JPH08137074A - Silver halide stereoscopic color photographic material - Google Patents

Abstract

PURPOSE: To provide a silver halide stereoscopic color photographic material that provides a sufficient sense of sharpness and stereoscopy for practical use. CONSTITUTION: A silver halide stereoscopic color photographic material having a lenticular face on at least one side of a transparent support has an optical reflection density of 0.80 or more at 680nm; the ratio (B/A) of its optical reflection density (B) at 550nm to that (A) at 680nm is 0.3 to 0.7, and the ratio (C/A) of its optical reflection density (C) at 470nm to that (A) at 680nm is 0.2 to 0.6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also simply referred to as "color light-sensitive material"), and more specifically, it comprises a lenticular film and a silver halide color photographic light-sensitive layer. , A silver halide three-dimensional color photographic light-sensitive material from which a three-dimensional color print can be obtained.

[0002]

2. Description of the Related Art It has been known for a long time about an image that can be viewed stereoscopically using the parallax of both eyes. For making a three-dimensional photo print having a lenticular sheet, how to make a lenticular sheet, a method of pasting a lenticular sheet, etc. There are some descriptions. For example US patent
1,918,705, 2,726,154, 3,751,258, 3,96
0,563, JP-A-49-29640, JP-A-62-6245, JP-A-3-26
No. 5844, No. 4-56849 and Japanese Patent Publication No. 58-48890.

However, the lenticular three-dimensional photographic print has some drawbacks. First, since the image is formed through the lenticular surface, the sharpness of the image is poor.

For improving sharpness, the use of an anti-irradiation dye is described in JP-A-51-93215, and in JP-A-3-293340, a photosensitive layer laminated with a lenticular film. A technique for improving sharpness by providing a colored layer on the uppermost layer is described. Further, a technique for providing a titanium dioxide layer for both reflection and reflection / transmission is described in Japanese Patent Laid-Open No. 3-278054, but although improvement in sharpness is seen, there is a limit to improvement in three-dimensional effect. On the contrary, when too much titanium was used, the three-dimensional effect was impaired. Further, it has been found that when the amount of titanium dioxide is large, the titanium dioxide layer is cracked when stored for a long period of time. Further, if the lenticular film is peeled off after exposure, the photosensitive material is developed and then re-bonded with the lenticular film, the positional deviation and the working process become complicated, which poses a serious problem in practical use.

Further, since a plurality of film images that have passed through two or more lenses are printed as one image, color misregistration is likely to occur, and the image is actually sharper than general viewing photographs (those not stereoscopic photographs). It has been found from various studies that the sharpness of appearance is inferior to that of the image, and that when the maximum density is increased, the whiteness is deteriorated and the sharpness is insufficient.

As described above, the conventional three-dimensional photographic technology has not been able to provide a silver halide three-dimensional color photographic light-sensitive material satisfying both practically sufficient sharpness and three-dimensionality.

[0007]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide three-dimensional color photographic light-sensitive material having practically sufficient sharpness and three-dimensionality. Another object is to provide a silver halide three-dimensional color photographic light-sensitive material which is sufficiently excellent in whiteness.

[0008]

The above object of the present invention is to provide a silver halide three-dimensional color photographic light-sensitive material having a lenticular surface on at least one surface of a transparent support. The optical reflection density at 0.80 or more, and the optical reflection density at 550 nm (B) and the optical reflection density at 680 nm (A)
A halogenated compound having a ratio (B / A) of 0.3 to 0.7 and a ratio (C / A) of optical reflection density (C) at 470 nm and optical reflection density (A) at 680 nm of 0.2 to 0.6. It is achieved by a silver three-dimensional color photographic light-sensitive material. The average gradation between the minimum density +0.2 and the minimum density +0.6 in the characteristic curve of the image obtained from at least one light-sensitive layer of the silver halide three-dimensional color photographic light-sensitive material is 2.2 or less, and The average gradation between the minimum density +1.0 and the minimum density +1.8 is 2.8 or more, and the layer farthest from the transparent support of the silver halide three-dimensional color photographic light-sensitive material or a layer containing a white pigment in the adjacent layer. And a total amount of the white pigment used is 3 to 12 g / m ² , and a layer containing the white pigment in a layer farthest from the transparent support of the silver halide three-dimensional color photographic light-sensitive material or a layer adjacent to the layer. The effect of the present invention is that the variation coefficient of the area occupied by the particles of the white pigment is 0.25 or less, and the optical brightener is contained in at least one layer of the silver halide three-dimensional color photographic light-sensitive material. Is more preferable and is preferable.

The present invention will be described in more detail below.

The silver halide three-dimensional color light-sensitive material having a lenticular surface on the transparent film surface in the present invention is
It means a light-sensitive material comprising a silver halide color light-sensitive layer on a transparent film having a lenticular surface.

The transparent film having a lenticular surface is a transparent film in which small convex pitches called lenticules are repeatedly arranged on the surface of the transparent film.

In the present invention, a polyester base usually used in a color film and a lenticular film having a convex lenticular surface may be bonded together, or a lenticular film having a convex lenticular surface (hereinafter referred to as a lenticular film Note) It may be alone.

The lenticular film used in the present invention is produced by using a thermoplastic resin by an injection molding method or a calendering method and a polymerization reaction of a liquid monomer.

The thermoplastic resin is not limited, but includes polyolefins (polyethylene, polypropylene, etc.), polystyrenes (polystyrene, butadiene, styrene resin, etc.), polyvinyl chlorides, polyvinylidene chlorides, polyesters, polymethacrylates. and so on.

As a joining method for laminating the polyester base and the lenticular film, a hot-melt type adhesive, solventless adhesion, and injection joining of molten polyethylene are preferable.

The thickness of the lenticular film is not particularly limited, but the total thickness of the lenticular film and the laminated films is preferably 500 μm or less. More preferably, it is between 430 and 180 μm. If it exceeds 500 μm, it becomes difficult to wind it during coating and drying, and if it is 180 μm or less, it is difficult to put it into practical use.

Although the refractive index of the lenticular depends on the thickness of the material used and the curvature of the lenticular, it is preferably 1.50 or more for the polyethylene resin, and other resins also preferably have the same refractive index.

In the present invention, the transparent film to be bonded to the lenticular film may be polyethylene terephthalate or the like which is generally used in photographic light-sensitive materials.

The optical reflection density measured from the transparent film side having a lenticular surface of the color light-sensitive material of the present invention is 68.
It is 0.80 or more at 0 nm, preferably 1.00 to 2.00. The ratio (B / A) of the optical reflection density (B) at 550 nm and the optical reflection density (A) at 680 nm is 0.3 to 0.7.
And the optical reflection density (C) at 470 nm and 680
The ratio (C / A) to the optical reflection density (A) in nm is 0.2.
~ 0.6.

The optical reflection density of the light-sensitive material in the present invention is measured by a reflection densitometer generally used in the art and is defined as follows.

Optical reflection density = log ₁₀ (F ₀ / F) F ₀ ; Reflected light flux of standard white plate F; Reflected light flux of sample However, from the back side of the sample to prevent measurement error due to light passing through the sample Set a standard white plate and measure.

In order to obtain such optical reflection density,
It is necessary to optimally adjust the amount of dye added for the purpose of preventing irradiation and halation, the amount of white pigment such as titanium dioxide, density, monodispersity and the like.

As the dye to be added, a plurality of dyes having absorptions in different wavelength ranges may be used, and the dye may be contained in any of the silver halide emulsion layer on the support and other hydrophilic colloid layers. It doesn't matter.

The dye may be added by, for example, dissolving in an aqueous solution or an organic solvent (for example, alcohols, glycols, cellosolves, dibutyl phthalate, tricresyl phosphate, etc.) and, if necessary, emulsifying and dispersing it into a coating solution. Various methods can be used, such as a method of adding and coating, or a method of dispersing a dye in the form of solid fine particles and adding it to a coating solution and coating.

Examples of dyes used in the present invention include oxonol type dyes, arylidene type dyes, styryl type dyes, cyanine type dyes, merocyanine type dyes, azo type dyes and azomethine type dyes. Among these, particularly preferable dyes include those described on pages 50 to 57 of Japanese Patent Application No. 4-80949 and those described on pages 6 to 12 of JP-A 3-207399.

It is also possible to use a colloidal metal in the same layer and other layers. As the colloidal metal, colloidal silver, colloidal manganese or the like is used. Colloidal silver, which is particularly useful, is prepared by keeping silver nitrate alkaline in gelatin in the presence of a reducing agent such as dextrin, hydroquinone, or phenidone, neutralizing, cooling, and removing the reducing agent and unnecessary salts by a washing method. can get. The amount of colloidal silver is not limited, but about 0.01 to 0.5 g / m ² is preferably used.

In the present invention, a layer containing a white pigment is preferably provided in a layer farthest from the transparent support or a layer adjacent thereto.

The white pigment to be used may be mainly surface-treated titanium dioxide or the like. Titanium dioxide may be either rutile type or anatase type, and may be used alone or in combination.

As the production method, those treated with an inorganic substance such as hydrous alumina treatment, hydrous silicon dioxide treatment or zinc oxide treatment, or those treated with an organic substance such as trimethylolmethane, trimethylolethane or trimethylolpropane , Or those treated with siloxane such as polydimethylsiloxane are appropriately used.

Besides titanium dioxide, white pigments such as barium sulfate, calcium carbonate, barium carbonate and zinc oxide may be used in combination at a ratio of 20% or less of the total white pigment.

As for the dispersity of the white pigment preferably used in the present invention, it is particularly preferable that the coefficient of variation of the occupied area is 0.25 or less because the effect of the present invention is great.

To measure the dispersity of the coated white pigment particles, the white pigment layer of the light-sensitive material is dissolved with a proteolytic enzyme and the obtained white pigment is photographed with an electron microscope. It can be obtained and evaluated by the coefficient of variation of the occupied area ratio (%).

The method of adjusting the variation coefficient of the white pigment to 0.25 or less is achieved by sufficiently kneading the white pigment in the presence of a surfactant. It can also be obtained by removing the large particle component and the small particle component by utilizing centrifugation or the like.

The occupied area ratio (%) per unit area of the white pigment is most typically the adjoining observed area.
It can be obtained by dividing into unit areas of μm × 6 μm and measuring the occupied area ratio Ri (%) of the particles projected on the unit area. The variation coefficient of the occupied area ratio is obtained by the ratio S / R of the standard deviation S of Ri to the average value R of Ri (the number of target unit areas is preferably 6 or more).

The particle size of titanium dioxide is not particularly limited, but the one having an average particle size of 0.1 to 0.5 μm is preferably used. The thickness of the white pigment layer is not particularly limited, but usually, the wet film thickness is about 5 to 100 μm, and preferably 5 to 100 μm.
It is about 50 μm.

The total amount of white pigment used in the present invention is 3 to.
It is preferably 12 g / m ^2, in particular 4~10g / m ² is preferred.

The white pigment layer of the present invention preferably has a porosity of 5 to 30% by weight based on the hydrophilic colloid layer. The porosity can be obtained from the specific gravity, the film thickness and the like.

In the present invention, the average gradation between the minimum density (hereinafter referred to as Dmin) +0.2 to Dmin + 0.6 in the characteristic curve of the image obtained from at least one photosensitive layer is
It is preferably 2.2 or less, and the average gradation between Dmin + 1.0 and Dmin + 1.8 is 2.8 or more.

In the former case, the average gradation is the average gradation obtained when the point (a) at which the characteristic curve intersects Dmin + 0.2 and the point (b) at which the characteristic curve intersects Dmin + 0.6 are connected (A below). ,
In the latter case, the point (c) where the characteristic curve intersects Dmin + 1.0 and Dmi
It is defined as the average gradation (a) below obtained when the point (d) intersecting n + 1.8 is connected.

Average gradation A = 0.4 / | b−a | Average gradation B = 0.8 / | d−c | To adjust the gradation of the characteristic curve, any of the techniques well known in the art can be used. Well, for example, in terms of silver halide emulsion, grain formation, crystal wall, grain size, halogen composition,
Physical ripening, chemical ripening, sensitizing dyes, sensitizers, inhibitors, etc .; in terms of oils, couplers, high boiling organic solvents, various additives, DIR compounds, polymers, dispersion methods, etc .; or supports, gelatin, It is carried out by adjusting the film thickness of each photographic constituent layer such as a hardener and a surfactant, the amount of silver halide and an oil agent, the layer constitution and the like.

In the present invention, it is preferable that at least one hydrophilic colloid layer contains a fluorescent whitening agent. Examples of the fluorescent whitening agent used include, for example, Japanese Patent Application No. 2-102521, 18-
Examples include those described on page 23.

The composition of the silver halide photographic emulsion used in the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. It may be present, but silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. A silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

In order to obtain a silver halide emulsion, a silver halide emulsion having a portion containing silver bromide in a high concentration is particularly preferably used. In this case, the portion containing silver bromide in a high concentration may be either epitaxy bonded to the silver halide emulsion grains or a so-called core / shell emulsion, or may not form a complete layer and may be only partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion in which silver bromide is present at a high concentration is particularly preferably the apex of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion used in the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include:
Group VIII metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group II transition metals such as cadmium, zinc, and mercury; and lead, rhenium, molybdenum, tungsten, and chromium. Ions can be mentioned. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the above-mentioned heavy metal ions form a complex, the ligands thereof are cyan ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chlorine ion, bromine ion, iodide ion, carbonyl ion,
Ammonia etc. can be mentioned. Among them, cyan ion, thiocyanate ion, isothiocyanate ion,
Chlorine ion, bromine ion and the like are preferable.

In order to contain heavy metal ions in the silver halide emulsion, the heavy metal ions are added before the formation of silver halide grains, during the formation of silver halide grains and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added over the whole or part of the grain forming process.

The amount of the above heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
^-1 × 10 ^-2 mol is preferable, and 1 × 10 ^-8 -5 × 10 ^-5 mol is particularly preferable.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
No. 756, No. 4,225,666, JP-A-55-26589, JP-B-55-4
The octahedron, the dodecahedron, the dodecahedron, etc. by the method described in the literature such as No. 2737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (1973). It is also possible to make particles having the same shape and use them. Further, grains having twin planes may be used. As the silver halide grains, grains having a single shape may be used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains is not particularly limited, but considering other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm.
It is in the range of 1.0 μm.

The above-mentioned particle size can be measured by using a projected area of the particle or a diameter approximation value. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains used in the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0.15 or less. It is to add two or more kinds of the monodisperse emulsions in the same layer.

Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = standard deviation of grain size distribution / average grain size As used herein, the grain size means the diameter of a spherical silver halide grain, or the grain size of a cubic or non-spherical grain. It represents the diameter when the projected image is converted into a circular image of the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the present invention is
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

A device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Patent 2,921,164, etc., and taking out the reaction mother liquor from the reactor described in JP-B-56-501776 and the like, You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion may be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur. The addition amount of the sulfur sensitizer, it is preferable to change the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^{- It} is in the range of ⁵ mol, preferably 5 × 10 ^{-8 to} 3 × 10 ^-5 mol.

As the gold sensitizer applicable to the present invention, a salt is used.
To be added as various gold complexes such as hydrauric acid and gold sulfide
Can be. The ligand compound used is dimethyl
Rhodanine, thiocyanate, mercaptotetrazole,
Examples thereof include mercaptotriazole. Monetization
The amount of compound used depends on the type of silver halide emulsion and the type of silver halide used.
Depending on the type of compound, aging conditions, etc.,
Usually 1 x 10 per mol of silver halide^-Four~ 1 x 10^-8Mole
It is preferred that More preferably 1 x 10 ^-Five~ 1x
Ten^-8Is a mole.

A reduction sensitization method may be used as a chemical sensitization method for the silver halide emulsion.

The silver halide emulsion used in the present invention is known for the purpose of preventing fog occurring during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Antifoggants and stabilizers can be used. Examples of the compound used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column. (IIa described on page 8 of
-1) to (IIa-8), (IIb-1) to (IIb-7) compounds, 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5- Examples thereof include compounds such as mercaptotetrazole.

These compounds are added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose.

When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ^{-5 to} 5 × 10 5 per mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 x 10 per mol of silver halide
^-6 to 1 × 10 ^-2 mol is preferable, and 1 × 10 ^{-5 to} 5 × is preferable.
10 ⁻³ mol is more preferable. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide.
It is more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol.

The three-dimensional color light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Known compounds can be used as the above-mentioned spectral sensitizing dye, and as the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, alone or in combination. Can be preferably used. Examples of the green-sensitizing sensitizing dyes include GS-1 to GS-5 described on page 28 of the publication.
Further, as the red-sensitive sensitizing dye, R described in page 29 of the same publication is used.
S-1 to S-8 are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used. The dyes of IRS-1 to 11 described in No. 6 to 8 are preferably used. or,
Supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the same publication.
Is preferably used in combination with these dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. The sensitizing dye may be added as a solution by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a fine particle solid dispersion. May be.

As the coupler used in the three-dimensional color light-sensitive material of the present invention, any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Compounds can also be used, but as typical ones, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, a wavelength range of 600 The one known as a cyan coupler having a spectral absorption maximum wavelength at ˜750 nm is typical.

A cyan coupler which can be preferably used is represented by the general formula (C) described on page 17 of JP-A-4-114152.
-I) and couplers represented by (C-II) can be mentioned, and specific compounds are shown in pages 18 to 21 of the same publication as CC-1 to C-C.
It is described as C-9. As a magenta coupler which can be preferably used, JP-A-4-114152-12.
Examples thereof include couplers represented by the general formulas (M-I) and (M-II) described on the page.
Pp. 16 to MC-11 to MC-11. Among them, MC-8 to MC described on pages 15 to 16 of the publication.
-11 is preferable because it is excellent in the reproduction of colors from blue to purple and red, and is also excellent in the depiction of details.

Examples of yellow couplers which can be preferably used include couplers represented by the general formula (YI) described on page 8 of JP-A-4-114152.
Specific compounds are described in YC-1 to YC-9 on pages 9 to 11 of the publication.
It is described as. Among them, YC-8 and YC-9 described on page 11 of the same publication are preferable because they can reproduce yellow of a preferable color tone.

When the oil-in-water type emulsion dispersion method is used to add the coupler to the photographic emulsion layer, the boiling point is usually 150 ° C.
If necessary, a low boiling point and / or water-soluble organic solvent may be used in combination with the above water-insoluble high-boiling point organic solvent, and dissolved, and emulsified and dispersed in a hydrophilic binder such as a gelatin aqueous solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. A step of removing the low boiling point organic solvent may be added after or at the same time as the dispersion.

As the high boiling point organic solvent which can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used. In place of the method using a high-boiling point organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to give a hydrophilic binder such as an aqueous gelatin solution. It is also possible to employ a method of emulsifying and dispersing by various dispersing means using a surfactant therein. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

The compound (d-11) described in JP-A-4-114152, page 33, for the purpose of shifting the absorption wavelength of the coloring dye,
Compounds such as the compound (A′-1) described on page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in No. 187 can also be used.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention, but if necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or copolymer can also be used.

Dyes having absorption in various wavelength regions can be used in the light-sensitive material of the present invention for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but as the dye having absorption in the visible region, the dyes of AI-1 to 11 described on page 308 of JP-A-3-251840 are preferably used. As the infrared absorbing dye, the compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column have preferable spectral characteristics and are suitable for use in photographic emulsions. It is preferable because it does not affect the photographic characteristics and stains due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) described on page 3, lower left column to page 5, lower left column.

The light-sensitive material of the present invention may be directly or undercoated (adhesiveness, antistatic property, size of the support surface) after corona discharge, ultraviolet irradiation, flame treatment, etc. It may be applied via one or more undercoating layers) to improve stability, abrasion resistance, hardness, antihalation property, frictional properties and / or other properties).

At the time of coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

In order to form a photographic image using the light-sensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the light-sensitive material to be printed, After the image is once converted into digital information, the image may be imaged on a CRT (cathode ray tube), and the image may be imaged and printed on a photosensitive material to be printed. You may print by changing the intensity of light and scanning.

As the aromatic primary amine developing agent used in the development processing of the light-sensitive material of the present invention, known compounds can be used. The following compounds can be mentioned as an example of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD- 6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD- 8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-N -(β-Ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline In the present invention, a color developer is used. Can be used in the pH range of meaning, is preferably pH9.5~13.0 in view of rapid processing, preferably used in the range of PH9.8～12.0.

The processing temperature of the color developing solution is preferably 35 to 70 ° C. The higher the temperature, the shorter the treatment time is, which is preferable. However, it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment at 37 to 60 ° C. is preferable.

The color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less.
It is particularly preferable to carry out the treatment within 25 seconds.

To the color developing solution, a known developing solution component compound can be added in addition to the above color developing agent.
Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent and the like are used.

The photographic material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment.

The developing processing apparatus used for developing the light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank and conveyed, but the light-sensitive material is fixed to a belt. Although it may be an endless belt method of transporting by a process, a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and a photosensitive material is transported, and a spray method of spraying the processing solution, A web method by contact with a carrier impregnated with a treatment liquid, a method by a viscous treatment liquid, or the like can also be used.

Examples of the negative film unit for photographing used in combination with the light-sensitive material of the present invention include a film unit with a three-lens type stereoscopic photographic lens described in Japanese Patent Application No. 4-85614. In order to more effectively give a stereoscopic effect, it is more preferable to use a multi-lens unit having three or more eyes as a negative film unit for photographing to form a stereoscopic image rather than a twin-lens unit.

[0087]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Support) Sample-1: Transparent film having lenticular surface and PE
A support having a T (polyethylene terephthalate) film bonded thereto. The polyethylene was melt-rolled, further biaxially stretched, and then processed with a cooling roller to obtain a lenticular film as shown below.

Lenticular film thickness 220 μm Lenticle pitch 120 μm Lenticle radius of curvature 100 μm A normal PET film (thickness 100 μm) and the above lenticular film were bonded together by extruding molten polyethylene. The thickness of the finished lenticular support is 35
It was 0 μm.

Sample-2: Transparent film having a lenticular surface After polyethylene was melt-rolled and further biaxially stretched, the following lenticular film was obtained in the same manner as in Sample-1.

Thickness of lenticular film 350 μm Pitch of lenticle 125 μm Curvature radius of lenticle 105 μm Gelatin and a hardener (H-1) were previously coated on the side opposite to the lenticular surface of the support of Sample-1 above, and then A three-dimensional color light-sensitive material R1-1 was prepared by coating a silver halide emulsion in the layer structure shown in. The coating liquid was prepared as follows.

Unless otherwise specified, the addition amount of the compound is shown in g per 1 m ² of the light-sensitive material, and the silver halide emulsion and colloidal silver are in terms of silver.

(Preparation of dispersion) Yellow coupler (Y-
1) 26.7 g, dye image stabilizer (ST-1) 3.34 g,
(ST-2) 3.34 g, additive (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g were dissolved by adding ethyl acetate 60 cc and 15% surfactant (SU-1) 9.5 cc. A yellow coupler dispersion liquid was prepared by dispersing 220 cc of a 10% aqueous gelatin solution contained therein using an ultrasonic homogenizer. Magenta coupler (M-1), cyan coupler (C-1,
C-2) was also made into a dispersion by the same method. This (C-
1, C-2) dispersion was mixed with a red-sensitive silver halide emulsion (Em-R) described below to prepare a coating solution for the first layer.

The second to seventh layers were prepared in the same manner as the first layer. In addition, (H-1) in the second and fourth layers as a hardener
And (H-2) was added to the seventh layer. Further, as coating aids, surfactants (SU-2, SU-3) were added.

A coating solution for the sixth white pigment layer was prepared by adding a rutile type titanium dioxide paste solution to a gelatin solution, stirring the mixture with a homomixer, and adding a surfactant (SU-3). The average particle size of titanium dioxide was 0.35 μm, the coefficient of variation of the occupied area was 0.14, and the porosity was 17%.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 0.8 Stain inhibitor (HQ-2) 0.002 Stain inhibitor (HQ-3) 0.002 Stain inhibitor (HQ-4) 0.004 Anti-staining agent (HQ-5) 0.02 Compounds B, C, D and E 2 × 10 ^-5 colloidal silver 0.05 Hardener (H-2) 0.08 Antifungal agent (F-1) 0.002 6th layer (white pigment) Layer) Gelatin 2.5 Titanium dioxide 5.0 Surfactant (SU-3) 0.03 UV absorber (UV-1) 0.1 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Fifth layer (blue sensitive layer) ) Gelatin 2.6 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.6 Yellow coupler (Y-1) 1.4 Dye image stabilizer (ST-1) 0.5 Dye image stabilizer (ST-2) 0.3 Anti-stain ( HQ-1) 0.3 compound A 4 × 10 ^-4 fourth layer (intermediate layer) gelatin 1.2 irradiation Anti-dye (AI-3) 0.003 Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.03 Anti-stain agent (HQ-4) 0.03 Anti-stain agent (HQ-5) 0.20 Fluorescent whitening agent (W -1) 0.1 Hardener (H-1) 0.03 Third layer (green-sensitive layer) Gelatin 2.5 Anti-irradiation dye (AI-1) 0.015 Green-sensitive silver chlorobromide emulsion (Em-G) 0.25 Magenta coupler (M) -1) 0.7 Dye image stabilizer (ST-3) 0.4 Dye image stabilizer (ST-4) 0.2 Dye image stabilizer (ST-5) 0.2 Anti-staining agent (HQ-1) 0.02 Second layer ( Middle layer) Gelatin 1.2 Anti-irradiation dye (AI-2) 0.02 Anti-staining agent (HQ-2) 0.03 Anti-staining agent (HQ-3) 0.03 DIDP 0.06 Hardener (H-1) 0.02 First layer (red feeling) Layer) Gelatin 3.0 Red-sensitive silver chlorobromide emulsion (Em-R) 0.4 Coupler (C-1) 0.35 cyan coupler (C-2) 0.5 dye image stabilizer (ST-1) 0.4 stain inhibitor (HQ-1) 0.02 HBS-1 0.4 DOP 0.6 ultraviolet absorber (UV-1) 0.2 Ultraviolet absorber (UV-2) 0.2 Ultraviolet absorber (UV-3) 0.4 Support Lenticular support Sample-1 The structural formula of the compound used for each layer is shown below.

HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone Compound A: Quinone compound of HQ-1 Compound B: HQ -2 quinone compound C: HQ-3 quinone compound D: HQ-4 quinone compound E: HQ-5 quinone compound F: 1-hydroxy-2-bromo-4-aminoanthraquinone compound G: 2,4-Di (butylamino) anthraquinone DIDP: Diisodecylphthalate DOP: Dioctylphthalate DNP: Dinonylphthalate PVP: Polyvinylpyrrolidone HBS-1: 4-{(4-dodecylphenyl) sulfamoyl}
Toluene SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sodium di (2-ethylhexyl) sulfosuccinate SU-3: Di (1,1,2,2,3,3,4) sulfosuccinate , 4-Octafluorobutyl) sodium H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0098]

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[0099]

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[0100]

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[0101]

[Chemical 4]

(Preparation of blue-sensitive silver halide emulsion) In 1000 cc of a 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (solution C) and (solution D) to pAg
= 7.3, pH = 5.5, and simultaneous addition over 180 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water to make 200 cc (Solution B) Silver nitrate 10 g Water to make 200 cc (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water To 300 cc (D solution) 300 g of silver nitrate Add water to 600 cc After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate. A monodisperse cubic emulsion EMP-1 having an average particle size of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.0 mol% was obtained by mixing with an aqueous gelatin solution.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) Addition time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.0 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for Preparing Sensitive Silver Halide Emulsion) Addition Time of Solution A and Solution B and Solution C and Solution D
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.0 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB- 1: 1- (3-acetamido) phenyl-5-mercaptotetrazole

[0110]

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Next, in Sample R1-1, the optical reflection density according to the present invention is shown in Table 1 by increasing or decreasing the addition amount of the anti-irradiation dye used in the second layer, the third layer and the fourth layer. And the amount of titanium dioxide in the white pigment layer of the sixth layer was also changed as shown in Table 1.
1-17 were produced.

[0112]

[Table 1]

* 1: As the sample R1-15, a sample in which the variation coefficient (S / R) of the occupied area of titanium dioxide of the white pigment of the sixth layer of the sample R1-8 was 0.30 was used.

* 2: In samples R1-16 and R1-17, the addition amount of the fluorescent whitening agent in the fourth layer of sample R1-8 was 0.
It was changed to g / m ² and 0.2 g / m ² .

Using each of the samples thus obtained, the three-dimensional printing performance was evaluated as follows.

An outdoor scene of a woman having a resolution test chart / a scene in which a mountain landscape and a scene of flowers and trees in front of and behind the woman are the main subjects, and is described in Japanese Patent Application No. 4-85614.
Images were taken using a film unit with an eye-type stereoscopic photographic lens to create a stereoscope negative. The negative photosensitive material was developed by a usual developing method.

The stereoscope negative was made to match the image by a stretching machine with a mirror, and the above-mentioned photosensitive materials for three-dimensional printing were cut into sheets and printed with the lenticular surface facing upward. Each three-dimensional print photosensitive material was stored at 40 ° C. and 80% RH for 21 days, and was printed before being printed to show its storage resistance over time.

Each of the baked samples was processed in the following processing steps by an ordinary roller transport type automatic developing machine.

Processing process Temperature Time Replenishment amount Color development 38 ± 0.3 ℃ 22 seconds 81cc Bleach-fix 35 ± 0.5 ℃ 22 seconds 54cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 40 seconds Composition of developing solution is as follows. Shown in.

Color developing solution and replenisher tank solution Replenisher solution Pure water 800cc 800cc Diethylene glycol 10g 10g Potassium bromide 0.01g-Potassium chloride 3.5g-Potassium sulfite 0.25g 0.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate 6.0g 10.5g N, N-diethylhydroxylamine 3.5g 6.0g N, N-bis (2-sulfoethyl) hydroxylamine 3.5g 6.0g triethanolamine 10.0g 10.0g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter, tank liquid pH = 10.10, Adjust the replenisher to pH = 0.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 65 g diethylenetriamine pentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 cc 100 cc 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0g 1g Ammonium sulfite (40% aqueous solution) 50cc 25cc Add water to make the total volume 1 liter. Adjust the pH of the tank solution to 7.0 with potassium carbonate or glacial acetic acid, and adjust the pH of the replenisher to 6.5. To do.

Stabilizer tank and replenisher o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g fluorescence Whitening agent (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (25% ammonium hydroxide solution) 2.5 g Ethylenediaminetetraacetic acid 1.0 g Ammonium sulfite (40 % Aqueous solution) Add 10 cc water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The evaluation criteria are as follows.

<Sharpness> Each of the obtained three-dimensional photographs was visually evaluated for sharpness by visual inspection at a clear visual distance of 40 cm based on the comparative sample R1-1.
Was evaluated by 20 evaluators at intervals of 0.5 and the average score was obtained. The larger the value, the better the sharpness.

<Three-dimensional effect> Similar to the evaluation of the sharpness, the three-dimensional effect by visual inspection was visually evaluated, and R1-1 equivalent grade was set to 2.5 and evaluated by 20 evaluators in 0.5 increments, and the average thereof. I asked for a point. The larger the number, the better the three-dimensional effect.

<Whiteness> Each sample was processed in a cabinet size by an automatic processor without exposure to light, and the white background was measured with a color analyzer 607 (manufactured by Hitachi Ltd.).
* Calculated the value.

The larger the value, the better the whiteness.

The results are shown in Table 2.

[0129]

[Table 2]

As is clear from Table 2, the sample of the present invention was superior to the comparative sample in the sharpness of the print, and the three-dimensional effect was also improved more than expected.

It was an unexpected effect that not only the optical reflection density of the light-sensitive material was increased, but also the ratio of the optical reflection density in the respective wavelength regions of B, G and R had an influence on the stereoscopic effect.

Example 2 In the sample R1-1 of Example 1, the composition other than the emulsion layer was not changed at all, that is, the optical reflection density and the amount of titanium dioxide at each wavelength were the same, and the composition of each silver halide emulsion was the same. Samples R2-1 to R2-4 having average gradations as shown in Table 3 were prepared by varying only the chemical ripening method, the addition amount, and the addition amount of each coupler used.

Similarly, by changing the chemical ripening method and addition amount of the silver halide emulsion in the emulsion layer and the addition amount of each coupler to be used, the composition is exactly the same except for the sample R1-8 and the emulsion layer. Sample R2-having gradation as shown in Table 3
5 to R2-10 were also produced.

[0134]

[Table 3]

Three-dimensional prints were prepared from Samples R2-1 to R2-10 and Samples R1-1 and R1-8 of Example 1 by using the same stereoscope negative as Example 1 and in the same manner as in Example 1. The evaluation was performed. The results are shown in Table 4.

[0136]

[Table 4]

As is clear from Table 4, the characteristic curve of the light-sensitive material has an average gradation (a) between Dmin + 0.2 and Dmin + 0.6.
It was found that the effect of the present invention is exerted particularly when the average gradation (b) between Dmin + 1.0 and Dmin + 1.8 is 2.8 or more at 2.2 or less.

[0138]

The silver halide three-dimensional color photographic light-sensitive material of the present invention can easily provide a three-dimensional photographic image having good whiteness and excellent sharpness and three-dimensional effect.

Claims (5)

[Claims] 1. A silver halide three-dimensional color photographic light-sensitive material having a lenticular surface on at least one surface of a transparent support.
The optical reflection density at 680 nm is 0.80 or more, and
The ratio (B / A) of the optical reflection density (B) at 50 nm and the optical reflection density (A) at 680 nm is 0.3 to 0.7, and the optical reflection density (C) at 470 nm and the optical reflection density (A) at 680 nm are the same. ) And the ratio (C / A) is 0.2 to 0.6. 2. The average gradation between the minimum density +0.2 and the minimum density +0.6 in the characteristic curve of an image obtained from at least one light-sensitive layer of the silver halide three-dimensional color photographic light-sensitive material is 2.2 or less. , And minimum density + 1.0 to minimum density +
The silver halide three-dimensional color photographic light-sensitive material according to claim 1, wherein the average gradation between 1.8 is 2.8 or more. 3. A silver halide three-dimensional color photographic light-sensitive material having a layer containing a white pigment in a layer farthest from a transparent support or a layer adjacent to the transparent support, and the total amount of the white pigment used is 3 to 12.
The silver halide three-dimensional color photographic light-sensitive material according to claim 1, which is g / m ² . 4. A silver halide three-dimensional color photographic light-sensitive material having a layer containing a white pigment in a layer farthest from a transparent support or a layer adjacent to the transparent support, and a coefficient of variation of an area occupied by particles of the white pigment is 0.25 or less. 2. The silver halide three-dimensional color photographic light-sensitive material according to claim 1, wherein 5. The silver halide three-dimensional color photographic light-sensitive material according to claim 1, wherein at least one layer of the silver halide three-dimensional color photographic light-sensitive material contains a fluorescent whitening agent.