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
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
  • G03C1/49836—Additives
  • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
  • G03C1/49854—Dyes or precursors of dyes

Definitions

• ABSTRACT A sensitized heat developable photographic material having at least one photosensitive layer on a support, said layer containing the following components:
• the compounds (e) are sensitizers providing particularly excellent sensitizing effects.
• a photographic process using silver halides is the process which has heretofore been most widely practiced due to the excellent photographic properties thereof, such as high sensitivity and good gradation, over all other processes such as an electrophotographic process or a diazo-photographic process.
• silver halide photographic materials used in the process are developed with a developer after image-wise expo sure, and then they are subjected to several aftertreatments such as stopping, fixation, washing with water or stabilization so that the developed images do not discolor or deteriorate under normal illumination or so that the non-developed part (hereunder referred to as background”) is not blackened.
• a first method is the so-called one-bath development and fixation method as described in, for example, US. Pat. No. 2,875,048, British Pat. No. 954,453 and German Patv No. 1,163,142, where the two operations of development and fixation in the conventional silver halide photographic process are carried out in one bath.
• a second method is to try to Change the wet-type treatment which has been used in the up-to-date silver halide photographic process, to a dry-type treatment, for example, as described in German Pat. No. 1,174,159, British Pat. Nos. 943,476 and 951,644, etc.
• a third method is to try to use, as photosensitive elements, a combination of a main component of a long chain aliphatic carboxylic acid silver salt, such as silver behenate, or another silver salt such as silver saccharin or silver benzotriazole, and a catalytic amount of a silver halide, for. example, as described in Japanese P a tent Publication No. 22185/70, US. Pat. Nos. 3,152,904, 3,457.075, and 3,635,719, British Pat. No.
• This invention belongs to the third method. of the above described methods. 1
• the sensitizing effect of the above described known sensitizers is not very good, and in addition, Eosine, Erythrocin and uranine and defective in that, although they have a sensitizing effect, images of low Dmax and severe fog are produced therewith.
• an object of this invention is to provide heat developable photographic materials having at least one sensitized photosensitive layer.
• the present invention provides a sensitized heat developable photographic material having at least one photosensitive layer on a support, this layer containing the following components:
• b a catalytic amount of a photosensitive silver halide or a compound which reacts with the organic silver salt (a) to produce a photosensitive silver halide.
• Z, and Z each represents or Z represents OM or Ar Ar Ar Ar, and Ar, each represents an unsubstituted or substituted aryl group;
• X represents an anion
• Ar contains at least one substituent of $0 M and COOM; at least one of Ar and Ar and at least one of Ar and Ar each contains at least one substituent of $0 M and COOM;
• the formula (IV) contains at least one substituent of $0 M and COOM in the nuclei or in the substituent(s) on the nuclei;
• M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an NH, group and each nucleus of the formulae (I) through (IV) can further contain additional substituent(s) other than the above defined substituents and the radical can be in the form of an inner salt.
• aryl groups represented by Ar through Ar of the above described general formulae are unsubstituted or substituted phenyl groups and unsubstituted or substituted aand ,B-naphthyl groups.
• Preferred substituents are alkyl groups (e.g., methyl, ethyl, isopropyl, butyl, etc. groups), halogen atoms (e.g., Cl, Br, I atoms), hydroxy groups, $0 M groups, COOM groups,
• aryl groups e.g., phenyl, tolyl, etc., groups
• nitro e.g., benzyl, tolyl, etc., groups
• alkali metals represented by the above M are Li, Na, K, Rb, etc, and examples of alkaline earth metals are Ca, Mg, Ba, etc.
• An anion represented by X is, for example, a halogen ion, a sulfate ion, a nitrate ion, etc.
• Preferred compounds of the above described formulae (I) through (IV) are those of the following formulae I (1) through (IV)'.
• the alkyl group, alkoxy group, acyl group and alkylamino group represented by the above described symbols Ar through Ar and R through R have in genera] 1 to 8, preferably 1 to 4, carbon atoms.
• substituents of the above described aryl groups and the groups R through R are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethoxy 10 group, an acetyl group, a dimethylamino group, etc.
• Alkyl groups represented by R through R have in general 1 to 8, preferably 1 to 4, carbon atoms, and examples thereof are a methyl group, an ethyl group, an isopropyl group, a butyl group, etc.
• Suitable substituents of the alkyl group are, for example, a phenyl group or a sodium sulfophenyl group.
• Suitable substituents of the aryl groups represented by R through R are, for example, a phenyl group, a sodium sulfophenyl group, and a tolyl group.
• the amount of the component (e) which is added is suitably about 10 to 10 mole per 1 mole of organic silver salt. This amount can be varied, depending upon the kind of the compound used, the kind of organic silver salt, the kind of catalytic amount of silver halide, the kind of reducing agent, the treating temperature, etc. If the amount of the component (e) exceeds the above described range, the degree of coloration of light sensitive layer increases very often, which is disadvantageous in some uses. However, when the material is applied to such uses where coloration is no problem or when compounds of a less degree of coloration are used as the component (e), the amount of the component (e) used can exceed this range.
• Suitable organic silver salt, component (a), which can be used in the present invention include, for example, silver salts of organic compounds containing imino, mercapto or carboxyl groups.
• organic silver salts are silver benzotriazole, silver saccharin, silver phthaladinone, the silver salt of 3-mercapto-4-phenyl- 1,2,4-triazole, the silver salt of 4-hydroxy-6-methyll,3,3a,7-tetrazaindene, the silver salt of 2-(S-ethylthioglycolamido)-benzothiazole, silver caprate, silver laurate, silver myristate, silver palmitate, silver stearate, silver behenate, silver adipate, silver sebacate, etc., as disclosed in US. Pat. Nos. 3,457,075 and 3,635,719.
• silver salts of organic carboxylic acids and silver benzotriazole are used.
• the component (b) of the present invention is (l) a compound which reacts with the silver salt of the component (a) to form asilver halide, or is (2) a silver halide.
• Representative examples of the former (l) are inorganic compounds of the formula MXn; where M represents a hydrogen atom, an ammonium group or a metal atom (such as a strontium, cadmium, zinc, tin, chromium, sodium, barium, iron, cesium, lanthanum, copper, calcium, nickel, magnesium, potassium, aluminum, antimony, gold, cobalt, mercury, lead, beryllium, lithium, manganese, gallium, indium, rhodium, ruthenium, palladium, iridium, platinum, thallium, bismuth, etc.
• X represents a halogen atom (such as a chlorine, bromine, or iodine atom), and n is 1 when M is a hydrogen atom or an ammonium group, but n is the valence of the metal, when M is a metal atom.
• organic halogen compounds such as triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo-2-methylpropane, 2-bromobutyric acid, 2- bromoethanol, benzophenone dichloride, iodoform, bromoform, carbon tetrachloride, etc. are also included in the scope of the compound (1).
• the silver halide of the latter (2) includes silver chloride, silver bromide, silver iodobromide, silver iodobromochloride, silver bromochloride and silver iodide.
• the photosensitive silver halide can be in any form of crude particles and fine particles, and in particular, an emulsion of extremely fine particles is especially useful.
• a suitable particle size ranges from about 0.003 ,u to 0.2 ;1., preferably 0.006 [.L to 0.1 u.
• An emulsion containing the photosensitive silver halide can be prepared according to any conventional methods known in the field of photography. For example, there may be mentioned emulsions by the singlejet process, emulsions by the double-jet process, for example Lippmann emulsions, ammonia process emulsions, thiocyanate or thioether digested emulsions; for exam Nos.
• the compound of the above described component (b) can be used alone or in the form of a mixture of two or more compounds.
• the amount of the component (b) which can be added is suitably in the range of about 0.001 to 0.5 mole, preferably 0.01 to 0.3 mole, per 1 mole of the organic silver salt. If the amount of the component (b) is less than this range, the sensitivity of the material is reduced, but on the contrary, if the amount thereof exceeds this range, the existence of too large an amount of this component (b) causes a disadvantageous phenomenon in that when the material is left under room light after the heat development thereof, the non-image part gradually becomes blackened, resulting in a decrease in the contrast between the non-image part and other image part.
• the reducing agent of the component ('0) of the present invention must be one suitable for the reduction of the organic silver salt to form silver images, when heated in the presence of the exposed silver halide as a catalyst.
• a suitable reducing agent is determined in accordance with the combination of organic silver salt used, and for example, substituted phenols, substituted or unsubstituted bisphenols, substituted or unsubstituted naphthols, dior poly-hydroxy benzenes, dior polyhydroxy napthalenes, hydroquinone monoethers, ascorbic acid or derivatives thereof, 3-pyrazolidones, pyrazoI-S-ones, reducing saccharides, kojic acid, hinokitiol, etc. are suitable for use.
• I-Iydroquinone chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroqui none, hydroquinone-monosulfonate, toctylhydroquinone, t-butylhydroquinone 2 ,S-dimethylhydroquinone, 2,6-dimethylhydroquinone methoxyhydroquinone, ethoxyhydroquinone, pmethoxyphenol, p-ethoxyphenol, hy-
• droquinonemonobenzylether catechol, pyrogallol, resorcin, p-aminophenol, o-aminophenol, N-methyl-paminophenol, 2-methoxy-4-aminophenol, 2,4- diaminophenol, 2-,8-hydroxyethyI-4-aminophenol, p-tbutylphenol, p-t-amylphenol, p-cresol, 2,6-di-t-butyl-pcresol, p-acetophenol, p-phenylphenol, ophenylphenol, 1,4-dimethoxyphenol, 3,4-xylenol, 2,4- xylenol, 2,6-dimethoxyphenol, l-amino-2-naphthol-6- sodium sulfonate, l-naphthylamine-7-sulfonic acid, 1- hydroxy-4-methoxy-naphthalene, l-
• binaphthyl bis(2-hydroxy-l-naphthyl)-methane, bisphenol A, l,l-bis-(2-hydroxy-3,S-dimethylphenyl)- 3,5,5-trimethylhexane, 2,4,4-trimethylpenthyl-bis-(2- hydroxy-3 ,S-dimethylphenyl)methane, bis( 2-hydroxy- 3-t-butyl-5-rnethylphenyl)-methane, bis(2-hydroxy- 3 ,S-di-t-butylphenyl )methane, 4,4 '-m'ethlenebis( 3- methyl-5-t-butylphenol), 4,4-methylenebis(2,6-di-tbutylphenol), '2,2'-methylenebis( 2-t-butyl-4- ethylphenol), 2,6-dimethylenebis(2-hydroxy-3-t-butyl- S-methyl-benzyl )-4-methylphenol, 3 ,
• a suitable reducing agent is selected in combination with the organic silver salt used.
• higher" fatty acid silver salts such as silver behenate are relatively difficultly reduced, and therefore relatively strong reducing agents, for example, bisphenols such as 4,4'-methylenebis(3-methyl-5-t-butylphenol) are suitable therefor.
• relatively weak reducing agents for example, substituted phenols such as p-phenylphenol, are suitable for silver salts which are relatively easily reduced, such as silver laurate.
• strong reducing agents such as ascorbic acid type reducing agents are suitable for silver salts which are extremely difficultly reduced, such as silver benzotriazole.
• the amount of reducing agent to be used in this invention as described above can be varied depending upon the organic silver salt used and the kind of reducing agent used, and therefore, the amount cannot be set forth unequivocally, but in general, a suitable amount ranges from about 0.1 to 5 moles, preferably 0.3 to 2 moles, per 1 mole of organic silver salt.
• an appropriate reducing agent can be selected and used in combination with a specific organic silver salt, and therefore it is unnecessary to specifically define the organic silver salt and the reducing agent to be used.
• the components (a), (b), (c) and (e) are preferably dispersed in a binder and applied on a support.
• all of the components (a) (b) (c) (e) can be together dispersed in a binder and applied on a support as one layer, or alternatively, these components (a) (b) (c) (e) can be divided into groups thereof and dispersed separately in the binder and then the respective dispersions are applied on a support as individual layers.
• the binder component (d) which can be used, any and every conventional binder which has heretofore been used in this field. In general, hydrophobic binders are preferred, but hydrophilic binders can also be used.
• These binders are preferably transparent or semi-transparent, and suitable examples are, for example, natural substances, such as gelatin, gelatin derivatives or mixtures thereof with latex type vinyl polymers, cellulose derivatives, and synthetic polymer substances, etc.
• binders are as follows: gelatin, gelatin phthalide, polyacrylamide, polyvi nyl butyral, cellulose acetate-butyrate, cellulose acetate-propionate, polymethylmethacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadi one-styrene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-malaic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, cellulose acetatephthalate, etc.
• binders can optionally be used in admixture.
• the amount of the binder is suitably in a ratio (by weight) of 4:1 to 1:4, preferably 3:1 to 1:3, on the basis of the organic silver salt. If the component (a) or (c) is a high ,molecular substance which has the function of a binder, the use of a binder can be omitted.
• supports are, for example, cellulose nitrate films, cellulose ester films, poly(vinylacetal) films, polystyrene films, poly(ethylene-terephthalate) films, polycarbonate films, and glass, paper, metaL'etc. supports.
• An antistatic layer or a conductive layer can be provided in the heat developable photographic materials of this invention.
• an ,anti-halation substance and an anti-halation dye can also be incorporated therein.
• the heat developable photographic materials of this invention can optionally contain matting agents, such as starch, titanium dioxide, zinc oxide and silica.
• matting agents such as starch, titanium dioxide, zinc oxide and silica.
• fluorescent brightening agents such as stilbine, triazine, oxazole and coumarin type fluorescent brightening-agents can also be contained therein.
• the heat developable photosensitive layer of this invention can be applied on a support using various coating methods, for example, using a dip method, an airknife method, a curtain coating method as well as an extrusion coating method with a hopper as describedin U.S. Pat. No. 2,681,294. If desired, two or more layers can simultaneously be applied.
• a suitable coating amount ranges from about 0.1 to 3 g'(as silver) per m preferably 0.3 to 2 g (as silver) per m of the support.
• optical sensitizing dyes which have heretofore been used for silver halide emulsions can advantageously be used in the heat developable photographic materials of the present invention for imparting additional sensitivity thereto.
• cyanine dyes and merocyanine dyes as the optical sensitizing dye as disclosed in US. Pat. Nos. 3,457,075 and 3,761,279 can be used in the present invention.
• Suitable merocyanine dyes are as follows:
• sensitizing dyes are preferably added to photographic materials in the form of a solution or dispersion dissolved or dispersed in an organic solvent.
• the use of the optical sensitizing dye together with the sensitizer component (e) of this invention causes an increase in the sensitivity of the resulting heat developable photographic material.
• the content of the optical sensitizing dye in the photographic material of this invention is about to 10 mole per 1 mole of the organic silver salt component (a). If the sensitizer of the present invention is effective also as optical sensitizer, the optical sensitizing dye need not necessarily be used.
• an over-coating polymer. layer can optionally be provided on thephotosensitive layer of the heat developable photographic material of this invention, for the purpose of increasing the transparency of the photosensitive layer, increasing the density of the formed image and improving the storability of the material which exists originally (that is, the ability to maintain the original photographic properties, or those immediately after the preparation of the photographic material, even after the storage thereof).
• the thickness of this over-coating polymer layer film is suitably l to 20 1.1..
• Suitable polymers are, for example, as follows: polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polystyrene, polymethylmethacrylate, polyurethane rubber, xylene resin, benzylcellulose, ethyl cellulose, cellulose acetate-butyrate, cellulose acetate, polyvinylidene chloride, chlorinated polypropylene, polyvinyl pyrrolidone, cellulose propionate, polyvinyl formal, cellulose acetate-phthalate, polycarbonate, cellulose acetatepropionate, etc.
• the above described heat developable photographic materials can be developed merely by heating the same, after imagewise exposure to a light source such as a xenon lamp, tungsten lamp, mercury lamp, etc.
• the temperature used in the heating is suitably in the range of 100 to 160C, more preferably 1 10 to 140C. A higher temperature or a lower temperature can be selected within the above described range, by prolonging or reducing the heating time.
• the time for development is in general about 1 to 60 seconds.
• the photographic material can be brought into contact with a simple hot plate or the like, or can be brought into contact with a heated drum, or as the case may be, can also be passed through a heated space.
• high frequency induction heating or laser beam heating can also be utilized.
• EXAMPLE 1 3.4 g of behenic acid were dissolved in 100 ml of toluene at 60C and the resulting solution was adjusted to 60C. While stirring with a stirrer, 100 ml of a diluted nitric acid aqueous solution (pH 2.0 at 25C) were added and mixed therewith. The resulting mixture solution was kept at 60C, and while continuously stirring with a stirrer, 100 ml of an aqueous solution containing silver-ammonium complex were added thereto.
• the complex solution was prepared as follows: Aqueous ammonia was added to about ml of an aqueous solution containing 1.7 g of silver nitrate to form a silver ammonium complex, and water was added thereto to make a total of ml of aqueous solution.) Thus, a dispersion containing fine crystals of silver behenate was obtained. This dispersion was left at room temperature (about 20 to 30C) for 20 minutes, whereby an aqueous layer and a toluene layer separated from each other.
• the aqueous layer was first removed, and 400 ml of water were added anew to the remaining toluene layer, which was then washed therewith according to a decantation method. This operation was repeated three times, and then 400 ml of toluene were added to separate the silver behenate by centrifuging. 4 g of silver behenate were obtained in the form of spindle-shaped crystals (long side: about 1 ;1.; short side: about 0.05 ,u).
• the aqueous phase was first removed, and 400 ml of water were added anew to the remaining phase to wash the same by a decantation method. This operation was repeated three times, and then 400 ml of methanol were added to separate silver benzotriazole by centrifuging. Thus, 8 g of silver benzotriazole were obtained.
• the particles of the silver benzotriazole were of a nearly spherical form, having a particle size of about 1 p. (diameter) 2.5 g of the thus formed silver benzotriazole were added to 40 ml of an isopropyl alcohol solution containing 4 g of polyvinyl butyral and sub- 20 jected to ball-milling for 4 hours to disperse the same,
• a silver salt-polymer dispersion was prepared.
• To 40 ml of the resulting silver salt-polymer dispersion were added the following components to form a heat developable photographic composition, which was then applied on a polyethylene terephthalate film support in an amount of 1.2 g (coated silver content)m (support) to produce a heat developing-out photographic material (A).
• EXAMPLE 9 The resulting photographic material was exposed to light of 200,000 CMS and heated at 120C for 17 seconds to obtain an image (Dmax 0.8; fog 0.4).
• a sensitized heat developable photographic mate- Compound (6) also is effective as a sensitizer, similar rial compriing a Support a thereon f least one to Compound (5) of Example 4O photographic layer containing the following componen s:
• the resulting photographic material was exposed to c. a reducing agent, light of 200,000 CMS and heated at C for 17 secd. a binder, n onds to obtain an image (Dmax 1.6; fog 0.2).
• a reducing agent light of 200,000 CMS and heated at C for 17 secd.
• a binder n onds to obtain an image (Dmax 1.6; fog 0.2).
• Z2 O /Zl Ar Ar 27 a 7 Oi :N N Ar N N and wherein Z and 2;, each represents 0 or Z represents OM or (III) Ar, contains at least one of $0 M and COOM as a substituent; at least one of Ar and Ar;,, and at least one of Ar, and Ar each contains at least one of $0 M and COOM as a substituent;
• the formula (IV) contains at least one of $0 M and COOM as a substituent in the nuclei thereof or in the substituent(s) on the nuclei thereof;
• M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an NH, group, and each nucleus of the formulae (I) through (IV) can further contain additional substituent(s) other than the above defined substituents, and the radical Ar Ar Ar AL, and Ar each represents an unsub- R2 stituted or substituted aryl group;
• X represents an anion; and
• R represents a hydrogen atom, an alkyl group or a COOM group
• R R R and R each represents a member selected from the group consisting of a hydrogen atom, an amino group, an alkylamino group, an arylamino group, an alkyl group, a halogen atom, a hydroxyl group, an $0 M group and a COOM group, and at least one of R through R is a radical having a $0 M group and/or a COOM group, and Z Z Z Ar Ar Ar;,, Ar,,, Ar and M are as defined in claim 1.
• aryl group is substituted with an alkyl group, a halogen atom, a hydroxy group, an $0 M group, a COOM group, an aryl group, a nitro group, an amino group, an acyl group or an alkoxy group.
• R through R each represents an alkyl group having 1 to 8 carbon atoms.
• the photographic material as claimed in claim 1, wherein said component (e') is selected from the group consisting of the following compounds 13.

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• Chemical & Material Sciences (AREA)
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• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (13)

Citations (7)

• 1973
  • 1973-01-31 JP JP48012587A patent/JPS49102328A/ja active Pending
• 1974
  • 1974-01-31 US US438320*A patent/US3909271A/en not_active Expired - Lifetime
  • 1974-01-31 DE DE2404591A patent/DE2404591A1/de active Pending
  • 1974-01-31 GB GB466874A patent/GB1444447A/en not_active Expired

Patent Citations (7)

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