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(11) | EP 0 175 311 A2 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Silver halide color photographic light-sensitive material |
| (57) A silver halide color photographic light-sensitive material comprising a reflective
support bearing thereon a photographic component layers including at least a blue-light-sensitive
silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer
and a red-light-sensitive silver halide emulsion layer; wherein at least one layer
of said photographic component layers contains at least one dye capable of being water-soluble
or being decolorized by a development processing liquid, and a compound capable of
releasing a development inhibitive substance or the precursor thereof through a reaction
with the oxidation product of a color developing agent, and the optical reflection
density of said silver halide color photographic light-sensitive material in 470 nm,
550 nm or 680 nm is not less than 0.5. |
BACKGROUND OF THE INVENTION
[0001] This invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for color printing paper use in which the image sharpness is improved.
[0002] Generally, a silver halide color photographic light-sensitive material is coated on the support thereof with three kinds of silver halide emulsion layers for photographic use which are spectrally sensitized selectively so as to have the sensitivity to blue-light, green-light, and red-light, respectively. For example, in a silver halide color photographic light-sensitive material for color-negative use, a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer are generally coated thereon in order from the side to be exposed, and between the blue-light-sensitive silver halide emulsion and the green-light-sensitive silver halide emulsion layer there is provided with a yellow filter layer capable of bleaching itself for absorbing blue-light transmitting through the blue-light-sensitive silver halide emulsion layer, and further, each of the emulsion layers is provided with other interlayers with a variety of special purposes and a protective layer as the outermost layer, and still further, in a silver halide photographic light-sensitive material for color printing paper use, a red-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a blue-light-sensitive silver halide emulsion layer are generally coated thereon in order from the side to be exposed, and similar to the case of the silver halide photographic light-sensitive material for color negative use, the interlayers with the particular purposes including a ultraviolet ray absorbing layer, the protective layer and the like are provided, respectively. Besides the above, it is also well known that each of these silver halide emulsion layers is provided in different arrangements, and that a double-layered light-sensitive silver halide emulsion layer sensitive to each color rays in the substantially same wavelength region may be used for the respective silver halide emulsion layers. In the above-mentioned silver halide color photographic light-sensitive material, a color developing agent such as an aromatic primary amine developing agent is used to develop the exposed silver halide grains and a dye image is formed by the reaction of the oxidation products produced of the color developing agent with a dye formable coupler. In this process, in order to form the dye image in cyan, magenta and yellow, a phenol or naphthol cyan coupler, a 5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indazolone or cyanoacetyl magenta coupler, or an acylacetamide yellow coupler are used, respectively. The above-mentioned dye forming couplers are contained in a light-sensitive silver halide emulsion layer or a developer. This invention relates to a silver halide photographic light-sensitive material for color printing paper use, in which the above-mentioned couplers are contained in advance in the silver halide emulsion layers.
[0003] The reasons why the silver halide photographic light-sensitive materials for color printing paper use are low in image sharpness are assumedly as follows: Namely, the most serious cause of the low sharpness is attributed to a large halation or irradiation caused by diffusing a light in a reflective support or by reflecting from the surface of the reflective support when exposing to light, because the reflective support used is in white. A well known technique among the techniques for preventing the deterioration of image sharpness caused by such halation or irradiation is that such a colored layer as an antihalation layer or a filter layer is provided, and a technique is also well known in which a coloring agent such as colloidal silver is added in an alkaline soluble resin or a hydrophilic colloid to use as a colored layer. It is not only a matter of course that such coloring agent of the above-mentioned colored layers shall completely be decolored in a process after exposing a silver halide color photographic light-sensitive material to light, such as in a developing process or the like, but also that the coloring agent is required to be excellent in spectral absorption and inert in photographic chemistry. In the case of using colloidal-silver, however, there are some disadvantages such as that not only the color reproductively is affected because satisfactorily desired spectral characteristics is not always obtained but also an undesired fog is caused on the silver halide emulsion layers because the colloidal silver is not completely inert in photographic chemistry.
[0004] On the other hand, there are known techniques in which a silver halide color photographic light-sensitive material is contained with such water-soluble dyes as described in British Patent Nos. 584,609 and 1,277,429, Japanese Patent Publication Open to Public Inspection (hereinafter called Japanese Patent O.P.I. Publication) Nos. 85130/1973, 99620/1974, 114420/1974, 129537/1974, 108115/1977 and 25845/1984, and U.S. Patent Nos. 2,274,782, 2,533,472, 2,956,879, 3,125,448, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, 3,653,905, 3,718,472, 4,071,312, and 4,070,352, and the like. However, it has been unable to obtain any satisfactorily high image sharpness through such an irradiation resistance or antihalation measure made only by the above-mentioned dyes.
[0005] Mostly in the silver halide photographic light-sensitive materials for negative use, there are well known techniques for improving an image sharpness by making use of a compound capable of producing a dye through a coupling thereof to the oxidation products of a color developing agent and releasing a development inhibitor, such as described in U.S. Patent No. 3,148,062 and 3,227,554, or by making use of a compound capable of releasing a developing inhibitor through a coupling thereof to the oxidation products of a color developing agent and not producing any dye (hereinafter called a DIR compound), such as described in U.S. Patent No. 3,632,345. However, in the ordinary constitution of the silver halide photographic light-sensitive materials for color printing paper use, almost no improvement effect can be obtained in an image sharpness, even if such DIR compound is used.
[0006] There is a further well known technique for improving an image sharpness by treating the surface of a support to be matted, such as described in Japanese Patent O.P.I. Publication No. 89731/1973. Few effect on improving an image sharpness can also be enjoyed in this technique.
SUMMARY OF THE INVENTION
[0008] It is, therefore, an object of the invention to provide a silver halide color photographic light-sensitive material having a high image sharpness, as a technical target thereof.
[0009] A silver halide color photographic light-sensitive material of the invention capable of achieving the above-mentioned technical target, which comprises a reflective support bearing thereon a photographic component layer including at least a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer, such silver halide color photographic light-sensitive material of the invention is characterized in that at least one layer of the photographic component layers contains at least one dye capable of being water-soluble or being decolorized by a development processing liqid, and a compound capable of releasing a development inhibitive substance or the precursor thereof through a reaction with the oxidation product of a color developing agent, and the optical reflection density of the silver halide color photographic light-sensitive material in 470nm, 550nm or 680nm is not less than 0.5.
[0010] The photographic component layer described herein means any of the hydrophilic colloidal layers taking part in forming an image. They include, for example, a silver halide emulsion layer, a subbing layer, an interlayer such as a simple interlayer, a filter layer, an ultraviolet ray absorbing layer, an antihalation layer, etc., a protective layer, and the like.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The typical examples of the DIR compounds of the invention include a DIR coupler having introduced into the coupling position thereof a group capable of forming a compound having a development inhibiting function when splitting off from the coupling position. Such couplers are described, for example, in British Patent No. 935,454 and U.S. Patent No. 3,227,554, 4,095,984, and 4,149,886, Japanese Patent O.P.I. Publication No. 151944/1982, and the like. The above-mentioned DIR couplrs have the functions that the parent nucleus forms a dye when the coupler makes a coupling reaction to the oxidation product of a color developing agent, and on the other hand, the DIR couplers also have the function to release development inhibitor. Futher, in the invention, the DIR couplers include such a compound as described in U.S. Patent No. 3,652,345, 3,928,041, 3,958,993, 3,961,959, and 4,052,213, and Japanese Patent O.P.I. Publication No. 110529/1978, 13333/1979 and 161237/1980, and the like, in which a development inhibitor is released but a dye is not formed when the compound makes a coupling reaction to the oxidation product of a color developing agent.
[0013] Still further, the invention includes the so-called timing DIR compounds, that is, a compound that the parent nucleus forms a dye or a colorless compound when coupling to the oxidation product of a color developing agent and on the other hand the timing group which was splitted off releases a development inhibitor through an intramolecular nuclephilic substitution reaction or an elimination reaction, such as described in Japanese Patent O.P.I. Publication Nos. 145135/1979, 114946/1981 and 154234/1982.
[0014] In addition, the invention also includes such a timing DIR compound that such a timing group as mentioned above is coupled to the parent nucleus of a coupler capable of producing a completely diffusible dye when making a reaction with the oxidation product of a developing agent, such as described in Japanese Patent O.P.I. Publication Nos. 160954/1983 and 162949/1983.
[0015] According to the invention, the more preferable DIR compounds may be represented by the following Formulas (I) and (II), and among them, in particular, the most preferable DIR compound is a compound represented by the following Formula (II);
Formula (I)
Coup-Inhibitor
[0016] wherein Coup represent a coupler component (i.e., a coupler residual group) capable of coupling to the oxidation product of a developing agent; including, for example, an open-chained ketomethylene compound such as an acylacetanilide, an arylacetic acid ester, and the like; such a dye-forming coupler residual group as a pyrazolone, a pyrazolotriazole, a pyrazolinobenzimidazole, an indazolone, a phenol, a naphthol and the like; and such a coupling component substantially incapable of forming any dye as an acetophenone, an indanone, an oxazolone and the like.
[0017] The inhibitors represented in the abovegiven formulas are a component of a compound (i.e., the residual group of the compound) capable of splitting off through a reaction with a color developing agent so as to inhibit a development of a silver halide.
[0018] The preferable compounds thereof include, for example, such a heterocyclic compound as benztriazole, 3-octylthio-1,2,4-triazole and the like, a heterocyclic mercapto compound.
[0019] The above-mentioned heterocyclic groups include, for example, a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group and the like; and typically include 1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, 1,3,4-thiazolyl group, 5-methyl-1,3,4-oxadiazolyl group, benzthiazolyl group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group and the like.
Formula (II)
Coup-TIME-Inhibitor
[0021] wherein Inhibitor is the same as defined in the above Formula (I), and Coup is the same as defined in the Formula (I) and includes a coupler component capable of producing a completely diffusible dye; and TIME is represented by the following Formulas (III), (IV), (V) and (VI), however, it shall not be limited to these Formulas.
[0022] Formula (III)
wherein X represents a group of atoms required for completing a benzene ring or a naphthalene ring; Y represents
in which R3 is hydrogen, an alkyl or aryl group, and Y is coupled in a coupling position; and R1 and R2 each represent respectively the synonymous groups with the R3, and a
is substituted in an ortho or para position and is coupled to a hetero atom contained in an inhibitor.
Formula (IV)
[0023]
wnerein W represents a synonymous group with Y in the above Formula (III); and R4 and R5 each are the synonymous groups with R1 and R2 in the Formula (III); R6 represents hydrogen, an alkyl group, an aryl group, an acyl group, a sulfon group, an alkoxycarbonyl group, or a heterocyclic residual group; and R7 represents hydrogen, an alkyl group, an aryl group, a heterocyclic residual group, an alkoxy group, an amino group, an acylamide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group; and, this timing group is coupled to a coupling position by W and is coupled to the hetero atom of an inhibitor by
[0024] Next, the Following Formula (V) gives an example of the timing groups each releasing an inhibitor through an intramolecular nucleophilic substitution reaction;
Formula [V]
[0025]
wherein Nu represents a nucleophilic group having oxygen, sulfur or nitrogen atom having abundant electrons and is coupled to the coupling position of Coup; E represents an electrophilic group having a carbonyl group, thiocarbonyl group, a phosphinyl group or a thiophosphinyl group having inabundant electrons, and is coupled to the hetero atom of an inhibitor; and V represents a coupling group which'is subjected to an intramolecular nucleophilic substitution reaction which is followed by forming a three-membered ring or a seven-membered ring after releasing Nu from Coup because V relates Nu to E in three dimensions, and thereby V is capable of releasing an inhibitor.
Formula (VI)
[0027] The following compounds are the typical examples of the DIR compounds relating to the invention, and it is however to be understood that the invention shall not be limited thereto. [Exemplified Compounds]
[0028] Optical reflection density (DR) according to the invention is well known in the skilled in the art and defined as follows:
wherein Ps is the radiant flux reflected by the sample, and Po is the radiant flux incident on the sample.
[0029] The DIR compounds of the invention may be added into a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer, and preferably into the blue-, green-, or red-light-sensitive silver halide emulsion layer.
[0030] It is also allowed to contain two or more kinds of the DIR compounds of the invention into the one and the same layer, and to contain the same DIR compound into two or more different layers.
[0031] The above-mentioned DIR compounds are ordinarily added in an amount of 2 x 10-4 to 5 x 10-4 mol per mol of silver in an emulsion layer, and more preferably 1 x 10-3 to 1 x 10-1 mol.
[0032] In order to contain the above-mentioned DIR compounds into a silver halide emulsion layer or the coating solutions of other photographic component layers relating to the invention, they may be added after they are changed into an alkaline solution when the DIR compounds are alkali-soluble, and when they are oil-soluble, it is preferred that the DIR compounds are dissolved in a high boiling solvent and, if necessary, a low boiling solvent in combination, and are then added in a silver halide emulsion after dispersing in the forms of fine particles in such a process as described in U.S. Patent Nos. 2,322,027, 2,801,170, 2,801,171, 2,272,191 and 2,304,940. In the case, it is allowed if occasion demands to use other hydroquinone derivatives, ultraviolet absorption agent, anti-discoloring agent and the like in combination. It is also allowed to use two or more kinds of the DIR compounds mixed together. More detailed description of how to add the preferred DIR compounds in the invention is that one or no less than two kinds of the DIR compounds are dissolved together with, if necessary, other couplers, a hydroquinone derivative, an anti-discoloring agent, a ultraviolet absorbing agent and the like are dissolved in an organic amide, a carbamate, an ester, a ketone, a urea derivative, an ether, a hydrocarbon, and in particular, a high boiling solvent such as di-n-butylphthalate, tricresylphosphate, triphenyl phosphate, di-isooctylazelate, di-n-butylsebacate, tri-n-hexylphosphate, N,N-di-ethyl-caprylamidebutyl, N,N-di-ethyl laurylamide, n-pentadecylphenyl ether, di-octyl phthalate, n-nonyl phenol, 3-pentadecylphenylethyl ether, 2,5-di-sec-amylphenylbutylether, monophenyl-di-o-chlorophenyl phosphate, fluorine paraffin or the like; and/or a low boiling solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethyleneglycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane, tetrahydrofuran, methyl alcohol, acetonitrile, dimethyl formamide, dioxane, methylethyl keton, and the like; and the resulting solution is mixed with an aqueous solution containing an anionic surface active agent such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid, and/or a nonionic surface active agent such as sorbitane sesquioleic acid esters and sorbitane monolauric acid esters, and/or a hydrophilic binder such as gelatin and the like; and the resulting mixture is emulsified and dispersed by a high-speed rotary mixer, colloid mill or ultrasonic disperser or the like; and the resulting dispersed matter is added onto a silver halide emulsion.
[0033] Besides the above-mentioned processes, the above couplers may also be dispersed in a latex dispersing method. Such latex dispersing method and the effects thereof are described in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976 and 32552/1979, and Research Disclosure No. 14850, pp. 77 - 79.
[0034] The suitable latexes include, for example, a homopolymer, copolymer and terpolymer each of such a monomer as styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetacetoxy ethyl methacrylate, 2-(methacryloyloxy)ethyltrimethyl ammonium methosulfate, 3-(methacryloyloxy)propane-1-sodium sulfonate, N-isopropyl acrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylropane sulfonic acid, and the like.
[0035] The above-mentioned DIR compounds can be synthesized in the processes described respectively in U.S. Patent Nos. 3,227,554, 3,615,506, 3,617,291, 3,632,345, 3,928,041, 3,933,500, 3,938,996, 3,958,993, 3,961,959, 4,046,574, 4,052,213, 4,063,950, 4,095,984, 4,149,886, and 4,234,678; Biritish Patent Nos. 2,072,363 and 2,070,266; Research Disclosure No. 21228, 1981; Japanese Patent O.P.I. Publication
Japanese Patent Applicaton Nos. 44831/1982 and 45809/1982; and the like.
[0036] A development inhibitor being released when developing from the DIR compounds of the invention corresponding to the density of an image, such development inhibitor are able to obtain two kinds of image effects; the one effect is the so-called intraimage effect in which the development inhibitor inhibits a development correspondng to an image density and improves the image sharpness in a layer when the layer is a light-sensitive emulsion layer, and the other effect is the so-called interimage effect such as a masking effect in which the development inhibitor inhibits the developments of other layers corresponding to the image density of a layer being the source of diffusion, when the released development inhibitor diffuses to the other layers.
[0037] The DIR compounds of the invention may be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer. It is good enough that, preferably, at least one of silver halide emulsion layers contains such DIR compound. For example, in the case of adding such a DIR compound to an ordinary multilayered color photographic light-sensitive material comprising a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer, it is good enough to contain in one or not less than two layers thereof.
[0038] Water-soluble dyestuffs or those decolorized by a developing liquid, (AI dyes) which are to be used in the photographic component layers of a silver halide color photographic light-sensitive material of the invention include an oxonol dye, a merocyanine dye, a hemioxonol dye and an azo dye. Among them, the oxonol, hemioxonol and merocyanine dyes and the like are useful. The examples of such dyes capable of being used may be given in British Patent Nos. 584,609 and 1,277,429; Japanese Patent O.P.I. Publication Nos. 85130/1973, 99620/1974, 114420/1974, 129537/1974, 108115/1977, 25845/1984, 111640/1984 and 111641/1984; U.S. Patent Nos. 2,274,782, 2,533,472, 2,956,879, 3,125,448, 3,148,187, 3,177,078, 3,247,127, 3,260,601, 3,540,887, 3,575,704, 3,653,905, 3,718,472, 4,071,312, and 4,070,352.
[Exemplified Compound]
[0041] The AI dyes of the invention may be added into a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic component layer.
[0042] No less than two of the AI dyes of the invention are allowed to be contained in one and the same layer. And, the same AI dye is allowed to be contained in not less than two different layers.
[0043] In general, the quantity of these AI dyes added is preferably from 2 x 10-4 to 5 x 10-1 mol per mol of a silver halide being contained in every blue-, green- and red-light-sensitive silver halide emulsion layer, and more preferably from 2 x 10 to 5 x 10-1 mol.
[0044] The silver halide color photographic light-sensitive materials of the invention are to be so contained with the AI dyes as to indicate a value of not less than 0.5 in at least one of the optical reflective densities of 470nm, 550nm or 680nm. When the every optical reflective density thereof is lower than 0.5, not only the effect is not expected on improving an image sharpness, but also the color reproductivity is deteriorated. The upper limit of the optical reflective density is not limitative, however, it is preferred to be not more than 2.0 from the view point of the sensitivity, decolorization property thereof and the like.
[0045] In a silver halide color photographic light-sensitive material of the invention, an amount of silver (i.e., a coating weight of silver) to be contained in the silver halide emulsion layer thereof is preferably from 0.3 to 1g per sq. meter in the total of the light-sensitive silver halide emulsion layers. In other words, it is preferred that the amount of silver is not more than 0.3g per sq. meter to obtain an excellent image quality, and is not less than 0.3g per sq. meter to obtain a relatively higher maximum density and a higher sensitivity.
[0046] A silver halide composition preferably used in the invention is silver chlorobromide or silver chloroiodobromide. Further, it is also allowed to use such a combined mixture as mixture of silver chloride and silver bromide. That is to say, for the purpose of realizing a high speed development, it is preferred to contain chlorine atoms in the halide composition of a silver halide, and more preferred that the silver halide is silver chlorobromide or silver chloroiodobromide each containing at least 1 mol% silver chloride.
[0047] The crystals of these silver halide particles may be of normal or twin type. The ratio of [100] plane to [111] plane is arbitrary to use. In addition, the crystal structures of these silver halide particles may be either uniform from the interior through the exterior thereof or of the layered structure (a core-shell type) in which the interior and the exterior are heterogeneous. These silver halides may be of either a type of forming a latent image mainly on the surface thereof or a type of forming a latent image inside the particles thereof. Further, tabular silver halide particles (described in Japanese Patent Application No. 170070/1984) may be used.
[0048] The silver halide particles which are preferably used in the invention are of the monodispersion type which may be obtined any one of the preparation processes such as an acidic process, neutral process, ammoniacal process, which have so far been known in the art.
[0049] It is also good enough to use such a process that core particles are prepared in the acidic process and are grown in the ammoniacal process which makes the growing speed faster, up to a certain size. In the case of growing silver halide particles, it is preferred that the values of a pH and pAg of the inside of a reaction chamber is controlled and both of silver ions and halide ions are injected and mixed gradually but at the same time in the amount corresponding to the growing speed of silver halide particles, such as described in Japanese Patent O.P.I. Publication No. 48521, for example.
[0050] The preparation of the silver halide particles relating to the invention is preferably carried out as mentioned above. The compositions containing the above-mentioned silver halide particles are hereby called a silver halide emulsion.
[0051] These silver halide emulsions may also be chemically sensitized with an active gelatin; a sulfur sensitizer such as alylthiocarbamide, thiourea, cystine and the like; a selenium sensitizer; a reduction sensitizer such as a stannous salt, thiourea dioxide, polyamine and the like; a noble metal sensitizer such as gold sensitizer including typically potassium aurothiacyanate, potassium chloroaurate, 2-aurothio-3-methyl benzothiazolium chloride and the like, or a sensitizer of a water-soluble salt of, for example, ruthenium, palladium, platinum, rhodium, iridium and the like including typically ammonium chloropalladate, potassium chloroplatinate, sodium chloropalladate (some kinds thereof function as a sensitizer, an antifoggant and the like, depending upon the quantity thereof.); which are used independently or in combination suitably (for example, in combination of gold sensitizer with a sulfur sensitizer, in combination of gold sensitizer with a selenium sensitizer, and the like).
[0052] It is also allowed that the silver halide emulsions relating to the invention may be chemically ripened by adding thereto a sulfur-containing compound, and may be contained thereto at least one kind of hydroxytetrazaindenes and at least one kind of nitrogen-containing heterocyclic compounds having a mercapto group before, during or after the chemical ripening.
[0053] Silver halide to be used in the invention can also be optically sensitized by adding thereto a suitable sensitizing dye in an amount of 5 x 10-8 to 3 x 10-3 mol per mol of the silver halide so as to endow each of the regions of desired photospectral wavelengths with photosensitivity. Therein, a variety of such sensitizing dyes may be used, and each of them may be used independently or in combination with two or more kinds thereof. Such sensitizing dyes which may be advantageously used in the invention may be given below, for example.
[0054] Namely, the sensitizing dyes to be used in a blue-light-sensitive silver halide emulsion include, for example, those described in West German Patent No. 929,080; U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 an 4,046,572; British Patent No. 1,242,588; and Japanese Patent Examined Publication Nos. 14030/1969 and 24844/1977; and the like. The sensitizing dyes to be used in a green-light-sensitive silver halide emulsion typically include, for example, a canine dye, a merocyanine dye or a compound cyanine dye such as described in U.S. Patent Nos. 1,939,210, 2,072,908, 2,739,149, and 2,945,763; British Patent No. 505979; and the like. And, the sensitizing dyes to be used in a red-light-sensitive silver halide emulsion include typically a cyanine dye, a merocyanine dye and a compound cyanine dye such as described in U.S. Patent Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629 and 2,776,280; and the like. In addition, the cyanine dyes, merocyanine dyes or the compound cyanine dyes such as described in U.S. Patent Nos. 2,213,995, 2,493,748, and 2,519,001; West German Patent No. 929,080; and the like may also advantageously be used in a green or red-light-sensitive silver halide emulsion.
[0055] These sensitizing dyes may be used independently or in combination. Such combination of sensitizing dyes is frequently used especially for the purpose of color-hypersensitizing. The typical example thereof are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707; Japanese Patent Examined Publication Nos. 4936/1968 and 12375/1978; Japanese Patent O.P.I. Publication Nos. 110618/1977 and 109925/1977.
[0056] In the silver halide emulsion layers relating to the invention, it is allowed to contain the other couplers than the DIR compounds of the invention, i.e., a compound capable of forming a dye through a reaction thereof with the oxidation products of a color developing agent.
[0057] As for the above-mentioned couplers capable of being used in the invention, a yellow coupler, a magenta coupler and a cyan coupler may be used without any special limitation. These couplers may be of the so-called two-equivalent type or four-equivalent type, and a diffusible dye releasing coupler and the like may also be used when combining with the above-mentioned couplers.
[0058] Such yellow couplers which are useful include, for example, an open-chained ketomethylene compound and further the so-called two-equivalent type couplers such as an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, an active point-hydantoin compound substituted coupler, an active point-urazol compound substituted coupler and an active point-succinic acid imide compound substituted coupler, an active point-fluorine substituted coupler, an active point-chlorine or bromine substituted coupler, an active point-o-sulfonyl substituted coupler, and the like. The typical examples of the useful yellow couplers include those described in U.S. Patent Nos. 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891,445; West German Patent No. 1,547,868; West German OLS Patent Nos. 2,219,917, 2,261,361, and 2,414,006; British Patent No. 1,425,020; Japanese Patent Examined Publication No. 10783/1976; Japanese Patent O.P.I. Publication Nos. 26133/1972, 73147/1973, 102636/1976, 6341/1975, 123342/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977, 115219/1977, and 95346/1983; and the like.
[0059] Magenta couplers which may be used in the invention include, for example, such a compound of a pyraxolone, a pyrazolotriazole, a pyrazolinobenzimidazole, an indazolone. The above-mentioned magenta couplers may include not only four-equivalent type couplers but also two-equivalent type couplers, similar to the case of the yellow couplers. The typical examples of such magenta couplers include, for example, those described in U.S. Patent Nos. 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, and 3,891,445; West German Patent No. 1,810,464; West German OLS Patent Nos. 2,408,665, 2,417,945, 2,418,959, and 2,424,467; Japanese Patent Examined Publication No. 6031/1965; Japanese Patent O.P.I. Publication Nos. 20826/1976, 58922/1977, 129538/1974, 74027/1974, 159336/1975, 42121/1977, 74028/1974, 60233/1975, 26541/1976, and 55122/1978; Japanese Patent Application No. 110943/1980; and the like.
[0060] Cyan couplers which are useful in the invention include, for example, a phenol coupler, a naphthol coupler and the like. These cyan couplers may be of not only the four-equivalent type but also the two-equivalent type, similar to the case of the yellow couplers. The typical cyan couplers include, for example, those described in U.S. Patent Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, and 4,004,929; West German OLS patent Nos. 2,414,830 and 2,454,329; Japanese Patent O.P.I. Publication Nos. 59838/1973, 26034/1976, 5055/1973, 146827/1976, 69624/1977, 90932/1977, and 95346/1983; and the like.
[0061] How to add the above-mentioned couplers capable of being used in the invention may be referred to the process for adding the aforementioned DIR compounds into the photographic component layers of the invention. The amount of the couplers added is not limitative, however, it is preferably from 1 x 10-3 to 5 mol per mol of silver, and more preferably, from 1 x 10-2 to 5 x 10-1 mol per mol of silver.
[0062] Besides the above, a variety of photographic additives may be contained in the silver halide color photographic light-sensitive materials of the invention. For example, there may be used an antifoggant, a stabilizer, an ultraviolet ray absorbing agent, an anti-color contamination agent, an optical brightening agent, an anti-fading agent for a color image, an antielectrostatic agent, a hardener, a surface active agent, a plasticizer, a wetting agent and the like.
[0063] In the silver halide color photographic light-sensitive materials of the invention, a hydrophilic colloid which is used for preparing an emulsion include anyone out of a protein such as gelatin, a derivative gelatin, a graft polymer of gelatin and other macromolecules, albumin, caseii, and the like; a cellulose derivative such as a hydroxyethylene cellulose derivative, carboxymethylene cellulose, and the like; a starch derivative, a synthetic hydrophilic macromolecule of a single or the polymer of polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like.
[0064] Supports of the silver halide color photographic light-sensitive materials of the invention may be anyone of the reflective type. For example, such supports include, for example, baryta paper; polyethylene coated paper; polypropylene synthetic paper; a transparent support provided with a reflective layer or a reflector, such as a glass plate, a polyester film, e.g., cellulose acetate film, cellulose nitrate film or a polyethyleneterephthalate film; a polyamide film; a polycarbonate film; a polystyrene film; and the like. These supports may suitably be selected to use according to the purpose of using a light-sensitive material.
[0065] In coating the silver halide emulsion layers and other photographic component layers of the invention, a variety of coating methods such as a dipping method, an air-doctor method, a curtain coating method, a hopper coating method and the like may be applied. Besides the above, a simultaneous coating method for not less than two layers may also be applied, such as described in U.S. Patent No. Nos. 2,761,791 and 2,941,898.
[0066] In the invention, the coating position of each emulsion layer may be determined arbitrarily. For example, in the case of light-sensitive materials for full-color printing paper use, it is preferred to arrange a blue-light-sensitive silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer and a red-light-sensitive silver halide emulsion layer in order from the support side. These light-sensitive silver halide emulsion layers each may comprise two or more layers.
[0067] In the light-sensitive materials of the invention, it is arbitrary to provide an interlayer in a suitable thickness according to the purpose of using the sensitive material. And, in addition, a variety of layers such as a filter layer, an anticurling layer, a protective layer and an antihalation layer may be suitably combined to use as the compound layers of the light-sensitive material. Into these compound layers, a hydrophilic colloid capable of being used in such an emulsion layer as mentioned above may similarly be used as a bonding agent. Also, in the compound layers, various photographic additives capable of being contained in such an emulsion layer as mentioned above may be contained.
[0068] The processes of a photographic light-sensitive material using the silver halide emulsions relating to the invention are not specially limited, but any of the processes may be applied. The typical examples of the processes include a process in which, after color developing, a bleach-fixing is carried out, and, if necessary, a washing and/or a stabilizing are further carried out; a process in which, after color developing, a bleaching and a fixing are separately carried out, and, if necessary, a washing and/or a stabilizing are further carried out; a process in which a prehardening, neutralizing, color developing, stopping and fixing, washing, bleaching, fixing washing, posthardening, and washing are carried out in order; a process in which a color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, and stabilizing are carried out in order; a developing process in which, after halogenation-bleaching a developed silver produced by a color development, an amount of dyes produced is increased by carring out another color development again; that is, any of the processes may be applied.
[0069] Color developers capable of being used in processing a silver halide emulsion of the invention are an alkaline solution each of which the pH value is preferably no less than 8 and more preferably from 9 to 12 when they contain a color developing agent. An aromatic primary amine which may be served as the above-mentioned developing agent is a compound having amino group on the aromatic ring and is capable of developing an exposed silver halide, and in addition, may be added if necessary with a precursor capable of forming such a compound.
[0070] Typical examples of the above-mentioned color developing agents include those of p-phenylenediamine type, and the preferable examples include the following;
[0071] 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N--diethylaniline, 4-amino-N-ethyl-N-p-hydroxyethylaniline, 3-methyl-4-amino-N-p-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-methanesulfonamideethylaniline, 3-methoxy-4-amino-N-ethyl-N-p-hydroxyethylaniine, 3-methoxy-4-amino-N-ethyl-N-p-methoxyethylaniline, 3-acetamido-4-amino-N,N-dimethylaniline, N-ethyl-N-β-[β--(β-methoxyethoxy)ethoxylethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and the salts thereof such as a sulfate, hydrochloride, a sulfite, a p-toluensulfonic acid salt and the like.
[0072] Besides the above, those described in, for example, Japanese Patent O.P.I. Publication Nos. 64932/1973, 131526/1975 and 95849/1976, and Journal of the American Chemical Society, Vol. 73, pp. 3100 - 3125, 1951 may be given as the typical examples.
[0073] An amount of the above-mentioned aromatic primary amine compound to be used depends upon what degree the activity of a developer is to be determined to. It is desired to increase the amount thereof if the activity should be raised. The amount thereof to be used is within the range og from 0.0002 mol per liter to 0.7 mol per liter. No less than two kinds of the compounds may also be used in combination according to silver halide purposes. For example, any arbitrary combination may freely be used purposively, such as a combination of 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-p-methanesulfonamidoethylaniline, a combination of 3-methyl-4-amino-N-ethyl-N-p-methanesulfonamido ethylaniline and 3-methyl-4-amino-N-ethyl-N-P-hydroxyethylaniline, and the like.
[0074] Color developers capable of being used in the invention are allowed to contain arbitrarily a variety of ingredients which are popularly added, such as an alkaline agent including, for example, sodium hydroxide, sodium carbonate and the like, an alkali metal sulfite, an alkali metal hydrogen sulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, a development accelerator, and the like.
[0075] Besides the above-mentioned additives to be added on the above-mentioned color developers, there are a stain preventive, a sludge preventive, a preservative, an interlayer effect accelerator, a chelating agent and the like, as well as a bromide such as potassium bromide, ammonium bromide and the like, a compound for rapid processing liquid use such as an alkali iodide, nitrobenzoimiazole, mercaptobenzoimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole and the like.
[0076] As for the bleaching agents for the bleaching liquids or bleaching-fixing liquids used in a bleaching process, there may be used generally known compounds coordinated a metallic ion such as that of iron, cobalt, copper or the like by an organic acid such as aminopolycarboxylic acid oxalic acid, citric acid or the like. The typical examples of the above-mentioned aminopolycarboxylic acid include the following;
[0087] Such bleaching liquids may contain a variety if additives as well as the above-mentioned bleaching agents. When a bleaching-fixing liquid is used in a bleaching process, a composite liquid containing a silver halide fixing agent is applied, besides the above-mentioned bleaching agents. In addition to the above, a halogen compound such as potassium bromide may further be contained in the bleaching-fixing liquid, and similar to the case of the above-mentioned bleaching liquid, it is allowed to contain or add various other additives such as a pH buffer, an optical brightening agent, an anti-foaming agent, a surface active agent, a preserving agent, a chelating agent, a stabilizing agent, an organic solvent and the like.
[0088] Such silver halide fixing agents include, for example, a compound capable of forming a water-soluble silver salt through a reaction with a silver halide and capable of being used in an ordinary fixing process, such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium tiocyanate or thiourea, thioether and the like.
[0089] In various processing steps for a silver halide color photographic light-sensitive material of the invention, such as a color developing, bleaching-fixing, (or bleaching and fixing), and, if necessary, washing, stabilizing, drying and the like steps, the processing temperature is desirably at no lower than 30°C from the viewpoint of rapid process.
[0090] Any silver halide color photographic light-sensitive material of the invention is also allowed to be processed in such a washing-substitutable stabilizing process as described in Japanese Patent O.P.I. Publication Nos. 14834/1983, 105145/1983, 134634/1983 and 18631/1983, and Japanese Patent Application Nos. 2709/1983 and 89288/1984, and the like.
[0091] According to the invention, it is characterized that at least one layer of the photographic component layers contains both DIR compounds and AI dyes and the optical reflection density of the silver halide color photographic light-sensitive material is not less than 0.5 at 470nm, 550nm or 680nm, therefore, it is endowed with a high image-sharpness and capable of obtaining an excellent color-reproductive image.
EXAMPLES
[0092] Typical examples of the invention will now be described, and it is however to be understood that the embodiments of the invention shall not be limited thereto.
Example 1
[0093] Sample No. 1 of a silver halide color photographic light-sensitive material was prepared in such a manner that each of the undermentioned layers was coated over to a paper support laminated on the both sides thereof with polyethylene, in order from the support side.
<Layer 1> ... A layer containing o.8og/m2 of a yellow coupler (Y-1) which was dissolved in 1.2g/m2 of gelatin, 0.32g/m2 (in terms of silver which shall apply hereafter) of a blue-light-sensitive silver chlorobromide emulsion (containing silver bromide at 80 mol%) and 0.50g/m2 of dioctylphthalate. <Layer 2> ... An interlayer comprising 0.70g/m2 of gelatin, 12mg/m2 of the exemplified AI dye (AI-34) and 6mg/m2 of the exemplified AI dye (AI-26).
<Layer 3> ... A layer containing 0.03g/m2 of the exemplified compound (D-64) and 0.62g/m2 of a magenta coupler (M-1) which were dissolved in 1.25g/m2 of gelatin, 0.25g/m2 of a green-light-sensitive silver chlorobromide emulsion (containing silver bromide at 70 mol%) and 0.30g/m2 of dioctylhthalate. <Layer 4> ... An interlayer comprising 1.20g/m2 of gelatin. <Layer 5> ... A layer containing 0.45g/m2 of a cyan coupler (C-1) which was dissolved in 1.20g/m2 of gelatin, 0.30g/m2 of a red-light-sensitive emulsion (containing silver bromide at 70 mol%) and 0.20g/m2 of dioctylphthalate.
absorbing agent (UV-1) which was dissolved in 1,00g/m2 of gelatin and 0.20g/m2 of dioctylphthalate.
<Layer 7> ... A layer containing 0.50g/m2 of gelatin.
[0094] To serve as a hardening agent, 2,4-dichloro-6-hydroxy--sym-sodium triazine was added in Layers 2, 4 and 7 in an amount of 0.017g per g of gelatin, respectively.
[0095] Samples No. 2 through 8 were prepared in the same manner applied to the above-mentioned Sample No. 1, except that the amount of the AI dye (AI-26) contained in Layer 2 and the DIR compound contained in Layer 3 of the Sample No. 1 were changed as shown in Table 1.
[0096] The above-mentioned Samples No. 1 through 8 of the light-sensitive materials were exposed to light through an optical wedge and processed in the following steps, respectively.
Processing Steps (at 38°C)
[0098] Add pure water to make 1 liter, and adjust the pH value to 10.1 with a 20% potassium hydroxide or a 10% dilute sulfuric acid.
eaching-Fixing Li
[0099]
Add pure water to make 1 liter, and adjust the pH value to 7.0 with aqueous ammonia or dilute sulfuric acid.
[0100] With respect to each of the samples processed as above, the MTF (Modulation Transfer Function) of the respective green-light-sensitive silver halide emulsion layers were obtained by a microdensitometer, and the MTF values thereof were compared with each other in terms of 5 lines/mm of the spatial frequency. The judgements of image sharpness by making use of such MTF have well known in the skilled in the art, and are described in T.H. James, 'The Theory of the Photographic Process', 3rd Edition, Macmillan Co. The results thereof are shown in Table 1.
[0101] As is obvious from the results shown in Table 1, in the case (of Sample No. 1) that the reflection density at 550nm is less than 0.5, the sharpness is improved a little even if a DIR compound is used in combination; and in the case (of Sample No. 4 through 8) that the reflection density at 550nm is not less than 0.5 and a DIR compound is contained, it is found that the sharpness can greatly be improved.
1. A silver halide color photographic light-sensitive material comprising a reflective
support bearing thereon a photographic component layers including at least a blue-light-sensitive
silver halide emulsion layer, a green-light-sensitive silver halide emulsion layer
and a red-light-sensitive silver halide emulsion layer; wherein at least one layer
of said photographic component layers contains at least one dye capable of being water-soluble
or being decolorized by a development processing liquid, and a compound capable of
releasing a development inhibitive substance or the precursor thereof through a reaction
with the oxidation product of a color developing agent, and the optical reflection
density of said silver halide color photographic light-sensitive material in 470nm,
550nm or 680nm is not less than 0.5.
2. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein said compound is a compound represented by the following Formula (I) or
(II);
Formula (I)
Formula (II)
wherein Coup represents a coupler capable of coupling to the oxidation product of
a color developing agent; Inhibitor represents a group which couples to a coupling
position of Coup and splits off through the reaction thereof with the oxidation product
of a color developing agent so as to become a compound capable of inhibiting the development
of a silver halide; and TIME represents a group represented by the following Formula
(III), (IV), (V) or (VI);
Formula (III)
wherein X represents a group of atoms required for completing a benzene ring or a
naphthalene ring; Y represents
in which R3 is hydrogen, an alkyl or aryl group, and Y is coupled in a coupling position; and
R1 and R2 each represent respectively the synonymous groups with the R3, and a group of
is substituted in an ortho or para position and is coupled to a hetero atom contained
in an inhibitor.
Formula (IV)
wherein W represents a synonymous group with Y in the above Formula (III); and R4 and R5 each are the synonymous groups with R1 and R2 in the Formula (III); R6 represents hydrogen, an alkyl group, an aryl group, an acyl group, a sulfon group,
an alkoxycarbonyl group, or a heterocyclic residual group; and R7 represents hydrogen, an alkyl group, an aryl group, a heterocyclic residual group,
an alkoxy group, an amino group, an acylamide group, a sulfonamide group, a carboxy
group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group; and, this timing
group is coupled to a coupling position by W and is coupled to the hetero atom of
an inhibitor by
Formula [V]
wherein Nu represents a nucleophilic group having oxygen, sulfur or nitrogen atom
having abundant electrons and is coupled to the coupling position of Coup; E represents
an electrophilic group having a carbonyl group, thiocarbonyl group, a phosphinyl group
or a thiophosphinyl group having inabundant electrons, and is coupled to the hetero
atom of an inhibitor; and V represents a coupling group which is subjected to an intramolecular
nucleophilic substitution reaction which is followed by forming a three-membered ring
or a seven-membered ring after releasing Nu from Coup because V relates Nu to E in
three dimensions, and thereby V is capable of releasing an inhibitor.
Formula (VI)
wherein Coup and Inhibitor are synonymous with the above.
3. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein at least one of said blue-light-sensitive silver halide emulsion layer,
green-light-sensitive silver halide emulsion layer and red-light-sensitive silver
halide emulsion layer contains said compound.
4. The silver halide color photographic light-sensitive material as claimed in claim
3, wherein the content of said compound is within the range of from 2 x 10-4 to 5 x 10-1 mol per mol of the silver halide contained in the blue-, green- or red-light-sensitive
silver halide emulsion layer containing said compound.
5. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein said dye is selected from the group consisting of n oxonol dye, hemioxonol
dye, merocyanine dye and azo dye.
6. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein the content of said dye is within the range of from 2 x 10-4 to 5 x 10-1 mol per mol of the silver halides in total contained in said blue-light-sensitive
silver halide emulsion layer, green-light-sensitive silver halide emulsion layer and
red-light-sensitive silver halide emulsion layer.
7. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein said optical reflection density in 470nm, 550nm or 680nm is not more than
2.0.
8. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein the total silver content of said blue-light-sensitive silver halide emulsion
layer, green-light-sensitive silver halide emulsion layer and red-light-sensitive
silver halide emulsion layer is within the range of from 0.3 to 1g/m2.
9. The silver halide color photographic light-sensitive material as claimed in claim
1, wherein the silver halide of said blue-light-sensitive silver halide emulsion layer,
green-light-sensitive silver halide emulsion layer and red-light-sensitive silver
halide emulsion layer comprises silver chloride or silver chloroiodobromide containing
at least 1 mol% of silver chloride.