GB2032449A - Creation of Inventions and Patents with Artificial Intelligence

GB2032449A – Spectrally sensitized silver halide photographic emulsions
– Google Patents

GB2032449A – Spectrally sensitized silver halide photographic emulsions
– Google Patents
Spectrally sensitized silver halide photographic emulsions

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Publication number
GB2032449A

GB2032449A
GB7932579A
GB7932579A
GB2032449A
GB 2032449 A
GB2032449 A
GB 2032449A
GB 7932579 A
GB7932579 A
GB 7932579A
GB 7932579 A
GB7932579 A
GB 7932579A
GB 2032449 A
GB2032449 A
GB 2032449A
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United Kingdom
Prior art keywords
group
silver halide
halide emulsion
carbon atoms
emulsion
Prior art date
1978-09-25
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GB7932579A
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GB2032449B
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Fujifilm Holdings Corp

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Fuji Photo Film Co Ltd
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1978-09-25
Filing date
1979-09-20
Publication date
1980-05-08

1979-09-20
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Fuji Photo Film Co Ltd

1980-05-08
Publication of GB2032449A
publication
Critical
patent/GB2032449A/en

1982-11-03
Application granted
granted
Critical

1982-11-03
Publication of GB2032449B
publication
Critical
patent/GB2032449B/en

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Classifications

G—PHYSICS

G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY

G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY

G03C1/00—Photosensitive materials

G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein

G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives

G03C1/08—Sensitivity-increasing substances

G03C1/10—Organic substances

G03C1/12—Methine and polymethine dyes

G03C1/22—Methine and polymethine dyes with an even number of CH groups

C—CHEMISTRY; METALLURGY

C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR

C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES

C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes

C09B23/10—The polymethine chain containing an even number of >CH- groups

C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof

Y10S430/15—Lithographic emulsion

Description

1 GB 2 032 449 A 1
SPECIFICATION Spectrally sensitized silver halide photographic emulsions
The preisent invention relates to silver halide emulsion spectrally sensitized by novel merocyanine dyes and particularly to silver halide photographic emulsions having high green sensitivity.
Hitherto, as spectral sensitizers for photographic emulsions, it has been known to use certain climethine merocyanine dyes as described in, for example, U.S. Patents 3, 480,439, 3,501,306, 3,567,458,3,625,698,3,698,910, 3,736,145, 3,765,900, 3,765,901, and 4,057, 430, Japanese Patent Publications Nos. 18105/71 and 549/71 and German Patent 1,234,522 and British Patent 800,244. However, silver halide photographic sensitive materials containing these known dimethine merocyanine dyes often suffer stains, deterioration of sensitivity with a lapse of time or increased 10 fogging.
Accordingly, a first object of the present invention is to provide silver halide photographic emulsions containing merocyanine dyes which have a high spectral sensitization function.
A second object of this invention is to provide spectrally sensitized silver halide photographic emulsions which suffer less deterioration of sensitivity and less fogging in the prepared sensitive materials over time.
A third object of this invention is to provide litho type silver halide emulsions containing novel merocyanine dyes.
A fourth object of this invention is to provide sensitizing dyes which do not stain after development processing and have excellent solubility.
The above described objects have been attained by incorporating compounds represented by the following formula (1) in silver halide photographic emulsions:
R2 C=CH-CHH N % ‘ N -S 1 ON> R N Rf R 4 3 (1) In the formula, Z represents an atomic group necessary to complete an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus, which may bear substituents on the carbon atoms. 25 Examples of the substituents include halogen atoms (for example, a fluorine atom, a chlorine atom or a bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms, which may be a straight or branched chain (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group), alkoxy groups having 1 to 4 carbon atoms, which may be a straight or branched chain (for example, a methoxy group, an ethoxy group, a propoxy group and a butoxy group), a hydroxyl group, 30 alkoxycarbonyl groups having 2 to 6 carbon atoms, which may be a straight or branched chain (for example, a methoxycarbonyl group and an ethoxycarbonyl group, etc.), alkylcarbon yl groups Raving 2 to carbon atoms, which may be a straight or branched chain (for example, an acetyloxy group and a propionyloxy group, etc.), a phenyl group and a hydroxyphenyl group, etc.
Examples of the nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-di methyl oxazole 35 and 4-phenyloxazole, as the oxazole nucleus, benzoxazole, 5- chlorobenzoxazole, 5-bromobenzoxazole, 5-methy[benzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5hydroxybenzoxazole, 5 ethoxycarbonyibenzoxazole, 5-acetyloxybenzoxazole, 5-phenyibenzoxazole, 6- methylbenzoxazole, 6 methoxybenzoxazole, 5,6-di methyl be nzoxazo le and 6-ch loro-5-m ethyl be nzoxazole, as the benzoxazole nucleus, and naphtho[1,2-dloxazole, naphtho[2,1 -d]oxazole and naphtho[2, 3-dloxazole, as the 40 naphthoxazole nucleus.
R, represents an unsubstituted or substituted alkyl group having a total of 1 to 10 carbon atoms (hereinafter, the carbon atom number means the total number including substituents). Examples of the substituents include a hydroxyl group, a suifo group, a sulfato group, a carboxyl group, halogen atoms (for example, a flurorine atom and a chlorine atom), unsubstituted or substituted alkoxy groups having 1 45 to 4 carbon atoms, which may be a straight or branched chain (which may be substituted by a suifo group or a hydroxyl group), alkoxycarbonyl groups having 2 to 5 carbon atoms, alkyisuifonyl groups having 1 to 4 carbon atoms, sulfamoyl groups, unsubstituted or substituted carbamoyl groups (including Walkylcarbamoyl groups in which the alkyl moiety contains 1 to 4 carbon atoms), substituted phenyl groups (examples of the substituents include a sulfo group, a carboxyl group and a hydroxyl group, etc.), 50 and a vinyl group, etc. R, is preferably a carboxyalkyl group, a hydroxyalkyl group, a sulfoaralkyl group, a sulfamoylalkyl group or a sulfoalkyl group, and is most preferably a sulfoalkyl group.
Examples of the unsubstituted alkyl groups include a methyl group, an ethyl group, a propyl group rZ 2 GB 2 032 449 A 2 and a butyl group, etc. Examples of the substituted alkyl groups include a 2-hydroxyethyl group and a 3hydroxypropyl group as hydroxyalkyl groups; a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4- sulfobutyl group, a 2-hydroxy-3-sulfopropyl group and a 2-chloro-3- sulfopropyl group as sulfoalkyl groups; a 2-sulfatoethyl group and a 3- sulfatopropyl group as sulfatoalkyl groups; a carboxymethyl group, a carboxyethyl group and a carboxypropyl group as carboxyalkyl groups; a 2, 2,2trifluoroethyl group, a 2-Q-su Ifopropyloxy) ethyl group, a 2-(2- hydroxyethoxy)ethyl group, an ethoxycarboxylethyl group, a methyl su Ifonyl ethyl group, a 2-sulfa moyl ethyl group as sulfamoylalkyl groups; a 2-carba moyl ethyl group, a 2-N, N-di methyl ca rba m oylethyl group, a phenethyl group, a pca rboxyphen ethyl group, a p-sulfophenethyl group and an o-su Ifophe n ethyl group as sulfoaralkyl groups; a p-hydroxyphenethyl group, an allyl group and a phenoxyethyl group.
R2 represents an alkoxycarbonylalkyl group having 3 to 7 carbon atoms (for example, a methoxycarbonyl methyl group, an ethoxyca rbonyl methyl group or an ethoxyca rbonyl ethyl group), a hydroxyalkyl group having 1 to 4 carbon atoms (for example, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group or a 2,3-dihydroxypropyl group), a hydroxyalkoxyalkyl group having 2 to 6 carbon atoms (for example, a hydroxymethoxymethyl group, a -(2- hydroxyethoxy)-ethyl group or a 2hyd roxyethoxym ethyl group), a carbamoylalkyl group having 2 to 8 carbon atoms (including N-alky] substituted N,N-dialkyl-suUstituted, Whydroxyalkyl-substituted, N-alkyl-N- hydroxyalkyl-substituted and N,N-di(hydroxyalkyi)-substituted carbamoylalkyl groups and carbamoylalkyl groups of 5- or 6 membered cyclic amines) (for example, a 2-carba moyl ethyl group, a 2-N- (2-hydroxyethyi) carbamoylethyl group, an N-dihydroxyethylcarbarnoyl methyl group, an N,N- di(2 hydroxyethyl)carba moyl methyl group, a 2-N,N-di(2- hydroxyethyi)carbamoylethyI group, an N,N di methyl ca rba moyl methyl group, a morpholinocarbamoyl methyl group or a piperidinoca rbamoyl methyl group), a hydroxyphenyl group or a hydroxya Ikyl phenyl group having 7 to 9 carbon atoms (for example, a p-(2-hydroxyethyi)phenyl group or an m-(1 -hydroxyethyl) phenyl group). R2 is preferably a hydroxyalkoxyalkyl group or a hydroxyalkyl group.
R3 and R4 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group or an ethyl group), an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group or an ethoxy group), a chlorine atom or a carboxyl group.
In dyes represented by the above described formula (1), particularly preferred are (a) those in which Z represents an atomic group necessary to complete a benzoxazole nucleus and R, represents a 30 sulfoalkyl group, a carboxyalkyl group, a hydroxyalkyl group, a sulfamoylalkyl group or a sulfoaralkyl group, the alkylene moieties of each of which have 1 to 5 carbon atoms; (b) those in which Z is a benzoxazole nucleus substituted at a carbon atom with a chlorine atom are also preferred.
Of benzoxazole dyes of the aforesaid preferred class (a), especially preferred are those represented by the formula (ii):
0 R7 RSJXN> CH-CH N — S 1 0 N R6 IN 9 8 In the formula, R. represents a hydrogen atom, a chlorine atom, a hydroxyl group, an alkylcarbonyloxy group having up to 3 carbon atoms (for example, an acetyloxy group or a propionyloxy group, etc.), an unsubstituted alkyl group having up to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or a butyl group), or an unsubstituted alkoxy group having up to 4 carbon 40 atoms (for example, a methoxy group, an ethoxy group or a propoxy group, etc.). R. is preferably a hydrogen atom or a chlorine atom.
R6 represents a sulfoalkyl group having 2 to 4 carbon atoms (for example, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a 2- chloro-3-sulfopropyl group or a 2 hydroxy-3-sulfopropyl group, etc.) or a sulfamoylalkyl group having up to 3 carbon atoms (for example, 45 a 2-su Ifa moyl ethyl group or a 3-sulfamoylpropyl group). R. is preferably a sulfoalkyl group.
R7 represents a hydroxyalkoxyalkyl group having 2 to 6 carbon atoms (for example, a 2-(2 hydroxyethoxy) ethyl group, a 2-hydroxyethoxymethyi group or a hydroxymethoxyrn ethyl group, etc.), a hydroxyalkyl group having 2 to 4 carbon atoms (for example, a 2,3- dihydroxypropyl group, a 2,3 dihydroxybutyl group, a 2-hydroxypropyl group, or a 2-hydroxyethyl group, etc.), an N-substituted or 50 N-unsubstituted carbamoylalkyl group having 3 to 6 carbon atoms excluding substituents (examples of the substituents of which include hydroxyalkyl groups such as a hydroxyethyl group, lower alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group and an n-butyl group) (for example, a 2-ca rba moyl ethyl group, a 2-(N-2-hydroxyethylcarbamoyi)ethyi group, a 2-[N,N-di(2-hydroxyethyl)- 3 GB 2 032 449 A 3 carbamoyllethyl group, an N-2-hydroxyethylcarba moyl methyl group, and an N,N-di(2-hydroxyethyi)carbamoyimethyl group), a hydroxyphenyl group (for example, a p-hydroxyphenyl group or an mhydroxyphenyl group) or a hydroxyalkylphenyl group having a hydroxyalkyl group of up to 3 carbon atoms (for exmple, a p-2-hyd roxyethyl phenyl group or an m-1 – hydroxyethylphenyl group). 5 R. represents a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group 5 or an ethoxy group. R. represents a hydrogen atom, a methyl group or a methoxy group. The merocyanine dyes should be used in an amount as conventionally used for spectral sensitization, for example, 5 x 10-3 to 1 x 10-6, preferably 1 X 10-4 to 1 X 10-3 mol of the sensitizing dye per mol of silver halide.
Typical examples of the compounds represented by the above formula (1) used in the present invention are as follows:
Compounds Nos. (1) to (13) and 17 to (10) exemplify Z completing benzoxazole; Compounds Nos. (14) and (15) exemplify Z completing naphthoxazole; and Compound No. (16) exemplifies Z completing oxazole. 15 0 CH2C02C2H5 1 H (1) a N >- CH-CH N S 0 > 1 N CCHZ) 2 N S03 K A MCON 488 nm max 0 CH2CH20H (2) >CH-CHn N N O’N>S 1 K ICH2)4S03 IN MeOH 490 nm max 0 OH 1 W12 CHCH2 OH 1 (3) 1-1 X’ CH-M- N N –>S 0, ‘N (CH 2) 2 1 N S02 NH 2 MeOH 490 nm max 0 CH2 CH 2 OCH2CH20H (4) “”‘1- 1 aN /- CH – Of N 0 X>S I I (CH2)4 I eIN MeOH S03K A max490 nm 4 GB 2 032 449 A 4_ CH2 CH 20CH2CH 2 OH I (5) O>CH-CH N WaN s 1 0 IN> (CH2) 3 I6,-N S03K X MeOH 488 nm max CH2C’f2OCH2CH2OH 0 > I C6) CH-CH N C”3CO’-aN 11 1 1 N>S 0 Lu’12J 3 N A MeOH 490 nm max OH I 0 un2CHCH3 (7) CH-CH N 00″N>S Ll,n2)4 I SO K 6–N 3 MeOH 489 nm max CH2CH20H (8) 0 >CH-CH N aN s I ON > (CH2) 4 1 6,.,N ZIU3A MeOH A max 491 nm OR I VHCH3 C9) ->CH-CH N 5 aNo s > N Hd 6N %. I S03K MeOH 490 nu max v GB 2 0?2 449 A 5 CH,,CONHCH,CH OH 0 1 & 22 (10) >CH-CH N (:1 N > s 0” N CCH2) 4 1 6,-N SO K MeOH A max, 490 nm CH, CH2CON I “ICH 2 CH 2 OH (11) CH3QCON >CH-CH N I N> Lf-n2J 3 1 6.,.,N so 3 K I MeOH 496 nm max CH 2 CON(CH 2 CH 2 OH)2 1 (12) >CH-CH N HO”‘aoN ‘x’ s 1 0, N > (CH2)3 I N S03 K X MeOH 491 nm max 0 CH 2 CONCH 2 CH 2 OH I ‘ (13) >CH-CH -N CH Oj N 3 ON>S CH2 1 6_,-,.N M-OH X Meoll 498 nm CH2SO3 K max 0 CH 2 CH 2 OCH 2 CH2 OH I >CH-CH. N k_ N >S (14) 1 IN (CH 0 1 2)3 IN bu3& I MeOH S09 nm max 0 CH2CH20CH2CH20H (15) CH-CH N > N>S (CH2)3 0 N I K IN S03 X MeOH 508 nm max 6 GB 2 032 449 A 6 OH I 0 t I r’2″k’L”2 OH (16) > CH-CH N CH3N or S 4 N U31’ CH MeOH 490 nm 3 max OH I 0 CH2CHCH20H (17) 1 N >CH-CH N I 0 N > (CH2)4 I 6N “‘J31′ X MeOH max 491 nm CH,CH,CONH, 0 1 & & 1.
CH-CH N aN S L”V4 – (5- N CH MeOR 488 nm 3 max 0 CH 2CO2C2HS (19) 1 N >CH-CH N ON>S (CH2)4 I ON I Otj.31’ MeOH max 490 nm The novel merocyanine compounds of the present invention can be used with other dyes as disclosed in the following patents to carry out supersensitization (remarkable additional increase of sensitivity) of silver halide emulsions; for example, U.S. Patents 3,617, 294, 3,667,960, 3,745,014, 3,628,964,3,615,635,2,527,641, 3,522,052, 3,617,293,3,703,377 and 2,519, 001, U.S. Patent Application (CIP) No. 354,421, Japanese Patent Publication No. 24888/72 and Belgian Patent 691,807. Particularly, in case of adding sensitivity to red light, thiacarbocyanine dyes are preferred. In 10 case of increasing sensitivity to violet or blue light, monomethine thiacyanine dyes and apomerocyanine dyes having a 5-(1,4-dihydro-4-pyridylidene) rhoda nine nucleus are preferred.
The compounds used in the present invention can be easily synthesized by persons skilled in the art with reference to the processes for synthesizing dimethine merocyanines described in Japanese Patent Publications Nos. 18105/71 and 549/7 1, U.S. Patents 3,625,698, 3,501,306, 3,736,145, 3,698,910, 15.
4,057,430, 3,480,439, and 3,567,458, German Patent 1,234,522 and British Patent 800,244. In the following synthesis examples, the synthesis of compounds used in the present invention are shown, and other compounds represented by the formula (1) can be synthesized by analogy to these examples.
1 7 GB 2 032 449 A 7 SYNTHESIS EXAMPLE 1 Synthesis of Compound (19) 18.9 g of diethyliminodiacetate and 18.4 g of methyl-2-pyridyldith ioca rba mate were put in a flask and heated to 1 001C for 5 hours. The product was subjected to silica gel column chromatography and fractions were extracted by a solvent mixture composed of n-hexane/ethyl acetate (1:1), and were 5 gathered to obtain 18.5 g of 1 -ethoxycarbonylmethyl-3-(2-pyridyl)-2thiohydantoin as a viscous oil. 5.6 g of this 2-thiohydantoin compound, 6.8 g of 4-[2-(2-a nil i novi nyl)-3- benzoxazol io] b uta nesu Ifonate and ml of ethanol were put in a flask. After adding 4 ml of acetic anhydride and 6 ml of triethylamine, the mixture was heated under refluxing for 30 minutes. After condensing to remove the solvent, 200 ml of ethyl acetate was added thereto. After stirring for 30 minutes, the supernatant liquid was removed by decantation. 10 ml of methanol was added to dissolve the residue, and a solution prepared by dissolving 2.4 g of potassium acetate in 10 ml of methanol was added. After heating for 10 minutes, it was allowed to stand. Separated crystals were filtered and recrystallized with methanol to obtain 6.2 g of Compound (19) as orange crystals having a melting point of 2020C.
SYNTHESIS EXAMPLE 2 ‘ Synthesis of Compound (4) 19. 5 g of methyl N-2-(2-hydroxyethoxy)ethyl acetate, 18.4 g of methyl 2- pyridyidithiocarba mate and 20 ml of toluene were put in the flask, and the mixture was heated to 1 00″C for 3 hours. Volatile materials were then distilled off with heating to 701C using an aspirator. To the resulting 1-[2-(2- hyd roxyethoxy) ethyl] -3-(2-pyridyl)-2 -thio hyd a ntol n (which had a boiling point of 2000C at 0.6 mmHg), 20 34 g of 4-[2-(2-anilinovinyl)-3-benzoxazolio]butanesulfonate and 30 ml of morpholine were added.
After heating to 900C for 30 minutes, 200 ml of ethyl acetate were added thereto, and the mixture was allowed to stand at room temperature. After the supernatant liquid was removed by decantation, a small amount of methanol was added to dissolve the residue. 50 ml of acetone was added with heating and the mixture was allowed to stand, upon which the whole of the mixture was crystallized. 25 The crystals were separated by filtration and dissolved in 20 ml of methanol. After a solution prepared by dissolving 16 g of potassium acetate in’50 ml of methanol was added thereto and heated for 10 minutes, it was allowed to stand and the precipitated crystals were separated by filtration. They were recrystallized with methanol to obtain 32.6 g of reddish voilet Compound (4) having a melting point of 2450C.
SYNTHESIS EXAMPLE 3 Synthesis of Compound (10) 4 g of the Compound 0 9) from Synthesis Example 1 and 10 ml of 2- aminoethanol were put in a flask. After heating to 1 501C for 2 hours, 100 ml of ethyl acetate was added thereto. The supernatant liquid was removed by decantation and a small amont of ethanol was added to the residue to crystallize 35 it. The crystals were separated by filtration and recrystallized from methanol by adding 2 g of potassium acetate. These crystals were further recrystallized from methanol to obtain reddish violet Compound (10) having a melting point of 2891C.
The merocyanine dyes in the present invention are particularly suitable for increasing the green sensitivity of lithographic type silver halide emulsions and for improving lithographic development. 40 In lithographic silver halide emulsions used in the present invention, it is possible to incorporate polyalkylene oxide compounds as a dot quality improving agent. The polyalkylene oxide compounds used in the present invention are defined as compounds having at least a polyalkylene oxide unit in their structure which improves the infectious development effect when used for silver halide photographic sensitive materials. They are, for example, compounds described in U.S. Patents 2,400,532, 3,294,537, 45 3,294,540 and 3,345,175, French Patents 1,491,805 and 1,596,673, and Japanese Patent Application (OPI) No. 156423/75 (the term “OPI” as used herein refers to a “published unexamined Japanese patent application”), 108180/77 and 3217/78. Preferred examples of the compounds include condensates of polyalkylene oxide composed of at least 10 alkylene oxide units having 2 to 4 carbon atoms (such as ethylene oxide, propylene-1,2-oxide or butylene-1,2-oxide and preferably ethylene 50 oxide) and a compound having at least one active hydrogen atom (such as water, aliphatic alcohols having up to 30 carbon atoms, mono-or bicyclic aromatic alcohols, aliphatic acids having 4 to 30 carbon atoms, organic amines or hexitol derivatives); and blocked copolymers of two or more polyalkylene oxides. Namely, as examples of the polyalkylene oxide compounds, it is possible to use polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene 55 glycol alkylaryl ethers, polyalkylene glycol esters, polyalkylene glycol aliphatic acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers and polyalkylene glycol graft polymers.
The polyalkylene oxides may contain not only one kind of alkylene oxide but also two kinds of alkylene oxide. In the latter case, each polyalkylene oxide chain may be composed of less than 10 alkylene oxide units, but the total number of alklylene oxide units in the molecule should be at least 10. 60 In case of having tow or more polyalkylene oxide chains in the molecule, each of them may have a different alkylene oxide unit such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide.
8 GB 2 032 449 A 5.
The polyalkylene oxide compounds used in the present invention preferably contain 14 to 100 alkylene oxide units.
The polyalkylene oxide compounds which may be used in the present invention preferably have a molecular weight of about 300 to 15,000 and preferably about 600 to 8,000, by number average.
Examples of the polyalkylene oxide compounds used in the present invention are as follows: 5 1. HO(CH2CH20),ffi 2. HO(CH,CHP9,1-1 3. C41-1,O(CH2CH20)151-1 4.C1,1-1,,O(CH2CH20)15141 C18HWO(CH2CH,0)151-1 6. Cl,H370(CH2CH20)40H 7.C.1—117CH = CHC.HWO(CH2CH20)15H 8. C9H19 -WO(CH 2 CH 20) 30H. CH3 -c 0 (CH 2 CH 20) 30H 1’5 10 WO- (CH2CH20)20H 11. C11H23COO(CH2CH20),0H 12. C11H23COO(CH2CH20)24OCC,,H23 / COO(CH2CH20).H 13. C,H17CH \ COO(CH2CH20).H 14.Cl,H23CONH(CH2CH20),5H 15.C 12H25N (CH,CH20)151-1 (CH2CH20)l 5H CH2–0-HCH20C11H23 1 1 16.H(OCH2tj’2)14u-t;H-CH-CH-(CH2CH20)14H 1 Ul;t’2t;t120)14H 17.H(CH2CH2OUqHCH2OWCH2CH20)rH 18. liocil 2CH2O(C112C1120)50 -CC9H 19 8 a+b+c=50, b:a+c=10:9 1 9 GB 2 032 449 A 9 0-(CH2CH20)50H 19.
20.HO(CH2CH20a(CH2CH2CH2CH20)b(CH2CH20),H a +c=30, b=14 21.HOCCH2CH20) (CHCH20)b(CH2CH20)CH b – b = 8, a + c = 50 These polyalkylene oxide compounds may be used alone or as a mixture of two or more.
The polyalkylene oxide compounds are added to the silver halide photographic emulsions by a conventional method. Namely, they are added to the emulsions before application thereof, preferably after chemical ageing, as an aqueous solution or a solution in a water- compatible organic solvent preferably having a low boiling point. A part of them may be added to non- light-sensitive hydrophilic colloid layers, for example, a protective layer, instead of to the photographic emulsions. A suitable amount of the polyalkylene oxide compounds is 0.0 1 to 10 g per mot of the silver halide in the emulsion 10 layer or the hydrophilic colloid layer which may be adjacent the emulsion layer when the polyalkylene oxide is also present in a hydrophilic colloid layer.
The silver halide emulsions used in the present invention can be produ ced by a neutral process, an acid process, a single jet process, a double jet process or a controlled double jet process, etc., described in The Theory of the Photographic Process, 3rd Edition, pp. 31–43, edited by Mees, published by 15 Macmillan Co. 0 967) and Chimie, Photographique, 2nd Edition, pp. 251-308, written by P. Glafkides published by Paul Monte[ Co. (1957).
As the silver halide compositions, silver chloride silver bromide, silver iodide, silver chlorobromide and silver chlorobromoiodide may be used. Particularly, silver chlorobromide and silver chloroiodobromide containing at least about 60% by mot (preferably 75% by mol) of silver chloride and 20 about 0 to 5% by mol of silver iodide are preferred. Silver halide particles are not restricted in crystal form, crystal habit, particle size and distribution of particle size, but those 0.7,u or less in particle size are preferred.
The silver halide emulsions may be chemically sensitized by gold compounds such as chloroaurate or gold trichloride, salts of noble metals such as rhodium oriridium or sulfur compounds which form 25 silver sulfide by reacting with silver salts or reducing materials such as stannous salts or amines.
As carriers for the silver halides, it is possible to use gelatin, modified gelatin, gelatin derivatives and synthetic hydrophilic polymers to form the emulsion layer.
For the purpose of increasing dimensional stability of photographic materials and improving film properties, it is possible to incorporate a polymer latex composed of homo-or copolymers of alkyl 30 acrylate, alkyl methacrylate, acrylic acid or glycidyl acrylate described in U.S. Patents 3,411,911, 3,411,912, 3,142,568, 3,325,286, 3,525,620 and 3,547,650, in silver halide emulsion layers or other layers.
In the photographic emulsions, it is possible to use, as stabilizers or antifogging agents, many heterocyclic compounds including 4hydroxy-6-methyi-1,3,3a,7-tetrazaindene, 3-methylbenzothiazole 35 and 1 -phenyl-5-mercaptotetrazole, mercury-containing compounds, mercapto compounds and well known antifogging agents as described in Japanese Patent Application (OPI) Nos. 6306/75 and 19429/75 and U.S. Patents 3,850,639 and 3,898,009.
The photosensitive emulsions of the present invention may contain inorganic or organic hardening agents. For example, there are chromium salts (chromium alum or chromium acetate), aldehydes 40 (formaldehyde, glyoxal or glutaraldehyde), N-methylol compounds (dimethylol urea or methylol di methyl hyda ntoi n), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5 triacryloyl-hexahydro-s-triazine or bis(vi nyl su Ifonyl) methyl ether), active halogen compounds (2,4 dichloro-6-hydroxy-s-triazine), mucohalogenic acids (mucochloric acid or mucophenoxychloric acid), isoxazoles, dialdehyde starch and 2-chloro-6-hydroxytriazinyl gelatin which may be used alone or as a 45 combination thereof. Examples of them have been described in U.S. Patents 1,870,354, 2,080,019, 2,726,162,2,870,013,2,983,611,2,992,109, 3,047,394, 3,057,723, 3,103,437, 3,321,313, 3,325,287, 3,362,827, 3,539,644 and 3,543,292, British Patents 676,628, 825,544 and 1,270,578, German Patents 872 153 and 1,090,427, Japanese Patent Publications Nos. 7133/59 and 1872/78 and Japanese Patent Applications (OPI) Nos. 57257/78 and 41221/78. 50 GB 2 032 449 A 10 To the photographic emulsions of the present invention, it is possible to add surface active agents as coating assistants or for the purpose of improving photographic properties. As the surface active agents, there are natural surface active agents such as saponin, nonionic surface active agents such as alkylene oxide type agents (for example, surface active agents described in U.S. Patents 3,915,713 and 4,011,082) or glycidol type agents, anionic surface active agents containing acid groups such as a carboxylic acid group, a sulfonic acid group (for example, surface active agents described in U.S. Patent 3,415,649), a phospohric acid group, a sulfuric acid ester group or a phosphoric acid ester group and ampholytic surface active agents such as aminoacids, aminosulfonic acids or sulfuric acid or phosphoric acid esters of aminoalcohols. As development accelerating agents, compounds described in, for example, U.S. Patents 3,288,612, 3,333,959, 3,345,175, 3,708,303 and 4, 070,189, British Patent 10 1,098,748, German Patents 1,141,531 and 1,183,784 and Japanese Patent Applications (OPI) Nos.
99031/74, 65436/77 and 114328/77 can be used. In addition, description of product Licensing Index,
Vol. 92 (197 1),pp. 107-110 can be referred to concerning additives for emulsions and methods for producing sensitive materials.
Exposure for obtaining photographic images in the present invention can be carried out by any 15 conventional method with using various known light sources such as a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arG lamp, a xenon flash lamp, a halogen lamp, an illuminant diode, a cathode-ray tube flying spot or a discharge tube such as a glow tube, etc. Concerning exposure time, it is possible to adopt exposure for less than 1/1,000 second, for example, exposure for 1/101 to 1/10’ second using a xenon flash lamp, a cathode ray tube or laser light (Ne-He laser or argon 20 laser) and exposure for more than 1 second, not to mention exposure for 1 /1,000 to 1 second. If necessary, the spectral composition of the light used for exposure can be controlled using a color filter.
The photographic processing of layers composed of the photographic emulsions of the present invention can be carried out by any known method. As processing solutions, known ones can be used.
The processing temperature is selected from the range from 18 1 C to 501C, but temperatures of lower 25 than 18 1 C or higher than 500C may be used, too. Any development processing for forming silver images (black-and-white photographic processing) and color photographic processing comprising development for forming color images may be used according to the desired purpose.
Developing solutions used for carrying out the black-and-white photographic processing may contain known developing agents. As the developing agents, there are dihydroxybenzenes (for example, 30 hydroquinone), 3-pyrazolidones (for example, 1 -phenyl-3-pyrazolidone), aminophenols (for example, Nmethyl-p- aminophenol), 1 -phenyl-3-pyrazolines and ascorbic acid, which may be used alone or as a combination thereof. The developing solution generally contains known preservatives, alkali agents, pH buffer agents and antifogging agents in addition to the developing agent. Further, it may contain, if necessary, dissolution assistants, color toning agents, development accelerators,surface active agents, 35 defoaming agents, hard water softeners, hardening agents or viscosity-increasing agents.
The photographic emulsions of the present invention can be processed by the so-called “lithographic” development processing. The “lithographic” development processing means development processing in which development is carried out infectiously using dihydroxybenzenes as a developing agent in a low sulfurous acid ion concentration in order to carry out photographic reproduction of line images or photographic reproduction of halftone images (refer to Photographic Processing Chemistry, pp, 163-165, written by Mason (1966)).
The lithographic developing solution suitably used in the present invention (infectious developing solution) is composed essentially of an o- or p-dihydroxybenzene, alkali agents, a small amount of free sulfite and a sulfurous acid ion buffer. The o- or p-dihydroxybenzene as the developing agent can be 45 suitably selected from compounds known in the photographic field. Examples of the o- orp dihydroxybenzene include hydroquinone, chlorohydroq u i none, brom ohydroq u i none, isopropy1hydroquinone, to[ u hydroqui none, methyl hydroqui none, 2,3dichlorohydroquinone and 2,5 dimethy[hydroquinone. Among them, hydroquinone is particularly practical.
These developing agents amy be used alone or as a mixture of two or more thereof. A suitable 50 amount of the developing agents is about 1 to 100 g, preferably about 5 to 80 g, per liter of the developing solution. The sulfurous acid ion buffer is used in an amount effective to keep the sulfite concentration in the developing solution at a nearly definite value, examples of which include aldehyde alkali hydrogen sulfite adducts such as formaldehyde sodium hydrogen sulfite adduct, ketone-alkali hydrogen sulfite adducts such as acetone-sodium hydrogen sulfite adduct and carbonyl bisulfurous 55 acid-amine condensation products such as sodium bis)2- hydroxyethyl)aminomethanesulfonate. The amount of the sulfurous acid ion buffer is about 13 to 130 g per liter of the developing solution.
In the developing solutions used in the present invention, it is possible to control the free sulfurous acid ion concentration by adding alkali sulfites such as sodium sulfite thereto. The amount of the sulfites is generally about 5 g or less and preferably about 3 g or less, but more than 5 g may be added, of 60 course.
In many cases, it is preferred to incorporate one or more alkali halide (particularly, bromides such as sodium bromide or potassium bromide) as a development controller. The alkali halides are preferably added in an amount of about 0.01 to 10 g, preferably about 0.1 to 5 g, per liter of the developing solution.
11 GB 2 032 449 A 11 In order to make the pH of the developing solution 9 or more (particularly, pH 9.7 to 11.5), an alkali agent is added. In conventional developing solutions, sodium carbonate or potassium carbonate is added as the alkali agent, the amount of which may be varied.
The developing solutions used for developing the emulsions of the present invention may contain, if necessary, a pH buffering agent such as water-soluble acids (for example, acetic acid, boric acid), alkalis (for example, sodium hydroxide) or salts (for example, sodium carbonate) in addition to the above described components. A certain kind of alkali not only makes the developing solution alkaline but also functions as a pH buffering agent and a development controlling agent. As the preservatives, diethanolamine, ascorbic acid and kojic acid can be used. A lithographic developing solution containing about 10 to 40 g/A of diethanolamine is preferred because it exhibits stabilized sensitivity and good 10 halftone quality. Further, other components which may be added to the developing solution comprise antifogging agents such as benzotriazole or 1 -phenyl-5-mercaptotetrazole and organic solvents such as triethylene glycol, dimethy1formamide or methanol.
It is sufficient for each component of the developing solution to be present when it is used, and the composition of the developing solution can be divided into two or more parts. For example, if one part 15 contains the developing agent and another part contains the alkali, they can be directly used by mixing and diluting both of them. Of course, it is possible to use either a powder type developing solution or a liquid type developing solution. 20 The development time, which depends on the development temperature, is usually about 10 to 20 250 seconds and preferably about 10 to 150 seconds. The development may be carried out manually or may be carried out using an automatic development apparatus. But preferred photographic efficiency is obtained if automatic development apparatus is used. In case of processing using an automatic development apparatus, the conveying method is not particularly restricted (for example, roll conveying or belt conveying), and-conveyor type 25 automatic development apparatus can be used. In addition, the composition of the processing solutions and the method of development are referred to in U.S. Patents 3,025,779, 3,078,024, 3,122,086, 3,149,551, 3,156,173, 3,224,356 and 3,573,914.
When a silver halide emulsion of the present invention is used in a color photosensitive material, color couplers and dispersing agents therefore are contained in the material, in the emulsion layer or 30 adjacent thereto. The finished emulsion is coated on a suitable base, such as baryta paper, resin-coated paper, artificial paper, a plastics film such as triacetate or polyethylene terephthalate, or a glass plate.
The merocyanine sensitizing dyes used in the present invention are added to the emulsion as an aqueous solution or as a solution in a water-miscible organic solvent such as methanol, ethanol, 2- methoxy ethanol or pyridine, as described in U.S. Patents 3,887,381 and 3, 822,135.
The following are examples to illustrate the present invention in more detail. The following compounds are used as comparison dyes in comparison samples.
OH 1 CH 2 CHCH 2 ON (a) (b) 1 0 1 N CN>_ S CH-CH 0 N (CH 2)4S03 K 6 0 c H > CH-CHN N S 0 > H N C2 5 N 12 GB 2 032 449 A (c) (d) (c) (f) (g) (h) 0 1 >CH-CH,, N >S eeN (CH 2)003Na6 eco> 1 CH-C N N >S 1 N (c K CH2)003 6__N 1 CH2CH.)OCH7CH70H CH2CH2OCH2CHZOH 0 CH,COH 1 && (aN-> S CH-CH, N > d,tN Na “‘2-‘3s03 (6 W>CH-C N C H 2 5 e7N Is C2H5 o>CH-CHI j- (CH (CH 2)20 2) 20H UO N)”S C2H5 6 r::’VO>CH -CH- -N-CH2 CH 20CH2CH20H O”LN)’cS (CH2)3S03Na. C 2 HS EXAMPLE 1
A silver halide emulsion comprising 69.5% by mol of silver chloride, 30% by mol of silver bromide and 0.5% by mol of silver iodide was prepared by gold sensitization and sulfur sensitization. The average 10 particle size of the silver halide particles was 0.35 y.
625 g of this emulsion was put in each of 27 pots and sensitizing dyes were added as shown in Table 2. After adding 0.3 g/AgX mol of 4-hydroxy-6-m ethyl- 1,3,3 a, 7- tetrazai ndene (stabilizing agent), 1 12 t 13 GB 2 032 449 A 13 0.70 g/AgX mol of polyalkylene oxide compound 21, 2 g/AgX mol of sodium dodecylbenzenesulfonate (surface active agent), 0.8 g/AgX mol of mucochloric acid (hardening agent) and 40 g/AgX mol of the polymer latex described in U.S. Patent 3,525,620 in order, they were applied to polyethylene terephthalate’film bases to prepare photographic sensitive materials and cut into strips. One strip was exposed to a light wedge using a sensitometer having a light source of 5, 400K (color temperature) by 5 putting a green filter (Wratten-58; “Wratten” is a registered Trade Mark) on the light source. Further, another strip was exposed to a light wedge using a blue filter (Wratten 47B) instead of the green filter. On the other hand, an exposure to determine the spectral sensitization maximum was carried out using a diffraction grating type spectrograph having a 2,6661K tungsten light source.
Further, a gray contact screen for positives (produced by Dainippon Screen Co., 150 L/inch) was 10 brought into close contact with a sample, and the sample was exposed to light using white tungsten light (5,4000 K) for 1 second through a stepwedge having 0. 1 (Log E) step difference.
After exposing to light, the samples were developed at 270C for 100 seconds using the lithographic developing solution shown in Table 1, by means of an automatic developing apparatus.
TABLE 1
Developing Solution Hydroquinone g Adduct of Formaldehyde and Sodium Bisuifite 50 g Potassium Carbonate Sodium Sulfite Potassium Bromide Boric Acid Sodium Hydroxide Triethylene Glycol Ethylene diamine tetraacetic acid, bisodium salt (EDTA.2Na) Water to make g 2.5 g 2.0 g 5.0 g 3.0 g g 1.0 g 1,000 mi After processing, 10% (9/10 clear, and 1/10 developed density), 50% and 90% dots of the above described samples were observed with a microscope of 100 magnification. The dot quality was evaluated on a 4-grade scale in which A was the best.quality and D was the worst.
Further, the blue sensitivity was measured as a relative sensitivity taking the sensitivity of Sample No. 1 as 100 and the green sensitivity was measured as a relative sensitivity taking the sensitivity of 20 Sample No. 2 as 100. The results are shown in Table 2.
A 14 GB 2 032 449 A 14 TABLE 2
Test Sensitizing Dye Green Blue Dot No. and Amount Sensitivity Sensitivity Quality (x 101 mol /kg) emulsion) Sensitization Maximum Remarks (nm) 1 – – 100 D – Control 2 (3) 20 100 125 B 538 Present Invention 3 It 40 110 130 A 540 35 4 33 80 99 130 A 540 $1 (4) 20 120 153 B 542 23 6 is 40 133 170 A 542 13 7 is 80 101 169 A 542 13 8 (5) 20 115 145 A 540 39 9 02 40 130 170 A 540 is 31 80 105 162 A 540 It 11 (7) 20 89 138 B 538 is 12 31 40 110 140 A 540 91 13 is 80 105 142 A 540 31 14 (10) 20 135 140 A 545 It 99 40 142 180 A 545 93 16 31 80 120 150 A 545 29 17 (17) 20 110 130 A 540 18 $3 40 120 150 A 540 19 Is 80 102 140 A 540 (c) 20 75 125 c 540 Comparison 21 is -40 70 110 c 540 $1 22 95 80 68 105 c 540 is 23 (d) 20 30 50 c 540 53 24 93 40 27 48 c 540 is 11 80 10 40 c 540 39 26 (e) 40 32 50 c 535 93 27 Is 80 29 46 c 535 3 3 GB 2 032 449 A 15 It is apparent from Table 2 that in Samples No. 2 to No. 19 using sensitizing dyes according to the present invention, green sensitivity is high and the quality of the halftone is excellent. However, in Samples No. 20 to No. 27 using other sensitizing dyes and Sample No. 1 containing no sensitizing dye, the green serrsitivity is low and the quality of the halftone is inferior to that of the present invention.
EXAMPLE 2
Photographic sensitive materials were obtained by adding the sensitizing dyes shown in Table 3 to emulsions prepared as in Example 1.
The storage stability of the resulting sensitive materials was examined by the following method.
Samples were allowed to stand in a room conditioned at 70% relative humidity (RH) and 501C.
They were exposed to alight wedge using the same green filter or the same blue filter as in Example 1 10 together with a sample which was stored at a normal temperature (about 20OC) and a normal humidity (about 50% RH). After exposure to light, they were developed in the same manner as in Example 1.
In Table 3, the relative sensitivity of samples allowed to stand at a high temperature and a high humidity, taking the sensitivity of the sample preserved at a normal temperature and a normal humidity aslOO,isshown.
TABLE 3
Green Blue Test Sensitizing Relative Relative No. Dyes and Amount Sensitivity Sensitivity Remarks (x 10-5 mol lkg) 1 – – – 80 Control 2 (4) 40 87 90 Invention 3 (5) 40 86 85 4 (7) 40 83 87 (10) 40 87 90 6 (14) 20 95 85 7 (15) 20 93 86 8 (17) 40 87 90 9 (e) 40 30 70 Comparison (h) 40 60 60 39 As is apparent from Table 3, Samples No. 2 to No. 8 using sensitizing dyes of the present invention show less desensitization as compared with Sample No. 1 containing no sensitizing dye and Samples No. 9 and No. 10 using sensitizing dyes for comparison.
EXAMPLE 3
Photographic sensitive materials were obtained by adding the sensitizing dyes shown in Table 5 to the same emulsion as in Example 1. In order to examine the degree of stain due to the sensitizing dyes after development, unexposed photographic sensitive materials were subjected to the following processing. Namely, development and fixation were carried out for 60 seconds each using the developing solution of Table 1 (Example 1) and a fixing solution shown in Table 4 using the same 25 automatic development apparatus as in Example 1.
A 16.
GB 2 032 449 A 16 TABLE 4 Composition of Fixing Solution Water Ammonium Thlosulfate Sodium Sulfite Sodium Acetate Ammonium Hydroxide EDTA 2Na -21-12 0 Aluminum Sulfate Sulfuric Acid Water to make 700 mI 140 16 9 9 18 2 0.1 g 11 g 9 9 4 g 1 1 After washing with water and drying, the amount of stain was observed and is shown in Table 5.
TABLE 5
Sensitizing Dye Test No. and Amount Stain Grade Remarks (x 10 mol lkg) 1 – A Control 2 (3) 40 B Invention 3 (4) 40 A 33 4 (7) 40 B 19 (10) 40 A 31 6 (11) 40 B 5 1 7 (16) 40 A 8 (17) 40 A 9 (18) 40 B (b) 20 D Comparison 11 40 E 12 20 D 13 40 E 14 (g) 40 E 93 A: Very clean. Only the base density is observed. B: Very slight stain. C: Weak coloration. D: Coloration. E: Strong coloration.
i 17 GB 2 032 449 A 17 As is apparent from Table 3, the dyes of the present invention cause very slight stain. This effect is obtained from a combination of substituents in the dyes, namely, the combination of the substituents R, and R2 and the substituent on the 3-position of the thiohydantoin nucleus of the formula (1). For example, substituents in dyes (a), (b), (f) or (9) used for comparison are partially the same as those in the dyes of the present invention, but the corr)binations are different from those in the present invention. 5 When the above described substituents have combinations represented by the formula (i) in the present invention, less stain is obtained.
EXAMPLE 4
A silver halide emulsion comprising 75% by mol of silver chloride and 25% by mol of silver bromide was prepared by gold sensitization and surlfur sensitization. The average particle size of the 10 silver halide particles was 0.33 p. After adding sensitizing dyes and other additives in the same manner as in Example 1, the emulsion was applied to film bases to obtain photographic materials. The resulting film sample was cut in strips, one of which was exposed to a light wedge by means of a sensitometer having a light source of 5,4001K color temperature using the above described green filter and the other was similarly exposed to a light wedge using the above described blue filter instead of the green filter. After 15 exposure to light, they were developed using the developing solution shown in Table 6 at 201C for 2 minutes. Sensitivities of each sample, based on the blue sensitivity of Sample No. 1 as 100 and the green sensitivity of Sample No. 8 as 100, are shown in Table 7.
TABLE 6
Composition of Developing Solution Water Metol Anhydrous Sodium Suifite Hydroquinone Sodium Carbonate (monohydrate) Potassium Bromide Water to make 700 mI 3.1 9 45.0 g 12.0 g 7.9 g 1.9 g 1 1 2 parts by volume of water are added to 1 part by volume of the above described developing solution for use.
Samples No. 2 to No. 4 and No. 8 to No. 10 using the sensitizing dyes according to the present 20 invention have high green sensitivity as compared with Samples No. 5 to No. 7 and No. 11 to No. 13.
using the sensitizing dyes for comparison.
18 GB 2 032 449 A 18 TABLE 7
Test Sensitizing Dye Green Blue No. and Amount Sensitivity Sensitivity Fog Remarks (x 10mol lkg) 1 – – – 100 0.03 Control 2 (4) 20 115 148 0.03 Invention 3 11 40 123 159 0.03 13 4 13 80 98 159 0.03 is (c) 20 89 126 0.03 Comparison 6 93 40 89 126 0.03 11 7 is 80 69 117 0.03 31 8 (17) 20 100 130 0.03 Invention 9 31 40 112 135 0.03 31 33 80 89 126 0.03 33 11 (a) 20 83 117 0.03 Comparison 12 13 40 89 120 0.03 31 13 33 80 66 110 0.03 33 EXAMPLE 5
The samples used in Example 2 were allowed to stand in the same manner as in Example 2. They were exposed to a light wedge by using a green filter or a blue filter in the same manner as in Example 1 and developed at 200C for 2 minutes using the developing solution shown in Table 6 (Example 4). In Table 8, relative sensitivity of the samples allowed to stand at a high temperature and a high humidity based on the sensitivity of the sample stored at a normal temperature and a normal humidity being 100 is shown.
i i 19 GB 2 032 449 A 19 TABLE 8
Green Blue Test Sensitizing Dye Relative Relative No. and Amount Sensitivity Sensitivity Remarks (x 10-1 mol /kg) 1 – – – 80 Control 2 (4) 40 83 80 Invention 3 (5) 40 87 80 95 4 (7) 40 81 80 (10) 40 80 80 6 (14) 20 93 83 7 (15) 20 91 83 8 (17) 40 83 80 9 (e) 40 28 74 Compan son (h) 40 62 65 33 As is apparent from Table 8, sensitizing dyes of the present invention cause less deterioration of photographic properties under severe conditions. Namely, in Sample No. 1 containing no sensitizing dye, the sensitivity reduces to 80% upon storage under high temperature and high humidity. In Samples No. 2 to No. 8 using the sensitizing dyes of the present invention, the deterioration of sensitivity under 5 the same conditions as described above is the same as or Ihss than that of Sample No. 1. On the other hand, deterioration of sensitivity of sensitizing dyes (e) and (h) is high.

Claims (26)

1. A silver halide photographic emulsion which comprises at least one compound represented by the general formula:
e Z’, R2 1 : % / C-CI4 – CH N N 1 0j-..’ N R N 1 R4 R3 wherein Z represents the atoms necessary to complete an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus, R, represents a substituted or unsubstituted alkyl group, R, represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a 15, hydroxyphenyl group or a hydroxyal kyl phenyl group, and R3 and R4 which may be the same or different 15 each represents a hydrogen atom, an alkyl group, an alkoxy group, a chlorine atom or a carboxyl group.

2. A silver halide emulsion as claimed in Claim 1, wherein Z represents the atoms neessary to complete a benzoxazolenucleus and R, represents a carboxyalkyl group, a hydroxyalkyl group, a sulfoaralkyl group, a sulfamoylalkyl group or a sulfoalkyl group.

3. A silver halide emulsion as claimed in Claim 2, wherein said dye is represented by the formula20 GB 2 032 449 A 20 0 R7 1 RS’Q)N>CH-CH N -S 1 0 N R6 f N 1 1 R 9 R8 where R, represents a hydrogen atom, a chlorine atom, a hydroxyl group, an alkylcarbonyloxy group having up to 3 carbon atoms, or an unsubstituted alkoxy group having up to 4 carbon atoms, or an unsubstituted alkoxy group having up to 4 carbon atoms; R6 represents a sulfoalkyl group having 2 to 5 4 carbon atoms, or a sulfamoylalkyl group having up to 3 carbon atoms; R7 represents a hydroxyalkoxyalkyl group having 2 to 6 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an N-substituted or an N-unsubstituted carbarnoylalkyl group having 3 to 6 carbon atoms wherein said N-substituent is afleast one hydroxyalkyl group and/or alkyl group having 1 to 4 carbon atoms; a hydroxyphenyl group, or a hydroxyalkylphenyl group wherein the hydroxyalkyl group contains up to 3 carbon atoms; R. represents a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group; and R, represents a hydrogen atom, a methyl group or a methoxy group.

4. A silver halide emulsion as claimed in Claim 1, wherein Z represents an unsubstituted benzoxazole nucleus or a chloro- substituted benzoxazole nucleus.

5. A silver halide emulsion as claimed in any preceding claim, wherein R, or R. represents a 15 sulfoalkyl group.

6. A silver halide emulsion as claimed in any preceding claim, wherein R2 represents a hydroxyalkoxyalkyl group or a hydroxyalkyl group.

7. A silver halide emulsion as claimed in Claim 1, wherein said compound is any of Compounds (1) to 0 9) shown hereinbefore.

8. A silver halide emulsion as claimed in any preceding claim, wherein the dye is present in an amount of 5 x 10-1 to 1 x 10-1 mol per mol of silver halide.

9. A silver halide emulsion as claimed in any preceding claim, wherein said silver halide is silver chlorobromide or silver chloroiodobromide containing at least 60 mol % silver chloride and 0 to 5 mol % silver iodide.

10. A silver halide emulsion as claimed in any preceding claim, which is chemically sinsitized.

11. A silver halide emulsion as claimed in any preceding claim, which additionally contains a polyalkylene oxide compound.

12. A silver halide emulsion as claimed in Claim 11, wherein said polyalkylene oxide compound is present in an amount of 0.01 to 10 grams per mol of silver halide.
–

13. A silver halide emulsion as claimed in Claim 11 or 12, wherein said polyalkylene oxide is selected from polyalkylene glycol, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryl ethers, polyalkylene glycol esters, polyalkylene glycol aliphatic acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers and polyalkylene glycol graft copolymers.

14. A silver halide emulsion as claimed in Claim 11, 12 or 13, wherein said polyalkylene oxide compound is a condensate of a polyalkylene oxide containing at least 10 alkylene oxide units and a compound having at least one active hydrogen atom.

15. A silver halide emulsion as claimed in Claim 13, wherein said compound having at least one active hydrogen atom is water, an aliphatic alcohol, an aromatic alcohol, an aliphatic acid,an organic 40 amine or hexitol.

16. A silver halide photographic emulsion as claimed in Claim 11, 12 or 13, wherein said polyalkylene oxide compound contains 14 to 100 alkylene oxide units.

17. A lithographic material as claimed in any of Claims 11 to 16, wherein said polyalkylene oxide compound has a molecular weight of 300 to 1 r500.

18. A silver halide emulsion as claimed in Claim 11 or 12, which includes any of the polyalkylene oxide Compounds Nos. 1 to 21 shown hereinbefore.

19. A silver halide photographic emulsion as claimed in Claim 1, substantially as hereinbefore described with reference to any of the Samples of the invention of the Examples.

20. A lithographic silver halide photographic material comprising a support having thereon a layer 50 of silver halide emulsion as claimed in any preceding claim.

21. A lithographic silver halide photographic material comprising a suport having thereon a layer of a silver halide emulsion as claimed in any of Claims 1 to 10 or 19 and a polyalkylene oxide compound as defined in any of Claims 11 to 19 in the said emulsion layer and also in a non-light-sensitive hydrophilic colloid layer.
i Ir M 21 GB 2 032 449 A 21

22. A method of forming a photographic image, which comprises imagewise exposing the lithographic material of Claim 20 or 21 and infectiously developing said material.

23. A method as claimed in Claim 22, wherein said infectious developing solution contains an o or p-dihydroxybenzene, an alkali, free sulfite and a sulfurous acid ion buffer.

24. A method as claimed in Claim 23, wherein said developing solution additionally contains 5 diethanolamine.

25. A method as claimed in Claim 22 of forming a photographic image, substantially as hereinbefore described with reference to any of the Samples of the invention of the Examples.

26. A photographic image obtained by the method of any of Claims 22 to 25.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office.
Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.

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1990-11-21
1992-06-24
Konica Corporation
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(en)

1986-05-27
1995-09-20
富士写真フイルム株式会社

Silver halide photographic light-sensitive material

JPH0748102B2
(en)

1987-07-07
1995-05-24
コニカ株式会社

Spectrally sensitized silver halide photographic material

JP2529884B2
(en)

1989-02-28
1996-09-04
富士写真フイルム株式会社

New methine compounds and methine dyes

JP2846480B2
(en)

1990-12-13
1999-01-13
三菱製紙株式会社

Silver halide photographic material

US5286598A
(en)

1991-10-28
1994-02-15
Fuji Photo Film Co., Ltd.
Silver halide photographic material

JPH05281642A
(en)

1992-04-01
1993-10-29
Fuji Photo Film Co Ltd
Silver halide photographic sensitive material and its processing method

JP3440155B2
(en)

1994-12-28
2003-08-25
富士写真フイルム株式会社

Silver halide photographic materials

JPH08227118A
(en)

1995-02-22
1996-09-03
Fuji Photo Film Co Ltd
Silver halide photographic sensitive material

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Publication date
Assignee
Title

BE550650A
(en)

1955-08-30

GB1335965A
(en)

1970-02-17
1973-10-31
Agfa Gevaert
Spectrally sensitized silver halide emulsions

GB1335964A
(en)

1970-02-17
1973-10-31
Agfa Gevaert
Spectral sensitization of light-sensitive silver halide emulsions

US4057430A
(en)

1973-04-25
1977-11-08
Fuji Photo Film Co., Ltd.
Silver halide photographic emulsion

US4014702A
(en)

1973-07-24
1977-03-29
Fuji Photo Film Co., Ltd.
Silver halide photographic emulsion

US4172728A
(en)

1977-12-16
1979-10-30
E. I. Du Pont De Nemours And Company
High contrast continuous tone developer and process of use

1978

1978-09-25
JP
JP53117668A
patent/JPS5852574B2/en
not_active
Expired

1979

1979-09-20
GB
GB7932579A
patent/GB2032449B/en
not_active
Expired

1979-09-25
US
US06/078,756
patent/US4266003A/en
not_active
Expired – Lifetime

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Publication number
Priority date
Publication date
Assignee
Title

EP0491176A1
(en)

1990-11-21
1992-06-24
Konica Corporation
Silver halide photographic light-sensitive material improved in anti-jamming property

Also Published As

Publication number
Publication date

US4266003A
(en)

1981-05-05

JPS5545015A
(en)

1980-03-29

JPS5852574B2
(en)

1983-11-24

GB2032449B
(en)

1982-11-03

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