DE2063669A1 - Silver halide photographic photosensitive materials - Google Patents

Description

Photosensitive photographic silver halide

According to the invention, photosensitive photographic silver halide materials are obtained which contain, on a support, at least one layer with a binder comprising (1) photosensitive silver halide grain particles, (2) at least one compound of a metal of group VIII in an amount of 1 × 10 "to 1 × 10"" ⁵ mol each 1 mole of the sirber halide, and (3) at least one optical sensitizer from the group of compounds of the general formula

where Ro,

R ₅ , Rg, Y ₁ , Y ₂ , X and m the ones after

have the following meanings, and compounds

108-830 / 1214

the general formula

- X- * 8

J ^ = L ₁ -L ₂ = C -Y ₃

R ₁₀

where R «, Rg, ^ in * ^ 1 * ^ 2 ^{un (} * ^ 3 ^ * ^{e 11810} ^ have the meanings given below.

The invention is concerned with silver halide photographic light-sensitive materials. In particular concerns the invention is silver halide photographic light-sensitive materials having a high sensitivity against green light under flash exposure. The term "flash exposure" is defined below.

The present age is one of information. Various schemes have been used to favor the rapid Transmission of information developed. For example, press facsimile systems quickly transmit the press ™ manuscripts to distant places, high-speed phototype typesetting systems speed up printing and type networking and cathode ray tube (CRT) * replacement systems the rapid output of letters or figures when providing information from computers. With such equipment of such rapid information transmission systems are often very short exposure times of less than t / 100,000 second or in particular about 1/1,000,000 second is frequently used. The demand for sensitive material for such equipment was in

1 0 9 8 3 0/1 2 U

particularly high in recent years.

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 will those whose fluorescence has a particularly short afterglow, which is known to be useful for flying spots is used as a cathode ray tube. For example, such fluorescent materials with P-11, P-15, P-16 and P-24 are designated and are used as light sources for used for these purposes. It is known that the light distribution of spectral energy at P-11 has a peak of 460 nm and at P-16 of .385 nm. This peak corresponds the range of the spectral absorption properties of photosensitive silver halides and therefore no visual sensitization necessary. On the other hand, P-15 is known to have its maximum fluorescence spectral energy at 505 nm or at P-24 it is 520 nm. The light-sensitive materials for recording of images at CRT must therefore be sensitive to green light. On the other hand, a xenon flash lamp emits Light over a relatively wide spectral range. The light from the light source produces images on the sensitive materials through an optical system consisting of a condenser lens, negative matrix, main lens, prism, reflector or deformation lens or other special lenses or prisms. The light of short wavelength becomes larger absorbed by the optical parts in the path. Therefore, in the light that reaches the sensitive material, the constituent is with shorter wavelength from ultraviolet to blue decreases and the component with longer wavelength richer in green. Therefore, a green sensitization is used to increase the sensitivity of the sensitive material

109830 / 12U

necessary * The afterglow of the Fluorescence from a cathode ray tube is in the range from i / 10,000,000 of a second to 1 / 100,000 of a second Second and in the case of a xenon flash, there are also those used with approximately the same radiation period. In the context of the invention, the short-term exposure is with these two types of light sources are generally called "Flash exposure".

The usual sensitizers for green light Beigen P have a markedly lower spectral serisibilization a flash exposure of -1/100 000 of a second or less compared to the results of the usual exposure of I / 10000 seconds or longer. Specifically occurs a strong indication of this tendency on where, to speed up the treatments after exposure, such as Fixation or stabilization, the silver halide is partly or wholly composed of silver chloride, i.e. Silver chloride emulsions i-chlorobromide emulsions or chloroiodobromide emulsions.

One object of the invention is photographic sensitive materials with high sensitivity to _. Green light with flash exposure, based on the invention he ™ are silver halide photographic light-sensitive materials on a support, on which at least one layer is applied, which is in the binder, such as gelatin and the like. " sensitive silver halide grain particles, at least one compound containing a Group VIII metal of the periodic table in a ratio of 10 to 10 "" ' Mole to 1 mole of silver halide and at least one optical sensitizer from the group of, compounds of

1098 3071214

general formula

J /

-C = CH-C

where Rq is a hydrogen atom or an alkyl group, R ₁ and R- are each a hydrogen atom, an alkyl group, a substituted alkyl group, an allyl group, an aryl or araikyl group, where at least one of the radicals R ₁ and Rp consists of a carboxyalkyl group or sulfoalkyl group, Y ₁ and Y «each represent an oxygen atom, a sulfur atom or a group> NR«, where R «represents an alkyl group, R ,, R., Re and Rg each represent a hydrogen atom, a halogen atom, an alkyl group, a cyano group, an alkoxy group or an aryl group, where, if at least one of the radicals R, and R- is an aryl group, the radicals Rk and Rg are not aryl groups, X is an anion, for example a halogen ion or thiocyanate ion and m is the number 1 or 2, where in the case of an intramolecular Salt m has the value 1, and mean compounds of the general formula _ ■ ■

NR ₈ .- ■ ;.

109830/1214

wherein Rg, Rg and R ₁ Q each represent a hydrogen atom, _f an alkyl group, a substituted alkyl group, an allyl group or an aryl group, Y, an oxygen atom, a sulfur atom or a> NR ^ ₁ group, wherein R _{11 is} a hydrogen atom, a Represents alkyl group or aryl group, and L-. and L «each denote the atoms of a methine chain.

In the accompanying drawing is the light permeability a glass filter V-Y5O, which is used in the examples to evaluate the effectiveness of the photosensitive photographic materials used.

In general, glass plates, metal plates, wooden plates, baryta papers, photographic papers, cellulose acetate film bases, Polyester film bases and the like can be used.

Suitable binders are water-soluble film-forming compounds of high molecular weight, such as gelatin, polyvinyl alcohol, Poly vinyl pyrol / iidone, sodium alginate, carboxymethyl cellulose. The binders can be used both individually and in combination.

As light-sensitive silver halides, silver chloride, Silver bromide, silver chlorobromide, silver iodobromide, Silver chloroiodobromide can be used. The so-called preparation of the sensitive silver halide emulsion, i.e. the preparation of the silver halide crystal grains in the Binders in the dispersed state and their growth to the appropriate one The crystal size for the formation of the silver halide emulsion can be determined by the usual methods. the metals belonging to group VIJI of the periodic table are iron, cobalt, nickel, ruthenium ^ rhodium, palladium, osmium, iridium, platinum, the compounds of these metals, which are conveniently used in the invention

109830 / 12H

BATH ORIGINAL

Iron (II) sulfate (FeSO ₄ .5H ₂ O), iron III chloride (PeCl ₃ ), potassium hexacyanoferrate (II) (K ₄ ^ Fe (CN) ₆ /. 3HgO), potassium hexacyanoferrate ( III) (K ₅ ^ eONg ¹ J), cobalt (II) chloride (CoCl ₂ j cobalt (II) nitrate (Oo ^ O, / «^ HgO), potassium hexacyanocobaltate (III) / Co (CN) ₆ /), nickel-dD-chloride (NiCl ₂ .6H ₃ O), nickel- (II) -nitrate (Ni / lKJj / g.eHgO), ruthenium chloride (RuCl ₅ ), potassium hexachlororuthenate-dV) (K ₂ RuCl ₆ ), Rhodium (III) chloride (RhCl ₅ , 4-ffgO), ammonium hexachlororhodate (III) (^ NH ₄ Z ₅ RhCl ₆ ), palladium nitrate (Pd ^ NO ₅ Z ₂ ), palladium bromide (PdBr ₂ ), potassium h & xaohlorpalladat -dV) (K ₂ PdCl ₆ ), Ä

Potassium tetrathiocy & nopalladat-dl) (K ₂ PdZcNsZ ₄ ), osmium (II) chloride (OeCl ₂ ), iridium (IIl) chloride (IrCl ₅ ), iridium (IV) chloride (IrCl ₄ ), iridium ( III) bromide (IrBr ₅ .4K ₂ 0), iridium (IV) bromide (IrBr ₄ ), potassium hexachloriridate (III) (K ₅ IrCl ₆ ), potassium hexachloriridate (rST) (KgIrCl ₆ ), ammonium hexachloroplatinate ( IV) (^ IfH ₄ Z ₂ PtCl ₆ ), potassium hexabromoplatinate (IV) (KgPtCl ₆ ), ammonium hexabromoplatinate (IV) (/ NH ₄ Z ₃ PtBr ₆ ).

The Group VIII metal compounds can either be singular as well as in combination of two or more compounds together in the silver halide emulsions in

-6 -3 entspreahend an amount 10 mol bit 10 'mole, preferably

10 "^ to 3x10 ■ moles, used for 1 mole of silver halide will. Me adding theeet compounds to the emulsion can at various stages of manufacture, for example in the formation of d & J · silver halide grain particles in the Preparation of the silver halide emulsion as an addition either to the halide solution or to the gelatin dispersion solution or at the beginning of the ripening of the emulsion or in intermediate stages take place. The compounds can also be used together with other known stabilizers, anti-fogging agents Anti-bronzing agents, surfactants, hardeners / plasticizers, matting agents ^

108830 / 12H ^:

Development accelerators or whitening agents and the like. Desirably before being applied to the Added emulsion »

One of the optical sensitizers according to the invention consists of compounds of the general formula

C = GH-C = CH-G

wherein R _{Q is} a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, for example a methyl group,

an ethyl group and the like., R- and

one water each

substance atom or an alkyl group with 1 to 4 carbon atoms, for example a methyl group, ethyl group or propyl group and the like, a substituted alkyl group, for example a β-hydroxyethyl group, β-acetoxylthyl group, carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, 2- ( 2-carboxyethoxy) -ethyl group, S- "J-sulphoethyl group, γ-sulfopropyl group, ε -sulfobutyl group, 2-hydroxy-i-sulfopropyl group, 2- (3-sulfopropoxyethyl group, 2-acetoxy-i-sulfopropyl group, 3-methoxy-2 * - (3-sulfopropoxy) propyl group, 2- ^ 2- (3-sulfopropoxyethox3i / ethyl group, 2-hydroxy-3- (3-sulfopropoxy) propyl group and the like, an aryl group such as a phenyl group or aralkyl group, but at least one of the radicals R «| and R ₂ consists of an oarboxyalkyl group or sulfoalkyl group, Y ^ and .Y ₂ an oxygen atom, a sulfur atom or a group> NR ₇ , in which R _{7 is} an alkyl group with 1 to 3 carbon

1 0 9 8 3 Q / 1 2 H.

represents atoms, for example a methyl group or an ethyl group and the like., R ,, R, R ₁ - and Rg each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and the like., a halogen atom, for example Fluorine, chlorine, bromine, a cyano group, an alkoxy group, for example a methoxy or ethoxy group, or an aryl group, for example a phenyl group, but if at least one of the radicals R. and R is an aryl group, neither R ₁ - nor Rg are an aryl group, X is an anion, for example a halogen ion, a thiocyanate ion, a sulfate ion, sulfanate ion, perchlorate ion, p-toluene sulfonate ion, benzenesulfonate ion, ethyl sulfate ion or methyl sulfate ion, and m the numbers 1 or 2, where in the case of an intramolecular salt m the value 1 owns, mean.

Specific examples of compounds from these optical sensitizers are given below:

Dye I.

^C 2 ^H 5

, C = CH-C-CH-C

Melting point

281T

109830/1 2U

Dye II

C ₂ H ₅

C = CH-C = CH-C

(CH ₂ ) ₃ SO 3 Na

Melting point 210 ^c C

Dye III

C = CH-CH = CH-C

Cl melting point 262 ^° C

Dye IY

Dye V

, C = CH-CH = CH-C

C ₂ H ₅

Melting point 233 ^° C

2> 3 ^S0 3 .

CH

C = CH

(CH ₂ J ₃ SO ₃ H

Melting point 2

(CH ₂ ) 3 SO 3

Dye VI

Enamel

. '- üunkt'

205 ⁰ C

₂ CH ₂ C00H

Dye VII

C = CH-CH = CH-C

1098 30

Melting point

210 ⁰ C

H ₂ CH ₂ CH ₂ COOH

BATH

Dye VIII

^l 2'4 ^SO 3 ^Na

(CH ₂ ) ₄ SO ₃

Melting point above 30O ⁰ C

Melting point above 30O ⁰ C

Such sensitizers are for example in the U.S. Patent Nos. 2,503,776, 2,912,329, 3,397,060, French Patent No. 1,108,788, Japanese Patent Publication 44-14030 described and the preparation of these sensitizers can be known per se Process according to the above patents and other technical literature. The other sensitizers used in the invention have the following general formula

N-

-N-

R ₉

/ N = L ₁ -L ₂ = G

[I.

1DS83Q / 12U

wherein R ₈ , R _q and R ₁₀ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, for example a methyl group, ethyl group, propyl group, butyl group, a substituted alkyl group, for example carboxymethyl group, ß-hydroxyethyl group, ß-sulfoethyl group, γ-sulfopropyl group , Allyl group or aryl group such as a phenyl group, a substituted phenyl group such as a chlorine atom, an alkyl group and the like substituted, Y, an oxygen atom, a sulfur atom or a group "^ -R ₁₁ in which R _{11 is} a hydrogen atom, an alkyl group with 1 to 8 carbon atoms or a phenyl group, and L ₁ and L ₂ each represent a methine chain from the group = CH-, = C (CH,) - and = C- ^,

mean.

Specific examples of compounds for these sensitizers are as follows:

109830/1214

Dye X

N N CH-

N. C = CH-CH = C S

C ₂ H ₅ ^ C _v C

Melting point 245 ^° C

Dye XI

CH

, N = CH-CH = C S

oHc ^{2 5} melting point 232 ⁰ C

.CH

H ₃ C CH ₃

Dye XII ν —Ν CH-

N N = CH-CH = C- ^ - T-S

CoH

n CH ο CH -ι melting point 19O ⁰ C

Dye XIII

C = CH-CH = C

^ c

Melting point 201 ⁰ C

109830 / 12U

Dye XIV

CH,

^ ^ N = CH-CK = C O

Melting point 233 ^° C

C ₂ H ₅

Dye XV

_CH melting point 240 ° -

.C = CH-CH = C -— Ο

CH ₂ = CH-

Dye XVI

N CH-

Melting point

I L

IL, C = CH-CH = 230 ^° C

CH = CO

^C 2%

CH ₂ -CH = CH ₂

Dye XVII

N N -—- CH-

Melting point 290 ^c C

N ^ JC = CH-CH = Q: S

^ I - 1

^C 2 ^H 5

Dye XVIII

K N CH-

Melting point 242 ^° C

.C = CH-CH = C S

CH ₂ COOH

109830 / 12U

■ ■ ^{: ί:} "" - · · ■ »«! HI! II !!! ¹ : -: <'.SS

Dye XIX $ - ^ - ^C 2 ^H 5 * L ^ Melting point 25O ⁰ C

Such sensitizers are described, for example, in British patent specification 801 275, and the sensitizers can be prepared according to processes known per se in accordance with the above patent specification and other technical literature references. These optical sensitizers are used either singly or ", preferably 10 2 mol""* to 5x10 '""Mol used in combination of two or more at a ratio of 10 ^-5 to 10 1 per mole of silver halide in the silver halide emulsion. The addition of the optical Sensitizers to the emulsion can be added in the same way as for the metal compounds described above. The addition to the emulsion can be carried out either simultaneously with the metal compound or separately. The order of addition is immaterial.

The manufacture of the photosensitive photographic g Silver halide materials can thus practically be used in the '

in the same way as usual, but with the the above metal compounds and optical sensitizers can be added, and the thus prepared Sensitive material can be developed and fixed in the usual way after flash exposure. The material can also be treated in what is commonly known as diffusion transfer processes. if beforehand an appropriate amount of the developing agent

109830 / 12U

2063668

incorporated into the photosensitive layer * can development according to the well-known activator development process that is, a process in which the photosensitive material containing the; Development> means contains, is developed in a solution in which no developing agent is included and only one. alkaline material is dissolved.

It was found that. with photosensitive Materials similar to those given above. Include metal compounds, but none of the foregoing optical sensitizers contain that sensitivity against green light is not obtained, although in some Cases their sensitivity to blue light is improved. On the other hand, it has been found that in the case of sensitive materials which do not contain the metal compounds, but only the optical sensitizers contain, ^ the sensitivity to greens is not very much is high. However, if these two types of materials simultaneously; can be used: the sensitivity: markedly improved against green light during flash exposure will.

In particular, in the case of silver, chlorine idemulsions. Silver chlorobromide emulsions or silver chlorobromoiodide emulsions. .if: the above sensitizers are used alone; a considerable degradation; the effectiveness of spectral sensitization in: flash exposure; established.; For ^: such emulsions the present invention is; particularly valuable.,.

Ea has long been: began that; the MeisBiElve ^ Mndungen-n various notable ones; Effects show and in US Pat. ^1; 2 di ^ ff Q6ö is given ,, that; ,, if lexa * alo: genrud; heniumr-tlir) / - acid-

1'09820 / 12TA

salts, hexahalogen rhodium (IV) acid salts, hexahalogenosmium (IV) acid salts, Hexahalogenir / idium (IV) acid salts or hexahalogplatinum (IV) acid salts to one Silver halide emulsion are added at the time of ripening, the sensitivity of this emulsion increases. Furthermore, US Pat. No. 2,566,745 describes that when these compounds are used in addition to Silver halide emulsion can be added, the stability of the sensitive material at high temperatures and Moisture is improved and continues to be in the US patent 2,517,541 describes that when potassium f hexacyanocobaltate-ClII) and according to FIAT report No. 360, Rhodium trichloride can be added to a silver halide emulsion, the contrast of that obtained on this emulsion Image is increased.

It was found that the iron compounds make the contrast of the emulsion higher.

The compounds of the elements of Group VIII of the The periodic table is presented for the purposes of the invention only added, but can also be used to achieve the various photographic images listed above Effects are used. One can also determine the sensitivity of the emulsion according to British patent specification 570,393 increase if the metal compounds are added at the time of ripening. If, in other words, they be used as sensitizers or as stabilizers or as additives to increase the contrast, the effect of sensitizing green light is further exhibited if the above dyes to be used in conjunction with this. The effectiveness that they show in the usual procedures is not affected by it with special needs.

109830 / 12U

The following examples serve to further illustrate the invention.

example 1

A silver chlorobromide emulsion was made according to the usual Acid process with a content of 30 mol- $ AgBr, which represents the metals of Group VIII of the Periodic table containing compounds, hereinafter referred to simply as metal compounds

Wl , and emulsion was further prepared by the same procedure, and at the time of formation of the silver halide grains, ammonium hexachloro-rhodate- (III) was added in an amount of 7x1 (T ⁶ moles per 1 mole of silver halide, and in the post-ripening stage, potassium hexachloroplatinate- (IV) was added in in an amount of 2 x 10 moles per 1 mole of silver halide, the emulsion thus prepared had a sensitivity similar to that of the usual emulsion. Each of these two emulsions was divided into two parts, one part not sensitized with dye, and the other became dye I was added in an amount of 4 × 10 mol per 1 mol of silver halide in the emulsion, then formaldehyde was added to these emulsions in an amount of 2.5 g per 100 g of gelatin in the emulsion, and then each emulsion was coated on a photographic baryta paper.

Using an EG and G Mark VII sensitometer and a V-Y50 colored glass filter from Tokyo Shibaura Electric Co. _v Ltd. and an optical wedge, the above samples were exposed at 1/100 of a second and 1 / 1,000,000-second, respectively. As can be seen from the drawing, the colored glass absorbs

'109830/1214

filter V-Y5O from Tokyo Shibaura Electric Go., Ltd. the light corresponding to the sensitive spectral range of the unsensitized silver halide and only allows the light corresponding to the optically sensitized range greater than about 500 nm to pass through. The exposed samples were developed in the following developer ^{at 20 ° C. for 2 seconds:}

N-methyl-para-amino phenol 2 g

Sodium sulfite, anhydrous 30 g

Hydroquinone Tg ™

Sodium carbonate (monohydrate) 53 g

Potassium bromide 1.5 g

Water to 11

After fixing, rinsing and drying, the reflection density of the images was determined.

The reciprocal of the amount of light giving a density of 0.5 was taken as the sensitivity value; However, since the absolute amount of light was not determined by the filter, the sensitivity is only relative j in the following table the sensitivities for the same exposure time are given correspondingly λ . The results obtained are summarized in Table ^:

109830/1214

Comparative emulsion

Group VIII metal only

dye I only

Group VIII metal + dye I.

Exposure for 1/100 of a second

0
4.9

4.6

Exposure during a

1/1 000 000

second

0
0.9

3.2

It turns out that by using the rhodate compound, of the platinum compound and the dye (I) the sensitivity to green light upon flash exposure was increased.

Example 2

A silver chlorobromide emulsion containing 50 mol $ AgBr was prepared in a neutral medium by a known method which did not contain any compound of a Group VIII metal, hereinafter referred to simply as metal compounds, and a sample was prepared with the addition of hexachlorohydate. (III) in an amount of 3 × 10 mol per 1 mol of silver halide in the above emulsion at the time of formation of the silver halide grains, and furthermore, after ripening, potassium chloroplatinate in an amount of 2 × 10 ^J. Mol per 1 mol of silver halide was added. The emulsion thus prepared had about the same sensitivity as the above emulsion. These two emulsions were divided into two parts each. One of these parts was used as is.

To the other part, the dye X became in one Quantity of 6x10 moles per 1 mole of silver halide in the

10 9 8 3 0/1214

Emulsion added. Then, formaldehyde was added to each emulsion in an amount of 2.5 g per 100 g of gelatin added to the emulsion and the emulsion applied to a photographic baryta paper.

With the samples obtained, the green sensitivity became determined in the manner indicated in Example 1 and obtained the following results:

Exposure exposure during

during a one

1/100 second 1/1 000 000 second f

Comparative emulsion 0 0

only metal the

Group YIII 0 0

only dye X 12.0 2.7

Metal of the group

VIII + dye X 10.5 7.2

It turns out that by simultaneous use of the rhodate salt, the platinum salt and the dye X the sensitivity to green light during flash exposure has been increased.

Example 3

A silver chlorobromide emulsion of 50 mol % AgGl and 50 mol% AgBr, which did not contain any metal compound of the present invention, was prepared in a neutral medium in the usual manner.

In the same procedure, in preparing the silver halide grains, 3x10 " ⁶ mol per 1 mol of silver halide of ammonium hexachlororhodate was added to the emulsion, and after ripening, platinum (IV) chloride was added in an amount of ² × 10 -5 mol per 1 mol of silver halide for preparation an emulsion with an equal

109830 / 12U

Sensitivity, like the emulsion without the metal compounds, trains sets. For each of these emulsions, as in Example 1, the dye V in an amount of 2 × 10 mol per 1 mol of silver halide further added. Furthermore, 2.5 g of formaldehyde were added to 100 g of gelatin and the emulsion was added to photographic baryta paper applied.

The optical sensitization of the obtained samples was determined in the same manner as in Example 1. The results obtained are given in the table below.

Exposure Exposure during a 1/100 second 1/1 000 000

second

Comparative emulsion 0 0 only metal the Group VIII 0 0 only dye V 12.7 2.9

Group VIII metal + dye V

10.8

7.5

In this case, too, the effect of using the rhodate compound, the platinate compound together and of the dye V are observed.

Example 4

A silver chlorobromide emulsion with 70 Mo1- $ AgBr and 30 mol $ AgCl, which is not a metal compound according to Invention was prepared in an alkaline ammonium medium in a conventional manner. Then became in the same Way an emulsion is made and potassium hexacyanoferrate

Mole per 1 mole of silver

l (III) in an amount of 1x10 ~ ⁵

109830/1214

halide is added to the emulsion at the time of formation of the silver halide grains. To these two Emulsions - the dye III was added in an amount of 2 × 10 moles per 1 mole of silver halide.

Furthermore, formaldehyde was added in an amount of 2.5 g per 100 g of gelatin and the emulsion was added photographic barite paper applied. The sensitivity for green light of the obtained samples was determined in the same manner as in Example 1. The results are included in the table below.

Comparison emulsictn

only metal the
Group VIII

only dye III

Metal of the group
VIII + dye III

Exposure for 1/100 of a second

Exposure for 1 / 1,000,000th of a second

0 13

In this case, too, the combined effect of Group VIII metal and dye III was observed.

Example 5

A silver chlorobromide iodide emulsion containing 70 mol% AgBr, 29 mol% AgCl and 1 mol% AgI containing no metal compound according to the invention was prepared in an ammonium alkali medium by a conventional method. Furthermore, using the same procedure, 4 × 10 mol per 1 mol of silver halide of potassium hexacyanoferrate- (III), 6 × 1 (T ⁸ -Mo per 1 mol of silver halide)

109830 / 12U

of potassium hexachloriridate (IV), 3x10 mol per 1 mol Silver halide on ammonium hexachlororhodate ClII) for Time of formation of the silver halide grains were added and furthermore 3x10 "" were added during post-ripening. Mol per 1 mol of silver halide of chloroauric acid added and an emulsion having the same sensitivity as the above emulsion was prepared.

Dye III was added to this emulsion and to the above emulsion in an amount of 6 × 10 ^J mol per 1 mol of silver halide. Furthermore, 2.5 g of formaldehyde were added to 100 g of gelatin and the emulsion was applied to photographic baryta paper. The sensitivity to green light of these samples was then determined in the same manner as in Example 1. The results are given in the table below.

Exposure Exposure during a 1/100 second l / l 000 000

second

Comparative emulsion 0 0 only metal the
Group VIII 0 0 only dye III 177 43 Metal of the group
VIII + dye III 111 98

In this case, too, the effect was common Use of Group VIII metal salt and dye III observed.

1 09 8 30 / 12U

Example 6

The dye YI was added to the emulsion used in Example 3 in an amount of 8x1 (Γ ³ mol per 1 mol of silver halide, and this sample was examined in the same manner as in Example 1. The results are shown in the following table.

Exposure Exposure during a 1/1000 1/100 second of a second

Comparative emulsion 0 0

only metal the

Group YIII 0 0

only dye VI 336 77

Metal of the group

VIII + dye VI 237 246

In this case too, the effect was straightforward Treatment with Group VIII metal salt and dye VI observed.

Example 7

A silver chlorobromide emulsion containing 50 mole AgCl and 50 mol $ AgBr containing no metal compounds of the present invention was in an ammonium alkaline medium produced in the usual way. Furthermore, using the same procedure at the time of Formation of the silver halide grains 1x10 "^ moles per 1 mole Silver halide added to potassium hexacyanoferrate (III) and an emulsion with an equal sensitivity, like the emulsion without metal compounds.

109830/1214 SADOB1G.NAU

For each such emulsion, as indicated in Example 1, the dye YIII was added in an amount of 4x10 moles per 1 mole of silver halide were added. Furthermore was added formaldehyde in an amount of 2.5 g per 100 g of gelatin and the emulsion on a photographic Baryta paper applied. The sensitivity to green light of the samples obtained was determined after same procedure as in Example 1, determined and thereby get the following results:

Exposure Exposure for a 1/100 second

_{0 (χ) 0 (χ)} second

Comparative emulsion O O

only metal the

Group VIII 0 O

only dye VIII 48 11

Metal of the group

VIII + dye VIII 49 35

In this case, too, the joint effect of ferrate and dye VIII was evident.

Example 8

A silver chloroiodobromide emulsion containing 70 Mo 1-5 * AgBr, 29 mol / 5 AgGl and 1 mol / £ AgI was prepared and contained no metal compounds according to the invention using the usual ammonium process. For an emulsion with the same composition, 4x10 "Eiol potassium hexacyanoferrate (III), 6x10 moles potassium hexachloriridate (IV), 3x10 ~ ⁷ moles ammonium hexachlororhodate ClII) were added to 1 mole

109830/1214 SADORiGINAL

Silver halide was added to the emulsion and then added to the single ripening resulted in 3 × 10 "" ° moles per 1 mole of silver halide added to chloroauric acid. The same sensitivity as the above ordinary one Emulsion was obtained.

To these emulsions, the dye VII in an amount of 2 χ 1O ~ ⁵ mol per 1 mol of silver halide was. Furthermore, formaldehyde was added to these emulsions in an amount of 2.5 g per 100 g of gelatin, and a photographic emulsion was obtained which was coated on a photographic baryta paper. The sensitivity to green light of the samples was determined in the same manner as in Example 1. The results are included in the following color code.

Exposure for 1 / 1,000,000th of a second

«- exposure
during a 1/100 second Comparative emulsion 0 only metal the
Group VIII 0 only dye VII 140

Group VIII metal + dye VII

100

O 27

The effect of the common can also be seen in this fur Use of Group VIII metal salt and dye VII.

Example 9

Dye XVI was added to the same emulsion as in Example 3 in an amount of ² × 10 "5 moles per 1 mole of silver halide. The emulsion was then added

109830/1214

_ß AD

treated in the same way as in example 3 and examined in the same way as in example 1 ·

Exposure for 1/100 of a second

Comparative emulsion

Group VIII metal only

only dye XVI

Group VIII metal dye XVI

139

89

Exposure for 1 / 1,000,000th of a second

0 30

79

In this case, too, the effect of applying the Group VIII metal salt and des Dye XVI observed.

1098 30 / 12U

BATH ORIGINAL

Claims (1)

Claims ί. Light-sensitive silver halide photographic materials which contain at least one layer on a support, characterized in that the layer contains a binder with (1) light-sensitive silver halide grains, (2) at least one compound of a metal of Group VIII in an amount of 1 × 10 ~ to 1 × 1 (Γ ⁵ moles per 1 mole of the silver halide; and (3) as at least one optical sensitizer, a compound of the general formula ^ C = CH-C = CH-C. where Ro is a hydrogen atom or an alkyl group, R and Rp are each hydrogen atoms, alkyl groups, substituted alkyl groups, allyl groups, aryl groups or aralkyl groups, where at least one of the radicals R ^ and Rg represents a carboxyalkyl group or a sulfoalkyl group, Y ₁ and Y «an oxygen atom, a sulfur atom or a group> NR ₇ , in which R _{7 represents} an alkyl group, R 1, R, R, - and Rg a hydrogen atom, a halogen atom, an alkyl group, a cyano group, an alkoxy group, an aryl group, where, if at least one of the radicals R and R. is an aryl group, the radicals Rc and Rg are not aryl groups, X is an anion, in particular a halogen ion or a thiocyanate ion, and m the 1 0 9 8 3 0/1 2 U Numbers 1 or 2, being in the pail of an intramolecular Salt m has the value 1, and / or a compound of the general formula wherein R _Q , Rq and R _{10 are} a hydrogen atom, an alkyl group, a substituted alkyl group, an allyl group or an aryl group, Y, an oxygen atom, a sulfur atom or a group> W-R ₁ ^ _v where R _{11 is} a hydrogen atom, an alkyl group or represents an aryl group, and L ₁ and L «each represent a methine chain. 2. Silver halide photographic light-sensitive material according to claim 1, characterized in that that the binder made of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, carboxymethyl cellulose and Mixtures of these consists. 3 »Light-sensitive silver halide photographic material according to claim 1 or 2, characterized in that the carrier is made of glass, metal, wood, baryta paper, Cellulose acetate film or polyester films. 4. Silver halide photographic light-sensitive material according to claim 1 to 3, characterized in that the metal compounds of potassium hexacyanoferrate (II) and - (III), rhodium chloride, ammonium hexachlorrhodate- (III), 1 098 30/121 Iridium (IV) chloride wad potassium hexaehlariridate (IV) exist. 5. Photosensitive photographiechee silver halide material according to Anapruoh 1 to 4 »characterized in that the sensitizers consist of compounds« where Ro is a hydrogen atom, a methyl group or an ethyl group »R ₁ and R _{2 are} a hydrogen atom, an alkyl group, a ß-hydroxyethyl group, a ß -Acetoxyäthylgruppe, a Carboxymethylgrupp *:., A ß-Carboxymethylgruppe, a ß-Carboxyäthylgruppe, a γ-Carboxypropylgruppe, λ a 2- (2-Carbo3tyätHoaty) -äthylgruppe, a B-sulfoethylgruppe, a γ-Sulphopropylgruppe, a J -Sulfobutyl group, a 2-hydroxy-i-sulfopfopyl group, a 2- (3-sulfopropoxy) ethyl group, a 2-ethoxy-i-bulfopropyl group, a 3-methoxy-2- (3-sulfopropoxy) propyl group, a 2- ^ 2- (3-sulfopropoxy) -äthoxjc / -äthylgruppe, a 2-Hydro3ty-3- (3-sulfopropoacy) -propylgruppe, a Phenyigruppe or an aralkyl group, whereby at least one of the radicals R ^ and Rg is a carboxyalkyl group or a sulfoalkyl group , Y ₁ and Yg an oxygen atom Sulfur atom or a group> NR ^, in which R ^ represents a methyl group or an ethyl group, R ^, R ^, R ^ and R _ß a hydrogen atom, a methyl group, an ethyl group, a chlorine atom, a (j brorine atom, a fluorine atom, a Cyano group, a methoxy group, an ethoxy group or a Phenyigruppe or where R _Q , R «and R ₁₀ denote a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a carboxymethyl group, a ß-hydroxyethyl group, a ß-sulfoethyl group, a γ-sulfopropyl group, an allyl group, a JPhenyl group, a chloro-substituted phenyl group or an alkylphenyl group. 10 9 8 3 0/1214 6. Photosensitive photographic silver halide. Nidmaterial according to claim 1 to 5 »characterized in that that as optical sensitizers 5,5 ', 6-Triehlor-1, 1 ', 3-triethyl-3' - (3-carboxypropyl) benzimidazole carbocyanine iodide or 3-allyl-5- / 2- (1-ethyl-4-methyltetrazolylidene) ethylidene / rhodanine exist. 7. Photosensitive photographic silver halide Nidmaterial according to claim 1 to 6, characterized in that -2 that the sensitizer in an amount from 1x10 to 1x10 "! ⁵ moles per 1 mole of silver halide is present. 1 0 8 8 3 0/1 2 U