) A reflective color according to claim (1) or (2), characterized in that a compound having a thiosulfonyl group is added to the silver chlorobromide emulsion before, during or after gold sensitization. photosensitive material. (4) The colored layer, which can be decolorized by photographic processing, has a pH of 7.0.
The halogen according to claim 1, comprising a solid fine particle dispersion of a dye that is substantially insoluble in water and soluble in water with a pH higher than 9.0. Silver chemical photographic material. (5) The following general formulas (X), (X I ), (XII), (XIII) and (X
Claim (1) characterized in that it comprises a solid fine particle dispersion of a dye selected from among the compounds represented by IV).
) to (4). General formula (X) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (X I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (XII) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (XIII ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (XIV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A_2 is a carboxyphenyl group, sulfamoylphenyl group, sulfonamidophenyl group, carboxyalkyl group represents an acidic nucleus having at least one substituent selected from acid, thiobarbituric acid, indanedione, and hydroxypyridone.B_2 represents a basic nucleus having at least one substituent selected from a carboxyl group, a sulfamoyl group, and a sulfonamide group; Selected from the group consisting of pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, and pyrrole.R_4_0 represents a hydrogen atom or an alkyl group, and R_4_1 and R_4_2 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted represents an aryl group, acyl group or sulfonyl group,
R_4_1 and R_4_2 may be connected to form a 5- or 6-membered ring. R_4_3 and R_4_6 are each hydrogen atoms,
Represents a hydroxy group, carboxy group, alkyl group, alkoxy group or halogen atom, R_4_4 and R_4_5
are each a hydrogen atom or R_4_1 and R_4_4 or R
Represents a group of nonmetallic atoms necessary for _4_2 and R_4_5 to connect to form a 5- or 6-membered ring. L_1, L_2, L_3 each represent a substituted or unsubstituted methine group, X_3, Y_3 each represent an electron-withdrawing group, and at least one carboxyphenyl group or sulfamoylphenyl group is present in either X_3 or Y_3. , a sulfonamidophenyl group, a carboxyalkyl group or a hydroxyphenyl group. m represents 0 or 1, n
represents 0, 1 or 2. p represents 0 or 1, but p
When is 0, R_4_3 represents a hydroxy group or a carboxy group, and R_4_4 and R_4_5 represent a hydrogen atom. ) (6) A color image forming method, which comprises printing the reflective color photosensitive material according to any one of claims (1) to (5) by a scanning exposure method, and then subjecting it to color development.