JPH086221A - Silver halide stereoscopic photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a highly stereoscopic image appreciable from the distance farther than the least distance of distinct vision by rendering the lenticle pitch of a transparent support larger than a specified value. CONSTITUTION:The silver halide stereoscopic photographic sensitive material has the repeating structure of the lenticles at least on one side of a transparent support and at least one silver halide emulsion layer on the other side, and the lenticle pitch on the transparent support is enlarged to >=300mum, and at least one of the emulsion layers contains a magenta coupler in an amount of >=0.30g/m<2>. The lenticles are a group of small convex lenses arranged 2- dimensionally or 3-dimensionally like fly eyes in the upper necessary limit of the pitch of >=300mum, preferably, >500mum in order to exhibit its effect more effectively, and especially, >700mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide three-dimensional photographic light-sensitive material, and more particularly to a silver halide three-dimensional photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) having an excellent three-dimensional effect.

[0002]

2. Description of the Related Art Conventionally, several methods for obtaining a stereoscopic image have been proposed. Among them, a stereoscopic photographic print having a lenticular sheet is excellent in convenience because it can be viewed directly without using a special device. ing. Among three-dimensional photographic prints having a lenticular sheet, there are many proposals for a method of laminating a lenticular film again after printing is made from a silver halide photographic light-sensitive material. However, if the silver halide photographic light-sensitive material is subjected to development processing after the exposure and then re-bonding with the lenticular film, the positional deviation and the working process become complicated, which poses a serious problem in practical use. There is also a method in which after forming a stereoscopic image on the lenticular sheet, the reflection support is attached to the opposite side of the lenticular sheet, but this method is also inferior in simplicity because it requires an extra attachment work step. It is easy for dirt to be disturbed. Therefore, in the method of applying a photosensitive layer on one surface of a support having a lenticular, and further providing a hydrophilic colloid layer containing titanium oxide, peeling and laminating of the lenticular film and the reflective support as described above are unnecessary. However, there is an advantage that displacement is unlikely to occur and a three-dimensional print can be formed relatively easily.

With such a technique, it has become possible to easily obtain a three-dimensional photographic image. On the other hand, as a method of viewing a three-dimensional image, it is desired to display a three-dimensional image on a large screen and view it from a distance from the image. There is a request. However, with conventional 3D printing, the clear visual distance (30
It has been found that there is a problem in that the stereoscopic effect is excellent when viewing from a cm to 60 cm), but the stereoscopic effect is lost when viewing from a long visual distance (1 m to 5 m from the image).

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a silver halide three-dimensional photographic light-sensitive material capable of obtaining a three-dimensional image in which an image having an excellent three-dimensional effect can be viewed from a long visual distance. It is in.

[0005]

The above object of the present invention can be achieved by the following constitutions.

1. In a silver halide three-dimensional photographic light-sensitive material having a lenticular repeating structure on at least one surface of a transparent support and at least one silver halide emulsion-containing layer on the opposite surface, the pitch of the lenticle of the transparent support is Silver halide 3D photographic light-sensitive material characterized by a size of greater than 300 μm 1. ^{2. The} silver halide three-dimensional photographic light-sensitive material as described in 1 above, wherein at least one silver halide emulsion-containing layer contains a magenta coupler and the magenta coupler content is 0.30 g / m ² or more. 3. The silver halide three-dimensional photographic light-sensitive material as described in 1 or 2 above, which has a hydrophilic colloid layer containing a white pigment. The silver halide three-dimensional photographic material described in 1, 2, or 3 above, wherein the pitch of the lenticule is larger than 500 μm. The present invention will be described in more detail below.

In the present invention, a transparent support having a lenticular repeating structure on at least one surface means a lenticle on at least one surface of the transparent support.
It is a transparent film in which small convex pitches called “icle” are repeatedly arranged. The lenticle is a small lens group in which small convex lenses are arranged in a kamaboko shape, that is, in a two-dimensional shape or a fly-eye shape, that is, in a three-dimensional shape.

In the present invention, the support may be formed by laminating a lenticular film having a convex lenticular surface with a polymer base usually used in a color film, or a lenticular film having a convex lenticular surface (hereinafter referred to as lenticular film). It may be used alone.

The lenticular film used in the present invention is prepared 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) polystyrenes (polystyrene, butadiene.styrene resin) polyvinyl chlorides, polyvinylidene chlorides, polyesters, polymethacrylates and the like.

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

In the present invention, the upper limit of the pitch of the lenticle is required to be larger than 300 μm, and in order to exert the effect of the present invention more effectively, it is preferably larger than 500 μm, and more preferably larger than 700 μm. Particularly preferred.
The upper limit of the pitch of the lenticle is not particularly limited and can be selected according to the size of the image used, but usually 30
It is preferable that the size is smaller than 00 μm because the image is less disturbed.

The upper limit of the thickness of the lenticular film is
The thickness of the support alone (total thickness of the supports in the case of a bonded type) is preferably 500 μm or less. More preferably, it is 300 μm or less. The lower limit of the thickness is preferably 150 μm or more. The thickness of the lenticular film is preferably determined so that the light of each wavelength of the image exposure is substantially focused on the silver halide photosensitive layer. Therefore, the thickness is determined by the refractive index of the lenticular film and the curvature of the lenticular lens. If it exceeds 500 μm, it is difficult to wind it during coating and drying, and if it is 150 μm or less, it is difficult to put it into practical use.

The lenticular has a refractive index of 1.50 or more and 1.65.
The following is preferable, and 1.53 or more and 1.58 or less are more preferable.

In the present invention, in order to exert the effect of the present invention more effectively, the radius of curvature of the lenticular lens is
It is preferable to make it less than 2.0 times the pitch of the lenticle.
It is more preferably 1.0 times or less, further preferably 0.8 times or less. It is particularly preferably 0.6 times or less. The radius of curvature of the lenticular lens is 0 of the lenticular pitch.
It is preferable to make it 5 times or more so that the image is not disturbed. It is also possible to mix a plurality of types of lenticular lenses having different radii of curvature.

Further, different repeating patterns having a small lenticle pitch may be mixed in the repeating structure of the lenticle pitch of the present invention.

As the transparent film to be bonded to the lenticular film used in the present invention, polyethylene terephthalate or the like usually used in photographic light-sensitive materials can be used.

In the present invention, it is preferable to have a hydrophilic colloid layer containing a white pigment in order to exert the effects of the present invention. It is preferable that the hydrophilic colloid layer containing a white pigment is added to a layer farthest from the support, as compared with a layer farthest from the support containing a silver halide emulsion, because an image having a good three-dimensional effect can be obtained. Further, it is preferable to provide a non-photosensitive layer farther from the white pigment layer with respect to the transparent support and add a coloring dye or pigment to the layer in order to improve the three-dimensional effect.

As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. Among the colorants, colloidal silver is preferable because of its excellent three-dimensional effect. The transmittance of the hydrophilic colloid layer containing colorant is 50
% Or less is preferable, and 30% or less is particularly preferable.

The white pigment used in the hydrophilic colloid layer (hereinafter referred to as the white pigment layer) containing the white pigment of the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, Alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable among them for various reasons. The white pigment is dispersed in a water-soluble binder of hydrophilic colloid such as gelatin so that the treatment liquid can permeate, and applied as a white pigment layer. Coating with the amount of white pigment, preferably in the range of ^{0.5g / m 2 ~50g / m 2} , more preferably in the range of ^{1g / m 2 ~20g / m 2} .

The white pigment may be produced by surface treatment with an inorganic substance such as hydrous alumina treatment, hydrous silicon dioxide treatment or zinc oxide treatment, or surface treatment with an organic substance such as trimethylolmethane, trimethylolethane or trimethylolpropane. A treated product or a siloxane-treated product such as polydimethylsiloxane is appropriately used. Other than 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.

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 is obtained from the specific gravity, the film thickness and the like.

It is particularly preferable that the coefficient of variation of the occupied area, which indicates the dispersity of the white pigment of the present invention, 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 silver halide photographic light-sensitive material is dissolved with a proteolytic enzyme and the resulting white pigment is photographed with an electron microscope. 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 using centrifugation or the like. The occupied area ratio (%) per unit area of the white pigment is most typically the observed area is divided into contiguous unit areas of 6 μm × 6 μm, and the occupied area of particles projected on the unit area. It can be determined by measuring the ratio (%) (Ri).
The coefficient of variation of the occupied area ratio (%) is the average value (R) of Ri.
Can be obtained by the ratio S / R of the standard deviation S of Ri with respect to. The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation S / R is

[0023]

[Equation 1]

It can be determined by

The addition ratio of the white pigment in the white pigment layer of the present invention is preferably 20% by weight or more, more preferably 40% by weight, in order to enhance the three-dimensional effect and the whiteness. More preferably, 50% by weight or more is most preferable. Further, if the addition ratio of the white pigment is too large, the white pigment layer is easily peeled off by pressure or the like. Therefore, the addition ratio of the white pigment is preferably 90% by weight or less, more preferably 90% by weight or less, and most preferably 80% by weight or less because of the effect of reducing film peeling.

The amount of the white pigment of the white pigment layer of the present invention is three-dimensional effect, in terms of enhancing the whiteness, 4.0 g / m ² or more, more 7.5 g / m ² or more is more preferable.

Further, it is preferable that the hydrophilic colloid layer containing the white pigment of the present invention contains hollow polymer particles because the effect of the present invention is great. Hollow polymer particles are those in which the inside of the polymer particles is not a polymer but a cavity. This is more preferable because the fine particles of bubbles can be stably present and the light reflectance can be improved. The average particle size of the hollow polymer particles is preferably 0.1 μm to 1.0 μm. As a material for the hollow polymer, a highly crosslinkable polymer is preferable in order to maintain cavities. As the hollow polymer, for example, a hollow polymer of styrene-acrylic resin manufactured by Nippon Synthetic Rubber Co., Ltd. can be used.

The hydrophilic colloid layer containing the white pigment of the present invention contains a high-boiling organic solvent having a boiling point of 300 ° C. or higher and /
Alternatively, it is particularly preferable to add a water-insoluble organic polymer from the viewpoint of improving curling, stereoscopic effect and whiteness. The high boiling point organic solvent and / or the water-insoluble organic polymer more preferably has a vapor pressure at 100 ° C. of 0.5 mmHg or less.

Any of the constituent layers of the light-sensitive material of the present invention,
It is also preferable to add an oil-soluble dye and / or a colored pigment that is not substantially decolorized by the treatment because the whiteness is improved.

The gradation of the image formed by the present invention can be freely set in each density range as needed, but a relatively high contrast is preferable because it provides a three-dimensional effect in hyperopia.

The sum of the amounts of gelatin contained in the light-sensitive material of the present invention (the sum of gelatin in all hydrophilic colloid layers (including white pigment layer and protective layer) coated on the support) is the effect of the present invention. In order to exert the above effect, it is preferably 12.0 g / m ² or less, and further preferably 10.0 g / m ² or less. Most preferably, it is 8.5 g / m ² or less. A preferred embodiment has a hydrophilic colloid layer containing at least one white pigment and has a total gelatin amount of 12.0 g / m ² or less, further 10.0 g /
It is more preferably m ² or less. The lower limit is preferably 3 g / m ² or more in order to suppress the decrease in physical strength of the film. The amount of gelatin is measured by the moisture measurement method described in the Paggy method.
It is calculated in terms of the weight of gelatin containing 11.0% water.

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. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. The present invention is a technique relating to characteristics during exposure, and it is preferable to use it in combination with a technique capable of obtaining stable characteristics during processing. From this viewpoint, it is preferably 97 mol% or more, more preferably 98 to 99.9 mol. Silver halide emulsions containing% silver chloride are preferred.

To obtain the silver halide emulsion used in the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide 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 partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion where 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 purpose include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and the like VIII
Examples thereof include group metals, group II transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. 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 heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to add a heavy metal ion to the silver halide emulsion used in the present invention, the heavy metal ion is added before the formation of silver halide grains and during the formation of silver halide grains.
It may be added at any place in each step during physical ripening after the formation of silver halide grains. 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 during the whole or part of the grain forming process.

The amount of the heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly preferably 1 × 10 ⁹ mol / mol of silver halide.
^It is preferably ^-8 mol or more and 5 × 10 ^-5 mol or less.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.
Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55
-26589, Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J.Photogr.Sci.)
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared by the method described in the literature such as 21, 39 (1973) and the like, and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
Although grains having a single shape may be used, it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains used in the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, more preferably 0.2 to 1.0 μm. The particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The particle 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 emulsion 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 = S ₁ / R ₁ (where S ₁ is the standard deviation of the grain size distribution and R ₁ is the average grain size.) The grain size as used herein means that of spherical silver halide grains. In the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having 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.

Further, 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 as described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. 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 and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the present invention is
A sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer can be used in combination.

As the chalcogen sensitizer applied to the silver halide emulsion used in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used.
Sulfur sensitizers are preferred. As the sulfur sensitizer, thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine and inorganic sulfur. The addition amount of the sulfur sensitizer used in the present invention is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × per mol of silver halide.
The range is 10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
The range of × 10 ^-5 mol is preferable.

As the gold sensitizer used in the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanate, mercaptotetrazole,
Examples thereof include mercaptotriazole. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization method of the silver halide emulsion used in the present invention may be a reduction sensitization method. The silver halide emulsion used in the present invention is for the purpose of preventing fogging that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fogging that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A No. 2-146036, page 7, lower column, and specific examples thereof include , (IIa-1) to (IIa-8), (IIb-1) to (IIa-1) described on page 8 of the publication.
The compound of (IIb-7) or 1- (3-methoxyphenyl) -5-
Mercaptotetrazole, 1- (4-ethoxyphenyl) -5-
Examples thereof include compounds such as mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide
An amount of about mol is preferable, and 1 × 10 ⁻⁵ mol to 5 × 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 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 ×
More preferably, it is 10 ⁻⁵ mol 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 mol to 1 × 10 ⁻³ mol.

The silver halide photographic light-sensitive material of the present invention comprises
Dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as a dye having absorption in the visible region, JP-A-3-
The dyes of AI-1 to 11 described on page 308 of Japanese Patent No. 251840 are preferably used.
General formula (I) described in the lower left column of page 2 of 280750 publication,
The compounds represented by the formulas (II) and (III) have preferable spectral characteristics and are preferable because they have no influence on the photographic characteristics of the silver halide photographic emulsion and there is no contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

As the amount of these dyes added, the spectral reflection density at 680 nm of an untreated sample of a normal silver halide photographic light-sensitive material is high. In terms of color variability, it is favorable and preferable. The spectral reflection density at 680 nm of silver halide photographic light-sensitive materials currently on the market is usually 0.8 or more, but in the present invention, it is preferably low, and 0.70 or less is preferable. More preferably, it is 0.50 or less.

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

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used, but as the blue-sensitive sensitizing dye, JP-A-3-251840. BS-1 to 8 described on page 28 can be preferably used alone or in combination. As the green-sensitive sensitizing dye, GS described on page 28 of the same publication
-1 to 5 are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. Further, when performing image exposure with infrared light such as using a semiconductor laser, it is necessary to use an infrared-sensitive sensitizing dye, as the infrared-sensitive sensitizing dye,
IRS-1 described in JP-A-4-285950, pages 6 to 8
The dyes of to 11 are preferably used. Further, the same publications 8 to 9
The supersensitizers SS-1 to SS-9 described on the page are 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. As a method of adding a sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be added as a solution by dissolving in water-miscible organic solvent such as dimethylformamide or water,
It may be added as a solid dispersion.

The coupler used in the silver halide three-dimensional photographic light-sensitive material of the present invention forms 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. Although any compound that can be used can be used, as a particularly typical example, 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 typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide three-dimensional photographic light-sensitive material of the present invention include:
General formula (CI) described in JP-A-4-114152, page 17,
The coupler represented by (C-II) may be mentioned.
Specific compounds are described in CC-1 to CC on pages 18 to 21 of the patent.
Those listed as -9 can be mentioned.

As the magenta coupler which can be used in the present invention, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm can be used, and examples thereof include 5-pyrazolone type couplers and pyrazoloazole type couplers. Can be done.

As the magenta coupler which can be preferably used in the silver halide three-dimensional photographic light-sensitive material of the present invention, the general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds are described in M on page 13 to 16 of the above patent.
Mention may be made of those described as C-1 to MC-11. Among them, MC-8 to MC-11 described on pages 15 to 16 of the above-mentioned patent are preferable because they are excellent in the reproduction of colors from blue to purple and red and are excellent in the depiction of details.

The magenta coupler according to the present invention is 0.30 g.
/ M ² or more coating amount is preferable, and 0.40 g
/ M ² or more is preferable.

As a yellow coupler which can be preferably used in the silver halide three-dimensional photographic light-sensitive material of the present invention, a yellow coupler described in JP-A-4-114152, page 8 can be used.
The couplers represented by I) can be mentioned. Specific compounds are described in YC-1 to YC on pages 9 to 11 of the patent.
Those listed as -9 can be mentioned.
Among them, YC-8 described on page 11 of the above patent,
YC-9 is preferable because it can reproduce a preferable yellow color.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide three-dimensional photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that 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, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. At this time, the water-insoluble organic solvent-soluble polymer used is poly (Nt-
Butyl acrylamide) and the like.

The compound (d-1) described on page 33 of JP-A-4-114152 is used for the purpose of shifting the absorption wavelength of the color forming dye.
1), compounds such as the compound (A'-1) described on page 35 of the patent can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide three-dimensional photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The silver halide three-dimensional photographic light-sensitive material of the present invention is, if necessary, subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the support surface, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a silver halide three-dimensional photographic 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.

To form a photographic image using the silver halide three-dimensional photographic light-sensitive material of the present invention, the image recorded on the negative is optically formed on the silver halide three-dimensional photographic light-sensitive material to be printed. The image may be formed and printed, or the image may be converted into digital information and then the image may be displayed on a CRT.
An image may be formed on a (cathode ray tube), and this image may be formed on a silver halide photographic light-sensitive material to be printed and printed, or scanning is performed by changing the intensity of laser light based on digital information. You may bake it.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples 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, the above is a color developer. Can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, and more preferably pH 9.8 to 12.0.

The processing temperature of the color developing solution used in the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment time is, which is preferable, but it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C or higher and 60 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less.
It is even more preferable to perform the treatment within a range of 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 development inhibitor such as chloride ion and benzotriazole, a preservative,
A chelating agent or the like is used.

The silver halide three-dimensional photographic light-sensitive 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, as a substitute for the washing treatment, a stabilizing treatment may be performed. The development processing apparatus used for the development processing of the silver halide three-dimensional photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the above-mentioned light-sensitive material sandwiched between rollers arranged in a processing tank, It may be an endless belt method in which the photosensitive material is fixed and conveyed, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is conveyed, and the processing solution is sprayed. It is also possible to use a spray method for forming a shape, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like.

As the negative film unit for photographing used in the present invention, for example, the film unit with a three-lens type stereoscopic photographic lens described in Japanese Patent Application No. 4-85614 is used. In order to make the stereoscopic effect more effective, it is more preferable to use a multi-lens unit having three or more eyes as the negative film unit for photographing to form a stereoscopic image.

[0076]

The present invention will be described in detail 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 stuck thereto was melt-rolled, polyethylene (refractive index 1.54) was further biaxially stretched, and then processed with a cooling roller to obtain a lenticular film as shown below.

Thickness of Lenticular Film 120 μm Pitch of Lenticle 100 μm Curvature Radius of Lenticle 100 μm A normal PET film (thickness 100 μm) and the above lenticular film were extruded with molten polyethylene and bonded together.

Gelatin 0.1 g and hardener (H-1) 0.1 g were previously prepared on the side opposite to the lenticular surface of the support sample-1.
And a silver halide emulsion having the layer structure shown below were coated to prepare a three-dimensional color light-sensitive material RT-1. Unless otherwise specified, the addition amount of the compound is shown in g per 1 m ² of the light-sensitive material. The silver halide emulsion and colloidal silver are equivalent to silver.

(Preparation of dispersion) Yellow coupler (Y-
1) 23.4 g, dye image stabilizer (ST-6) 5.01 g, dye image stabilizer (ST-1) 3.34 g, dye image stabilizer (ST
-2) 3.39 g, dye image stabilizer (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.33 g, high boiling organic solvent (DNP) 2.34 g, high boiling organic solvent (DBP) 2.67 g Add 60 ml of ethyl and dissolve, 15% surfactant (SU
-1) A yellow coupler dispersion was prepared by dispersing 220 cc of 10% gelatin aqueous solution containing 9.5 cc using an ultrasonic homogenizer.

For the second to seventh layers, each coating solution was prepared in the same manner as the first layer so that the coating amounts were as follows. Further, (H-1) and (H-2) were added as a hardener. Further, as coating aids, surfactants (SU-2, SU-3) were added to adjust the surface tension. The total amount of F-1 in each layer is 0.04g
/ M ² was added.

The coating solution for the white pigment layer of the sixth layer was prepared by adding a paste solution of surface-treated rutile-type titanium dioxide to a gelatin solution and stirring with a homomixer to prepare a surfactant (S
After adding U-3), an anti-irradiation dye (AI-
1, 2, 4) etc. were added and prepared.

The average particle size of titanium dioxide was 0.35 μm, and the variation coefficient (S / R) of the occupied area was 0.14. Further, gelatin E (iron content 2.5 ppm) of each layer was used.

Layer composition Addition amount (g / m ² ) Eighth layer (protective layer) Gelatin 0.8 DIDP 0.005 Anti-stain agent (HQ-2) 0.002 Anti-stain agent (HQ-3) 0.002 Anti-stain agent (HQ-4) ) 0.004 Anti-staining agent (HQ-5) 0.02 Colloidal silver 0.05 Silicon dioxide 0.003 7th layer (white pigment layer) Gelatin 2.5 Titanium dioxide 5.0 Surfactant (SU-3) 0.03 Anti-irradiation dye (AI-1) 0.05 b Anti-radiation dye (AI-2) 0.05 Anti-radiation dye (AI-4) 0.02 UV absorber (UV-1) 0.1 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 LP 0.50 6th Layer (Blue-sensitive layer) Gelatin 1.20 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.52 Yellow coupler (Y-1) 1.40 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-6) 0.1 5 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) 0.01 DBP 0.08 DNP 0.07 Fifth layer (intermediate layer) Gelatin 1.20 DIDP 0.06 Stain inhibitor (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 Anti-irradiation dye (AI-3) 0.01 Fluorescent whitening agent (W- 1) 0.1 4th layer (green-sensitive layer) Gelatin 1.30 Anti-irradiation dye (AI-1) 0.01 Green-sensitive silver chlorobromide emulsion (Em-G) 0.28 Magenta coupler (M-1) 0.40 Dye image stabilizer ( ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Third layer (intermediate layer) Gelatin 0.94 Anti-irradiation dye (AI-2) 0.02 Anti-staining agent (HQ-5) 0.10 UV protection (UV-1) 0.28 UV inhibitor (UV-2) 0.09 UV inhibitor (UV-3) 0.38 Second layer (red sensitive layer) Gelatin 1.30 Red sensitive silver chlorobromide emulsion (Em-R) 0.41 Cyan coupler ( C-1) 0.50 Cyan coupler (C-2) 0.16 Dye image stabilizer (ST-1) 0.10 Anti-staining agent (HQ-1) 0.004 HBS-1 0.4 DOP 0.34 First layer (UV absorbing layer) Gelatin 0.40 UV Absorber (UV-1) 0.12 Ultraviolet absorber (UV-2) 0.04 Ultraviolet absorber (UV-3) 0.16 PVP 0.03 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-tetradecyl hydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone DIDP: diisodecyl phthalate DOP: dioctyl phthalate DBP: dibutyl phthalate DNP : Dinonyl phthalate 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 LP: Liquid paraffin No150-S (Sanko Chemical Co., Ltd. ST-6: p- (t) -octylphenol

[0086]

Embedded image

[0087]

Embedded image

[0088]

[Chemical 3]

[0089]

[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 Add water to make 200 cc (Solution B) Silver nitrate 10 g Add 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 above 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) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, 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) (solution A) and (B)
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of 0.08, and a silver chloride content of 99.0 mol% was obtained.

For EMP-3, the following compounds were used.
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

[0098]

[Chemical 5]

The sample thus obtained is called sample 101. Next, in Sample 101, the same samples as Sample 101 were prepared except that the lenticular pitch, the radius of curvature, and the thickness of the lenticular film were changed as shown in Table 1.

The three-dimensional printing performance was evaluated using each of the samples thus obtained.

The negative photosensitive material used was Konica Color XG100 and Konica Color Professional SRG160 film, which are already well known in the art, and a camera with a five-lens lens was used. A stereoscopic negative was created by taking a photograph of a scene with flowers and trees in front of and behind the mountains and a woman in the distance. The negative photosensitive material was developed by a usual developing method.

Images of this stereoscope negative were matched by a stretcher with a mirror, and each sample was cut into a sheet and baked with the lenticular surface facing upward.

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 81ml Bleaching fixing 35 ± 0.5 ℃ 22 seconds 54ml Stabilization 30-34 ℃ 60 seconds 150ml Dry 60-80 ℃ 40 seconds Composition of developing solution is as follows. Shown in.

Color developing solution and replenishing solution Tank solution Replenishing solution Pure water 800 ml 800 ml Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g 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.
Adjust to 10 and replenisher to pH = 10.60.

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 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make a total volume of 1 liter, and adjust the pH of the tank solution to 7.0 with potassium carbonate or glacial acetic acid and the pH of the replenisher to 6.5. To do.

Stabilizer tank and replenisher Orthophenylphenol 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 enhancement 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 aqueous solution) 2.5 g Ethylenediaminetetraacetic acid 1.0 g Ammonium sulfite (40% Aqueous solution) Add 10 ml water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

Each of the obtained three-dimensional photographs was examined at a clear viewing distance of 3 m.
In, the three-dimensional effect by visual inspection, according to the following evaluation criteria,
Evaluation was performed by 10 evaluators (compared with a normal plane photograph of the same scene created separately), and the average score was obtained.

1; Same level as ordinary plane image photograph 2; Fairly good 3; Good 4; Excellent 5; Especially excellent Table 1 shows the obtained results.

[0110]

[Table 1]

As is clear from Table 1, as compared with the comparative sample,
With the sample of the present invention, a good stereoscopic image excellent in stereoscopic effect in hyperopia was obtained.

Example 2 The same samples 201 to 207 were prepared as the sample 106 of Example 1 except that the changed items shown in Table 2 were changed.

Using these samples and Samples 101 and 106 of Example 1 using the same stereoscope negative as in Example 1, evaluation of formation of a three-dimensional print was performed in the same manner as in Example 1. Table 2 shows the results.

[0114]

[Table 2]

As is clear from Table 2, in the sample of the present invention, a good stereoscopic image excellent in stereoscopic effect in hyperopia was obtained as compared with the comparative sample.

[0116]

INDUSTRIAL APPLICABILITY The silver halide three-dimensional photographic light-sensitive material according to the present invention can obtain a three-dimensional image in which an image having an excellent three-dimensional effect can be viewed from a long visual distance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 7/14 7/38

Claims (4)

[Claims] 1. A silver halide three-dimensional photographic light-sensitive material having a lenticular repeating structure on at least one surface of a transparent support and at least one silver halide emulsion-containing layer on the opposite surface thereof. A silver halide 3D photographic light-sensitive material, characterized in that the pitch of the body lenticle is larger than 300 μm. 2. The silver halide according to claim 1, wherein at least one silver halide emulsion-containing layer contains a magenta coupler, and the magenta coupler content is 0.30 g / m ² or more. 3D photographic light-sensitive material. 3. The silver halide three-dimensional photographic light-sensitive material according to claim 1, which has a hydrophilic colloid layer containing a white pigment. 4. A silver halide three-dimensional photographic light-sensitive material according to claim 1, 2 or 3, wherein the pitch of the lenticle is larger than 500 μm.