US3890154A - Light-sensitive silver halide photographic materials - Google Patents

Abstract

WHEREIN Ro, R1, R2, R3, R4, R5, R6, Y1, Y2, X and m are defined hereinafter, and compounds of the general formula

WHEREIN R8, R9, R10, L1, L2 and Y3 are defined hereinafter.
There is provided a light-sensitive silver halide photographic material comprising at least one layer on a support which comprises a binder containing (i)light-sensitive silver halide grain particles characterized as exhibiting a high surfacesensitivity; (ii) at least one compound containing a Group VIII metal at a level of from 1 X 10 6 to 1 X 10 3 mol per 1 mol of said silver halide (iii) at least one optical sensitizer selected from the group consisting of compounds of the general formula

Description

United States Patent 1 1 1111 3,890,154

Ohkubo et al. 1 June 17, 1975 1 1 LIGHT-SENSITIVE SILVER HALIDE Primary Examiner-J. Travis Brown PHOTOGRAPHIC MATERIALS Anorney, Agent, or Firm-Sughrue, Rothwell. Mion,

' M 'k 175 inventors: Kinji Ohkub;Junpe1Noguchi;

Kunioki Ohmura; Masanao Hinata, [57] ABSTRACT all of Kanagawa, Japan I There is provided a hght-sensmve sliver halide photo- 1731 Assign: Fuji Phmo graphic material comprising at least one layer on a Kanagawa, Japan support which comprises a binder containing (i)light- [22] Filed; Mar. 23, 1973 sensitive silver halide grain particles characterized as exhibiting a high surface-sensitivity; (ii) at least one [21] Appl 3441401 compound containing a Group VIII metal at a level of Rented Appncation m from l X to l X l0" mol per 1 mol of said silver {63] continuuflommpan of Ser No ml 233 Dec 24 halide (iii) at least one optical sensitizer selected from 1970 abandoned the group consisting of compounds of the general for mula I i R" L; n l C=C1l-C ce-c li R (if'lm-l Foreign Application Priority Data wherein m 1. 2, 3, 4. 5. 11. 1. 2. X n m are Dec. 24. 1969 Japan ..44-1o4009 defined hereinafter, and Compounds of the general Jan 9, 1970 Japan -002819 formula [52] US. Cl. 96/125; 96/108; 96/126; 96/137; 96/140 51} 1111. C1 G03c 1/08 F N s [53} Field of Search 96/l25, 126, 137, 140, i

96/108 N c=1d L =CY [56] References Cited 1 1 UNITED STATES PATENTS R C- N /C\\\ 5 2.912329 11/1959 Jones et a1. 96/137 0 3,206,313 9/1965 Porter ct a1 96/108 1 3,672,901 6/1972 Ohkubo et al 96/108 R10 3,741,767 6/1973 Baylis ct a1. 96/108 $761,266 9/1973 Milton r r 96/108 3,761,267 9/1973 Gilman et a1. t 96/108 3,782,957 l/l974 Ohkubo et al 1. 96/l25 wherein R R R L,, L and Y, are defined h i FOREIGN PATENTS OR APPLICATIONS 801.275 9/1958 United Kingdom...1............... 96/140 23 Claims, 1 Drawing Figure PATENTEBJUN 17 m5 M TRANSMITTANCE 550 400 450 560 a so '00 WAVE LENGTH (nm) INVENTORS KINJI OHKUBO JUNPEI NOGUCHI KUNIOKI OHMURA MASANAO HINATA LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIALS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part application of our earlier co-pending application Ser. No. 101,233 filed Dec. 24, 1970, now abandoned which claims priority from Dec. 24, 1969 and Jan. 9, i970, respectively, based on Japanese Patent Applications 104009169 and 2819/70, respectively.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic silver halide light sensitive materials. More particularly, the present invention relates to photographic silver halide light sensitive materials having high sensitivity to green light under flash exposure. The term flash exposure is defined hereinafter.

2 Description of the Prior Art The present age is one of information. Various systems have been developed to promote the speedy transmission of information. For instance, press facsimile systems a speedily transmit press manuscripts to distant places, high speed phototypesetting systems expedite printing and typesetting, and cathode ray tube (CRT) display systems represent speedily in letters of figures the information output of computers. With such equipment used for such rapid information transmitting systems, a short time exposure of less than l/l00,000 of a second or especially about 1 1,000,000 of a second is most often used. The demand for sensitive materials to be used for such equipment has in recent years been particularly high.

There are two types of light sources used in connection with these types of equipment, viz., xenon flash lamps and cathode ray tubes. Of these, the one whose fluorescence has an especially short afterglow known generally to be usable for flying spot, is used as the cathode ray tube. For instance, such fluorescent materials are called P-l l, "*P-lS," P-l6 and P-24" and are used as the light source in question. It is known that the luminous distribution of spectral energy reaches a peak when P-l l reaches 460 nm. and when P-l6 reaches 385 nm. This peak corresponds to the region of the spectral absorption characteristic of light sensitive silver halides and hence does not need any optical sensitization. On the other hand, it is known that P-l5 has its maximum fluoroscent spectral energy at 505 nm. and for P-24 at 520 nm. The sensitive materials for recording images on CRT must therefore be given sensitivity to green light. On the other hand, a xenon flash lamp emits light over a comparatively broad spectral region. The light from the light source gives images on the sensitive materials through an optical system composed ofa condenser lens, a negamatrix, a main lens, a prism. a reflector or a deformation lens or other special lenses, or prisms. The light of short wave length is absorbed to a greater extent by the optics in the path. As a result of the light reaching the sensitive material, the shorter wave length component of from ultraviolet to blue diminishes and the longer wave length component from the green becomes richer. For this reason, green sensitization is indispensable in order to enhance the sensitivity of the sensitive material. The above-described afterglow of the fluorescence of a cathode ray tube ranges from l/l0,000,000 to l/100,000 of a second and with a xenon flash lamp also one of about the same radiation period is used. In the present invention the short time exposure of these two kinds of light sources described above is generically called flash exsposure.

The conventional sensitizer for green light shows markedly lower spectro sensitization under a flash exposure of l/l00,000 of a second or less in comparison with the result of a conventional exposure of l/l,000 ofa second or longer. Specifically there is a fair indication of this trend where, in order to expedite after exposure the treatments such as fixing or stabilization, silver halide is partly or wholly composed of silver chloride, i.e., a silver chloride emulsion, a chlorobromide emulsion or a chloroiodobromide emulsion.

An object of this inventoin is to provide photographic sensitive materials having high sensitivity to green light under flash exposure.

SUMMARY OF THE INVENTION This invention provides silver halide light sensitive photographic materials comprising a support on which at least one layer having in the binder (such as gelatin and the like) sensitive silver halide grain particles characterized as exhibiting a high surface sensitivity, at least one compound containing a Group VIII metal of the periodic table at the ratio of from 10* to [0 mo] per 1 mol of silver halide, and at least one optical sensitizer selected from the group consisting of compounds of the general formula:

wherein R represents a hydrogen atom or an alkyl group; wherein R and R each represents a hydrogen atom, an alkyl, a substituted alkyl, an allyl, an aryl or an aralkyl group, in which at least one of R and R, must be a carboxyalkyl group or a sulfoalkyl group; wherein Y and Y each represents an oxygen atom, a sulfur atom or a l-lR group in which R, is an alkyl group; wherein R R R and R each represents a hydrogen atom, a halogen atom, an alkyl, a cyano, an alkoxy or an aryl group, when at least one of R and R is an aryl group, R and R are not an aryl group; wherein X represents an anion, such as a halogen ion or a thiocyanate ion; and wherein m is l or 2, in which an intramolecular salt is formed when m is l, and compounds of the general formula wherein R,,, R and R each represents a hydrogen atom. an alkyl, a substituted alkyl, an allyl, or an aryl group; wherein Y represents an oxygen atom, a sulfur atom or a NR,, group, in which R is a hydrogen atom, an alkyl or an aryl group; wherein L, and L each represents the atoms of a methine chain.

DESCRIPTION OF THE ACCOMPANYING DRAWINGS The accompanying drawing shows the light transmittance of a glass filter V-YSO used in the examples in evaluating the effectiveness of the light sensitive photographic materialsv DETAILED DESCRIPTION OF THE INVENTION silver chloroiodobromide, can be used. The so-called preparation of the sensitive silver halide emulsion, that is, the preparing of the silver halide crystal grains in the binder in a dispersive state, and making them grow into the proper crystal size thus preparing the silver halide emulsion, can be done by conventional techniquesv With respect to the light sensitive silver halide particles employed in the present invention, it must be emphasized that these particles are characterized as exhibiting a high surface sensitivity. Therefore, the silver halide particles of this invention are quite different from particles of the core shell type, which exhibit low surface sensitivity and high internal sensitivity.

The metals belonging to Group VIII of the periodic tables are iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum. Examples of the compounds containing these metals desirably used in this invention contain a single salt, or a hexagonal complex, tetragonal complex, or square plane complex of an alkali metal or ammonium such as ferrous sulfate (FeSO,.5H O); ferric chloride (FeCl potassium hexacyanoferrate (II)(K,,]Fe(CN) l ,3H O); potassium hexacyanoferrate (lII)(K ]FeCN l); cobalt (ll) chloride (CoClzl; Cobalt (II) nitrate (Co[NO 6 H O); potassium hexacyanocobaltate (Ill) (K {Co(CN nickel (II) chloride (NICI .6H O); nickel (II) nitrate (Ni[N0;,] .6H O); ruthenium chloride (RuCl );potassium hexachlororuthenate (IV) (K RuCl6); rhodium (lll) chloride (RhCl .4H ammonium hexachlorohodate (III) (INH J RhC'I palladium nitrate (Pd[BO palladium bromide (PdBr potassium hexachloropalladate (IV) (K PdCI potassium tetrathiocyanopalladate (II) (K Pd[CNS] osmium (II) chloride (OsCl iridium (III) chloride (lrCl iridium (IV) chloride (lrCl iridium (III) bromide (lrBr .4- H O); iridium (IV) bromide (IrBr potassium hexachloroiridate (III) (K IrCl potassium hexachloroiridate (IV) (K lrCl ammonium hexachloroplatinate (IV) magma potassium hexachloroplatinate (IV) (K PtCI ammonium hexabromoplatinate (IV) ((NH PtBr These metallic compounds of Group VIII are used either singly or in combinations of two or more compounds together in the silver halide emulsion in a quantity corresponding from (0 mol to 10 mol, preferably 10 to 3 X 10", per l mol of silver halide. The addition of these compounds in the emulsion can be made suitably at various stages in the preparation, viz., at the formation of silver halide grain particles in the preparation of silver halide emulsion added either in the halide solution or in the dispersive gelatin solution, or at the beginning of the ripening of the emulsion or at intermediate steps. Also, the compound can be added together with other various prior well known stabilizers, antifoggants, antibronzing agents, surface active agents, hardeners, plasticizers, matting agents, development accelerators or brightening agents and the like as desired, prior to the coating of the emulsion.

One of the optical sensitizers in the present invention is the compound having the following general formula:

wherein R represents a hydrogen atom or an alkyl group having from 2 to 3 carbon atoms, such as a methyl group, an ethyl group and the like; wherein R and R each represents hydrogen or an alkyl group having from I to 4 carbon atoms, such as a methyl group, an ethyl group or propyl group and the like, a substituted alkyl group of the type usually used as an N- substituent of a cyanine dye such as a hydroxyalkyl group (e.g., B-hydroxethyl), an acetoxyalkyl group (e.g., ,B-acetoxyethyl), an alkyl group having a carboxy group such as a carboxy-(alkoxy),, ,-alkyl group wherein n is l or 2 (eg, carboxymethyl, B-carboxyethyl, y-carboxypropyl, 2-(2-carboxyethoxy) ethyl), an alkyl group having a sulfo group such as a sulfo -(alkoxy),, ,-alkyl group wherein n is I, 2 or 3, a hydroxysulfo- (alkoxy),, alkyl group wherein n is I or 2 or an acyloxysulfoalkyl group (e.g., flsulfoethyl, y-sulfopropyl, S-sulfobutyl, 2hydroxyl-l-sulfopropyl, 2-(3sulfopropoxy)ethyl, Z-acetoxy-l-sulfopropyl, 3-methoxy-2- (3-sulfopropoxy )propyl, 2-]2-(3-sulfopropoxy) ethoxy]ethyl, 2-hydroxy-3-(3-sulfopropoxy)propyl, and the like, an aryl group such as phenyl group or an aralkyl group, but at least one of R and R is a carboxyalkyl group or a sulfoalkyl group; wherein Y and Y each group but when at least one of R and R is an aryl are an oxygen atom. a sulfur atom or a N R group group then neither R nor R is an aryl group; wherein in which R is an alkyl group having from 1 to 3 carbon X is an anion such as a halogen ion, a thiocyanate ion, atoms, such as a methyl group or an ethyl group and the sulfate ion, sulphamate ion, perchlorate ion, p-toluene like; wherein R R R and R ea h re r t a h d 5 sulphonate ion, benzensulphonate ion. ethyl sulphate gen atom, an alkyl gro h in f 1 1 3 carbon ion, or methyl sulphate ion, and wherein m represents atoms, such as a methyl group or an ethyl group and the l or 2, in which an intramolecular salt is formed when like, a halogen atom (such as fluorine, chlorine, brom =1- mine), a cyano group, an alkoxy group (such as a math Specific compounds of these optical sensitizers are oxy or an ethoxy group) or an aryl such as a phenyl 10 h w" 118 W I i N C H LH CH COOH C=CH-CH=CH- C Dye lXb I (c H2)3 coon c H where R,,, R, and R, each represents a hydrogen atom; an alkyl group having from l to 8 carbon atoms, such Dye X m.pover 300C Cl n as a methyl group, an ethyl group, a propyl group, a butyl group; a substituted alkyl group of the type usu- 40 ally used as an N-substituent of a cyanine dye such as a carboxyalkyl group, (e.g., a carboxymethyl group), a hydroxyalkyl group (e.g., a B-hydroxyethyl group), a sulfoalkyl group (e.g., a B-sulfoethyl group, a 'y-sulfopropyl group); an ally] group; or an aryl group such as 45 a phenyl group, a substituted phenyl group (for example, substituted with a halogen atom e.g., a chlorine atom, an alkyl group and the like); wherein Y is an oxygen atom, a sulfur atom or a N-R group, in which R is a hydrogen atom, an alkyl group having from I 50 to 8 carbon atoms, or an aryl group (e.g., a phenyl group); wherein L, and L in each a methine chain (e.g., =CH-, =C(alkyl); =C(aryl wherein examples of the alkyl group and the aryl group are a methyl group and a phenyl group, respectively).

Specific compounds of these sensitizers are as follows:

N N-CH i CH in c s 45C N p-2 c c c H o s Dye xvn Dye XVIII DyaXlX c C H C =C| C 4 \T/ C 2 H These sensitizers are described, for example, in the British Pat. No. 801,275 and the synthesis of these sen sitizers is well known by reference to the patent cited above and also to the relevant technical literature.

These optical sensitizers are applied, either singly or in combination of two or more, at a ratio of from l0 to 10 mol, preferably 10" to 3 X 10 mol, per l mol of silver halide in the silver halide emulsion. This addition of the optical sensitizer to the emulsion is the same as with the metal compounds above described. The addition into the emulsion can be made either simulta neously with the metal compound, or separately. The sequence of the addition is immaterial.

Thus, it can be seen that the silver halide lightsensitive photographic material can be made essentially in the same manner as usual except that the above metal compound and optical sensitizer are added and the sensitive material thus prepared can, after flash exposure, be developed and fixed in a conventional manner. Also, the material can be treated in a manner known generally as the diffusion transfer process. Or, by adding beforehand an ample quantity of the developing agent in the light-sensitive layer, the develop ment can be treated by the generally known activator development process (a process by which the lightsensitive material containing a developing agent is developed in a solution which does not contain a develop ing agent and in which only alkaline material is dis solved).

It has been observed that with light-sensitive materi als containing the above-described metal compounds but not containing the optical sensitizers, the sensitivity to the green light is not obtained, although, in some cases, their sensitivity to blue light improves. On the other hand, it is recognized that in the case of the sensitive material not containing the metal compounds but containing only the optical sensitizers, the green light mp. 290C sensitivity is not very high. However, by using these two types of materials simultaneously the green light sensitivity in the flash exposure can be markedly improved.

Specifically, with a silver chloride emulsion, a silver chlorobromide emulsion, or a silver chlorobromoiodide emulsion, if the above sensitizer is used alone, a considerable lowering of the efficiency of spectral sensitization in the flash exposure is experienced. For such emulsions the present invention is particularly useful.

It has long been known that the metal compounds described above show various noticeable effects, and as is shown in US. Pat. No. 2,448,060, when hexahalogenoruthenium (lll) acid salts, hexahalogenorhodium (IV) acid salts, hexahalogeno osmium (IV) acid salts, hexahalogenoiridium (IV) acid salts, or hexahalogenoplatinum (lV) acid salts are added to a silver halide emulsion at the time of ripening, the sensitivity of this emulsion increases. And further, as is disclosed in US. Pat. No. 2,566,745, when these compounds are added additionally to the silver halide emulsion the stability of the sensitive material under high temperatures and humidity improves, and further, as is disclosed in US. Pat. No. 2,517,54], potassium hexacyanocobaltate (Ill) and in FIAT Report No. 360 rhodium trichlo ride, when this compound is added to a silver halide emulsion the contrast of the image obtained from this emulsion increases.

We have found that the iron compounds make the contrast of the emulsion higher.

The compounds of Group Vlll elements in the periodic table are added solely for the objects of this invention, but they can also be used to obtain various photo graphic effects as described above at the same time. Also, as is shown in British Pat. No. 570,393, one can apply the method of increasing the sensitivity of the emulsion by adding the metal compounds at the time of ripening. In other words, when used as a sensitizer or as a stabilizer or as an additive for increasing contrast, the effect of sensitization to green light is displayed if the above dyes are used together. The efficiency which the usual techniques aim at is not hindered.

The present invention will be illustrated in greater detail by the following examples.

EXAMPLE I An ordinary acid process silver chlorobromide cmulsion was prepared (containing 30 mol 71 AgBr) not containing the compounds containing metals of Group Vlll of the periodic table (hereinafter simply called metal compounds) and by the same method an emulsion was prepared. and at the time of forming the silver halide grains, ammonium hexachlororhodate (Ill) was added in a quantity equivalent to 7 X l mol per silver halide 1 mol, and at the after-ripening step, potassium hexachloroplatinate (IV) was added in a quantity corresponding 2 X 10' mol per silver halide l mol and the thus prepared emulsion was similar in sensitivity to the conventional emulsion. Each of these 2 emulsions was divided into two parts. One part was not dye-sensitized. To the other was added Dye l in a quantity of 4 X mol per 1 mol of silver halide in the emulsion. Next, formaldehyde was added to each of these in a quantity of 2.5 per IOO g of gelatin of the emulsion, and then each was applied to a photographic baryta paper.

Using an EG & G Sensitometer Mark Vll and through a colored glass filter V-YSO (made by Tokyo Shibaura Electric Co, Ltd.) and an optical wedge, the above described samples were each given exposures of 1/100 and of l/l,000,000 of a second. As is shown in the drawing, the colored glass filter V-Y50 (made by Tokyo Shibaura Electric Co., Ltd.) absorbs the light corresponding to the sensitive spectral region of the unsensitized silver halide and transmits only the light corresponding to the optically sensitized region of greater than about 500 nm. The exposed samples were developed at C for 2 seconds in the following developer:

NMethyl-para-aminophenol 2 g Sodium Sulfite, Anhydrous 30 g Hydroquinone 7 g Sodium Carbonate (Monohydrate) 53 g Potassium Bromide 1.5 g Water up to l liter l/l00th lll .0O0.000th Second Second Exposure Exposure Control Emulsion 0 0 Group Vlll Metal Only 0 0 Dye l Only 4.9 0.9 Group Vlll Metal Dye l 4.6 3.2

it was observed that by using the rhodate compound, the platinate compound and Dye (l) the green light sensitivity to flash exposure was increased.

EXAMPLE 2 A silver chlorobromide emulsion (containing 50 mol percent AgBr) was prepared in a neutral medium by a well known process and which does not contain the compounds of a Group Vlll metal of the periodic table (hereinafter simply called metal compounds), and one was also prepared by adding hexachlororhodate (III) in a quantity of 3 X 10 mol per 1 mol of silver halide in the above emulsion at the time of the formation of the silver halide grains, then further after ripening potassium chloroplatinate was added in a quantity of 2 X 10' mol per silver halide 1 mol. The thus prepared emulsion had about the sensitive as the abovedescribed emulsion. These two emulsions were each divided in two parts. One was left intact.

To the other part was added the Dye X in a quantity of6 X 10* mol per l mol of silver halide in the emulsion. Next, formaldehyde was added to each of these in the quantity of 2.5 g per g of gelatin of the emulsion, and the emulsion was applied to a photographic baryta paper.

The green light sensitivity was measured for the sample thus obtained in the manner as described in Example l and the following results were obtained.

It was observed that by using simultaneously the rho date salt, the platinate salt and Dye X, the green light sensitivity to the flash exposure was increased.

EXAMPLE 3 A silver chlorobromide emulsion (AgCl 50 mol percent, AgBr 50 mol percent) which does not contain the metal compounds of this invention was prepared in a neutral medium in a conventional manner.

Next, by the same method, at the formation of the silver halide grains, 3 X 10" mol per 1 mol of silver halide of ammonium hexachlororhodate was added to the emulsion, and then after ripening, platinum (IV) chloride in the quantity of 2 X 10 mol per silver halide 1 mol was added to prepare an emulsion having a sensitivity similar to that of the emulsion without the metal compounds. To each of these emulsions, as in Example I, Dye [V at a level of 2 X lo mol per 1 mol of silver halide was further added. In addition, 2.5g of formaldehyde was added per 100g of gelatin, and the emulsion was applied to a photographic baryta paper. The optical sensitization of the sample obtained was measured in the same manner as described in Example 1. The results obtained are shown in the following table.

In this case the effect of using the rhodate compound, the platinate salt and Dye IV together was observed.

EXAMPLE 4 A silver chlorobromide emulsion (AgBr 70 mol percent, AgCl 30 mol percent) which does not contain the metal compounds of this invention was prepared in an ammonium alkali medium in a conventional manner. Next, in the same manner potassium hexacyanoferrate (III) was added in a quantity of l X 10 mol per 1 mol of silver halide of the emulsion at the formation of silver halide grains. To these two emulsions Dye III was added in quantity of2 X mol per 1 mol of the silver halide.

Further, formaldehyde in a quantity of 2.5g per 100g of gelatin was added and the emulsion was applied to a photographic baryta paper. The sensitivity to green light of the samples thus obtained was measured in the same manner as described in Example I. The results obtained are shown in the table below.

l/lOOth l/l,000.000th In this case the combined effect of a Group VIII metal compound and Dye III was observed.

EXAMPLE 5 A silver chlorobromoiodide emulsion (AgBr 70 mol percent, AgCl 29 mol percent, Agl I mol percent) which does not contain the metal compounds of this invention was prepared in an ammonium alkali medium using a conventional method. Next, using the same pro cedure, 4 X I0 mol per I mol of silver halide of potassium hexacyanoferrate (III), 6 X 10 mol per 1 mol of silver halide of potassium hexachloroiridate (IV), 3X 10" mol per 1 mol of silver halide of ammonium hexachlororhodate (III) were added at the time of formation of the silver halide grains, and again at the afterripening 3 X l0 mol per l mol of silver halide of chloroauric acid was added, and prepared an emulsion having a sensitivity similar to that of the ordinary sensitivity.

To this emulsion as well as to the emulsion described above, Dye III in a quantity of 6 X 10 mol per silver halide 1 mol was added. Further, formaldehyde 2.5g per 100g of gelatin was added and the emulsion was applied to a photographic baryta paper. The green light sensitivity of this sample was then measured in the same manner as in Example I. The results obtained are shown in the table below.

Also, in this case the effect of the joint application of the Group VIII metal salt and Dye III was observed.

EXAMPLE 6 To the emulsion as used in Example 3 Dye VI was added corresponding to a quantity of 8 X IO mol per silver halide I mol, and this sample was tested in the same manner as described in Example I. The results obtained are shown in the table below.

In this case also, the effect of the combined treatment of Group VIII metal salt and Dye VI was observed.

EXAMPLE 7 A silver chlorobromide emulsion (AgCl 50 mol percent, AgBr 50 mol percent) which does not contain the metal compounds of this invention was prepared in an ammonium alkali medium in a conventional manner. Next, using the same procedure, at the formation of the silver halide grains, I X 10 mol per 1 mol of silver halide of potassium hexacyanoferrate (III) was added and the emulsion having a sensitivity similar to that of the emulsion not containing metal compounds was obtained. To each of these emulsions, as described in Example 1, Dye VIII was added in a quantity of4 X 10* mol per 1 mol of silver halide. Further, formaldehyde in a quantity of 2.5g per lOOg of gelatin was added, and the emulsion was applied to a photographic baryta paper. The sensitivity to green light of the thus obtained samples was measured using the same method as used in Example 1 and the following results were obtained.

In this case also, the combined effect of the ferrate and the Dye VIII was observed.

EXAMPLE 8 A chloroiodobromide silver halide emulsion (AgBr mol percent, AgCl 29 mol percent, Agl I mol percent) was prepared not containing metallic compounds of the present invention, using the conventional ammonium method. To an emulsion of the same composition we re added at the formation of silver halide grain particles, 4 X I0 mol potassium hexacyanoferrate (III) 6 X 1O- mol potassium hexachloroirridate (IV), 3 X IO" ammonium hexachlororhodate (III) per l mol silver halide in the emulsion, and then, at the after-ripening, 3 X IO per l mol of silver halide of chloroauric acid was added. A sensitivity similar to that of the abovedescribed ordinary emulsion was obtained.

To these emulsions was added Dye VII in a quantity corresponding to 2 X I0 mol per silver halide I mol. Again, to these emulsions was added formaldehyde in a quantity of 2.5g per IOOg of gelatin to prepare a photographic emulsion which was applied to a photographic baryta paper. The green light sensitivity of the sample was measured in the same manner as in Example l. The results obtained are shown in the table below.

In this instance also the effect of the combined use of the Group Vlll metal salt and Dye Vll was observed.

EXAMPLE 9 Dye XV] was added to an emulsion which was the same as used in Example 3 in a quantity of 2 X mol per l mol of silver halide. The emulsion was then treated the same as in Example 3 and tested in the same way as Example I.

l {100th l/l ,000.000th Second Second Exposure Exposure Control Emulsion 0 0 Group Vlll Metal Only 0 l] Dye XVI Only l3) Group Vlll Metal Dye XVI 89 79 In this case also the effect of the combined use of the Group Vlll metal salt and Dye XVI was observed.

In all the foregoing Examples, the silver halide particles employed were those which exhibited a homogeneous structure and further, exhibited a high surface sensitivity.

While the present invention has been adequately described in the foregoing specification and Examples included therein, it is readily apparent that various changes and modifications can be made to the same without departing from the spirit and scope thereof.

What is claimed is:

l. A light-sensitive silver halide photographic material comprising at least one layer having high sensitivity to green light under flash exposure on a support which comprises an emulsion consisting essentially of:

l. a binder,

2. light-sensitive silver halide grain particles of homogeneous structure exhibiting high surface sensitivity, compared to core-shell type particles,

3. at least one simple salt or complex salt of a Group Vlll metal selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and 4. at least one optical sensitizer selected from the group consisting of compounds of the general forwherein R is a member selected from the group consisting of a hydrogen atom and an alkyl group; wherein R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 4 carbon atoms, a substituted alkyl group selected from the group consisting of a hydroxyalkyl group, an acetoxyalkyl group, an alkyl group having a carboxy group and an alkyl group having a sulfo group, an ally] group, an aryl group, and an aralkyl group, in which at least one of R and R must be selected from the group consisting of a carboxyalkyl group and a sulfoalkyl group; wherein Y and Y each is selected from the group consisting of an oxygen atom, a sulfur atom, and a =NR group, in which R represents an alkyl group, wherein R R R and R each is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a cyano group, an alkoxy group, and an aryl group, in which if at least one R and R is an aryl group, then R and R,,- are not an aryl group; wherein X represents an anion selected from the group consisting ofa halogen ion and a thioeyanate iron; and wherein m represents an integer of 1 or 2, in which an intramolecular salt is formed if m is 1; and compounds of the formula:

R o s wherein R R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from I to 8 carbon atoms, a substituted alkyl group selected from the group consisting of a carboxyalkyl group, a hydroxyalkyl group and a sulfoalkyl group, wherein Y is a member selected from the group consisting of an oxygen atom, a sulfur atom, and a =NR group in which R is a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group, and wherein L and L each represents a methine chain.

2. The light-sensitive silver halide photographic material of claim 1, wherein said binders are selected from the group consisting of gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, sodium alginate, carboxymethyl cellulose and mixtures thereof.

3. The light-sensitive silver halide photographic material of claim 1, wherein said support is selected from the group consisting of glass, metal, wood, baryta paper, cellulose acetate film and polyester film.

4. The light-sensitive silver halide photographic material of claim 1, where the aryl group is selected from the group consisting of a phenyl group and a substituted phenyl group whose substituents are selected from the group consisting of a halogen atom and an alkyl group.

5. The light-sensitive silver halide photographic material of claim I, wherein said optical sensitizers are selected from the group consisting of 5.5',o-trichlorol.l '.3-triethyl-3' l 3carhoxypropyl l-henzimidazole carhocyanine iodide and F-allyl-S-E 2-( l-ethyl-4- methyl-tetrazolylidene lcthylidenc lrhodamine.

6. The light'scnsitive silver halide photographic material of claim I, wherein said sensitizer is used at a level of from l X 10 to l X 10"" mol per 1 mol ot said silver halide.

7. The light-sensitive silver halide photographic material of claim I, wherein said compound containing a Group VIII metal is potassium hexacyanoferrate (Ill) and wherein said optical sensitizer is 5,5',6-trichloro- I ,l ',3-triethyl-3-( 3carhox vpropyl )-benzimidazolecarhocyanine iodide,

8. The light'sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is ammonium hexachloro rhodate (Ill) and wherein said optical scnsitizer is 5,5',6- trichloro-l ,l ',3-triethyl-3'-( 3-carboxypropyl )-benzimidazolo-carbocyanine iodide.

9. The light-sensitive silver halide photographic material of claim I, wherein said compound containing a Group VIII metal is potassium hexachloroiridate (IV) and wherein said optical sensitizer is S,5',6-trichlorol,l ,3-t riethyl-3 3-carboxypropyl )-benzimidazolocarbocyanine iodide.

10. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexacyanoferrate (III) and wherein said optical sensitizer is 3-allyl-S-[2-( lethyl-4-methyl-tetrazolylidene)-ethylidenelrhodanine.

11. The lightsensitive silver halide photographic material of claim I, wherein said compound containing a Group VIII metal is ammonium hexachlororhodate (Ill) and wherein said optical sensitizer is 3'allyl-5-(2- (l-ethyl-4-methyl-tetrazolylideneJ-ethylidenelrhodanine.

12. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexachloroiridate (IV) and wherein said optical sensitizer is 3-allyl-5-l2-(lethyl4-methyl-tetrazolyiidene)-ethylidenelrhodanine.

IS. The light-sensitive silver halide photographic ma Combi nation System No The Simple or Complex Salt terial of claim I, wherein said R represents a member selected from the group consisting of a methyl group and an ethyl group; wherein R represents a member selected from the group consisting of a methyl group and an ethyl group; and wherein R R R and R each represents a member selected from the group consisting ola methyl group, an ethyl group, a chlorine atom, a bromine atom, a fluorine atom, a methoxy group, an ethoxy group, and a phenyl group.

14. The |ight-sensitive silver halide photographic material ofclaim 1, wherein said complex salt is a member selected from the group consisting of a hexagonal com plex salt, a tetragonal complex salt, and a square-plane complex salt.

15. The light-sensitive silver halide photographic material of claim 14, wherein said complex salt is an alkali metal or ammonium salt selected from the group consisting of hexacyanoferrate (ll), hexacyanoferrate (III hexachloroiridate (Ill).

16. The light-sensitive silver halide photographic material of claim 1, wherein said simple salts are rhodium (Ill) halide or iridium (IV) halide.

17. The light-sensitive silver halide photographic ma terial of claim 4, wherein the alkyl group having a carboxy group in R and R is a carboxy-(alkoxy),, ,-alkyl group wherein n is I or 2; wherein the alkyl group having a sulfo group in R and R is selected from a sulfo (alkoxy),, -alkyl group (rt-=1, 2 or 3), a hydroxy sulfo'(alkoxy),, ,-alkyl group (n=1 or 2) and an acyloxy-sulfo group.

18. The light-sensitive silver halide photographic material of claim 1, wherein the substituted alkyl group in R and R is selected from the group consisting of a betahydroxyethyl group, a beta-acetoxyethyl group, a carboxymethyl group, a beta-carboxyethyl group, a gamma-carboxypropyl group, a 2-(2-carboxyethox y)ethyl group, a beta-sulfoethyl group, a gammasulfopropyl group, a delta-sulfobutyl group, a Z-hydroxy-l-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, a Z-acetoxy-I-sulfopropyl group, a 3- methoxy-2-(3-sulfopropoxy)propyl group, a 2-[2-(3- sulfopropoxyJethoxy]ethy] group and a 2-hydroxy-3- (3-sulfopropoxy)-propyl group; wherein the substituted alkyl group in R R and R is selected from the group consisting of a carboxymethyl group, a betahydroxyethyl group, a beta-sulfoethyl group and a gamma-sulfopropyl group.

19. The light-sensitive silver halide photographic material of claim 1 wherein the optical sensitizer and the simple or complex salt is selected from the following combination systems:

The Optical Sensitizer l Ammonium hexachlororhodate (III) Potassium hexachoroplatinate (IV) N N CH, 2 do.

? CIHS (ontinued Combination System No The Simple or Complex Salt The Optical Sensitizer 3 Ammonium hexuchlororhodute (Ill) 32 H 5 Platinum (IV) chloride y C] C=CH-CH=CH-C (9 N N S I I 2 5 fla s 4 Potassium hexacyanoi 5 ferrule (III) c] C=CH-CH=CH-C (9n gv C I Potassium hexacyano- 5 ferrute (Ill) Potassium hexachloroiridate (IV) Ammonium hexaclorodo. rhodate (Ill) C2H5 6 The same as Nov 1 h C] g): C-CH- cH=cH-c n v 2s cu cu coou H 7 Potassium hexacyano- 2 H 5 c] femmmn :I QcH-GcH-c H 3 co N N 9 C H (CH $O 8 The same as No. 5 :2 5

C=CH-CH:CH-Ci@:\ NC t d N c1 l 2 5 CH CH CH COOH N N CH 9 The same as No. 3 If C,H,, N

CH,CH=CH,

20. The light-sensitive silver halide photographic maprises exposing to a flash light the silver halide phototerial of claim 1, wherein flash exposure is exposure to the afterglow of the fluorescence of a cathode ray tube or a xenon flash lamp for time ranging from l/l0,000,000 of a second to 1/l00,000 of a second.

21. A photographic recording process which comgraphic material comprising at least one layer having high sensitivity to green light under flash exposure on a support which comprises an emulsion consisting essentially of:

1. a binder,

2. light-sensitive silver halide grain particles of homo geneous structure exhibiting high surface sensitivity, compared to core-shell type particles.

3. at least one simple salt or complex salt of a Group VIII metal selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and

4 at least one optical sensitizer selected from the group consisting of compounds of the general for mula:

wherein R is a member selected from the group con sisting of a hydrogen atom and an alkyl group; wherein R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 4 carbon atoms, a substituted alkyl group selected from the group consisting of a hydroxyalkyl group, and acetoxyalkyl group, an alkyl group having a carboxy group and an alkyl group having a sulfur group, an ally] group, an aryl group, and an aralkyl group, in which at least one of R and R must be selected from the group consisting of a carboxyalkyl group and a sulfoalkyl group; wherein Y, and Y2 each is selected from the group consisting of an oxygen atom, a sulfur atom, and a =l\lR group, in which R represents an alkyl group wherein R R R and R each is selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a cyano group, an alkoxy group, and an aryl group, in which if at least one R 3 and R is an aryl group, then R and R are not an aryl group; wherein X represents an anion selected from the group consisting of a halogen ion and thiocyanate ion, and wherein m represents an integer of l or 2, in which an intramolecular salt is formed if m is l; and compounds of the formula:

A] N R8 "w I Y l 2 C 3 N l C C R O4 S wherein R R and R each represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 8 carbon atoms, a substituted alkyl group selected from the group consisting of a carboxyalkyl group, a hydroxyalkyl group and a sulfoalkyl group, wherein Y is a member selected from the group conslisting of an oxygen atom, a sulfur atom, and a =NR group in which R is a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group; and wherein L, and L each represents a methine chain, said exposing being for a time shorter than 1 X 10 seconds, and thereafter developing said photographic material.

22. The photographic recording process of claim 20 wherein the photographic material is exposed to a flash light for a time of at most l X l0" seconds.

23. The photographic recording process as claimed in claim 20 wherein the light-sensitive silver halide particles are formed by a process which comprises forming silver halide precipitates, and further wherein a salt of a Group VIII metal is added at the stage of forming said silver halide precipitate.

Claims (33)

1. A LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL COMPRISING AT LEAST ONE LAYER HAVING HIGH SENSITIVITY TO GREEN LIGHT UNDER FLASH EXPOSURE ON A SUPOORT WHICH COMPRISES AN EMULSION CONSISTING ESSENTIALLY OF,

1. A BINDER,

2. The light-sensitive silver halide photographic material of claim 1, wherein said binders are selected from the group consisting of gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, sodium alginate, carboxymethyl cellulose and mixtures thereof.

2. light-sensitive silver halide grain particles of homogeneous structure exhibiting high surface sensitivity, compared to core-shell type particles,

2. light-sensitive silver halide grain particles of homogeneous structure exhibiting high surface sensitivity, compared to core-shell type particles,

2. LIGHT-SENSITIVE SILVER HALIDE KGRAIN PARTICLES OF HOMOGENEOUS STRUCTURE EXHIBITING HIGH SURFACE SENSITIVITY, COMPARED TO CORE-SHELL TYPE PARTICLES,

3. at least one simple salt or complex salt of a Group VIII metal selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and

3. The light-sensitive silver halide photographic material of claim 1, wherein said support is selected from the group consisting of glass, metal, wood, baryta paper, cellulose acetate film and polyester film.

3. at least one simple salt or complex salt of a Group VIII metal selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, and

3. AT LEAST ONE SIMPLE SALT OR COMPLEX SALT OF A GROUP VIII METAL SELECTED FROM THE GROUP CONSISTING OF IRON, COBALT, NICKEL, RUTHENIUM, RHODIUM, PALLADIUM, ISNUYNM IRIDIUM AND PLATINUM, AND

4. LEAST ONE OPTICAL SENISITIZER SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OF THE GENERAL FORMULA:

4. at least one optical sensitizer selected from the group consisting of compounds of the general formula:

4. at least one optical sensitizer selected from the group consisting of compounds of the general formula:

4. The light-sensitive silver halide photographic material of claim 1, where the aryl group is selected from the group consisting of a phenyl group and a substituted phenyl group whose substituents are selected from the group consisting of a halogen atom and an alkyl group.

5. The light-sensitive silver halide photographic material of claim 1, wherein said optical sensitizers are selected from the group consisting of 5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazole -carbocyanine iodide and 3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)ethylidene)-rhodamine.

6. The light-sensitive silver halide photographic material of claim 1, wherein said sensitizer is used at a level of from 1 X 10 2 to 1 X 10 5 mol per 1 mol of said silver halide.

7. The light-sensitive Silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexacyanoferrate (III) and wherein said optical sensitizer is 5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazole -carbocyanine iodide.

8. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is ammonium hexachloro rhodate (III) and wherein said optical sensitizer is 5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazolo -carbocyanine iodide.

9. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexachloroiridate (IV) and wherein said optical sensitizer is 5,5'',6-trichloro-1,1'',3-triethyl-3''-(3-carboxypropyl)-benzimidazolo -carbocyanine iodide.

10. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexacyanoferrate (III) and wherein said optical sensitizer is 3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.

11. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is ammonium hexachlororhodate (III) and wherein said optical sensitizer is 3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.

12. The light-sensitive silver halide photographic material of claim 1, wherein said compound containing a Group VIII metal is potassium hexachloroiridate (IV) and wherein said optical sensitizer is 3-allyl-5-(2-(1-ethyl-4-methyl-tetrazolylidene)-ethylidene)-rhodanine.

13. The light-sensitive silver halide photographic material of claim 1, wherein said R0 represents a member selected from the group consisting of a methyl group and an ethyl group; wherein R7 represents a member selected from the group consisting of a methyl group and an ethyl group; and wherein R3, R4, R5 and R6 each represents a member selected from the group consisting of a methyl group, an ethyl group, a chlorine atom, a bromine atom, a fluorine atom, a methoxy group, an ethoxy group, and a phenyl group.

14. The light-sensitive silver halide photographic material of claim 1, wherein said complex salt is a member selected from the group consisting of a hexagonal complex salt, a tetragonal complex salt, and a square-plane complex salt.

15. The light-sensitive silver halide photographic material of claim 14, wherein said complex salt is an alkali metal or ammonium salt selected from the group consisting of hexacyanoferrate (II), hexacyanoferrate (III), hexachloroiridate (III).

16. The light-sensitive silver halide photographic material of claim 1, wherein said simple salts are rhodium (III) halide or iridium (IV) halide.

17. The light-sensitive silver halide photographic material of claim 4, wherein the alkyl group having a carboxy group in R1 and R2 is a carboxy-(alkoxy)n 1-alkyl group wherein n is 1 or 2; wherein the alkyl group having a sulfo group in R1 and R2 is selected from a sulfo-(alkoxy)n 1-alkyl group (n 1, 2 or 3), a hydroxy-sulfo-(alkoxy)n 1-alkyl group (n 1 or 2) and an acyloxy-sulfo group.

18. The light-sensitive silver halide photographic material of claim 1, wherein the substituted alkyl group in R1 and R2 is selected from the group consisting of a beta-hydroxyethyl group, a beta-acetoxyethyl group, a carboxymethyl group, a beta-carboxyethyl group, a gamma-carboxypropyl group, a 2-(2-carboxyethoxy)ethyl group, a beta-sulfoethyl group, a gamma-sulfopropyl group, a delta-sulfobUtyl group, a 2-hydroxy-1-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, a 2-acetoxy-1-sulfopropyl group, a 3-methoxy-2-(3-sulfopropoxy)propyl group, a 2-(2-(3-sulfopropoxy)ethoxy)ethyl group and a 2-hydroxy-3-(3-sulfopropoxy)-propyl group; wherein the substituted alkyl group in R8, R9 and R10 is selected from the group consisting of a carboxymethyl group, a beta-hydroxyethyl group, a beta-sulfoethyl group and a gamma-sulfopropyl group.

19. The light-sensitive silver halide photographic material of claim 1 wherein the optical sensitizer and the simple or complex salt is selected from the following combination systems:

20. The light-sensitive silver halide photographic material of claim 1, wherein flash exposure is exposure to the afterglow of the fluorescence of a cathode ray tube or a xenon flash lamp for time ranging from 1/10,000,000 of a second to 1/100,000 of a second.

21. A photographic recording process which comprises exposing to a flash light the silver halide photographic material comprising at least one layer having high sensitivity to green light under flash exposure on a support which comprises an emulsion consisting essentially of:

22. The photographic recording process of claim 20 wherein the photographic material is exposed to a flash light for a time of at most 1 X 10 7 seconds.

23. The photographic recording process as claimed in claim 20 wherein the light-sensitive silver halide particles are formed by a process which comprises forming silver halide precipitates, and further wherein a salt of a Group VIII metal is added at the stage of forming said silver halide precipitate.

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