US3788859A - Fine grain silver halide photographic emulsion containing hemicyanine sensitizing dye - Google Patents
Fine grain silver halide photographic emulsion containing hemicyanine sensitizing dye Download PDFInfo
- Publication number
- US3788859A US3788859A US00187494A US3788859DA US3788859A US 3788859 A US3788859 A US 3788859A US 00187494 A US00187494 A US 00187494A US 3788859D A US3788859D A US 3788859DA US 3788859 A US3788859 A US 3788859A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- agbri
- dye
- hemicyanine
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 title abstract description 75
- 229910052709 silver Inorganic materials 0.000 title abstract description 56
- 239000004332 silver Substances 0.000 title abstract description 56
- 239000000839 emulsion Substances 0.000 title abstract description 54
- 230000001235 sensitizing effect Effects 0.000 title description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 9
- 230000036211 photosensitivity Effects 0.000 abstract description 9
- 239000000975 dye Substances 0.000 description 37
- 239000013078 crystal Substances 0.000 description 14
- 206010070834 Sensitisation Diseases 0.000 description 10
- 230000008313 sensitization Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- QQOPAWAPLFHEEP-UHFFFAOYSA-M [7-(dimethylamino)-2-methylphenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].O1C2=CC(N(C)C)=CC=C2N=C2C1=CC(=[N+](CC)CC)C(C)=C2 QQOPAWAPLFHEEP-UHFFFAOYSA-M 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- HCCNHYWZYYIOFM-UHFFFAOYSA-N 3h-benzo[e]benzimidazole Chemical class C1=CC=C2C(N=CN3)=C3C=CC2=C1 HCCNHYWZYYIOFM-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical group [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
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
Definitions
- This invention relates to a spectrally sensitized silver halide photographic emulsion, in particular, to a silver halide photographic emulsion of fine grains having remarkably high photosensitivity in the region of wavelengths of absorption intrinsic to silver halile, not only in the region of the absorption wavelengths of a sensitizing dye, by spectrally sensitizing with hemicyanine dye.
- sensitizing dyes having small desensitizing actions of this kind are desired in the selection of sensitizing dyes used in the production of silver halide photographic sensitive materials.
- Capri-blue effect is known as another phenomenon of a rise in photosensitivity by sensitizing dyes in the region of absorption intrinsic to silver halide.
- the Capri-blue effect is the phenomenon which appears at the short time expose with high illuminance when desensitizing or sensitizing dyes are added to the silver halide emulsion which have not been sensitized with sulfur or have not undergone reduction sensitization.
- An object of the present invention is to obtain a silver halide photographic emulsion whose photosensitivity in the region of wavelengths of absorption intrinsic to silver halide is remarkably raised in addition to the region of wavelengths of sensitivity thereof being extended.
- the elfect found by this invention is quite different from the aforestated Capri-blue in that the photosensitivity of the silver halide in the region of wavelengths of absorption intrinsic to silver halide is remarkably raised by adding a hemicyanine dye to the emulsion containing silver halide crystals of certain size even when this emulsion is sensitized by the sulfur sensitization, reduction sensitization or gold sensitization, and that this effect is especially great in long time exposure.
- the above-mentioned objects are accomplished by adding at least one of the hemicyanine dyes having the following general Formula I or II to a silver halide emulsion containing silver halide crystals 95% by number of which is no more than 0.2 micron in diameter or to a silver halide emulsion. containing silver halide crystals whose mean particle diameter by number is no more than 0.18 microns:
- Z represents a group of atoms necessary to complete a fiveor six-membered heterocyclic nucleus, such as oxazoline, thiazoline, oxazole, thiazole, selenazole, benzoxazole, benzothiazole, benzoselenazole, naphthoxazole, naphthothiazole, indolinine, imidazol, benzimidazole, naphthiomidazole, pyridine, quinoline nucleus, etc., which may be substituted, R represents lower alkyl group such as methyl, ethyl, n-propyl, hydroxyalkyl (e.g.
- A represents a hydrogen atom or, when taken together with B, represents a group of atoms necessary to complete a ring, preferably containing at least one heterocyclic
- hemicyanine dyes used in this invention 5 are illustrated as follows, but are not limited wherein Z, R, L, m and n are the same meanings as those in the general Formula I, B represents an aryl group, 'such Dye 19...-
- sensitizing dyes used in this invention represented by the general Formula I or II can be readily prepared according to the procedure described for example, in the specification of the British Pat. No. 355,693, or U.S. Pat. Nos. 2,298,732 and 2,369,509.
- the hemicyanine dyes used in this invention are capable of not only extending the wavelength region of sensitivity of the photographic emulsion, but at the same time, raising the photosensitivity of silver halide in the region of wavelengths of absorption intrinsic to silver halide, when used in combination with a photographic emulsion containing silver halide crystals at least 95% by number of which is no more than 0.2 micron in diameter or with a photographic emulsion containing silver halide crystals whose mean particle diameter by number is no more than 0.18 micron.
- This is especially eflective for a gelatin-silver halide emulsion, but it is also elfective for a silver halide emulsion containing a hydrophilic colloid other than gelatin, such as agar-agar, collodion, water-soluble cellulose derivative or synthetic or natural hydrophilic resins such as polyvinylalcohol, etc.
- a hydrophilic colloid other than gelatin such as agar-agar, collodion, water-soluble cellulose derivative or synthetic or natural hydrophilic resins such as polyvinylalcohol, etc.
- Silver halide photographic emulsions used in this invention may be any of silver chloride, silver bromochloride, silver bromide, and silver bromiodide emulsion, but especially excellent eifect is obtained in the case of silver bromide or silver bromiodide emulsions.
- the sensitizing efliect of the hemicyanine dyes in this invention to the region of wavelengths of absorption intrinsic to silver halide largely depends on the grain size of silver halide crystals. Even between the photographic emulsions having the same halogen composition, the sensitizing eifect differs according to the grain size of silver halide crystals. Especially, in the case of a photographic emulsion containing silver halide crystals whose mean particle diameter by number is more than 0.18 micron, the sensitizing efiectin the region of wavelengths of absorption intrinsic to silver halide decreases greatly.
- the sensitization ratio is given as the ratio based on the sensitivity value without adding the hemicyanine dye to the silver halide emulsion, which is calculated as 1.
- one or several of the sensitizing dyes are added in a usual manner to a silver halide photographic emulsion previously sensitized by the chemical sensitization using one or more of unstable sulfur compoundsfprecious metal complex compounds and reducing compounds.
- the hemicyanine dye is usually dissolved in a suitable solvent such as methanol, ethanol, etc., then added to an emulsion.
- a suitable solvent such as methanol, ethanol, etc.
- the amount of the hemicyanine dye contained in an emulsion can be varied widely in the range of from 5 mg. to 500 mg. per 1 kg. of emulsion according to the desired effect.
- photographic emulsions of this invention can further be hypersensitized and supersensitized.
- photographic silver halide emulsions of this invention are, for example, employed for IC plate, holography, electrobeam records, etc.
- conventional additives such as other chemical sensitizing agents, stabilizers, anti-fogging agents, tone-adjusting agents, hardeners, surface active agents, plasticizers, antistatic agents, lubricants, development ac celerators, color couplers and fluorescent brightening agents can be used together in a conventional manner.
- A represents a hydrogen atom
- CH B represents an aryl group
- L represents a 0113i methine chain such that L and R may be connected with 0 each other through a polymethylene chain
- X represents an anion
- m represents 1, 2 or 3
- n represents 0 or 1
- p represents 0 or 1
- said Z is selected from the group consisting of oxazolines, thiazolines, oxazoles, thiazoles, selenazoles, benzoxazoles, benzothiazoles, benzoselenozoles, naphthoxazoles, naphthothiazoles, indolinines, imidazoles, .benzimidazoles, naphthoimidazoles, pyridines, and quinolines.
- R is selected from the group consisting 'of methyl, ethyl, n-propy1,'hydroxyalkyl, acetoxyalkyl, alkyl groups con taining a carboxy group, alkyl groups containinga sulfo group, vinylmethyl and aralkyl groups 5.
- X is selected from the group consisting of chloride, bromide, iodide, and perchlorate.
- emulsion according-to claim 1 wherein said emulsion also contains at least one member selected from the group consisting of chemical stabilizing agents, stabilizers, anti-fogging agents, tone adjusting agents, hardeners, surface active agents, plasticizers, antistatic agents, lubricants, development accelerators, color couplers and fluorescent brightening agents.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A HEMICYANINE DYE IS USED TO SPECTRALLY SENSITIZE SILVER HALIDE PHOTOGRAPHIC EMULSIONS TO PRODUCE EMULSIONS HAVING HIGH PHOTOSENSITIVITY IN THE REGION OF WAVELENGTHS OF ABSORPTION INTRINSIC TO SILVER HALIDE AND IN THE REGION OF WAVELE WAVELENGTHS OF THE DYE.
Description
United States Patent Office 31,788,859 Patented Jan. 29, 1974- US. Cl. 96139 8 Claims ABSTRACT OF THE DISCLOSURE A hemicyanine dye is used to spectrally sensitize silver halide photographic emulsions to produce emulsions having high photosensitivity in the region of wavelengths of absorption intrinsic to silver halide and in the region of wavelengths of the dye.
BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a spectrally sensitized silver halide photographic emulsion, in particular, to a silver halide photographic emulsion of fine grains having remarkably high photosensitivity in the region of wavelengths of absorption intrinsic to silver halile, not only in the region of the absorption wavelengths of a sensitizing dye, by spectrally sensitizing with hemicyanine dye.
(2) Prior art It is well known in the art of producing silver halide photographic emulsions that the region of photosensitive wavelength of silver halide emulsions can be extended by adding a certain kind of sensitizing dye to the silver halide emulsion. Generally, however, when the silver halide emulsion containing silver halide crystals, whose size is that used in the production of normal silver halide photographic sensitive material, is spectrally sensitized, the photosensitivity in the region of wavelengths of absorption intrinsic to silver halide is lowered. This well known phenomenon is called densensitization. Therefore, sensitizing dyes having small desensitizing actions of this kind are desired in the selection of sensitizing dyes used in the production of silver halide photographic sensitive materials. On the other hand, it is preferable to make the grain size of silver halide crystals contained in the silver halide emulsion as small as possible in order to improve the image quality such as resolving power, state of grains therein, etc., obtained from the silver halide photographic sensitive material. However, this lowers the sensitivity of the photographic material in general.
Accordingly, in the field of correlated arts, the art to make the grain size of silver halide crystals as small as possible and to prepare a silver halide emulsion having sufficient sensitivity has resulted in chemical sensitization such as sulfur sensitization or reduction sensitization and the like, becoming a necessity.
Capri-blue effect is known as another phenomenon of a rise in photosensitivity by sensitizing dyes in the region of absorption intrinsic to silver halide. However, the Capri-blue effect is the phenomenon which appears at the short time expose with high illuminance when desensitizing or sensitizing dyes are added to the silver halide emulsion which have not been sensitized with sulfur or have not undergone reduction sensitization.
(3) Objects of the invention An object of the present invention is to obtain a silver halide photographic emulsion whose photosensitivity in the region of wavelengths of absorption intrinsic to silver halide is remarkably raised in addition to the region of wavelengths of sensitivity thereof being extended.
Other objects will be apparent to those skilled in the art as the description of this invention proceeds.
BRIEF SUMMARY OF THE INVENTION The elfect found by this invention is quite different from the aforestated Capri-blue in that the photosensitivity of the silver halide in the region of wavelengths of absorption intrinsic to silver halide is remarkably raised by adding a hemicyanine dye to the emulsion containing silver halide crystals of certain size even when this emulsion is sensitized by the sulfur sensitization, reduction sensitization or gold sensitization, and that this effect is especially great in long time exposure.
We have found that when silver halide emulsion containing silver halide crystals at least by number of which is no more than 0.2 micron in diameter or silver halide emulsion containing silver halide crystals whose mean particle diameter by number is no more than 0.18 micron is spectrally sensitized in the usual way using hemicyanine dye, the photosensitivity of the silver halide in the region of wavelengths of absorption intrinsic to silver halide can be remarkably raised in addition to the region of wavelengths of sensitivity of the dye used being extended.
DETAILED DESCRIPTION OF THE INVENTION The above-mentioned objects are accomplished by adding at least one of the hemicyanine dyes having the following general Formula I or II to a silver halide emulsion containing silver halide crystals 95% by number of which is no more than 0.2 micron in diameter or to a silver halide emulsion. containing silver halide crystals whose mean particle diameter by number is no more than 0.18 microns:
wherein Z represents a group of atoms necessary to complete a fiveor six-membered heterocyclic nucleus, such as oxazoline, thiazoline, oxazole, thiazole, selenazole, benzoxazole, benzothiazole, benzoselenazole, naphthoxazole, naphthothiazole, indolinine, imidazol, benzimidazole, naphthiomidazole, pyridine, quinoline nucleus, etc., which may be substituted, R represents lower alkyl group such as methyl, ethyl, n-propyl, hydroxyalkyl (e.g. betahydroxyethyl, beta-methoxyethyl), acetoxyalkyl (such as beta-acetoxyethyl), an alkyl group containing a carboxy group (such as beta-carboxyethyl, gamma-caboxypropyl, delta-carboxybutyl, omega-carboxypentyl, p-carboxyphenylethyl), an alkyl group containing a sulfo group (such as beta-sulfoethyl, gamma-sulfopropyl, 'gamma-sulfobutyl, delta-sulfobutyl, p-sulfophenylethyl), vinylmethyl, an aralkyl (such as benzyl and phenylethyl),and the like, A represents a hydrogen atom or, when taken together with B, represents a group of atoms necessary to complete a ring, preferably containing at least one heterocyclic atom connected through a polymethylene chain, such as morpholine, pyr'rolidine, piperazine, and piperadine, B represents an aryl group (such as phenyl, tolyl, etc.) or, when taken together with A, represents a group of atoms necessary to complete a ring, L represents a methine chain or L and R may be connected with each other through a polymethylene chain, X represents anion such as usually salt thereof is formed.
as phenyl, tolyl group, etc.
Representative hemicyanine dyes used in this invention 5 are illustrated as follows, but are not limited wherein Z, R, L, m and n are the same meanings as those in the general Formula I, B represents an aryl group, 'such Dye 19...-
Dye 20..::
Dye 22:
Dye 23..=
Dye 24":
Dye 25":
Dye 26...:
DYB 27..::
Cam
TABLE Contlnued Dye 28..-:
Dye 29":
The sensitizing dyes used in this invention represented by the general Formula I or II can be readily prepared according to the procedure described for example, in the specification of the British Pat. No. 355,693, or U.S. Pat. Nos. 2,298,732 and 2,369,509.
The hemicyanine dyes used in this invention are capable of not only extending the wavelength region of sensitivity of the photographic emulsion, but at the same time, raising the photosensitivity of silver halide in the region of wavelengths of absorption intrinsic to silver halide, when used in combination with a photographic emulsion containing silver halide crystals at least 95% by number of which is no more than 0.2 micron in diameter or with a photographic emulsion containing silver halide crystals whose mean particle diameter by number is no more than 0.18 micron.
This is especially eflective for a gelatin-silver halide emulsion, but it is also elfective for a silver halide emulsion containing a hydrophilic colloid other than gelatin, such as agar-agar, collodion, water-soluble cellulose derivative or synthetic or natural hydrophilic resins such as polyvinylalcohol, etc.
Silver halide photographic emulsions used in this invention may be any of silver chloride, silver bromochloride, silver bromide, and silver bromiodide emulsion, but especially excellent eifect is obtained in the case of silver bromide or silver bromiodide emulsions.
The sensitizing efliect of the hemicyanine dyes in this invention to the region of wavelengths of absorption intrinsic to silver halide largely depends on the grain size of silver halide crystals. Even between the photographic emulsions having the same halogen composition, the sensitizing eifect differs according to the grain size of silver halide crystals. Especially, in the case of a photographic emulsion containing silver halide crystals whose mean particle diameter by number is more than 0.18 micron, the sensitizing efiectin the region of wavelengths of absorption intrinsic to silver halide decreases greatly.
An example using the hemicyanine dye (18) is given below in Table 1:
TABLE 1 Mean particle diameter (11.) 0.07 0.1 0.15 0.20 0.60 Sensitization ratio 5.0 3 1.3 1.0 0.45
The sensitization ratio is given as the ratio based on the sensitivity value without adding the hemicyanine dye to the silver halide emulsion, which is calculated as 1.
It can be understood from Table 1 that the influence of the grain size of the silver halide crystal is quite great.
In order to prepare spectrally sensitized photographic emulsions according to this invention, one or several of the sensitizing dyes are added in a usual manner to a silver halide photographic emulsion previously sensitized by the chemical sensitization using one or more of unstable sulfur compoundsfprecious metal complex compounds and reducing compounds.
In practice, the hemicyanine dye is usually dissolved in a suitable solvent such as methanol, ethanol, etc., then added to an emulsion. The amount of the hemicyanine dye contained in an emulsion can be varied widely in the range of from 5 mg. to 500 mg. per 1 kg. of emulsion according to the desired effect.
The photographic emulsions of this invention can further be hypersensitized and supersensitized.
The photographic silver halide emulsions of this invention are, for example, employed for IC plate, holography, electrobeam records, etc.
In the production of the photographic emulsions of this invention, conventional additives such as other chemical sensitizing agents, stabilizers, anti-fogging agents, tone-adjusting agents, hardeners, surface active agents, plasticizers, antistatic agents, lubricants, development ac celerators, color couplers and fluorescent brightening agents can be used together in a conventional manner.
This invention will be further explained by the following example.
Photographic emulsions were prepared by adding the hemicyanine dyes given in Table 3 to silver bromiodide emulsion (AgI:AgBr=1 molz99 mols). The resulting emulsions were coated on the film base of cellulose triacetate and dried, which were then exposed to 1000 lux electric light (2666 K.) through Wratten No. 47B filter and developed. The developer having the composition described in Table 2 was used.
TABLE 2 G. Metol 2 Hydroquinone 8.8 Anhydrous sodium sulfite u 96 Anhydrous sodium carbonate 48 Potassium bromide 5 Water, enough to make 1 liter.
TABLE 3 Amount of dye Mean Mean added] parti- Sensi- Comparti- Sensikg. emulole tizapare16 tiza- Ex. Dye sion,mol- Emuldiamtion ison dlamtion No. No. gram slon eter ratio mark eter ratio 1 10-5/6 AgBrI 0.07 3.0 a 0.6 0. 50 2 10-5/ AgBrI 0.07 3.2 b 0.6 0. 45 3 10-5 AgBrI 0.07 3.4 0.6 0. 49 4 105 6 AgBrI 0.07 3.0 d 0.6 0.46 6 10- AgBrI 0.07 3.1 e 0.6 0.45 6 10-5 6 AgBrI 0.07 3.0 t 0.6 0.48 7 10-5/6 .AgBrI 0.07 g 0.6 0.30 8 -5/6 AgBrI 0.07 4.5 11 0.6 0.80 9 10-5 AgBrI 0. 07 4.5 1 0.6 0. 75 10 10-5 6 AgBrI 0.07 4.0 1 0.6 0.55 11 10*5/6 AgBrI 0. 07 42 k 0.6 0.42 12 10-6/6 AgBrI 0.07 4.2 1 0.6 0.48 13 10- 6 AgBrI 0. 07 4.5 m 0.6 0.37 14 105 6 AgBrI 0.07 3.7 n 0.6 0.48 15 105 6 AgBrI 0.07 3.0 O 0.6 0.40 16 10-5 .AgBrI o. 07 4.0 p 0.6 0. 45 17 10-5/6 AgBrI 0. 07 4.5 q 0.6 0.50 18 10-5 6 AgBrI 0. 07 5.0 r 0.6 0.45 19 10-5/6 AgBrI 0. 07 4.2 s 0.6 0.45 20 10-5/6 AgBrI 0.07 3.6 t 0.6 0.48 21 10-5/6 AgBrI 0.07 4.6 u 0.6 0.46 22 10-5 6 AgBrI 0. 07 4.0 v 0.6 0.46 23 10-5/6 AgBrI 0.07 4.5 w 0.6 0.46 24 10-5/6 .AgBrI 0.07 5.0 x 0.6 0.45 25 10-5/6 AgBrI 0.07 4.8 y 0.6 0.40 26 10- 6 AgBrI 0.07 4.0 2 0.6 0.37 27 10-5 6 AgBrI 0. 07 4.2 a 0.6 0.35 28 10-5/6 AgBrI 0.07 4.0 b 0.6 0.42 29 5 AgBrl 0. 07 4.5 0' 0.6 0.14 30 10-5/6 AgBrI 0.07 4.0 d 0.6 0.38
What is claimed is: O 1. A silver halide photographic emulsion comprising 30 at least one of the hemicyanine dyes represented by the g CH=CH OH=CH NH following general Formulae I or II and silver halide crys- H tals, at least 95% by number of which are no more than 0.2 micron in diameter, or whose mean particle diameter I by number is no more than 0.18 micron: 2
S --z A g I OH=OH-CH=CHNH- R-N= cn-o11)=- L=L m-N H Q l B 40 N 's) zH I" wherein Z represents a group of atoms necessary to com- S plete a fiveor six-membered heterocyclic ring, R repree sents a. lower alkyl group, A represents a hydrogen atom, CH B represents an aryl group, or A and B taken together CH=CH CH=CH NH* may represent groups of atoms necessary to complete a ring containing at least one heterocyclic atom connected through a polymethylene chain, L represents a 0113i methine chain such that L and R may be connected with 0 each other through a polymethylene chain, X represents an anion, m represents 1, 2 or 3, n represents 0 or 1, p represents 0 or 1, and 11:0 if an intramolecular salt HCCH CH OH NH thereof is formed;
I, --Z zHs I. R--N(OH=CH)nC=(L-L)m=NB (II) 8 wherein Z, R, L, n and m are the same meanings as those in general Formula I, B represents an aryl group.
2. The emulsion according to claim 1 wherein said dye is selected from the group consisting of 1 S Se 4 6H, -on=on-on=on-Nn- -on=on-on=on-Nnand 3. The emulsion according to claim 1 wherein said Z is selected from the group consisting of oxazolines, thiazolines, oxazoles, thiazoles, selenazoles, benzoxazoles, benzothiazoles, benzoselenozoles, naphthoxazoles, naphthothiazoles, indolinines, imidazoles, .benzimidazoles, naphthoimidazoles, pyridines, and quinolines.
4. The emulsion according to claim 1 wherein said R is selected from the group consisting 'of methyl, ethyl, n-propy1,'hydroxyalkyl, acetoxyalkyl, alkyl groups con taining a carboxy group, alkyl groups containinga sulfo group, vinylmethyl and aralkyl groups 5. The emulsion according to claim 1 wherein X is selected from the group consisting of chloride, bromide, iodide, and perchlorate.
6. The emulsion according to claim 1 wherein the amount of said dye in the emulsion is in the range of 5-500 rug-per 1 kg. of emulsion. 7
7. The emulsion according-to claim 1 wherein said emulsion also contains at least one member selected from the group consisting of chemical stabilizing agents, stabilizers, anti-fogging agents, tone adjusting agents, hardeners, surface active agents, plasticizers, antistatic agents, lubricants, development accelerators, color couplers and fluorescent brightening agents.
8. The emulsion according to claim 1 wherein said ring containing at least one heterocyclic 'atom is selected from the group consisting of morpholine, pyrrolidine, piperazine, and piperadine. Y
References Cited UNITED STATES PATENTS 3,038,800 6/1962 Luckey et a1. 96140 3,482,981 12/1969 Van Lare 96-140 3,615,635 10/1971 Shiba et al. 96140 3,575,704 4/1971 -Sa1esin -1. 96-94 3,652,280 3/ 1972 De Belder et al. 96--94 3,661,592 5/1972 Philippaerts et al. 96--94 3,415,650 12/1968 Frame et al. 96-94 3,600,167 8/1971 Judd et a1. 96-94 3,706,566 12/ 1972 Shiba et a1. 96-139 NORMANHG, TORCHIN, Primary Examiner R. L. SCHILLING, Assistant Examiner US. Cl. X.R. 96l40
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45088133A JPS4917525B1 (en) | 1970-10-07 | 1970-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3788859A true US3788859A (en) | 1974-01-29 |
Family
ID=13934411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00187494A Expired - Lifetime US3788859A (en) | 1970-10-07 | 1971-10-07 | Fine grain silver halide photographic emulsion containing hemicyanine sensitizing dye |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3788859A (en) |
| JP (1) | JPS4917525B1 (en) |
| DE (1) | DE2150138A1 (en) |
| FR (1) | FR2111005A5 (en) |
| GB (1) | GB1361089A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322494A (en) * | 1980-01-23 | 1982-03-30 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material |
| US4581329A (en) * | 1983-03-11 | 1986-04-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| US5981162A (en) * | 1997-05-08 | 1999-11-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0512483A1 (en) * | 1991-05-09 | 1992-11-11 | Eastman Kodak Company | Hemicyanine sensitizing dyes for photographic materials |
-
1970
- 1970-10-07 JP JP45088133A patent/JPS4917525B1/ja active Pending
-
1971
- 1971-10-05 FR FR7135830A patent/FR2111005A5/fr not_active Expired
- 1971-10-06 GB GB4653171A patent/GB1361089A/en not_active Expired
- 1971-10-07 DE DE19712150138 patent/DE2150138A1/en active Pending
- 1971-10-07 US US00187494A patent/US3788859A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322494A (en) * | 1980-01-23 | 1982-03-30 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material |
| US4581329A (en) * | 1983-03-11 | 1986-04-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| US5981162A (en) * | 1997-05-08 | 1999-11-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2111005A5 (en) | 1972-06-02 |
| DE2150138A1 (en) | 1972-05-10 |
| GB1361089A (en) | 1974-07-24 |
| JPS4917525B1 (en) | 1974-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3537858A (en) | Reversal silver halide emulsions | |
| US3953215A (en) | Silver halide photographic emulsions | |
| GB2038494A (en) | Process of preparing silver halide photographic emulsion | |
| US3706566A (en) | Photographic emulsion containing optically dye-sensitized silver halide grains of less than 0.2 micron | |
| US2701198A (en) | Supersensitized photographic emulsions containing simple cyanine dyes | |
| US3922170A (en) | Spectrally sensitized silver halide photographic emulsion | |
| US3788859A (en) | Fine grain silver halide photographic emulsion containing hemicyanine sensitizing dye | |
| US3632349A (en) | Silver halide supersensitized photographic emulsion | |
| US3583870A (en) | Emulsions containing a bipyridinium salt and a dye | |
| US4040841A (en) | Silver halide photographic emulsion | |
| US3808009A (en) | Light-sensitive super-sensitized silver halide photographic emulsions | |
| US3988513A (en) | Silver halide emulsions for recording electron rays | |
| US3718470A (en) | Surface development process utilizing an internal image silver halide emulsion containing a composite nucleating agent-spectral sensitizing polymethine dye | |
| US2944901A (en) | Multicontrast photographic emulsions | |
| US3971664A (en) | Fine grain silver halide emulsions with polyheteronuclear sensitizing dyes | |
| US3694217A (en) | Silver halide photographic emulsion | |
| US3481742A (en) | Silver halide photographic emulsion | |
| US3367780A (en) | Direct-print photographic silver halide emulsions | |
| US3567456A (en) | Photographic direct-reversal emulsions | |
| US3804634A (en) | Photographic supersensitized silver halide emulsion | |
| US3615643A (en) | Direct positive silver halide emulsion containing a dye with at least one naptho (2 3 ) oxazole nucleus | |
| US4039335A (en) | Photographic silver halide emulsions | |
| US2398778A (en) | Sensitized photographic emulsion | |
| US3687674A (en) | Direct positive fogged silver halide emulsion sensitized with a cyclo-heptatriene cyanine dye | |
| US3726684A (en) | Spectrally sensitizing quick-processing photographic material |