United States Patent m
Aono et al.
4,283,486 [45] Aug. 11,1981
[54] SILVER HALIDE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL
[75] Inventors: Toshiaki Aono; Takeshi Hirose, both of Minami-ashigara, Japan
[73] Assignee: Fuji Photo Film Co., Ltd., Minami-ashigara, Japan
[21] Appl. No.: 145,090
[22] Filed: Apr. 30,1980
[30] Foreign Application Priority Data
Oct. 2, 1979 [JP] Japan 54/126971
[51] IntCU G03C1/76
[52] U.S. CI 430/505; 430/372;
430/537; 430/538; 430/556; 430/557; 430/552;
430/554; 430/961
[58] Field of Search 430/495, 538, 537, 961,
430/543, 372, 505, 556, 557, 552, 554
[56] References Cited
U.S. PATENT DOCUMENTS
2,358,056 9/1944 Clark 430/538
3,277,041 10/1966 Sieg et al 430/538
3,364,028 1/1968 Konig 430/538
3,582,337 6/1971 Griggs et al 430/538
3,582,339 6/1971 Martens et al 430/537
3,669,709 6/1972 Kasugai et al 430/954
3,700,449 10/1972 Lerner 430/961
FOREIGN PATENT DOCUMENTS 1584280 11/1969 France 430/961
OTHER PUBLICATIONS
Research Disclosure, No. 15162, p. 82, Nov. 1976.
Primary Examiner—J. Travis Brown
Attorney, Agent, or Firm—Sughrue, Mion, Zinn,
Macpeak and Seas
[57] ABSTRACT
A silver halide color photographic light-sensitive material comprising a paper support, at least one color image-forming emulsion layer, and an oxygen-impermeable layer having an oxygen permeability of not more than 2.0 ml/m2-hr-atm, said color image-forming layer and oxygen-impermeable layer being provided on the same side of the paper support.
20 Claims, 2 Drawing Figures
SILVER HALIDE COLOR PHOTOGRAPHIC
LIGHT-SENSITIVE MATERIAL
BACKGROUND OF THE INVENTION 5
1. Field of the Invention
This invention relates to silver halide color photographic light-sensitive material, and more particularly to silver halide color photographic light-sensitive mate- 10 rial which permits the prevention of discoloration and fading by light of dye image areas and unexposed areas of dye images obtained by development after imagewise exposure.
2. Description of the Prior Art 15 In general, dye images obtained by the development
of silver halide color photographic light-sensitive material comprise azomethine or indoaniline dye formed by the reaction of an oxidation product of an aromatic primary amine developing agent and a color coupler. 20 These dye images have limited stability to light and to heat under humid conditions; when they are exposed to light for extended periods of time or stored under conditions of high temperature and humidity, discoloration and fading of the dye image areas and discoloration of 25 white areas (that is, areas where a dye image is not present) occurs, leading to reductions in image quality.
Such discoloration or fading of the dye image and discoloration of the white areas is a major problem in silver halide color photographic light-sensitive mated- 30 als.
The discoloration and fading of the dye image and discoloration of the white areas is considered to be caused mainly by ultraviolet or visible rays, and therefore a number of techniques using ultraviolet ray- ^5 absorbing agents or anti-fading agents have been developed to prevent the discoloration and fading due to light. In addition, a number of techniques have been proposed in which couplers of low fading are used.
Examples of such methods using magenta couplers are described in U.S. Pat. No. 3,519,429. Use of hydroxycumarones as an antioxidant is described in U.S. Pat. No. 3,432,300. The use of anti-fading agents containing phenolic hydroxy groups is described in U.S. Pat. No. 45 3,698,909, and the use of alkyl ethers as an antioxidant is described in Japanese Patent Application (OPI) No. 77526/78 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application").
Although these compounds have some effect in pre- 50 venting the discoloration and fading of dye images, the effect is not always sufficient, and, moreover, many of them exert adverse side effects, such as reduction of hue, fog formation, insufficient dispersion of an antioxidant into oils (organic solvents having a high boiling 55 point) which prevents the formation of stable oil droplets, and cause crystallization of the antioxidant. Thus, compounds exhibiting sufficiently excellent effects have not yet been discovered.
It is known that oxygen is also responsible for the go discoloration and fading of the dye image and discoloration of the white areas, and therefore techniques for preventing the discoloration and fading by preventing oxygen from coming in contact with the dye images have been proposed. For example, such techniques are 65 described in Research Disclosure, Vol. 15162, page 82 (November 1976), and Japanese Patent Application (OPI) Nos. 11330/74 and 57223/75 wherein an oxygen
2
shielding layer formed from a substance having a low oxygen permeability is used to cover the dye images.
According to such methods, after the development of the color photographic light-sensitive material, the dye images are covered with the oxygen-shielding layer, for example, by laminating a polyethylene terephthalate film thereon. If the dye images are completely covered with the oxygen-shielding layer and prevented from coming into contact with oxygen, the magenta and yellow color dye images are greatly improved in their discoloration and fading properties. However, the discoloration and fading of the cyan color image formed from cyan couplers which are normally used in silver halide color photographic light-sensitive material (such as those represented by the formula (VI), as will be explained infra) is accelerated.
For silver halide color photographic lightsensitive material including a sheet of paper as a support (referred to hereinafter merely as "a color light-sensitive material"), anilinopyrazolone based couplers are preferably used because of good hue and color-forming efficiency. However, these couplers have the serious drawback that their use results in occurrence of discoloration and fading of the dye image and discoloration of the white areas.
Therefore it has been strongly desired to develop a technique which permits the use of such couplers as are described above without the occurrence of discoloration and fading.
With respect to the development of more recent color light-sensitive materials, rapid processing has increasingly been of great importance, and the conventional so-called three-bath processing (consisting of color development, bleach-fixing, and stabilization) is often being replaced with two-bath processing (consisting of color development and bleach-fixing). This twobath processing, however, suffers from the disadvantages that the dye images obtained are inferior in stability and are subject to discoloration and fading.
Moreover, in the rapid development processing of color light-sensitive material, benzyl alcohol is sometimes incorporated into the color-forming developer for the purpose of shortening the development time by accelerating the color development. Such a developer, however, readily causes rapid discoloration and fading of the dye images formed.
Therefore it has been strongly desired to develop a color light-sensitive material which, even when subjected to such a rapid development processing, does not result in discoloration and/or fading of dye images.
SUMMARY OF THE INVENTION
An object of this invention is to provide a color lightsensitive material that, when subjected to development processing, produces dye images which are less subject to discoloration and fading.
Another object of this invention is to provide a color light-sensitive material which is improved with respect to the discoloration and fading of dye images, without exhibiting adverse side effects on its photographic properties.
Another object of this invention is to provide a color light-sensitive material in which couplers having good hue and color-forming efficiency are used, and which is less subject to discoloration and fading of dye images after processing.
Another object of this invention is to provide a color light-sensitive material that, when subjected to rapid
3
processing (such as a two-bath process), produces dye images which are less subject to discoloration and fading.
Other objects of this invention will become apparent from the following description. 5
According to the invention, therefore, a color lightsensitive material is provided comprising a paper support, a color image-forming layer containing a photographic color coupler which forms a dye on coupling with an oxidation product of an aromatic primary 10 amine, and an oxygen-impermeable layer (oxygen-barrier layer) having an oxygen permeability of not more than 2.0 ml/m2-hr-atm (20° C, dry state) on the same side of the support as that on which the color imageforming layer is provided. 15
The oxygen permeability is measured acccording to the method defined in ASTM D-1434-63.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of an embodiment of a 20 paper support provided with an oxygen-impermeable layer according to the invention; and
FIG. 2 is a sectional view of another embodiment of a paper support provided with an oxygen-impermeable layer according to the invention. 25
DETAILED DESCRIPTION OF THE
INVENTION
The expression term "discoloration and fading" as used herein refers to the discoloration and fading of 30 color images and formation of stains in white areas. This invention is particularly useful for the prevention of fading upon exposure to light of magenta and yellow color dye images and the prevention of the formation of stains in white areas upon exposure to light and/or heat. 35
The layer having an oxygen permeability of not more than 2.0 ml/m2-hr-atm (20° C, dry state) for use in this invention (hereinafter referred to as the "oxygenimpermeable layer" which is synonym to "oxygen-barrier layer") is provided on the support at the same side 40 thereof as that on which the color image-forming layer is to be provided, but they are not always required to be adjacent to each other.
Thus the invention includes, for example:
(1) a color light-sensitive material having a layer 45 made of polyolefin (for example, polyethylene or polypropylene) on one side of the paper support and, in sequence, an oxygen-impermeable layer, a polyolefin layer and a color image-forming layer on the other side
of the paper support; 50
(2) a color light-sensitive material having a polyolefin layer on one side of the paper support and, in sequence, a polyolefin layer, an oxygen-impermeable layer and a color image-forming layer or, if desired, a polyolefin layer, an oxygen-impermeable layer, a polyolefin layer, 55 and a color image-forming layer on the other side of the paper support;
(3) a color light-sensitive material having a polyolefin layer on one side of the paper support and, in sequence,
an oxygen-impermeable layer, a polyolefin layer, an 60 oxygen-impermeable layer and a color image-forming layer on the other side of the paper support; and
(4) a color light-sensitive material having in sequence an oxygen-impermeable layer and a color imageforming layer on one side of the paper support, and a polyolefin 65 layer on the other side thereof.
In the above embodiments, between the color imageforming layer and the polyolefin layer or oxygenim
4
permeable layer a hydrophilic organic colloidal layer may be provided, such as a gelatin undercoating layer, an undercoating layer consisting of a polymer, etc. Furthermore, this polymer layer may be subjected to corona discharge, as is described in West German Pat. No. 1,921,641. Multiple color image-forming layers may also be provided, as well as other layers conventionally used therewith, such as an intermediate layer, a surface protective layer, and so forth. The silver halide emulsion and the coupler may exist in the same color imageforming layer or may be present in separate layers.
The reverse side of the paper support, which has no color image-forming layer thereon, may be provided with a layer of a polymer other than polyolefin, or may not be provided with any polymer layer. Any polymer capable of forming a waterproof film can be used for the formation of such a polymer layer. For example, homoand copolymers of olefin, vinyl chloride, vinylidene chloride, acrylonitrile, acrylate, methacrylate, acrylic acid amide, methacrylic acid amide, vinyl alcohol, styrene, fluorinated vinyl, ethylene terephthalate, and vinyl acetate, cellulose acetate, polyamide, polycarbonate and cellophane can be used. This polymer layer may be a single layer or a laminate comprising two or more layers.
The oxygen permeability of the oxygen-impermeable layer of this invention is not more than 2.0 ml/m2-hr-atm (20° C, dry state), and is preferably not more than 1.0 ml/m2-hr-atm (20° C, dry state).
The thickness of the oxygen-impermeable layer of this invention is not critical, provided that the oxygen permeability is not more than 2.0 ml/m2-hr-atm (20° C, dry state). Preferably it is from about 1 to 100 u,m, and more preferably from 2 to 50 u,m. When the thickness is less than 1 u.m, pin-holes are easily formed in the oxygen-impermeable layer, and oxygen may thus be permeated. However, the polymer constituting the oxygenimpermeable layer sometimes partly permeates into the paper support, in which case the desired oxygen permeability can be obtained even if the oxygen-impermeable layer is less than 1 u.m. On the other hand, when it is more than 100 jam, the total thickness of the color lightsensitive layer is increased to an undesirable extent.
If desired, the oxygen-impermeable layer of this invention can contain, in addition to the polymer used as the binder, a filler, such as titanium oxide and/or barium sulfate, a fluorescent brightener, an antistatic agent, or an ultraviolet ray-absorbing agent, and combinations thereof. The amount of filler such as titanium oxide and barium sulfate being added is preferably not more than 50% by weight, based upon the weight of the binder, and preferably is from 5 to 30% by weight.
Polymers which can be used as the binder constituting the oxygen-impermeable layer of this invention include homo- and copolymers of acrylonitrile, alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, methacrylonitrile, alkyl vinyl esters such as vinyl acetate, vinyl propionate, vinyl ethyl butyrate and vinyl phenyl acetate, alkyl vinyl ethers such as methyl vinyl ether, butyl vinyl ether and chloroethyl vinyl ether, vinyl alcohol, vinyl chloride, vinylidene chloride, vinyl fluoride, styrene and vinyl acetate (in the case of copolymers, ethylene and/or propylene can be used as comonomers), cellulose acetates such as diacetyl cellulose and triacetyl cellulose, polyesters such as polyethylene terephthalate,
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