DE2063669C3 - Photographic material having a spectrally sensitized silver halide emulsion layer - Google Patents

Description

= L ₁ -L ₂ = C

R ₄

Y ₃

contains, wherein R ₈ . R ₉ and R _{10 represent} 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> N — R ₁₁ . wherein R _{11 represents} a hydrogen atom, an alkyl group or an aryl group, and L ₁ and L ₁ each represent a methine group.

2. Recording material according to claim 1, characterized in that the metal compound Potassium hexacyanoferrate (II) and - (Hl). Rhodium chloride. AmmoniumhexachlorrhodaKIIl), iridiumdVt-chloride and potassium hexachloriridate (IV).

3. Recording material according to claim 1, characterized in that it is used as a spectral sensitizer 3 - Allyl -5- [2- (I - ethyl - 4 - methyltetrazolylidene) ethylidene] -i contains hodanine.

4. Recording material according to claim 1, characterized in that the layer is additionally at least one dye of the general formula below

45

Y ₁

C-CH-C = CH-C

(X

R ₁ ,

I ₁₁₁ 1

contains, wherein R _{0 is} a hydrogen atom or an alkyl group. R ₁ and R ₁ each hydrogen atoms, alkyl groups. substituted alkyl groups, allyl groups. Aryl groups or aralkyl groups, at least one of the radicals R ₁ and R _{2 being} a carboxyalkyl group or a sulfoalkyl group. Y ₁ and Y _{2 represent} an oxygen atom

Sulfur atom or a group> N R-. wherein R _{7 represents} an alkyl group. R ,. R ₄ . R ₅ and R ₍ , a hydrogen atom, an halogen atom, an alkyl group, a cyano group, an alkoxy group. An aryl group. Where, if at least one of _{the radicals R 1 and R 4 is} an aryl group, the radicals R 1 and R _{h are} not aryl groups are. X is an anion.

in particular a halogen ion or a rh.ocyanato “and m the numbers 1 or 2 where .m hall! ines intramolecular salts, m has the value 1.

^bC 5 ^e record, smateriai according to claim 4, characterized in that in the above, "-" c "also general formula R ₁₁ cn water; -to (Tatom. a methyl group or emc ethyl and R ₂ a hydrogen atom a ^ -hydroxyethyl group, a bhl

ygp

--Sulfopropyl group emc a 2-hydroxy-2-sulfo _P rohl

p
-> (^ rcarboxy

ätby "l» group. a
vSulfobunlgruppe.
nvloruppe.'an i- (3-sulfopropoxylethyl group.

a 2 - acetoxy - 1 - sulfopropyl group. cmc 1 - Mc'thoxv - 2 - (3 - sulfopropoxy) - propyl group c. an M2- (VSulfopropoxy) -ä'lIioxy] -ethylgruppe. a ^"Ί - hydroxy - 3 - (3 - sulfopropoxy) - propylüruppe a Phcny group or a Aralkvl-" roup wherein at least one of R, and R is a carboxyalkyl group or a sulfoalkyl group Y ₁ and Y ₂ is an oxygen atom..!. a sulfur atom or a group> N K-. where K- is a methyl group or an ethyl

represents oruppc. R, R ^ - ^ «" JV, ", ^WaSSa 'stoffatom. a methyl group, cmc ethyl group. a chlorine atom. a bromine atom, a fluorine atom, a c vami group. a Melhox \ group. an Atho group or a Phcnylgruppc mean. ^r 6 AufzeiehnuiTJsmaterial according to claim 4, characterized cekenn / .cichnet. that the 1-arbsiolT of the ancillary formula is S-.V.Ö-trichloro-l-1 .3-trichloro-^! (VcarboxypropyD-ben / imida / olcarbocyanininjodid.

Green light at as readjusting

The invention relates to photographic recording materials. those on a layer support at least one spectrally sensitized silver halide emulsion layer have and which have a high spectral sensitivity to the application of a lightning bolt. defined in more detail, own.

It has been used so far for achieving a rapid

libermitlluna of information different systems developed. For example, press facsimile systems quickly transmit the press manuscripts to remote places, high-speed phototype setting systemc speed up printing and oscilloscope

graphenröhrensyslemc effect the rapid output of letters or figures when delivering information of computers. In such equipment of such rapid information transfer systems are often used photographic recording materials that require very short exposure times of less than! 100,000 seconds or even 1 1,000,000 seconds. the Demand for photosensitive recording materials for such facilities has been particularly high in recent years. Ice cream are of two types of light sources used in connection with these types of devices, namely xenon light bulbs and cathode ray tubes.

Cathode ray tubes, their 1 -luores / en / an especially has a short afterglow, are known to be recorded! of wandering points of light used. Such fluorescent light sources can have peaks in their spectral energy distribution at 460 mn or at 3S5 mn, in which case at Use of photographic recording materials no visual sensitization nolwer.Jig is. since these peak values correspond to the range of the spectral Absorption of light-sensitive silver halides.

On the other hand, light sources are used whose spectral fluorescent radiation maximum is 505 nm. These light sources require a high spectral sensitivity of the light-sensitive recording material to green light. A xenon flash lamp emits light over a relatively wide spectrum. where light of short wavelength is absorbed to a greater extent by the optical elements in the light path. Therefore, in the light reaching the photosensitive material, the proportion of shorter wavelengths from ultraviolet to blue is decreased and the proportion of longer wavelengths in the region of green is increased. Therefore, especially when using xenonblit / tubes, intensive green sensitization is necessary to increase the photosensitivity of the photographic recording material. The above-mentioned afterglow of the hiorescence of a calhode ray tube is in the range of IK) 000 (X) 0 of a second to 1,100,000 of a second, and such short exposure times must also be recorded for a xenon flash lamp. In the context of the invention, brief exposure to these two types of light sources is generally referred to as "flash exposure".

When conventional sensitizers for green light are used, the sensitized silver halide layers show a noticeably lower spectral (green (sensitivity, vwhen a flash exposure of I 100,000 seconds or less is made, compared with the results of the usual exposure for 1,100 seconds or longer. In particular This tendency is noticeable when accelerating the treatments after the Exposure, such as fixation or stabilization, the silver halide partially or completely from silver chloride exists, d. H. from silver chloride emulsions. Silver chlorobromide emulsions or silver chloroiodobromide emulsions.

Photosensitive photographic direct positive silver halide emulsions containing a rhodium compound and a sensitizing dye and one or more magenta, yellow, and / or cyan couplers are known (cf. German Offenlegungsschrift 1815 967). This becomes a sensitizing dye used which is sensitive to long wave light, e.g. B. a merocyanine dye or trimethine cyanine dye. The use of a rhodium salt in a gelatin-silver halide emulsion. which also contains a trimethine cyanine sensitizing agent is for example described in British patent specification 775 197.

British patent specification 979 251 relates to cyanine and meroeyanine dyes and thus sensitized ones pholographic emulsions.

It is also known to use certain silver halide

emulsions salts of metals of the VIII. group de To add PSE (cf. P. Glafkides. Photographic Chemistry. Vol. I. London 1960, p. 31X. Recipes dei

s pp. 351 to 353).

It has long been known that the metal prevents fertilizing metals of group VIII of PSl show different effects. Sc is in the USA. Patent Font 2 44S060 stated that. if hexahalogen

ίο ruthenium! IU) acid salts. Hexahalogrhodium (IV) acid salts. Hexahalogenosmium (IV) - acid salts Hexahalogeniridium (IV) - acid salts or Hexahalo genplatinl IV) acid salts to form a silver halide mul sion to be added at the time of ripening, you

ι; Sensitivity of this emulsion increases. It is also described in U.S. Patent 2,566,745. when these compounds are added in addition to the silver halide emulsion, the Stabilitä aes-sensitive material at high Temperature!

and moisture is improved and continues to be ^! in US Pat. No. 2,517,541 describes that when potassium hexacyanocobaltaKlII and, according to FlAT report No. 360, rhodium trichloride are added to a silver halide emulsion, the contrast de:

2s image obtained on this emulsion is increased So far, however, have been known using the

th measures have not yet created any photographic recording materials that are sufficient had adequate sensitivity when using flash exposure to green light.

The object of the invention is to provide photographic recording materials with a high spectral sensitivity to green light when using a flash exposure.

The object of the invention is based on a photographic recording material with at least one applied to a layer support! A spectrally sensitized silver halide emulsion layer comprising at least one compound of a metal from Group VIII of the PSE. containing ¹ mole per I mole of silver Halo genids, and is characterized in that the layer least min as spectral sensitizer, a merocyanine of the formula - in an amount voi 1 ■ 10 "to 1 x 10

N - - NR ₈

C- L ₁ L ₂

V T- ¹

C C

N ^V S

contains, wherein R _H , R ₁ , and R ₁₀ 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> NR _n

(, "Wherein R _{11 represents} a hydrogen atom, an alkyl group or an aryl group, and L ₁ and L, each represent a methine group.

In the formula given above, the radicals R ₈ . R ₄ and R ₁₁₁ e.g. B. an alkyl group mi

f, ₅ 1 to X carbon atoms, such as a methyl group ethyl group. Propyl group. Butyl group. a substituted alkyl group. such as Carboxymethylgruppc, i'-Hydroxyäthylgruppe. , / - sulfoethyl group. y-sulfo

5 6

propyl group, allyl group or aiyl group. like a dye F.

Phenyl group, a substituted phenyl group such as.,,. , ...

with a chlorine atom or an alkyl group sub- ι,, '

be a stylish phenyl group, the radical R _n can / .. B. J ^,,! . ..... ₍ ,,, ..,.

an alkyl group with 1 to S carbon atoms oiler ^s ι

be a phenyl group. '' ,,

Specific examples of compounds for this j ^

Sensitizers siml the following: | '■' \. ,.

₁₀ CH, CH, (JH

Dye Λ CIU

_N N-CH, m.p. 233 C

^N _{x /} C ---- CH -CH = -C-- S _IS dye 1

N C C N · ■■ N CH,

CH, ONS N C --- Cl I CH-C C)

! 20 / ' '■

H N C C

Melting point 245 C. ONS

ClI CH CH,!

Dye B ² ^

Melting point 240 C N NCH,

N C-CH CH-C S dyes;

N ^/ CC ³ ° NN CH,

C ₂ H ₅ C) ⁷ NS ^N C-ΓΗ CH C- C)

CH is N ' CC

H, C CH, C _: II, () "NS

M.p. 232 C CH ₂ CH CH ₂

40 melting point 230 ° C

Dye C

N - -N CH dye H

■: ■ '4s ^N N - CM,

N C-CH CH CS ⁴ -;

^: NC -CH-CH = C -—- S

N C C

N C- C-

C ₁ H ₅ ONS! J , /

^{; !} ONS

CH ₂ CH ₂ CH, C ₁ H ₁ SO ₁ K

Melting point 190 CC ₂ H ₅

Melting point 290 ° C

Dye D

Dye I.

NN - /% N N-CH ₃

NC = CH-CH = CS ^6o NC = CH-CH = CS

N CC N CC

C ₂ H ₅ ONS ₆₅ CH ₃ ο NS

^C 2 ^H 5 CH ₂ COOH

Melting point 201 C, melting point 242 C

EarbsioiT

j;

N N (Ml,!

^ji ! "'I

NC CII CC

N (■

■ 4 ·

C ₁ W, () "

NickeKIIJ chloride (NiCi ₂ 6
ik

1.0).
6H ₂ O).

(', H ₅

Melting point 250 ° C

Sensitizers of this type are described, for example, in British patent specification KOI 275 the sensitizers can be prepared using processes known per se in accordance with the above Patent specification and other technical literature take place. These optical sensitizers are used either individually or in combination of two or more are used in the silver halide emulsion. The addition of the optical sensitizers The emulsion can be made at any desired point during manufacture. So the spectral sensitizer can either be used at once with the Vlelallverhindimg or separately on it be added, the order being immaterial

In general, as a layer carrier (ilas plates. Metal plate !!. I Inl / plates. Baryta papers, photographic Papers. (Elluloseaectallilmriiger or PoIvesierli protrusions be used.

(leeignete binders are water-soluble IIIm-I ¹ IiUCiHIe compounds of high molecular weight. W'k- (ielatine. polyvinyl alcohol. polyvinyl pyrrolidone. V'iti iumalginal and (ai box \ nieihyleellulose. The Bindepiiiid can be used both individually and in Konibinaiinn.

\ K hchtempliniMiche silver halides can contain silver chloride. Silver bromide. Silver chlorobromide. Silver! "Dhi dog. Silheichlorjodhronnd \ erwendel be. The preparation of the silver halide emulsion, i. 'lic preparation of the silver halide crystal grains in the binder in a dispersed state and their growth to the appropriate crystal gröl.k · for the Formation of the silver halide emulsion can be carried out in usual! Succeed in a wise way.

Through the I iTmdung it is achieved that photoyr.iphische Drawing materials with a high spectral sensitivity to green light are available, which have their high spectral sensitivity maintained even when short flash exposures. in particular for a duration of at most up to 1 KX) OOO second or even only can be applied up to 1 1 000 000 seconds.

The compounds of Group VIII of the PSE, namely iron. Cobalt. Nickel. Ruthenium. Rhodium. Palladium. Osmium. Iridium. Platinum, are z. B.

Iron I (sulfate (FeSO ₄ · 5H ₂ O).
Iron (III) chloride (FeCl ₃ ).
Potassium hexacyanoferratejIIMK ^ FeiCNU-lHjO). Potassium hexacyanoferrate (III) (K ₃ [FeCN ₆ T]).
Cobalt dD chloride (C OCl ₂ ).
Cobalt (II) nitrate (Co [NO ₃ L "6H ₂ O).
Potassium hexacyanocobaltate (III) [Co (CN) ,,]).

J ( ₂

Nickcl () l) nitrate (Ni [NO,] ₂
Ruthenium chloride (RuCI ₃ ),
Potassium hexachlororuthcnaU IV) (KjRuCl ,,).
Rhodium (III) chloride (RhCl., 4H ₂ O),
Ammonium hexachloro rhodate III) ([NII ₄ ], RhCl ,,) palladium nitrate (Pd [NOj] ₂ ).
Palladium bromide (PdBr ₂ ),
Potassium hexachloropalladate (IV) (K ₂ PdCI ,,).
KaliumlctrathiocyanopalladutUl) (K ₂ Pd [CNSJ ₊ ) Osmium (II) chloride (OsCI ₂ ),
iriditim (III) chloride (IrCl ₃ ) ',
Iridium (IV) chloride (IrCl ₄ ),
Iridium (III) bromide (IrBr, ■ 4H ₂ O),
iridium (IV) bromide (IrBr ₄ ),
Potassium hexachloriridate (111) (K _-1 IrCI ,,),
Potassium hexachloriridate (IV) (K ₂ IrCl ₆ ),
AmmoniumhcxachlorplalinatflV) ([NH _{4 I 2} PtClJ. Kaliumhexachlorplatinatf IV) (K ₂ PtCl ,,),
Ammonium hexabromoplatinal (IV) ([NH ₄ ], PtBr ,,).

The Group VIII metal compounds can

both individually and in combination of two or more compounds together in the silver halide emulsion, preferably in an amount of K) ⁵ to

3 K) ⁴ . to 1 mole of silver halide can be used. These compounds can be added to the emulsion at various stages of the preparation, for example in the preparation of the silver halide grain particles, ie in the preparation of the silver halide emulsion either as an additive to the halide solution or in the glacial dispersion solution or at the beginning of the ripening of the emulsion or in intermediate stages. The compounds can also be used together with other known stabilizers, antifoggants, anti-bronzing agents, surface-active agents. Hardening agents. Plasticizers. Matting mills. Emulsion additives or dissolving agents and the like can be added in the desired manner before the emulsion is applied to the substrate.

According to one embodiment of the invention, potassium hexacyanofenalllll and - (MI). Rhodium chloride. Ammonium hexachlororhodate (III). Iridium dVl chloride and potassium hydroxachloriridal (IV) used.

According to a further embodiment of the invention, 3-AIIyl-5- | 2- (l-ethyl-

4 - methylietrazolylidcn) - ethereallidcn] - rhodanine is used.

This results in a particularly good sensitization of the photographic recording material to it Get green light.

According to a further embodiment of the invention, in addition to the merocyanine dye specified above a dye represented by the general formula below

Y,

R,
C = CH-C = CH-C

Y,

' V

^ y

N
R,

is used, wherein R _{0 is} a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, for example a methyl group, or an Älhvlarunnc.

K ₁ and R, each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, for example a methyl group. Ethyl group or propyl group. a substituted alkyl group, for example a // - hydroxyethyl group. / i-aceloxyethyl group. s carboxymethyl group. ,; - carboxyethyl group. ; ■ - carboxypropyl group. 2 - (2 - carboxyethoxylethyl group. // - sulfoethyl group.; ■ - sulfopropyl group. 3-methoxy-2- (3-sulfopropoxy) propyl group, 2-1 2- (3-sulfopropoxyithoxy] ethyl group or 2-1 hydroxy-3- (3-sulfopropoxy) propyl group, an aryl group such as a phenyl group or aralkyl group , but at least one of the radicals R, and R ₂ consists of a carboxyalkyl group or sulfoalkyl group. Y, and Y, an oxygen atom, a sulfur atom or a group> N - R _7. in which R _{7 represents} an alkyl group with 1 to 3 carbon atoms, for example an methyl group or an ethyl group, R _1, R _4, R ₅ and R ₁ ,

each a water slippery flaiom,
I to 3 carbon atoms,
group, an alliyl group. em I l
w 1l Chl

yg
wise 1-luor. chlorine

^c " ^u 'Alkoxygi lip,
Alh

an alkyl group with a methyl logenalom. for example or bromine, a (yangriippe.-C-- ■■, ·, - · for example a melhoxv or alhyoxy group. or an aryl group is we «.. ei R, nor R ₁ , are an aryl group. X is an anion, for example an ilalogen ion, a thiocyanate ion, cm sulphate ion, silfonal ion, perchioralion, p-toluene sulphonate, benzene sulphate sulphate, ethyl sulphate or methyl sulphate and," the Numbers I or 2 where in the case of a molecular salt »1 has the value I, means.

According to this refinement, there is still a more inisive one Educate green awareness

Spezilische examples Kr addition to the erlindungsgen-IASS Ί used elrazolmerocvaninen one-SLtzDaie Grunscnsibilisalorcn of these optical sensitizers are given nachfolcend ·

, O.

C = CH

Dye IC ₁ H, C-CH-C

Cl

Vo-,

Dye II C ₂ H,

C - CH

(CH ₂ )., SO, Na

i 1

(CH ₂ I ₁ SO.,

C il

'CH ₂ J ₁ SO,

Ci

Melting point 2Hl C

Dye I. Melting point 210 ° C

ί J ^ C = CH-CH-CH C ^{N Cl}

C ₂ H,

I ₂ I ₃ SO,

Cl

Dye IV m.p. 262 C

C ₂ H ₅

(CH ₂ J ₃ SO, Schmel7minlil ~> ϊ] C

Dye V

CW,

Ii C CH C-CH C Jl

cn,

12th

(CH ₁ I ₁ SO ₁ H

CH,

(CH ₂ ) (SO ₁

Dye VI

Melting point 295 (

Cl

■ Ο / N ,. - //

C-CH CU CH C Il J

■ • ν- ^; Ν -; \ / \

CH,

Br V II ι
I. CH ₂ Cl CH ₂ COOH - 'dye

Melting point 205 <

/ · _Ν ο ·

! ι C CW CH-CH C

/ '■■■■ / N-' '■■

CN

C ₂ H,

Br

Cl

CH, CH, CHXOOH

Melting point 210

H ₁ CO

Dye VIII

C ₂ H, if C ■ - ■ CH -C --- CH-C

CH,

Cl

.'Nw /

Cl

(CH ₂ I ₁ SO ₃

Melting point above 3 (K)

Dye IX

CH,

Cl

c ch ch-ch c

To '' ■

Cl

egg

(CH, USO ₁ Na

CI

(CH ₂ USO ₃

Melting point over 300

Such sensitizers are, for example, according to methods known per se

U.S. Patents 2,503,776, 2,912,329.65, the above patents and others

3 397 060, the French patent specification I 108 788. nischer literature.

of Japanese Patent Publication 44-14 030- The manufacture of photosensitive photoc

and the manufacture of these sensitizers phic silver halide materials can be practical

can be carried out in the usual manner with the addition of the above-mentioned sensitizing components, and the material thus obtained can be developed and fixed in the usual way after the flash exposure. The recording material may according ■ "> known as Diffusionsübertragungsvcrfahren manner to be treated. If previously, an appropriate amount of a developing agent of the photosensitive layer incorporated \ Λ. Can be carried out the development by the generally known ι ο Aktivatorentwicklungsverfahren, ie, a method in which the photosensitive material . that contains the developing agent is developed in a solution which does not contain any developing agent and only an alkaline material is dissolved.

E 'was found to be photosensitive Recording materials which contain the above-mentioned metal compounds but do not contain any of the above optical sensitizers. no increase in sensitivity to green light is obtained, although in some cases it is Sensitivity to blue light is improved. On the other hand, it was found that in the case of sensitive Recording materials containing the metal compounds do not contain, but only contain the optical sensitizers which increase the sensitivity is not very pronounced compared to green light. However, if the spectral sensitizer according to of the invention is used in combination with the metal compound, the wedge is sensitive to Significantly improved green light during flash exposure.

In particular, in the case of silver chloride emulsions. Silver chlorobromide emulsions or silver chlorobromoiodide emulsions when the special ones are used alone Sensitizers considerably reduce the effectiveness of spectral sensitization detected by the flash exposure. The photographic recording materials according to the invention are therefore particularly suitable for flash exposures.

The compounds of the elements of Group VIII of the PSE can besides those provided according to the invention Effects may have additional effects that. as described above, in the art were already known. One can also determine the sensitivity according to British patent specification 570,393 of the emulsion if the metal compounds are added at the time of ripening. if these compounds as sensitizers or as stabilizers or as additives to increase the so Contrast are used, when used together with the sensitizing dyes according to the invention achieved the desired high level of sensitization to green light.

In the drawing is the light transmittance of a glass filter, which is used in the examples to evaluate the Effectiveness of photographic light-sensitive materials used has been demonstrated.

Example I.

A Süberehlorbromideinulsion with a content of 50 mol% AgBr in a neutral medium prepared by a known method, which did not contain a compound of a Group VIII metal, fts which are hereinafter referred to simply as metal compounds, and a sample was with the addition of HcxachlorrhoJaUIII) in an amount of 3-lu "" mol per 1 mol of silver halide in the above emulsion at the time the silver halide grains were formed, with potassium chloroplatinate further being added after ripening in an amount of 2 mol per 1 mol of silver halide emulsion prepared in this way had about the same sensitivity as the first emulsion. These two emulsions were each divided into two parts, one of which was used as is.

The E'arbstof became the other part! Λ in an amount of 6 · 10 ³ mol per 1 month! Silver halide added in the emulsion. Then, formaldehyde was on to each emulsion in an amount \ 2.5 to Kitig gelatin added to the emulsion and the emulsion coated on a photogiaphisches Barylpapier.

The green sensitivity of the obtained samples was determined in the following manner.

Using a Sensiloinek-r and through a colored glass filter, the light transmission of which is shown in the drawing. and using an optical wedge, the above samples were each marked with a 1,100 second and a

1 1 000 000 seconds exposed. As shown in the drawing results, the colored lilac absorbs. that of the "sensitive spectral range of the unsensitized Silver halide corresponding light and only allows the light according to the optically sensitized Area above about 500 nm through the exposed samples were hot 20 (during

Developed for 2 seconds in the following developer:

N-methyl-para-ammophenol 2 g

Sodium sulfile. anhydrous M) g

I lydroquinone 7 g

Sodium carbonate (monohydral) .... 53 u

Potassium bromide 1.5 g

Water to 11

After fixation. Rinsing and drying, the density of the images was determined.

The reciprocal value of the amount of light that gave a density of 0.5 was used as the sensitivity factor assumed: however, since the absolute amount of light was not determined by the filter, the sensitivity is only relatively; the following table shows the sensitivities at the same exposure time indicated accordingly. The results obtained are summarized in the table:

Comparative emulsion
Only metal the

Group VIII

Only dye A. .
Group VIII metal

+ Dye Λ

lidieliliinu
ui'yourcl

one
ι ,,, second

0 0

Helielilunu

whiul

unites

', "Sec

0 0

12.0 i 2.7

10.5 i 7.2

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

Ml ¹ Il

le
ie
η

Example j

The procedure of Example 2 was repeated except that a dye 1 was also used was added to the emulsion in an amount of 4 x 10 8 moles per 1 mole of silver halide. There were the following results were obtained:

j Kd.iihe I-.mptitullichkcit

j 'sec ■ sec

Free of dyes j O j (i

Dyes alone j 15.0 [3.3

Dyes and a j: - ¹

Metal connection j 13.0 ^! 9.5

Example 3

A silver chlorobromide emulsion containing 50 mil percent AgCl and 50 mole percent AgBr. which did not contain metal compounds according to the invention was prepared in an alkaline ammonium medium in a conventional manner. Further, using the same procedure, at the time of forming silver halide ^{grains, 1 x 10 5} mol per 1 mol of silver halide of potassium hexacyanofrate (III) was added to obtain an emulsion having the same sensitivity as the emulsion containing no metal compounds. As indicated in Example 1, dye VIII was added to each such emulsion in an amount of 4 × 10 ^-3 mol per 1 mol of silver halide. Further, dye III was added to the emulsion in an amount of 2 x 10 ^-3 moles per 1 mole of silver halide. Finally, formaldehyde was added in an amount of 2.5 g per 100 g of gelatin, and the emulsion was applied to a photographic baryta paper. The sensitivity of the samples obtained to green light was determined by the same method as in Example I. The following results were obtained:

Color-free
Dyes alone ....
Dyes and a
Metal connection

Rclalivc l. Susceptibility

¹ , "" Sec.
exposure

58

60

'"" ", Sec.

Bcliclii unii

15th

48

Example 4

A silver chloroiodobromide emulsion containing 70 mole percent AgBr, 29 mole percent AgCl and 1 mole percent AgI was prepared and contained no metal compounds according to the invention using the conventional ammonium process. To form an emulsion with the same composition, during the formation of the silver halide grain parts, 4 x 10 4 ^{moles of potassium hydroxacyanofcrrat (III), 6 x 10 7 K} moles of potassium hexachloriridate (IV). 3 · K) " ⁷ moles of ammonium hexachloro rhodate (III) per 1 mole of silver halide were added to the emulsion and then 3 · 10" moles per 1 mole of silver halide were added during post-ripening

Ciilorgauric acid added. Same sensitivity as in the above ordinary emulsion was obtained.

Dye VI was added to these emulsions in an amount of 2 x 10 ^-3 moles per 1 mole of silver halide.

Furthermore, the dye VI of the emulsion was added in an amount of 2 × 10 5 mol per 1 mol of silver halide added. Furthermore, d, V. Emulsions formaldehyde in an amount of 2.5 g per 100 g Gelatine was added and a photographic emulsion was obtained, which was applied to a photographic baryta paper was applied. The sensitivity to green light of the samples was determined in the same way, as determined in Example I. The results are given in the table below.

! Rcl; iti \ c I \ mpliiullichkcil

I.

j 'sec. l · "sec.

Exposure I exposure

I 0 j 0

! 190! 35

I-rei N ¹ OH dyes. .

Dyes alone

Dyes and a
Metal connection.

145

105

example

A silver chlorobromide emulsion with 50 mol percent Ag (and 50 mol percent AgBr was dissolved in a neutral Medium produced in the usual way.

According to the same procedure, 3 · 10 '''MoI were added to the emulsion for every 1 mol of silver halide of ammonium hexachloro rhodate in the preparation of the silver halide grains, and after ripening, platinum (IV) chloride was added in an amount of 2 · H) "' Moi per 1 mol of silver halide to produce an emulsion having the same sensitivity as the emulsion without the metal compounds. The dye Ci was ^{further added to each of these emulsions in an amount of 2 × 10 −8} mol per 1 mol of silver halide.

Furthermore, 2.5 g of formaldehyde were added to 100 g of gelatin and the emulsion to a photographic Baryta paper applied.

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

55

60 comparative emulsion
Only metal the

Group VIII

Only dye G ..
Group VIII metal

4 dyes

exposure

while

one

0
139

89

Exposure during

one
V ₁ , """sec.

0
30th

79

In this case, too, the effect of the joint application of the metal salt became the Group VIII and Dye G observed.

1 sheet of drawings

Claims (1)

Palent claims: ! A photographic recording material comprising at least one spectrally sensitized silver halide emulsion layer which is applied to a support and which reveals at least one compound of a metal from Group VIII of the PSE in an amount of 1 x 10 ^{7 "h} to 1 x 10" ⁽ mol per 1 mol of the silver halide, characterized in that, that the layer acts as a spectral sensitizer at least one merocyanine of the formula