Silver halide color photographic light sensitive material stored in roll and the photographic unit therefor

FIELD OF THE INVENTION
This invention relates to a silver halide color photographic light sensitive material and, particularly, to a silver halide color photographic light sensitive material stored in roll, which is excellent in pressure resistive characteristics and preventive of scratching troubles, and to the photographic unit therefor.
BACKGROUND OF THE INVENTION
With the advance of the miniaturization of photographic cameras, the freedom of designing cameras has been restricted by the diameters of roll-shaped silver halide light sensitive materials. In 1982, Eastman Kodak Company announced the so-called disk camera system for making use of a discoidal photographic film so as to solve the above-mentioned problem. When making use of this kind of discoidal photographic films, however, they have the defects such as that the sizes and numbers of taking pictures are limited and so forth. Therefore, the roll-shaped films have recently been getting reviewed.
Japanese Patent Publication Open to Public Inspection--hereinafter referred to as `Japanese Patent O.P.I. Publication`-- No. 1-224750/1989 discloses that a miniaturized and lightweight roll-shaped film can be provided by making the thickness of the support thereof to be within the range of 25 to 125 .mu.m. Japanese Patent O.P.I. Publication No. 1-291248/1989 discloses a technique for solving a roll-set curling trouble that is a defect of the roll shaped films by replacing the film by a highly moisture-containing polyester film.
The studies on the minaturization of the roll-shaped films have been progressed on one hand and, at the same time, there have raised the problems on the other hand that a scratching trouble is produced by scratching the front side of a film with the rear side thereof or by scratching the film with a film cartridge or a camera body, when dragging out the film stored in roll after every shooting, and a pressure desensitization is produced when the film is made in the roll-shaped.
SUMMARY OF THE INVENTION
It is, therefore, an object of the invention is to provide a miniature-sized silver halide color photographic light sensitive material stored in roll, which is .excellent in pressure desensitization resistance and preventive from producing a scratching trouble, and to provide the photographic unit therefor.
A color photographic light sensitive material of the invention comprises a film base and a light sensitive silver halide emulsion layer which is stored in roll having a value of ##EQU2## wherein at least one out of the light sensitive silver halide emulsion layers contains a silver halide emulsion containing silver chloride in a proportion of not less than 10 mol%. The color photographic light sensitive material may compose a photographic unit having an exposure means. In this specification, the term, a `roll diameter`, means a outer diameter L of a film stored in roll.

BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a cross-sectional view illustrating an example of the photographic units relating to the invention.
FIG. 2 is an illustration of a photographic unit comprising the cartridge of the invention and a unit body;
FIG. 3 is a cross-sectional view showing the cartridge of the invention; and
FIG. 4 is a perspective view of a cartridge.

DETAILED DESCRIPTION OF THE INVENTION
The silver halide color photographic light sensitive materials stored in roll are each to have a value of a ##EQU3## within the range of, desirably, 23 to 55 .mu.m and, preferably, 25 to 50 .mu.m.
The film base is desirably to have a thickness within the range of 25 to 120 .mu.m and, preferably, 50 to 100 .mu.m.
The raw materials for the films applicable thereto include, for example, the following semisynthetic or synthetic polymers:
Cellulose esters (including, particularly, triacetyl cellulose, cellulose diacetate, cellulose propionate, cellulose acetate propionate, cellulose butylate and cellulose acetate butylate), polyaimides, polycarbonates, polyesters (including, particularly, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate, a copolymeric polyester comprising a copolymerizing component of an aromatic dicarboxylic acid having a polyethylene phthalate metal sulfonate, and a copolymeric polyester comprising a copolymerizing component of an aromatic dicarboxylic acid having a metal sulfonate and an aliphatic dicarboxylic acid), polystyrene, polypropylene, polyethylene, polymethyl pentene, polysulfone, polyether sulfone, polyallylate, an aromatic polyetherimide, an aromatic polyamide, an aromatic polyamidoimide, and polyphenylene sulfide.
Among them, triacetyl cellulose and polyethylene terephthalate are preferavely be applicable in particular.
In the invention, every roll-shaped film is not necessarily wound round a spool, but some of them may each have a space in the center of the roll. If this is the case, the term, a `spool diameter` expressed in the invention is defined as a diameter of the space in the center of a roll.
The invention can be applied to a roll-shaped color photographic light sensitive material and a photographic unit having an exposure means.
In the invention, the term, "a photographic unit", means a unit having an exposure function, which is loaded therein in advance with an unexposed silver halide photographic light sensitive material.
The photographic units of the invention include, for example, a so-called throwaway type unit typified by that shown in FIG. 1, which is destroyed so as to take out an exposed light sensitive material after completing photographic exposures, and a cartridge-replacing type unit typified by that shown in FIG. 2, which replaces one cartridge by another after completing photographic exposures. According to the invention, in the cases of either types thereof, a camera can be miniaturized in size and a scratch can be prevented.
In the invention, a constitutional example capable of functioning as a photographic unit is shown in FIG. 1.
FIG. 1 shows the cross-sectional view taken on the plane determined by the optical axis of a lens and the straight line in the film transportation direction intersecting the optical axis of the lens.
In FIG. 1, reference numeral 1 is a lens, 2 is a shutter, 3 is a silver halide light sensitive material -hereinafter referred simply to as a `film`-, 4 is a photographic unit member, 5 is a light shielding film holder marking off the exposure area of a film, 6 is a cartridge holder, 7 is a lens holder applying a conical surface converging on a lens with a stray-radiation invading prevention process, and 8 is a cartridge for storing a film roll.
In the specification of the above-described photographic unit, there uses a spherical or aspherical fix-focussed single-component lens as a lens with a fixed aperture and a shutter having a fixed shutter speed with in the range of 50th to 1/200th second.
Next, the detailed descriptions of a photographic unit comprising a cartridge section and a camera section such as shown in FIG. 2.
In the invention, the above-mentioned cartridge section means a section where a light sensitive material is loaded into a cartridge comprising a film roll chamber storing therein a rolled unexposed light sensitive material, a take-up chamber for taking up an exposed light sensitive material, and a bridging member having an opening of not less than 400 mm.sup.2 in area for connecting the above-mentioned two chambers to each other.
Taking the balance between the sizes of an image and a camera into consideration, the area of the above-mentioned opening is desirably within the range of 600 to 2,500 mm.sup.2 and, preferably, 800 to 1,200 mm.sup.2. In the invention, the area of the opening is substantially the effective area of an image.
The configuration of the opening is preferably to be in the rectangular form. Taking the shapes of the cameras used into consideration, the ratio of the longer side of the rectangle to the shorter side thereof is within the range of 1.2 to 2,0, desirably, 1.3 to 1.7 and, preferably, 1.4 to 1.6. When the raiot thereof is within the above-given range, the resulting images can be stable in visual psychology.
For the rolled light sensitive materials to be loaded in cartridges, the sizes thereof including the widths and lengths are preferable to meet the systems employed in the current market. It is preferable that the widths are to be 35 .+-.1 mm and the lengths are of the order of the lengths of the 135 size, 12ex, 20ex and 36ex films; provided, a rolled film can be made longer to be, for example, 72ex, 100ex and so forth, without making a camera size larger, by making the films more thinner.
The above-mentioned light sensitive materials are each preferable to be made adhered to a spool at least either one of a roll film chamber or a film take-up chamber.
For the materials of the cartridge section of a cartridge, plastics are preferable to be used, from the viewpoints of making a photographic unit lighter in weight, improving the simple operability, making the cost to be inexpensive, and recycling the materials.
The requirements for a preferable plastic-made cartridge are that (1) the light shielding property is to be excellent; (2) the photographic characteristics of a light sensitive material are to hardly be affected; and (3) the recycling is readily be performed. When the known plastic cartridges can satisfy the above-mentioned requirements, they can be used in the invention. The preferable examples of the plastic cartridges applicable thereto include, typically, those made of polystyrene, polypropylene, polyethylene, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, cellulose acetate ester and the copolymers thereof, each of which is provided with a light-shielding property by adding thereinto with carbon black or a pigment. For the purpose of improving the recycling efficiency, it is preferable that the spool of a cartridge is to be made of the same plastic as in the cartridge.
In the invention, it is preferable that a cartridge to be loaded a light sensitive material is to be applied with a light-shielding means, because the cartridge has an opening for making image exposures, including, for example, an elastic light-shielding member such as that disclosed in Japanese Patent O.P.I Publication No 60-120448/1985; a light shielding member such as that disclosed in Japanese Utility Model O.P.I. Publication No. 2-136247/1990; a pressure light-shielding member such as that disclosed in Japanese Utility Model O.P.I. Publication No. 2-136248/1990; a light-shielding paper such as those disclosed in Japanese Patent O.P.I. Publication Nos. 2-175441/1990 and 2-275442/1990; and a light-shielding paths such as those disclosed in Japanese Patent O.P.I. Publication No. 54-111832/1979 and Japanese Utility Model Examined Publication No. 46-30055/1971.
In the invention, it is preferable that a cartridge section and a camera section are to be correlatively detachable and, it is, therefore, preferable that at least either one of the two sections has a coupling member for detachment and attachment from one to the other section. It is, further, preferable that a stopper member is to be provided for preventing any detachment from any erroneous operation or any operations against one's will.
In the invention, from the viewpoints of making a photographic unit lighter in weight, making an operation simpler, and making a recycling easier, it is preferable that a cartridge section can also perform the role of the back lid of a camera section when the cartridge section is attached to the camera section. The typical example of the above-mentioned preferable cases is shown in FIG. 3.
In the photographic units of the invention, a camera section is attached to a cartridge section and, preferably, one part or the whole of the outside of a photographic unit is to be covered by a covering member The above-mentioned measure is not only effective for absorbing any shock when a user drops a photographic unit so as to prevent a driving, optical and electrical systems from causing a trouble, but also effective for a valuable exposed image information from being damaged by separating a camera section from a cartridge section due to the erroneous operation or an operation against one's will.
The materials for the covering members are preferably made of a shock-absorbable materials including, for example, paper, sponge, rubber, leather and fabric.
The covering members are regardless of any configurations. However, the belt-shaped or the box-shaped thereof is preferably used. It is particularly preferable to use the box-shaped covering members which are each so made a hole as not to hinder the functions and operations for the lens, finder, strobe, shutter-button, and film take-up sections.
It is preferable that the photographic units of the invention are to be sealed up in a pack such as a plastic case or a moisture-proof bag, until they are used after they are manufactured. In the sealed packs, the relative humidity therein at a temperature of 25.degree. C. is within the range of 30 to 70%, preferably 40 to 60% and particularly 45 to 55%. It is further preferable that the partial oxygen pressure is to be made lower than the atmospheric pressure by filling inert gasses.
The above-mentioned camera sections may be those newly manufactured and may also be a recycled camera sections which were already marketed, exposed, and separated from a cartridge section. For the purposes of effectively utilizing the resources, preventing environment from the pollution produced by waste materials, and making the recycling application easier, the above-mentioned camera sections are preferably reused or used in repetition. When making the reuse of the above-mentioned camera sections, they are preferable to be inspected if required in advance of the attachment thereof to a cartridge section, and the frequencies of the repetition uses are preferable to be recorded on the body of the camera section.
When a power source section, i.e., a battery, is provided to a camera section, the residual voltage of the battery is checked up and replaced if required so that the camera section can be reused. When the battery is rechargeable, the camera section can be reused upon recharging the battery. In the latter case, it is particularly preferable, because an environmental pollution produced by waste batteries can sharply be reduced.
The photographic units of the invention are preferable to have the whole volume within the range of 150 to 190 cm.sup.3. When the photographic unit is regarded as a rectangular parallelopipedon, the second logest side out of the three sides is preferable to be within the range of 5.0 to 8 0 cm. The photographic unit satisfying the above-mentioned requirements can be right fit in the pocket of a shirt and, therefore, the portability thereof can be so excellent that the camera can not be slipped out of the pocket.
The silver halide emulsions of the invention contain each silver chloride having a proportion of not less than 10 mol %. The silver chloride contents is desirably not less than 50 mol % and, preferably, not less than 80 mol %.
Besides the silver chloride, silver bromide or silver iodide may desirably be contained as the silver halides, and the silver halide emulsion contains silver chlorobromide, silver chloroiodide, silver chloride and silver chloroiodobromide.
In the case where the silver halide emulsion of the invention comprises mixed crystals such as those of silver chlorobromide, silver chloroiodide or silver chloroiodobromide, it is desirable to locate silver bromide or silver iodide in the specific positions of the crystals of silver halide grains.
In the case where a silver halide emulsion of the invention is comprised of silver chlorobromide, it is desirable to locate silver bromide in the peak points each of the silver halide crystals or in the neighborhood of the peak points. Such a silver halide emulsion as mentioned above can be prepared by adsorbing a sensitizing dye or a inhibitor onto the crystals of silver chloride or silver chlorobromide grains and then by ripening them by adding a water-soluble bromide solution so as to make a halogen-substitution.
In the case that a silver halide emulsion of the invention is comprised of silver chloroiodobromide, it is desirable to locate silver iodide inside the grains of the silver halides.
A silver halide emulsion located silver iodide in the grains thereof can be prepared by depositing silver chloride or silver chlorobromide on core grains each containing silver iodide. When depositing silver chloride or silver chlorobromide, any well-known silver halide crystal growing processes such as a double-jet precipitation process and the Ostward ripening process may be used.
The core grains have each a silver iodide content of, desirably, not less than 10 mol %, preferably, not less than 15 mol % and, particularly, not less than 40 mol %.
The core grains may desirably be those of silver iodobromide.
The above-described silver halide emulsions may be prepared in any one of the processes disclosed in, for example, Japanese Patent O.P.I. Publication Nos. 64-6941/1989, 64-26839/1989, 1-121548/1989 and 1-138550/1989, respectively.
When the silver halide emulsion of the invention contains silver iodide, the silver iodide content of the whole emulsion is, desirably, not more than 20 mol %; preferably, not more than 12 mol %; and particularly, within the range of 0 to 5 mol %.
The silver halide emulsions of the invention may be either of the regular crystals such as those in the tetrahedral and octahedral forms or of the twinned crystals such as those in the tabular form. However, they are preferably cf the regular crystals and, the crystals are preferably to have the cubic configuration. The crystal configurations may be controlled by suitably selecting the pAg and pH values in the mixing course. The grains in the octahedral or tabular form may be prepared by growing the crystals in the presence of a sensitizing dye or an inhibitor each having an adsorbing property, as described in, for example, Japanese Patent O.P.I. Publication Nos. 58-11935/1983, 58-11936/1983, 58-11937/1983, 58-108528/1983, 62-163046/1987, 63-41845/1988 and 63-212932/1988.
The silver halide emulsions of the invention are to have an average grain size within the range of, desirably, 0.05 to 10 .mu.m; preferably, 0.1 to 5 .mu.m; and, particularly, 0.2 to 3 .mu.m.
The silver halide emulsions of the invention may be used by mixing together with the other silver halide emulsions, provided, the effects of the invention cannot be spoiled. The silver halide emulsions of the invention are to be used in a proportion of, desirably, not less than 30 wt %; preferably, not less than 50 wt%; and, particularly, not less than 80 wt %.
In silver halide grains, the local presence of the halogen components can be confirmed in an X-ray diffraction method or in an X-ray microanalyzing method in which the chips of silver halide grains dispersed in a resin are investigated.
The silver halide emulsions of the invention are desirable to be monodispersive.
The term, `grain size`, herein means a diameter of the circular image having the same areas as the projective image has.
The above-mentioned grain sizes can be measured in the following manner, for example Subject grains are dispersed on a flat sample table so as not to be superposed together and they are photographed upon magnifying them 10000 to 50000 times through an electron microscope and then printed. On the resulting print, the diameters of the grains or the areas of the resulting projective grain images are practically measured, provided, the numbers of the subject grains are to be not less than 1000 at random.
In the highly monodispersive emulsions particularly desirable for the invention, the distribution degrees are defined by the following equation; ##EQU4##
The above-mentioned highly monodispersive emulsions have each a grain size distribution of not higher than 20% and, desirably, not higher than 15%.
A silver halide color photographic light sensitive material can be prepared by making use of the silver halide emulsions of the invention.
In the invention, silver halide emulsions are to be used after completing both physical and chemical ripening steps and a spectral sensitizing step. In the above-mentioned steps, the additives applicable thereto are given in Research Disclosure Nos. 17643, 18716 and 308119, -hereinafter abbreviated to as RD17643, RD18716 and RD308119, respectively.
The following table shows where they are given:
______________________________________[Additive] [Page in RD308119] [RD17643] [RD18716]______________________________________Chemical 996 III-A 23 648sensitizerSpectral 996 IV-A-A, B, C, D, 23-24 648-9sensitizer H, H, I, JSuper 996 IV-A-E, J 23-24 648-9sensitizerAntifoggant 998 VI 24-25 649Stabilizer 998 VI 24-25 649______________________________________
The well-known photographic additives applicable to the invention are also given in the above-mentioned Research Disclosures. The following table shows where they are given:
______________________________________[Additive] [Page in RD308119] [RD17643] [RD18716]______________________________________Color 1002 VII-I 25 650contaminationpreventiveDye image 1001 VII-J 25stabilizerWhitening 988 V 24agentUV absorbent 1003 VIII C, XIII C 25-26Light absorbent 1003 VIII 25-26Light diffuser 1003 VIIIFiltering dye 1003 VIII 25-26Binder 1003 IX 26 651Antistatic agent 1006 XIII 27 650Layer hardener 1004 X 26 651Plasticizer 1006 XII 27 650Lubricant 1006 XII 27 650Activator 1005 XI 26-27 650coating aidMatting agent 1007 X VIDeveloping 1011 XX-Bagentcontained in a light sensitive material______________________________________
A variety of couplers can be used in the invention. The concrete examples thereof are given in the above-mentioned Research Disclosures. The following table shows where they are given;
______________________________________[Coupler] [Page in RD308119] [RD17643] [RD18716]______________________________________Yellow coupler 1001 VII-D VII C-GMagenta coupler 1001 VII-D VII C-G VII C-GCyan coupler 1001 VII-D VII C-GDIR coupler 1001 VII-F VII FBAR coupler 1002 VII-FOther useful 1001 VII-Fresidual group-releasing couplerAlkali-soluble 1001 VII-Ecoupler______________________________________
The additives applicable to the invention can be added in the dispersing methods such as that described in RD308119 XIV.
In the invention, it is allowed to use the supports described in p. 28 of the above-given RD17643, pp. 647-8 of RD18716 and XIX of RD308119.
To the light sensitive materials of the invention, the auxiliary layers such as a filtering layer and an interlayer such as those described in the RD308119 VII-K may be provided.
The light sensitive materials of the invention may have a variety of layer arrangements including a normal, inverted or unit layer arrangement such as those described in the RD308119 VII-K.
The invention can be applied to a variety of light sensitive materials including, typically, a color negative film for general or cinematographic use, a color reversal film for slide or TV use, and a color positive film.
The light sensitive materials of the invention can be developed in the ordinary processes described in pp. 28-29 of RD17643, p. 647 of RD18716 and X VII of RD308119.
EXAMPLES
Some concrete examples of the invention will now be detailed below.
In the every example given below, the amounts of the materials added to the silver halide light sensitive materials are expressed in terms of grams per sq. meter, unless otherwise expressly stated. The amounts of silver halide and colloidal silver are indicated by converting them into the amounts of silver, and the amounts of the sensitizing dyes are indicated in terms of mol numbers per mol of silver.
EXAMPLE 1
A multilayered color photographic light sensitive material sample 101 was prepared in the manner that each of the layers having the following compositions were formed on a 120 .mu.m thick triacetyl cellulose film support, in order from the support side.
______________________________________Sample 101 for comparison______________________________________Layer 1: An antihalation layer, HCBlack colloidal silver 0.15UV absorbent, UV-1 0.20Colored cyan coupler, CC-1 0.02High boiling solvent, Oil-1 0.20High boiling solvent, Oil-2 0.20Gelatin 1.6Layer 2: An interlayer, IL-1 1.3GelatinLayer 3: A low speed red-sensitive emulsion layer, R-LSilver iodobromide emulsion, 0.4Em-1Silver iodobromide emulsion, 0.3Em-2Sensitizing dye, S-1 3.2 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-2 3.2 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-3 0.2 .times. 10.sup.-4 mols/mol of silverCyan coupler, C-1 0.50Cyan coupler, C-2 0.13Colored cyan coupler, CC-1 0.07DIR compound, D-1 0.006DIR compound, D-2 0.01High boiling solvent, Oil-1 0.55Gelatin 1.0Layer 4: A high speed red-sensitive emulsion layer, R-HSilver iodobromide emulsion, 0.9Em-3Sensitizing dye, S-1 1.7 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-2 1.6 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-3 0.1 .times. 10.sup.-4 mols/mol of silverCyan coupler, C-2 0.23Colored cyan coupler, CC-1 0.03DIR compound, D-2 0.02High boiling solvent, Oil-1 0.25Gelatin 1.0Layer 5: An interlayer, IL-2 0.8GelatinLayer 6: A low speed green-sensitive emulsion layer, G-LSilver iodobromide emulsion, 0.6Em-1Silver iodobromide emulsion, 0.2Em-2Sensitizing dye, S-4 6.7 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-5 0.8 .times. 10.sup.-4 mols/mol of silverMagenta coupler, M-1 0.17Magenta coupler, M-2 0.43Colored magenta coupler, CM-1 0.10DIR compound, D-3 0.02High boiling solvent, Oil-2 0.70Gelatin 1.0Layer 7: A high speed green-sensitive emulsion layer, G-HSilver iodobromide emulsion, 0.9Em-3Sensitizing dye, S-6 1.1 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-7 2.0 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-8 0.3 .times. 10.sup.-4 mols/mol of silverMagenta coupler, M-1 0.03Magenta coupler, M-2 0.13Colored magenta coupler, CM-1 0.04DIR compound, D-3 0.004High boiling solvent, Oil-2 0.35Gelatin 1.0Layer 8: A yellow filtering layer, YC Yellow colloidal silver 0.1Additive, HS-1 0.07Additive, HS-2 0.07Additive, SC-1 0.12High boiling solvent, Oil-2 0.15Gelatin 1.0Layer 9: A low speed blue-sensitive emulsion layer, B-LSilver iodobromide emulsion, 0.25Em-1Silver iodobromide emulsion, 0.25Em-2Sensitizing dye, S-9 5.8 .times. 10.sup.-4 mols/mol of silverYellow coupler, Y-1 0.60Yellow coupler, Y-2 0.32DIR compound, D-1 0.003DIR compound, D-2 0.006High boiling solvent, Oil-2 0.18Gelatin 1.3Layer 10: A high speed blue-sensitive emulsion layer, B-HSilver iodobromide emulsion, 0.5Em-4Sensitizing dye, S-10 3.0 .times. 10.sup.-4 mols/mol of silverSensitizing dye, S-11 1.2 .times. 10.sup.-4 mols/mol of silverYellow coupler, Y-1 0.18Yellow coupler, Y-2 0.10High boiling solvent, Oil-2 0.05Gelatin 1.0Layer 11: The first protective layer, PRO-1Silver iodobromide emulsion, 0.3Em-5UV absorbent, UV-1 0.07UV absorbent, UV-1 0.1Additive, HS-1 0.2Additive, HS-2 0.1High boiling solvent, Oil-1 0.07High boiling solvent, Oil-3 0.07Gelatin 0.8Layer 12: The second protective layer, PRO-2Alkali-soluble matting agent, 0.13the average particle size: 2 .mu.mPolymethyl methacrylate, 0.02the average particle size: 3 .mu.mGelatin 0.5______________________________________
Besides the above-given compositions, a coating aid SU-2, a dispersing aid SU-1, layer hardeners H-1 and H-2, and dyes AI-1 and AI-2 were suitably added into each of the layers.
The emulsions used in the above-mentioned sample were those shown below, and every one of them was the monodispersive core-shell emulsion of the internal high iodide-containing type.
Em-1: Average AgI content: 7.5 mol %; Octahedral grains; Average grain size: 0.55 .mu.m; Monodispersion degree: 14%; and so forth on;
Em-2: Average AgI content: 2.5 mol %; Octahedral grains; Average grain size: 0.36 .mu.m; Monodispersion degree: 14%;
Em-3: Average AgI content: 8.0 mol %; Octahedral grains; Average grain size: 0.84 .mu.m; Monodispersion degree: 12%;
Em-4: Average AgI content: 8.5 mol %; Octahedral grains; Average grain size: 1.02 .mu.m; Monodispersion degree: 12%; and
Em-5: Average AgI content: 2.0 mol %; Octahedral grains; Average grain size: 0.08 .mu.m; Monodispersion degree: 12%. ##STR1##
Next, samples 102 through 106 were each prepared by making use of the emulsions shown in Table-1 in place of emulsions Em-1 through Em-4 each used in sample 101.
The resulting samples 101 through 106 were each cut into 35 mm in width and 120 cm in length, and each of the sample pieces was wound round a spool having a diameter of 11.0 mm so as to be a roll having a diameter of 18.0 mm. The resulting number of turns was 24. ##EQU5##
After the resulting rolled samples were each stored for 3 days at ordinary temperature of 25.degree. C. and ordinary humidity of 30% RH, they were unwound and exposed to light uniformly to have a color density of 1.0, and were then developed as shown below.
In the color developments, sample 101 was made for 3 min. 15 sec., and the other samples each, for 2 min., respectively.
______________________________________Processing Processing Processing Processing*step time temperature replenishment______________________________________Color developing As aforestated 38.degree. C. 540 mlBleaching 45 sec. 38.degree. C. 155 mlFixing 1 min 45 sec. 38.degree. C. 500 mlStabilizing 90 sec. 38.degree. C. 775 mlDrying 1 min. 40-70.degree. C. --______________________________________ *Amount of replenishment is expressed by an amount per sq. meter of a subject light sensitive material.
The stabilizing steps were carried out in a three-bath counter-current processing system. The replenishments were made to the final bath of the stabilizer and the overflows were flown into the bath preceedent to the above-mentioned final bath.
A part -275 ml/m.sup.2 - of the overflows from the stabilizing bath following the fixing bath was flown into the fixing bath.
The compositions of the color developer used therein were as follows:
______________________________________Potassium carbonate 30 gSodium hydrogencarbonate 2.7 gPotassium sulfite 2.8 gSodium bromide 1.3 gHydroxylamine sulfate 3.2 gSodium chloride 0.6 g4-amino-3-methyl-N-ethyl-N-(.beta.- 4.6 ghydroxylethyl)aniline sulfateDiethylenetriamine pentaacetate 3.0 gPotassium hydroxide 1.3 gAdd water to make 1 literAdjust pH with potassium hydroxide or pH = 10.01a 20% sulfuric acid solution to be______________________________________
The compositions of the color developing replenisher used therein were as follows:
______________________________________Potassium carbonate 40 gSodium hydrogen carbonate 3 gPotassium sulfite 7 gSodium bromide 0.5 gHydroxylamine sulfate 3.2 g4-amino-3-methyl-N-ethyl-N-(.beta.- 6.0 ghydroxylethyl)aniline sulfateDiethylenetriamine pentaacetate 3.0 gPotassium hydroxide 2 gAdd water to make 1 literAdjust pH with potassium hydoxide or pH = 10.12a 20% sulfuric acid solution to be______________________________________
The compositions of the bleaching solution used therein were as follows:
______________________________________Ferric ammonium 1,3-diaminopropane- 0.35 molstetraacetateDisodium ethylenediaminetetraacetate 2 gAmmonium bromide 150 gGlacial acetic acid 40 mlAmmonium nitrate 40 gAdd water to make 1 literAdjust pH with aqueous ammonia or pH = 4.5glacial acetic acid to be______________________________________
The compositions of the bleaching replenisher used therein were as follows:
______________________________________Ferric ammonium 1,3-diaminopropane- 0.40 molstetraacetateDisodium ethylene diamine tetraacetate 2 gAmmonium bromide 170 gAmmonium nitrate 50 gGlacial acetic acid 61 mlAdd water to make 1 literAdjust pH with aqueous ammonia or pH = 3.5glacial acetic acid to beControl suitably the pH of the bleachingsolution constant in the bleaching bath.______________________________________
The compositions of the fixer and the fixing replenisher each used therein were as follows:
______________________________________Ammonium thiosulfate 100 gAmmonium thiocyanate 150 gSodium bisulfite, anhydrous 20 gSodium metabisulfite 4.0 gDisodium ethylenediaminetetraacetate 1.0 gAdd water to make 1 literAdjust pH with glacial acid and pH = 6.5aqueous ammonia to be______________________________________
The stabilizer and the stabilizing replenisher each used therein were as follows:
______________________________________1,2-benzisothiazoline-3-one 0.1 gC.sub.8 H.sub.17 --C.sub.6 H.sub.4 --(--CH.sub.2 CH.sub.2 O--).sub.10 2.0 ml<in a 50% solution>Hexamethylenetetramine 0.2 gHexahydro-1,3,5-trifluoro(2- 0.3 ghydroxyethyl)-5-triazineAdd water to make 1 literAdjust pH with potassium hydroxide and pH = 7.0a 50% sulfuric acid solution to be______________________________________
TABLE 1__________________________________________________________________________ Sample 101 Sample 102 Sample 103 Sample 104 Sample 105 Sample 106__________________________________________________________________________Em-1Composition AgBr 0.925 AgBr 0.01 AgCl AgBr 0.7 AgBr 0.15 AgCl I 0.075 Cl 0.99 Cl 0.3 Cl 0.75 I 0.10Configuration Octahedron Cube Cube Cube Cube OctahedronAve. grain size 0.55 .mu.m 0.46 .mu.m** 0.46 .mu.m** 0.46 .mu.m** 0.46 .mu.m** 0.57 .mu.m*Monodisper- 14% 12% 10% 10% 12% 14%sion degreeEm-2Composition AgBr 0.975 AgBr 0.01 AgCl AgBr 0.7 AgBr 0.15 AgCl I 0.025 Cl 0.99 I 0.3 Cl 0.75 I 0.10Configuration Tetradeca- Cube Cube Cube Cube Octahedron hedronAve. grain size 0.36 .mu.m* 0.30 .mu.m** 0.30 .mu.m** 0.30 .mu.m** 0.30 .mu.m** 0.38 .mu.m*Monodisper- 14% 12% 11% 11% 13% 14%sion degreeEm-3Composition AgBr 0.92 AgBr 0.01 AgCl AgBr 0.7 AgBr 0.15 AgCl I 0.08 Cl 0.99 Cl 0.3 Cl 0.75 I 0.10Configuration Octahedron Cube Cube Cube Cube CubeAve. grain size 0.84 .mu.m* 0.70 .mu.m** 0.70 .mu.m** 0.30 .mu.m** 0.30 .mu.m** 0.86 .mu.m*Monodisper- 12% 11% 9% 9% 12% 12%sion degreeEm-4Composition AgBr 0.915 AgBr 0.01 AgCl AgBr 0.7 AgBr 0.15 AgCl I 0.085 Cl 0.99 Cl 0.3 Cl 0.75 I 0.10Configuration Octahedron Cube Cube Cube Cube CubeAve. grain size 1.02 .mu.m* 0.85 .mu.m** 0.85 .mu.m** 0.85 .mu.m** 0.85 .mu.m** 1.05 .mu.m*Monodisper- 12% 11% 9% 9% 12% 12%sion degree__________________________________________________________________________ *A diameter of the circle having an area equivalent to that of the projective image **Length of a side
The density uniformity of the resulting developed samples were examined and the presence of the areas where the densities were lowered were also confirmed. The results thereof are shown in Table-2 given below.
TABLE 2______________________________________ Presence ofSample No. density lowered area______________________________________101 for Comparison Yes102 for Invention Nil103 for Invention Nil104 for Invention Nil105 for Invention Nil106 for Invention Nil______________________________________
EXAMPLE 2
Samples 101-106 prepared in Example 1 were each cut into 35 mm in width and 120 mm in length and each of them was so wound round without using spools as to be 15 mm in diameter of the roll. The resulting rolls were stored in photographic units having an exposure function shown in FIG. 1, respectively. The films stored in the respective photographic units were each exposed to light and they were taken up in cartridges. Thereafter, the films taken out of the cartridges were each developed in the same manner as in Example 1 and were then checked up on whether any scratch troubles -a linear shaped color production- were produced or not on the films. The results thereof are shown in Table-3 given below.
TABLE 3______________________________________ Presence ofSample No. scratch trouble______________________________________101 for Comparison D102 for Invention Nil A103 for Invention Nil A104 for Invention Nil A105 for Invention Nil A106 for Invention Nil A______________________________________
In the Table-3, the grade of scratch trouble is shown according to the following standard:
______________________________________ Number of scratchGrade troubles per film______________________________________A 0-3B 4-8C 9-15D over 16______________________________________
It can be proved in the invention that any scratch troubles can hardly be produced.
The invention can provide a roll-shaped and small-sized silver halide color photographic light sensitive material capable of displaying an excellent pressure resistance characteristics and inhibiting any scratch trouble from occuring, and the photographic units thereof.

Number	Name	Date
4827298	Sasaki et al.	May 1989
4866469	Shiba et al.	Sep 1989
4933267	Ishigaki et al.	Jun 1990
5004675	Yoneyama et al.	Apr 1991
5057403	Kume et al.	Oct 1991
5093227	Nakazyo et al.	Mar 1992

Number	Date	Country
2-62534	Mar 1990	JPX
2-62535	Mar 1990	JPX

Silver halide color photographic light sensitive material stored in roll and the photographic unit therefor

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