US3627534A - Direct positive photographic emulsion stabilized against development stain - Google Patents
Direct positive photographic emulsion stabilized against development stain Download PDFInfo
- Publication number
- US3627534A US3627534A US801180A US3627534DA US3627534A US 3627534 A US3627534 A US 3627534A US 801180 A US801180 A US 801180A US 3627534D A US3627534D A US 3627534DA US 3627534 A US3627534 A US 3627534A
- Authority
- US
- United States
- Prior art keywords
- group
- emulsion
- photographic
- nucleus
- direct positive
- 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
- 239000000839 emulsion Substances 0.000 title abstract description 52
- -1 SILVER HALIDE Chemical class 0.000 abstract description 26
- 229910052709 silver Inorganic materials 0.000 abstract description 19
- 239000004332 silver Substances 0.000 abstract description 19
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 abstract description 14
- 150000002918 oxazolines Chemical class 0.000 abstract description 9
- 150000003236 pyrrolines Chemical class 0.000 abstract description 9
- 150000003549 thiazolines Chemical class 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000000975 dye Substances 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 7
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 6
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- VLBGIFUKQYTZCN-UHFFFAOYSA-N (+)-2,3-Dihydro-3-methyl-1H-pyrrole Chemical compound CC1CNC=C1 VLBGIFUKQYTZCN-UHFFFAOYSA-N 0.000 description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- SRGCYOMCADXFJA-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-thiazole Chemical compound CC1CSC=N1 SRGCYOMCADXFJA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- PKRBEFKAKUDLJX-UHFFFAOYSA-N 3-phenyl-2,3-dihydro-1H-pyrrole Chemical compound C1NC=CC1C1=CC=CC=C1 PKRBEFKAKUDLJX-UHFFFAOYSA-N 0.000 description 2
- KOAMXHRRVFDWRQ-UHFFFAOYSA-N 4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC=N1 KOAMXHRRVFDWRQ-UHFFFAOYSA-N 0.000 description 2
- QFJLDRWTXZTXPP-UHFFFAOYSA-N 4-methyl-2,3-dihydro-1h-pyrrole Chemical compound CC1=CNCC1 QFJLDRWTXZTXPP-UHFFFAOYSA-N 0.000 description 2
- IFIUFEBEPGGBIJ-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC=N1 IFIUFEBEPGGBIJ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 150000008061 acetanilides Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 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
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- DHHNSJJTDFVVSG-UHFFFAOYSA-L disodium;benzene-1,4-diol;sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O.OC1=CC=C(O)C=C1 DHHNSJJTDFVVSG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- G03C1/485—Direct positive emulsions
- G03C1/48515—Direct positive emulsions prefogged
- G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
- G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes
Definitions
- Z represents a group which completes a thiazoline nucleus, an oxazoline nucleus, or pyrroline nucleus;
- R represents an alkyl group or a substituted alkyl group, L and L each represents a methine group or a substituted methine group;
- R and R each represents an aryl group; and
- n represents 0, l or 2.
- the present invention relates generally to silver halide photographic emulsions and more particularly to direct positive photographic emulsions.
- the photographic density of a silver image obtained by light exposure and development of a photographic light-sensitive element becomes higher as the amount of the light exposure increases, but occassionally, when the amount of the light exposure reaches a given value, the photographic density reaches a maximum value and when the image is further exposed, a reversal phenomenon occurs and the photographic density degrades to below the maximum value.
- This reversal phenomenon is called solarization.
- solarization when an area where the solarization will occur is exposed over the maximum exposure value, the photographic density is reduced and hence a positive image is obtained there.
- the present invention is concerned with a direct positive photographic emulsion wherein this phenomenon is utilized.
- the solarization emulsion is a silver halide photographic emulsion which has been previously fogged in an amount corresponding to the aforesaid maximum photographic density.
- an object of the present invention is to provide a direct positive photographic emulsion which is preliminarily fogged and has a high maximum density (D max.) and low contrast,
- Another object of this invention is to provide previously fogged direct positive photographic emulsion wherein the formation of stains after development, due to the presence of a sensitizing dye is reduced and thus reduces contrast.
- Z represents a group which forms a thiazoline nucleus, an oxazoline nucleus, or a pyrroline nucleus
- R represents an alkyl group of a substituted alkyl group
- L and L each represents a methine group or a substituted methine group
- R and R each represents an aryl group
- n is 0, 1 or 2.
- Z in the above formula, is a group that forms a thiazoline nucleus, such as thiazoline, 4-methyl thiazoline; and oxazoline nucleus, such as oxazoline, 4 methyloxazoline, 4,4-dimethyloxazoline, etc.; or pyrroline nucleus, such as pyrroline, 3-methylpyrroline, 4-methylpyrroline, 4-phenylpyrroline, S-methylpyrroline, etc.
- thiazoline nucleus such as thiazoline, 4-methyl thiazoline
- oxazoline nucleus such as oxazoline, 4 methyloxazoline, 4,4-dimethyloxazoline, etc.
- pyrroline nucleus such as pyrroline, 3-methylpyrroline, 4-methylpyrroline, 4-phenylpyrroline, S-methylpyrroline, etc.
- R represents an alkyl group such as methyl, ethyl, n-propyl, n-butyl, etc., or a substituted alkyl group such as fi-ethoxymethyl, fl-methoxyethyl, allyl (or vinylmethyl), benzyl, ,B-phenylethyl, carboxymethyl, fl-carboxyethyl, fl-sulfoethyl, 'y-sulfopropyl or 6-sulfobutyl.
- the particularly effective sensitizing dye is the merocyanine dye having general Formula I wherein the heterocyclic ring is a mono-cyclic thiazoline nucelus, oxazoline nucleus, or pyrroline nucleus.
- the merocyanine dye may be prepared by condensing an aniline derivative or an acetanilide derivative represented by the general formula:
- Z, R, L and L have the same meanings as in general Formula I and R represents a hydrogen atom or an acetyl group.
- R represents a hydrogen atom or an acetyl group.
- the compound represented by general Formula III is condensed in the presence of an organic base such as triethylamine.
- Example I Typical examples of preparing the abovementioned dyes are as follows:
- dyes 3 and 4 above were prepared.
- the melting point and the spectral absorption maximum of dye 3 were 254 C. and 437 my. (in methanol) and those of dye 4 were 226 C. and 452 III/1.. (in methanol), respectively.
- the merocyanine dye represented by aforesaid general Formula I is highly soluble in organic solvents such as methanol and ethanol, and, hence, is usually added to a silver halide emulsion in a solution of such solvents.
- a particularly effective amount of the dye is 30 mg. to 250 mg. per kilogram of emulsion, but the optimum concentration of dye in the emulsion depends on the type of dye and the emulsion used, and is determined by means of wellknown sensitometry.
- silver halide emulsions used in the present invention there may be employed various kinds of silver halides, such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.
- the silver halide emulsion of this invention has been previously fogged to the maximum density by light exposure or by means of a chemical fogging agent.
- chemical fogging agents that can be used to fog the silver halide in the emulsion without harmful side effects to the silver halide emulsion are, for example, thiourea, dioxide, stannous chloride, formaldehyde, and hydrazine.
- ком ⁇ онентs such as coating aids or hardening agents may be added to the emulsion if desired.
- a solution of the merocyanine dye is added to the emulsion with stirring and the resulting emulsion is applied to a support.
- the support there may be employed, e.g., a glass plate, a cellulose derivative film such as triacetyl cellulose film, a synthetic resin film such as polyethylene terephthalate film, or a baryta-coated paper.
- a cellulose derivative film such as triacetyl cellulose film
- a synthetic resin film such as polyethylene terephthalate film
- a baryta-coated paper e.g., a glass plate, a cellulose derivative film such as triacetyl cellulose film, a synthetic resin film such as polyethylene terephthalate film, or a baryta-coated paper.
- the previously fogged silver halide emulsion of this invention contains the merocyanine dye represented by general Formula I, mentioned above, and the dye causes a reduction in contrast.
- the emulsion can be effectively used for soft direct positive photographic light-sensitive elements, such as copying light-sentitive elements for X- ray photographs.
- the direct positive photographic light-sensitive elements having a layer of the silver halide emulsion of the present invention gives a film image with less color. That is, a film having significantly fewer stains, a reduction in contrast can be attained without lowering the maximum density (D max.).
- Example II A silver bromide emulsion fogged to the maximum density by means of hydrazine dihydrochloride was prepared, and the pH and pAg of the emulsion were adjusted to 6.0 and 9.0, respectively. The emulsion was divided into proportions, and each of the merocyanine dyes shown below was added to one of the emulsions and thereafter the emulsions were applied to triacetyl cellulose films and then dried.
- the light-sensitive film thus prepared, was exposed through an optical step wedge and developed in an aqueous developer having the following composition;
- the developed emulsion layer was then fixed in a conventional fixing solution containing sodium thiosulfate and, after washing, was dried.
- the optical density of the positive image, thus obtained, was measured by means of a sensitometer and the gamma value was determined. The results are shown in Table 1.
- the density of stains shown in Table 1 was measured as follows. After exposing the sample to give the minimum density (D min.), the sample was developed in the aforesaid developer for one minute, fixed for 10 minutes, washed, and dried. The stain density of the thus processed sample was detained using a green filter having a transmission maximum at 525 m. The stain density of the sample wherein no dye was added was shown as 0.
- Z represents a group which completes a member selected from the group consisting of a thiazoline nucleus, an oxazoline nucleus, and a pyrroline nucleus
- R represents a member selected from the group consisting of a lower alkyl group and a substituted lower alkyl group whose substitutents are members selected from the group consisting of lower alkoxy lower alkyl, allyl, aryl lower alkyl, carboxy lower alkyl, and sulfo lower alkyl
- L and L each represents a member selected from the group consisting of a methine group and a substituted methine group, said substituent being a member selected from the group consisting of a lower alkyl group and an aryl group
- n represents 0, 1, or 2.
- a silver halide photographic light-sensitive element having a layer of a preliminarily fogged direct positive silver halide photographic emulsion containing at least one merocyanine dye represented by the general formula:
- Z represents a group which completes a member selected from the group consisting of a thiazoline nucleus
- R represents a member selected from the group consisting of a lower alkyl group and a substituted lower alkyl group whose substituents are members selected from the group consisting of lower alkoxy lower alkyl, allyl, aryl, aryl lower alkyl, carboxy lower alkyl, and sulfo lower alkyl
- L and L each represents a member seected from the group consisting of a methine group and a substituted methine group, said substituent being a member selected from the group consisting of a lower alkyl group and an aryl group
- n represents 0, 1, or 2 on a support.
- thiazoline nucleus is a member selected from the group consisting of thiazoline and 4-methyl thiazoline.
- oxazoline nucleus is a member selected from the group consisting of oxazoline, 4-methyl oxazoline and 4,4-dimethyloxazoline.
- pyrroline nucleus is a member selected from the group consisting of pyrroline, 3-methyl pyrroline, 4-methyl pyrroline, 4-phenyl pyrroline, and S-methyl pyrroline.
- thiazoline nucleus is a member selected from the group consisting of thiazoline and 4-methyl thiazoline.
- oxazoline nucleus is a member selected from the group consisting of oxazoline and 4-methyl oxazoline.
- pyrroline nucleus is a member selected from the group consisting of pyrroline, 3-rnethyl pyrroline, 4-methyl pyrroline, and S-methyl pyrroline.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087768 | 1968-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3627534A true US3627534A (en) | 1971-12-14 |
Family
ID=11762546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US801180A Expired - Lifetime US3627534A (en) | 1968-02-21 | 1969-02-20 | Direct positive photographic emulsion stabilized against development stain |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3627534A (xx) |
| BE (1) | BE728590A (xx) |
| CA (1) | CA918992A (xx) |
| DE (1) | DE1908570A1 (xx) |
| FR (1) | FR2002361A1 (xx) |
| GB (1) | GB1238257A (xx) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077191A (en) * | 1989-12-26 | 1991-12-31 | Eastman Kodak Company | Photographic sensitizing dyes |
| US20040180942A1 (en) * | 2001-12-21 | 2004-09-16 | X-Ceptor Therapeutics, Inc. | Heterocyclic modulators of nuclear receptors |
| US20210079267A1 (en) * | 2019-09-12 | 2021-03-18 | Transportation Ip Holdings, Llc | Applicator nozzles |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0050558B1 (en) * | 1980-10-16 | 1985-07-17 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic emulsions and elements capable of forming direct-positive images |
| FR2497367B1 (fr) * | 1980-10-16 | 1987-08-14 | Kodak Pathe | Emulsion positive-directe aux halogenures d'argent avec agent de nucleation incorpore |
-
1969
- 1969-02-15 CA CA043046A patent/CA918992A/en not_active Expired
- 1969-02-18 BE BE728590D patent/BE728590A/xx unknown
- 1969-02-20 GB GB1238257D patent/GB1238257A/en not_active Expired
- 1969-02-20 DE DE19691908570 patent/DE1908570A1/de active Pending
- 1969-02-20 US US801180A patent/US3627534A/en not_active Expired - Lifetime
- 1969-02-21 FR FR6904541A patent/FR2002361A1/fr not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077191A (en) * | 1989-12-26 | 1991-12-31 | Eastman Kodak Company | Photographic sensitizing dyes |
| US20040180942A1 (en) * | 2001-12-21 | 2004-09-16 | X-Ceptor Therapeutics, Inc. | Heterocyclic modulators of nuclear receptors |
| US7115640B2 (en) | 2001-12-21 | 2006-10-03 | X-Ceptor Therapeutics, Inc. | Heterocyclic modulators of nuclear receptors |
| US20210079267A1 (en) * | 2019-09-12 | 2021-03-18 | Transportation Ip Holdings, Llc | Applicator nozzles |
| US11827820B2 (en) * | 2019-09-12 | 2023-11-28 | Transportation Ip Holdings, Llc | Applicator nozzles |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2002361A1 (xx) | 1969-10-17 |
| DE1908570A1 (de) | 1969-09-18 |
| CA918992A (en) | 1973-01-16 |
| BE728590A (xx) | 1969-08-01 |
| GB1238257A (xx) | 1971-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3672898A (en) | Multicolor silver halide photographic materials and processes | |
| US3615615A (en) | Photographic emulsions including reactive quaternary salts | |
| US2933390A (en) | Supersensitization of photographic silver halide emulsions | |
| US3522052A (en) | Photographic supersensitized silver halide emulsions | |
| US2497917A (en) | Method of producing direct positive photographs having increased density | |
| US3734738A (en) | Silver halide emulsions containing reactive quaternary salts nucleating agents | |
| JPS5852574B2 (ja) | ハロゲン化銀写真乳剤 | |
| US3782945A (en) | Mercaptotetrazaindene in photographic printing plate development | |
| US4309500A (en) | Silver halide color photographic light-sensitive material | |
| US3627534A (en) | Direct positive photographic emulsion stabilized against development stain | |
| US3910795A (en) | Fogged, direct positive silver halide emulsion sensitized with a nitrophenyl mercapto heterocyclic compound | |
| US3326689A (en) | Photographic direct-print silver halide emulsions | |
| US4925780A (en) | Direct positive silver halide light-sensitive color photographic material | |
| JP2557252B2 (ja) | ハロゲン化銀写真感光材料 | |
| JPH03217837A (ja) | ハロゲン化銀写真感光材料 | |
| US4059448A (en) | Dye containing photographic sensitive elements | |
| US3933505A (en) | Fogged, direct positive silver halide emulsion containing a nitro-substituted fluorene desensitizer | |
| US3930860A (en) | Spectrally sensitized color photographic materials suitable for high temperature rapid development | |
| US3764327A (en) | Color photographic light sensitive material | |
| JPH0731386B2 (ja) | 直接ポジ型ハロゲン化銀写真感光材料 | |
| US3702251A (en) | Light-sensitive silver halide photographic emulsion for microfilm use | |
| US3567456A (en) | Photographic direct-reversal emulsions | |
| US3687674A (en) | Direct positive fogged silver halide emulsion sensitized with a cyclo-heptatriene cyanine dye | |
| JPH01293343A (ja) | ハロゲン化銀写真感光材料 | |
| US3364026A (en) | Fogged silver halide direct positive solarizing elements containing merocyanine dyes |