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(11) | EP 0 271 005 A2 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Silver halide photographic light-sensitive material excellent in dye-image preservability |
| (57) A silver halide photographic light-sensitive material improved in light fading resistance
of cyan dye-images and, particularly, in discoloration resistance in low density
area of the images. The photographic material is comprises a support having thereon
at least one silver halide emulsion layer and at least one non-light-sensitive layer,
and the silver halide emulsion layer contains a cyan-dye forming coupler represented
by the following formula [I] or [II] and at least one of the silver halide emulsion
layer containing the above cyan-dye forming coupler and the non-light-sensitive layer
adjacent to the emulsion layer contains an liquid UV absorbent which is liquid state
at an ordinary temperature together with a high boiling organic solvent having the
dielectric constant of not more than 0.6 in the ratio by weight of from 0.65 to zero
to said UV absorbent contained in said layer.
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Field of the Invention
[0001] This invention relates to a silver halide photographic light-sensitive material excellent in preservability of dye-image formed thereon.
Background of the Invention
[0002] Generally, a silver halide color photographic light-sensitive material is coated on the support thereof with three kinds of silver halide color photographic emulsion layers selectively sensitized so as to enable the emulsion layers to have the sensitivity to a blue-light, green-light and red-light, respectively.
[0003] It is well-known that dye-images are generally faded or discolored in various preservation conditions of the above-mentioned color photographic light-sensitive materials. For example, like the display of color prints in the show window of a photo studio, there is a fading-discoloration caused in the case of preserving it being exposed to light for a long time. this type of fading-discoloration is called a light fading-discoloration. On the other hand, like the preservation of color prints in an album, there is another fading-discoloration caused when they are preserved in the dark at relatively high temperature and humidity for a long time, although an exposure to light is relatively short. This type of fading-discoloration is called a dark fading-discoloration.
[0004] When regarding photographic products including color prints as recording materials, it is demanded to reduce the above-mentioned fading-discoloration to the utmost even in any preservation conditions, and such demand is getting incresed year by year. Especially in cyan-dye forming couplers, the improvements of heat and moisture resistance thereof, i.e., a dark fading-discoloration resistance, have recently become an essential subject to be achieved.
[0005] The conventionally known cyan-dye forming couplers include, for example, a 2,5-diacylaminophenol type cyan-dye forming coupler substituted with an acylamino group in the 2nd and 5th positions of the phenol group of the coupler. They are described in, for example, U.S. Patent No. 2,895,826 and Japanese Patent Publication Open to public Inspection (hereinafter called Japanese Patent O.P.I. Publication) Nos. 112038-1975, 109630-1978 and 163537-1980.
[0006] These 2,5-diacylaminophenol type cyan-dye forming couplers are popularly used, because cyan dye-images excellent in dark-fading and discoloration resistance may be obtained. However, they have a defect in general that both of the light-fading resistance of color dye-images and the yellow discoloration, hereinafter simply called a Y-stain, of unreacted cyan-dye forming couplers caused by light are seriously inferior to others. Together with the above-mentioned light-fading, a phenomenon that a low density area is discolored into pink is particularly seen, so that even a problem of amplifying the visual color-fading may be caused.
[0007] Accordingly, as to the means of improving the light-fading resistance of such a 2,5-diacylaminophenol type cyan-dye forming coupler, there are proposed, for example, to use a benzotriazole compound in combination, as described in Japanese Patent O.P.I. Publication No. 151149-1975. However, this particular compound is serious in crystallization property, so that it cannot practically be used.
[0008] It is also known that such a high boiling organic solvent as dibutyl phthalate which has so far been used is used by inceasing its content. When having used this solvent, there has caused such a problem that photographic characteristics including color tones and the like are affected and dark-fading resistance is deteriorated; light-fading resistance may have been improved a little though. In addition, there has had few effects of inhibiting Y-stains caused by light.
[0009] On the other hand, Japanese Patent O.P.I. Publication No. 173835-1982 proposes a method of improving color tones and dye fastness in such a manner that, a 2,5-diacylaminophenol cyan-dye forming coupler substituted with an ortho-sulfonamidophenylacylamino group in the 2nd position of the phenol group of the cyan-dye forming coupler, such cyan-dye forming coupler is dispersed by making use of a high boiling organic solvent having a specific dielectric constant. With respect to the method, it was confirmed that the light-fading resistance of a cyan dye-image was seriously spoiled.
[0010] Further, Japanese Patent O.P.I. Publication No. 222852-1985 proposes a method of using both liquid type and solid type UV absorbers, and U.S. Patent No. 4,587,346 proposes a method of using a liquid type UV absorbent and other methods.
[0011] However, these methods have almost no effect particularly on the discoloration in a lowe density area; but a certain degree of effect on light-fading resistance though.
[0012] It is the present state of things that any method of obtaining cyan dye-images excellent in resistance against both dark-fading and light-fading and also in discoloration resistance in low density areas has not been discovered, and the improvements thereof have, therefore, been desired.
Summary of the Invention
[0013] It is, therefore, an object of the invention to provide a silver halide photographic light-sensitive mterial improved in light-fading resistance of cyan dye-images and, particularly, in discoloration resistance in low density areas of the images.
[0014] Another object of the invention is to provide a silver halide photographic light-sensitive material which is excellent in dark-fading resistance and is improved in dark-fading resistance.
[0016] The above-mentioned objects of the invention can be achieved with a silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer and at least one non-light-sensitive layer; wherein at least one of the above-mentioned silver halide emulsion layers contains at least one cyan-dye forming coupler represented by the following formula [I] or [II], and at least one of above-mentioned cyan-dye forming coupler-containing silver halide emulsion layer and the non-light-sensitive layers adjacent to the cyan-dye forming coupler-containing emulsion layer contains a UV absorbent which is in liquid state at an ordinary temperature and, further, the layer containing the UV absorbent also contains a high boiling organic solvent having a dielectric constant of not more than 6.0 in an amount by weight within the range of from 0.65 to zero to the total content of the UV absorbent.
wherein R₁ is an alkyl group or an aryl group; R₂ is an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R₃ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, provided that R₃ and R₁ may be bonded together to complete a ring; and Z₁ is a hydrogen atom or a group capable of releasing upon reaction with the oxidized product of a color developing agent.
wherein R₄ is an alkyl group having 2 to 6 carbon atoms; R₅ is a ballast group; and Z₂ is a hydrogen atom or an atom or a group capable of releasing upon reaction with the oxidized product of a color developing agent.
Detailed Description of the Invention
[0018] In the cyan-dye forming couplers represented by Formula [I], hereinafter called the cyan-dye forming coupler of the invention, the preferable alkyl groups represented by R₁ are those having one to 32 carbon atoms. They may also be either straight-chained or branch-chained and include those having substituents.
[0019] The preferable aryl groups represented by R₁ are a phenyl group including those having substituents.
[0020] The preferable alkyl groups represented by R₂ are those having one to 32 carbon atoms. They may also be either straight-chained or branch-chained and include also those having substituents.
[0021] The preferable cycloalkyl groups represented by R₂ are those having 3 to 12 carbon atoms and they include also those having substituents.
[0022] The preferable aryl groups represented by R₂ are a phenyl group and include also those having substituents.
[0023] The preferable heterocyclic groups represented by R₂ are those of 5- to 7-membered, which may be either substituted or condensed.
[0024] R₃ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Among them, a hydrogen atom is preferable.
[0025] The preferable rings completed by R₁ and R₃ bonded together are those of 5- or 6-membered. The examples of the 5- or 6-membered rings include the following rings:
and the like rings.
[0026] In Formula [I], the groups represented by Z₁ each capable of releasing upon reaction with the oxidized product of a color developing agent include, for example, a halogen atom, an alkoxy group, an aryloxy group, a acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an imido group and the like and, preferably, a halogen atom, an aryloxy group and an alkoxy group.
[0027] The particularly preferable cyan-dye forming couplers of the invention are those represented by the following formula [I-A].
wherein RA1 is a phenyl group substituted with at least one halogen atom and such phenyl groups may further have other substituent than halogen atoms; RA2 is synonymous with R₁ denoted in the above-given Formula [I]; and XA1 is a halogen atom, an aryloxy group or an alkoxy group.
[0028] The typical examples of the cyan-dye forming couplers represented by the Formula [I] will be given below:
[0029] The above-given cyan-dye forming couplers include 2,5-diacylamino type cyan-dye forming couplers described in, for example, Japanese Patent Application No. 21853-1986, pp.26-35; Japanese Patent O.P.I. Publication No. 225155-1985, the lower left column of p.7 to the lower right column of p.10; Japanese Patent O.P.I. Publication No. 222853-1985, the upper left column of p.6 to the lower right column of p.8; and Japanese Patent O.P.I. Publication No. 185335-1984, the lower left column of p.6 to the upper right column of p.9. These couplers may be synthesized in the methods described in the above-given specification.
[0031] In the Formula [II], the alkyl groups represented by R₄ may be either straight-chained or branch-chained and include those having substituents.
[0032] The ballst groups represented by R₅ are an organic groups each having such a size and a shape as are capable of giving couplers a sufficient volume so as not to diffuse the couplers substantially from a coupler-containing layers to other layers. The preferable ballast groups are those represented by the following formula:
wherein R₆ is an alkyl group having one to 12 carbon atoms; and Ar is such an aryl group as a phenyl group, which include those having substituents.
[0033] The typical examples of the couplers represented by Formula [II] will be given below. It is, however, to be understood that the invention shall not be limited thereto.
[0034] The typical examples of the cyan-dye forming couplers represented by Formula [II] including the above-given typical examples thereof are described in Japanese Patent Examined Publication No. 11572-1974, Japanese Patent O.P.I. Publication Nos. 3142-1986, 9652-1986, 9653-1986, 39045-1986, 50136-1986, 99141-1986 and 105545-1986, and so forth.
[0035] The cyan-dye forming couplers represented by Formula [I] or [II] may be used with other cyan-dye forming couplers in combination, provided that it shall not be contrary to the objects of the invention.
[0036] The cyan-dye forming couplers relating to the invention may be used in an amount within the range of, usually, from about 0.05 to 2 mol and, preferably, from 0.1 to one mol per mol of silver halide used.
[0037] The cyan-dye forming couplers relating to the invention may usually be contained in a red-sensitive silver halide emulsion layer and may also be contained in either a non-light-sensitive layer or an emulsion layer sensitive to the primary color spectral regions other than red spectral region.
[0038] In the invention, a liquid UV absorbent. hereinafter called the liquid UV absorbent of the invention, is used at an ordinary temperature.
[0039] In the invention, the expression, "liquid at an ordinary temperature", means an amorphous and fluid liquid having an almost constant volume at 25°C, as defined in 'Encyclopedia Chemica', 1963, Kyoritsu Publishing Co. and so forth. There is no limitation to the melting points thereof, provided they have the above-mentioned properties. It is, however, preferable that such compounds have a melting point of not higher than 30°C and more preferably not higher than 15°C.
[0040] The liquid UV absorbents of the invention may be either a single compound or a mixture. As for such mixtures, those comprising a group consisting of structural isomers may preferably be used. (Such structural isomers are described in U.S. Patent No. 4,587,346 and so forth.)
[0041] The liquid UV absorbents of the invention may have any type of structures, provided that the above-mentioned requirements can be satisfied. From the viewpoint of the light-fastness of such UV absorbents themselves, it is preferable to use a 2-(2ʹ-hydroxyphenyl)benzotriazole type compound represented by the following formula [a].
[0042] In the above-given Formula [a], R₁₁, R₁₂ and R₁₃ each are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group.
[0043] The halogen atoms represented by R₁₁, R₁₂ and R₁₃ include, for example, a fluorine atom, an chlorine atom, a bromine atom and so forth and, among them, a chlorine atom is particularly preferable.
[0044] The alkyl and alkoxy groups represented by R₁₁, R₁₂ and R₁₃ include, preferably, those having one to 30 carbon atoms. The alkenyl groups preferably include those having 2 to 30 carbon atoms and these groups may be either straight-chained or branch-chained.
[0046] The typical examples of the alkyl, alkenyl and alkoxy groups include, for example, a methyl group,. an ethyl group, an isopropyl group, a t-butyl group, a sec-butyl group, an n-butyl group, an n-amyl group, a sec-amyl group, a t-amyl group, an octyl group, a nonyl group, a dodecyl group, an eicosyl group, an α,α-dimethylbenzyl group, an octyloxycarbonylethyl group, a methoxy group, an ethoxy group, an octyloxy group, an allyl group and so forth.
[0047] The particularly preferable aryl and aryloxy groups out of those represented by R₁₁, R₁₂ and R₁₃ include, for example, a phenyl group and phenyloxy group and which may be substituted. The typical examples of such substituents include a phenyl group, a 4-t-butylphenyl group, a 2,4- di-t-amylphenyl group and so forth.
[0048] Out of the groups represented by R₁₁ and R₁₂, a hydrogen atom, an alkyl group, an alkoxy group and an aryl group is preferable and, in particular, a hydrogen atom, an alkyl group and an alkoxy group are more preferable.
[0049] Out of the groups represented by R₁₃, a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group are particularly preferable and a hydrogen atom, an alkyl group and an alkoxy group are further preferable from the viewpoint of light-fading resistance.
[0050] In order to become liquid at an ordinary temperature. it is preferable that at least one group out of the groups represented by R₁₁, R₁₂ and R₁₃ is an alkyl group and it is more preferable that at least two groups are alkyl groups.
[0051] The alkyl groups represented by R₁₁, R₁₂ and R₁₃ may be of any types. It is, however, preferable that at least one is a tertiary alkyl group or a secondary alkyl group and it is particularly preferable that the alkyl group represented by at least one of R₁₁ and R₁₂ is a tertiary or secondary alkyl group.
[0052] The typical examples of the liquid UV absorbents relating to the invention will be given below:
[0053] The liquid UV absorbents relating to the invention may be added in any amount. However, the amount thereof added is, for example, within the range of from 0.1 to 300% by weight to the binder content of the photographic component layers each containing the UV absorbent, preferably within the range of from one to 200% and, more preferably, within the range of from 5 to 100%. The amount of the UV absorbent coated is preferably from 0.01 to 100 mg/100 cm², further preferably from 0.1 to 50 mg/100 cm² and still further preferably from 0.5 to 30 mg/100 cm².
[0054] In the invention, the aforementioned cyan-dye forming couplers relating to the invention are contained in silver halide emulsion layer and the above-mentioned liquid UV absorbent relating to the invention is contained in at least one layer selected from the group consisting of the aforementioned cyan-dye forming coupler-containing silver halide emulsion layer and the non-light-sensitive layers adjacent to the above emulsion layer. It is, however, preferable that the liquid UV absorbent relating to the invention is contained at least in the non-light-sensitive layer adjacent to the silver halide emulsion layer arranged to the opposite side from the support, seeing from the support. It is more preferable that the UV absorbents are contained in both non-light-sensitive layers adjacent to the both sides of the silver halide emulsion layer, respectively.
[0055] When containing the liquid UV absorbent relating to the invention into a silver halide emulsion layer containing the cyan-dye forming couplers relating to the invention, how to add them is that the liquid UV absorbent relating to the invention and cyan-dye forming coupler are simply mixed up or the UV absorbent is finely dispersed in such a hydrophilic binder as an aqueous gelatin solution by making use of a surface active agent, together with a low boiling solvent such as ethyl acetate or the like, if required, because the liquid UV absorbent relating to the invention is liquid at an ordinary temperature and is capable of serving as a solvent for the cyan-dye forming coupler relating to the invention.
[0056] If required, it is also allowed to jointly use such a high boiling solvent as phenol derivatives, phthalic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkyl amides, fatty acid esters, trimesic acid esters and so forth.
[0057] When adding the liquid UV absorbent relating to the invention to a non-light-sensitive layer adjacent to a cyan-dye forming coupler-containing silver halide emulsion layer, the liquid UV absorbent relating to the invention is finely dispersed in a hydrophlic binder such as an aqueous gelatin solution by making use of a surface active agent, or by making use of a low boiling solvent such as ethyl acetate or the like, if required.
[0058] Further if required, a high boiling solvent similar to the above may also be used in combination.
[0059] In addition to the above, the liquid UV absorbent relating to the invention may also be used at an ordinary temperature in combination with a solid UV absorbent. Even in this case, the above-mentioned adding method can also be applied.
[0060] In the case that the UV absorbent of the invention which is in liquid state at an ordinary temperature is jointly used at an ordinary temperature with a solid UV absorbent, it is particularly preferable that at least one kind of the liquid UV absorbent is jointly used with at least two kinds of solid UV absorbents.
[0061] Such combination of the above-mentioned UV absorbents are effective in preventing or inhibiting the surfaces of processed light-sensitive materials from fogging or causing the so-called haze.
[0062] The UV absorbents in solid state at an ordinary temperature preferably include the compounds which have the same formula [a] as that of the liquid UV absorbents and become solid at 25°C.
[0063] Now, the typical examples of the UV absorbents which are in solid state at an ordinary temperature will be given as follows:
[0064] In the above-mentioned case, any mixture proportion of a liquid UV absorbent to a solid UV absorbents may be applied. However, in an ordinary temperature condition, the amount by weight of such a liquid UV absorbent is preferably not less than 30%, more preferably from not less than 30% to not more than 99% and, particularly from not less than 30% to not more than 95% to the whole UV absorvent used.
[0065] The solid UV absorbent is comprised of the combination of not less than 2 kinds of solid UV absorbents as the components of the above-mentioned absorbent and the component solid UV absorbents each have the different structures. At least one of the component solid UV absorbents has not less than 8 carbon atoms in total in the groups represented by R₁ and R₂ denoted in Formula [a]. The total content of all the component solid UV absorbents each having not less than 8 carbon atoms in total in the groups represented by R₁ and R₂ should preferably be not less than 35% by weight, more preferably be from not less than 35% upto 100% and particularly be from not less than 50% upto 100%.
[0066] However, the solid UV absorbent should preferably be comprised of not less than 2 kinds of the component solid UV absorbents having the different structures from each other, when the whole content of the component solid UV absorbents having not less than 8 carbon atoms in total in the groups represented by R₁ and R₂ is 100%.
[0067] In at least one of the UV absorbents which are in liquid state at an ordinary temperature, the groups represented by R₁ and R₂ nenoted in the aforegiven Formula [a] preferably have a total carbon number of not less than 8 and, however, the upper limit of the carbon numbers is preferably about not more than 12; such a upper limit may be varied by the groups represented by R₁ and R₂ and, further, by R₃ though.
[0068] Any of a total amount of both solid and liquid UV absorbents may be added, however. it is allowed to add them in total amount within the range of from 0.1 to 300% by weight to the amount of binders to be added to the photographic component layers each containing the UV absorbents. respectively, and preferably from 1 to 200% and particularly from 5 to 100%.
[0069] A total amount of the respective UV absorbents to be coated is preferably from 0.01 to 100 mg/dm², more preferably from 0.1 to 50 mg/dm² and particularly from 0.5 to 30 mg/dm².
[0070] In the case that a silver halide photographic light-sensitive material of the invention used is a multicolor light-sensitive material, the particularly preferable arrangement of the component layers is that a silver halide emulsion layer containing a yellow dye-forming coupler, a first interlayer, a silver halide emulsion layer containing a magenta dye-forming coupler, a second interlayer, a silver halide emulsion layer containing the cyan dye-forming coupler relating to the invention, a third interlayer and a protective layer are arranged over to a support in order from the support side.
[0071] Particularly, in the case that a silver halide photographic light-sensitive material of the invention has the above-mentioned layer arrangement, it is preferable to contain one of the liquid UV absorbents of the invention in at least the third interlayer and it is further preferable to contain them in both of the second and third interlayers.
[0072] Also, in the invention, the layers containing the liquid UV absorbents further contain a high boiling organic solvent having a dielectric constant of not lower than 6.0 in an amount within the range of from 0 to 0.65 parts by weight per part of a total amount of the UV absorbents added and preferably from 0 to 0.30 parts.
[0073] The above-mentioned high boiling organic solvents relating to the invention may be any compound, if it has a dielectric constant of not higher than 6.0. The lower limit of the dielectric constant thereof shall not be specially limitative, however, it is preferably not lower than 1.9. For example, such compounds include esters such as a phthalic acid ester, a phosphoric acid ester and the like; organic acid amides; ketons; hydrocarbon compounds; and so forth, and more preferably the phthalic acid esters or the phosphoric acid esters; provided that they have a dielectric constant of not higher than 6.0.
[0074] The preferable high boiling organic solvents are those having a vapor pressure of not higher than 0.5 mmHg at 100°C. Such organic solvents may be a mixture of two or more of them, provided that the dielectric constant thereof is not higher than 6.0. Every dielectric constant mentioned in the invention expresses those shown at 30°C.
[0075] The above-mentioned phthalic acid esters are represented by the following formula [HA]:
wherein RH1 and RH2 are each an alkyl group, an alkenyl group or an aryl group, provided that a total number of the carbon atoms of the groups represented by RH1 and RH2 is from 9 to 32 and more preferably from 16 to 24.
[0076] The alkyl groups represented by RH1 and RH2 in Formula [HA] are those straight-chained or branched and the include, for example, a butyl, hexyl, octyl, nonyl, dodecyl, tetra-decyl, hexadecyl, heptadecyl, octadecyl and the like groups.
[0077] The aryl groups represented by RH1 and RH2 include, for example, a phenyl, naphthyl and the like groups and, in addition, an alkenyl, hecenyl, heptenyl, octadeenyl and the like groups.
[0078] These alkyl, alkenyl and aryl groups are also allowed to have a single or plural substituents.
[0079] In the above-given Formula, the groups represented by RH1 and RH2 are preferably alkyl groups including, for example, 2-ethylhexyl group, 3,5,5-tromethylhexyl group, n-octyl group, n-nonyl group and the like groups.
[0080] The above-mentioned phthalic acid esters are represented by the following formula [HB]:
wherein RH3, RH4 and RH5 are each an alkyl, alkenyl or aryl group, provided that a total number of the carbon atoms of the groups represented by RH3, RH4 and RH5 is from 24 to 54.
[0081] The alkyl groups represented by RH3, RH4 and RH5 may be those straight-chained or branched which include, for example, a butyl, pentyl, hexyl, octyl, nonyl, dodecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl and the like groups.
[0082] These alkyl, alkenyl and aryl groups are allowed to have a single or plural substituents. They groups represented by RH3, RH4 and RH5 are preferably alkyl groups which include, for example, a 2-ethylhexyl, n-octyl, 3,5,5-trimethylhexayl, n-nonyl, n-decyl, sec-decyl, sec-dodecyl, t-octyl and the like groups.
[0083] The typical examples of the organic solvents will be given below and it is, however, to be understood that the invention shall not be limited thereto.
[0084] Among the high boiling organic solvents having a dielectric constant of not higher than 6.0, which may be used in the invention, the preferable ones are those represented by the above-given Formulas [HA] and [HB] and the more preferable ones are phthalic acid ester type high boiling organic solvents having the above-given Formula [HA].
[0085] In the silver halide light-sensitive material of the invention, it is allowed to contain simultaneously both of a high boiling organic solvent having a dielectric constant exceeding 6.0 and another one having a dielectric constant of not higher than 6.0. The total content of the former to that of the latter is not more than 0.5 by weight, preferably not more than 0.25 and further preferably not more than 0.1.
[0086] The silver halide photographic light-sensitive materials of the invention which have the above-mentioned structure may be in the forms of, for example, a color negative or positive film, a color print paper and the like and, inter alia, the advantages of the invention can effectively be displayed especially when they are used as a color print paper for direct appreciation of color photographs.
[0087] The dye-image forming couplers used in the invention shall not specially limited, except the cyan-dye forming couplers relating to the invention, but various types of such couplers may be used. For example, the typical ones include the following compounds:
[0088] The yellow-dye image forming couplers include, for example, those of the acylacetamide type and the benzoylmethane type.
[0089] The magenta-dye image forming couplers include, for example, those of the 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type and cyanoacetyl type.
[0090] The silver halides used in the silver halide photographic light-sensitive materials of the invention include, for example, anyone used in the popular silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and so forth.
[0091] The silver halide emulsions used in the invention may be chemically sensitized in, for example, a sulfur sensititization, a selenium sensitization, a reduction sensitization, a noble-metal sensitization and the like.
[0092] The silver halide emulsions used in the invention may be optically sensitized to a desired spectral wavelength region by making use of the dyes which are well-known as spectral sensitizing dyes in photographic industry.
[0093] As for the binders (or protective colloids) used in the silver halide photographic light-sensitive materials of the invention, gelatins may advantageously be used. Besides the gelatins, hydrophilic colloids may also be used, for example, gelatin derivatives, graft-polymers of gelatin and other macromolecules, proteins, sugar derivative, cellulose derivatives, synthesized hydrophilic macromolecular substances such as mono- or co-polymers.
[0094] If required, the silver halide photographic light-sensitive materials of the invention may further be added with additives such as a hardener, a color contamination inhibitor, an image stabilizer, a plasticizer, a latex, a surface active agent, a matting agent, a sliding agent, an antistatic agent and so forth.
[0095] The silver halide photographic light-sensitive materials of the invention may be able to form photographic images when they are treated in any color development processes which are well-known in the art.
[0096] As described above, the silver halide photographic light-sensitive materials of the invention are those which improved the light color-fading property of cyan-dye images and particularly eliminated the discoloration caused in low density areas, so as to form cyan color images which are stable against light, heat and moisture even if they are stored for a long time; and to reduce the possibility of changing cyan dyes into a leuco dyes during a development process.
Examples
[0097] The invention will now be described in detail, with reference to the examples. It is, however, to be understood that the embodiments of the invention shall not be limited thereto.
[Example-1]
[0098] There prepared a multilayered silver halide photographic light-sensitive material having the layer arrangement shown in Table-1, about which will be described in detail below.
[0099] AS-1, DS-1, Y-1, M-1 and UV-S1 used in the above compositions are the compounds having the following structures, respectively.
[0100] These samples No. 1 through No. 23 were exposed to white light through an optical step wedge by making use of a photosensitometer (Model KS-7 manufactured by Konishiroku Photo Ind. Co., Ltd.) and were then processed in the following steps.
Processing liquid composition
(Color developer)
[0101] Benzyl alcohol 15 ml
Ethylene glycol 15 ml
Potassium sulfite 2.0 g
Potassium bromide 0.7 g
Sodium chloride 0.2 g
Potassium carbonate 30.0 g
Hydroxylamine sulfate 3.0 g
Polyphosphoric acid, (TPPS) 2.5 g
3-methyl-4-amino-N-ethyl-N-(β-methane-sulfonamidoethyl)-aniline sulfate 5.5 g
Optical brightening agent, (a 4,4ʹ-diaminostilbenedisulfonic acid derivative) 1.0 g
Potasium hydroxide 2.0 g
Water to make in total 1 liter
pH to be adjusted to pH 10.20
(Bleach-fixer A)
[0102] Ferric ammonium ethylenediaminetetraacetate, dihydride 60 g
Ethylenediaminetetraacetic acid 3 g
Ammonium thiosulfate, (a 70% solution) 100 ml
Ammonium sulfite, (a 40% solution) 27.5 ml
pH to be adjusted with potassium carbonate or glacial acetic acid to pH 7.1
Water to make in total 1 liter
[0103] With respect to the samples obtained from the above-mentioned process, the light color-fading, dark color-fading, yellow-staining and discoloring properties were tested in the following manner:
[Light color-fading test]
[0104] By making use of an under-glass type outdoor exposure table, the samples were exposed to sun light for 5 days and for 15 days, respectively. The resulted light color-fading of each sample was expressed by the ratio of the residual color density of the respective cyan color images to the initial color density D=1.0 of the same images.
[0105] Residual ratio = (D/Do)×100, (in which D is a color density obtained after the color was faded.)
[Dark color-fading test]
[0106] The samples were stored for 14 days in an atmosphere of a high temperature at 70°C and a high humidity at 80%RH, respectively. The resulted dark color-fading of each sample was expressed by the ratio of the residual color density of the respective cyan color images to the initial color density D=1.0 of the same images.
[0107] Residual ratio = (D/Do)×100, (in which D is a color density obtained after the color was faded.)
[Yellow-staining test]
[0108] In both of the above-mentioned light and dark color fading tests, the degrees of the yellow stains (hereinafter sometimes simply called a YS) caused in each undeveloped color area were obtained in the following manner.
Yellow stain ΔDB = ΔDB -DoB, wherein
DB = A blue-light density after stored, and
DoB = A blue-light density before stored.
[0109] These samples were measured by making use of an optical densitometer (model PDA-65 manufactured by Konishiroku Photo Ind. Co., Ltd.).
[Discoloration test]
[0110] In order to express the degrees of discoloration of cyan dye images, a 'P variation degree' is defined as follows.
[0111] When an initial cyan density (Dr) of 0.50 is disclored after test and both of a red-light density DRʹ and green-light density DG are obtained after the discoloration. Thus, a discoloration degree P is expressed by a ratio (%) of the red-light density DRʹ to the green-light density DG. Namely, a value of P (%) can be obtained by the following equation:
P (%) = DG/DRʹ × 100
[0112] Now, the dielectric constants of the high boiling organic solvents used in the example are shown below:
[0114] It is found from the results shown in Table-2 that, as compared with Sample No. 1. Samples No. 2 through No. 5 and No. 23, that is, the samples containing a solid UV absorbent different from those of the invention and the samples containing a boiling organic solvent, an amount thereof added or a UV absorbent added to other layers each different from those of the invention, even if the liquid UV absorbents of the invention were added therein, such a sample has a problem that a pinkish discoloration is seriously caused; a light color-fading and light yellow-staining were somewhat improved though.
[0115] In contrast to the above-mentioned comparative samples, it is also found that Samples No. 6 through No. 22 each having the structures of the invention obtained the excellent results satisfiable for every evaluation and displayed an excellent image preservability.
[0116] In addition to the above, Samples No. 6 through No. 13, No. 15 through No. 17, No. 19 through 21 and No. 22 each of which used the liquid UV absorbents not containing any halogen atom in R₁₃ denoted in the liquid UV absorbents represented by the aforegiven Formula [a] are more preferable from the viewpoint of pinkish discoloration prevention, and it is still further found that Samples No. 6, No. 8 through No. 16 and No. 20 through 22 each using a phthalic acid ester type high boiling organic solvents out of the high boiling organic solvents of the invention are also preferable from the viewpoint of dark yellow staining prevention.
[0117] The same effects were also found in Samples No. 19 and No. 20 which used the liquid UV absorbents of the invention to serve as a high organic solvent for the cyan-dye forming couplers of the invention.
[Example-2]
[0118] Samples No. 31 through No. 44 were prepared in the same manner as in Example-1, except that the contents of UV absorbents, the layers containing the same and the kinds of cyan-dye forming couplers added to the 5th layers of each sample were changed as shown in Table-3, and the resulted samples were evaluated, respectively.
[0119] The UV absorbents, the high boiling organic solvents and the proportions by weight thereof were the same as in Example-1, and the details thereof are indicated by the respective sample numbers of Example-1.
[0121] From the results shown in Table-3, it is found that the effects of the invention can satisfactorily be displayed in Samples No. 32 through No. 36, No. 43 and No. 44, even in either cases where the constitutional requirements of the invention are applied to at least one or not less than two layers of the photographic component layers of the invention, or the different constitutional requirements are applied to the respective photographic component layers in Samples No. 41 and No. 42.
[0122] It is also found therefrom that there are particularly preferable results displayed, from the viewpoints of the prevention of both light fading and light yellow-staining, in Samples No. 32, No. 35 through No. 42 and No. 44 each containing the constitutional requisites of the invention in the non-light-sensitive layer (that is the 6th layer) which was arranged to the opposite side of the cyan-dye forming coupler-containing silver halide emulsion layer of the invention, seeing from the support side.
[Example-3]
[0123] The multilayered silver halide photographic light-sensitive material having the layer arrangement shown in Table-4 was prepared, of which will be described in detail below.
[0124] The resulted samples No. 51 through No. 66 were exposed to white light through an optical step wedge by making use of a sensitometer (Model KS-7 manufactured by Konishiroku Photo Ind. Co., Ltd.) and were then treated in the same process as in Example-1.
[0125] The treatments were made with bleach-fixer B having the same composition as in the aforementioned bleach-fixer A, except that 300 cc of the above-given developer were added to bleach-fixer A. After the treatments, the resulted samples were variously tested in the following manner.
(1) Dark color-fading test
[0126] The samples were stored for 20 days in an atmosphere of a high temperature at 70°C and a high humidity at 80%RH, respectively. After then, each of the residual color-dye density (%) faded from the initial color density 1.0 of the dyes was measured.
(2) Light color-fading test
[0127] The samples were irradiated with light by making use of a Xenon fade-o-meter (having 100,000 lux.) for 200 hours, After then, each of the residual color-dye density (%) faded from the initial color density 1.0 was measured.
(3) Yellow-staining test
[0128] With respect to the samples irradiated with light for 200 hours in the above-mentioned test (2), the light yellow-stains (hereinafter sometimes simply called a light YS) caused in the undeveloped color areas were evaluated in the following manner.
Light YS: ΔDB = ΔDB - DoB, wherein
DB = A blue-light density after irradiation, and
DoB = A blue-light density after irradiation.
(4) Cyan-color recurring test
[0129] Each of the maximum cyan-color density was obtained by processing with a color developer, bleach-fixer A and bleach-fixer B, respectively, was evaluated in the following manner.
Cyan-color recurring property (%) = DRB / DRA, wherein
DRA: A maximum cyan-color density obtained by processing with bleach-fixer A.
DRB: A maximum cyan-color density obtained by processing with bleach-fixer B.
[0130] The above-mentioned densities were measured by making use of an optiacal densitometer Model PDA-65 (manufactured by Konishiroku Photo Ind. Co., Ltd.)
[0131] The results obtained in the above-mentioned tests (1) through (4) are shown in Table-5. The dielectric constant of the high boiling organic solvent of the invention other than those given in Example-1 is as follows.
High boiling organic solvent No. H-7
The dielectric constant thereof is 4.4
[0133] From the results shown in Table-5, it is found that Samples No. 52 through No. 54 each containing the cyan-dye forming coupler of the invention and the UV absorbent in combination have almost no effect on dark color-fading prevention and cyan-color recurring property; they are effective to some extent on the prevention of light color-fading and light yellow-staining though.
[0134] It is also found that Sample No. 55 containing the other cyan-dye forming coupler than that of the invention and the constitutional requisites for the invention in combination is seriously poor in the prevention of dark color-fading, in particular.
[0135] In contrast to the above, it is found that Samples No. 56 through No. 67 of the invention are endowed with excellent characteristics capable of answering to every evaluation so as to display the effects of the invention satisfactorily.
[0136] When the samples of the invention were checked up in further detail, it is found that Samples No. 56 through No. 60 and No. 62 through No. 65 each not containing anu halogen atom in R₃ out of the liquid UV absorbents represented by Formula [a] are more preferable.
[0137] In addition to the above, it is found that Samples No. 56 through No. 63 using a phthalic acid ester type solvent out of the high boiling organic solvents or Sample No. 65 not using any high boiling organic solvent at all are particularly preferable from the viewpoint of light color-fading prevention.
[Example-4]
[0138] Samples No. 71 through No. 83 were prepared in the same manner as in Example-3, except that the contents of both UV absorbents and high boiling organic solvents and the layers containing them were changed as shown in Table-6 and were then evaluated, respectively. The UV absorbents, high boiling organic solvents and the contents by weight thereof were the same as those in Example-3. The details thereof are indicated by the sample numbers of Example-3.
[0139] Besides the above, in the evaluation of color recurring property, bleach-fixer B used in Example-1 was replaced by the fatigued liquid having used in an automatic processor for processing color papers. The results obtained are shown in Table-6 below.
[0140] From the results Shown in Table-6, it is found that these samples have displayed the effects of the invention satisfactorily even in either cases that the constitutional requisites of the invention were applied to not less than two photographic component layers or that the diffierent constitutional requisites were applied to the respective component layers.
[0141] It is also found therefrom that there are particularly preferable results displayed, from the viewpoints of the prevention of light color-fading, in Samples No. 75 through No. 81 and No. 83 each containing the constitutional requisites of the invention in the non-light-sensitive layer (that is the 6th layer) which was arranged to the opposite side of the cyan-dye forming coupler-containing layer, seeing from the support side.
[0142] On the other hand, it is found that Samples No. 77, No. 78 and No. 81 further improved in dark color-fading preventability and color-recurring property, so that the preferable results can be displayed.
[Example-5]
[0143] In Samples No. 78 and No. 80 used in Example-4, cyan-dye forming coupler II-4 of the invention were replaced by II-8, II-9, II-12, II-14, II-16 and II-17, so that the samples for this example were prepared, respectively. The resulted samples were then evaluated in the same manner as in Example-4. It is found therefrom that the effects of the invention were displayed satisfactorily and the excellent results were obtained.
1. A silver halide photographic light-sensitive material comprising a support having
thereon at least one silver halide emulsion layer and at least one non-light-sensitive
layer wherein said silver halide emulsion layer contains a cyan-dye forming coupler
represented by the following formula [I] or [II] and at least one of said cyan-dye
forming coupler-containing silver halide emulsion layer and said non-light-sensitive
layer adjacent to said cyan-dye forming coupler-containing silver halide emulsion
layer contains an liquid UV absorbent which is liquid state at an ordinary temperature
together with a high boiling organic solvent having a dielectric constant of not more
than 0.6 in the ratio by weight of from 0.65 to zero to said UV absorbent contained
in said layer.
wherein R₁ is an alkyl group or an aryl group; R₂ is an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R₃ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group in which R₁ and R₃ are allowed to be bond each other to form a ring, and Z₁, is a hydrogen atom or a group capable of releasing upon reaction with the oxidiized product of a color developing agent,
wherein R₄ is an alkyl group containing two to six carbon atoms; R₅ is a ballast group and Z₂ is a hydrogen atom or a group capable of being releasing upon reaction with the oxidized product of a color developing agent.
wherein R₁ is an alkyl group or an aryl group; R₂ is an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R₃ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group in which R₁ and R₃ are allowed to be bond each other to form a ring, and Z₁, is a hydrogen atom or a group capable of releasing upon reaction with the oxidiized product of a color developing agent,
wherein R₄ is an alkyl group containing two to six carbon atoms; R₅ is a ballast group and Z₂ is a hydrogen atom or a group capable of being releasing upon reaction with the oxidized product of a color developing agent.
2 The silver halide photograpgic light-sensitive material of claim 1, wherein said
liquid UV absorbent is represented by the formula [a]
wherein R₁₁, R₁₂ and R₁₃ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group an alkenyl group, a nitro group or a hydroxy group, respectively.
wherein R₁₁, R₁₂ and R₁₃ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group an alkenyl group, a nitro group or a hydroxy group, respectively.
3. The silver halide photographic light-sensitive material of claim 2, wherein R₁₃
is a hydrogen atom, an alkyl group or an alkoxy group.
4. The silver halide photographic light-sensitive material of claim 1, an amount of
said liquid UV absorbent is within the range of from 0.1 % to 300 % by weight to a
binder contained in said layer containing said UV absorbent.
5. The silver halide photographic light-sensitive material of claim 4, an amount of
said UV absorbent is within the range of from 1 % to 200 % by weight to a binder contained
in said layer containing said UV absorbent.
6. The silver halide photographic light-sensitive material of claim 5, an amount of
said UV absorbent is within the range of from 5 % to 100 % by weight to a binder contained
in said layer containing said UV absorbent.
7. The silver halide photographic light-sensitive material of claim 1, wherein at
least two solid UV absorbents which is solid state at an ordinary temperature are
contained in said layer together with said liquid UV absorbent.
8. The silver halide photographic light-sensitive material of claim 7, said solid
UV absorbents are represented by the the formula [a], respectivery.
9. The silver halide photographic light-sensitive material of claim 7, wherein the
ratio by weight of the amount of said liquid UV absorbent to the total amount of said
UV absorbents contained in said layer is not less than 30 %.
10. The silver halide photographic light-sensitive material of claim 9, wherein the
ratio by weight of the amount of said liquid UV absorbent to the total amount of said
UV absorbents contained said layer is within the range of from 30 % to 99 %.
11. The silver halide photographic light-sensitive material of claim 10, wherein the
ratio by weight of the amount of said liquid UV absorbent to the total amount of said
UV absorbents contained in said layer is within the range of from 30 % to 95 %.
12. The silver halide photographic light-aensitive material of claim 7, wherein the
total amoun of said liquid UV absorbent and said solid UV absorbents is 0.1 % to 300
% by weight to a binder contained in said layer containing said UV absorbents.
13. The silver halide photographic light-sensitive material of claim 12, wherein the
total amount of said liquid UV absorbent and said solid UV absorbents is 1 % to 200
% by weight to a binder contained in said layer containing said UV absorbents.
14. The silver halide photographic light-sensitive material of claim 13, wherein the
total amount of said liquid UV absorbent and said solid UV absorbents is 5 % to 100
% by weight to a binder contained in said layer containing said UV absorbents.
15. The silver halide photographic light-sensitive material of claim 1, wherein an
amount of said high boiling organic solvent is within the range of from 3.0 to zero
parts by weight per part of the total amount of said UV absorbent.
16. The silver halide photgraphic light-sensitive material of claim 1, wherein said
high boiling organic solvent is not contained.
17. The silver halide photographic light-sensitive material of claim 1, wherein a
dielectric constant of said high boiling organic solvent is within the range of from
1.9 to 6.0.
18. The silver halide photographic light-sensitive material of claim 1, wherein said
high boiling organic solvent is a phthalate represented by the following formula [HA]:
wherein R ₁ and R ₂ are each an alkyl group, an alkenyl group or an aryl group, provided that a total number of the carbon atoms of the groups represented by R ₁ and R ₂ is from 9 to 32.
wherein R ₁ and R ₂ are each an alkyl group, an alkenyl group or an aryl group, provided that a total number of the carbon atoms of the groups represented by R ₁ and R ₂ is from 9 to 32.
19. The silver halide photographic light-sensitive material of claim 7, wherein an
amount of said high boiling organic solvent is within the range of from 0.3 to zero
parts by weight per part of the total amount of said UV absorbents.
20. The silvewr halide photographic light-sensitive material of claim 7, wherein said
high boiling organic solvent is not contained.
21. The silver halide photographic light-sensitive material of claim 7, wherein a
dielectric constant of said high boiling organic solvent is within the range of from
1.9 to 6.0.
22. The silver halide photographic light-sensitive matrial of claim 7, wherein said
high boiling organic solvent is a phthalate represented by the formula [HA].