JPH0488338A - Manufacture of stereoscopic color photographic recording material - Google Patents

Abstract

PURPOSE:To coat the multilayers incorporating an image forming layer on a supporting base providing a lenticule on a rear side simultaneously and continuously by using a specified flexible supporting base. CONSTITUTION:In a manufacturing method of a stereoscopic color recording material having a substantial repeating structure of lenticule L0 at the rear side of the transparent flexible supporting base B and on the other hand, being applied a forming layer C of yellow, magenta and cyan images on the surface of the supporting base B, the flexural rigidity of the flexible supporting base B; E.I value = EXbXd<3>/12 is 10kg.cm<2>. Besides, such a step is included that on the surface of the supporting base, plural layers incorporating at least one layer of the image forming layer are substantially applied simultaneously and are dried. In formula, E is a coefficient of flexural elasticity of the supporting base with the lenticule, I is a secondary moment of a web cross-section, (b) is a length of the supporting base with being held with a transfer roller, and (d) is the average thickness of the supporting base. Hence on the supporting base providing the lenticule at the rear side, the plural layers incorporating the image forming layer are applied simultaneously and continuously.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a three-dimensional color photographic recording material that easily and quickly provides high-quality stereoscopic color photographic prints at low cost, stably and with high productivity. This invention relates to a manufacturing method that enables substantially continuous and integrated production.

(Prior art) Euclid (
Euclid) pointed out that ``a sense of perspective is created by the parallax between the two eyes.''Especially in the 17th century, improvements have been made.
Page) (Published by Corona Publishing, January 1987).

How to make photo prints with lenticular sheets,
In particular, there are several descriptions of how to make lenticular sheets and how to attach lenticular sheets to photographic prints. For example, U.S. Patent No.
No. 918705, No. 2726154, No. 375125
No. 8, No. 3960563, No. 4037950, No. 4
No. 806407, JP-A-49-29640, JP-A No. 62-
No. 6245, and Japanese Patent Publication No. 58-48890.

There are many methods for photographing, printing, or projecting displays using the lenticular method. For example, U.S. Pat. No. 3,852,787, U.S. Pat.
No. 869, No. 4059354, No. 4132468,
No. 4650282, No. 4766684, No. 4852
No. 972 and Japanese Patent Publication No. 53-33847.

However, there is a method for making the lenticules provided on the lenticular sheet finer, for example, by setting the pitch to about 130 μm or less to achieve high image quality, and for simultaneously connecting multiple layers using the lenticular sheet as a support. ! ! There is no specific description of methods for printing, methods for increasing the quality of color photographs that can be viewed stereoscopically, and reducing costs.

(Problem R to be solved by the present invention) Conventionally, special cameras, so-called stereo cameras, have been used to take stereoscopic photographs, but they are expensive and, despite this, the color obtained with these cameras is - Photographic prints obtained by printing from negative originals using the lenticular method had poor image sharpness, and the image quality was poor in color unevenness such as color shift and poor texture.

Conventionally, color photographic materials for printing with lenticular sheets have a thick lenticular pitch of 130 μm or more (and the thickness of the photographic material including the support is also thick; for example, the thickness of the support alone is usually around 700 μm). It was difficult and the image quality was poor.

Even if the pitch of the lenticles is set to 130 μm or less, if the structure is the same as that of a conventional color photographic photosensitive layer, the image sharpness will be poor, and the three-dimensional effect will be impaired and the image quality will deteriorate.

Furthermore, since the support was thick, simultaneous multilayer coating was extremely difficult, and productivity was also extremely low.

Therefore, an object of the present invention is, firstly, to have a substantially repeating structure of lenticules on the back side of a transparent flexible support;
Another object of the present invention is to provide a method for producing a high-quality three-dimensional color photographic recording material in which multiple layers including at least one color image forming layer can be simultaneously and continuously applied to the surface of the support.

The second object is to provide a color photographic print that has high image quality, is inexpensive, and can be viewed stereoscopically as easily as a normal color print.

(Means for Solving the Problems) The present inventors analyzed the factors contributing to the high image quality of 3D color photographs, and researched the factors that enable stable and continuous integrated production.
It has been found that various aspects of the present invention can be effectively achieved by the following manufacturing method.

(1) A three-dimensional color photographic recording material having a substantially repeating structure of lenticules on the back side of a transparent flexible support, and yellow, magenta, and cyan image forming layers applied on the other side of the support. In the manufacturing method, the bending rigidity E-1E・I value of the flexible support described above = EXbXd''/12 (where E is the bending elastic modulus of the support with lenticules, The width of the support held by the conveyance roller (d means the average thickness of the support) is 0.2 to 10 kg-cm, and at least one layer is formed on the surface of the support. 1. A method for producing a three-dimensional color photographic recording material, comprising the steps of substantially simultaneously applying and drying a plurality of layers including an image forming layer.

(2) The frictional resistance between the back surface of the support and the surface of the support or the surface of the image forming layer that comes into contact during the manufacturing process of the three-dimensional color photographic recording material is 0°2 to 0.9.
The method for producing a three-dimensional color photographic recording material according to the preceding item (1).

The present invention will be described in detail.

The term lenticle in the present invention refers to small convex lenses, which are arranged densely on the back surface of the support in the present invention in a semicylindrical or fly's-eye shape with a substantial repeating structure. be. "Substantially" means that the pitch, radius of curvature, etc. of the lenticule in the central and peripheral parts of the observation west surface can be modified. It is also possible to reduce aberrations by modifying the curved surface of the lenticule to be non-circular or aspheric.

In the present invention, by increasing the total thickness of the support, the direct image resolution is increased, and high-quality stereoscopic color images can be easily viewed.

One embodiment of the image forming layer in the present invention is a color image fixing layer used in a dye diffusion transfer system (for example, the one described in Japanese Patent Application No. 2-151854), and another embodiment is a color coupler. a silver halide photosensitive layer containing, for example, a blue-sensitive layer (BL) containing a yellow coupler,
These include a green sensitive layer ((,L) containing a magenta coupler and a red sensitive layer (RL) containing a cyan coupler.

The lenticle of the present invention can be used in each photosensitive layer during printing, especially in G.
The radius of curvature is set so as to focus on L and RL, and more preferably, so as to focus on the image forming layer during observation. Such radius of curvature exists in the thickness of the support and the thickness of the undercoat layer and its refractive index. In order to reduce the thickness of the support, it is necessary to use a material with a high refractive index for the support and to reduce the radius of curvature. In order to keep the aperture angle of the lenticule small and reduce blur caused by aberrations, it is preferable to reduce the pitch of the lenticule. The pitch of the lenticule depends on the convergence angle required of the lenticule.

Therefore, the radius of curvature of the lenticule, the pitch, and the thickness of the support are determined so that distinct images are reproduced for the left and right eyes of the person viewing the lenticule, and the image forming layer and each photosensitive layer are Sufficient sharpness is required to distinguish between images.

The total thickness of the support having a lenticule structure in the present invention (not including the undercoat layer for applying the hydrophilic colloid layer) is approximately 300 mm. The pitch of the lenticule is preferably 13 μm or less, preferably 250 μm or less, more preferably 100 μm to 250 μm (all average thickness).
It is 0 μm or less, more preferably about 120 μm or less, and even more preferably 8θ to 100 μm. Further, the radius of curvature of the lenticule is preferably about 1100a or less.

The resolution of the three types of silver halide photosensitive layers, especially the GL and RL, on the support according to the present invention is
A silver halide photosensitive layer group or an image forming layer group having a layer structure of 12 layers/layer or more, preferably 15 layers/layer or more, and further 18 layers/layer or more in terms of value (20%) is preferably provided.

The above-mentioned MTF value refers to the amplitude modulation transfer function that is widely used.
ge 5science, Academic P
ress), 241-2, London, 1974.
This is an evaluation value of sharpness obtained by the method detailed on page 43.

In order to improve image quality, yellow, magenta and cyan image forming layers or BL, GL and RL silver halide photosensitive layers are preferably disposed on the support within about 1111 m, more preferably within 10 μm, even more preferably. 9μm
When printing a color original, the image is preferably focused within this relatively narrow film thickness.

In particular, the magenta and cyan image forming layers are within 8 μm,
More preferably, the thickness is within 7 μm.

Preferably, an antihalation layer is provided above any one of the yellow, magenta and cyan image forming layer units. The antihalation layer is obtained by incorporating a coloring agent having spectral absorption in a wavelength range overlapping with the spectral sensitivity distribution of the intermediate layer adjacent to the image forming layer (above the support). Preferably, the colorant is fixed in the hydrophilic colloid layer.

Examples include colloidal silver, water-soluble dyes, and dyes dispersed in solid fine particles. Patent application Hei 2-94121
The dyes and mordants described in the specification are used. Colloidal silver is preferably used in an amount of about 0.02 g/if to 0.35 g/nf.

In the present invention, during the printing process, each photosensitive layer is aligned and easily focused, and during observation, the image seen by the left eye and the image seen by the right eye are distinguished, resulting in a strong three-dimensional effect, and the effect of preventing Halley's silane. It can be effectively expressed and the sharpness of images can be improved.

The bending stiffness of the flexible support, which is important in achieving the purpose of the present invention, is a measure of the so-called "back strength" of the support.
It is expressed as an E-1 value. As defined earlier, ■ is the moment of inertia of the cross section of the web of the support having a lenticule structure, but in the present invention, I is considered to be a beam, and b
It can be estimated as x d”/12 (for this, refer to the Japan Society of Mechanical Engineers, “Mechanical Engineering Handbook”, Part A4, Chapter 2, Mechanics of Materials (published April 15, 1986)).

In achieving the purpose of the present invention more efficiently, the bending stiffness is
1.0 to 4.1 kg-d is more preferable.

Also, the surface of the support having the lenticle structure of the present invention is static against steel balls! The friction coefficient is preferably 0.1 or more, more preferably 0.2 or more.

Furthermore, the coefficient of friction between the back surface of the support having a lenticule structure of the present invention and the surface of the support that comes into contact with it during the manufacturing process or the surface on the image forming layer side is particularly important, and is preferably 0.2. ~0.9.

The coefficient of friction can be determined according to ASTM standard D324B-73 (tilt method). Specifically, one surface to be measured is set on a horizontal table, and a 80m x 3 surface is placed on it.
Another surface to be measured of the 7 cabinets was placed on it, a load of 200 g was applied thereto, the horizontal table was tilted, and the coefficient of static friction was measured.

Further, the transmittance of the material itself constituting the support used in the present invention is preferably 70% or more. Furthermore, the surface of the lenticule is coated with an anti-reflection treatment (for example, a single layer or multiple layers such as a vanadium oxide film or a magnesium fluoride film is coated so that the optical thickness of the film corresponds to 174 wavelengths (λ) of the irradiating light). etc.) should be applied.

Furthermore, as a lenticule, the surface pressure is preferably 2
It is preferable to use a material that can withstand at least 4 kg/d, more preferably 4 to 5 kg/d.

The tensile strength of the support is preferably 5 kg/m or more, more preferably 8 to 20 kg/m.

The various embodiments of the present invention described above are capable of producing three-dimensional color photographic recording materials, particularly three-dimensional color photographic silver halide light-sensitive materials, stably and with high productivity, and furthermore, can be developed with high quality and stably. This is important for obtaining three-dimensional color photographic silver halide light-sensitive materials.

In order to satisfy the various characteristics of the present invention, it is preferable to use a support that is a composite of a lenticule-forming material and a material to be held in the image forming layer.

The support according to the invention has a refractive index of 1 in transparent visible light.
．． It is composed of more than 40 resins, and is best made by molding or calendering using a thermoplastic resin.Other methods include injecting a liquid upper layer into a mold and causing a polymerization reaction to turn it into a resin. It can also be made by hot melting and molding resins. The resins used in the present invention include polyolefins, especially polyethylene, polypropylene, polystyrenes, such as boristythrene, acrylonitrile, butadiene, styrene, resins, etc. P-xylylenes, polyacrylates, polymethacrylates, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl ethers, polyethers, polycarbonates, polyesters (e.g. polyethylene terephthalate and polybutylene terephthalate) etc.), polyacids, polyurethanes, etc., and the term "class" here means to include homopolymers and copolymers.

More specifically, for example, U.S. Pat.
No. 5494, No. 3484403, No. 3419408
British Patent No. 1133224, Special Publication No. 4, etc.
No. 6-41116, No. 47-14952, JP-A-62
The method described in, for example, No.-6245 is used.

On the one hand, the support of the present invention has properties compatible with lenticules, that is, high transparency, refractive index, scratch resistance, and heat resistance.
It also satisfies the thermoplastic properties that make it easy to form, and also satisfies the stiffness, tensile strength, and coefficient of friction (ease of conveyance and winding) as a support for a silver halide photosensitive layer. For this reason, a composite film composed of at least two types of resin films is used as a preferred support.

For example, lenticular sheets are made of polypropylene, polyacrylate, polymethacrylate, polystyrene, polyurethane, etc. as lenticular materials, and sheets made of polyethylene terephthalate, polystyrene, cellulose acetate, etc. as materials for carrying color images. and laminated with a solvent-free adhesive.

Other methods for joining lenticular sheets, such as:
Methods described in JP-A-62-6245, JP-A-49-29640, JP-B-5B-48890, JP-A-248654, etc. can also be used.

For bonding the lenticular sheets of the present invention, it is preferable to use a hot melt adhesive, a polycondensed trapezoidal adhesive, or a solvent-free adhesive. Polyvinyls, polyurethanes, polyacrylate emulsions, etc. are used.

The refractive index of the lenticule forming material is determined by ASTM test method D54.
2, which affects the thickness and curvature of the lenticule.For example, it is preferably 1.48 or more and stable. Examples of such materials include polypropylene (refractive index 1.49) and polystyrene (refractive index 1.59 to 1.59).
60), polyurethane (1.50-1.60), high-density polyethylene (refractive index 1.54L acrylic resin or methacrylic resin (refractive index 1.50-1.58), etc.).

The surface of the support, which has a repeating lenticule structure on the back, can be treated with flame treatment, plasma treatment, corona discharge treatment,
It is preferable to provide an undercoat layer after modification treatment such as oxidation treatment, ultraviolet irradiation treatment, and bleed heat treatment.

The support with lenticules according to the present invention is preferably provided with a convex portion on the edge by knurling or embossing, which not only prevents the web from unwinding or deforming the web, but also has the following features: It is useful for physically protecting the lenticule and for eliminating adverse photographic effects such as pressure increase/decrease due to the lenticule in the image forming layer, especially the silver halide emulsion layer. The height of the unevenness of the lenticule according to the present invention is preferably 5 μm to 30 μm, and the height of the protrusion forming portion is preferably about 20 μm to 100 μm.

Conventionally, when using the support with a lenticule according to the present invention,
This is a major improvement over the manufacturing method in which lenticular sheets were coated layer by layer, allowing multiple layers to be coated in succession substantially simultaneously, followed by drying, winding, or cutting into sheets.

The above-mentioned "capable of coating continuously at substantially the same time" means that at least two layers can be consistently coated on a continuously conveyed web, dried and rolled up, or cut to a predetermined size. means.

For example, “Research Disclosure Magazine” RDNc
Description of Chapter W of No. 30B119 (Research Dis
closure volume 308, December 1989 issue), or U.S. Patent Nos. 2,761,791 and 32,063.
Simultaneous coating can be performed by the method described in No. 23, No. 3508947, No. 4297396, No. 4490418, etc. It can also be dried and rolled up by the method described in British Patent No. 1.207°222.

It is more preferable to apply means for reducing sliding friction resistance to the back surface of the support or to the protective layer, especially in the present invention, to the protective layer.As these means, a substance that improves specific sliding properties (slip agent) is used. methods, and particulate matter (
There is a method of making the surface uneven using a matting agent), but any of these methods may be used as long as the coefficient of friction between the two surfaces is 0.90 or less.

Examples of the slip property improving substance present on the surface of the photosensitive material used in the present invention include U.S. Pat.
Organosilicon compounds typified by polydimethylsiloxane described in No. 4,047,958, etc.
Higher fatty acids and their salts described in U.S. Patent No. 2.976.148, higher fatty acid amides described in U.S. Patent No. 2,732.305 and U.S. Patent No. 4.275.146,
U.S. Patent No. 3,121,060, Japanese Patent Publication No. 49-462
No. 58, Special Publication No. 50-40664, Special Publication No. 57-90
57, Japanese Patent Publication No. 58-33541, and esters of higher fatty acids or higher aliphatic alcohols, as well as paraffins described in U.S. Patent Nos. 3,786,002 and 9.779771. , wax, etc. are preferably used. Among these, organic silicon compounds, esters of higher aliphatic acids, or esters of higher aliphatic alcohols are particularly preferred.

Examples of preferred compounds used in the present invention are shown below.

Useful silicone polymers include, for example, trialkyl and trialkoxy endblocks, dialkylpolysiloxanes such as dimethylpolysiloxane, diethylpolysiloxane, trimethoxy endblock, dimethylpolysiloxane and triethoxy endblock,
Contains commercially available silicone oils such as dimethylpolysiloxane.

These silicone compounds have a molecular weight of 162 to 15
0,000, preferably from 10,000 to 20,000, and the viscosity is from 2 to 100,000 centistokes, preferably from 200 to 800 centistokes at 25°C.

The following can be mentioned as representative examples of compounds of general formula (1).

H2 -CJw Polydimethylsiloxane (I (OCH,CH+T(OCHICI!h-(JR'R'
, (If) Examples of compounds represented by general formulas (II), (II-1), and (I[-2) include the following.

(OCHgCHz) 5OH x+y+z±30 (II-1) (OCHICHI)IlIOc489 Here, R represents a hydrocarbon group having at least one double bond and having 18 to 23 carbon atoms, preferably 21 to 23 carbon atoms. , R2 and R3 each have a hydrogen atom or a carbon number of 1
~4 lower alkyl group.

The hydrocarbon group represented by R1 may be linear or branched, but preferably linear.

Examples of R8 are C21H41, C23Ha+, etc.

Examples of R,,R, are CH3, C, Hl, C3H&,
CaHq etc.

Among the compounds represented by the general formula (I[[], specific examples of representative compounds are shown below.

■-1 Erucic acid amide m-2 Erucic acid-N-methylamide ■-3 Erucic acid-N-ethylamide m-4 Ceracoleic acid-N-methylamide ■-5 Ceracoleic acid-N,N-diethylamide x+y 10z=40 CH ,0COR.

R, cooRs (V) CHOCOR.

(IV) CH20COR.

Specific compound examples of the compound represented by general formula (IV) include (IV-1) CHxOCOC+oHz+(n)CH
OCOC,. )(z+(b) CHl OCOC+oHz+(n) As a specific compound example of general formula (V), n C+1
HzvCOOC+, Hs+(”) (V 1)n
C+sHs+C00C4Hsx(n) (V
2) n-C+1HttCOOCzoHat(n)
(V-3)n-C+sHi+C00CzoHn+(n
) (V-4) CH,0R (IV-2) CH,0COC,, Hl3(n)R
a 0CHZ CCHz OR*CH,OR.

(Vl) CHOCOC++Hz, (n) CHz 0COCzHzx (n) CH20COC+sHs+ (n) CHOCOC+sHs+ (n) CH20COC+sHs+ (n) Specific compound examples of general formula (Vl) include CH, 0)
l Haset+C00C)lx-C-C)lzOcOc+
sFh+CHzOCOC+SH31(Vl 1
)CHz-OCOC++Hzs Hz3C+ +C00CHz-C-CLOCOC+ +
HtsC1(zOcOc+IH23 (Vl-2) CHzOCOC+Jzv Hs+C+5C00CIh-C-CI(tOcOc+5
FIx+C1(zOcOc+ Jz7(Vl 3)
These compounds can be used alone or in combination. In addition, various other additives can be added to improve the dispersibility of these compounds or to make them easier to apply, and it is preferable to add additives suitable for each system.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iod)chlorobromide, silver iodobromide, etc. can be used, but especially for the purpose of rapid processing, silver iodide can be used substantially. It is preferable to use silver chlorobromide or silver chloride milk which has a silver chloride content of at least 90 mol %, more preferably at least 95 mol %, particularly at least 98 mol %.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277.589A2 together with a coupler.

Particularly preferred is the combination with a pyrazolozole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

Furthermore, in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and cause image deterioration, the light-sensitive material according to the present invention is added with an anti-mildew agent as described in JP-A No. 63-271247. It is preferable to do so.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the photosensitive material of the present invention, and processing methods and processing materials applied to process this sensitive material. As additives, the following patent publications, especially European Patent EP0.355.660A2 (Japanese Patent Application No. 1-1999)
07011) are preferably used.

In addition, as a cyan coupler, in addition to the diphenylimidazole cyan coupler described in JP-A No. 2-33144, the cyan coupler described in European Patent EP 0,333.185A2
-Hydroxypyridine-based cyan couplers (among them, the 4-equivalent coupler listed as a specific example, coupler (42), with a chlorine leaving group to make it 2-equivalent, and couplers (6) and (9) are preferred for poetry) and Japanese Unexamined Patent Publication No. 64-322
60 (including the cyclic active methylene cyan couplers listed as specific examples 3.8.
34 is particularly preferred).

Next, an example will be described.

Example 1-1 (Creation of support with lenticules) Sample - ■ Polypropylene was melt-rolled, further stretched to make it transparent, and then heated and processed using an embossing roller and a rolling roller to form the following material. Obtained lenticular film.

Lenticular film thickness: 85 μm Lenticular pitch: 100 μm
Radius of curvature of lenticule・・・・・・・・・・・・・・・
After ozone treatment of the surface of 80 μm polyethylene terephthalate (PET) film (thickness 101001I),
A transparent support with lenticules was obtained by melt-coating polyethylene and laminating the polypropylene lenticular film on the surface opposite to the surface on which the lenticules were provided. After the surface of the support was subjected to a corona discharge treatment, a gelatin undercoat treatment was performed.

The polyethylene adhesive layer thickness was 45 μm.

Sample - (1) Polymethyl methacrylate was melt-rolled and further heat-processed using an embossing roller and a rolling roller to obtain the following lenticular film.

L/7 Chikyura film thickness...100μm
Lenticle pitch・・・・・・・・・・・・・・・
...Radius of curvature of 100μm lenticule...
・・・・・・・・・ 85 μm PET film (thickness 100
μm) and the lenticular film, and between them, a molten film of polyethylene-methyl acrylate copolymer was injected and bonded, so that the total support thickness was 250 μm.
It was laminated so that it became m. After the surface of the support was subjected to a corona discharge treatment, a gelatin undercoat treatment was performed.

Sample A (for comparison) Using polymethyl methacrylate, the pitch of the lenticule is 300 μm, and the radius of curvature of the lenticule is 310 μm.
, a sheet with a thickness of 0.70 mm was created.

A PET film (thickness: 200 um) was adhered to the surface opposite to the surface having the lenticule using an epoxy adhesive side to obtain a support having a thickness of approximately 0.91 m.

Sample B (for comparison) A support with a lenticule having the following configuration was obtained with reference to the example of JP-A-62-6245.

Polyethylene was melted and extruded at about 310°C onto a PET film (thickness 254 μm), further cooled,
Further, a molten polypropylene was extruded and coated, and immediately after that, pressure was applied using an embossing roll to form a lenticule on the surface, followed by cooling.

The sum of the thicknesses of polyethylene and polypropylene is approximately 152
The pitch of the lenticule is 140 μm, and the radius of curvature of the lenticule is approximately 100 μm. Each characteristic of the support was as shown in Table 1.

"Transmittance of support material" in Table 1 refers to the visible light transmittance of a sheet or film that is made of the same material as the support, has the same average thickness, and is not provided with a lenticule.

(Preparation of light-sensitive material sample by lenticular photo viewing method) Magenta coupler dispersion; 10 g of magenta coupler (ExM), 1 color image stabilizer (C
0.6g of pd-2), 6g of color image stabilizer (Cpd-3)
゜0g, color image stabilizer (Cpd-4) 0.3g, color image stabilizer (Cpd-8) 0.8g, color image stabilizer (Cpd-
9), 20°Og of solvent (Solv-2) and 25d of ethyl acetate were mixed and dissolved at 50°C, and this solution was dissolved in 20% sodium dodecylbenzenesulfonate 11
Added to 158d of 20% gelatin aqueous solution mixed with paper,
The mixture was stirred at high speed using a homogenizer to obtain an emulsified dispersion.

Cyan coupler dispersion: 13.5 g of dye stabilizer (Cpd-7), 10 g of cyan coupler (ExC), 5 g of color image stabilizer (Cpd-6)
5g of solvent (Solv-6) and 20i of ethyl acetate were mixed and dissolved at 50°C.
% sodium dodecylbenzenesulfonate (21d) and stirred at high speed using a homogenizer to obtain an emulsified dispersion.

Yellow coupler dispersion; 19°1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1) and (Cpd-7)
27.2 cc of ethyl acetate and solvent (S
4.1 g each of Solv-3) and Solv-6 were added and dissolved, and this solution was emulsified and dispersed in 135 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

(How to make a silver halide emulsion) Emulsion BL-1i Silver chlorobromide emulsion (silver bromide content 70 mol%, cubic, average grain size 0.65 μm, coefficient of variation 0.08, and average grain size 0.52 μm) , coefficient of variation o,.

6 in a ratio of 1=3 (Ag molar ratio) and sulfur sensitized.

Sensitizing dye S-1 was added and adsorbed in an amount of 5.0×10 −' mol per mol of silver.

1-(5-methylureidophenyl)-5-mercaptotetrazole per mole of silver halide, 4.0X
10-mol of Hatake, and 2-methyl-5-tert-octylhydroquinone was added in an amount of 8X10-' mole per mole of silver halide, and 4-hydroxy-6-methyl-1,3,3
a, 7-chitrazaindene at 1 mole of silver halide
．． 2X10-' moles were added.

Similarly, RL-1, GL-1, BL-2, RL-2
, CL-2 silver chlorobromide emulsion was obtained.

Table 1 shows the composition of each silver chloride emulsion.

As the gelatin hardening agent for each layer, 1-oxy-3°5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used for each emulsion.

Blue-sensitive emulsion (BL-1 and BL-2) (S-1) (CHz) a (CHz) 4sOJ ' N (CJs) 303e (5°0 x 10 4 mol per mol of silver halide) Green-sensitive emulsion ( GL-1 and GL-2) 503eSOzH'N(CJs)s (4.0゜0XIO-' mol) Red-sensitive emulsions (RL-1 and IIL-2) zl15 C5) II+ (0゜9XIO-' mol per mol of silver halide) For red-sensitive emulsions, the following compounds are halogenated. silver 1
2.6×10 −″ moles were added per mole.

There are also blue-sensitive emulsions (BL-1 and BL-2), green-sensitive emulsions (GL-1, GL-2), and red-sensitive emulsions (RL-1 and R
For L-2), 1-(5-methylureidophenyl)
-5-mercaptotetrazole, 4.0XIO-' mol, 3.0 x 10 mol, respectively, per mol of silver halide. , 0XIO-' moles and 2-methyl-5t-octylhydroquinone were added in amounts of 8X10-" moles and 2X10-" moles per mole of silver halide, respectively.

In addition, 4-hydroxy-6-
1.2 x 10 mol of methyl-1,3,3a, 7-titrazaindene per 1 mol of halogenated tli, respectively;
1. 1×10-” moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and a total of 8 layers listed in Table 3 on the support sample ①,
It was applied in two batches using a slide bead type multilayer simultaneous continuous coating machine as shown in Figure 1 of JP-A No. 61-174,970 (however, five slots are provided). , simultaneous sequential multilayer coating followed by drying and rolling. On the other hand, for Support Sample I, it was possible to apply eight layers in succession simultaneously, dry and roll up.

As will be described later, with respect to comparative support samples A and B, it was not possible to install and coat them on the multilayer simultaneous continuous coater described above.

Regarding support sample B for comparison, it was not possible to apply multiple layers at the same time as it was, so a photosensitive material was created by applying multiple layers in the same way as PET film, and then adhered to a lenticular sheet using an epoxy adhesive. As a result, a lenticule-attached sample B-1 having the same layer structure as the multilayer coating on the support sample B was obtained.

The results of the production are summarized in Table 2.

Table 3 shows sample 11kL11 (12), floor 101 (Ni
1102), except that "
→” means the same as on the left.

(Cpd-1) Color Image Stabilizer (Cpd) Color Image Stabilizer (Cpd-3) Each color image stabilizer shows the chemical structure of the compound used to prepare a sample of a color photosensitive material.

(Cpd Color image stabilizer 0M tt (Cpd Color mixture prevention agent 0■ υn (cpa 6) Color image stabilizer (Cpd Color image stabilizer C1 (Cpd-7) Color image stabilizer 1←CH2 CH→1- (uV Ultraviolet light Absorbent CON HCa H9('') Average molecular weight 80,000 I (So'l Sea 4) 4:2:4 mixture of solvents (weight ratio) (Solv-5) Solvent (Solv-1) Solvent C00CsH17 (CHz)s COOCIHI7 (Solv-6) Solvent (Solv-2) Solvent CsH+vCHCH(CHZ)+C00C1H+t\1 (Solv-7) 2:1 mixture of solvents (weight ratio) (ExY) 1:1 mixture of yellow coupler ans (mole ratio) (ExM) 1:1 mixture of magenta coupler (molar ratio) CJ+5(n) Table 4 In Sample 11, the amount of gelatin used in the third and fifth layers was increased as shown in Table 4 to increase the film thickness to 11 Comparative sample 11a was obtained by setting the thickness to .2 μm.

On the other hand, in sample 101, as shown in Table 4, the amount of gelatin used in the second to fifth layers was reduced to make the film thickness 8.4.
Sample 103 was obtained as μm. Sample 104 was obtained by increasing the amount of colloidal silver in the eighth layer, which is an antihalation layer, to 0.20 g/rrt.

In Sample 11a, instead of the 8th protective layer, an anatase type surface treated with aluminum oxide was used in accordance with the series 8th layer (reflective layer) in Example-1 of U.S. Patent No. 3,751,258. A gelatin dispersion of titanium oxide (primary average particle diameter of about 0.11 Im) was coated in such a manner that the coating amount of gelatin was 2 g/rrr and the coating amount of titanium oxide was 4 g/nf.

Sample 105 was obtained by providing a similar reflective layer on the eighth layer of sample 104, which obtained sample 11b (comparison).

Example-2 In photosensitive material sample N11ll, sample Nn1lc was prepared without adding liquid paraffin (slip agent) and polyvinyl-alcohol-acrylic variable copolymer from the protective layer (eighth layer).
Samples 13 to 17 were prepared using the slipping agents and matting agents shown in Table 5.

The coefficient of static friction between the back surface of the obtained photosensitive material sample and the surface on the image forming layer side was measured.

The results are shown in Table 5.

Table 5 A method for preparing a coating solution containing a slipping agent for a protective layer is shown below.

<Preparation of aqueous dispersion of slip agent> Solution E Gelatin aqueous solution 7% 50ml 1 IC
The solution and D solution were mixed and emulsified at a pressure of 250 kg/rrf using a pulp type homogenizer manufactured by Manton-Gaulin to obtain an O/W type fractional dispersion. At this time, the particle size of the dispersion in the gelatin aqueous solution was 0. Control it so that it is 8μ. Ei was added to the obtained dispersion, water was added, and 80 m
This is finished to form an aqueous slip agent dispersion, and this is added to the coating solution for the protective layer.

<Preparation of aqueous dispersion of matting agent> Add 5% sodium dodecylbenzenesulfonate aqueous solution 10I11 to 100 Jd of 10% gelatin aqueous solution, and heat at 45°C.
While stirring vigorously while maintaining the
After the dispersion is completed by stirring vigorously with a homogenizer for 0 minutes, the ethyl acetate is distilled off by heating. A matting agent having an average particle size of 3.5 μm is obtained.

Example-3 (Creation of original color negative using a color photosensitive material packaging unit with twin lenses) The manufacturing method described in JP-A-64-544 and Utility Model Application Nos. 2-16507, 2-16508, and 1983 2-
No. 16509, No. 2-16510, No. 2-16511
A color photosensitive material packaging unit with a binocular lens was prepared according to the description in each specification of the No. 1, but with the configuration changed as follows.

It has a first storage chamber in which unexposed photosensitive film is wound and stored in advance, and a second storage chamber in which it is wound and stored in a cartridge after photographing, and two openings having the same optical system are provided between them. The optical system includes a photographing lens with a focal length of 34 mm, an aperture with an aperture value (F value) of 11, and a shutter speed of 1.
/100 second lens/shutter is certified, and the regulating surface of the photosensitive surface of the photosensitive film is set to be an arc with a radius of curvature of 125 degrees. The distance between the optical axes of the two optical systems was 62 degrees. The shutter button is linked to the two optical systems, and the take-up knob is common, moving approximately 1051 degrees for each frame taken and then remaining fixed. The finder was placed approximately in the center of the two optical systems.

The photographing distance of this optical system was from infinity to close range 1 m.

The photographing optical system for creating the color original used in the present invention has a deep depth of field, and is preferably a pan-focus system.

Fuji Color Super HG400 film (trade name, manufactured by Fuji Photo Film Co., Ltd.) was cut into 135 size pieces and wound up to a length of 1201 mm so that 10 frames could be taken.

Using this color photographic light-sensitive material packaging unit equipped with a twin-lens photographing function, photographs were taken in the following manner to obtain a color negative original. I took photos outdoors under clear skies, with trees in the foreground and mid-distance, a woman sitting at a table at a height of about 3.6m, and flowers (red, yellow, white, etc.) while keeping the camera level.

After the photo was taken, the film was wound up and removed from the packaging unit together with the cartridge, and standard color development was performed using a Fuji Photo Film ■ minilab Champion 23S model to obtain original prints.

(Printing and development of stereoscopic photographs) From the original color negative for printing mentioned above
Using a stereoscopic photo enlarger with a mechanism similar to that shown in Figure 4 of Specification No. 33847, the screen size is 117 x 82.5 cm and the clear viewing distance is about 30 CI+ through the lenticule. Each sample was printed as follows.

Samples 11.12, B-1, 11-a, and 11-b were subjected to the following color development process-1, and samples 101-1
02.103.104.105 was developed by the following color development process-2.

Color development process-1! Melon - once u Color development 37°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 24-34°C 3 minutes drying 70-80'' The composition of the C1 pollution treatment solution is as follows.

Left: Former 1-part water diethylene triamine pentaacetic acid nitrilotriacetic acid benzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate hydroxyl Amine sulfate optical brightener (WHITEX 4B Add water to pH (25℃) Ammonium thiosulfate (70%) 00d 1, Og 2, 0g 5d 0I11 2, Og 1, Og 0g 4, 5g 3.0g 000d 10.25 001d 50d Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (II) Ammonium 55g Ethylenediaminetetraacetic acid disodium
5 Add water and make 1000d
pH (25°C) 6.70 Color development process-2 Shirikomame 1 degree Mitsuke Ill” 9 ■ Kasagakura color development 35°C 45 seconds 161d l?!
Bleaching 30-35℃ 45 seconds 2151d
l? ffi rinse■ 30-35℃ 20 seconds -10ffi rinse■ 30-35℃ 20 seconds -lOl rinse■ 30-35℃ 20 seconds
-10ffi drying 70-80℃ 60 seconds
The replenishment amount of 3501d0 was equivalent to 1 of the photosensitive material (a 3-tank countercurrent system was used from rinsing ■ to ■). The composition of each processing solution was as follows.

Hidachi Nikodoshi l Hill LIL Hill Sumimitsu Hill Water
800 Jd 80
0d Ethylenediamine-N, N N, N-tetramethylenephosphonic acid 1.5 g 2.0 g Triethanolamine 8.0 g 12.0
g Sodium chloride 1.4 g Potassium carbonate 25 g 25 g N-ethyl-
N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 7.0gN,
N-bis(carboxymethyl)hydrazine 5.5g 7.0g Fluorescent whitening (WHI TEX 4 B).

, 0.0 Add water 1oood 1000
dpH (25°C) 10.05 10.
451n constant I hill (tank fluid and refill fluid are the same) water
400d ammonium thiosulfate (70%) 100d sodium sulfite 17g ethylenediaminetetraacetic acid iron (drunk) Ammonium 55g ethylenediaminetetraacetic acid disodium 5g Add ammonium water to 1000dpH (2
5℃) 6.0 1-λ spray (tank liquid and replenisher liquid are the same) Ion exchange water (calcium and magnesium are each app
- Below) In the case of sample B-1, using a treatment liquid with a predetermined composition,
This was done using a hanging type developing machine.

The photo print that can be viewed in 3D is patented in Japanese Patent Application No. 276972.
The sample was bonded to the high whiteness support WP-3 used in Example 1 of the specification, and observed in a bright room at about 600 lux.

The results are shown in Table 6.

(1) By using supports I and (2) of the present invention, which have an E-1 value of 10 kg-cd or less, multilayer coating can be performed simultaneously.

On the other hand, as long as support samples A and B were used, simultaneous multilayer coating was extremely difficult or impossible with the slide bead type multilayer AT fabric according to the present invention.

(2) The photosensitive material provided with the Halley silane prevention layer has excellent three-dimensional effect and sharpness, especially when the distance between the image forming layers is 10
．． Those with a diameter of 0μ or less, especially 9.6μ or less, were particularly excellent in both three-dimensional effect and sharpness.

(3) The photosensitive material according to the present invention could be subjected to color development using a sea urchin-knob transport type automatic developing machine.

(Effects of the present invention) The production method of the present invention not only allows multiple layers including an image forming layer to be simultaneously and continuously coated on a support provided with a lenticule on the back surface, but also Three-dimensional color photographic recording materials, particularly three-dimensional color photographic silver halide light-sensitive materials, can also be used in web conveyance automatic processors.

The three-dimensional color photographic silver halide light-sensitive material obtained by the present invention is unprecedented and can provide three-dimensional color photographic prints with excellent detail and image sharpness.

[Brief explanation of the drawing]

FIG. 1a is a schematic cross-sectional view of a three-dimensional color photographic silver halide light-sensitive material in which an image forming layer unit is provided on the surface of a transparent support having a lenticule structure on the back surface, and FIG. FIG. 3 is an enlarged view of an image forming layer unit.

Claims (2)

[Claims] (1) A three-dimensional color photographic recording material having a substantially repeating structure of lenticules on the back side of a transparent flexible support, and yellow, magenta, and cyan image forming layers applied on the other side of the support. In the manufacturing method, the bending rigidity E・I value of the flexible support E・I value=E×b×d^3/12 (where E is the bending elastic modulus of the support with lenticules, and I is the bending modulus of the web The second moment of area, b is the width of the support,
d means the average thickness of the support) is 0.2 to 10
kg・cm^2, and further on the surface of the support,
A method for producing a three-dimensional color photographic recording material, comprising the steps of substantially simultaneously applying and drying a plurality of layers including at least one image forming layer. (2) The coefficient of friction between the back surface of the support and the surface of the support or the surface on the image forming layer side that comes into contact in the manufacturing process of the three-dimensional color photographic recording material is 0.2 to 0.9. (1) A method for producing a three-dimensional color photographic recording material.