Title:
PHOTOGRAPHIC MATERIAL COMPRISING BIS-ACYLHYDRAZINIUM COMPOUNDS
United States Patent 3811887
Abstract:
Antistatic agents for use in light-sensitive silver halide photographic material comprise bis-aminimide compounds having the formula: ##SPC1## Wherein R1, R3, R5 and R7 are individually a lower alkyl group; R2 and R6 are individually an alkyl, arakyl or aryl group or a hetero ring; and R4 is a divalent group.
Inventors:
Ishihara, Masao (Tokyo, JA)
Walda, Tsuneo (Tokyo, JA)
Yamaguchi, Hisashi (Tokyo, JA)
Sugita, Sadao (Hanno, JA)
Walda, Tsuneo (Tokyo, JA)
Yamaguchi, Hisashi (Tokyo, JA)
Sugita, Sadao (Hanno, JA)
Application Number:
05/208890
Publication Date:
05/21/1974
Filing Date:
12/16/1971
View Patent Images:
Export Citation:
Assignee:
Konishiroku Photo Industry Co., Ltd (Tokyo, JA)
Primary Class:
Other Classes:
430/527, 430/434, 430/429
International Classes:
C07D207/34; C07D211/62; C07D213/54; C07D307/68; G03C1/85; G03C5/305; C07D207/00; C07D211/00; C07D213/00; C07D307/00; G03C1/82
Field of Search:
96/87A,114.2,50,61,66,67
Primary Examiner:
Smith, Ronald H.
Attorney, Agent or Firm:
Waters, Roditi, Schwartz & Nissen
Claims:
1. A method for the prevention of static in a light-sensitive silver halide photographic material comprising a support and at least one photographic layer coated on said support, said method comprising treating said photographic material with a bis-aminimide compound of the formula: ##SPC8##
2. A method as claimed in claim 1, wherein the bis-aminimide compound is incorporated into at least one of the photographic layers constituting
3. A method as claimed in claim 1, wherein the light-sensitive silver halide photographic material is treated with a photographic treating bath containing the bis-aminimide compound and being one member selected from the group consisting of a developing bath, a stopping bath and a fixing
4. A method as claimed in claim 1, wherein the light-sensitive silver halide photographic material is sprayed with a solution of the
5. A light-sensitive silver halide photographic material which comprises a support and coated thereon photographic layers at least one of which contains a bis-aminimide compound of the general formula ##SPC9##
2. A method as claimed in claim 1, wherein the bis-aminimide compound is incorporated into at least one of the photographic layers constituting
3. A method as claimed in claim 1, wherein the light-sensitive silver halide photographic material is treated with a photographic treating bath containing the bis-aminimide compound and being one member selected from the group consisting of a developing bath, a stopping bath and a fixing
4. A method as claimed in claim 1, wherein the light-sensitive silver halide photographic material is sprayed with a solution of the
5. A light-sensitive silver halide photographic material which comprises a support and coated thereon photographic layers at least one of which contains a bis-aminimide compound of the general formula ##SPC9##
Description:
This invention relates to new bis-aminimide compounds. More particularly, this invention relates to a light-sensitive silver halide photographic material which comprises a bis-aminimide compound of the general formula shown later.
A principal object of the present invention is to provide a light-sensitive silver halide photographic material less subject to problems caused by static.
Another object of the invention is to provide a light-sensitive radiographic material having improved color tone and a light-sensitive color photographic material having excellent resolution and graininess.
When developed, a light-sensitive silver halide photographic material frequency forms branch-like or fluffy linear spots on the surface. These linear spots are so-called static marks, and it is considered that the formation of such marks is ascribable to the fact that the surface of the light-sensitive material is statically charged due to friction and this static charge is discharged to excite the light-sensitive material. Problems derived from such static charge are not limited merely to the formation of static marks but bring about the adhesion of dust onto the surface of the light-sensitive material. Such static troubles are necessarily brought about at substantially all stages where light-sensitive materials undergo friction, e.g., at stages where photographic emulsions are coated on supports, and the resulting sheet films are cut and packed in boxes, or the sheet films are taken out of the boxes and subjected to photographing, and particularly cinefilms which subjected to photographing or handled before development. The static troubles are brought about also at the time when light-sensitive materials are released. That is, a light-sensitive material, which has been coated with a photographic emulsion and dried, is rolled up, in general, and when this rolled film is successively released in order to subject the film to the subsequent step or to printing, a static charge is generated between the surface and the back of the film at the moment when the film is released from the roll. Further, when a light-sensitive photographic printing paper is subjected to ferrotype drying, a static charge is generated between the surface of the paper and the metal surface at the time when the film is taken up, to cause the phenomenon that the paper cannot be superposed immediately on another one.
For the prevention of such static problems, a moisture-absorptive material is frequently incorporated into a layer of the light-sensitive material. This procedure, however, is effective only when the humidity is relatively high and is ineffective dry periods when static problems are brought about frequently. Further, when the humidity is excessively high, the light-sensitive material incorporated with the moisture-absorptive material becomes sticky on the film surface. In addition to such moisture-absorptive material, a considerable number of compounds have been known as antistatic agents. For application to light-sensitive photographic materials, however, they are required to satisfy such conditions as not to have any detrimental effect on the photographic properties of the light-sensitive material such as sensitivity, gradation, fog, storability, etc. Accordingly, it is extremely difficult to find excellent antistatic agents applicable to light-sensitive silver halide photographic materials.
We made extensive studies on antistatic agents having no detrimental effect on light-sensitive silver halide photographic materials to find that compounds of the general Formula I, II or III shown below are excellent antistatic agents. ##SPC2##
wherein R 1 , R 3 , R 5 and R 7 are individually a lower alkyl group; R 2 and R 6 are individually an alkyl, aralkyl or aryl group or a hetero ring; and R 4 is a divalent group.
When any of the above-mentioned compounds is incorporated into at least one of the silver halide emulsion layer, sub layer, inter layer, filter layer, antihalation layer, protective layer and backing layer, which are constitutive elements of a light-sensitive silver halide photographic material, it is possible to obtain a light-sensitive silver halide photographic material which is extremely less subject to static problems. The incorporation of said compound not only does not have any detrimental effect on the sensitivity, gradation, fog and the like properties of the light-sensitive material but also displays, depending on the kind of light sensitive material, such favorable effects as to inhibit the fog and enhance the storability of the light-sensitive material. Further, when the compound is applied to a light-sensitive radiographic material, there is attained the effect, in addition to the prevention of antistatic troubles, that the color tone of the developed silver image can be made bluish black, and when the compound is applied to an internal color photographic emulsion, the dispersibility of the coupler is enhanced to make it possible to obtain a light-sensitive color photographic material having excellent in resolution and graininess.
Typical examples of certain bis-aminimide compounds having the aforesaid general formulas are as follows: ##SPC3##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 1 48.45 8.35 11.90 7.53 48.72 8.25 11.50 7.33 2 73.78 12.70 8.61 74.00 12.56 8.62 3 71.67 11.05 8.30 71.47 11.20 8.40 4 70.64 12.15 8.04 70.76 12.26 8.15 5 78.45 11.82 8.01 78.10 12.15 8.26 6 58.54 6.25 12.41 15.41 58.48 6.16 12.32 15.21 7 72.22 7.02 13.01 72.10 7.06 13.09 8 32.84 4.82 9.58 32.76 4.69 9.72 9 63.37 7.98 10.56 63.31 8.01 10.42 10 59.07 6.87 15.90 59.21 6.99 15.50 11 55.62 7.31 11.28 55.61 7.21 11.50 12 61.20 8.22 14.28 61.72 8.19 14.50 13 60.99 8.53 14.23 60.71 8.92 14.01 14 70.07 9.34 9.61 70.51 9.40 9.29 15 62.00 7.92 15.72 61.98 8.02 15.70 16 64.10 9.72 9.65 64.30 9.60 9.55 ____________________________________________________________ ______________ ##SPC4##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 17 66.42 10.22 8.61 66.60 10.01 8.21 18 70.91 9.57 7.19 70.56 9.40 7.31 19 66.42 10.22 8.61 66.21 10.50 8.71 20 61.11 10.90 17.82 61.21 10.99 17.51 21 60.12 6.73 11.69 60.90 6.60 11.50 22 67.65 9.81 14.35 67.21 9.75 14.50 23 60.40 9.42 10.06 60.56 9.31 10.26 24 67.07 10.86 9.31 67.21 10.75 9.21 25 66.39 8.54 10.32 66.21 8.45 10.50 26 65.79 8.92 11.80 65.31 9.05 11.60 27 41.40 7.92 15.19 9.61 41.01 8.15 15.01 9.82 28 68.29 10.39 9.96 68.50 10.29 10.01 ____________________________________________________________ ______________ ##SPC5##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 29 70.28 10.69 10.25 70.50 10.80 10.15 30 73.55 10.47 7.46 73.40 10.48 7.66 31 66.31 7.59 14.06 66.10 7.75 14.21 32 63.50 9.87 10.97 63.60 10.05 11.21 33 61.69 8.63 15.99 61.31 9.05 16.01 ____________________________________________________________ ______________
The bis-aminimide compounds of the aforesaid general formulas can be synthesized according to the methods disclosed in W. H. Berry & P. Brocklehurst: "J. Chem. Soc." 2264 (1964); R. L. Hinman & M. C. Flores: "J. Org. Chem," 24 660 (1959); and R. C. Slagel: "J. Org. Chem.," 33 1374 (1968).
Typical procedures for synthesizing the above-mentioned compounds are set forth below with reference to synthesis examples.
SYNTHESIS EXAMPLE 1
Synthesis of the exemplified Compound 2: ##SPC6##
7.75 Grams of 1,4-iodobutane and 17.9 g. of N,N-dimethyl-N'-hexadecanoyl-hydrazine were dissolved in 20 ml. of dioxane, and the resulting solution was reacted at 73°C. for 48 hours. After completion of the reaction, the liquid reaction mixture was concentrated, and the concentrate was dissolved in 20 ml. of methanol. To the resulting solution was added 300 ml. of ether to deposit white crystals, which were then recovered by filtration and repeatedly recrystallized from a methanol-ether mixture to obtain crystals of bishydrazinium iodide (1), m.p. 109°-110°C., yield 90.2%.
Elementary analysis:
Found (%) C: 52.86 H: 9.25 N: 6.36 I: 28.05 Calculated (%) C: 52.97 H: 9.34 N: 6.18 I: 27.98 (for C 40 H 84 N 4 O 2 I 2 )
10 Grams of the thus obtained bishydrazinium iodide was added to a solution of 0.5 g. of sodium hydroxide in a mixed solvent comprising 50 ml. of water and 20 ml. of methanol. After being allowed to stand for about 30 minutes, the resulting mixture was concentrated, freed from the methanol and then extracted 3 times with 80 ml. of chloroform. The chloroform layer was washed 3 times with 30 ml. of a saturated aqueous sodium chloride solution, dehydrated with anhydrous sodium sulfate and then concentrated to form crystals. Subsequently, the crystals were recrystallized from petroleum benzine to obtain the bis-aminimide Compound 2, yield 97.8%, m.p. 43°-44°C.
Elementary analysis:
Found (%) C: 74.00 H: 12.56 N: 8.62 Calculated (%) C: 73.78 H: 12.70 N: 8.61 (for C 40 H 82 N 4 O 2 )
SYNTHESIS EXAMPLE 2
Synthesis of the exemplified compound (18): ##SPC7##
31.5 Grams of p-octylphenyl glycidyl ether, 7.20 g. of N,N-dimethylhydrazine and 8.81 g. of dimethyl adipate were dissolved in 40 ml. of isopropyl alcohol, and the resulting solution was reacted at room temperature for 6 days. After completion of the reaction, the liquid reaction mixture was concentrated, and the concentrate was dissolved in 1 liter of water. The resulting solution was washed four times with 100 ml. of ether, and the water layer was concentrated to obtain the bis-aminimide Compound 18 in the form of an oil, yield 89.5%.
Elementary analysis:
Found (%) C: 70.56 H: 9.40 N: 7.31 Calculated (%) C: 70.91 H: 9.57 N: 7.19 (for C 46 H 74 N 4 O 6 )
For incorporation of any of the compounds having the aforesaid general formulas into the silver halide emulsion layer, sub layer, inter layer, filter layer, antihalation layer, protective layer or backing layer of a light-sensitive silver halide photographic material, the compound in the form of a solution in a suitable solvent such as water or an alcohol may be incorporated into said layer or applied by spraying onto the surface of the light-sensitive material, or the light-sensitive material may be immersed in said solution. Further, the compound of the present invention may be incorporated into a developing solution, stopping solution, fixing solution, water mark-preventing solution or the like treating bath. In incorporating the compound into any of the layers constituting a light-sensitive material, the amount of the compound is about 0.1 mg. to 1 g. per m 2 of the light-sensitive material, though the amount varies depending on the nature of the compound and of the layer in which the compound is to be incorporated.
The compounds of the present invention are usable as well for static charge prevention of cellulose ester, polyester, polystyrene, polycarbonate, polyethylene, polypropylene and the like synthetic resin films, moldings and fibers.
The following examples illustrate the invention.
EXAMPLE 1
Each of the exemplified compounds 2, 5, 10, 17, 19, 23 and 30 was dissolved in ethyl alcohol to form a 1 percent solution. This solution was spray-coated on the surface of a high speed roentgen film and then dried to prepare a sample. On the other hand, the said high speed roengten film was dipped in the above-mentioned solution for 1 minute and then dried to prepare another sample. For comparison, two control samples were prepared in the same manner as above, except that the above-mentioned treatment was not effected or was effected by use of only an ethanol solution. The thus prepared samples including an untreated roentgen film were allowed to stand for 24 hours under conditions of RH 30% and 25°C., rubbed on the surfaces with nylon and polyester cloths, and then developed, without exposure, according to an ordinary procedure by use of a radiographic developing solution. Subsequently, the developed samples were individually subjected to scanning by use of Sakura Densitometer (a product of Konishiroku Photo Industry Co., Ltd.) to measure the average values of blackened density. The samples were further measured in amount of developed silver according to X-ray analysis and, at the same time, in specific surface resistivity. The results obtained were as set forth in Table 1.
Table 1 ____________________________________________________________ ______________ Spray coating Dip coating Sample Antistatic Average Amount of Specific Average Amount of Specific No. agent density developed surface density developed surface measured silver resis- measured silver resis- by densi- (mg/100cm 2 ) tivity by densi- (mg/100 cm 2 ) tivity tometer (Ω) tometer (Ω) ____________________________________________________________ ______________ 1 Non-treatment 1.82 65.2 10 14 1.72 59.1 10 14 Ethanol solution 2 containing no 1.73 59.9 10 14 1.65 48.9 10 14 antistatic agent 3 Exemplified 0.08 2.6 10 12 0.04 1.3 10 12 compound 2 4 Exemplified 0.07 2.1 10 12 0.05 1.8 10 12 compound 5 5 Exemplified 0.05 1.6 10 11 0.03 1.2 10 11 compound 10 6 Exemplified 0.04 1.2 10 11 0.03 1.1 10 11 compound 17 7 Exemplified 0.07 2.4 10 12 0.05 2.0 10 12 compound 19 8 Exemplified 0.05 1.8 10 12 0.03 1.4 10 12 compound 23 9 Exemplified 0.04 1.4 10 11 0.03 1.0 10 11 compound 30 ____________________________________________________________ ______________
As is clear from Table 1, the sample treated with the solution containing no exemplified compound and the untreated sample were high in average density value and large in amount of developed silver, and showed a considerable increase in fog density due to formation of static marks, whereas no formation of static marks was observed in the samples according to the present invention (Samples 3 to 9).
On the other hand, these samples were exposed to light, developed at 20°C. for 4 minutes and 30 seconds with a strongly alkaline roentgen film developer containing 1-phenyl-3-pyrazolidone hydroquinone (PQ), and then measured in speed and fog. Further, the samples were subjected to sensitometry after incubation for 3 days in a thermostat chamber kept at 55°C. and under conditions of 50°C. and RH 80%. The results obtained were as set forth in Table 2.
Table 2 ____________________________________________________________ ______________ Spray coating Dip coating After incubation After incubation Sample Relative Relative Fog Relative Relative Fog at 55°C. for at 50°C. and RH No. speed gamma speed gamma 3 days 80% for 3 days Relative Fog Relative Fog speed speed ____________________________________________________________ ______________ 1 100 1.0 0.13 100 1.0 0.15 100 0.24 100 0.19 2 101 1.1 0.13 109 1.1 0.14 102 0.30 88 0.18 3 103 1.0 0.13 111 1.0 0.13 108 0.23 100 0.18 4 108 1.1 0.12 105 1.0 0.14 103 0.26 101 0.19 5 100 1.1 0.12 105 1.1 0.14 102 0.23 99 0.16 6 100 1.0 0.13 102 0.99 0.13 100 0.22 98 0.16 7 103 1.0 0.13 101 1.0 0.14 100 0.25 103 0.15 8 100 1.0 0.11 100 0.98 0.12 99 0.26 99 0.17 9 100 1.0 0.12 103 1.0 0.14 100 0.23 100 0.16 ____________________________________________________________ ______________
From Table 2, it is understood that even when incubated not only at normal temperature but also at high temperature and humidity, the samples according to the present invention (Samples 3 to 9) were not deteriorated at all in speed, gradation and fog. In addition, the color tone of the developed silver changed to bluish black to give favorable results.
EXAMPLE 2
Each of the exemplified compounds 3, 6, 9, 15, 20, 25, 29 and 33 was dissolved in a 4 percent solution of sodium decyl-isoamyl succinate-2-sulfonate so that the concentration of the compound became 2 percent, and 20 cc. of the resulting solution was added to 1 liter of a 2 percent gelatin solution to be used as a protective layer. Subsequently, the solution was coated as a protective layer on a high sensitivity roentgen film. Samples prepared in the above manner and a sample having a protective layer containing no exemplified compound were subjected to the same tests as in Example 1 to obtain the results as set forth in Table 3.
Table 3 ____________________________________________________________ ______________ Antistatic property Photographic properties After incubation After incubation Average Amount of Immediately after at 55°C. at 50°C. and RH Sample Antistatic density developed preparation 3 days 80% for 3 days No. agent measured silver by densi- (mg/100 cm 2 ) Relative Relative Fog Relative Fog Relative Fog tometer speed gamma speed speed ____________________________________________________________ ______________ Protective layer con- 10 taining no 1.58 39.2 100 1.00 0.12 100 0.23 100 0.15 antistatic agent 11 Exemplified 0.13 4.0 104 1.05 0.11 101 0.24 100 0.17 compound 3 12 Exemplified 0.11 3.3 101 1.02 0.10 100 0.20 100 0.16 compound 6 13 Exemplified 0.12 3.9 102 1.00 0.10 105 0.23 103 0.16 compound 9 14 Exemplified 0.14 4.2 100 1.00 0.11 102 0.22 100 0.15 compound 15 15 Exemplified 0.11 3.2 99 1.01 0.09 108 0.18 110 0.12 compound 20 16 Exemplified 0.11 3.3 98 1.02 0.10 107 0.17 115 0.12 compound 25 17 Exemplified 0.13 4.1 101 1.00 0.12 100 0.21 100 0.16 compound 29 18 Exemplified 0.12 4.0 105 1.00 0.11 101 0.20 105 0.15 compound 33 ____________________________________________________________ ______________
As is clear from Table 3, it is understood that the samples according to the present invention (Samples 11 to 18) could be prevented from the formation of static marks without being deteriorated in photographic properties.
EXAMPLE 3
To 1 liter of a green-sensitive high sensitivity color photographic silver iodobromide emulsion was added 10 cc. of a 5 percent methanol solution of each of the exemplified compounds 2, 4, 8, 15, 18 and 31. To the emulsion was further added a solution of 20 g, of an internal color photographic magenta coupler 1-(4'-phenoxy-3'-sulfophenyl)-3-heptadecyl- 5-pyrazolone in a 1N-caustic soda solution which had been adjusted to pH 6.8 by addition of citric acid. Subsequently, the emulsion was coated on a cellulose triacetate film base and then dried. Samples prepared in the above manner and a sample, which had not been incorporated with any exemplified compound, were subjected to the same tests as in Example 1. The results obtained were as set forth in Table 4. Provided that in this example, the average density value was measured by using a green filter as a light source of the densitometer, and the development was effected according to an ordinary procedure using diethyl p-phenylenediamine as the developing agent.
Table 4 ____________________________________________________________ ______________ Antistatic property Photographic properties Average Specific Immediately after After incubation Sample Antistatic density surface preparation at 50°C. for No. agent measured resis- 3 days by densi- tivity Relative Relative Fog Relative Fog tometer (Ω) speed gamma speed ____________________________________________________________ ______________ 19 None 0.67 10 12 100 1.00 0.12 100 0.22 20 Exemplified 0.20 10 11 101 1.01 0.13 100 0.22 compound 2 21 Exemplified 0.23 10 10 100 1.00 0.15 100 0.20 compound 4 22 Exemplified 0.21 10 10 103 1.00 0.13 105 0.21 compound 8 23 Exemplified 0.22 10 11 100 1.01 0.15 100 0.23 compound 15 24 Exemplified 0.20 10 11 99 1.08 0.12 100 0.20 compound 18 25 Exemplified 0.21 10 11 100 1.00 0.12 99 0.21 compound 31 ____________________________________________________________ ______________
From Table 4, it is understood that by addition of the exemplified compounds to the emulsion, the samples according to the present invention were inhibited from formation of static marks and improved in dispersibility of formed dyes without any detrimental effect on photographic properties.
EXAMPLE 4
To a 5 percent aqueous gelatin solution containing an antihalation dye was added 2 cc. of a 2 percent aqueous solution of each of the exemplified compounds 2, 3, 10 and 18. The resulting solution was charged with 3 cc. of a 5 percent saponin solution and then coated on a cellulose triacetate film base, followed by drying. On the opposite side of the film base was coated a high speed photographic emulsion for negative and a protective layer was formed on the resulting emulsion layer by application of a gelatin solution incorporated with 300 mg. per liter of said solution of the above-mentioned exemplified compound. Samples prepared in the above manner were subjected to the same tests as in Example 1 to obtain the results set forth in Table 5.
Table 5 ____________________________________________________________ ______________ Antistatic property Photographic properties Sample Antistatic Average Amount of Immediately after After incubation No. agent density developed preparation at 50°C. for measured silver 3 days by densi- (mg/100 cm 2 ) Relative Relative Fog Relative Fog tometer speed gamma speed ____________________________________________________________ ______________ 26 None 1.10 33.6 100 1.00 0.12 100 0.30 27 Exemplified 0.12 3.8 100 1.00 0.11 102 0.28 compound 2 28 Exemplified 0.10 3.2 100 1.02 0.12 105 0.30 compound 3 29 Exemplified 0.08 2.8 98 1.00 0.14 100 0.28 compound 10 30 Exemplified 0.12 3.3 97 1.01 0.11 101 0.28 compound 18 ____________________________________________________________ ______________
As is clear from Table 5, the samples according to the present invention (Samples 27 to 30) were inhibited from formation of static marks and were not deteriorated in photographic properties.
A principal object of the present invention is to provide a light-sensitive silver halide photographic material less subject to problems caused by static.
Another object of the invention is to provide a light-sensitive radiographic material having improved color tone and a light-sensitive color photographic material having excellent resolution and graininess.
When developed, a light-sensitive silver halide photographic material frequency forms branch-like or fluffy linear spots on the surface. These linear spots are so-called static marks, and it is considered that the formation of such marks is ascribable to the fact that the surface of the light-sensitive material is statically charged due to friction and this static charge is discharged to excite the light-sensitive material. Problems derived from such static charge are not limited merely to the formation of static marks but bring about the adhesion of dust onto the surface of the light-sensitive material. Such static troubles are necessarily brought about at substantially all stages where light-sensitive materials undergo friction, e.g., at stages where photographic emulsions are coated on supports, and the resulting sheet films are cut and packed in boxes, or the sheet films are taken out of the boxes and subjected to photographing, and particularly cinefilms which subjected to photographing or handled before development. The static troubles are brought about also at the time when light-sensitive materials are released. That is, a light-sensitive material, which has been coated with a photographic emulsion and dried, is rolled up, in general, and when this rolled film is successively released in order to subject the film to the subsequent step or to printing, a static charge is generated between the surface and the back of the film at the moment when the film is released from the roll. Further, when a light-sensitive photographic printing paper is subjected to ferrotype drying, a static charge is generated between the surface of the paper and the metal surface at the time when the film is taken up, to cause the phenomenon that the paper cannot be superposed immediately on another one.
For the prevention of such static problems, a moisture-absorptive material is frequently incorporated into a layer of the light-sensitive material. This procedure, however, is effective only when the humidity is relatively high and is ineffective dry periods when static problems are brought about frequently. Further, when the humidity is excessively high, the light-sensitive material incorporated with the moisture-absorptive material becomes sticky on the film surface. In addition to such moisture-absorptive material, a considerable number of compounds have been known as antistatic agents. For application to light-sensitive photographic materials, however, they are required to satisfy such conditions as not to have any detrimental effect on the photographic properties of the light-sensitive material such as sensitivity, gradation, fog, storability, etc. Accordingly, it is extremely difficult to find excellent antistatic agents applicable to light-sensitive silver halide photographic materials.
We made extensive studies on antistatic agents having no detrimental effect on light-sensitive silver halide photographic materials to find that compounds of the general Formula I, II or III shown below are excellent antistatic agents. ##SPC2##
wherein R 1 , R 3 , R 5 and R 7 are individually a lower alkyl group; R 2 and R 6 are individually an alkyl, aralkyl or aryl group or a hetero ring; and R 4 is a divalent group.
When any of the above-mentioned compounds is incorporated into at least one of the silver halide emulsion layer, sub layer, inter layer, filter layer, antihalation layer, protective layer and backing layer, which are constitutive elements of a light-sensitive silver halide photographic material, it is possible to obtain a light-sensitive silver halide photographic material which is extremely less subject to static problems. The incorporation of said compound not only does not have any detrimental effect on the sensitivity, gradation, fog and the like properties of the light-sensitive material but also displays, depending on the kind of light sensitive material, such favorable effects as to inhibit the fog and enhance the storability of the light-sensitive material. Further, when the compound is applied to a light-sensitive radiographic material, there is attained the effect, in addition to the prevention of antistatic troubles, that the color tone of the developed silver image can be made bluish black, and when the compound is applied to an internal color photographic emulsion, the dispersibility of the coupler is enhanced to make it possible to obtain a light-sensitive color photographic material having excellent in resolution and graininess.
Typical examples of certain bis-aminimide compounds having the aforesaid general formulas are as follows: ##SPC3##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 1 48.45 8.35 11.90 7.53 48.72 8.25 11.50 7.33 2 73.78 12.70 8.61 74.00 12.56 8.62 3 71.67 11.05 8.30 71.47 11.20 8.40 4 70.64 12.15 8.04 70.76 12.26 8.15 5 78.45 11.82 8.01 78.10 12.15 8.26 6 58.54 6.25 12.41 15.41 58.48 6.16 12.32 15.21 7 72.22 7.02 13.01 72.10 7.06 13.09 8 32.84 4.82 9.58 32.76 4.69 9.72 9 63.37 7.98 10.56 63.31 8.01 10.42 10 59.07 6.87 15.90 59.21 6.99 15.50 11 55.62 7.31 11.28 55.61 7.21 11.50 12 61.20 8.22 14.28 61.72 8.19 14.50 13 60.99 8.53 14.23 60.71 8.92 14.01 14 70.07 9.34 9.61 70.51 9.40 9.29 15 62.00 7.92 15.72 61.98 8.02 15.70 16 64.10 9.72 9.65 64.30 9.60 9.55 ____________________________________________________________ ______________ ##SPC4##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 17 66.42 10.22 8.61 66.60 10.01 8.21 18 70.91 9.57 7.19 70.56 9.40 7.31 19 66.42 10.22 8.61 66.21 10.50 8.71 20 61.11 10.90 17.82 61.21 10.99 17.51 21 60.12 6.73 11.69 60.90 6.60 11.50 22 67.65 9.81 14.35 67.21 9.75 14.50 23 60.40 9.42 10.06 60.56 9.31 10.26 24 67.07 10.86 9.31 67.21 10.75 9.21 25 66.39 8.54 10.32 66.21 8.45 10.50 26 65.79 8.92 11.80 65.31 9.05 11.60 27 41.40 7.92 15.19 9.61 41.01 8.15 15.01 9.82 28 68.29 10.39 9.96 68.50 10.29 10.01 ____________________________________________________________ ______________ ##SPC5##
________________________________________________________ __________________ Elementary analysis Calculated Found Compound C H N X C H N X ____________________________________________________________ ______________ 29 70.28 10.69 10.25 70.50 10.80 10.15 30 73.55 10.47 7.46 73.40 10.48 7.66 31 66.31 7.59 14.06 66.10 7.75 14.21 32 63.50 9.87 10.97 63.60 10.05 11.21 33 61.69 8.63 15.99 61.31 9.05 16.01 ____________________________________________________________ ______________
The bis-aminimide compounds of the aforesaid general formulas can be synthesized according to the methods disclosed in W. H. Berry & P. Brocklehurst: "J. Chem. Soc." 2264 (1964); R. L. Hinman & M. C. Flores: "J. Org. Chem," 24 660 (1959); and R. C. Slagel: "J. Org. Chem.," 33 1374 (1968).
Typical procedures for synthesizing the above-mentioned compounds are set forth below with reference to synthesis examples.
SYNTHESIS EXAMPLE 1
Synthesis of the exemplified Compound 2: ##SPC6##
7.75 Grams of 1,4-iodobutane and 17.9 g. of N,N-dimethyl-N'-hexadecanoyl-hydrazine were dissolved in 20 ml. of dioxane, and the resulting solution was reacted at 73°C. for 48 hours. After completion of the reaction, the liquid reaction mixture was concentrated, and the concentrate was dissolved in 20 ml. of methanol. To the resulting solution was added 300 ml. of ether to deposit white crystals, which were then recovered by filtration and repeatedly recrystallized from a methanol-ether mixture to obtain crystals of bishydrazinium iodide (1), m.p. 109°-110°C., yield 90.2%.
Elementary analysis:
Found (%) C: 52.86 H: 9.25 N: 6.36 I: 28.05 Calculated (%) C: 52.97 H: 9.34 N: 6.18 I: 27.98 (for C 40 H 84 N 4 O 2 I 2 )
10 Grams of the thus obtained bishydrazinium iodide was added to a solution of 0.5 g. of sodium hydroxide in a mixed solvent comprising 50 ml. of water and 20 ml. of methanol. After being allowed to stand for about 30 minutes, the resulting mixture was concentrated, freed from the methanol and then extracted 3 times with 80 ml. of chloroform. The chloroform layer was washed 3 times with 30 ml. of a saturated aqueous sodium chloride solution, dehydrated with anhydrous sodium sulfate and then concentrated to form crystals. Subsequently, the crystals were recrystallized from petroleum benzine to obtain the bis-aminimide Compound 2, yield 97.8%, m.p. 43°-44°C.
Elementary analysis:
Found (%) C: 74.00 H: 12.56 N: 8.62 Calculated (%) C: 73.78 H: 12.70 N: 8.61 (for C 40 H 82 N 4 O 2 )
SYNTHESIS EXAMPLE 2
Synthesis of the exemplified compound (18): ##SPC7##
31.5 Grams of p-octylphenyl glycidyl ether, 7.20 g. of N,N-dimethylhydrazine and 8.81 g. of dimethyl adipate were dissolved in 40 ml. of isopropyl alcohol, and the resulting solution was reacted at room temperature for 6 days. After completion of the reaction, the liquid reaction mixture was concentrated, and the concentrate was dissolved in 1 liter of water. The resulting solution was washed four times with 100 ml. of ether, and the water layer was concentrated to obtain the bis-aminimide Compound 18 in the form of an oil, yield 89.5%.
Elementary analysis:
Found (%) C: 70.56 H: 9.40 N: 7.31 Calculated (%) C: 70.91 H: 9.57 N: 7.19 (for C 46 H 74 N 4 O 6 )
For incorporation of any of the compounds having the aforesaid general formulas into the silver halide emulsion layer, sub layer, inter layer, filter layer, antihalation layer, protective layer or backing layer of a light-sensitive silver halide photographic material, the compound in the form of a solution in a suitable solvent such as water or an alcohol may be incorporated into said layer or applied by spraying onto the surface of the light-sensitive material, or the light-sensitive material may be immersed in said solution. Further, the compound of the present invention may be incorporated into a developing solution, stopping solution, fixing solution, water mark-preventing solution or the like treating bath. In incorporating the compound into any of the layers constituting a light-sensitive material, the amount of the compound is about 0.1 mg. to 1 g. per m 2 of the light-sensitive material, though the amount varies depending on the nature of the compound and of the layer in which the compound is to be incorporated.
The compounds of the present invention are usable as well for static charge prevention of cellulose ester, polyester, polystyrene, polycarbonate, polyethylene, polypropylene and the like synthetic resin films, moldings and fibers.
The following examples illustrate the invention.
EXAMPLE 1
Each of the exemplified compounds 2, 5, 10, 17, 19, 23 and 30 was dissolved in ethyl alcohol to form a 1 percent solution. This solution was spray-coated on the surface of a high speed roentgen film and then dried to prepare a sample. On the other hand, the said high speed roengten film was dipped in the above-mentioned solution for 1 minute and then dried to prepare another sample. For comparison, two control samples were prepared in the same manner as above, except that the above-mentioned treatment was not effected or was effected by use of only an ethanol solution. The thus prepared samples including an untreated roentgen film were allowed to stand for 24 hours under conditions of RH 30% and 25°C., rubbed on the surfaces with nylon and polyester cloths, and then developed, without exposure, according to an ordinary procedure by use of a radiographic developing solution. Subsequently, the developed samples were individually subjected to scanning by use of Sakura Densitometer (a product of Konishiroku Photo Industry Co., Ltd.) to measure the average values of blackened density. The samples were further measured in amount of developed silver according to X-ray analysis and, at the same time, in specific surface resistivity. The results obtained were as set forth in Table 1.
Table 1 ____________________________________________________________ ______________ Spray coating Dip coating Sample Antistatic Average Amount of Specific Average Amount of Specific No. agent density developed surface density developed surface measured silver resis- measured silver resis- by densi- (mg/100cm 2 ) tivity by densi- (mg/100 cm 2 ) tivity tometer (Ω) tometer (Ω) ____________________________________________________________ ______________ 1 Non-treatment 1.82 65.2 10 14 1.72 59.1 10 14 Ethanol solution 2 containing no 1.73 59.9 10 14 1.65 48.9 10 14 antistatic agent 3 Exemplified 0.08 2.6 10 12 0.04 1.3 10 12 compound 2 4 Exemplified 0.07 2.1 10 12 0.05 1.8 10 12 compound 5 5 Exemplified 0.05 1.6 10 11 0.03 1.2 10 11 compound 10 6 Exemplified 0.04 1.2 10 11 0.03 1.1 10 11 compound 17 7 Exemplified 0.07 2.4 10 12 0.05 2.0 10 12 compound 19 8 Exemplified 0.05 1.8 10 12 0.03 1.4 10 12 compound 23 9 Exemplified 0.04 1.4 10 11 0.03 1.0 10 11 compound 30 ____________________________________________________________ ______________
As is clear from Table 1, the sample treated with the solution containing no exemplified compound and the untreated sample were high in average density value and large in amount of developed silver, and showed a considerable increase in fog density due to formation of static marks, whereas no formation of static marks was observed in the samples according to the present invention (Samples 3 to 9).
On the other hand, these samples were exposed to light, developed at 20°C. for 4 minutes and 30 seconds with a strongly alkaline roentgen film developer containing 1-phenyl-3-pyrazolidone hydroquinone (PQ), and then measured in speed and fog. Further, the samples were subjected to sensitometry after incubation for 3 days in a thermostat chamber kept at 55°C. and under conditions of 50°C. and RH 80%. The results obtained were as set forth in Table 2.
Table 2 ____________________________________________________________ ______________ Spray coating Dip coating After incubation After incubation Sample Relative Relative Fog Relative Relative Fog at 55°C. for at 50°C. and RH No. speed gamma speed gamma 3 days 80% for 3 days Relative Fog Relative Fog speed speed ____________________________________________________________ ______________ 1 100 1.0 0.13 100 1.0 0.15 100 0.24 100 0.19 2 101 1.1 0.13 109 1.1 0.14 102 0.30 88 0.18 3 103 1.0 0.13 111 1.0 0.13 108 0.23 100 0.18 4 108 1.1 0.12 105 1.0 0.14 103 0.26 101 0.19 5 100 1.1 0.12 105 1.1 0.14 102 0.23 99 0.16 6 100 1.0 0.13 102 0.99 0.13 100 0.22 98 0.16 7 103 1.0 0.13 101 1.0 0.14 100 0.25 103 0.15 8 100 1.0 0.11 100 0.98 0.12 99 0.26 99 0.17 9 100 1.0 0.12 103 1.0 0.14 100 0.23 100 0.16 ____________________________________________________________ ______________
From Table 2, it is understood that even when incubated not only at normal temperature but also at high temperature and humidity, the samples according to the present invention (Samples 3 to 9) were not deteriorated at all in speed, gradation and fog. In addition, the color tone of the developed silver changed to bluish black to give favorable results.
EXAMPLE 2
Each of the exemplified compounds 3, 6, 9, 15, 20, 25, 29 and 33 was dissolved in a 4 percent solution of sodium decyl-isoamyl succinate-2-sulfonate so that the concentration of the compound became 2 percent, and 20 cc. of the resulting solution was added to 1 liter of a 2 percent gelatin solution to be used as a protective layer. Subsequently, the solution was coated as a protective layer on a high sensitivity roentgen film. Samples prepared in the above manner and a sample having a protective layer containing no exemplified compound were subjected to the same tests as in Example 1 to obtain the results as set forth in Table 3.
Table 3 ____________________________________________________________ ______________ Antistatic property Photographic properties After incubation After incubation Average Amount of Immediately after at 55°C. at 50°C. and RH Sample Antistatic density developed preparation 3 days 80% for 3 days No. agent measured silver by densi- (mg/100 cm 2 ) Relative Relative Fog Relative Fog Relative Fog tometer speed gamma speed speed ____________________________________________________________ ______________ Protective layer con- 10 taining no 1.58 39.2 100 1.00 0.12 100 0.23 100 0.15 antistatic agent 11 Exemplified 0.13 4.0 104 1.05 0.11 101 0.24 100 0.17 compound 3 12 Exemplified 0.11 3.3 101 1.02 0.10 100 0.20 100 0.16 compound 6 13 Exemplified 0.12 3.9 102 1.00 0.10 105 0.23 103 0.16 compound 9 14 Exemplified 0.14 4.2 100 1.00 0.11 102 0.22 100 0.15 compound 15 15 Exemplified 0.11 3.2 99 1.01 0.09 108 0.18 110 0.12 compound 20 16 Exemplified 0.11 3.3 98 1.02 0.10 107 0.17 115 0.12 compound 25 17 Exemplified 0.13 4.1 101 1.00 0.12 100 0.21 100 0.16 compound 29 18 Exemplified 0.12 4.0 105 1.00 0.11 101 0.20 105 0.15 compound 33 ____________________________________________________________ ______________
As is clear from Table 3, it is understood that the samples according to the present invention (Samples 11 to 18) could be prevented from the formation of static marks without being deteriorated in photographic properties.
EXAMPLE 3
To 1 liter of a green-sensitive high sensitivity color photographic silver iodobromide emulsion was added 10 cc. of a 5 percent methanol solution of each of the exemplified compounds 2, 4, 8, 15, 18 and 31. To the emulsion was further added a solution of 20 g, of an internal color photographic magenta coupler 1-(4'-phenoxy-3'-sulfophenyl)-3-heptadecyl- 5-pyrazolone in a 1N-caustic soda solution which had been adjusted to pH 6.8 by addition of citric acid. Subsequently, the emulsion was coated on a cellulose triacetate film base and then dried. Samples prepared in the above manner and a sample, which had not been incorporated with any exemplified compound, were subjected to the same tests as in Example 1. The results obtained were as set forth in Table 4. Provided that in this example, the average density value was measured by using a green filter as a light source of the densitometer, and the development was effected according to an ordinary procedure using diethyl p-phenylenediamine as the developing agent.
Table 4 ____________________________________________________________ ______________ Antistatic property Photographic properties Average Specific Immediately after After incubation Sample Antistatic density surface preparation at 50°C. for No. agent measured resis- 3 days by densi- tivity Relative Relative Fog Relative Fog tometer (Ω) speed gamma speed ____________________________________________________________ ______________ 19 None 0.67 10 12 100 1.00 0.12 100 0.22 20 Exemplified 0.20 10 11 101 1.01 0.13 100 0.22 compound 2 21 Exemplified 0.23 10 10 100 1.00 0.15 100 0.20 compound 4 22 Exemplified 0.21 10 10 103 1.00 0.13 105 0.21 compound 8 23 Exemplified 0.22 10 11 100 1.01 0.15 100 0.23 compound 15 24 Exemplified 0.20 10 11 99 1.08 0.12 100 0.20 compound 18 25 Exemplified 0.21 10 11 100 1.00 0.12 99 0.21 compound 31 ____________________________________________________________ ______________
From Table 4, it is understood that by addition of the exemplified compounds to the emulsion, the samples according to the present invention were inhibited from formation of static marks and improved in dispersibility of formed dyes without any detrimental effect on photographic properties.
EXAMPLE 4
To a 5 percent aqueous gelatin solution containing an antihalation dye was added 2 cc. of a 2 percent aqueous solution of each of the exemplified compounds 2, 3, 10 and 18. The resulting solution was charged with 3 cc. of a 5 percent saponin solution and then coated on a cellulose triacetate film base, followed by drying. On the opposite side of the film base was coated a high speed photographic emulsion for negative and a protective layer was formed on the resulting emulsion layer by application of a gelatin solution incorporated with 300 mg. per liter of said solution of the above-mentioned exemplified compound. Samples prepared in the above manner were subjected to the same tests as in Example 1 to obtain the results set forth in Table 5.
Table 5 ____________________________________________________________ ______________ Antistatic property Photographic properties Sample Antistatic Average Amount of Immediately after After incubation No. agent density developed preparation at 50°C. for measured silver 3 days by densi- (mg/100 cm 2 ) Relative Relative Fog Relative Fog tometer speed gamma speed ____________________________________________________________ ______________ 26 None 1.10 33.6 100 1.00 0.12 100 0.30 27 Exemplified 0.12 3.8 100 1.00 0.11 102 0.28 compound 2 28 Exemplified 0.10 3.2 100 1.02 0.12 105 0.30 compound 3 29 Exemplified 0.08 2.8 98 1.00 0.14 100 0.28 compound 10 30 Exemplified 0.12 3.3 97 1.01 0.11 101 0.28 compound 18 ____________________________________________________________ ______________
As is clear from Table 5, the samples according to the present invention (Samples 27 to 30) were inhibited from formation of static marks and were not deteriorated in photographic properties.