Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/02—Sensitometric processes, e.g. determining sensitivity, colour sensitivity, gradation, graininess, density; Making sensitometric wedges
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/0357—Monodisperse emulsion
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
  • G03C2007/3025—Silver content
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C2200/00—Details
  • G03C2200/58—Sensitometric characteristics

Definitions

• the present invention relates to a silver halide photographic light-sensitive material for CRT picture taking, specifically of an ultrarapidly processable silver halide photographic light-sensitive material for CRT picture taking with good image contrast.
• Silver halide photographic light-sensitive materials for CRT picture taking used to obtain hard copy films of CRT images and for other purposes.
• Improvement in such rapid processability and processing stability may be achievable by reducing the amount of silver in the light-sensitive silver halide.
• the amount of silver is reduced for this purpose, for example below 3.60 g/m2
• Sensitivity reduction necessitates the lengthening of taking time or increase in the luminance of CRT, causing image quality degradation.
• the object of the present invention is to solve these problems and provide and ultrarapidly processable silver halide photographic light-sensitive material for CRT picture taking having good processing stability and satisfactory levels of sensitivity and maximum density.
• the silver halide photographic light-sensitive material for CRT picture taking of the present invention has at least one orthochromatically spectrally sensitized light-sensitive silver halide emulsion layer on one side of the support.
• the silver content in the light-sensitive emulsion layer side of the silver halide photographic light-sensitive material is not more than 3.60 g/m2, and the characteristic curve obtained by 1 seconds of exposure with a CRT of RMA No. P.
• G A /G B value of not less than 0.69 and not more than 0.88, wherein G A represents the gamma value of the linear line between densities 0.5 and 1.5 G B represents the gamma value of the linear line between densities 1.5 and 2.5, with a G C value of not less than 2.4, wherein G C represents the gamma value of the linear line between densities 1.0 and 2.0.
• the characteristic curve is defined as a photographic characteristic curve showing the relationship between the logarithmic amount of exposure logE plotted on the abscissa and image density D plotted on the ordinate.
• Gamma value is defined as the gradient of the linear line between two points on the characteristic curve (tan ⁇ , if the angle of the linear line and the abscissa is represented by ⁇ ).
• the characteristic curve to specify the gamma values G A , G B and G C in the present invention is obtained by exposing the silver halide photographic light-sensitive material using a CRT of RMA No. P. 45 for 1 second.
• the light-sensitive material of the present invention satisfies the above-mentioned requirements as to gamma values when the developing time is less than 16 seconds, wherein developing time is defined as the time for the light-sensitive material sample to become in contact with the surface of the fixer from its contact with the surface of the developer.
• the gamma value G A , G B and G C in the characteristic curve in the present specification represent figures obtained by processing the light-sensitive material after exposure for 1 second using the above-mentioned CRT in the Konica automatic developing machine SRX-501 with a total processing time of 45 seconds (corresponding to 14.8 seconds of developing), using the developer XD-SR at developing temperature of 35°C (a starter was used), and the fixer XF-SR at a fixing temperature of 33°C.
• the CRT used for exposure had the RMA number mentioned above, by which the phosphor emitting the exposure light and its emission spectrum are specified.
• any mode can be employed to make the gamma values fall in the above ranges; the gamma values can be kept in the ranges according to the present invention by controlling the average grain size, grain size distribution and other parameters of the emulsion.
• the silver halide grains should contain silver iodide at not less than 0.2 mol% and not more than 3.80 mol%; the silver iodide should be AgBrI, AgClBrI or AgClI, and AgBrI is preferable. Also it is preferable that the silver iodide content be not less than 0.5 mol% and not more than 3.0 mol%.
• a preferred mode of embodiment of the present invention is to use a monodispersed emulsion for the light-sensitive silver halide emulsion layer.
• the use of a monodispersed emulsion yields high gamma values and good linearity in the characteristic curve, and is advantageous as to sensitivity.
• the effect of the present invention is enhanced, since the variance of the G A/ G B ratio is small even when processing conditions have changed.
• monodispersed emulsion has the following relationship: where r represents the number-average grain size and S represents the standard deviation.
• Grain size may be calculated from the diameter of a circle converted from the projection area of the silver halide grain in electron micrograph. Grain size may also be calculated by Stokes diameter measurement based on the centrifugal precipitation liquid phase method. Grain size distribution may also be determined from electron micrograph and other means.
• the light-sensitive material of the present invention may comprise two or more emulsions with different average grain sizes (it is preferable that all constituent emulsions be monodispersed).
• the silver halide photographic light-sensitive material of the present invention has at least one orthochromatically spectrally sensitized light-sensitive silver halide emulsion layer on one side of the support.
• This emulsion layer may have a single-layer structure or multilayer structure. It is preferable to form a protective layer on the emulsion layer (opposite side to the support).
• a hydrophilic colloidal layer may be formed for a backing layer.
• This backing layer may have a single-layer structure of multilayer structure.
• Any orthochromatically spectrally sensitizing dye can be used to orthochromatically spectrally sensitizing the silver halide emulsion layer.
• the grain shape, structure or other feature of the silver halide grains used in the light-sensitive silver halide emulsion layer there is no particular limitation posed on the grain shape, structure or other feature of the silver halide grains used in the light-sensitive silver halide emulsion layer, but it is preferable to use the grains described in Japanese Patent Publication Open to Public Inspection No. 23154/1988 and Japanese Patent Application No. 6890/1987 and it is possible to use tabular grains as disclosed in Japanese Patent Publication Open to Public Inspection Nos. 113927/1983, 113928/1983, 105636/1984 and 147727/1985.
• the support for the present invention be a flexible support which is normally used for photographic light-sensitive materials.
• the support may be colored with dyes or pigments. It may be colored black for the purpose of shading.
• These supports may be subbed as usual to ensure good adhesion to the photographic emulsion layer etc.
• the light-sensitive silver halide etc. used in the light-sensitive emulsion layer of the light-sensitive material may be present in dispersion in an appropriate binder in the photographic structural layer.
• Various hydrophilic colloids can be used as binders; typically, gelatin is preferably used.
• Gelatins which can be used include lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin hydrolyzates, gelatin enzymolyzates and other gelatin derivatives. It is also possible to use gelatins comprising synthetic polymers such as polyvinyl alcohol.
• hydrophilic colloid used to form the backing layer.
• the amount of water absorption can be adjusted to the desired level by controlling the amount of the hardener, as stated above.
• the silver halide photographic light-sensitive material of the present invention may contain a hardener in any layer.
• the hardener is normally used as needed in combination with other various film property improving agents to improve the physical properties of the coated film prepared in the presence of a hydrophilic colloid as binder.
• the amount of water absorption can be adjusted to the desired level by controlling the amount of the hardener.
• the vinyl sulfone hardener means a compound having a vinyl group bound to a sulfonyl group or a group capable of forming a vinyl group. It is preferable that the vinyl sulfone hardener have at least two vinyl groups each bound to a sulfonyl group or two groups each capable of forming a vinyl group.
• the compound represented by the following formula is preferably used in the light-sensitive material of the present invention. L-(SO2-X) m
• L represents a m-valent group
• Y represents a group capable of splitting off in the form of HY in the presence of a base, e.g. a halogen atom, sulfonyloxy group, sulfoxy group (including salts) and tertiary amine.
• n represents an integer of 2 to 10; when m is 2 or more, the -SO2-X units may be identical or not.
• the m-valent binding group L is formed with one or more of aliphatic hydrocarbon groups (e.g. alkylene, alkylidine, alkylidine groups and groups formed by their binding), aromatic hydrocarbon groups (e.g. arylene and other groups and groups formed by their binding), and bonds represented by -0-, NR′- (R′ represents a hydrogen atom or alkyl group preferably having 1 to 15 carbon atoms), -S-, -N-, -CO-, -SO-, -SO2- or -SO3-; when two or more NR′- units are contained, their R′ moieties may bind together to form a ring.
• the binding group L also include those having a hydroxy group, alkoxy group, carbamoyl group, sulfamoyl group, alkyl group, aryl group or other substituent.
• vinyl sulfone hardener in solution in water or organic solvent at 0.005 to 20% by weight relative to the binder (e.g. gelatin), more preferably 0.02 to 10% by weight.
• the hardener may be added to the uppermost layer, lowermost layer, at least one other layer, or all layers.
• the light-sensitive material of the present invention may contain other additives as needed.
• the light-sensitive material of the present invention has a light-sensitive silver halide emulsion layer on only one side of the support. It is preferable that the thickness of the structural layer on the emulsion layer side be not more than 3.9 ⁇ m. It is also preferable that the dissolution time of the light-sensitive emulsion layer in an aqueous solution of sodium hydroxide at 50°C be between 12 minutes and 130 minutes. Here, the dissolution time is defined as the time for a 1 cm wide emulsion layer sample being vertically immersed and kept standing in a 1.5 wt% aqueous solution of sodium hydroxide to become dissolved.
• the light-sensitive material of the present invention may contain other additives as needed, which are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol.187, No. 18716 (November 1976).
• Any method can be used as appropriate to process the light-sensitive material of the present invention according to the specific light-sensitive material.
• the processing solutions such as developers and fixers used to process the light-sensitive material can also be chosen as appropriate according to the light-sensitive material.
• the automatic developing machine be of the roller transportation type.
• the number of transportation rollers by such that the quotient obtained by dividing the processing length 1 by the number of rollers falls in the range of from 0.01 to 0.04.
• the time for each processing procedure be in the following range: Insertion + development + transition 25 to 40% Fixation + transition 12 to 25% Washing + transition 10 to 25% Squeezing + drying 25 to 45% Total 100%
• Monodispersed emulsion silver iodobromide grains of 0.395 ⁇ m in average grain size having an average silver iodide content of 2.2 mols were prepared by growing silver iodobromide containing 30 mol% silver iodide at pH 9.8 and pAg 7.8 in the presence of monodispersed silver iodobromide grains of 0.2 ⁇ m in average grain size containing 0.2 mol% silver iodide as core grains, and subsequently adding equal mols of potassium bromide and silver nitrate at pH 8.2 and pAg 9.1.
• the emulsion was desalted to remove excess salts by an ordinary coagulation method. Accordingly, coagulation was conducted by adding a formalin condensation product of sodium naphthalenesulfonate and an aqueous solution of magnesium sulfate while maintaining the emulsion at 40°C. After supernatant removal, pure water below 40°C was added, and this was followed by the addition of an aqueous solution of magnesium sulfate to coagulate the emulsion. The resulting supernatant was removed.
• a polydispersible emulsion was prepared by the normal mixing method as follows: Solution A Silver nitrare 100 g Aqueous ammonia (28%) 60 cc Add water to reach 240 cc. Solution B Ossein gelatin 8 g Potassium bromide 80 g Potassium iodide 2.2 g Add water to reach 550 cc. Solution C Aqueous ammonia 6 cc Glacial acetic acid 10 cc Water 34 cc Solution D Glacial acetic acid 226 cc Add water to reach 400 cc.
• Solutions B and C were fed into a reaction vessel for emulsion preparation and agitated using a propeller type agitator at 300 rpm, while maintaining a reaction temperature of 48°C. Then, Solution A was divided into two portions in a volume ratio of 1 to 2. The one-volume portion (100 ml) was added to the mixture of Solutions B and C over a period of 55 seconds. After agitation for 10 seconds, the two-volume portion (200 ml) was added over a period of 2 minutes, and agitation was continued for 20 minutes. To the resulting mixture of Solutions A, B and C, was added Solution D; the mixed solution in the reaction vessel was adjusted to pH 6 and the reaction was stopped.
• a polydispersied emulsion of 0.390 ⁇ m in average grain size having an average iodide content of 2.2 mol% was thus obtained.
• potassium iodide Fifteen minutes before completion of the chemical ripening (70 minutes after initiation of the chemical ripening), potassium iodide was added at 200 mg per mol silver; after 5 minutes, 10% (W/V) acetic acid was added to reduce the pH value to 5.6 and this pH value was maintained for 5 minutes. Then, a 0.5% (W/V) potassium hydroxide solution was added to increase the pH value to 6.15, and this was followed by the addition of 4-hydroxy-6-methyl-1, 3,3a,7-tetraazaindene to stop the chemical ripening to yield a photographic emulsion for coating.
• the photographic emulsion for coating had a pH of 6.10 and a silver potential of 81 mV at 35°C immediately after preparation.
• This coating emulsion was used to prepare samples as follows: Samples were prepared by coating the emulsion so that the photographic emulsion layer had a gelatin content of 2.0 g/m2 and a silver content of 2.8 to 4.2 g/m2 as shown in Table 1 having a thickness of 3.8 ⁇ m in case of silver content is 4.2 g/m2 and the protective layer as prepared with the additives listed below had a gelatin content of 1.15 g/m2, and coating the lower and upper backing layer solutions shown below on the back of the photographic emulsion layer so that the lower backing layer had a gelatin content of 3.0 g/m2 and the upper backing layer had a gelatin content of 1.2 g/m2.
• Coating was conducted simultaneously on both faces of a polyethylene terephthalate film base of 175 ⁇ m in thickness coated with an aqueous copolymer dispersion for subbing obtained by diluting a copolymer comprising three monomers of 50 wt% glycidyl methacrylate, 10 wt% methyl acrylate and 40 wt% butyl methacrylate to a copolymer concentration of 10 wt%, using two units of slide hopper type coater at a speed of 80 m per minute, and this was followed by drying for 2 minutes and 20 seconds.
• the resulted samples had an emulsion layer having a dissolution time of 47-51 min in an aqueous solution of 1.5 wt% sodium hydroxide.
• the obtained samples were exposed to gray scale light for 1 second using a Konica imaging camera M.M (P. 45 phosphor), and then processed using a Konica automatic developing machine SRX-501, developer XD-SR and fixer XF-SR in the 45-second mode (developing temperature 35°C and 32°C) or the 90-second mode (developing temperature 32°C) to yield samples 1 through 30.
• the 45-second mode corresponded to 14.8 seconds of development
• the 90-second mode corresponded to 25.5 seconds of development.
• the fixing temperature was 33°C and washing water was supplied at 18°C at a flow rate of 1.5 1 per minute.
• Sensitivity is expressed by relative values to the recip­rocal of the exposure amount by which a blackening density of +1.0 fogging is obtained in Sample No. 1, taken as 100.
• the following additives were used in the emulsion (light-sensitive silver halide coating solution). The amount of addition is expressed per mol silver halide.
• the following additives were used in the protective layer solution.
• the amount of addition is expressed per 1 coating solution.
• the following compound (1) was added to the coating emulsion in accordance with the method described in Example 1 (3) of Japanese Patent Publication Open to Public Inspection No. 285448/1986. Specifically, the compound (1) was dissolved in an oil comprising the compound (2) and then dispersed in a hydrophilic colloidal solution; the resulting dispersion was added so that the compound (1) and (2) were contained at the following contents per mol silver ahlide.
• the samples in accordance with the present invention show a small variance of gamma values G A , G B and G C and sensitivity due to changes in processing temperature and processing time, having stable performance. It is also evident that the performance is not easily affected by changes in the amount of silver adhesion during the production process.
• Sample Nos. 1 through 30 were rated as to post-processing residual silver in the fogged portion by dripping an aqueous solution of sodium sulfide to determine the degree of coloring; it was found that significant deterioration occurs and the preservability is questionable in the samples processed by the 45-second mode with silver coating ratio of 3.7 g/m2 or more.
• the present invention provides an ultrarapidly processable silver halide photographic light-sensitive material for CRT picture taking having good processing stability and satisfactory levels of sensitivity and maximum density.
• a potassium bromide solution and a silver nitrate solution were concurrently added over a period of 13 minutes, while maintaining a pBr value of 1.2 and accelerating the addition so that the addition flow rate at completion of the addition was 2.5 times that at initiation of the addition (43.6% of the total amount of silver nitrate used was consumed).
• the addition of the potassium bromide solution was stopped and a silver nitrate solution was added over a period of 1 minute (4.7% of the total amount of silver nitrate used was consumed).
• the total amount of silver nitrate consumed was about 11 mols.
• An emulsion containing tabular silver iodobromide grains of 1.62 ⁇ m in average grain size having an aspect ratio of about 16 to 1 was thus obtained. These grains occupied over 80% of the total projection area of silver iodobromide grains, though the above-mentioned spectrally sensitizing dyes A and B, in a weight ratio of 200 to 1, were added thereto at 1000 mg in total per mol silver halide before desalting.
• the spectrally sensitizing dyes were added at pH 7.60; 15 minutes after, phenylcarbamylated gelatin was added and the pH value was reduced with acetic acid to cause coagulation, and this was followed by supernatant removal.
• Samples were prepared by chemical ripening in the same manner as in Example 1 and subsequent coating and drying in the same manner as in Example 1 using the same emulsion additives and protective layer solutions as those in Example 1.
• Example 2 Other samples were prepared in the same manner as in Example 1 except that the vinyl sulfone hardeners listed in Table 2 were used in place of the hardeners used in the protective layer solutions in Example 1, i.e., sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine, formalin and glyoxal, and were rated in the same manner as in Example 1.
• the each resulted sumples had an emulsion layer having the dissolution time of 38-44 min.
• Table 2 The results are given in Table 2.

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• Engineering & Computer Science (AREA)
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• Crystallography & Structural Chemistry (AREA)
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Citations (4)

• 1989
  • 1989-10-16 JP JP1268673A patent/JP2835344B2/ja not_active Expired - Fee Related
  • 1989-10-24 EP EP19890310961 patent/EP0366418A3/fr not_active Withdrawn

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