Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
  • G03C1/89—Macromolecular substances therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/38—Dispersants; Agents facilitating spreading
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/16—Blocked developers

Definitions

• ABSTRACT A light-sensitive photographic material comprising a support having coated thereon at least one silver halide emulsion layer containing (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof, and
• At least one of a cationic surface active agent and a betaine-type amphoteric surface active agent is disclosed.
• the present invention relates to a light-sensitive photographic material, and more particularly to a lightsensitive silver halide photographic material having a good antistatic property.
• a light-sensitive photographic material is generally prepared bycoatingone' or more silver halide emulsion layers and/or subsidiary layers on an electroinsulating support, for example, .cellulose'acetate or polyethylene terephthalate.
• the silver halide emulsion has also an electroinsulating property. Therefore, in case of preparing and using the photographic material, an electric charge is often accumulated on the material when the surfaces thereof contact each other. The thus accumulated electrostatic charge exposes the photographic material, even if it is not imagewise exposed, and causes comet like spots on development, which are socalled static marks. The static marks result in some damage to the photographic material which isnot, in many cases, used as a'commercially available product.
• electrostatic charges are also generated by friction between the machine parts and the film in changing the winding of film, especially in case of movie film, and by contact with or separation from the machine parts and/or fluorescence-sensitized paper during automatic photographing of X-ray film.
• contact with packing materials generates electrostatic charges.
• Themechanism of the electrification by friction and separation is considered to depend on the ionic state'of molecules of the material in contact. But it is difficult to forecast from structural chemistry'what material is electrified positively or negatively at present. But it is easily considered that said electrification can be prevented if the electric conductivity of the materialsurface can be increased and the electrostatic charges can be scattered in an extremely short time. Therefore, some ways to increase electric conductivity of supports of light-sensitive materials and coating surface layers of many kinds have been devised. It has been tried to use many kindsof moistureabsorbingmaterials and watersoluble inorganic salts; But there were few ways which satisfactorily prevented electrification. On the contrary, they adversely influence the photographic characteristics. Recently, however, high molecular weight materials and synthetic surface active agents have been studied for use as antistatic agents, and applications of effective materials are described in some patents.
• said antistatic agent brings forth favorable results in case of particular phptographic emulsions and gelatin compositions, but in other compositions, said antistatic agents are not only useless for preventing electrification, but also do damage to the photographic characteristics.
• an antistatic agent is often limited as above, applications of many antistatic agents of different types for photography are proposed.
• An object of the present invention is to provide a light-sensitive photographic material having a good antistatic property without giving rise to any harmful influence to the photographic characteristics.
• the present inventors have found that the above object can be attained by incorporating (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof, and (b) at least one of a cationic surface active agent and an amphoteric surface active agent into one or more coating layers. If the anionic polymer in the present invention is used singly as an antistatic agent, the effect is very weak as will be shown in the examples hereinafter. If the amount of the addition of said anionic polymer is increased,-little improvement is obtained, which is, however, not satisfactory for practical use.
• the cationic or amphoteric surface active agent in the present invention when used singly, gives not only small results but causes fog. The formation of fog is remarkable when the cationic surface active agent is used singly.
• the anionic polymer and the cationic surface active agentor amphoteric surface active agent are incorporated into or coated on one or more coating layers, better results in antistatic property of photographic material are surprisingly obtained without being accompanied by adverse influences to other photographic properties.
• an anionic polymer having a carboxyl group or an alkali metal salt thereof used in the present invention the following are used: polyacrylic I acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer, and maleic anhydride-vinyl butyl ether copolymer or an alkali metal salt thereof.
• cationic and amphoteric surface active agents the following are effective: N-octadecyl-N,N,N-trimethyl ammonium chloride, N-octadecyl-N,N,N-tris-(2-hydroxyethyl)ammonium chloride, 3-tetradecyloxy-Z-hydroxy propyl pyridinium chloride, N-dodecyl-N,N-dimethyl-acarboxylic acid betaine, and the like.
• the cationic surface active agent and/or amphoteric surface active agent may be used with the anionic polymer.
• the anionic polymer and one of the cationic and amphoteric surface active agents in combination are incorporated into a photographic coating composition or coating layer.
• the anionic polymer, and the cationic surface active agent and/or the amphoteric surface active agent may be dissolved individually in a solvent such as water or methyl alcohol and mixed with each other.
• the solvent may be one used in the photographic art.
• the two or more ingredients may be mixed simultaneously in the solvent.
• the solution is added to the pho-
• the weight ratio of the cationic surface active agent and/or the amphoteric surface active agent to the anionic polymer is not particularly limited, but is generally in the range of l/ 100 to l/l, and preferably 1/20 to H2. If the ratio of the cationic surface active agent or amphoteric surface active agent is too high, the mixture composition produces a white cloud in an aqueous solution.
• the complex composition of the anionic polymer and cationic surface active agent and/or amphoteric surface active agent used in the present invention may be applied to a coating layer, for example, a silver halide emulsion layer or a subsidiary layer, such as an antihalation layer, an intermediate layer or a protective or overcoat layer simultaneously or separately. Especially, when these are added to a surface layer, more effective results can be obtained.
• a coating layer for example, a silver halide emulsion layer or a subsidiary layer, such as an antihalation layer, an intermediate layer or a protective or overcoat layer simultaneously or separately.
• the antistatic composition used in the present invention is excellent as a wetting agent which is important in high speed coating.
• high molecular weight materials of the polyanionic type have little surface active action and weak characteristics as a wetting agent.
• the cationic surface active agent is apt to increase fog. According to the present invention, it was confirmed that fog is not generated when the cationic surface active agent is used with the anionic polymer.
• the antistatic composition used in the present invention is added at a ratio of 0.05 g 100 g, preferably 0.1 g 2.0 g per 1 kg of a silver halide emulsion or gelatin coating composition.
• a processed light-sensitive photographic material may be dipped in an aqueous solution of the antistatic composition.
• concentration of the aqueous solution should be in the range of 0.01 1.0 wt. percent.
• the light-sensitive emulsion used in the present in vention is prepared by dispersing a silver halide, such as silver chloride, silver bromide, silver iodide, silver bromochloride, silver iodobromide or silver chloroiodobromide, into an aqueous solution of a natural or synthetic high molecular weight material, as a protective colloid, such as gelatin, casein, polyvinyl alcohol, or polyacrylic acid.
• a natural or synthetic high molecular weight material such as gelatin, casein, polyvinyl alcohol, or polyacrylic acid.
• a protective colloid such as gelatin, casein, polyvinyl alcohol, or polyacrylic acid.
• the coating layer may contain a water-insoluble vinyl polymer.
• the light-sensitive photographic material of the present invention is used for black and white, which may include electronic recording material or for color. And the use of the light-sensitive materials are not restricted specifically.
• Compound 6 CH3 o rruocm oncmr swm H CH; B r" 8-dodecyloxy-2-hydroxypropyl-trimethylammonium bromide
• Compound 7 CHzCHr OH QMQoomgmmir-cmomon H HrCHrOH C1- 3-p-nonylphenyl-z-hydroxyprofilyhtisfi-hydroxyethyDammonium c o e [QaHnOCHaZHCHa-I H T- 3-tetradecyloxy-(2-hydroxypropyl)pyfldinium chloride
• Compound 8 cabana 9
• the Antistatic Agent 1 percent aqueous solution of a polymer having a side chain of a carboxyl group (Solution A). 1 percent aqueous solution of cationic surface active agent and- /or amphoteric surface active agent (Solution B). By mixing with stirring, Solution B is gradually added to Solution A until the ratio of Solution A Solution B becomes 2:] to 10:1.
• the obtained mixed solution is a transparent solution or turbid dispersion. preferably a transparent solution.
• the solution is a complex composition of an anionic polymer and a cationic surface active agent and/or an amphoteric surface active agent, which is nothing other than the antistatic agent of the present invention.
• the antistatic agent of the present invention that is, the mixed complex composition of the anionic polymer and the cationic surface active agent or the amphoteric surface ac- 5 tive agent, however, shows a surprisingly high degree of Warm Water (50C) 700 ml i NMehYLWaminoPhenYl Sumac 4 g antiitattcity. There also no appearance of static Sodium Sulfurous Anhydride 60 g mar gygf g I h d 10 g The quantity of electric charge generated on the surgg g ggmfi y me) 5 face of the sampledeviates greatly to the negative s de Adding Water.
• Antistatic Agent lll complex composition.
• anionic polymer Compound 8 shown above
• cationic surface active agent Compound 4 shown above
• Antistatic Agent IV complex composition.
• anionic pol mcr Compound B shown above
• cationic surface active agent Compound 4 shown above
• amphoteric surface active agent Compound 9 shown above
• the respective solutions 55 of the anionic polymer, the cationic surface active agent and the amphoteric surface active agent has no EXAMPLE 2
• the state of the solution, the degree of antistaticity and the photographic properties of the mixed complex composition were determined.
• the degree of antistaticity at various concentrations of the dipping process solution were also determined.
• the solution of the mixed complex composition is transparent and the photograph is also good.
• the degree of antistaticity was determined with good results when the mixing ratio is more than 3/1.
• the use of the antistatic agent of the present invention leads to no static marks, and thedegree of antistatic i ty is ver y h igh.
• the states of the coating layer are best, and the photographic characteristics are also good.
• EXAMPLE 4 5 ml of a 4 percent aqueous solution of saponin were added to 1 kg of a negative photographic high sensitivity emulsion containing 7 percent gelatin and 8 percent silver iodobromide. The processed emulsion was applied to a cellulose triacetate support which was undercoated in advance, and then was cooled and set. Further, solutions of a surface protection layer, obtained by adding ml of a 1 percent aqueous solution of Antistatic Agent I or II of the present invention prepared as in the process of Example 1 to 1 kg of a 2 percent aqueous solution of gelatin, were applied on the support, and were dried after being cooled and set. The state of the applied surface was extremely uniform and in good condition without blur and repellence. After being left at 20 percent RH for enough time, the film was passed through a high speed camera (Mitchell) and was examined as to the state of static marks. The results are shown in Table 5.
• EXAMPLE 6 A light-sensitive emulsion obtained by successive application of a high speed light-sensitive photographic emulsion containing a color coupler and an aqueous solution of gelatin without an antistatic agent as a surface protection layer was treated by a soaking processing in the aqueous solution of antistatic agent of the present invention prepared in the same way as in Example l.
• the photographic film samples processed by soaking respectively were left at 40 percent RH for enough time after drying. Then, the samples were passed between two rollers and led into a Faraday Gauge. The quantity of electric charge generated on the samples was measured by a vacuum voltmeter. F urther, a white rubber sheet was put on the surface of the photographic film sample.
• the white rubber sheet After being subjected to reg ular friction by rolling on the white rubber sheet under the conditions of 23C and 40 percent Rl-l, the white rubber sheet was removed. The obtained film was developed, and the degree of aritistaticity was estimated by the quantity of built-up static marks.
• said anionic polymer is polyacrylic acid, polymethacrylic acid, maleic anhydride-isobutylene copolymer or maleic anhydridevinylbutyl ether copolymer.
• R is an alkyl group having one to four carbon K
• said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyla-carboxylic acid betaine, N-tetradecyl-N,N-(2- hydroxyethyl)-acarboxylic acid betaine, 2-dodecyl-N- (2-hydroxyethyl)imidazolium-d-carbortylic acid betaine, N-dodecyloxy-methyl-N,N-diethyl-a-carboxylic acid betaine, N-tetradecyi-N,N-di(poly-oxyethylene)- a-carboxylic acid betaine, or N-3-dodecylaminopropyl- N,N-dimethyl-a-carboxylic acid betaine.
• a light-sensitive photographic material comprising a support having coated thereon one or more silver halide emulsion layers and at least one subsidiary layer, at least one of said layers having therein or thereon an antistatic composition consisting essentially of A. an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof having at most only a slight antistatic effect, and
• a cationic surface active agent selected from the group consisting of: N-octadecyl-N,N,N- tris(2-hydroxyethyl)ammonium chloride, N- octadecyl-N,N,N -tris(2-hydroxyethyl)ammonium bromide, N-tetradecyl-N,N,N-(Z-hydroxyethyl- )ammonium chloride, N-octadecyl-N,N,N- trimethylammonium chloride, vN-tetradecyl-N,N- dimethyl-N-benzyl-ammonium chloride, '3- dodecyloxy-2-hydroxypropyl-trimethylammonium bromide,v 3-p-nonylphnyl-Z-hydroxypropyl-tris( 2- hydroxy
• anionic polymer is polyacrylic acid, polymethacrylic acid maleic anhyl5 dride-isobutylene copolymer ormaleic anhydridevinyl-butyl ether copolymer.
• anionic polymer is selected from the group consisting of sodium alginate and a polymer having repeating units of the following formulas:
• said betaine-type amphoteric surface active agent is N-octadecyl-N,N-dimethyla-carboxylic acid betaine, N-tetradecyl-N,N-(2- hydroxyethyl)-a-carboxylic acid betaine, N- tetradecyloxy-(2-hydroxypropyl)-N,N-di(2- hydroxyethyl)-a-carboxylic acid betaine, 2-dodecyl-N- (2-hydr0xyethyl)imidazolium-a-carboxylic acid betaine, N-dodecyloxymethyl-N,N-diethyl-a-carboxylic acid betaine, N-tetradecyl-N,N-di(polyoxyethylene)-acarboxylic acid betaine, or N-3-dodecylamino-propy

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Applications Claiming Priority (1)

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Cited By (10)

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• 1970
  • 1970-09-04 JP JP45077644A patent/JPS4843807B1/ja active Pending
• 1971
  • 1971-08-31 CA CA121,739A patent/CA985554A/en not_active Expired
  • 1971-09-03 US US00177815A patent/US3811889A/en not_active Expired - Lifetime
  • 1971-09-03 GB GB4130771A patent/GB1357583A/en not_active Expired
  • 1971-09-03 FR FR7131943A patent/FR2107240A5/fr not_active Expired
  • 1971-09-03 BE BE772145A patent/BE772145A/xx not_active IP Right Cessation
  • 1971-09-03 DE DE2144286A patent/DE2144286C3/de not_active Expired

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