US 3775128 A
A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion containing a compound represented by the following general formula (I); wherein R1, R2 and R3 each represents a hydrogen atom or an alkyl group substituted by a hydroxyl group, wherein R1, R2 and R3 are not simultaneously a hydrogen atom, is disclosed.
Claims available in
Description (OCR text may contain errors)
Yamamoto et al.
[111 3,775,128 [4 1' Nov. 27, 1973 1 SILVER HALIDE EMULSION CONTAINING A TRIAZINE AS ANTIFOGGANT  Inventors: Nohuo Yamamoto; Yoshisato Minagawa; Tohru Sueyoshi, all of Kanagawa, Japan  Assignee: Fuji Photo Film Co., Ltd., Kanagawa, Japan  Filed: Aug. 21, 1972  App]. No.: 282,094
 Foreign Application Priority Data Aug. 25, 1971 Japan 46/64990  US. Cl. 96/76 R, 96/109  Int. Cl G03c 1/48, G03c 1/34  Field of Search ..L 96/109, 76 R  References Cited UNITED STATES PATENTS 2,586,168 2/l952 Kaszuba 96/109 2,708,162 5/1955 Carroll et al 96/109 Primary Examiner--Norman G. Torchin Assistant ExaminerWon H. Louie, Jr. Att0rney-Richard C. Sughrue et al.
[5 7] ABSTRACT wherein R R and R each represents a hydrogen atom or an alkyl group substituted by a hydroxyl group, wherein R R and R are not simultaneously a hydrogen atom, is disclosed.
5 Claims, 1 Drawing Figure SILVER HALIDE EMULSION CONTAINING A TRIAZINE AS ANTIFOGGANT BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide lightsensitive material. More particularly, it relates to a silver halide photographic light-sensitive material wherein fog formation and curling tendency are reduced by an improvement in the physical properties thereof.
2. Description of the Prior Art In general, a silver halide photographic emulsion is prepared using a high molecular weight material such as gelatin, polyvinyl alcohol, etc., as a protective colloid and dispersing the crystals of silver iodide, silver bromide or silver chloride, or the mixed crystals thereof in the protective colloid.
Photographic printing papers, dry plates, films, etc. are prepared by applying such a silver halide photographic emulsion in the form of a thin film to a support such as a synthetic high polymer-laminated paper, glass, cellulose ester, or synthetic high molecular film, e.g., polyethylene terephthalate, etc.
In recent years, the amount of silver halide photographic light-sensitive material used has been markedly increased, and the range of the use thereof tends to be steadily broadened. Therefore, in the production of the light-sensitive materials, it is required to design silver halide photographic light-sensitive materials such that the properties thereof can be maintained stable under various conditions of use,
Silver halide emulsion-coated materials obtained by applying the emulsion to various supports and drying as described above are known to undergo an undesirable photographic change referred to as kink desensitization or kink fog when a mechanical stress is exerted externally thereon momentarily or for a short time. In addition, it is also known that a silver halide photographic emulsion layer applied to a hydrophobic support and dried as described tends to undergo cracking due to its brittleness under low humidity conditions or to curl due .to the differences in planar contraction between the emulsion layerand the support. These undesirable physical characteristics will cause various difficulties in the production of photographic lightsensitive materials, in photographic processing steps such as development, in handling such as in storage, on projection, etc. As methods for improving these difficulties, it has been reported that it is effective, for example, to add a certain heterocyclic compounds (British Patent No. 738,618 alkyl phthalates (British Patent No. 738,637), alkyl esters (British Patent No. 738,639), or a certain kind of hydrophilic compounds (US. Pat. Nos. 2,960,404; 3,042,524; and 3,520,694; West German Patent OLS No. 1,942,326) and the like to a silver halide photographic emulsion layer or a supplementary layer.
However, in some of the above-described materials, the defects in that the physical properties of the silver halide photographic emulsion-coated materials when left under high temperature and high humidity are not sufficiently improved, that adverse effects on the photographic properties, such as fogging and desensitization are brought about, in that the curl-reducing effect is poor although deterioration in photographic properties due to the mechanical stress is prevented to some extent, or in that, although the curling tendency is suppressed to some extent, the surface of the coated material is too tacky resulting in adhesion to other surfaces have occurred.
On the other hand, it has recently been observed that, in the loading of a silver halide photographic lightsensitive material in a camera, a printer or the like be fore the development processing, when the photographic material is left with a curvature within a certain range for a long period of time, for example, with curvature as small as 3 to 10 mm in diameter for a period of l to 10 days, in such a condition that the silver halide emulsion surface faces toward the outside of the curvature, the formation of fog or desensitization will sometimes occur at the curved portion of the photographic material. This phenomenon is a newly found phenomenon and is different from the previously known kink fog or kink desensitization caused by bending the element sharply for a short period of time in that the former occurs when a photographic light-sensitive material is kept in a kink or curved condition for a comparatively long period of time. The deterioration in photographic properties caused by maintaining the silver halide emulsion-coated material in the above-described state will spoil the practical value of the photographic lightsensitivematerial. However, an application of most of the foregoing known methods which are considered to be effective for the general kink fog or kink desensitization has been determined to be quite ineffective for preventing the above-described newly found phenomenon, or is accompanied by a secondary adverse effect such as an increase in the tackiness of the surface of the coated material although some effects are obtained.
An object of this invention is to provide a method for effectively controlling the curling of a silver halide photographic layer applied to a support without degrading the other physical and photographic properties thereof.
Another object of the invention is to provide a method for preventing fog formation or desensitization which is caused by leaving the silver halide photographic light-sensitive material for a long period of time in a kinked or bent state, without degrading the other physical and photographic properties thereof.
SUMMARY OF THE INVENTION As the result of extensive investigations, it has been found that the above-stated object can be attained by adding to a silver halide photographic light-sensitive material a compound represented by the following general formula (I);
wherein R, R and R each represents a hydrogen atom or an alkyl group substituted by hydroxyl group, wherein R R and R are not simultaneously a hydrogen atom.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING The accompanying drawing is a FIGURE illustrating the bending stress-fog test, wherein I, II, and III designate an emulsion layer, a support and a cylinder made of iron, respectively.
DETAILED DESCRIPTION OF THE INVENTION The term alkyl group" as used herein is intended to include alkyl groups containing hetero atoms (for example, an oxygen atom) in the carbon chain as well. As
the substituted alkyl group for R R or R CH-,CH OH, CH CH OCH OH or -CH1CHCH3 is preferred.
Representative examples of the compounds of the general formula (I) which can be used in the invention are illustrated hereinafter.
HO CII:CHaN \N 'CHICHIOH N CH: C H 1 O H Compound (4) (T NCHzCI-I:O CHzO H 110 CH,CI-I4N N (EH HzO-CHzOH Compound (5) Compound (7) (I? C llU OIIzCIIzO CIIzC lIzO CIIzCIIzN III-CIIzCIIzOII 0:2: (1:0 I UlhUIhUII These compounds which can be used in the invention can be synthesized, for example, by reacting cyanuric acid with an alkylene oxide according to the process described in Journal of Organic Chemistry, Vol. 28, p. 85, or by treating the resulting reaction product with formaldehyde.
The above-illustrated compounds which can be used in the invention are hydrophilic compound which are soluble in water in high concentrations, but have such a small hygroscopic property that the coated photographic layer containing these compounds cause less sticking to other surfaces in comparison with the coated photographic layer to which the known hydrophilic compounds are added. Therefore, no difficulty in that the amount thereof added must be restricted due to the tackiness resulting occurs. The compounds are usually added in an amount of from 0.1 to 30 percent by weight (hereinafter all percents are by weight) based on the amount of silver contained in the silver halide photographic emulsion. Especially, in a silver halide photographic coated material to which the compounds are added at a level ranging from 0.5 to 20 percent, not only is desensitization, fog formation and curling tendency of the material occurring when a mechanical bending stress is exerted thereon for a long period of time markedly controlled, but also the tackiness of the surface of the coated material can be maintained at a far lower level than when other known gelatin plasticizers are added.
The compounds may be added in an amount outside the abovedescribed range. However, the addition of less than 0.1 percent of the compounds is not sufficient to obtain sufficient effects, while the addition above 30 percent does not further enhance the effect and it is therefore disadvantageous from the viewpoint of cost. Two or more of these compounds may be used in combination. In addition, these compounds may be used together with a suitable amount of other known photographic hydrophilic compounds.
The point at which the compounds used in the invention are incorporated in a photographic emulsioncoated material is not particularly limited, but incorporation between the after-heating step of the silver halide emulsion and the step of coating and drying is pref- I erable. In adding the compounds, they can be added as a solution of the solvent exerting no adverse effects on a silver halide photographic emulsion, such as water, a lower alcohol (e.g., methanol, ethanol, isopropanol, etc.), etc.
The photographic coated layer containing the compounds of the invention can be a photographic emulsion layer containing silver halide, a layer adjacent to the silver halide photographic emulsion layer, such as a protective layer or a intermediate layer in the photographic light-sensitive material, or can be a combination thereof. In addition, in preventing the pressure fogging in a multi-layer coated photographic material such as a color film caused by exerting a bending stress for a long period of time, the addition of the compound of the invention to only one layer of the layers constituting the material can provide the other layers with the effect of preventing fogging due to pressure through the diffusion effect.
The present invention can be applied to various silver halide photographic emulsions used in photography such as silver chloride,.silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver iodochlorobromide, etc. The emulsion can be used in conventional black and white and color photographic materials as well as those used in a diffusion transfer process and a silver dye bleach process.
As the dispersion medium (or a binder) for a photographic emulsion, gelatin, coloidal albumin, collodion, gum arabic, agar-agancellulose derivatives (e.g., alkyl esters of carboxylated cellulose such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl-cellulose, etc.), synthetic resins (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, etc.) and others well known in the art, as well as a mixture of these materials can be used.
The'photographic emulsion is applied to various supports such as a cellulose ester film, a polyvinyl acetal film, a polyethylene'jfierephthalate film, a polystyrene film, a paper, a polyethylene-laminated paper, a paper substitute, and the like.
The silver halide photographic emulsion employed in the invention may be sensitized with the chemically sensitizing agents, spectrally sensitizing agents, polyalkylene oxide derivatives, etc. known in the art, or by the combined use thereof. In addition, the photographic emulsion layer may be stabilized by the addition of various anti-foggants, stabilizers, etc. known in the art, or may be hardened with various known photographic hardeners. To the photographic emulsion layer and the adjacent layers may be added coating agents well known in the art, such as natural surface active agents (e.g., saponin), nonionic surface active agents,
anionic surface active agents, cationic surface active.
agents or amphoteric surface active agentsTo the photographic emulsion layer and the adjacent'layers may be added a photographic water-dispersingvinyl poly-v mer well known in the art. In addition, the surface layer of the silver halide photographic light-sensitive material of the invention may be subjected to a static charge-preventing processing using various kinds of antistatic agents. v
The present invention will be described in greater detail hereinafter by reference to the following examples.
EXAMPLE 1 A gelatino-silver bromoiodide photographic emulsion of a mean grain size of 0.35 p. containing 0.6 mol percent of silver iodide was prepared in a conventional manner. The composition by weight of the major components in the photographic emulsion was percent of silver halide, 6 percent of gelatin and 69 percent of water, to which suitable amount of saponin as a coating aid and mucochloric acid as a hardening agent had been added. 100 grams of the photographic emulsion were removed, and 1 ml or 3 ml of a 25 percent aqueous solution of compound (2) or compound (3) (described hereinbefore) of the invention was added to each of the emulsions to prepare coating solutions B,C,D and E. For comparison, coating solutions F and G were prepared by adding 1 ml or 3 ml ofa 25 percent aqueous solution of a conventional gelatin plasticizer, 1,2,4 -butanetriol, to the above-described photographic emulsion. As an additional comparison, a coating solution A to which neither the compound of the invention nor 1,2,4 -butanetriol was added was prepared.
The resulting photographic emulsion coating solutions of A to G were applied to a subbed support of polyethylene terephthalate film of a thickness of 180 p. in an amount of 6 ml/ 100 cm and then dried under the conditions of a temperature of 23C, a relative humidity of 75 percent and a wind velocity of 1.5 m/sec.
The photographic films thus obtained were slit into pieces of 3 mm in width x mm in length. The strips were left for 24 hours under the conditions of a temperature of 23C and a relative humidity of percent, with one end of the strips being stationarily fixed, and the distance of the movement of the other end due to the curling phenomenon caused by the contraction of the photographic emulsion layer was measured to examine thereby the degree of curling.
Apart from this, four kinds of photographic films obtained by applying the photographic emulsion coating solutions of A to B and then drying as described above were left for 48 hours under the conditions of a temperature of 50C and a relative humidity of 10 percent, and, after imagewise exposing the resulting samples in a conventional manner, they were developed for 6 minutes at 20C in the following developer. After fixing, washing and drying, the photographic characteristics thereof were compared.
N-Methyl-p-aminophenol Sulfate 2.0 g
Anhydrous Sodium Sulfite 90.0 g
Hydroquinone 8.0 g
Sodium Carbonate Monohydrate 52.5 g
Potassium Bromide 5.0 g
Water to make the total 1000 ml TABLE 1 Photographic Compound Amount Addcd Curling Properties Added (ml) 25 aq.
solution/100 Amount Relative Fog Sample g'of emulsion Sensi- (mm) tivity A No additive 9.8 100 0.02 B Compound (2) l '8.8 98 0.02 C do. 3 965.6 0.01 D Compound (3) l 8.6 100 0.02 E do. 3 5.4 97 0.01 F 1,2,4- 1 9.0 97 0.03
butanetriol G do. 3 7.8 0.04
As is apparent from the results contained in Table 1 above, curling could be markedly reduced without substantially degrading the photographic properties by adding compound (2) or (3) to a photographic film in comparison with the case wherein nothing was added or the conventional plasticizer was added.
EXAMPLE 2 The same silver bromoiodide photographic emulsion A as described in Example 1 was applied to a polyethylene terephthalate support of a thickness of 180 having thereon a subbing layer in a silver amount of 50 mg/ cm and dried, to which a 5 percent gelatin aqueous solution containing the following additives was applied in such an amount per unit area (100 cm") that the following samples H,l,.l and K were prepared, and dried to prepare the four kinds of double-layer coated photographic films.
TABLE 2 Sample Additive Additive (amount added) (amount added) Compound (3) 1,6-hexanediol mg. mg. H 0 l O .l O S K 2 3 The samples H, l, J and K (double-layer coated photographic films) obtained according to Table 2 were left for 24 hours as described in Example 1 under the conditions of a temperature of 23C and a relative humidity of 40 percent, and the curling tendency occurring in films was measured in the same manner as described in Example 1.
TABLE 3 Sample Curling Amount mm) H 9.8 l 3.0 .l 5.2 K 3.8
As is obvious from the results contained in Table 3 above, it can be seen that sample I to which compound (3) of the invention was added showed remarkably less curling tendency in comparison with sample H to which nothing was added and sample J to which a convent onal gelatin plasticizer, 1,6 -hexanediol, was added. In addition, it can be understood that, in sample K in which the compound of the invention and the conventional plasticizer were used in combination so that they were incorporated in the coating composition in the same ratio by weight, the curling tendency was markedly controlled in comparison with sample 1. Furthermore, when each sample of this Example was superposed one on the other contacting the coated surface with the back surface of the film and left for 24 hours under a static pressure of 50 g/cm and under a high humidity condition, for example, a relative himidity of 80 percent, sample adhesion between the coated surface and the back surface of the film partially resulted for sample J, whereas sample K in accordance with the invention had only a slight amount of adhesion phenomenon and, in sample I, no adhesion phenomenon appeared similar to sample H to which nothing had been added.
EXAMPLE 3 A red sensitive photographic emulsion was prepared as follows. To 1000 g of a negative silver bromoiodide emulsion containing 4.5 g of silver bromoiodide (containing 6.0 mol percent of silver iodide) per 100 g of the emulsion and 16 g of gelatin were successively added the following additives: 90 g of a DJ percent methanol solution of a spectrally sensitizing agent (a) g of a 1 percent aqueous solution of S-methyl- 7-hydroxy-2,3,4 triazaindolizine and 450 g of cyan coupler emulsion prepared according to the following composition;
5 percent Aqueous Solution of Gelatin 100 g 5 percent Aqueous Solution of Sodium Dodecylbenzene Sulfonate 8 ml Cyan Coupler (b) 5 g Acetone 10 ml Tricresyl Phosphate 10 ml l Optically Sensitizing Agent (a);
The red sensitive color emulsion thus obtained was divided into four equal portions, and to each portion was added 10 g of a 30 percent aqueous solution of compound (1) of the invention, compound (2) of the invention or compound (3) of the invention, or 10 g of water for comparison. Each of the above-described emulsions was applied to a subbed support of cellulose triacetate in a dry thickness of 5 p. then dried to obtain samples L, M, N and O of the four films, each of which was then slit in a 35 mm width and bent, as illustrated in the accompanying drawing, along a cylinder (lll) made of iron having a diameter (r) of 5 mm in such manner that the emulsion layer (I) faced away from the cylinder surface and the surface of the support (ll) faced toward the cylinder surface, and fixed so that the film was superposed tightly on the cylinder, then left for 24 hours under the conditions of a temperature of 50C and a relative humidity of 50 percent while shielding from light (this condition provides approximately the same results as the case of leaving the same for 7 days under the condition of a temperature of 25C and a relative humidity of 50 percent). Subsequently, the usual photographic processings of color development, bleaching, fixing and washing were conducted according to the following.
1. Color Development (20C, 8 minutes) Diethyl-p-phenylenediamine Sulfate 2.75 g Hyd'roxylamine Sulfate 1.2 g Anhydrous Sodium Sulfite 2, g Potassium Bromide 2, g Sodium Carbonate g Water to make the total amount 1000 ml 2. Hardening Processing (20C, 8 minutes) Anhydrous Sodium Sulfate g Water to make the total amount 1000 ml 3. First Fixation (20C, 5 minutes) Sodium Thiosulfate g Water to make the total amount 1000 ml 4. Washing (20C, 5 minutes) 5. Bleaching (20C, 5 minutes) Potassium Ferricyanide 100 g Water to make the total amount 1000 ml 6. Washing (20C, 5 minutes) 7. Second Fixation (20C, 5 minutes) The same formulation as in the first fixation. 8. Washing (20C, 20 minutes) The fog density of each photographic film sample at the portion closely superposed on the cylindrical part was measured through a red filter, the sample having been subjected to the bending stress and then photo- -9 graphically processed. The results obtained are given in Table. 4.
As is clear from the results contained in Table 4 i above, the degree of the cyan color fog of the sample to which the compound of the invention had been added was remarkable less than that of the cyan color fog of the sample to which no compound of the invention had been added.
EXAMPLE 4 In order to compare samples P and Q to which compounds (3) and (4) of the invention were added, respectively, with samples R and S to which a conventional compound, glycerin or 1 ,1 1 trimethylolpropane, reported to be effective for the socalled kink desensitization or kink fog was added, samples P to S of fourphoto'graphic films were prepared in the same manner as described in Example 3 except that 3 ml of a 25 percent aqueous solution of each of four compounds was added per 100 g of the emulsion, and then the bending stress-fog test was conducted.
ln parallel with the above-described test, each of the four film samples of P to S and sample in Example 3 containing none of the additives (3), (4), glycerin, and 1,1,1-trimethylolpropane was cut into two pieces of 35mm 50 m n in size, and left for 24 hours under Table 5 Sample Compound Added Fog Density Adhesion Area (M O No Additive 0.70 P (3) 0 O (4) 0.08 30 R Glycerin 0.16 '70 S 1,1,1-
Trimethylolpropane 0.64 35 As is apparent from the results contained in Table 5 above, sample S to which 1,1,l-trimethy1olpropane had been added exhibited almost no fog-controlling effect although there was no problem in the adhesive properties thereof, and sample R to which glycerin had been added showed the defect that the adhesive properties of the surface of the emulsion layer was degraded although a fog-controlling effect was obtained. On the contrary, it can be seen that, for samples P and Q to which the compounds of the present invention had been added, fog was markedly controlled without degrading the adhesive properties.
EXAMPLE 5 A red sensitive photographic emulsion obtained in the same manner as described in Example 3 was divided into four equal portions, and-to each portion was added 10 g of a 30 percent aqueous solution of compound (5) or (6) of the invention, or of the conventional compound, l,4-cyclohexanedimethanol, for comparison, instead of the compounds (1 (2) and (3) added in Example 3, or 10 g of water for comparison without an additive.
Each of the above-described red sensitive photographic emulsions was applied to a subbed support in a dry thickness of 5p. To each of the red sensitive emulsion-coated films thus obtained were successively applied the following coating layer, then dried to prepare thereby multi-layer color film samples T, U, V and W.
1. An intermediate gelatin layer; a 5 percent gelatin aqueous solution was applied in a dry thickness of 1p.
2. A green sensitive photographic emulsion layer; the following photographic emulsion (c) was applied in a dry thickness of 4.5;;.. v
3. .A yellow filter layer; a 5 percent gelatin aqueous solution containing yellow colloidal silver was applied in a dry thickness of 1.2
4. A blue sensitive photographic emulsion layer; the following photographic emulsion (d) was applied in a dry thickness of 5.0;].. i
5. A protective gelatin layer; a 5 percent gelatin aqueous solution was applied in a dry thickness of 1.2a. The green sensitive photographic emulsion (c) was prepared as follows. That is, to 1000 g of a negative silver bromoiodide emulsion containing 8 g of silver bromoiodide (containing 6.0 mol percent of silver iodide) per 100 g of the emulsion and 12 g of gelatin were added successively the following additives at 40C; 150 g of a 0.1 percent methanol solution of a spectrally sensitizing agent (e) 20 g of a 1 percent aqueous solution of S-methyl- 7-hydroxy- 2,3,4-triazaindolizine and 450 g of a magenta coupler emulsion prepared according to the following formulation;
* 4 Magenta Coupler (f) aHn- The blue sensitive photographic emulsion (d) was prepared as follows. To 1000 g of a negative silver bromoiodide emulsion containing 4.5 g of silver bromoiodide (containing 6.0 mol percent of silver iodide) per 100 g of the emulsion and 16 g of gelatin were added 5 successively the following additives at 40C: 20 g of a 1 percent aqueous solution of S-methyl- 7-hydroxy- 2,3,4-triazaindolizine and 500 g of a yellow coupler emulsion prepared according to the following formulation;
5 percent Gelatin Aqueous Solution 100 g 5 percent Aqueous Solution of Sodium l ml Dodecylbenzenesulfonate Yellow Coupler (g) 6 g Acetone 10 ml Tricresyl Phosphate 10 ml.
'5 Yellow Coupler (g) TABLE 6 Compound Added (only to the red sensitive layer) Compound (5) Compound (6) l,4-Cyclohexanedimethanol No Additive Fog Density Magenta Yellow Cyan 0 +0.06
As is apparent from the results contained in Table 6 above, in the samples of the invention, colored fog of cyan and yellow due to the bending stress was markedly reduced in comparison with that of the comparative samples, and, in addition, the decrease in the density of magenta was also reduced.
While the invention has been described in detail and in terms of specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
What is claimed is:
1. A silver halide photographic emulsion containing a compound represented by the following general formula (l);
wherein R R and R each represents a hydrogen atom or an alkyl group substituted by a hydroxyl group wherein R R and R are not simultaneously a hydrogen atom, said compound being present in an amount of at least 0.] percent by weight based on the amount of silver present.
2. The silver halide photographic emulsion of claim 1, wherein said alkyl group for R, and R is -CH CH OH, CH CH OCH OH or CH1CHCH:
and wherein said alkyl group for R is -CH CH OH or l L (Jrllu Compound (1) Compound (2) N JHiCHjOH Compound (3) Compound (4) HO CH2CHr-N N JHzCHIO -CH20 H Compound (5) 0 Compound (7) (i H O CHgCHz CH CH: O ClhCmN silver halide photographic emulsion layer and containing in said photographic emulsion layer or in another emulsion layer onsaid support a compound represented by the following general formula (I) wherein R R and R each represents a hydrogen atom or an alkyl group substituted by a hydroxyl group wherein R R and R are not simultaneously a hydrogen atom, said compound being present in an amount of at least 0.1 percent by weight based on the amount of silver present.