US 3656956 A
A photographic light-sensitive material wherein at least one emulsion layer contains polyglycidol. Improved stress resistance under low temperature and low humidity conditions is illustrated and desensitization, fogging, etc. are reduced.
Description (OCR text may contain errors)
United States Patent Yamamoto et al.
SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Inventors: Nobuo Yamamoto; Fumihiko Nishio; Masaji Yoshida; l-lideo Kawano, all of Kanagawa, Japan Assigneei Fuji Photo Film Co., Ltd., Kanagawa,
Japan Filed: Jan. 30, 1969 Appl. No.: 795,330
Foreign Application Priority Data Jan. 30, 1968 Japan ..43/5558 u.s. Cl ..'..L.,.96/114 Int. Cl ...G03 c 1/72 Field of Search ..96/1 14 Primary Examiner-Norman G. Torchin Assistant Examiner-Edward C. Kimlin Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak [5 7] ABSTRACT A photographic light-sensitive material wherein at least one emulsion layer contains polyglycidol. Improved stress resistance under low temperature and low humidity conditions is illustrated and desensitization, fogging, etc. are reduced.
14 Claims, No Drawings 3,656,956. [4 1 Apr. 18, 1972 SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a graphic lightsensitive material.
2. Description of the Prior Art A gelatino-silver halide photographic emulsion coating on a support of a naturalor synthetic high molecular material, such aspaper, acellulose ester or apolyester, often deteriorates as to softness and other physical properties under low temperature and low humidity conditions, and if a mechanical stress, such as torsion, bending or friction is applied thereto during manufacturing or handling prior to development, it sometimes acquires unfavorable photographic properties such as desensitization, fogging and the like. Moreover, it is generally .accepted that in the case of drying a gelatino-silver halide photographic emulsion coating by .the so-called Festoon drying gelatino-silver halide photosystem, an unfavorable ring-like pattern (the so-called stick mark) appears on unevenly dried areas after development. (See E. Z und; Zeitschrift fur Wissenschaftliche Photographic Photophysic und Photochemie Vol. 49, pp. 25-103.)
It has been reported, as a method of overcoming such disadvantages, to incorporate into the gelatin coating composition a polyhydric alcohol, such as glycerine, ethylene glycol or 1,6- hexanediol (See U.S. Pat. No. 2,960,404) or a dialkyl phthalate (See British Pat. No. 738,637).
However, some of these materials cause importantdefects, i.e., the physical properties and the photographic character of the gelatin containing coating is worsened under sever conditions of high temperature and high humidity, although the physical properties thereof are improved at low temperature and low humidity. In addition, the adhesive strength of the gelatin coating layer to the support is weakened, though deterioration of the photographic character due to mechanical stress is somewhat prevented. In effect, this results in excessive stickiness of the surface of the coating, which results in adhesion of the coating to other surfaces which may come into contact with it.
SUMMARY OF THE INVENTION By incorporating from about 1 to about 30 percent by weight, based on the dry weight of gelatin of polyglycidol in an emulsion layer of a gelatin-containing photographic coating composition, improved properties thereof are obtained. The exact properties which are improved are recited in the Objects of the Invention.
It is the principal object of this invention to provide an improved gelatino-silver halide photographic light-sensitive material whereby generation of the above mentioned faults, such as pressure desensitization, pressure fog, stick marks, etc. is suppressed, without any worsening in the adhesiveness of the material to a support or its physical properties, and further wherein the stickiness of the gelatin coating to other surfaces is decreased and the preservation of the other properties thereof is good.
DESCRIPTION OF THE PREFERRED EMBODIMENTS We have found as a result of many studies that the foregoing object can be accomplished by incorporating polyglycidol into a gelatin-containing photographic coating composition.
Polyglycidol contains the repeating unit represented by the formula:
1,253) a caustic alkali, such as NaOI-I, KOH or BaOI-l, a metal alkoxide such as sodium alkoxide or potassium alkoxide, pyridine, a Lewis acid such as aluminum chloride, sulfuric acid, stannic chloride, or an organometallic compound (See Japanese Pat. publication No. 5443/63) such as zinc diethyl or aluminum triethyl, as a catalyst. The obtained polyglycidol, being soluble in water, is added as it is formed or in an aqueous or alcoholic solution to thereby give a photographic coating composition wherein the polyglycidol is uniformly mixed.
In the case of synthesizingthe above mentioned water-soluble polyglycidol by the polymerization of glycidol, the properties of the polymer depend upon the polymerization conditions, for example, the type and the amount of a catalyst used, the presence or absence of a promoter, the reaction temperature, the reaction time, etc. For example, the polymer obtained by thermopolymerization is liquid because of its low degree of polymerization, whereas the polymer obtained by a polymerization method using an organometallic compound as a catalyst is sometimes a wax-like solid. However, the polyglycidol of the present invention is effectively used irrespective of such differences in the polymerization method, the degree of polymerization and state if the resulting polyglycidol is water-soluble.
The polyglycidol which has an intrinsic viscosity of 0.03 0.8 in methanol at 32.5 C. is preferred in the present invention.
The amount of polyglycidol incorporated in the gelatin-containing photographic coating composition is not limited particularly in this invention, but the foregoing object can favourably be accomplished by addition at a proportion of l-30 percent by weight, based on the dry weight of the gelatin. In the case of addition not within this scope, that is, less than 1 percent, no effect is noted, and in the case of a greater than 30 percent addition, the coated layer becomes somewhat sticky. In a gelatino-silver halide coating composition in which polyglycidol is added at a proportion of 3-20 percent by silver halide photographic emulsion may be carried out at any stage before the emulsion is coated on a support, but it is preferably added between the steps of after-ripening and coatmg.
The polyglycidol containing gelatin coating composition of this invention may be an aqueous solution of gelatin used only as a protective layer or an intermediate layer of a photographic light-sensitive material, or it may be a gelatino-silver halide photographic emulsion or combinations thereof.
Silver halide photographic emulsions which may be employed in the invention are, for example, emulsions for use as black-and-white positives or negative photographic light-sensitive materials and/or light-sensitive graphic art materials, emulsions for use as photographic X-ray film, coupler-inemulsion type color photographic emulsions wherein a color fomiing coupler is incorporated in the emulsion, and couplerin-developer type color photographic emulsions wherein a color-forming coupler is incorporated in a developer. Further, polyglycidol may be incorporated with good results in various silver emulsions and mixed silver halide emulsions, such as silver chlorobromide emulsions and silver iodobromide emulsons.
The silver halide emulsion may have been previously chemically sensitized by any well known method, for example by using a labile sulfur-containing compound such as ammonium thiosulfate, or allylthiourea, (See The Theory of the Photographic Process 3rd Edition, published by MacMillan Co. New York (1966), pp. 113-116), by complex salts of monovalent gold and thiocyanate (ibid p. 116), by reducing sensitizers such as an amino compound or a hydrazine compound, by
heavy metal salts such as stannous chloride (ibid. pp. 1 13-116), or by a polyalkylene oxide derivative, or by combinations thereof. The emulsion may be optically sensitized by the addition of a sensitizer, such as a cyanin dye or a merocyanine dye (ibid pp. l98-232). The emulsion, moreover, may be stabilized with any of the well known various fog inhibitors of the art (ibid pp. 344-346), and may be hardened by any of the various prior art hardeners (ibid pp. 55-60). The emulsion, or other gelatin-containing coating composition, moreover, may contain saponin and other known coating agents, for example, an amphoteric surfactant, anionic surfactants and nonionic surfactants, such as N-alkanoyl-N-alkyl tourate, sodium alkylbenzenesulfonate and polyoxyethylene nonyl phenyl ether, or anionic surfactants containing ethylene oxide chains, as disclosed in Belgian Pat. No. 650,004.
The following examples are given in order to illustrate the invention in greater detail without limiting the same.
EXAMPLE 1 Forty g of glycidol and 0.4 g of powdered sodium methoxide were charged to a glass tube rinsed with nitrogen gas, closed and shaken for 97 hours with a thermostatic control at 23 C.. To the reaction mixture were then added 40 ml of methanol, 10 ml of water, and 20 ml of a swollen, strongly acidic type cation exchange resin, and this mixture was stirred for 20 minutes. After separating the resin by filtering, the filterate was heated at 140 C. under a reduced pressure of 0.5 mmHg to remove unreacted material and solvent. 33 g of polyglycidol was obtained as a residue in the form of a colorless syrup havingan intrinsic viscosity of 0.060 in methanol at 325 C..
A 20 percent aqueous solution of the thus obtained polyglycidol was added to a sulfur-sensitized and gold-sensitized high-speed gelatin-silver iodobromide negative emulsion containing 7 percent by weight of gelatin, and the emulsion was coated onto a cellulose triacetate substrate so that the dried thickness of the coating was 10 i 1 microns. The coating was then set in a steam of clean air cooled to 7 C. and then dried by passing the thus coated film through a drying chamber controlled so as to gradually raise the drying temperature from 18 to 45 C. for 50 minutes. Test pieces of cm X 12 cm were cut from the resulting photographic film and subjected to humidity conditioning for 48 hours in an atmosphere at 23 C. and 65 percent relative humidity (65 percent R.l l.). The opposite ends of the test pieces were faced so that the emulsion layers were inside. A stress was imparted thereto by passing them through a slig 3 mm in width along the long axis. The photographic films were then developed for 5 minutes at 20 C. with a developing solution having the following composition, fixed, water-washed and dried using standard photographic processings. The density of the area blackened by pressure was measured, and this data is shown in Table 1.
Developing Solution Utilized N-methyl-pqtminophenol sulfate g. anhydrous sodium sulfite 75.0 g. hydroquinone 9.0 g. sodium carbonate monohydrate 30.0 g. potassium bromide 5.0 g. water to 1,000 ml.
The photographic films were also subjected to humidity conditioning at 35 C. and 85 percent RH. for 48 hours, then allowed to stand for 24 hours in the same atmosphere while their emulsion layers were faced downward under a static pressure of 50 g/cm The proportion of adhered areas was measured, these results being shown in Table 1.
As stated, the results obtained are shown in Table 1, together with comparative results obtained using the same processing without the addition of the compound of this invention (other conditions being the same) and with the addition of glycidol or glycerine (other conditions being the same) instead of the compound of this invention. lt will be apparent from these results that the formation of fog due to pressure is markedly suppressed, and the stickiness of the coating surface was less in the case of the addition of the compound of this invention.
TABLE 1 Additive Addition amount Blackened Adhered (gJgelatin g.) density area ('i) polyglycidol 7 0.14 40 14 0.06 50 glycidol 7 0.25 50 14 0.30 55 glycerine 7 0.20 75 14 0.16 85 no addition 0.25 45 EXAMPLE 2 Forty g of glycidol was charged to a flask equipped with a reflux cooler, heated while stirring at C. under atmospheric pressure and then heated at C. under a reduced pressure of 0.5 mml-lg to distil off unreacted material. 17 g of polyglycidol was obtained as a colorless viscous liquid, having an intrinsic viscosity of 0.049 in methanol at 325 C..
A 20 percent aqueous solution of the thus obtained polyglycidol and the polyglycidol (in separate runs) described in Example 1 was added to a sulfur sensitized silver chlorobromide emulsion intended for graphic arts use (containing 6 percent by weight of gelatin) and coated onto a polyethylene terephthalate base so that the dried thickness of the coating was 6.5 i 1 microns. Then, the coating was set in a steam of clean air cooled to 7 C. and then dried for about 40 minutes by passing the thus coated film through a drying chamber controlled so as to gradually raise the drying temperature from 18 to 35 C. Test pieces were prepared from the resulting photographic film in a manner as in Example 1, and they were subjected to humidity conditioning after which a bending stress was applied. The test piece was exposed to light so as to yield an optical density of about 1.0 after developing, developed at 20 C. for 3 minutes with a developing solution having the following composition and then fixed, waterwashed and dried in a conventional manner. The difference between the density of the portions wherein the sensitivity was reduced due to pressure and the density of the portions not exposed to pressure were measured.
Developing Solution Used anhydrous sodium sulfite 90.0 g. hydroquinonc 45.0 g. caustic soda 37.5 g. potassium bromide 30.0 g.
water to 1,000 ml.
These films were processed in the same manner as in Example 1 and the proportion of the adherent areas was measured.
The results obtained are shown in the following table (Table 2) together with a comparison of the results encountered without the addition of compound of this invention (other conditions being the same) and a comparison of the case when 1.6-hexanediol is added instead of the compound of this invention (other conditions being the same). It will be un- 1 Synthesized in example 1 Synthesized in example 2 EXAMPLE 3 Fifty-two g of glycidol was dissolved in 260 ml of methylene chloride, mixed with l ml of a methylene chloride solution containing 3 ml of stannic chloride while stirring at 50- 55 C., and then further stirred for 20 hours at the same ternperature. Then, the temperature was gradually raised to room temperature for about 2 hours. The resulting precipitate was washed with methylene chloride and ether and dried under reduced pressure to obtain 50 g of a light yellow paste of polyglycidol having an intrinsic viscosity of 0.075 in methanol at 325 C.
A 20 percent aqueous solution of the thus obtained polyglycidol and the polyglycidol synthesized in Example 1 were added to a sulfur-sensitized and gold-sensitized silver iodobromide negative emulsion (separate runs) with a high ratio of silver to gelatin (containing 7 percent by weight of gelatin) and coated onto a polyethylene terephthalate base so that the dried thickness of the coating was 10 i 1 microns. The coating was then set in a stream of clean air cooled to 7 C. Test pieces 20 cm X 20 cm in area were cut off from the films and adhered to a horizontally placed flat plate so that the uncoated side of the film was in contact with the plate. The test pieces were dried by an uniform flow of air at about 23-25C. to a moisture content of 55 :t 5 percent, and thereafter air at 34 C. and 50 i 5 percent relative humidity were blown onto the film for 30 seconds through a nozzle having an inner diameter of 1.5 cm positioned 20 cm above the central part of the test piece. The air blow was then interrupted for 1 minute, and this intermittent blowing of air was repeated until the whole surface of the test piece was completely dried. The test piece was then developed at 20 C. for 6 minutes with a developing solution having the following composition and fixed, water-washed and dried in a conventional manner.
Developing Solution Used N-methyl-p-aminophenol sulfate 2.5 g. anhydrous sodium sulfite 30.0 g. hydroquione 2.5 g. sodium metaborate tetrahydrate [0.0 g. potassium bromide 0.5 g.
water to 1000 ml The density difference between the high density areas and the low density areas of the ring-like pattern formed (due to uneven drying) was measured. In addition, the proportion of adhered areas was measured on a test piece dried uniformly by the same method as that of Example I.
The results obtained are shown in the following table (Table 3) together with the results for the case of not adding the compound of this invention (other conditions being the same) and for the case of adding glycerine (other conditions being the same) instead of the compound of this invention. It will be understood from these results that generation of the ring like pattern due to uneven drying, and the so-called stick mark" is markedly suppressed, and that the (proportion of) adhered areas was less in the case of adding the compound of this invention.
no addition 0. l0 l0 Synthesized in example 1 Synthesized in example 3 To amplify somewhat further on the present invention, it will be obvious that the polymerization range of the polyglycidol which is utilized corresponds to the intrinsic viscosity of the polymer which has been heretofore defined.
Further, state of the art reaction conditions for the formation of the polyglycidol may be utilized. The literature described in the specification, such as the Journal of Polymer Science and the Japanese Pat. publication No. 5443/63 are representative. For instance, the standard state of the art conditions for the ring-opening polymerization of epoxy compounds, as described in this literature, can be taken as representative.
In Example 1, the cation exchange resin which is utilized merely to eliminate sodium methoxide present therein, and no criticality is attached to the resin used.
It should be noted that when the term stress is utilized in the specification, it actually means that pressure was applied to the material. It can be seen that the result of pressure application provide a very useful comparison test to the constant results obtained.
What is claimed is:
1. A photographic light sensitive material comprising a support carrying at least one gelatino-silver halide emulsion layer containing water soluble polyglycidol, said polyglycidol containing repeating units of the formula lorr-om-O 2. The photographic material of claim 1 wherein said polyglycidol has an intrinsic viscosity of 0.03 0.8 in methanol at 32.5" C.
3. The photographic material of claim 1 wherein said gelatino-silver halide emulsion layer contains said polyglycidol in a proportion of 1 30 percent by weight based on the dry weight of gelatin in said emulsion layer.
4. A photographic light sensitive material comprising a support carrying thereon at least one gelatino-silver halide emulsion layer and a layer adjacent thereto, said adjacent layer containing water soluble polyglycidol, said polyglycidol containing repeating units of the fonnula ion-011F0 $29. 5.
5. The photographic material of claim 4, wherein said adjacent layer is a gelatino protective layer or a gelatino intermediate layer which contains said polyglycidol in a proportion of l 30 percent by weight based on the dry weight of gelatin in said adjacent layer.
6. The photographic material of claim 1 wherein said gelatino-silver halide emulsion layer contains said polyglycidol in a proportion of 320 percent by weight based on the dry weight of gelatin in said emulsion layer.
7. The photographic material of claim 4 wherein said adjacent layer is a gelatino protective layer or a gelatino intermediate layer which contains said polyglycidol in a proportion of 3-20 percent by weight based on the dry weight of gelatin in said adjacent layer.
8. The photographic material of claim 1 wherein said polyglycidol is a solid.
9. The photographic material of claim 1 wherein said polyglycidol is a liquid.
10. The photographic material of claim 4 wherein said polyglycidol is a solid.
11. The photographic material of claim 4 wherein said polyglycidol is a liquid.
12. The photographic material of claim 4 wherein said jacent layer is the protective layer. polyglycidol has an intrinsic viscosity of 0.03 0.8 in methanol 14. The photographic material of claim wherein said adat 325 C. jacent layer is the intermediate layer.
13. The photographic material of claim 5 wherein said adm w a