US3778268A - Light-sensitive silver halide photographic material - Google Patents
Light-sensitive silver halide photographic material Download PDFInfo
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- US3778268A US3778268A US00288160A US3778268DA US3778268A US 3778268 A US3778268 A US 3778268A US 00288160 A US00288160 A US 00288160A US 3778268D A US3778268D A US 3778268DA US 3778268 A US3778268 A US 3778268A
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- silver halide
- light
- sample
- sensitive silver
- emulsion
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- -1 silver halide Chemical class 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 17
- 239000011229 interlayer Substances 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 31
- 230000015572 biosynthetic process Effects 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 11
- 239000000654 additive Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 230000005070 ripening Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004247 glycine and its sodium salt Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000896 monocarboxylic acid 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940029258 sodium glycinate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009498 subcoating Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- G03C1/33—Spot-preventing agents
Definitions
- ABSTRACT A light-sensitive silver halide photographic material containing as anti-spotting agent, at least one compound represented by the general formula e 1 N/CH mCHC OOM 4 Claims, No Drawings I LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part application of Ser. No. 39,568 filed May 21, 1970 now abandoned.
- the present invention relates to light-sensitive silver halide photographic materials containing a novel antispotting agent for preventing so-called spots (white or black stains) which are formed on the surfaces of lightsensitive silver halide photographic materials after development due to such causes as dusts, heavy metal powders or the like which are present in the air.
- a principal object of the present invention is to overcome the above-mentioned drawbacks of the conventional anti-spotting agents and to provide light-sensitive photographic materials having excellent photographic properties.
- R and R aliphatic, aromatic, alicyclic or heterocyclic groups, which may be optionally substituted;
- R an alkyl or substituted alkyl group
- R R R and R hydrogen atoms or methyl groups, but R and R and R and R cannot be methyl groups at the same time;
- M and M hydrogen atoms, alkali metals, ammonium or organic amine salts
- p a positive integer of l to 6;
- the filtrate is concen- CH2COOK CHZCOOK l isoCdl o CIIzClIClIzN-CH2CIICHZNCHZCIICHZO C4HylSO II II H (17) OH OH 0112011 011200011 trated, and the concentrate is dissolved in 220 ml. of 3 00 methanol at an elevated temperature and then filtered. 011,011 H CHQCHCOOH
- the filtrate obtained is again concentrated, and the CH concentrate is refluxed over a water bath together with 250 ml. of ethyl acetate, followed by cooling and filtra- 19 CHZCI'IZSCHI; tion.
- the resulting crystals are dried to obtain 71 g. of CHF O OH2CHCH2N J:HC00N8 pale yellow, hygroscopic crcystals, m.p. 163C.
- Synthesis Example 2 filtration.
- the filtrate is Concentrated, and the concentrate is formed into a sodium salt by addition of a mixture comprising 300 ml. of water and 14 g. of anhydrous sodium carbonate, followed by concentration.
- the concentrate is precipitated from ethanol to obtain 2.3 g. of white crystals.
- aforesaid compounds employed :in the present invention do not substantially vary in effectiveness at a pH range of ordinary silver halide emulsions, regardless of whether they are acidic or alkaline. and hence are markedly effective. Further, the compounds employed in the present invention are not injured. Moreover, the effects of the compounds are not dominated by the kind of supports and of materials of sub layers, and thus the compounds are effectively applied to all the lightsensitive silver halide photographic materials such as usual black-white and color films specific specif lightsensitive printing and X-ray materials.
- Example 1 An ordinary speed ortho-type photographic emulsion comprising g. of silver bromide was subjected to gold sensitization at the time of second ripening, incorporated with the usual additives, and divided into two portions A and B.
- Emulsion A was incorporated with 0.5 g. of the compound of exemplification l0 and then coated on a polyester support to prepare a sample A.
- emulsion B was coated as it was on a polyester support to prepare a sample B. After setting, each sample was sprinkled with a nickel powder, dried, cut and then subjected to development. As a result, a large number of spots were formed in sample B, whereas no formation of spots was observed in sample A.
- Example 2 A high speed regular type photographic emulsion comprising 100 g. of silver bromide was subjected to gold sensitization at the time of second ripening, incorporated with the usual additives, and divided into two portions C and D. Emulsion C was coated as it was on a polyester support to prepare a sample C. On the other hand, emulsion D was incorporated with l g. of the compound of exemplification 5 and then coated on a polyester support to prepare a sample D. Each sample was sprinkled with dust collected from the air and then dried, out and subjected to development. As a result, a large number of spots were formed in sample C, whereas no formation of spots was observed in sample D. Further, no degradation in photographic and physical properties was observed in sample D.
- Example 3 A high speed panchromatic type photographic emulsion comprising 100 g. of silver iodobromide was subjected to gold sensitization at the time of second ripening, and then incorporated with the usual additives. Subsequently, the emulsion was coated on a cellulose triacetate support, and then set and divided into two portions to prepare samples E and F. Sample E was coated with an aqueous gelatine solution containing 2 g. of the compound of exemplification 14 to form a protective film thereon. On the other hand, sample F was coated with an aqueous gelatine solution. Each sample was sprinkled with dust collected from the air and then dried, out and subjected to development.
- portion G was incorporated with 3 g. of the compound of exemplification l5 and then coated on a polyester support, followed by drying, to prepare a sample G.
- portion H was coated as it was on a polyester support, followed by drying, to prepare a sample H.
- Each sample was coated with a low speed regular type silver iodobromide photographic emulsion and, after setting, the
- sample was sprinkled with iron powder, dried, cut and subjected to development. As a result, no formation of spots was observed in sample G, whereas a large number of spots were formed in sample H.
- Example 5 A silver chlorobromide photographic emulsion, after second ripening, was incorporated with the usual additives and divided into two portions of] and J.
- Emulsion l was incorporated with 0.1 g. of the compound of exemplification 8 and coated on a baryta paper to prepare a sample I.
- emulsion J was coated as it was on a baryta paper to prepare a sample .1.
- each sample was sprinkled with chromium powder, dried, cut and subjected to development. As a result, no formation of spots was observed in sample 1, whereas a large number of spots were formed in sample J.
- R and R are aliphatic, aromatic, alicyclic or heterocyclic groups, which may be optionally substituted;
- R is an alkyl or substituted alkyl group
- R R R and R are hydrogen atoms or methyl groups, but R and R and R and R cannot be methyl groups at the same time:
- Y is a divalent organic residue
- M and M are hydrogen atoms, alkali metals ammonium or organic amine salts
- P is a positive integer of l to 6;
- m 0 or 1.
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A light-sensitive silver halide photographic material containing as anti-spotting agent, at least one compound represented by the general formula
Description
United States Patent [191 Ushiyama et al.
[ Dec. 11, 1973 LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPIIIC MATERIAL [73] Assignee: Konishiroku Photo Industry Co.,
Ltd., Tokyo, Japan 221 Filed: Sept. 11, 1972 21 Appl. No.: 288,160
Related US. Application Data [63] Continuation-impart of Ser. No. 39,568, May 21,
1970, abandoned.
[30] Foreign Application Priority Data May 28, 1969 Japan 44/40991 [52] US. Cl. 96/74, 96/94 R, 96/1145, 260/513 [51] Int. Cl. G03c l/38, G03c 1/40, G03c l/04 [58] Field of Search 96/74, 94 R, 114.5; 260/513 [56] References Cited UNITED STATES PATENTS 3,003,877 10/1961 McLaughlin 96/1145 3,084,187 4/1963 Gaerther 260/513 3,165,409 l/l965 Knox 96/94 Primary Examiner-J. Travis Brown Assistant Examiner-Alfonso T. S'uro Pico AttorneyEric H. Waters et al.
[57] ABSTRACT A light-sensitive silver halide photographic material containing as anti-spotting agent, at least one compound represented by the general formula e 1 N/CH mCHC OOM 4 Claims, No Drawings I LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part application of Ser. No. 39,568 filed May 21, 1970 now abandoned.
The present invention relates to light-sensitive silver halide photographic materials containing a novel antispotting agent for preventing so-called spots (white or black stains) which are formed on the surfaces of lightsensitive silver halide photographic materials after development due to such causes as dusts, heavy metal powders or the like which are present in the air.
It has been known that certain kinds of dusts or fine particles of heavy metals which are present in the air become causes for formation of spots on the surfaces of light-sensitive photographic materials. It is considered that spots are formed when such dust-like materials have migrated into light-sensitive photographic materials during the production thereof. In order to inhibit the formation of spots, which injure the photographic properties of light-sensitive materials, it is an ordinary practice to remove dust like materials present in the atmosphere surrounding the steps for production of lightsensitive photographic materials. However, the removal of dust-like materials in the air is quite difficult and is substantially impossible, in practice, because they are generated during the steps for production of light-sensitive materials or brought into the steps to gether with starting materials for the production thereof. It has therefore been desired to prevent the influence on photographic properties of the dust-like materials which have undesirably been contained in lightsensitive photographic materials. In order to accomplish this, there have been adopted processes in which anti-spotting agents are incorporated into layers constituting light-sensitive photographic materials such as, for example, silver halide emulsion layers, inter layers, sub layers or protective layers. However, the conventional anti-spotting agents are not satisfactory yet, and have the disadvantage of undesirably reacting with other photographic additives present together therewith or with the developers.
A principal object of the present invention is to overcome the above-mentioned drawbacks of the conventional anti-spotting agents and to provide light-sensitive photographic materials having excellent photographic properties.
As the result of extensive studies, we have found that compounds represented by the general formulas l and II are excellent anti-spotting agents and that lightsensitive photographic materials incorporated with said compounds have such excellent characteristics that they are not affected at all by dust or fine powders of such heavy metals as iron, copper, tin, lead, chromium and nickel and oxides thereof which are present in the air, and they are not degraded in inherent photographic properties.
G eneral formula I:
General formula ll:
wherein:
R and R aliphatic, aromatic, alicyclic or heterocyclic groups, which may be optionally substituted;
R an alkyl or substituted alkyl group;
R R R and R]: hydrogen atoms or methyl groups, but R and R and R and R cannot be methyl groups at the same time;
Y: an divalent organic residue;
M and M hydrogen atoms, alkali metals, ammonium or organic amine salts;
p: a positive integer of l to 6; and
m: 0 or 1.
Typical examples of the compounds represented by the above-mentioned general formulas are set forth below, but it is needless to say that compounds usable in the present invention are not limited only to these.
IIC4I'IQOCII'JCIICI'I2N/ OH CH2COONa CH2=CHCHzOOHzCHCH2N OH CIIZCHQCOOK (3) CH2CH(CH3)COOH HOCHQCIIZOCI'IZCHCIIQN )I'I CHZCOOH CHQCOOK CHCOOK OCH2CHCHzN )H CH2C OOK 5 ongooom nC-tHoOCHzCHCHzN OH CHZCOOH (6) CHzGHzCO OH HOGIIECHCHQOCHZCHCHZN )13: OH CH2CH2SO H CHzCOOH CHzOCHzCHzOOI-IzOHCHzN )H CIIQCIICH20II (8) H H2 H2 H CHZCII2COONII-l CH3 OCHzCHCHzN H H OH CH2CH2PO(ONH )3 (9) l cmormooon O CH2OCH2(]3HCH2N\ OH CH2PO(OH)2 (10) .CII CH CH S 03K n-CrHq-Q-O CH2CHCH2N OH lCH2COOK 110 o c-c11zcH2 15 rcooccng KO 0 C CH2 II N N H CHzCOOK (16) CHzCOONIL CHzCOONH4 CHzCOOK CHzCHzC OOH .CHQQQQM Synthesis Example 1 The compound of exemplification 5 is synthesized in such a manner as described below.
54 g. of iminodiacetic acid, 200 ml. of water and 42.4 g. of anhydrous sodium carbonate are dissolved together to neutral pH, and the resulting solution is heated. Into this solution is added 52 g. of rectified nbutyl glycidyl ether. After completion of the dropping, the resulting mixture is reacted at 90C. for 4 hours. Subsequently, the mixture is cooled, adjusted to pH 3.2 to 3.4 by addition of 1:1 hydrochloric acid and then concentrated over a water bath. The concentrate is dissolved in 200 ml. of ethanol at an elevated temperature and then subjected to filtration. The filtrate is concen- CH2COOK CHZCOOK l isoCdl o CIIzClIClIzN-CH2CIICHZNCHZCIICHZO C4HylSO II II H (17) OH OH 0112011 011200011 trated, and the concentrate is dissolved in 220 ml. of 3 00 methanol at an elevated temperature and then filtered. 011,011 H CHQCHCOOH The filtrate obtained is again concentrated, and the CH concentrate is refluxed over a water bath together with 250 ml. of ethyl acetate, followed by cooling and filtra- 19 CHZCI'IZSCHI; tion. The resulting crystals are dried to obtain 71 g. of CHF O OH2CHCH2N J:HC00N8 pale yellow, hygroscopic crcystals, m.p. 163C.
lmtaranaior (BH omooom E e s. yis HHZONOhNa z C (70 H N 0 Calculated 44.91 7.14 4.76 (20 /CHzCOONa Found 4501 7.19 4.81 OGH2fi3HCH:N\ When the above procedure is repeated, except that n M 0H OHNOOH allyl glycidyl ether is used in place of the n-butyl glyci- (|)H CHQCOONa NaOOCCHz C| H c1120 CHZOHCI'IZN NCHzCHCHzOCH CHzCOONa NaOOCCHz NaO 0 0 CH2 OH NCHzCHCHzO CH OH CHzOOONa NaOOGCHz E H OCH: HCHZN NaO 0 0 OH: OH
c1120 0 ONa NCHaCHCHaOCH OH CHZC 0 0N2. M10 0 0 CH2 1 CH2OCH2CHCI'I2N\ g CHzCOONa The above-mentioned anti-spotting agents are synthesized, for example, according to the procedures set forth in the following synthesis examples:
dyl ether, there is obtained the compound of exemplification l3 in the form of pale yellowish brown, hygroscopic crystals, m.p. 45C.
Synthesis Example 2 filtration. The filtrate is Concentrated, and the concentrate is formed into a sodium salt by addition of a mixture comprising 300 ml. of water and 14 g. of anhydrous sodium carbonate, followed by concentration. The concentrate is precipitated from ethanol to obtain 2.3 g. of white crystals.
Elementary analysis for C l-l NNaO c H N Calculated 49.78 8.36 5.81 Found 49.54 8.50 5.69
Synthesis Example The compound of exemplification 16 is synthesized as described below.
9 g. of N-isobutyloxyglycerine-sodium glycinate is dissolved in 80 ml. of water and the resulting solution is added with 6 g. of anhydrous sodium carbonate. Further, 2.6 g. of glycerol-1,3-dichlorhydrin is added thereto and the total mixture is heated on a water bath for 6 hours. After cooling, 13 ml. of HCl aq. (1:1) is added to make the pH value of the reaction mixture to 3.0 The mixture is concentrated and the yellowish brown concentrate obtained is taken into 200 ml. of 80 percent methanol. After filtration and concentration, the residual mass is washed with 50 ml. of acetone and 100 ml. of ether. After decantation, washing with 100 ml. of acetone is effected and the remaining mass is concentrated under reduced pressure. A viscous pale yellow product it obtained. By dissolving in excess am moniac water and then concentrating, an yellow viscous product which is identified as the exemplified compound 16 on page 6 of the specification is obtained. This has thefollowing elementary analysis:
C H N Calcd. 48.64 9.67 18.18 Found 48.58
Other compounds employed in the present invention can also be synthesized according to the abovementioned synthesis procedures. The thus obtained compounds of the aforesaid general formulas may be used either singly or in admixture, and are incorporated into silver halide emulsion layers in an amount within the range of 1 X to l X 10" mols per mol of silver halide, or are incorporated into sub layers, inter layers or protective layers in an amount within the range of 5 X 10' to l X 10 mols per square meter, whereby the formation of spots due to dusts, heavy metals or oxides thereof in the air or due to other causes can be effectively prevented. If necessary, the compounds may be added in an amount out of the above-mentioned ranges.
Ordinarily, the extent of spot formation varies de' pending on the pH values of silver halide emulsions, and some of the known anti-spotting agents have a tendency to be varied in anti-spotting action clue to variation in PH of silver halide emulsions. However, the.
aforesaid compounds employed :in the present invention do not substantially vary in effectiveness at a pH range of ordinary silver halide emulsions, regardless of whether they are acidic or alkaline. and hence are markedly effective. Further, the compounds employed in the present invention are not injured. Moreover, the effects of the compounds are not dominated by the kind of supports and of materials of sub layers, and thus the compounds are effectively applied to all the lightsensitive silver halide photographic materials such as usual black-white and color films specific specif lightsensitive printing and X-ray materials.
The present invention is illustrated in further detail below with reference to examples, but it is needless to say that the present invention is not limited to these examples.
Example 1 An ordinary speed ortho-type photographic emulsion comprising g. of silver bromide was subjected to gold sensitization at the time of second ripening, incorporated with the usual additives, and divided into two portions A and B. Emulsion A was incorporated with 0.5 g. of the compound of exemplification l0 and then coated on a polyester support to prepare a sample A. On the other hand, emulsion B was coated as it was on a polyester support to prepare a sample B. After setting, each sample was sprinkled with a nickel powder, dried, cut and then subjected to development. As a result, a large number of spots were formed in sample B, whereas no formation of spots was observed in sample A.
Example 2 A high speed regular type photographic emulsion comprising 100 g. of silver bromide was subjected to gold sensitization at the time of second ripening, incorporated with the usual additives, and divided into two portions C and D. Emulsion C was coated as it was on a polyester support to prepare a sample C. On the other hand, emulsion D was incorporated with l g. of the compound of exemplification 5 and then coated on a polyester support to prepare a sample D. Each sample was sprinkled with dust collected from the air and then dried, out and subjected to development. As a result, a large number of spots were formed in sample C, whereas no formation of spots was observed in sample D. Further, no degradation in photographic and physical properties was observed in sample D.
Example 3 A high speed panchromatic type photographic emulsion comprising 100 g. of silver iodobromide was subjected to gold sensitization at the time of second ripening, and then incorporated with the usual additives. Subsequently, the emulsion was coated on a cellulose triacetate support, and then set and divided into two portions to prepare samples E and F. Sample E was coated with an aqueous gelatine solution containing 2 g. of the compound of exemplification 14 to form a protective film thereon. On the other hand, sample F was coated with an aqueous gelatine solution. Each sample was sprinkled with dust collected from the air and then dried, out and subjected to development. As a result, no formation of spots and no degradation in photographic and physical properties were seen in sample E, whereas a large number of spots were formed in sawmi l- A sub-coating liquid for a polyester support was divided into two portions G and H. Portion G was incorporated with 3 g. of the compound of exemplification l5 and then coated on a polyester support, followed by drying, to prepare a sample G. On the other hand, portion H was coated as it was on a polyester support, followed by drying, to prepare a sample H. Each sample was coated with a low speed regular type silver iodobromide photographic emulsion and, after setting, the
sample was sprinkled with iron powder, dried, cut and subjected to development. As a result, no formation of spots was observed in sample G, whereas a large number of spots were formed in sample H.
Example 5 A silver chlorobromide photographic emulsion, after second ripening, was incorporated with the usual additives and divided into two portions of] and J. Emulsion l was incorporated with 0.1 g. of the compound of exemplification 8 and coated on a baryta paper to prepare a sample I. On the other hand, emulsion J was coated as it was on a baryta paper to prepare a sample .1. After setting, each sample was sprinkled with chromium powder, dried, cut and subjected to development. As a result, no formation of spots was observed in sample 1, whereas a large number of spots were formed in sample J.
A comparison of the anti-spotting activity of compounds according to the invention with structurally similar compounds of the prior art are given in the two examples which follow.
Example 6 Compound A (F.P. 1,581,866)
l O H Compound B (according to the invention) CIhCOONa ClhzClIClhOClhCIIClI N on CHaCOONa A high speed light-sensitive silver halide photographic emulsion (1 Kg.) comprising 100 g. of silver iodobromide was subjected to gold sensitization at the time of second ripening, incorporated with usual additives, and divided into three equal portions of A, B and C. The emulsions A and B were incorporated with 0.5 g. of the above compounds A and B, respectively, and then coated on a polyester support to prepare samples A and B. On the other hand, the emulsion C was coated as it was on a polyester support to prepare a sample C. After setting, each sample was sprinkled with an iron powder, dried, cut and then subjected to development. As a result, a large number of spots were formed in samples A and C, whereas no spot formation was observed in sample B. The results are tabulated below.
Compound Amount No. of Sample used (g./%Kg. emulsion) spots/dm A Compound A 0.5 g. 80 B Compound 8 0.5 g. 2 C 98 Example 7 Compound D (U.S.P. 3,084,187)
OH: CI I3 O CI'I2CHCH2NOHzCHzSOQN;
Compound E (according to the invention) CIhCOONa C H OCHiCHCHiN OH CHaCOONa A high speed light-sensitive silver halide photographic emulsion comprising 100 g. of silver iodobromide was subjected to gold sensitization at the time of second ripening, incorporated with usual additives, and divided into three equal portions of D, E and F. The emulsions D and E were incorporated with 0.5 g. of the above compound D and E, respectively and then coated on a polyester support to prepare samples D and E. On the other hand, the emulsion F was coated as it was on a polyester support to prepare a sample F. After setting, each sample was sprinkled with an iron powder, dried, out and then subjected to development. As a result, a large number of spots were formed in samples D and F, whereas no spot formation was observed in sample E. The results are tabulated below.
Compound Amount No. of Sample used (g./%Kg. emulsion) spots/dm D Compound D 0.5 g. E Compound E 0.5 g. 3 F 97 We claim:
C H mCHCOOM R1O CH7CHCH1-N l a 1, 4 CH mCHCOOM R1-OCHiCHCH2 R1'O CHgCH CHr-N wherein:
R and R are aliphatic, aromatic, alicyclic or heterocyclic groups, which may be optionally substituted;
R is an alkyl or substituted alkyl group;
R R R and R are hydrogen atoms or methyl groups, but R and R and R and R cannot be methyl groups at the same time:
Y is a divalent organic residue;
M and M are hydrogen atoms, alkali metals ammonium or organic amine salts;
P is a positive integer of l to 6; and
m is 0 or 1.
2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said emulsion layer is a color former-containing color photographic emulsion layer.
3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said anti-spotting agent has been incorporated into a silver halide emulsion layer in the amount of l X 10 to l X 10 mole per mole of silver halide contained in said silver halide emulsion layer.
4. A light-sensitive silver halide photographic mate- 10 mole per square meter of the layer concerned.
Claims (3)
- 2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said emulsion layer is a color former-containing color photographic emulsion layer.
- 3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said anti-spotting agent has been incorporated into a silver halide emulsion layer in the amount of 1 X 10 4 to 1 X 10 1 mole per mole of silver halide contained in said silver halide emulsion layer.
- 4. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said anti-spotting agent has been incorporated into a sub layer; inter layer or protective layer in the amount of 5 X 10 6 to 1 X 10 2 mole per square meter of the layer concerned.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44040991A JPS4835372B1 (en) | 1969-05-28 | 1969-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3778268A true US3778268A (en) | 1973-12-11 |
Family
ID=12595877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00288160A Expired - Lifetime US3778268A (en) | 1969-05-28 | 1972-09-11 | Light-sensitive silver halide photographic material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3778268A (en) |
| JP (1) | JPS4835372B1 (en) |
| DE (1) | DE2025573A1 (en) |
| GB (1) | GB1298705A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120728A (en) * | 1973-07-23 | 1978-10-17 | Fuji Photo Film Co., Ltd. | Thermally developable light-sensitive material |
| US4214102A (en) * | 1978-04-14 | 1980-07-22 | Henkel Inc. | Amino-ether amphoteric surface-active compounds |
| AU635908B2 (en) * | 1988-10-31 | 1993-04-08 | Godecke Aktiengesellschaft | 2-aminocarboxylic acid derivatives, their manufacture and use as drugs |
| EP0943956A1 (en) * | 1998-03-18 | 1999-09-22 | Imation Corp. | Radiographic material having antispot protection and improved speed to Dmin ratio |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2756720B2 (en) * | 1990-03-30 | 1998-05-25 | コニカ株式会社 | Silver halide photographic material |
| US5739178A (en) * | 1995-05-15 | 1998-04-14 | Allergan | Polymer, article and method for inhibiting the growth of ocular pathogens in eye care products |
| MX368309B (en) * | 2014-12-11 | 2019-09-26 | Mexicano Inst Petrol | Hydroxypropyl betaine based zwitterionic geminal liquids, obtaining process and use as wettability modifiers with inhibitory/dispersants properties of asphaltenes. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3003877A (en) * | 1957-06-27 | 1961-10-10 | Eastman Kodak Co | Spot prevention in photographic emulsions and colloid layers |
| US3084187A (en) * | 1959-03-18 | 1963-04-02 | Monsanto Chemicals | Substituted aminoalkanesulfonic acids |
| US3165409A (en) * | 1962-02-07 | 1965-01-12 | Eastman Kodak Co | Derivatives of certain highly branched chain acids as coating aids |
-
1969
- 1969-05-28 JP JP44040991A patent/JPS4835372B1/ja active Pending
-
1970
- 1970-05-26 DE DE19702025573 patent/DE2025573A1/en not_active Withdrawn
- 1970-05-27 GB GB25489/70A patent/GB1298705A/en not_active Expired
-
1972
- 1972-09-11 US US00288160A patent/US3778268A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3003877A (en) * | 1957-06-27 | 1961-10-10 | Eastman Kodak Co | Spot prevention in photographic emulsions and colloid layers |
| US3084187A (en) * | 1959-03-18 | 1963-04-02 | Monsanto Chemicals | Substituted aminoalkanesulfonic acids |
| US3165409A (en) * | 1962-02-07 | 1965-01-12 | Eastman Kodak Co | Derivatives of certain highly branched chain acids as coating aids |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120728A (en) * | 1973-07-23 | 1978-10-17 | Fuji Photo Film Co., Ltd. | Thermally developable light-sensitive material |
| US4214102A (en) * | 1978-04-14 | 1980-07-22 | Henkel Inc. | Amino-ether amphoteric surface-active compounds |
| AU635908B2 (en) * | 1988-10-31 | 1993-04-08 | Godecke Aktiengesellschaft | 2-aminocarboxylic acid derivatives, their manufacture and use as drugs |
| US5401875A (en) * | 1988-10-31 | 1995-03-28 | Godecke Aktiengesellschaft | 2-aminocarboxylic acids and their derivatives, processes for their preparation and their use as medicaments |
| EP0943956A1 (en) * | 1998-03-18 | 1999-09-22 | Imation Corp. | Radiographic material having antispot protection and improved speed to Dmin ratio |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1298705A (en) | 1972-12-06 |
| JPS4835372B1 (en) | 1973-10-27 |
| DE2025573A1 (en) | 1971-02-25 |
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