|Publication number||US3778268 A|
|Publication date||Dec 11, 1973|
|Filing date||Sep 11, 1972|
|Priority date||May 28, 1969|
|Also published as||DE2025573A1|
|Publication number||US 3778268 A, US 3778268A, US-A-3778268, US3778268 A, US3778268A|
|Inventors||Haga T, Horigome K, Sugino O, Ushiyama R|
|Original Assignee||Konishiroku Photo Ind|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (4), Classifications (20)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent [191 Ushiyama et al.
[ Dec. 11, 1973 LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPIIIC MATERIAL  Assignee: Konishiroku Photo Industry Co.,
Ltd., Tokyo, Japan 221 Filed: Sept. 11, 1972 21 Appl. No.: 288,160
Related US. Application Data  Continuation-impart of Ser. No. 39,568, May 21,
 Foreign Application Priority Data May 28, 1969 Japan 44/40991  US. Cl. 96/74, 96/94 R, 96/1145, 260/513  Int. Cl. G03c l/38, G03c 1/40, G03c l/04  Field of Search 96/74, 94 R, 114.5; 260/513  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.
 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:
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.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3003877 *||Jun 27, 1957||Oct 10, 1961||Eastman Kodak Co||Spot prevention in photographic emulsions and colloid layers|
|US3084187 *||Mar 18, 1959||Apr 2, 1963||Monsanto Chemicals||Substituted aminoalkanesulfonic acids|
|US3165409 *||Feb 7, 1962||Jan 12, 1965||Eastman Kodak Co||Derivatives of certain highly branched chain acids as coating aids|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4120728 *||Apr 26, 1976||Oct 17, 1978||Fuji Photo Film Co., Ltd.||Thermally developable light-sensitive material|
|US4214102 *||Apr 14, 1978||Jul 22, 1980||Henkel Inc.||Amino-ether amphoteric surface-active compounds|
|US5401875 *||Oct 30, 1989||Mar 28, 1995||Godecke Aktiengesellschaft||2-aminocarboxylic acids and their derivatives, processes for their preparation and their use as medicaments|
|EP0943956A1 *||Mar 18, 1998||Sep 22, 1999||Imation Corp.||Radiographic material having antispot protection and improved speed to Dmin ratio|
|U.S. Classification||430/505, 562/11, 562/44, 562/105, 430/631|
|International Classification||G03C1/38, G03C7/26, G03C1/06, C07C227/00, C07F9/38, C07F9/40, C07C67/00, C07D251/34, C07D251/00, G03C1/33, C07F9/00|
|Cooperative Classification||G03C1/33, G03C1/06|
|European Classification||G03C1/33, G03C1/06|