US3701663A

US3701663A - Photographic light-sensitive material

Info

Publication number: US3701663A
Application number: US863645A
Authority: US
Inventors: Asaji Kondo; Hiroshi Fujisaki; Shizuo Miyano; Kenichiro Yazawa
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1968-10-04
Filing date: 1969-10-03
Publication date: 1972-10-31
Anticipated expiration: 1989-10-31
Also published as: JPS4933783B1

Abstract

THIS INVENTION RELATES TO A PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL COMPRISING A HIGHLY-REFLECTIVE SUPPORT WITH A LUSTROUS SURFACE COATED WITH AT LEAST ONE LAYER OF MICROCAPSULES CONTAINING A SILVER HALIDE EMULSION.

Description

Oct. 3l, 1972 ASAJI KoNDo ErAL 3,701,663

PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Filed Oct. 5. 1969 FIG. I

FIG. 3

IOR |06 FIG. 5

IOB

INVENTORS ASAJI KONDO HIROSHI FUJISAKI` SHIZUO MIYANO KENICHIRO YAZAWA SLLW, WI

ATTORNEYS United States Al-"atent Oice .'i,70l,ti63l Patented Oct. 3 1, 1972 3,701,663 PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Asaji Kondo, Hiroshi Fujisaki, Shzuo Miyano, and Kenichiro Yazawa, Asaka-sh, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed Oct. 3, 1969, Ser. No. 863,645 f Claims priority, application Japan, Oct. 4, 1968, 43/ 72,273 Int. Cl. G03c 1/94 U.S. Cl. 96-86 16 Claims ABSTRACT oF THE DISCLOSURE This invention relates to a photographic light-sensitive material comprising a highly rellective support with a lustrous surface coated with at least one layer of microcapsules containing a silver halide emulsion.

. DESCRIPTION OF THE INVENTION 1 .This invention relates to a photographic light-sensitive material for use as a print and, more particularly, it is concerned with a photographic light-sensitive material for use as a print in which a microcapsule-type emulsion used in black-and-white or color photography is coated onto a support which reilects light well and has a metallic luster.

The microcapsule-type emulsion described in the invention is intended to cover a particulate emulsion in which photographic elements, such as silver halide, coupler and additives, are coated with a gelatin coacervate, as disclosed in Japanese Pat. 496,245, a particulate emulsion in which a gelatin silver halide emulsion is coated with a hydrophobic polymer iilm, as disclosed in British Pat. 864,060, or a packet emulsion as disclosed in U.S. Pat. 2,698,794.

The present invention will now be illustrated by reference to the accompanying drawings, in which the photographic light-sensitive material of this invention is compared with a well-known photographic light-sensitive material for use as a print.

FIG. 1 and FIG. 2 are cross-sectional views of the known photographic light-sensitive material used in blackand-white and color printing, respectively;

FIG. 3 and FIG. 4 are cross-sectional views of the microcapsule-type emulsions used in black-and-white photography and color photography, respectively; and

' FIG. 5 and FIG. 6 are cross-sectional views of the photographic light-sensitive materials used in this invention in black-and-white and color printing, respectively.

The commonly used photographic light-sensitive materials for printing comprise a lilm or a paper having a ,white pigment layer, for instance, baryta paper, and one vormore emulsion layers coated on the paper. FIG. 1

shows a cross-sectional view of the commonly used photographic light-sensitive material used in black-and-white printing, in which the light-sensitive emulsion layer 6, consisting of gelatin 4 and silver halide S, is coated onto support consisting of paper 1 and baryta layer 2. Referring to FIG. 2, the blue-sensitive emulsion layer 6B,

the green-sensitive emulsion layer 6G and the red-sensio'f a microcapsule-type emulsion 10 for color printing used in this invention wherein silver halide S and coupler 7 are coated with gelatin coacervate 8. The type of silver halide and coupler diifer depending on whether the emulsionv is to be used as the blue-sensitive layer, the greensensitive layer or the red-sensitive layer, of course. FIG. 5 shows a cross-sectional View of the photographic lightsensitive material for black-and-white printing used in this invention in which a black-and-white microcapsule type emulsion 9 is coated on a metallic lustrous surface of an aluminum plate 12 with a binder 11. FIG. 6` shows a cross-sectional view of the photographic light-sensitive material for color printing used in this invention in which a blue-sensitive microcapsule-type emulsion 10B, a greensensitive microcapsule-type emulsion 10G, and a red-sensitive microcapsule-type emulsion 10K are coated onto an aluminum plate 12 having a subbing layer 13 on its metallic lustrous surface.

According to this invention, when a microencapsulated black-and-white emulsion or color emulsion is applied to a lustrous surface of an aluminum plate, the image, obtained on exposing and developing, is unexpectedly bright. Furthermore, this image has the appearance of a transparent positive and the feeling of printing'paper. This effect is remarkably evident, specifically in this color areas or highly lighted areas, giving the image a number of bright points in the depth of a uniform color as if a metal powder coated surface or metallic coating were being viewed.

While not desiring to be bound by theory the following reasons may give rise to this phenomenon:

1) The aluminum surface used as the support reflects light well;

(2) The particles on the surface of the aluminum plate consist mainly of gelatin and light passes through it well and is scattered;

(3) With a color image, in the red area, the green-sensitive capsules and blue-sensitive capsules form colors, such as magenta and yellow, respectively, forming the red image. The red-sensitive microcapsules, which are unexposed and thus uncolored, exist as transparent particles. Light passing through these particles causes the bright points. Y p.

Although the image obtained on a photographic lightsensitive material in which the usual emulsion is applied to an aluminum plate is generally brighter than the image obtained when the same photographic light-sensitive materials are applied to a baryta paper, the above-mentioned phenomenon is not observed.

'I'he photographic material of the invention has another advantage in that the surface is naturally matted because the microcapsules are exposed as particles. As a result, the visual stimulus is different than that obtained with prior art images. Moreover, the microcapsule-type emulsion used in making a photographic light-sensitive material for color printing, by mixing the three color capsules, can be coated all at once. Accordingly, a thick metal plate can readily be coated as a support, as well as aluminum foil and iilms of vacuum-deposited aluminum.

Commonly used photographic elements can be incorporated into the microcapsule, e.g., oils, dyes and additives, in addition to the silver halides, couplers and protective colloids normally used.

The microcapsule-type emulsion used in the invention can be prepared according to the method disclosed in Japanese Pat.r 496,245.

As the support to which the microcapsule-type emulsion is applied, a support having a metallic luster or high reflectance factor for light is desirable. As the uniformly smooth surface, a surface of metals and alloys, such as aluminum plates and foils, laminates, such as aluminumpolyethylene-paper or aluminum-vinyl chloride-paper, and

metals, such as stainless steel, chromium and nickel and alloys thereof can be used. In addition, a polyester iilm on which a metal has been vacuum-deposited, for example, Metalmie (manufactured by Toyo 'Rayon Co., Ltd.) can be used. Where a black-and-white image is to be obtained, a pink, green or gold support gives a photographic image having the color characteristics of the support. In addition, some aluminum or alloy sheets are manufactured with narrow lines in one direction during rolling and can Ibe used as the support having anisotropy. The support can previously be subbed to protect the surface as well as to improve the adhesion of adhesives.

The following examples are given to illustrate the invention in detail without limiting the scope thereof.

EXAMPLE 1 Photographic light-sensitive material containing a microcapsule type emulsion for black-and-white photography In the presence of a photographically safe light, a gelatino silver iodobromide emulsion (100 g.) containing 4% silver halide (based on silver nitrate) and 12% gelatin was added to a solution of 30 ml. of a 4% naphthalenesulfonic acid-formalin condensate in 840 m1. of water, held at 40 C. and then mixed with agitation with 39` ml. of a 1% aqueous solution of acetic acid to lower the pH to 4.5. A complex coacervate of gelatin and the foregoing condensate surrounded the silver halide crystal forming a spherical microcapsule of about 5 microns. This product was then poured into a second vessel containing 3 liters of ice water and 0.6 g. of chrome alum, and the pH was raised to 6 by adding sodium carbonate. After stirring the mixture for l hour, the mixture was allowed to stand at room temperature. The following day, the supernatant liquid was removed and a hardened c psule slurry was obtained by centrifugal separation. 100 g. of 110% gelatin was added to the slurry as a binder to obtain a black and white microcapsule-type emulsion.

The black-and-white microcapsule-type emulsion'prepared as above was applied to an aluminum sheet, 210 microns thick and having a mirror surface at a level of 500 g./m.2. The material was allowed to set and then dried.

When the coated light-sensitive aluminum sheet is exposed to light using a black and white negative, and subsequently developed, a print having unexpectedly bright image is obtained.

EXAMPLE 2 Photographic light-sensitive material containing a microcapsule-type emulsion for color photography Microcapsules conventionally used in color photography, i.e., microcapsules containing a blue-sensitive silver halide and a yellow coupler, microcapsules containing a green-sensitive silver halide and a magenta coupler and microcapsules containing a red-sensitive silver halide and a cyan coupler, were prepared according to the method described in Japanese patent publication No. 12948/ 1965. The size of the microcapsules prepared ranged from 15 to 30 microns, 25 g. of each of they microcapsule slurry were mixed, the slurry added to 60 g. of 20% gelatin and then the mixture was diluted with water to 7010 ml.l 1 30 ml. of the resulting mixture was coated onto an aluminum sheet having a mirror surface and allowed to set and be dried. The mirror surface aluminum sheet had previously been undercoated with a polyester resin and then with gelatin. The film thickness of the dried microcapsule emulsion was approximately 35 microns The resulting photographic material was exposed to light through a color negative and then subjected to development. A color image of unexpected brightness was obtained.

What is claimed is: l

'.l. In a conventional photographic light-sensitive material for use in forming a positive black-and-white or 4 color image, which consists essentially of a support material having coated thereon, a silver halide photographic emulsion, the improvement which comprises:

employing a support material which exhibits a high reillectance factor for light and further exhibits a metallic lustrous surface and employing said silver halide emulsion in the form of at least one layer of microcapsules.

2. The photographic light-sensitive material of claim 1, wherein said support is an aluminum foil vacuum deposited on polyethylene terephthalate film. y

3. The photographic light-sensitive material of claim 1, wherein said support has a subbing layer.

4. The photographic light-sensitive material of claim 1,', wherein said micropsule contains a color coupler capable of forming a color dye image by reaction of an oxidation product of a developer.

5. The photographic light-sensitive material of claim 1, wherein said microcapsules are produced by a coacervation of gelatin.

6. The photographic light-sensitive material of claim 11, wherein said support is a metal selected from the group consisting of aluminum, stainless steel, chromium, nickel, and alloys thereof.

7. 'Ihe photographic light-sensitive material of claim 6, wherein said aluminum represents a member selected from the group consisting of aluminum plate and aluminum foil.

8. The photographic light-sensitive material of claim 7, wherein the surface of said aluminum contains elongated irregularities.

9. The photographic light-sensitive material of claim 7, wherein the surface of said aluminum is a rellecting mirror surface.

10. The photographe light-sensitive material of claim 9, wherein the mirror surface is at a level of 500 g./m.'2.

11. The photographic light-sensitive materiall of claim 7, wherein the thickness of said aluminum plate and foil is 210 microns.

12. The photographic light-sensitive material of claim 1, wherein said support is a laminate.

13. The photographic light-sensitive material of claim 12, wherein the laminateis a laminate of aluminum foil on a vinyl chloride-coated paper.

14. The photographic light-sensitive material of claim 12, wherein the laminate is a laminate of aluminum foil on a polyethylene-coated paper.

15. The photographic light-sensitive material of claim 14, wherein the surface of said aluminum contains elongated irregularities.

16. The photographic light-sensitive material of claim 14, wherein the surface of said aluminum is a reflecting mirror surface. References Cited UNITED STATES PATENTS 2,215,128 9/1940 Meulendyke 96-86 X `2,257,143 9/1941 Wood 96-86 X 2,637,929 5/ 1953 Hausman 96-86 UX 3,342,601 9/'1967 Houle et al 96-86 3,365,350 1/ 1968 Cahn 161--6 3,551,150 12./ 1970 Woodward et al 96-86 X 2,698,794 1/ 1955 Godowsky 96-97 3,061,435 10/1962l Tomanek et al 96-86 X 3,161,518 12/ 1964 Deal et al 96-86 X e FOREIGN PATENTS 864,060 3/1961I Great Britain.

ROBERT F.. BURNETT, Primary Examiner I.. C. GIL, Assistant Examiner U.S. Cl. X.R. 96-96; 99