DE2063669B2 - Photographic material having a spectrally sensitized silver halide emulsion layer - Google Patents

Description

N NR ₈

Il I

NC = L ₁ -U = C-

N C

Ro O

Contains where R _s , R ^, and R _{10 represent} a hydrogen atom. an alkyl group, a substituted alkyl group. an allyl group or an aryi group. Y, an oxygen atom, a sulfur atom or a group> N — R ₁₁ , in which R _{11 represents} a hydrogen T atom, an alkyl group or an aryl group, and L, and L ₂ each represent a methine group.

2. Recording material according to claim! characterized by el. · Metal connection Potassium hexacyanofcrratdl) and - (HI), rhodium chloride. Ammonium hexachlorrhodalHII). Iridium! IV) chloride and potassium hexachloride tllV) is.

3. Recording material according to claim! through this marked, dal! it as a spectral sensitizer 3 -Allyl - 5 - [2 - II - ethyl -4- m »; ethyl tetrazolylidene) ethylidene Contains! -rhodanine.

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

Y,

R ₁ ,

Y,

C = CH -C CH C

N N

v>

R,

R: (X), "

contains, in which R _(l represents a hydrogen atom or an alkyl group. R ₁ and R, respectively Wasserstoffatoine. alkyl. substituted alkyl. AlIyI-jjl'uppen. aryl or Aralkylgruppeti. w Ihei nindcstens one of the radicals R, and R ₂ is a carboxyalkyl group or a Sulfoalkyliiruppe ^ ₀ , Y ₁ and Y _{2 represent} an oxygen atom, a sulfur atom or a group> N R-. In which It _{7 represents} an alkyl group. Rj, R _4, R ₅ and R "are 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 ₃ and R _{4 is} an aryl group, the radicals R 1 and R _{6 are} not aryl groups. X is an anion.

in particular a halogen ion or a thiocyanate ion, and m the numbers 1 or 2, in the case of an intramolecular salt m being the value I bat.

5. Recording material according to claim 4, characterized in that in the above general formula K _{0 is} a hydrogen atom, a methyl group or an ethyl group, R ₁ and R _{2 are} a hydrogen atom, an alkyl group, a "/ i-hydroxyethyl group, a / i- Acetoxyethyl group, a carboxymethyl group, a / f-Cai boxymelhylgruppe, an / i-carboxyethyl group, a γ-carboxypropyl group, a 2- (2-carboxyethoxy) ethyl group, an ΐ-sulfoethyl group, a-sulfopropyl group, a Λ-sulfobutyl group, a 2-hydrony-2-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-Sulft) propoxy) -atht, xyj-ethyl group, a 2-hydrow-3 - (3-sulfopropoxy) -propyl group, a phenyl group or an aralkyl group, where at least one of the radicals R 1 and R 1 is a carboxyalkyl group or is a sulfoalkyl group, Y ₁ and V _{2 are} an oxygen atom, a sulfur atom or a group> N R-. wherein R ₁ cmc represents a methyl group or an ethyl group. R.,. R ₄ . R <and R _h a hydrogen atom. a methyl groupc. an ethyl group, a chloratoin. a bromine atom, a fluoroalome. a cyan group ;. mean a methoxy group, an ethoxy group or a phenyl group.

6. Auf / calibration material according to claim 4 thereby characterized because 1.1 the dye of: mgegebcnen (onnel 5.5.6- "! richloi -1 -1 .3 - triäthy! - 3 '- (3 - (.arbev, propy!) - ben / imida / olcarbocyaninjodui is.

Pic invention relates to photographicc Reference materials. those on a layer support at least one spectrally sensitized silver halide emulsion layer and which have a high spectral sensitivity to green light Use of a blit / exposure. As follows defined in more detail, own

Various systems have hitherto been developed for achieving rapid transmission of information. For example, press facsimile systems quickly transmit press manuscripts to remote parties. High-speed phototypesetting systems accelerate printing and the oscilloscope tube systems effect the rapid output of letters or figures in the display of information from computers. Used in such equipment from such rapid Infonnalionsübermittlungssystemen be membranous pholographischc On / cichmin! ". Naterialien 'that in the very short Bclichtungs / nits must jndc appeal even 1 1000000 seconds less than 1 100,000 seconds or more. The demand for light-sensitive materials for Such facilities have been particularly high in recent years. Two types of light sources are used in conjunction with these types of equipment, namely xenon lights and cathode ray tubes.

Cathode ray tubes, the fluorescence of which has a particularly brief afterglow, are known used to record moving points of light. Such fluorescent light sources can have peaks in their spectral energy distribution at 460 nm or at 385 nm, in which case at The use of photographic recording materials, no optical sensitization is necessary, since these peaks correspond to the spectral absorption range of light-sensitive silver halides is equivalent to.

On the other hand, light sources are used whose spectral fluorescence radiation maximum is 505 nm. These light sources require a high spectral sensitivity of the light-sensitive recording materials to green light. A xenon flash lamp emits light over a relatively broad spectral range, with light of short wavelengths being absorbed to a greater extent by optical elements in the light path. Therefore, in the light that reaches the photosensitive recording material, the proportion of shorter wavelengths from ultraviolet to blue is increased, and the proportion of nm longer wavelengths in the region of green is increased. Therefore, especially when using xenon flash tubes, an intensive green sensitization is necessary to increase the light sensitivity of the photographic recording material. The above-mentioned afterglow of the fluorescence of a K-ilhodensnahlrohr is in the range of 1-10000000 of a second to 1/100000 of a second, and with a. \ Enonnliu'ainpe, such short exposure times must also be recorded. As part of the i-.rlindung short-term exposure is mils these two aria "of light sources in general: designated <], '" BIU / -belLhtiing ".

When conventional sensitizers for greenish tones are used, the sensitized silver halide films have a noticeably lower spectral (green! , ¹ KXX) second or longer, this tendency is particularly noticeable if the silver halide consists partly or completely of silver chloride, ie of silver chloride emulsions, to accelerate the treatments with exposure, such as fixation or stabilization. Silver chlorobromide emulsions or silver! lorjo.lbromide emulsions.

Photosensitive photographic directly positive Ikilog silver emulsions containing a rhodium compound and a sensitizing dye and one or more magenta, yellow and / or cyan couplers are known (see German Offenlegimgssehrift 1815 967). This becomes a sensitizing dye used, which is sensitive to long-wave light. / .. B. a microcyanine primary or trimethine cyanine dye. The use of a rhodium salt in a gelatin-silver halide solution. which also has a trimethine cyanine sensitization agent is described, for example, in British patent specification 775 197.

The British patent specification 979 751 concerns (yanin- and Mcroeyanine dye and thus sensitized photographic ». Emulsions.

It is also known to use certain silver halide emulsions To add salts of metals from Group VIII of the PSE (cf. P. G 1 a fk i d es, Photographic Chemistry, Vol. I, London 1060, p. 318, recipes of P. 35 Ibis 353).

It has long been known that the metal compounds of metals of Group VIII of the PSE show different effects. For example, US Pat. No. 2,448,060 states that when Hexahalogenruthemum (III) acid salts, Hexahalogenrhodiiim (IV) acid salts, Hexahalogenosmium (IV) - acid salts. Hexahalogenidium (IV) acid salts or hexahalogenplatinum (IV) acid salts can be added to a silver halide emulsion at the time of ripening, which Sensitivity of this emulsion increases. In addition, US Pat. No. 2,566,745 describes that when these compounds are added in addition to the silver halide emulsion, the stability of the sensitive material at high temperatures and moisture is improved and furthermore it is described in U.S. Patent 2,517,541 that. if Kaliumhexacyanocoh-iliatl 11 hund according to FlAT-Report No. 360. Rhodium chloride of a silver halide emulsion are added, the contrast of the image obtained on this emulsion is increased.

However, no photographic drawing materials have yet been made using the known measures created that have sufficient sensitivity when using a Bh; / - he'ichtung with green light.

The object of the invention is the creation of [historical recording materials with eiiv.r high spectral sensitivity to green light when using a Blilzhelichtunc.

The subject of the i-.rtindung vhi from a photographic Aufzeichnungsnui.jriai Mn IV; R.- least one applied on a substrate; spectral sensitizer. Silherlialogcnidemnlsionschicht. the at least emc \> ■: ivndung an N ^- U ¹ VdIs dor group VIII of the PSE in a Mctisj-j \ ί · ι · - I ItI "up to 1-10 ~ Mol j ·. · i Mol -.Us Si! contains athal> nenids, and is thereby gckcniizeiclipr; that the layer, ils spectral sensitizer at least one 'vU'iOcyaniü der 1 oi; nel

S --- N -R,

N CI, L. ---- C ^ ι

H.,

contains, wherein R is _H. R ₁ , and R ₁ , a \ V; ts., Crsi.) LfatMn an alkyl group. a substiluicrli · Alkvlgmppe, -v allylgr .ppe or an aryl group. >. a Saiicrsl · ': Mom. a sulfur atom or a (irupp 'N'
where R _{n is} a water column. represents an Alk> Irrup or an aryl group, and E ₁ and I - jcv ·. ·>. mean a something group

In the formula given above, i. the radicals R _s . R ₁ and R ₁₁ , for example an alkyl group η 1 to 5 carbon atoms, such as a Mellnl group Athvlgruppe. Propyl group. Bulyl group. a -; i slituierle alkyl group. like (arn '.)>, \ methyl;: rupf.: -II yiliow al hy! group. ; -Siilioälh \ k'uippr. -SuIf

5

propylgnippe. Allyl group or aryl group. like cine l-.irbsiofl K

Phcnylgruppc. a substituted alkyl group. like ^ ₁ ...

with a chlorine atom or an alkyl group sub ''

stituicrtc Phcnylgruppc, the remainder R _n can / .. B. _, ... .... -,

an alkyl group with I to 8 carbon atoms or * · '~ ι

be a phenyl group. ^. J-,

Specific examples of compounds for these ',,

Sensitizers are the following: q ''

CH ₁ CH ₁ OII

C ₂ H,

Dye A

Melting point 23 ^ C

Dye F
-N CH,

C- (ΊΙ CW CO

N C C

i ONS

CHCH-CH,!

C ₂ H ₅

Melting point 240 '.

Dye G

N N CH,

C-CH --CH = C O

H ₃ C CH, C ₂ IF ONS

Melting point 232 C CH ₂ -CH-CH

Schmcl '/ punkl 230

Dye C
_{N N} _. _CH , dye H

Il I., N N-CH,

N C = CH -CH = C S i | i

\ / i! N C = CH-CH = C S

N cc \ ζ "'I!

¹ y \ / ν

η \
^X N
I. -N - CH,
ι -N-CH,
I. C H- C O N S. -S
I. 1 p N • punki 245 C 3 ° S. Il
N ₁ I.
C ₂ I C-CH- I.
C = CH- I.
C.
\ 1
H ( C. S N \
O :O H ₅ S. chmcl arbstofl B F. "N ~ N
I. -CH = C- Il
N C. C. "n

C ₂ H ₅ ONS

I ⁵

/ N / V ONS

CH ₂ CH ₂ CH ₃ C ₃ H ₆ SO ₃ K

Melting point 190 C Melting point 290> C

55 Dye D Dye I.

1 i "^ - CH-C S - N C = CH-CH = C S

\ / lc NCC

I ^ \ / \ CH ₃ ONS

CH ₂ COOH

, inter- melting point 242 ° C

Melting point 201 ° C

l-'arb-ioff.l

NN CfU '

N ■ CH C

S C

C; ll.

Melting point ?> 0 C, _ς

Such sensitizers are, for example, in British patent specification serial SOI .T ^":; beschriebi-n and <lie I icrstclluni: the sensitizers can be performed at visit to known methods in accordance with the above animal I'alentschrift and other technical literature m liiellen These optical sensitizers who. Either singly or in a combination of two of the several in four Si fvhaio: _ 'enidemi.ilsion ange-Vandl. The addition of d-; t-piisclvii Sensibilisaloren Vu to the emulsion can be made at any desired point during the isolation So ILinn the spectral sensitizer cnlvwder üieich; / .: üii! With <\ cv MetalUei binding or running on it, / ih'.beübei, uobc the sequence is insignificant.

Mkemein not have Scluchtiräger '■ daspliMen. Meia'llplalten. ilolzpiatten. Shark \ ipapiere. Phologra · see papers, ('dluloseacetaililmträgcr or i'olvi, s! u iiimtiäucr can be used

Most of the time, binding agents are water-soluble oil-forming agents High molecular weight compounds. ·. '. u- ι iclatine. Pob. \ Invlalk-Ίιοί. Polyvinyl pyrrolidone \ .imumalgmal and <arl-oxymethvleellulose. The Hmdeniitiel can be used both individually and in combination. -1 °

\ is lich'.hensible silver halide!. · can SiI- ^:. -ei chlond. SilK-rhromid. Silivrchl "! Bromid. Silver-'t'dbroniid. Silberehioriodbromid can be used the formation of the silver halide emulsion can be carried out in the usual manner.

Through the crinkling it is achieved that photographic Recording materials with a high spectral sensitivity to green light for Are available that maintain their high spectral sensitivity even when short flash exposures, in particular for a duration of at most up to! / 100,000 seconds or even only can be applied up to 1/1 000 000 of a second.

The compounds of Group VIII of the PSE, namely iron, cobalt, nickel. Ruthenium. Rhodium, palladium, osmium, iridium. Platinum, are z. B.

Iron D sulfate (FeSO ₄ 5H ₂ O), iron ID chloride (FeCl ₃ ),
Potassium hexacyanoferrate (II) (K4 [Fe ((- N) t]: m ₂ O), Kaliumhexacyanoferratdll) (K ₃ [FeC N ₆ Tj), KobaltdIVchlortd (CoCl ₂ ),
Cobalt (li) -nitrai (Co [NOj] ₂ · 6H ₂ O), potassium hexacyanocobaltate II) [Co (CN ^,] |, Nickcldll-clilond INK K · MI-Oi. MickcliHi-niirat (Ni [Nt),] - Ml ₂ (M. K ill hen in mc hl 01 id (RuC I ₁ I.
KaliUinhc \ aehl``inithenat (IV) (K ₂ RuCl ,,). Rhodiuminii-rhlorul (Rh (I, ■ 4H, O). AmmoniumhexachlorrhodatdH) ([NH _-1 ], Rh ('! ,, 1. Pilladium nitrate iPd [NC),],). Pallium bromide (PdBr,). '
Potassium hexaehlorpilladaUlV) (K ₂ PdC l "). Potassium tetrathiocyanopalladatdl) | K _: Pd [CNS] ₄ I. () smiiim (II) chloride (Os ('I ₂ I.
iridium dlll chloride (IrCl.,).
Iridium! IV) chloride (IrC I _x ).
Iridium (III) bromide (IrBr ₁ 411.0). Iridiuin! IV) -bromitl (IrBr,).
Potassium hexachloride (III) (K, IrCl ,,). Potassium hexaehloriridate (IV) (K ₂ IrCl ,,). AmmoniumhexachlorplatinaKlV) ([NH ₄ ] -, PtCl,>. Potassium hexachloropiatinate (I \ | (K ₂ PtCI ,,). AmmoniumhexabromplatinatllVl ([NHj I ₂ PtBr ₁ , 1.

The Group VIlI metal compounds can both individually and in combination of two or more compounds together in the silver halide emulsion preferably in an amount of 10 "V-; * · IO \ can be used on 1 mole of silver halide. The addition of these compounds to the emulsion can take place at various stages of the preparation, for example in the preparation of the silver halide grain particles. in the preparation of the silver halide emulsion either as an additive to the halide solution (Hler in tier (Ή-latinedispersionslösung) or to Beuinn the ripening τ emulsion or take place in intermediate stages. The \ erbindungen can also be used together with andcen known stabilizers. Antifoggants. Anti-bronze medication. surfactants. Hardeners. Plasticizers. Matting agents, Development accelerators or training agents i and the like added in the desired% before the application of the emulsion to the substrate will.

According to one embodiment of the F.rtindunn is called Metal compound potassium hexacyanoferrate III) and -(HI). Rhodium eliloride. Ammonium hexachlororhodate (HI). iridiumd \ ') ehlorid and potassium hexachloriridate (IV) are used.

According to a further embodiment of the invention, 3-allyl-5- [2- (1-ethyl-4-methyltetraz.olylidene) ethylidene] rhodanine is used as the spectral sensitizer .

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

Ro

C = CH-C = CH-C

PC "),

¹ HI -1

used in which R _{0 is a} hydrogen atom or alkyl group having 1 to 3 carbon atoms, eme methyl group, or

R, and R ₂ each represent 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 / Ϊ-hydroxyethyl group. , (- acetoxyethyl group. Carboxymethyl group, (- carboxyethyl group. Γ - carboxypropyl group. 2 - (2 - carboxyethoxy) ethyl group, jt - sulfoethyl group. - ■ - sulfopropyl group. Λ - sulfobutyl group. 2-hydroxy- I - sulfo- ^ propyl group, 2- (3-Sulfopropoxyethyl group. 2-Aeet- % y - 1 - sulfopropyl group. 3 - Methoxy - 2 - (3 - sulfoftropoxy) propyl group. 2- [2 -13 - SulCopropowath | »xy] ethyl group or 2- Hydroy ". - 3-i3 - <uli <ipropl> xy) -propy! Group. An aryl group. Like eme Pheinlfruppc or aralkylgroup. Wnhci iodcch at least finer the '^ este R _: and R- au> one (. '.rhoxyu! k \! - (group (here sulfoalkyl group hokhi. ^ · and Ί _: an oxygen atom, em sulfur atom ι «the one (i group:> N R-. where R- is an alkali group with 1 to? carbon atoms, for example a Me-Ihylgrupp ·: or a Ath_ \ lyruppe.R ,. R ^ ^1;. _ and R ,.

each a hydrogen atom. an alkyl group having 1 to 3 carbon atoms, for example a methyl group, an ethyl group, a halogen atom, for example fluorine, chlorine or bromine, a cyano group. an alkoxy group. for example a metho or ethyoxy group. or an aryl group such as a phenyl group. where, however, foils π at least one of the radicals Rj. and R, an Arvli: i uppe '■ <. neither R ₅ nor R ₁ , an Aiyigruppe ^ ind. X an A.ik'n. for example a haloücnion. an Ih uv - \ ..nation. a sulfite ion. Sulionatiou. lVrcli'.or.itioti. p-IOiuoisulfonate ion. Ben / iiNulfonation. ^: \ ih \ lsu; ianon oiK'i Methylsu ¹ '.! ¹ -on and m die / aiilen i or 2. wolv im l ^; a] l an> intramolecular salts- · »; the West ^: owns. means.

According to this Aiisiiostaltunü no · .i 'becomes a; nt ·:;: sivere (.irünsensibiüsieruni: he / ielt.

Specific examples fiii / usiit / hcli to Jen erli: ' According to the individual l'eirazolmerocvanmen e.r: settable green sensitizers vi-n this optical · Sensitizers are used as follows:

• dead I

C; H,

C-CH

V
C \ H _:

(CH, 1, SO.,

CH,

dye

Dye IV

Sehmelzpimk; 2Sl '.

Dye C-H,

'■. ο ^; * 'O _x

('- "CH C CH C

N ^ N

Cl

(CH-I ₁ SC-.,

Sehmei punki 210 (

C --- CH-CH = CH C Cl

Cl

Melting point 262

C = CH-CH = CH-C N ^/ ■

C ₂ Hs

CI

Melting point 233 °

Dye V CH.,

C- = CH C = CH C

Ov

CH,

CH,

Melting point 29> C

Dye Vl

CMK

Cl

O _x II C-CH-CH-CH-C

N ../ V /

p I

^λ ν; \ / \

CMK

Br VI ι
ι CH Cl C. , COOH dye

Melting point Γ.05 C

C ₂ H,

C = CH-CH-CH C

CN

C ₂ H ₅

Br

Cl

CH ₁ CH ₁ CHXOOH

Melting point 210 (

If ₃ CO

Dye VIII C ₂ H ₅

= CH-C-CH-C

C ₁ H,

CI

C ₂ H,

(CH,)., SO,

Melting point üL-jr l <00

Cl

Dye IX C ₂ H ₅

^X C = CH-CH = CH-C ^ (CH ₂ J ₄ SO ₃ Na

Cl

egg

I (CHj) ₄ SOf

Melting point above 3 (K Such sensitizers are, for example, according to methods known per se

4en USA patents 2,503,776, 2,912,329.6s the above patents and others

Ϊ 397 060, the French patent specification. 1 108 788, niche literature.

Japanese Patent Publication 44-14030- The manufacture of photosensitive photo;

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

carried out in the usual manner with the addition of the sensitizing components indicated above and the material obtained can be developed in the usual way after the flash observation be fixed. The recording material can be prepared by what is known as a diffusion transfer process Be bandaged wisely. If in advance an appropriate amount of a developing agent of the photosensitive Layer is incorporated, the development according to the well-known ι ο Activator development processes take place, d. H. a process in which the photosensitive material, containing the developing agent is developed in a solution containing no developing agent and only an alkaline material is dissolved.

It has been found that light-sensitive materials having the above-mentioned Contain 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 theirs Sensitivity to blue light is improved. On the other hand, it was found that in the case of sensitive Recording materials which do not contain the metal compounds, but only the optical ones Contain sensitizers, which increase the sensitivity to green light is not very pronounced is. However, when the spectral sensitizer according to the invention is combined with the metal compound is used, the sensitivity to green light in the flash exposure is markedly improved.

In particular, in the case of silver chloride emulsions. Silver chlorobromide emulsions or silver chlorobromoiodide emulsions a considerable decrease when the spectral sensitizers are used alone the effectiveness of spectral sensitization on flash exposure. The photographic Recording materials according to the invention are therefore particularly suitable for flash exposures.

The connections of the elements of group V111 of the In addition to the effects envisaged according to the invention, PSEs can optionally have additional effects 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 Contrasts are used when used together with the sensitizing dyes in accordance with 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! ^ ⁰

A silver chlorobromide emulsion containing 50 mole percent AgBr in a neutral medium was prepared by a known method which did not contain a Group VIII metal compound. hereinafter referred to simply as metal compounds, and a sample was prepared with the addition of hexachloro rhodate (III) in a Mcnjic of 3 x 10 " ⁶ moles per 1 mole of silver halide in the above emulsion at the time of formation of the silver halide grains, and furthermore after ripening potassium urachloroplasm was added in an amount of 2 x 10 "~ ⁵ moles per 1 mole of silver halide. 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 like this.

To the other part, dye A was added in an amount of 6 x 10 ^-3 moles per 1 mole of silver halide in the emulsion. Then, formaldehyde was added to each emulsion in an amount of 2.5 per 100 g of gelatin of the emulsion, and the emulsion was dissolved a photographic baryta paper applied.

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

Using a sensitometer and through a colored glass filter, the light transmitting wedge of which is shown in the drawing, and using an optical wedge, the above samples were exposed at 1/100 second and 1/1,000,000 second, respectively. As can be seen from the drawing, the colored glass fiber absorbs. the light corresponding to the sensitive spectral range of the unsensitized silver halide and only lets through the light corresponding to the optically sensitized range of above about 500 nm. The exposed samples were developed in the following developer ^{at 20 3 C for 2 seconds.}

N-methyl-para-aminophenol 2 g

Sodium sulfite, anhydrous 30 g

Hydroquinone 7 g

Sodium carbonate (monohydrate) 53 g

Potassium bromide 1.5 g

Water to 11

After fixation. Rinsing and drying were used to determine the reflection density of the images.

The reciprocal value of the amount of light, the one Density of 0.5 was assumed to be the sensitivity wide: since, however, the absolute amount of light was not determined by the filter, the sensitivity is only relative; in the table below the sensitivities for the same exposure time are given accordingly. The received The results are summarized in the table:

exposure
while
one
Vio <i second Comparative emulsion
Only metal the
Group VIII
Only dye A
Group VIII metal
+ Dye A 0
0
12.0
10.5

2.7

7.2

It turns out that by simultaneous application of the rhodate salt. of the platinum salt and the dye A increase the sensitivity to green light Flash exposure was increased.

exposure

while

one
'; ,, "Sec.

Example 2

The procedure of Example 2 was repeated except that a dye I was further added to the emulsion in an amount of 4 x 10 ^-3 moles per 1 mole of silver halide. The following results were obtained:

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

Relulivc sensitivity

'/, «. Sec.
Belicht clothes

0
15.0

13.0

I, cot

Ίικκιίιηη ^3C * exposure

3.3

9.5

Example 3

A silver chlorobromide emulsion containing 50 mole percent AgCl and 50 mole percent AgBr, which did not contain any metal compounds according to the invention, was prepared in an alkaline ammonium medium in a conventional manner. Further, in the same method were each 1 mol of silver halide at the time of formation of the silver halide grains 1 ■ 10 ~ ⁵ moles of Kaliumhexacyanofcrrat (III) and an emulsion having a same sensitivity as the emulsion without metal compounds obtained. To each such emulsion, as indicated in Example 1, the dye VI11 was added in an amount of 4 × 10 -4 mol per 1 mol of silver halide. Furthermore, a dye HI was added to the emulsion in an amount of 2 × 10 ^{-3 mol.} Finally, formaldehyde was added in an amount of 2.5 g per 10U g of gelatin, and the emulsion was coated on a photographic baryta paper. The sensitivity of the obtained samples to green light was determined by the same procedure as in Example 1. The following results were obtained:

RcUiiive sensitivity

j '"», sec. j ¹ - "" sec.

ι exposure | exposure

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

58

60

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 an emulsion having the same composition of the Silberhalogenidkornteile were 4 x 10 ~ ^h mole of potassium hexacyanoferrate (lll) in the formation. 6 · 10 ~ * moles of potassium hexachloriridate (IV). 3 · 10 "" Mol ammonium hexachlororhodate (IIl) was added to I mol of silver halide in the emulsion, and then in the subsequent ripening 3 x 10 ^h mol per 1 mol of silver were to

Chlorgoldliure added. Same sensitivity as with the above ordinary emulsion was obtained.

To serve emulsions, the dye VU was added in an amount of 2 × 10 ^-3 mol per 1 mol of silver halide

Furthermore, the dye VI was added to the emulsion in an amount of 2 × 10 " ³ mol per 1 mol of silver halide. Furthermore, formaldehyde was added to these emulsions in an amount of 2 ^ g per 100 g of gelatin, and a photographic emulsion was obtained which was based on a The sensitivity to green light of the samples was determined in the same manner as in Example 1. The results are shown in the following table.

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

ve sensitivity

'/, oo sec. exposure

0 190

145

/ ιοαούοη Sck exposure

35

Example 5

A silver chlorobromide emulsion containing 50 mole percent AgCl and 50 mole percent AgBr became in a neutral Medium produced in the usual way.

Using the same procedure, dor Production of the silver halide grains 3 - 10 ~ "mol per 1 mol of silver halide of ammonium hexachloro

rhodate was added to the emulsion and, after ripening, platinum chloride was added in an amount of 2 × 10 ⁵ mol per 1 mol of silver halide to produce an emulsion with the same sensitivity as the emulsion without the metal compounds. To each of these emulsions, the dye G was ^{further added in an amount of 2 × 10 3} mol per 1 mol of silver halide.

Furthermore, 2.5 g of formaldehyde were reduced to! 0Og Gelatin added and the emulsion on a photographic Baryta paper applied.

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

: I exposure during

Comparative emulsion
Only metal the
Group VIII

Only dye G ..

Group VIII metal

+ Dyes

Exposure during

0 139

89

one

'ιnonnoo ■>'

0 30

79

In this case, too, the effect was the joint application of the Mctallsal / cs of the Group VIII and Dye G observed.

In addition 1 E'att drawings

Claims (1)

Patent claims: 1. Photographic recording material with at least one spectrally sensitized syllable, halide emulsion layer, applied to a layer support, which contains at least one compound of a metal from group VIII of the PSE in an amount of 1 · 10 " ⁶ to 1 · \ 0 ^-3 mol per 1 Mol of the silver halide "contains, characterized in that the layer acts as a spectral sensitizer at least one merocyanine of the formula