US 3811887 A
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United States Patent [191 Ishihara et al.
[451 May 21,1974
[ PHOTOGRAPHIC MATERIAL COMPRISING BlS-ACYLHYDRAZINIUM COMPOUNDS  Inventors: Masao lshihara; Tsuneo Walda;
Hisashi Yamaguchi, all of Tokyo; Sadao Sugita, Hanno, all of Japan  Assignee: Konishiroku Photo Industry C0.,
Ltd, Tokyo, Japan  Filed: Dec. 16, 1971 21 Appl. No.: 208,890
 Foreign Application Priority Data Dec. 18, 1970 Japan 45-113102  References Cited UNITED STATES PATENTS 3,704,128 11/1972 Koda et a1. 96/87 A Primary ExaminerRonald H. Smith Attorney, Agent, or Firm-Waters, Roditi, Schwartz & Nissen  ABSTRACT Antistatic agents for use in light-sensitive silver halide photographic material comprise bis-aminimide compounds having the formula:
wherein R,, R R and R are individually a lower alkyl group; R and R are individually an alkyl, arakyl or aryl group or a hetero ring; and R is a divalent group.
5 Claims, N0 Drawings PHOTOGRAPH-TIC MATERIAL COMPRISING BIS-ACYLHYDRAZINIUM COMPQUNDS 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 mate- 6 e i RzCONIII-Rr- NCO-Ru cite thelight-sensitive material; l r obl fiskfer ivedfrom such static charge are not limited merely to the fonnation of static marks but bring about the adhesion of dust onto the surface of the light-sensitive material. Such static troubles are necessarilybrought about at substantially all stages where light-sensitive materials undergo friction, e.g,, at stages where photographic 7 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 lightsensitive 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. Ac-
cordingly, it is extremely difficult to find excellent antistatic agents applicable to light-sensitive silver halide photographic materials.
wherein RQRQIR and R are individually a lower alkyl group; R and R are individually an alkyl, aralkyl or aryl group or a hetero ring; and R is a divalent group. "fwhfiih'iof 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 lightsensitive radiographic material, there'is attained the effeet, 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 com pounds having the aforesaid general formulas are as follows:
Table Continued Compound R1 R2 3 R4 Ra Ra R7 2 H 3 C 3 (I) CH3 CH2CH2- CH3 CH3 CrzHtsOCHzCHCHz O 33 CH: CH CH: CH2CH2- CH: CH;
1 CH2 CHJCHCH:
Elementary analysis Calculated Found Compound H N X C H N X The bis-aminimide compounds of the aforesaid general formulas can be synthesized according to the methods disclosed in W. H. Berry & P. Brocklehurst: .1. Chem. Soc." 2264 (1964); R. L. Hinman & M. C. Flores: .1. Org. Chem, 24 660 (1959); and R. C. Slagel: J. Org. Chem, 33 1374(1968).
Typical procedures for synthesizing the abovementioned compounds are set forth below with reference to synthesis examples.
7.75 Grams of 1,4-iodobutane and 17.9 g. of W dimethyl-N'-hexadecanoyl-hydrazine were dissolved in 20 ml. of dioxane, and the resulting solution was reacted at 73C. 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), mp. l09l 10C., yield 90.2%.
Found C: 52.86 H: 9.25 N: 6.361: 28.05
C: 52.97 H: 9.34 N: 6.18 l: 27.98 w iu e z -zl Calculated 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 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. 4344C.
Found c; 74.00 H: 12.56 N: 8.62
Calculated C: 73.78 H: 12.70 N: 8.61
SYNTHESIS EXAMPLE 2 Synthesis of the exemplified compound (18):
O (caQ-ocm ofibazucanman 01130 C O(CH1)4COOCH;
$9 CaHnQ-JNZHAJHCHHIINC ocmcm 2011.011
31.5 eaa sf'psaylgiaaggza l 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 ml. of ether, and the water layer was concentrated to obtain the bisaminimide Compound 18 in the form of an oil, yield 89.5%.
Found Calculated C: 70.56'Hi946 Ni 7.31
CZ 70.91 1119.57 N17.19 4IH14 4 A) 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 maybe incorporated into 9 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 l g. per
tion. The thus prepared samples including an untreated roentgen film were allowed to stand for 24 hours under conditions of RH 30% and 25C., 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
m of the light-sensitive material, though the amount 10 measure the average values of blackened density. The
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 samples were further measured in amountof 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 Din coating Sample Antistatic Average Amount of Specific Average Amount of Specific No. agent density developed surface density developed surface measured silver resismeasured silver resisby densi- (mg/lcm tivity by densi- (mg/100 cm") tivity tometer (Q) tometer (Q) 1 Non-treatment 1.82 65.2 l0 1.72 59.1 l0
Ethanol solution 2 containing no 1.73 59.9 10 1.65 48.9 1O
antistatic agent 3 Exemplified 0.08 2.6 10 0.04 1.3 10' compound 2 4 Exemplified 0.07 2.1 10 0.05 1.8 l0
compound 5 5 Exemplified 0.05 1.6 [0 0 03 1.2
compound 10 6 Exemplified 0.04 1.2 l0" 0.03 1.1 l0
compound 17 7 Exemplified 0.07 2.4 10 0.05 2.0 10
compound 19 8 Exemplificd 0.05 1.8 10' 0.03 1.4 10
compound 23 9 Exemplified 0.04 1.4 l0 0.03 1.0 l0
compound EXAMPLE 1 Each of the exemplified compounds 2, S, l0, l7, 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- 6 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, ex-
cept that the above-mentioned treatment was not ef- As is clear from Table l, 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 20C. for 4 minutes and 30 seconds with a strongly alkaline roentgen film developer containing l-phenyl-3-pyrazolidone hydroquinone (PO), 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 55C. and under conditions of 50C. and RH 80%. The results obtained fected or was effected by use of only an ethanol soluwere as set forth in Table 2.
Table 2 Spray coating Din coating R After inctubation After glCUbBllOfl Sample Relative Relative F Relative elative Fo at 5 C. gr a 50" a d RH No. E5533" gamma 8 speed gamma g 3 y 85% for 3 Hays Relative Fog Relative Fog speed speed 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-Z-sulfonate so that the concentration of the compound became 2 percent, and 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 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, l5, l8 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 lN-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 Antistatic property Photographic properties After incubation After incubation WW 4 Average Amount of lmmediajely after at C. for at 50C. and Sample Antistatic density developed preparation 3 days "N for 3 days No. agent measured silver by densi- (mg/ cm) Relative Relative Fog Relative Fog Relative Fog tometer speed gamma speed speed Protective layer con- 10 laining 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 Exemplificd 0.11 3.3 101 1.02 0.10 100 0.20 100 0.16
compound 6 13 Excmplificd 0.12 3.9 102 1.00 0.10 105 0.23 103 0.16
compound 9 14 Excmplified 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 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 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 abovementioned 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 0C. for
measured silver 3 ays by densi- (mg/100 cm) 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 i 3.8 100 1.00 0.11 102 0.28
compound 2 28 Ex emplified 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 v 30 Exemplified 0.12 3.3 97 1.01 0.11 101 0.28
compound 18 Table 4 Antistatic property Photographic properties 4 Average Specific Immediately after After incubation Sample Antistatic density surface Preparation at 50C. for
No. agent measured resis- 3 y by densitivity Relative Relative Fog Relative Fog tometer (.0) speed gamma speed 19 None 0.67 10' 100 1.00 0.12 100 0.22
20 Exemplified 0.20 10 101 101 0.13 100 0.22
compound 2 21 Excmplified 0.23 10' 100 1.00 0.15 100 0.20
compound 4 22 Exemplified 0.21 10 103 1.00 0.13 105 0.21 compound 8 i 23 Exemplified 0.22 10" 100 1.01 0.15 100 0.23
compound 15 24 Exemplified 0.20 10" 99 1.08 0.12 100 0.20
compound 18 25 Exemplified 0.21 10 100 1.00 0.12 99 0.21
compound 31 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.
7 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.
What we claim is:
l. A method for the prevention of static in a lightsensitive silver halide photographic material comprising a support and at least one photographic layer coated on said support, said method comprising treatof a 5 percent saponin solution and then coated on aing said photographic material with a bis-aminimide cellulose triacetate film base, followed by drying. On
compound of the formula:
(II) (III) 3 8 1 1 ,8 87 15 16 wherein R R R and R are individually a lower alkyl 4. A method as claimed in claim 1, wherein the lightgr p; 2 and e r dual y an a kyl, ar kyl or sensitive silver halide photographic material is sprayed aryl gr up or a h e o g; nd R4 is a divalent group. with a solution of the bis-aminimide compound.
2. A method as claimed in claim 1, wherein the bis- 5. A light-sensitive silver halide photographic mateaminimide compound is incorporated into at least one 5 rial which comprises a support and coated thereon phoof the photographic layers constituting said lighttographic layers at least one of which contains a bissensitive silver halide photographic material. aminimide compound of the general formula R i i if 'Ri Ri R? 6% G3 9 6A9 e 89 9'9 69 9 RiCNN-Ri-NNco-Ri Ri- NCORCONNR Rz-NNCOIh-NNCO-Rr B l! 1 I 3 11 B ll $1 (I) (II) (III) A method as claimed in claim wherein the g wherein R R R and R, are individually a lower alkyl sensitive silver halide photographic material is treated group; R and R are individually an alkyl, aralkyl or with a photographic treating bath containing the bisaryl group or a hetero ring; and R is a divalent group. aminimide compound and being one member selected from the group consisting of a developing bath, a stopping bath and a fixing bath.