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
  • G03C1/005—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
  • G03C1/061—Hydrazine compounds
• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

• This invention relates to high-contrast silver halide photographic materials for use in the ield of graphic arts and to a process for reducing black spots ("pepper") in exposed photographic materials of the foregoing type.
• a lith-type developer contains, as a developing agent, hydroquinone and, as a preservative, a sulfite usually in the form of an adduct with formaldehyde at a concentration of not more than 0.1 mol/l, thereby preventing deterioration of the infectious development ability of the developing agent.
• the lith developer has a serious disadvantage in that it is very susceptible to air oxidation and cannot withstand use for a period of time exceeding 3 days. Increasing the sulfite content of the developer improves its useful life but deteriorates its high-contrast development characteristics.
• hydrazine or hydrazide derivatives as described for example in U.S. Patent Nos. 4,224,401, 4,168,977, 4,166,742, 4,311,781, 4,272,606, 4,211,857 and 4,243,739 all incorporated by reference in their entirety.
• Use of hydrazine or hydrazide compounds in image formation systems provides super-high contrast and high sen ⁇ sitivity, and also ensures greatly improved stability of the developer against air oxidation as compared to the conventional lith developer because hydrazine (and/or derivative) presence in the film or in the developer permits use of a higher sulfite ion concentration in the developer.
• U.S. Patent No. 4,851,321 issued 7/25/889 to Takag discloses hydrazide-containing, low-sensitivity, high-contras photographic materials in which sensitivity (and pepper) ha been lowered by use of a development restrainer. Suc restrainers are said to ordinarily also lower contrast. According to this patent, contrast is not lowered because th photographic material also contains a contrast-enhancing com pound.
• the hydrazides specifically contemplated are for y phenyl hydrazides with various ⁇ ubstituents and other function alities appended to the phenyl ring.
• the restrainers con templated are compounds having positive polarographic half-wave potential (Col. 24:57-65) an are represented by formulas disclosed at Col. 25-26. Specifi restrainer examples are disclosed at Col. 27-31 and include
• Takagi photographic materials must contain a contrast-enhancing compound and are intended to have low sen ⁇ sitivity. Thus, Takagi does not provide a solution to the pepper problem of a high-sensitivity, high-contrast photographic material.
• U.S. Patent No. 4,737,442 issued 4/12/88 to Yogihara discloses photographic materials containing a formyl phenyl hydrazide (or certain derivatives) as well as a restrainer of the type C A -B wherein C A is a blocking group capable of releasing during the development process a development restrainer or a precursor thereof regardless of the degree of exposure of the photographic material, and D is a restrainer or a precursor of a restrainer.
• restrainers include: 1-(2,4-dihydroxyphenyl)-5-mercaptotetrazole, 4-phenyl-5-methyl-3-mercaptotetrazole, 5-nitro-2-mercaptobenz.imidazole,
• the purpose of adding the restrainer is to avoid pepper.
• the amount of restrainer ranges between about 5.4x10" ⁇ to 1 10"! mole/mole Ag.
• the restrainers disclosed in the '442 patent are of the so-called “stabilizer” type which form strong silver salts and not of the "antifoggant” type. Stabilizer- type restrainers would decrease speed markedly more than antifoggant-type compounds when used with hydrazides, notably the hydrazides of the Formula I, below.
• U.S. Patent No. 4,839,259 issued 6/13/89 to Sasaoka discloses hydrazide-containing photographic materials that are said to have simultaneously high sensitivity (gamma) and are free (or substantially free) of black spots or pepper.
• the pepper-free quality according to the patent is imparted by the use of dual developing agents in combination with a sulfite preservative and a pH in the range of 10.5-12.3.
• Optional ingredients include sensitizing dyes to improve emulsion sensitivity and/or various conventional antifoggant/stabilizers such as benzothiazole ⁇ , nitrobenzothiazoles, benzotriazoles, etc. (Col. 10:26-46).
• the antifoggant ⁇ can be added to the developer.
• U.S. Patent No. 4,789,618 is ⁇ ued 12/06/88 to Inoue et al di ⁇ clo ⁇ e ⁇ "black-spot" prone hydrazide-containing photographic material ⁇ in which black spot ⁇ are ⁇ aid to be reduced or prevented by incorporation of an oxidizing agent (at 10 ⁇ 5 _ i mole/mole Ag) such a ⁇ N-bromo ⁇ uccinimide, hydrogen peroxide and its addition products, peroxy acid salt ⁇ , peroxy complexe ⁇ , ozone, etc.
• Conventional antifoggant ⁇ tabilizers such as azoles, mercaptobenzothiazoles, nitrobenzotriazoles, etc. are listed as optional ingredients (Col. 11:4-24) for their conventional antifoggant/stabilizer purpose, as i Sa ⁇ aoka.
• European Application No. A2 306,833 of Fuji Photo Fil published on 3/15/89 discloses photographic materials of hig contrast and sensitivity containing a hydrazine derivative an two additional compounds; a photographic restrainer bearing a late-absorbin group P R (Time) t - LA(1) and a tetrazole derivative. Antifog- gants/ ⁇ tabilizers are also added. Pepper reduction i ⁇ at ⁇ tributable to the electron-withdrawal propertie ⁇ of the nitro group.
• European Application No. A ⁇ 286,840 discloses allegedly reduced-pepper photographic material ⁇ compri ⁇ ing a hydrazine compound of the Formula:
• an object of thi ⁇ invention is to provide a highly sensitive high-contrast silver halide photographic material which can be developed with a stable developer in the presence (in the photographic material or in the developer) of a hydrazine or hydrazide contrast-enhancing compound to obtain a super-high contrast image with substantial reduction or elimination of black spots.
• Another object of this invention is to provide a method for reducing or eliminating black spots upon development of a silver halide photographic material which contains, or which is developed in a developer containing, a hydrazine or hydrazide compound and which yields a super-high contrast negative image.
• the above objects can be accomplished by the incorpora ⁇ tion in a photographic material or in its developer of a compound within Formula II below in an amount effective to reduce or eliminate black spot formation but not capable of ⁇ ub ⁇ tantially affecting ⁇ ensitivity or contra ⁇ t (i.e. not reduce ⁇ en ⁇ itivity more than about 10% or ⁇ peed more than about a quarterstop or decrease the value of gamma below 10) .
• this compound is made in a negative-working surface-latent image sy ⁇ tem (but the pre ⁇ ent invention is not limited to such systems) .
• the Formula II compound is preferab ⁇ ly incorporated in the photographic material, in at least one of the emulsion layer or in another (e.g. a hydrophilic colloid) layer coated on the photographic material support.
• the photographic material comprise ⁇ the following: a ⁇ upport having provided thereon at lea ⁇ t one ⁇ ilver halide emulsion layer, wherein said emulsion layer or another layer of the ⁇ ilver halide photographic material provided on the support contain ⁇ at lea ⁇ t one compound repre ⁇ ented by the Formula I and al ⁇ o contain ⁇ at lea ⁇ t one compound of the Formula II.
• the pre ⁇ ent invention i ⁇ not limited to hydrazide deriva ⁇ tives of Formula I not to hydrazines or hydrazide ⁇ pre ⁇ ent in the film.
• Formyl phenyl hydrazide could, for example, be u ⁇ ed in the developer with a compound of Formula II in the film in accordance with the pre ⁇ ent invention.
• a super-high contra ⁇ t negative image i ⁇ formed by a process comprising i agewise exposing a hydrazine- o hydrazide- containing photographic material (preferably material containing a Formula I compound) to light and develop ing the exposed material with a developer containing dihydroxybenzene derivative (as a developing agent), a ben zotriazole antifoggant, a sulfite pre ⁇ ervative and an effectiv amount of an amine compound.
• a hydrazine- o hydrazide- containing photographic material preferably material containing a Formula I compound
• Ri and R 2 are independently hydrogen and substituted o unsubstituted (i) alkyl, having up to 18 carbons; (ii) cycloalkyl; (iii) phenyl or naphthyl or (iv) aryl sulfonyl.
• R3 is hydrogen, phenyl or benzyl, the latter tw substituted or unsub ⁇ tituted, but if neither ⁇ nor R 2 i ⁇ hydrogen then R3 is hydrogen.
• R 5 , Rg, and R7 are independently hydrogen, ⁇ ub ⁇ titute or un ⁇ ubstituted (i) alkyl having up to 12 carbon ⁇ ; (ii) cycloalkyl; (iii) phenyl or naphthyl.
• -L and R3 or R ⁇ and R 2 can be linked to form a heterocyclic ring ⁇ y ⁇ tem with the ring containing three to ten ato ⁇ .
• R 5 and Rg can be linked to form a heterocyclic ring ⁇ y ⁇ tem with the ring containing 3-10 atom ⁇ .
• Suitable ⁇ ub ⁇ tituent ⁇ include without limitation halogen, hydroxy, alkoxy, amino, alkylamino, aryl, arylamino, cyano, acylamino. The ⁇ ubstituents themselves may be further sub ⁇ tituted.
• Compound ⁇ of Formula II include compounds containing one moiety selected from the group consisting of ben- zothiazoles, quinolines, indolenine benzotriazoles, and rhodanines having one or more nitro groups attached to a benzene nucleus, which is either a part of the heterocyclic compound or is attached to it through a doubly-bonded carbon- to-carbon chain.
• the quaternary ⁇ alts such as ammonium, triethylamine, piperidine and alkali metal salts, preferably methanol- ⁇ oluble
• Compounds of Formula II are defined as follows:
• R ⁇ is selected from the group con ⁇ i ⁇ ting of benzothiazole, quinoline, indolenine, nitrobenzothiazole, benzotriazole and rhodanine, each of which may be un ⁇ ub ⁇ tituted or ⁇ ub ⁇ tituted by, e.g. halogen, hydroxy, alkoxy, aryl, amino, arylamine, ⁇ ulfuric acid, carboxylic acid, phenyl, etc., or fused to the nitroben ⁇ zene nucleus.
• ⁇ is substituted by hydrogen or carboxy and m is 1.
• substituent ⁇ in R j are preferably in the 3-po ⁇ ition if the ring S is 1 and numbering is clock ⁇ wise.
• DETAILED DESCRIPTION OF THE INVENTION Several of the compounds repre ⁇ ented by Formula II according to the pre ⁇ ent invention were previou ⁇ ly known and u ⁇ ed as photographic stabilizer ⁇ /antifoggant ⁇ (in amount ⁇ generally ranging between about 10 ** ⁇ and about 1 mole ⁇ /mole Ag) to improve the speed constancy of photographic emulsions.
• the compound of the Formula I or another contra ⁇ t enhancing hydrazide and the compound of the Formula II ar preferably incorporated into the same layer, but may al ⁇ o b incorporated into different layers or the compound of Formula I can be used in the developing solution.
• R ⁇ preferably represents a hydrogen atom, an unsubstituted or ⁇ ub ⁇ titute alkyl group ( ⁇ uitable preferred ⁇ ubstituents include without limitation alkyl, cyano, halo, or alkoxy), a substituted or unsubstituted cycloalkyl group or a substituted or unsub ⁇ stituted arylsulfonyl group.
• the total number of carbon atoms in ⁇ can be up to 18 but preferably, should be les ⁇ than 12.
• Mo ⁇ t preferably, R ⁇ is un ⁇ ub ⁇ tituted alkyl or cycloalkyl containing 1-6 carbon atom ⁇ .
• R is independently chosen from the group representing R ⁇ _; preferably, however, the total number of carbon atoms between Rj and R 2 ⁇ hould not exceed 12. 3 preferably repre ⁇ ent ⁇ a hydrogen atom, an unsub- ⁇ tituted or ⁇ ub ⁇ tituted benzyl group (suitable preferred sub- ⁇ tituent ⁇ include without limitation alkoxy, halo or alkyl).
• R3 must be hydrogen. Most preferably, R3 i ⁇ hydrogen.
• R4 preferably repre ⁇ ents either an unsubstituted or substituted divalent aromatic group.
• Suitable sub ⁇ tituent ⁇ include without limitation alkyl, alkoxy, halo, or acylamino functionalitie ⁇ .
• R4 is phenylene with the thioamide or amido group in the ortho- or para-posi- tion relative to the hydrazido group.
• any suitable ⁇ ub ⁇ tituent a ⁇ de ⁇ cribed herein be attached at a remaining, unoccupied ortho- or para-po ⁇ ition relative to the hydrazine group.
• R5 preferably repre ⁇ ent ⁇ either a hydrogen atom, an un ⁇ ub ⁇ tituted or sub ⁇ tituted alkyl group (suitable preferred ⁇ ub ⁇ tituent ⁇ include hydroxy, halo, alkoxy, alkylamino, acylamino, amino and aryl ⁇ uch as phenyl), a cycloalkyl group, an unsub ⁇ tituted or ⁇ ub ⁇ tituted aryl group ( ⁇ uitable preferred substituents include alkyl, cyano, halo or alkoxy) or an unsub ⁇ stituted or sub ⁇ tituted amine.
• the total number of carbon atoms in R5 ⁇ hould be up to 12.
• R5 ⁇ alkyl, cycloalkyl, dialkylaminoalkyl or acylaminoalkyl each -containing 1-6 carbon atoms.
• Rg and R7 are independently chosen from the group representing R5; preferably, however, the total number of carbon atoms between R5 and Rg ⁇ hould not exceed 12.
• R5 and Rg preferably do not contain amino functionalitie ⁇ that are directly linked to the nitrogen atom of X.
• R5 and Rg can be linked to form a heterocyclic ring sy ⁇ tem with the ring containing 3-10 atom ⁇ .
• R ⁇ and R3 or R ⁇ and R 2 can be linked to form a heterocyclic ring ⁇ y ⁇ tem with the ring containing 3-10 atom ⁇ .
• the preferred compound ⁇ repre ⁇ ented by the general Formula I are tho ⁇ e repre ⁇ ented by the general Formula (IA) .
• th present invention broadly involves the .use or incorporation o a Formula XI compound, in an amount sufficient to reduce o eliminate pepper, in any high-contrast image forming syste (photographic material and/or developer ⁇ containing a contrast enhancing amount of a hydrazine or hydrazide compound.
• amounts from about 10 -m-B to about 5x10 -3 moles/mole Ag and preferably from about 10 -5 to about 5x10-4 mole/mole Ag are u ⁇ ed.
• the electron-accept ⁇ ing compounds are compounds having one or more nitro groups attached to a benzene nucleus which is either a part of the heterocyclic compound or i ⁇ attached to it through a doubly bonded carbon-to-carbon chain as described in US Patent 2,541,472 (incorporated by reference) .
• Specific but non-limiting examples of Formula II according to our present invention are shown below.
• suitable amounts of the Formula II compound are within the range of about 10- ⁇ to about 10 " ⁇ moles/mole Ag, with about l l0 ⁇ -to about x10" ⁇ being preferred. This is different from the stabilizer effective amounts, which as stated above, are much
• the pepper-reducing amount ⁇ of the Formula II compounds ⁇ hould not be higher than about 10" ⁇ mole ⁇ /mole Ag in order to avoid de ⁇ en ⁇ itization and lo ⁇ of contra ⁇ t, the latter due to interference with the contra ⁇ t- enhancing function of the (e.g. Formula I) hydrazide.
• the compounds of Formula I and II can be incorporated in the photographic element by well-known techniques u ⁇ ed for the incorporation of additives to photographic emulsion ⁇ or element ⁇ .
• the compounds are typically dis ⁇ olved in a ⁇ olvent ⁇ elected from organic solvents compatible with water, such a ⁇ alcohol ⁇ , glycol ⁇ , ketones, esters, amides, and the like which exert no adverse influences on photographic characteristic ⁇ , and the ⁇ olution i ⁇ added to the photographic element.
• Preferred ⁇ olvents include dimethylformamide (DMF), dimethylsulfoxide (DMSO) and N-methyl-2-pyrrolidinone (NMP).
• the compound of Formula I and II can be added to an emulsion in a disper ⁇ ion by known method ⁇ u ⁇ ed when water-in ⁇ oluble ( ⁇ o-called "oil ⁇ oluble”) coupler ⁇ are added to emulsions.
• Preferred oils include N-butyl acetanilide, N-methyl formanilide and N,N-diethyl-m-toluamide. These oils are commer ⁇ cially available. Ultrasound can be employed to dis ⁇ olve (more preci ⁇ ely finely di ⁇ per ⁇ e) marginally ⁇ oluble ethanedioic acid hydrazide ⁇ .
• solutions or dispersions can be added to the photographic emulsion at any stage ⁇ ub ⁇ equent to the emul ⁇ ion precipitation and wa ⁇ hing ⁇ tep ⁇ .
• the ⁇ e agent ⁇ ⁇ hould be added during chemical ripening or ju ⁇ t prior to coating.
• proteins such as a ⁇ albumin or ca ⁇ ein
• Suitable gelatin deriva ⁇ tives are prepared by reacting gelatin with various * compounds ⁇ uch as acid halides, acid anhydrides, isocyanate ⁇ , bromoacetic acid, alkane ⁇ ulfone ⁇ , vinyl ⁇ ulfonamide ⁇ , maleinimide compound ⁇ , polyalkylene oxides or epoxy compounds and, preferably, with phthalic anhydride or succinic anhydride. Specific examples of these gelatin derivatives are described in e.g., U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846 and 1,005,784, all incorporated by reference.
• Example ⁇ of ⁇ uitable gelatin graft polymer ⁇ include tho ⁇ e prepared by grafting a homopolymer or a copolymer of a vinylic monomer ⁇ uch a ⁇ acrylic acid, methacrylic acid, the derivatives thereof (such as the esters or the amides thereof), acrylonitrile or styrene to gelatin.
• graft polymer ⁇ prepared from polymers which are compatible with gelatin to some degree, such as those of acrylic acid, methacrylamide or a hydroxyalkyl methacrylate which are preferred.
• Example ⁇ of those polymers are described in, e.g., U.S. Patent No ⁇ . 2,763,625, 2,831,767 and 2,956,884.
• Typical ⁇ ynthetic hydrophilic high molecular weight materials are described in, e.g., German Patent Application (OLS) 2,312,708, U.S. Patent No ⁇ . 3,620,751 and 3,879,205, all incorporated by reference.
• the photographic emul ⁇ ion u ⁇ ed in thi ⁇ invention can be prepared u ⁇ ing the well-known method ⁇ described in, e.g., P.
• the ⁇ e method ⁇ include the acid method, the neutral method, the ammonia method and others.
• a ⁇ oluble ⁇ ilver ⁇ alt can be reacted with a soluble halogen ⁇ alt using any of the ⁇ ingle jet method, the double jet method and a combination thereof.
• the well-known method of forming grain ⁇ in " the presence of an exces ⁇ of ⁇ ilver ion ⁇ can al ⁇ o be u ⁇ ed.
• the "controlled double jet method” (al ⁇ o called “controlled diffu ⁇ ion method”) i ⁇ preferred.
• the ⁇ ilver halide grain ⁇ in the photographic emul ⁇ ion u ⁇ ed in thi ⁇ invention can have a relatively wide grain ⁇ ize distribution, but a narrow grain size distribution is preferred.
• the ⁇ ize of the ⁇ ilver halide grain ⁇ amounting to 90% of the total, based on the weight or number of the grains, i ⁇ preferably within + 40% of the average grain ⁇ ize ( ⁇ uch an emul ⁇ ion i ⁇ usually called a monodi ⁇ per ⁇ ed emul ⁇ ion).
• Grain ⁇ ize can be controlled by known technique ⁇ ⁇ uch a ⁇ are di ⁇ clo ⁇ ed in, e.g. U.S. Patents No. 3,271,157; No. 3,704,130; No. 3,574,628; No. 4,276,374 and No. 4,297,439 and in Research Disclo ⁇ ure ⁇ RD No. 17643, December 1978 and 18716, November 1979, all incor ⁇ porated by reference.
• the individual reactant ⁇ can be added to the reaction ve ⁇ sel through surface or ⁇ ub- ⁇ urface delivery tube ⁇ by gravity feed or .by delivery apparatu ⁇ for maintaining control of the pH and/or pAg of the reaction ve ⁇ sel content ⁇ , a ⁇ illustrated by Culhane et al U.S. Patent No. 3,821,002, Oliver U.S. Patent No. 3,031,304 all incorporated by reference.
• ⁇ pecially con ⁇ tructed mixing device ⁇ can be employed, a ⁇ il- lu ⁇ trated by Audran U.S. Patent No. 2,996,287, McCrossen et al U.S. Patent No. 3,342,605, Frame et al U.S. Patent No. 3,415,650, Porter et al U.S. Patent No. 3,785,777, Saito et al German OLS 23
• the grain ⁇ ize distribution of the silver halide emulsions can be controlled by ⁇ ilver halide grain separation technique ⁇ or by blending ⁇ ilver halide emul ⁇ ion ⁇ of differing grain sizes.
• the emul ⁇ ion ⁇ can include ammoniac l emulsions, as illustrated by Glafkides, Photographic Chemi ⁇ try, Vol. 1, Fountain Pre ⁇ , London, 1958, pp. 365-368 and pp. 301-304; thiocyanate ripened emul ⁇ ions, a ⁇ illu ⁇ trated by Illing ⁇ worth U.S. Patent No. 3,320,069; thioether ripened emulsions, as il ⁇ lustrated by McBride U.S.
• the crystal form of the ⁇ ilver halide grain ⁇ in the photographic emul ⁇ ion may be regular ( ⁇ uch a ⁇ cubic or oc ⁇ tahedral) or irregular ( ⁇ uch a ⁇ ⁇ pherical or plate-like) or it may be a compo ⁇ ite of the ⁇ e forms.
• the grains may comprise mixed grains having various crystal forms.
• the interior and the surface layer of the silver halide grain may be different or the grain ⁇ may be uniform throughout.
• cadmium salt ⁇ , zinc salt ⁇ , lead ⁇ alt ⁇ , thallium ⁇ alt ⁇ , rhodium ⁇ alt ⁇ or complex salt ⁇ thereof, iron ⁇ alt ⁇ or iron complex ⁇ alt ⁇ , and the like can be pre ⁇ ent, a ⁇ can mixture ⁇ thereof.
• Preferred as ⁇ uch dopants, are rhodium or iridium salts or mixtures thereof.
• Two or more of silver halide emul ⁇ ions which are separately prepared can be mixed and then used, if desired.
• the ⁇ oluble ⁇ alt ⁇ are usually removed from the emulsion.
• the well known noodle washing method may be u ⁇ ed.
• the flocculation method may be u ⁇ ed.
• Thi ⁇ method employ ⁇ an inorganic ⁇ alt having a polyvalent anion ⁇ uch a ⁇ ⁇ odium ⁇ ulfate, an anionic ⁇ urface active agent, an anionic polymer ( ⁇ uch as polystyrene ⁇ ulfonic acid) or a gelatin derivative ( ⁇ uch as an aliphatic acylated gelatin, an aromatic acylated gelatin or an aromatic carbamoylated gelatin) .
• the removal of the soluble ⁇ alt ⁇ may be omitted, if de ⁇ ired.
• the ⁇ ilver halide emul ⁇ ion ⁇ u ⁇ ed in the pre ⁇ ent invention do not need to be chemically ⁇ en ⁇ itized, chemically ⁇ en ⁇ itized ⁇ ilver halide emul ⁇ ions are preferred.
• Proces ⁇ es for chemical ⁇ en ⁇ itization of the ⁇ ilver halide emulsions which can be used include known sulfur sensitization, reduction ⁇ en ⁇ itization and noble metal ⁇ en ⁇ itization proce ⁇ e ⁇ .
• selenium, tellurium, rhenium or pho ⁇ phoru ⁇ ⁇ ensitizer ⁇ or combination ⁇ of these sen ⁇ itizer ⁇ can be u ⁇ ed.
• Chemical ripening can be performed at pAg level ⁇ of from 5 to 10, pH level ⁇ of from 5 to 8 and at temperature ⁇ from 30° to 80 ⁇ C.
• Complexe ⁇ of noble group VIII metals other than gold can al ⁇ o be u ⁇ ed a ⁇ chemical ⁇ en ⁇ itizer ⁇ .
• a reduction ⁇ ensitization process may be used if the process does not generate fog to a degree which causes practical difficulties (with or without the use of known antifoggent ⁇ ) .
• a particularly preferred chemical ⁇ en ⁇ itization proce ⁇ for the present inven ⁇ tion is the use of a sulfur sen ⁇ itization proce ⁇ .
• ⁇ ulfur ⁇ ensitizing agents which can be used include not only sulfur compounds present in the gelatin per ⁇ e, but al ⁇ o various ⁇ ulfur compound ⁇ ⁇ uch as thiosulfates, thioureas, thiazoles or rhodanines, etc.
• suitable ⁇ ulfur compound ⁇ are described in U.S. Patent Nos. 1,574,994, 2,410,689, 2,278,947, 2,728,668 and 3,656,955, all incorporated by reference.
• Typical example ⁇ of reduction-sensitizing agent ⁇ include ⁇ tannou ⁇ ⁇ alts, amines, formamidine sulfinic acid and ⁇ ilane compound ⁇ , methyldichloro ⁇ ilane, hydrazine derivative ⁇ , boranes such a ⁇ aminoborane ⁇ , thiourea dioxide, hydrogen, and other boron hydrides ⁇ uch as cyanoborohydrides.
• Reduction sen ⁇ itization can al ⁇ o be obtained by low pAg (le ⁇ than 5) or high pH (greater than 8) treatment, a ⁇ i ⁇ well-known in the art. Specifically contemplated i ⁇ the combined u ⁇ e of ⁇ everal of the aforementioned chemical ripening technique ⁇ ; in particular gold- ⁇ ulfur ⁇ en ⁇ itization combinations are highly preferred.
• a photographic material used in thi ⁇ invention may contain an antifoggant.
• antifoggants which can be advantageously used for the photographic material u ⁇ ed in thi ⁇ invention are 1,2,4-triazole compound ⁇ ⁇ ub ⁇ tituted with a mercapto group at the 3-po ⁇ ition, benzotriazole compounds, 2-mercaptobenzimidazole compounds (which do not contain a nitro group), 2-mercaptopyrimidines, 2-mercaptothiazole ⁇ , 2-mercap- tobenzothiazole ⁇ , benzothiazolium compound ⁇ ( ⁇ uch a ⁇ N-alkylben- zothiazolium halide ⁇ , nitrobenzindazole, ⁇ ubstituted triazain- dolizine ⁇ (tetraazaindene ⁇ ) or N-allylbenzothiazolium halide ⁇ ), and 2-mercapto-l,3,4-thiazole ⁇ .
• Antifoggants which are not effective when used alone, such
• Useful benzotriazoles can be chosen from among conven ⁇ tional benzotriazole antifoggants, ⁇ uch as those disclosed by Land U.S. Patent No. 2,704,721 and Rogers et al U.S. Patent No. 3,265,498, both incorporated by reference.
• the preferred benzotriazoles for use in this invention are benzotriazole (that is, the unsubstituted benzotriazole compound), halo-substituted benzotriazoles (e.g., 5-chlorobenzotriazole, 4-bromobenzotriazole and 4-chlorobenzotriazole) and alkyl-substituted benzotriazoles wherein the alkyl moiety contains from about 1 to 12 carbon atoms (e.g., 5-methylbenzotriazole) .
• 5-methylbenzotriazole is most preferred.
• the use of 5-methylbenzotriazole as an antifoggant is illustrated by Baldassari et al U.S. Patent No. 3,925,086, incor ⁇ porated by reference.
• the effect of this invention is enhanced even more by adding a small amount of an iodide salt (such as potassium iodide) to the emulsion after the formation of the grains, before chemical ripening, after chemical ripening or before coating.
• an iodide salt such as potassium iodide
• a suitable amount of iodide added ranges from about 10 -4 to about
• the photographic emulsions used in this invention can be used for camera exposure.
• UV absorbing compounds such as those in U.S. Patents Nos. 3,533,794; 3,314,794 and 3,352,681, all incorporated by reference.
• Safelight dyes such as oxonols, hemioxonols, styryl dyes, merocyanine dyes and aso dyes can also be used, as long as such dyes are easily removed or decolorized during processing (see US Patents Nos. 2,274,782; 2,956,879; 3,423,207; 3,976,661 and 3,384,487, all incorporated by reference).
• Desensitizing dyes see, e.g. U.S. Patent No. 3,501,307, incorporated by reference) can al ⁇ o be u ⁇ ed.
• the pre ⁇ ent emulsion can be spectrally sensitized (e.g. to long blue, green, red or infrared) with at least one methine- type and/or other spectrally-sensitizing dye.
• Suitable sensitiz- ing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly 07 54
• 27 u ⁇ eful dye ⁇ are cyanine dyes, merocyanine dyes and comple merocyanine dyes. These dyes can contain, as a basi heterocyclic nucleus, any of the nuclei which are usuall employed in cyanine dyes: a pyrroline nucleus, an oxazolin nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazol nucleus, a thiazole nucleus, a ⁇ elenazole nucleus, an imidazol nucleus, a tetrazole nucleus, a pyridine nucleu ⁇ and the like; one of the above-de ⁇ cribed nuclei conden ⁇ ed with an alicyclic hydrocarbon ring; and one of the above-described nuclei conden ⁇ e with an aromatic hydrocarbon ring, such as an indolenine nucleus, a benzindolenine nucleu ⁇
• the carbon atoms of the above-described nuclei may be mono- di- or poly- ⁇ ub ⁇ tituted with ⁇ uch diver ⁇ e ⁇ ub ⁇ tituent ⁇ as alkyl, aryl, carboxy, ⁇ ulfo, phenyl, alkoxy and halo, without limitation, and, optionally them ⁇ elve ⁇ further ⁇ ub ⁇ tituted.
• the merocyanine dye ⁇ or complex merocyanine dye ⁇ can contain, as nucleus having a ketomethylene structure, a 5- to 6-membered heterocyclic nucleus ⁇ uch as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleu ⁇ .
• U ⁇ eful ⁇ en ⁇ itizing dyes include those described in, e.g., German Patent No. 929,080, U.S. Patent Nos.
• Preferred ⁇ en ⁇ itizing dye ⁇ include dicarbocyanine derivative ⁇ and tricarbocyanine derivative ⁇ (mo ⁇ t preferably symmetric) sensitizing within the range of about 680 to about 850 nm.
• the ⁇ e ⁇ ensitizing dyes may be used individually or as a combination.
• a combination of sensitizing dyes is often employed particularly for the purpo ⁇ e of ⁇ uper ⁇ en ⁇ itization.
• Typical example ⁇ of ⁇ uch combination ⁇ are de ⁇ cribed in, e.g., U.S. Patent
• Preferred sensitizing dye combina ⁇ tions are mixtures of cyanine and merocyanine dye ⁇ that or- thochromatically ⁇ en ⁇ itive at wavelength ⁇ between 400 and 580 nm.
• the ⁇ ensitizing dyes may be present in the emul ⁇ ion together with dye ⁇ which them ⁇ elve ⁇ do not have any ⁇ pectral ⁇ en ⁇ itizing effect ⁇ but exhibit a ⁇ uper ⁇ en ⁇ itizing effect when u ⁇ ed in combination with ⁇ en ⁇ itizing dye ⁇ , or with other material ⁇ which do not substantially absorb visible light but exhibit a ⁇ uper ⁇ ensitizing effect when used in combination with sen ⁇ itizing dye ⁇ .
• Example ⁇ of ⁇ uch material ⁇ are dye ⁇ , heterocyclic mercaptan ⁇ , ⁇ tyryl bases, "Q" salts (e.g.
• example ⁇ include ⁇ tilbene ⁇ uch a ⁇ amino ⁇ tilbene compounds preferably ⁇ ub ⁇ tituted with a nitrogen-containing heterocyclic ring group (e.g., tho ⁇ e described in U.S. Patent Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (e.g., those described in U.S. Patent No. 3,743,510), azaindene compounds, and the like, can be present.
• a nitrogen-containing heterocyclic ring group e.g., tho ⁇ e described in U.S. Patent Nos. 2,933,390 and 3,635,721
• aromatic organic acid formaldehyde condensates e.g., those described in U.S. Patent No. 3,743,510
• azaindene compounds and the like
• a water- ⁇ oluble dye may be pre ⁇ ent in any of the hydrophilic colloid layer ⁇ in the photographic light- ⁇ en ⁇ itive material ⁇ u ⁇ ed in thi ⁇ invention, for example, a ⁇ a filter dye or for prevention of light ⁇ cattering, or for antihalation.
• Example ⁇ of the ⁇ e dye ⁇ include oxonol dye ⁇ , hemioxonol dye ⁇ , ⁇ tyryl dye ⁇ , merocyanine dye ⁇ , cyanine dye ⁇ and azo dye ⁇ .
• oxonol dye ⁇ oxonol dye ⁇ , hemioxonol dye ⁇ and merocyanine dye ⁇ are particularly u ⁇ eful.
• Specific example ⁇ of dye ⁇ which can be u ⁇ ed are tho ⁇ e de ⁇ cribed in Briti ⁇ h Patent No ⁇ . 584,609 and 1,177,429, and U.S. Patent Nos. 2,274,782, 2,533,472, 2,956,879, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, 3,653,905 and 3,718,472, all incorporated by reference.
• An inorganic or organic hardener may be present in any of the hydrophilic colloid layers in the light-sensitive material used in thi ⁇ invention.
• the ⁇ e hardeners include, for example, chromium salts (such a ⁇ chrome alum or chromium acetate), aldehydes ( ⁇ uch as formaldehyde, glyoxal or glutaraldehyde), N-methylol compounds (such as dimethylolurea or methyloldimethyl- hydantoin), dioxane derivatives (such a ⁇ 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-tri- acryloyl-hexahydro-s-triazine or bis(vinyl ⁇ ulfonyl)methyl ether), active halogen compound ⁇ (such a ⁇ 2 , 4-dichloro- 6-hydroxy- ⁇ -triazine), mucohalic acid ⁇ ( ⁇ uch a ⁇ mucochloric acid or muco
• a preferred hardener is one that will not cause reduction-sen ⁇ itization (formaldehyde, for example, ⁇ hould be avoided).
• An example of a preferred hardener i ⁇ dichlorohydroxytriazine.
• the light- ⁇ en ⁇ itive material of thi ⁇ invention may contain various known surface active agents for variou ⁇ purpo ⁇ es, e.g., as a coating aid, for preventing the generation of static charges, improving slip characteri ⁇ tic ⁇ , improving emul ⁇ ion di ⁇ per ⁇ ion, preventing adhe ⁇ ion, improving photographic charac ⁇ teri ⁇ tic ⁇ (e.g., accelerating development, increa ⁇ ing contra ⁇ t, sensitization) , etc.
• various known surface active agents for variou ⁇ purpo ⁇ es e.g., as a coating aid, for preventing the generation of static charges, improving slip characteri ⁇ tic ⁇ , improving emul ⁇ ion di ⁇ per ⁇ ion, preventing adhe ⁇ ion, improving photographic charac ⁇ teri ⁇ tic ⁇ (e.g., accelerating development, increa ⁇ ing contra ⁇ t, sensitization) , etc.
• nonionic ⁇ urface active agent ⁇ such as saponin ( ⁇ teroids) , alkylene oxide deriva- tives ( ⁇ uch a ⁇ polyethylene glycol, polyethylene glycol/polypropylene glycol conden ⁇ ate ⁇ , polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides or ⁇ ilicone/polyethylene oxide adducts), glycidol derivatives (such as alkenyl ⁇ uccinic acid polyglyceride ⁇ or alkylphenol polyglycerides) , aliphatic e ⁇ ter ⁇ of polyhydric alcohols, alkyl ester ⁇ of sucrose, urethanes or ethers; anionic surface active agent ⁇ containing an acidic group ⁇ uch a ⁇ a carboxy group, a ⁇ ulfo group, a pho ⁇ pho group,
• the photographic emulsion used in thi ⁇ invention can contain a di ⁇ per ⁇ ion of a ⁇ ynthetic polymer which is in ⁇ oluble or ⁇ lightly ⁇ oluble in water for the purpo ⁇ e of improving the dimen ⁇ ional ⁇ tability, the development and the fixing and drying rate ⁇ .
• polymer ⁇ which can be u ⁇ ed examples include polymer ⁇ compo ⁇ ed of one or more alkyl acrylate ⁇ or methacrylate ⁇ , alkoxyalkyl acrylates or methacrylates, glycidyl acrylates or methacrylates, acyl or methacrylamide, vinyl e ⁇ ter ⁇ (for example, vinyl acetate), acrylonitrile, olefin ⁇ and ⁇ tyrene, etc., and polymer ⁇ comprising a combination of the above de ⁇ cribed monomer ⁇ and acrylic acid, methacrylic acid, un ⁇ aturated dicarboxylic acid ⁇ , hydroxyalkyl acrylates or methacrylates or ⁇ tyrene ⁇ ulfonic acid, etc.
• the photographic elements can contain developing agents (de ⁇ cribed below in connection with the proce ⁇ ing ⁇ tep ⁇ ), development modifier ⁇ , pla ⁇ ticizer ⁇ and lubricant ⁇ , coating aids, antistatic material ⁇ , matting agent ⁇ , brightener ⁇ and color material ⁇ , the ⁇ e conventional material ⁇ being illu ⁇ trated in Paragraphs V, VIII, XI, XII and XVI of Research Di ⁇ closure, December 1978 Item 17643, all incorporated by reference.
• the photographic emul ⁇ ion al ⁇ o contain ⁇ anti-ageing agent ⁇ , " useful to prolong the shelf life of the emul ⁇ ion.
• Suitable anti-ageing agent ⁇ include polyhydroxy ⁇ piro-bi ⁇ -indane a ⁇ di ⁇ clo ⁇ ed in U.S. Patent No. 4,346,167 of E. Imatomi and preferably phenidone (up to 2 g/kg of emul ⁇ ion) a ⁇ di ⁇ clo ⁇ ed in U.S. Patent No. 2,751,297 of G. Hood.
• the layers can be applied on photographic supports by various procedures, including immersion or dip coating, roller coating, reverse roll coating, air knife coating, doctor blade coating, gravure coating, spray coating, extru ⁇ ion coating, bead coating, ⁇ tretch-flow coating and curtain coating.
• ⁇ imultaneou ⁇ multilayer coating varied coating hopper ⁇ can be u ⁇ ed, a ⁇ illu ⁇ trated by Ru ⁇ ell et al U.S. Patent No. 2,761,417, Ru ⁇ sell U.S. Patent No ⁇ . 2,761,418 and 3,474,758, Mercier et al U.S. Patent No. 2,761,419, Wright U.S. Patent No. 2,975,754, Padday U.S. Patent No. 3,005,440, Mercier U.S. Patent No. 3,627,564, Tim ⁇ on U.S. Patent No ⁇ .
• Silver halide layer ⁇ can also be coated by vacuum evaporation, a ⁇ illu ⁇ trated by Lu Valle et al U.S. Patent No ⁇ . 3,219,444 and 3,219,451.
• the photographic emulsion ⁇ are coated on conventional ⁇ upport ⁇ which do not undergo ⁇ eriou ⁇ dimen ⁇ ional change ⁇ during proce ⁇ ing.
• Typical ⁇ uitable ⁇ upport ⁇ which can be u ⁇ ed are a cellulo ⁇ e acetate film, a poly ⁇ tyrene film, a polyethylene terephthalate film, a polycarbonate film, a laminate thereof, paper, baryta paper, paper coated on laminated with a hydrophobic polymer ⁇ uch a ⁇ polyethylene, polypropylene, etc. a ⁇ are commonly u ⁇ ed for photographic light- ⁇ en ⁇ itive material ⁇ .
• Tran ⁇ parent ⁇ upport ⁇ can be employed for certain end u ⁇ e ⁇ of the light- ⁇ en ⁇ itive material.
• Al ⁇ o, tran ⁇ parent ⁇ upports may be 33 colored by adding a dye or a pigment thereto a ⁇ de ⁇ cribed in
• a ⁇ ubbing layer (an adhe ⁇ ive layer) that adhere ⁇ to bot the ⁇ upport and the photographic emulsion layer(s) can b employed.
• Al ⁇ o in order to improve the adhe ⁇ ion, ⁇ urface of th support may be subjected to a preliminary proce ⁇ ing such a corona di ⁇ charge, irradiation with ultraviolet light, flam treatment, etc.
• the photographic element ⁇ can be i agewi ⁇ e expo ⁇ ed wit various forms of energy, which encompas ⁇ the ultraviolet an vi ⁇ ible (e.g., actinic) and infrared region ⁇ of the electromag netic spectrum a ⁇ well a ⁇ electron beam and beta radiation, gamm ray.
• X-ray, alpha particle, neutron radiation and other forms o corpuscular and wavelike radiant energy in either noncoheren (random phase) form ⁇ or coherent (in phase) forms, as produced b laser ⁇ ("flash exposure").
• Exposures can be monochromatic orthochromatic or panchromatic.
• Imagewi ⁇ e expo ⁇ ure ⁇ at ambient elevated or reduced temperature ⁇ and/or pre ⁇ ures, including hig or low intensity exposure ⁇ , continuous or intermittent exposures exposure times ranging from minutes to relatively ⁇ hort duration in the millisecond to microsecond range and solarizing exposure ⁇ can be employed within the u ⁇ eful re ⁇ pon ⁇ e range ⁇ determined b conventional ⁇ ensitometric technique ⁇ , a ⁇ illu ⁇ trated by T. H Jame ⁇ , The Theory of the Photographic Proce ⁇ , 4th Ed., Macmil lan, 1977, Chapter ⁇ 4, 6, 17, 18 and 23, incorporated b reference.
• the photographic light- ⁇ en ⁇ itive material of thi invention can be photographically processed u ⁇ ing known method and known proce ⁇ ing solutions.
• Thi ⁇ invention is particularly useful for the formation of a image by development in which a ⁇ ilver image i ⁇ formed ( black-and-white photographic proce ⁇ ing).
• the developers used for black-and-white photographic proces ⁇ ing preferably contain, a ⁇ a developing agent, aminophenol ⁇ (such a ⁇ N-methyl-p-aminophenol), 3-pyrazolidones (such as l-phenyl-3-pyrazolidone) , l-phenyl-3-pyrazolines, dihydroxybenzene ⁇ ( ⁇ uch a ⁇ hydroquinone) and other of the aforementioned developing agent ⁇ .
• aminophenol ⁇ such a ⁇ N-methyl-p-aminophenol
• 3-pyrazolidones such as l-phenyl-3-pyrazolidone
• l-phenyl-3-pyrazolines such as dihydroxybenzene ⁇ ( ⁇ uch a ⁇ hydroquinone) and other of the aforementioned developing agent ⁇ .
• u ⁇ eful developing agent ⁇ examples include hydroquinone alone, hydroquinone plu ⁇ N-methyl-p-aminophenol, hydroquinone plu ⁇ 1 -pheny1-3-pyrazolidone , and hydroquinone plu ⁇ N-methyl-p-aminophenol plu ⁇ l-phenyl-3-pyrazolidone.
• the developer u ⁇ ually contain a known antioxidant, an alkali agent, a pH buffer or the like and, if de ⁇ ired, a di ⁇ olving aid, a color toning agent, a development accelerator, a ⁇ urface active agent, an anti-foaming agent, a water ⁇ oftener, a hardener, a tackifier, etc., may be pre ⁇ ent.
• An anti-fogging agent ( ⁇ uch as an alkali metal halide or benzotriazole) may be present in the developer.
• a gamma of more than 8 can be obtained.
• the pH of the developer is preferably about 11 to about 12.3. If the pH exceeds about 12.3, the developer i ⁇ un ⁇ table even when a high concentration of ⁇ ulfite ion ⁇ i ⁇ pre ⁇ ent, and it i ⁇ dif ⁇ ficult to maintain ⁇ table photographic characteri ⁇ tic ⁇ for more than 3 days under usual use condition ⁇ .
• Fixing ⁇ olution ⁇ having a compo ⁇ ition generally employed in the art can be u ⁇ ed in the pre ⁇ ent invention.
• thio ⁇ ulfate ⁇ and thiocyanate ⁇ but al ⁇ o organic ⁇ ulfur compound ⁇ known a ⁇ fixing agent ⁇ can be u ⁇ ed a ⁇ fixing agent ⁇ in the pre ⁇ ent invention.
• Preferred example ⁇ of fixing agent ⁇ which can be u ⁇ ed in the fixing ⁇ olution include water- ⁇ oluble thio ⁇ ulfate ⁇ ⁇ uch as ⁇ odium thio ⁇ ulfate, pota ⁇ ium thio ⁇ ulfate, ammonium thio ⁇ ulfate, etc., water- ⁇ oluble thiocyanate ⁇ ⁇ uch a ⁇ ⁇ odium thiocyanate, potas ⁇ ium thiocyanate, ammonium thiocyanate, etc., water- ⁇ oluble organic diol fixing agent ⁇ containing an oxygen atom or a ⁇ ulfur atom ⁇ uch a ⁇ 3-thia-l,5-pentanediol, 3,6-dithio-l,8-octanediol, 9-OXO-3,6,12,15-tetrathio-l,17-heptadecanediol, etc., wat ⁇ oluble sulfur-containing organic dib
• a particularly preferred developing ⁇ y ⁇ tem in acco dance with the pre ⁇ ent invention contain ⁇ a hydroquinone develo ing agent, a benzotriazole antifogging agent (developme restrainer), diethylamino-propanediol, ⁇ odium sulfite, and a modifier (preferably NaOH and/or Na 2 C ⁇ 3) to adjust the pH to 11. ⁇ 0.5.
• a hydroquinone develo ing agent e.g., a benzotriazole antifogging agent (developme restrainer), diethylamino-propanediol, ⁇ odium sulfite, and a modifier (preferably NaOH and/or Na 2 C ⁇ 3) to adjust the pH to 11. ⁇ 0.5.
• the most preferred developing ⁇ y ⁇ tem i ⁇ set forth in t Example ⁇ below.
• the preferred ethanedioic acid hydrazide ⁇ of t pre ⁇ ent invention are listed in Table I.
• 5-nitroquinoline are commercially available from Eastman Kodak, Rochester, N.Y. and/or Aldrich Chemical, Milwaukee, Wise, and compounds II-3 and
• 11-25 are commercially available from A ⁇ itec, Binghamtom, N.Y.
• the following example ⁇ are given to illu ⁇ trate the present invention in more detail.
• the scope of the pre ⁇ ent invention i ⁇ not limited to the ⁇ e example ⁇ .
• the ⁇ olid ⁇ are ⁇ tirred for 1 hou in 900 cc of methanol at room temperature, filtered and washed o funnel with the addition of 450 cc of methanol and left to dry. Maximum 371 nm in methanol.
• This emulsion contained gelatin in the amount of 71.3 g per mole ⁇ ilver halide.
• a gelatino( ⁇ ilver bromide) emul ⁇ ion was prepared at 65*C for 37 minutes by a controlled double jet addition technique while the pAg was maintained an 8.3.
• the emulsion was chemically ripened using both labile ⁇ ulfur and gold agent ⁇ at 65"C for 65 minute ⁇ .
• Thi ⁇ ⁇ urface ⁇ ensitized emulsion contained gelatin in the amount of 81.9 g per mole silver bromide.
• Example 3 The emulsion described in Example 3 was ⁇ plit into 250 g portion ⁇ . Each portion wa ⁇ identically prepared for coating by the addition of an infrared ⁇ en ⁇ itizing dye ( ⁇ ub ⁇ tituted dicar- bocyanine) and ⁇ urfactant coating aid ⁇ (ethoxylated phenol).
• an infrared ⁇ en ⁇ itizing dye ⁇ ub ⁇ tituted dicar- bocyanine
• ⁇ urfactant coating aid ⁇ ethoxylated phenol
• the exposed element wa ⁇ proce ⁇ ed in an "exhausted" development chemi ⁇ try (run through a table top proce ⁇ or for 8 hour ⁇ at 90 ⁇ F) having the following compo ⁇ ition (EDTA i ⁇ ethylene-diaminetetraacetate)
• Type I compounds can be anticipated yield comparable results when tested with the above and oth Type II compounds.
• the amount of compound II that could be used in t developing solution would be about 500-1000 times larger (p liter of solution) than in the photographic material.

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  • 1990-12-17 JP JP50326790A patent/JPH05502739A/ja active Pending
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