BE691807A

BE691807A -

Info

Publication number: BE691807A
Authority: BE
Priority date: 1965-12-27
Filing date: 1966-12-27
Publication date: 1967-05-29

Description

  

   <Desc/Clms Page number 1> 
 



  Monsieur le Ministre,
Nous avons l'avantage de vous faire savoir qu'à la 
 EMI1.1 
 date du. 27 décembre 1966, nous avons opéré lé dépt-b d'una demande de brevet au nom de la société dite: FUJI SI1&SHIN FILM KAJ3USHIKI KAISHA eo-us le 1'4  PV 37.758, pour: "1ment photographique d'haloàénur* d'argent sensible à la luaiére" . 



  La. présente a pour but de rectifier aoa orroiiro fi!0.tériel1es cosuises aura l'ex6c:ution do lu spécification. En effet, il y aurait lieu d'effectuer   le,--     Modifications     ci-?.Près ;    
 EMI1.2 
 â-StS-1 " les t'orinulex deu colorants XII - XII - XIV et   XV   doivent se lire comme   suit ;   

 <Desc/Clms Page number 2> 

 
 EMI2.1 
 
Ces rectifications se justifient par   elles-mêmes.   



   Le soussigné n'ignore pas qu'aucun   document   joint au dossier d' un brevet d'invention ne peut être de nature à apporter,soit à la description,soit aux dessins,des modifications de fond et déclare que le contenu de cette note n'apporte pas de telles modifications et n'a d'autre objet que de signaler une ou plusieurs erreurs ma-   térielles.   



   Il reconnaît que le contenu de cette note ne peut avoir pour effet de rendre valable, totalement ou   partiellement,le   brevet No. 



    PV.37.758   si   celui-ci ne   l'était pas en tout on en partie en vertu de la   législation actuellement   en vigueur. 



   Il autorise l'administration à joindre cette note au dossier du brevet et à on   délivrer photocopie.   



   Pour la   bonne   règle,il nous serait agréable si vous vouliez bien noua accuser réception de la   présente,stipulant   que les rectifications   sont     admises   pour valoir comme de droit. 



   A vous   lire,   nous vous prions d'agréer, Monsieur le Ministre, l'assurance de notre   considération     distingues. -   Annoxe : 100 W. en timbres fiscaux 

 <Desc/Clms Page number 3> 

   Elément   photographique   d 'halogénure   d'argent sensible à la lumière.   La   présente a pour but de rectifier une erreur matérielle   commise   dans   l'exécution   de la spécification. 



   En effet: page 21 la formule doit se lire 
 EMI3.1 
 
Il y a en   conséquence   lieu de supprimer aux lignes 19 et suivantes le membre de phrase: " et A représente un membre choisi dans le groupe consistant en un groupe polyméthylène et un groupe alcoylpolyméthylène. 



   Le soussigné n'ignore pas qu'aucun document joint au dossier d'un brevet d'invention ne peut être de nature à apporter,soit à la description, soit aux dessins, des modifications de fond et déclare que le contenu de   cet.le     note n'apporte pas de telles modifications et n'a d'autre objet que de signaler une ou plusieurs erreurs matérielles.   

**ATTENTION** fin du champ DESC peut contenir debut de CLMS **.



   <Desc / Clms Page number 1>
 



  Minister,
We have the advantage of letting you know that at the
 EMI1.1
 dated. December 27, 1966, we filed a patent application in the name of the company known as: FUJI SI1 & SHIN FILM KAJ3USHIKI KAISHA eo-us on 1'4 PV 37.758, for: "1ment photographique d'haloàénur * d ' light sensitive money ".



  The present is intended to rectify aoa orroiiro fi! 0.tériel1es cosuises will have the execution of the specification. Indeed, it would be necessary to carry out the, - Modifications here - ?. Close;
 EMI1.2
 â-StS-1 "the orinulex deu coloring agents XII - XII - XIV and XV should read as follows;

 <Desc / Clms Page number 2>

 
 EMI2.1
 
These rectifications are justified by themselves.



   The undersigned is aware that no document attached to the file of a patent for invention can be of a nature to make, either to the description or to the drawings, substantive changes and declares that the content of this note no 'make no such changes and has no other purpose than to report one or more material errors.



   He recognizes that the content of this note cannot have the effect of making valid, in whole or in part, patent No.



    PV.37.758 if this was not entirely or partly under the legislation currently in force.



   It authorizes the administration to attach this note to the patent file and to issue a photocopy.



   For the good rule, it would be pleasant for us if you would kindly acknowledge receipt of the present, stipulating that the rectifications are admitted to be valid as of right.



   If you read this, we ask you to accept, Mr. Minister, the assurance of our distinguished consideration. - Annoxe: 100 W. in fiscal stamps

 <Desc / Clms Page number 3>

   Light sensitive silver halide photographic element. This is intended to rectify a clerical error made in the execution of the specification.



   Indeed: page 21 the formula should read
 EMI3.1
 
The phrase: "and A represents a member selected from the group consisting of a polymethylene group and an alkylpolymethylene group should therefore be deleted from lines 19 and following.



   The undersigned is aware that no document attached to the file of a patent for invention can be of a nature to make, either to the description or to the drawings, substantive changes and declares that the content of this. note does not make such changes and has no other purpose than to point out one or more material errors.

** ATTENTION ** end of DESC field can contain start of CLMS **.

Claims

He acknowledges that the content of this note cannot have the effect of making the award n PV 37.75 valid, in whole or in part, if it was not fully or partially valid by virtue of the legislation currently in force. . <Desc / Clms Page number 4>

He authorizes the administration to attach this note to the document of the patent and to issue a photocopy.

For the good rule, it would be pleasant for us if you would kindly acknowledge us receipt of this, stipulating that the rectification is admitted to be valid retort of right. ** CAUTION ** end of field CLMS may contain start of DESC **.

Reading this from you, we ask you to accept, Mr. Minister, the assurance of our highest consideration. <Desc / Clms Page number 5> EMI5.1 Minister, EMI5.2 The purpose of this is to rectify a :: 'r (:' nr material committed in the execution of the specification. Indeed, we have introduced t uW: letter of amendment fart dated June 14, 196 ?, r, ' : Dis pax 'following an error, .le; s :;: EMI5.3 mission au 'l' (: JP, nous 8'.r: Lon ::: s: Gr :: i ".t,.> zq> ii; iL y ovam .1: 6G, l, - du modify the formulate in; 'éDJ.: \.', ::; f; ij needed an rlUU'ol .: t; ': "!: 1 t between C and 1; 1 covme indicates in 7.'ûltlje in P ",:. 'Ùl, 1. T ;.

The member of phraHf aux 1 ..; fl'nps 7.! .,; .'1,15 VQntee d 1s p ': c 21 must therefore be understood den.],> 1 a z p é <3 t'i c:, J .I; L i: .ti, <. Ast - :. ï, r¯ '- "- a.c, and 18 fQ r;?; 1), e of; ^ f8 µil of :)." "31. n: EMI5.4 EMI5.5 The undersigned is aware of pcr:; a ', <i cu m docMnt: joint'. in the file- ci'un patent re 2.nvçrit,.; ii ;; can Scr ij. hpt'.u "'-? bring, tioit to the <1, is <> ifi, ptlit,>;.:,: .., ii, 1 .ouit d <; ca.cJ :, NuH me dit'i CD tien s de fond et de.c1.v: l: 'o the con {; NlU of dctztc note does not bring aHJ) f..1 nio c; µ, l? Ic ati oni; and,! t () Si't; ut1:;: object that to report or plustoL11S frcur3 met01'lelJ -a.

He recognizes that the cost of this: iote not be afraid of making it valMtoha'nt '; ru pnità, (pj¯īcment the patent does not il'I; à? '7 aµ- .eoi, v ;; ci, does not have all or part of it in vr-Lu from 1.a l' .isic'cion;> ctiel; jment on vir; tH, \ 1.r. <Desc / Clms Page number 6>

It authorizes the administration to attach this note to the buttock of the patent and to issue a photocopy of it. Afraid of the right rule, it would be nice if you would acknowledge receipt of this, stipulating that the rectification is admitted to be valid as of right.

Reading you, we ask you to accept, Mr. Minister, the assurance of our highest consideration. <Desc / Clms Page number 7> Sensitive silver halide photographic element The present invention relates generally to a light sensitive silver halide photographic element and more particularly to a light sensitive silver halide photographic element having at least one photographic halide emulsion layer. silver which has been supersensitized to dyes by the combination of benzimidazolo-carbocyanine and benzoxazolo-carboeyanine.

It is well known that one class of cyanine dyes is very effective in increasing the light sensitivity of photographic emulsions. In this case the cyanine dye incorporated in a silver halide emulsion is adsorbed on the particles. <Desc / Clms Page number 8> of silver halide in the emulsion, thereby adding an absorption band on the side of the longer wavelengths relative to the specific absorption band of the silver halide.

On the other hand it is known that if some other kind of dyes or an organic material is present together with the cyanine dye, the effect of sensitization by the dye is remarkably increased and in particular a combination of certain dyes increases by. markedly the sensitivity of the silver halide emulsion, this effect being termed dye supersensitization (cf. for example CEK Mees: "The Theory of the Photography Process", 2nd ed. 474 pages, 1954, New York ).

A large number of combinations of sensitizing dyes have been cited with a view to increasing the sensitivity of photographic silver halide emulsions by supersensitization to dyes. However, these conventionally known combinations of dyes are usually unsuitable for use in light-sensitive silver halide elements for color photography because the sensitivity is low, the spectral range of sensitization is poor. not suitable for a light-sensitive element of color photography, because fog formation and color contamination is important, or because sensitivity is lowered by other additives.

Therefore, a major object of the present invention is to provide a light sensitive silver halide photographic element having a photographic silver halide emulsion layer forming less haze and fog. color contamination, having a high sensitivity and having a spectral region of <Desc / Clms Page number 9> Light sensitivity particularly desirable for light sensitive elements of color photography.

Another object of the present invention is to provide a light sensitive silver halide photographic element having a green sensitive silver halide photographic emulsion layer, showing no reduction in light sensitivity. light by a magenta color coupler when it contains a magenta chromogenic coupler, that is to say an agent forming a magenta color image, capable of coupling with the oxidation product of a primary aromatic amine color developer such as p-phenylene diamine to produce a colored image.

Still another object of the present invention is to provide multi-layered color photography equipment having at least one green-sensitive silver halide emulsion layer as mentioned above, without accompanying the aforementioned drawbacks.

Applicants have found that these objects can be achieved by adding a specific benzimidazolo-carbocyanine and a specific benzoxazolo-carbocyanine as a dye-supersensitizing dye combination in a photographic silver halide emulsion.

The specific benzimidazolo-carbocyanine employed in the present invention is represented by the following general formula; EMI9.1 in which R1 and R2 each represent an alkyl group <Desc / Clms Page number 10> such as methyl group, ethyl group, propyl group, n-butyl group, R3 and R4 each represent an alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, etc. , or a substituted alkyl group having as a substituent a hydroxyl group, a hydroxyalkoxy group, an acyloxy group, a sulfoalkoxy group, a (sulfoalkoxy) alkoxy group, a sulfate group, an alkoxy sulfate group, a carboxyl group, a carboxyalkoxy group , etc,

such as 2-hydroxyethyl, 3-hydroxypropyl, 2- (2-hydroxyethoxy) ethyl, 2-acetoxy-ethyl, 3-acetoxypropyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2- (3-sulfopropoxy) groups -ethyl, 2- (2-sulfoethoxy) -ethyl, 3- (2-sulfoethoxy) -propyl, 2- (2-- (3-sulfopropoxy) -ethoxy) -ethyl, 2-hydroxysulfonyloxy-ethyl, 2- (2 -hydroxysulfonyloxyethoxy) -ethyl, carboxy-methyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2- (2-carbethoxy) -ethyl and 2- (2-carbethoxy) - propyl, at least one of these groups R3 and R4 being a substituted alkyl group, m and n each represent 1 or 2 and X- represents an acid anion such as a chloride ion,

a bromide ion, an iodide ion, a perchlorate ion, a p-toluenesulfonate ion, etc.

Likewise, the benzoxazolo-carbocyanine used in the present invention is represented by the following general formula: <Desc / Clms Page number 11> EMI11.1 wherein R5 represents an alkyl group such as a methyl group, an ethyl group, a propyl group, etc., 6 represents an alkyl group such as a methyl group, an ethyl group, a propyl group, etc., or a sulfoalkyl group such as 2-sulfoethyl group, 3-sulfoethyl group, 3-sulfoethyl group, 4sulfoethyl group, etc., and A represents polymethylene group such as ethylene group, trimethylene group, tetramethylene group, etc., or an alkylpolymethylene group such as a methyltrimethylene group, etc.

As typical examples of the benzimidazolo-carbocyanine dye represented by the general formula (A), the following dyes will be mentioned: EMI11.2 <Desc / Clms Page number 12> Dye; 1) ¯; @ EMI12.1 <Desc / Clms Page number 13> EMI13.1 CsSEâSJ # -S <,! C2H5 EMI13.2 As typical examples of the benzoxazolo-carbocyanine dye represented by general formula (B), the following dyes are exemplified:

EMI13.3 <Desc / Clms Page number 14> In accordance with the present invention, the light sensitive photographic element has at least one photographic silver halide emulsion layer containing at least one benzimidazolo-carbocyanine dye represented by general formula (A) together with at least one benzoxazolo-carbocyanine dye represented by the general formula (B).

The silver halide emulsion employed in the present invention may be a color photograph emulsion containing a coupler to form a magenta dye, a color photograph emulsion of a type to be developed by a developer containing a coupler, or a general black and white photographic emulsion, and particularly good results can be obtained when a gelatin-bromo-silver iodide emulsion is used. However, the invention is of course also applicable to various other silver halide emulsions, such as silver chloride emulsion, silver bromide emulsion and silver chlorobromide emulsion.

The sensitizing dyes of the present invention can be incorporated into the silver halide emulsion in any stages preceding the coating. The benzimidazolo-carbocyanine dye represented by the general formula (A) may be incorporated into the silver halide emulsion before or after the addition of the benzoxazolo-carbocyanine dye represented by the general formula (B), or well they can be incorporated in the form of a mixture of these.

The concentrations of the sensitizing dye used in the present pulses are, influenced by the Rature of the pho emulsion. The silver halide chart to be employed or the Rature of the dyestuffs .... however, in general, the suitable amount of the benzimidazolo-carbocyanine dye represented by the general formula (A) is 0.01 to 0.64 mg per mole <Desc / Clms Page number 15> of silver halide in the emulsion and the appropriate amount of the benzoxazero-carbocyanine dye represented by the general formula (B) is 0.03 to 1.28 mg per mole of silver halide in the emulsion. emulsion and the ratio between colorant (A) and colorai (B)

is preferably 4: 1 to 1:20. However, other concentrations or other ratios may be employed in the present invention.

The addition of the sensitizing dyes is preferably carried out by employing their solutions in suitable solvents; as the solvent one can be used which does not adversely affect the photographic silver halide emulsion, for example methanol and ethanol.

The photographic silver halide emulsion used in the present invention can be chemically sensitized by a conventionally known process, in particular by a compound containing unstable sulfur, for example ammonium thiosulfate and allyl-thiourea (cf. for example P. Glafkides, Chimie de la Photographie, 2e.'éd, Publication Photocinéma, Paul Montel, Paris (1957), 297-299), a gold compound, for example the complex salt of thiocyanic acid ( cf. ib. page 301), a derivative of polyalkylene oxide, or a combination thereof.

Further the photographic emulsion of the present invention may contain a stabilizer such as benzimidazol or 1-phenyl-5-mercaptotetrazol (cf. for example Shinichi Kikuchi, Kagaku Shashin Binran, 29-50 (1959), published by Maruzen Co.) or a curing agent such as formaldehyde or mucobromic acid (ib. Page 29-50).

Additionally the photographic emulsion of the present invention may contain a magenta coupler such as 1- (4-phenoxy-3-sulfophenyl) -3-heptadecyl-5-pyrazolone, 1-phenyl-3- (2-octadenyl) succinamido -5-pyrazolone, 1- (2,4,6-trichlorophenyl) - <Desc / Clms Page number 16> EMI16.1 5 {1 = (2-octa4ecenylsuocinamido) -benzamido) -5-pyrazolon, iaf-.alfophdnyl) ¯-stearoylamino-5-pyrazolone, 1- (2,4, -fi chl orophenyl) 3 - t 3- p.¯d.-t-YlPhenoxyac etamido) -5 ¯ pyrazolone, l- (2,4,6-trichlorophenyl) -3- (3- (2,4-di-tsra; .lpaenoxyactamido) -benzamido) - i-.-ethoxy-pheny3azo) - - pyrazolone, etc.

The invention will be described in still more detail with reference to the following examples.

Example,!., A highly sensitized gelatin-bromo-silver iodide emulsion, which has been sensitized with sulfur and gold, is melted by heating, divided into several parts and each of the divided emulsions is incorporated with a solution of one or several sensitizing dyes mentioned in Table 1. After curing for 30 minutes at 40 C, the emulsion is applied to a base film and dried. The film thus dried is exposed to the NSG-II sensitometer (manufactured by Tokyo Shibaura Electric Co. in Japan) through a yellow filter.

Then the film is developed for 10 minutes in a developer having the following composition: EMI16.2 N-methyl-p-axiinophenol sulfate 2 g EMI16.3 <tb> <tb> <SEP> sodium <SEP> sulphite <SEP> (anhydrous) <SEP> 100 <SEP> g <tb> hydroquinone <SEP> 5 <SEP> g <tb> borax <SEP> 2 <SEP> g <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb>

The relative sensitivity and the haze thus developed are measured and the results thus obtained are reproduced in Table 1 in which the relative sensitivity is given assuming that the sensitivity of a sample, in which the dye 1 (3) is added in an amount of 0.08 g per mole of silver halide, is 100. <Desc / Clms Page number 17>

Table 1. EMI17.1 <tb> <tb> Test <SEP> Colorant <SEP> and <SEP> concentration <SEP> Sensibi- <SEP> Haze <tb> N <SEP> (g./mole-Ag) <SEP> ity <tb> relative <tb> @I (3) <SEP> (0.01) <SEP> 32 <SEP> 0.06 <tb> 1 <SEP> @XII <SEP> (0.03) <SEP> 42 <SEP> 0.06 <tb> @I (3) <SEP> (0.01) <SEP> + <SEP> XII <SEP> (0.03) <SEP> 95 <SEP> 0.06 <tb> @I (3) <SEP> (0.03) <SEP> 50 <SEP> 0.06 <tb> 2 <SEP> @ <SEP> XII <SEP> (0.08) <SEP> 89 <SEP> 0.06 <tb> I <SEP> @ <SEP> (3) <SEP> (0.03) <SEP> + <SEP> XII <SEP> (0.08) <SEP> 200 <SEP> 0.06 <tb> CI (3) <SEP> (0.08) <SEP> 100 <SEP> 0.09 <tb> 3 <SEP> @XII <SEP> (0.16) <SEP> 100 <SEP> 0.06 <tb> @I <SEP> (3) <SEP> (0.08) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 220 <SEP> 0.08 <tb> @I (3) <SEP> (0.32) <SEP> 270 <SEP> 0.12 <tb> 4 <SEP> @I <SEP> (3) <SEP> (0.32) <SEP> 270 <SEP> 0.12 <tb> @XII <SEP> (0.64) <SEP> XII <SEP> (o, 64) <SEP> 152 <SEP> 0.14 <tb> @I (3)

<SEP> (0.03) <SEP> XII <SEP> (0.64) <SEP> 209 <SEP> 0.14 <tb> wire <SEP> 11 <SEP> (0.16) <SEP> 174 <SEP> 0.07 <tb> @II <SEP> (0.16) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 276 <SEP> 0.09 <tb> The results of the table show that by the combinations of the dye supersensitization dyes of the present invention, for example by the combination of. Sensitizing dyes having relative sensitivities of 50 and 89, respectively, a sensitivity of 200 can be obtained.

Example 2.

By the procedure described in Example 1, an emulsion containing the sensitizing dye or the combination of sonibilizing dyes indicated in Table 2 is applied to a base film and exposed as in Example 1. The film thus exposed is subjected to the following treatments:

EMI17.2 <tb> <tb> (1) <SEP> development <SEP> negative <SEP> 27 C <SEP> 7 <SEP> minutes <tb> (2) <SEP> wash <SEP> to <SEP> water <SEP> 27 C <SEP> 2 <SEP> ninutes <tb> (3) <SEP> exposure <SEP> flash <SEP> reverse <tb> (4) <SEP> chromogenic <SEP> development <SEP> 27 C <SEP> 5 <SEP> minutes <tb> <Desc / Clms Page number 18> EMI18.1 <tb> <tb> (5) <SEP> wash <SEP> to <SEP> water <SEP> 27 C <SEP> 1 <SEP> minute <tb> (6) <SEP> laundering <SEP> of <SEP> money <SEP> 27 C <SEP> 5 <SEP> minutes <tb> (7) <SEP> fix <SEP> 27 C <SEP> 3 <SEP> minutes <tb> (8) <SEP> washing <SEP> to <SEP> water <SEP> and <SEP> drying. <tb>

The compositions of the above treatment baths are as follows: EMI18.2 <tb> <tb> revealing <SEP> negative: <SEP> <tb> N-methyl-p-aminophenol <SEP> <SEP> <SEP> <SEP> 2 <SEP> g <tb> <SEP> sodium <SEP> sulphite <SEP> (anhydrous) <SEP> 90 <SEP> g <tb> hydroquinone <SEP> 8 <SEP> g <tb> sodium <SEP> carbonate <SEP> <SEP> monohydrate <SEP> 52.5 <SEP> g <tb> <SEP> potassium <SEP> bromide <SEP> 5 <SEP> g <tb> thiocyanate <SEP> of <SEP> potassium <SEP> 1 <SEP> g <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb> chromogenic <SEP> developer <SEP>:

<SEP> <tb> <SEP> sodium <SEP> sulphite <SEP> 5.0 <SEP> g <tb> EMI18.3 .-am.r.o-3-methyl..P, '- diethylanü.ine hydrochloride 2 g potassium bromide 0.2 g -p $ êny.-3t3Gnitrobonzoylsrnino) -.- pyrazo2one 1.4 g EMI18.4 <tb> <tb> <SEP> sodium <SEP> hydroxide <SEP> 2.5 <SEP> g <tb> n-butylamine <SEP> 5 <SEP> cm3 <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb> <SEP> money laundering <SEP> bath <SEP>:

<tb> <SEP> potassium <SEP> ferricyanide <SEP> 100 <SEP> g <SEP> <tb> <SEP> potassium <SEP> bromide <SEP> 10 <SEP> g <tb> borax <SEP> 2 <SEP> g <tb> boric <SEP> acid <SEP> 1 <SEP> g <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb> <SEP> fixture <SEP> bath <tb> sodium <SEP> thiocyanate <SEP> <SEP> 150 <SEP> g <tb> sulfite <SEP> of <SEP> sodium <SEP> 10 <SEP> g <tb> EMI18.5 water to make up to 1 liter. <Desc / Clms Page number 19> .After processing, c @ measures the density using EMI19.1 a green filter.

The relative sen8i; lity thus obtained is given in Table 2 as well as the value of the color contamination produced by the dyes remaining in the coating, without having been removed by washing after treatment, that is to say the value the density of the portion having the density EMI19.2 lowest me> 5; using a green filter.

In addition, we show in table 2, for comparison, the results when using the combination of dyes XIV and XV mentioned on page 7. The combination of dyes indicated for comparison. EMI19.3 Ratative is described in the United States patent dtlmr.que Xyz f.oC% 9m, ^. /. Table 2. EMI19.4 sssal Colorant and concentration 5enslbl- Contamination N (F / moleAE) 1 unit of g.

relative mole color (xiv ($ 0.0) 95 0.08 1 txx v (0.16) 80 0.08 XIV la, 08) + XV (0.16) 105 0.10 EMI19.5 <tb> <tb> @I (E) <SEP> (0.08) <SEP> 100 <SEP> 0.04 <tb> 2 <SEP> @XII <SEP> (0.16) <SEP> 100 <SEP> 0.04 <tb> EMI19.6 LI (3) (0.08) + XII (0.16) 200 0.04 / II (o, o8) '95 0.04 EMI19.7 <tb> <tb> @II <SEP> (0.08) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 190 <SEP> 0.04 <tb> EMI19.8 flll (0.08) 125 0.04 4 XII (0.16) 105 0.04XIII (0.08) + XII (0.16) 269 0.04 EMI19.9 <tb> <tb> 5 <SEP> @IV <SEP> (0.08) <SEP> 125 <SEP> 0.03 <tb> @IV <SEP> (0.08) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 225 <SEP> 0.04 <tb> @V <SEP> (0.08) <SEP> 177 <SEP> 0.04 <tb> 6 <SEP> @V <SEP> (0.08) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 225 <SEP> 0.04 <tb> @V <SEP> (0.08) <SEP> 168 <SEP> 0.04 <tb> 7 <SEP> @XIII <SEP> (0.16) <SEP> 95 <SEP> 0.04 <tb> EMI19.10 V (0.08) + XIII (0.16) 192 0,

04 8 1 (0.98) XIII (o, 16) 85 0.04 EMI19.11 <tb> <tb> @VI <SEP> (0.08) <SEP> XIII <SEP> (0.16) <SEP> 172 <SEP> 0.04 <tb> <Desc / Clms Page number 20> EMI20.1 <tb> <tb> Test <SEP> Colorant <SEP> and <SEP> concentration <SEP> Sensibi- <SEP> Contamination <tb> N <SEP> ity <SEP> beyond <tb> (g / mole <SEP> Ag) <SEP> relative <SEP> color <tb> @VII <SEP> (0.08) <SEP> 80 <SEP> 0.04 <tb> XII <SEP> (0.16) <SEP> 99 <SEP> 0.04 <tb> @VII <SEP> (0.08) <SEP> + <SEP> XII <SEP> (0.16) <SEP> 185 <SEP> 0.04 <tb> The results in the table show that the combination of the supersensitizing dyes of the present invention produces extremely low color contamination and gives high sensitivity compared to the conventional combination or control dyes (XIV + XV), In addition,

from the spectral sensitivity curves shown in Figures 1 to 3, the following emerges; in figure 1 we give a spectral sensitivity curve of a silver bromo-iodide emulsion containing 0.08 g of dye 1 (3) per mole of silver bromo-iodide, figure 2 gives a curve of spectral sensitivity of a silver bromo-iodide emulsion containing 0.16 g of dye XII per mole of silver halide and Figure 3 is that of a silver bromo-iodide emulsion containing the combination of 0.08 g of dye 1 (3) and 0.16 g of dye VII per mole of silver halide.

Figure 3 shows that the combination of the two dyes of the present invention exhibits a single mixed set maximum at wavelengths between those of the dyes used individually.

This characteristic shows that the following faults are eliminated. The shortcomings are eliminated which are that, using only the benzimidazolo-carboccyanine dye represented by the general formula (A), the wavelength range of sensitization is on the wavelength side somewhat. longer to achieve optimum color reproduction in a color film, and that, using only the benzoxazolo- dye <Desc / Clms Page number 21> carbocyanine represented by the general formula (B), the sensitization wavelength range is on the shorter length side.

Further, by changing the addition ratio of the dye represented by the general formula (A) relative to the dye represented by the general formula (B), it is possible to sensitize up to a desired range of wavelengths; therefore, the invention is particularly beneficial for multi-layered color photographic elements.

Example 3.

In 2 cm3 of dibutyl phthalate is dissolved in EMI21.1 hot 1 g of Nn-dodecyl-1-hydroxy-4-ehloro-2-naplitamide and the solution thus obtained is dispersed as an emulsion in 20 g of gelatin solution at 1% using a dispersing agent such as sodium dodecyl sulfate. EMI21.2 To a high sensitivity silver ela tinobxonao..crduro negative emulsion which has been sensitized with sulfur and gold, 0.2 g of anhydro-5,5'-dichloro-9- is added. ethyl3, I'-disulfopropylselena-carbocYGine as red sensitizing dye and 400 g of the emulsified coupler dispersion prepared above, then, after adjusting its pH to 6.5, the resulting emulsion is applied to a support in one thickness. of 5 microns.

Further, to a negative emulsion (the high sensitivity gelatin-bromo-iodide silver which was sensitized with sulfur and gold was added a combination of the solutions of the sensitizing dyes shown in Table. 3. In 3 cm3 of dibutyl phthalate we EMI21.3 1 g of 1-phnyl-dodcy, l,. ,, c .. -pyrazolone as magenta coupler is dissolved by heating and the solution is then dispersed in a 10% gelatin solution using a dispersing agent. In the silver halide emulsion <Desc / Clms Page number 22> prepared above, 500 g of this coupler contained in emulsified dispersion are added and after adjusting the pH to 6.5, the emulsion is applied to a support with a thickness of 6 microns.

A yellow filter layer consisting of colloidal silver is applied to the layer thus formed.

In 2.5 em3 of dibutyl phthalate is added 1 g of 4- EMI22.1 dodée..bnzo.-2 '.. m, sthoy aetan.7.d sum yellow coupler hot and the solution is dispersed as an emulsion in a 10% gelatin solution. In the silver halide emulsion prepared above, 550 g of the emulsion thus obtained containing a coupler are added and after adjusting its pH to 6.5, the emulsion is applied to a support with a thickness of 5 microns. .

The light-sensitive multilayer element thus obtained is exposed to the NSG-11 type sensitometer and then subjected to the following procedures: EMI22.2 <tb> <tb> (1) <SEP> development <SEP> negative <SEP> 24 C <SEP> 10 <SEP> minutes <tb> (2) <SEP> wash <SEP> to <SEP> water <SEP> 24 C <SEP> 3 <SEP> minutes <tb> (3) <SEP> exposure <SEP> flash <SEP> reverse <tb> (4) <SEP> chromogenic <SEP> development <SEP> 24 C <SEP> 15 <SEP> minutes <tb> (5) <SEP> wash <SEP> to <SEP> water <SEP> 24 C <SEP> 2 <SEP> minutes <tb> (6) <SEP> money laundering <SEP> <SEP> 24 C <SEP> 5 <SEP> minutes <tb> (7) <SEP> fix <SEP> 24 C <SEP> 3 <SEP> minutes <tb> (8) <SEP> washing <SEP> to <SEP> water <SEP> and <SEP> drying <tb> The same compositions are used as in Example 2 EMI22.3 for cimdessu5 treatments,

with the exception of the composition of the color developer. , Chromogenic developer: EMI22.4 <tb> <tb> <SEP> benzyl alcohol <SEP> 6 <SEP> cm3 <tb> <SEP> sodium <SEP> sulphite <SEP> (anhydrous) <SEP> 4 <SEP> g <tb> phosphate <SEP> trisodium <SEP> 40 <SEP> g <SEP> <tb> <SEP> potassium bromide <SEP> <SEP> 0.5 <SEP> g <tb> <SEP> sodium hydroxide <SEP> 1.5 <SEP> g <SEP> <tb> ethylene <SEP> diamine <SEP> 5 <SEP> cm " <tb> <Desc / Clms Page number 23> EMI23.1 <tb> <tb> <SEP> citrazinic acid <SEP> 1 <SEP> g <tb> EMI23.2 -amino-N-ethYl-N) 8 -methanesullanam3.c? rethyl.-m-ta.uidîn H s sulfate EMI23.3 <tb> <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb>

After the treatments, the density is measured using blue, green and red filters. The relative sensitivity thus obtained and the contamination of the color are given in Table 3. From the results it is clear that by the combination of the sensitizing dyes of the present invention, the contamination of the magenta color is less compared to the combination. dyes XIV and XV serving as control samples and also that the sensitivity of the magenta coupler layer is higher.

Table 3. EMI23.4 <tb> <tb>

Test <SEP> Colorant <SEP> and <SEP> concentra- <SEP> blue-green <SEP> magenta <SEP> yellow <tb> N <SEP> tion <tb> (g./mole <SEP> of <SEP> Ag) <SEP> A <SEP> B <SEP> A <SEP> B <SEP> A <SEP> B <tb> EMI23.5 1 XIV (O / l6} + xv (o, 16) 100 0.06 100 0.21 100 0.16 2 I () (Ot16) + XII (0.16) 98 oeo5 130 0.12 105 O, l4 3 II {Oj16) + XII (OJ16) 105 0.05 145 0.11 110 0.13 EMI23.6 Note: A: relative sensitivity; ; color contamination.

Example d.

After melting 1 kg of a negative emulsion of silver gelatin-bromo-iodide, containing 0.43 mol of silver and sensitized with sulfur and gold, by heating at 450 ° C., the emulsion is divided into six equal parts and the methanolic solutions of the sensitizing dyes listed in Table 4 are added to each emulsion, in isolation or as a mixture.

After ripening for 20 minutes at 45 ° C, 100 g of the emulsion is mixed with 50 an3 of a 5-fold aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 25 g of a 5 cl aqueous solution of 1- (4-phenoxy-3-sulfophenjrl) -3-heptadecyl-5-pyrazolone as a magenta coupler and mixed therein EMI23.7 additionally 1 g of an aque solution "3f to 5% 1-odeylbc" "' <Desc / Clms Page number 24> EMI24.1 .:. J. sodium funonate and 2 g of a 1 ruble aqueous solution of nonylphenyl-polyethylene glycol as a wetting agent for the coating.

Then, the resulting emulsion was applied to a transparent cellulose triacetate film and dried. The sample thus obtained is exposed through a yellow filter by the method described in Example 1 and is treated for 10 minutes at 20 ° C. in a developer having the following composition: color developer: EMI24.2 <tb> <tb> <SEP> sodium <SEP> sulphite <SEP> (anhydrous) <SEP> 2 <SEP> g <SEP> <tb> <SEP> N-ethyl-N-hydroxyethyl-3-methyl- nitrate <SEP> <tb> 4-aminoaniline <SEP> 2.5 <SEP> g <tb> <SEP> sodium <SEP> carbonate <SEP> (anhydrous) <SEP> 35 <SEP> g <tb> EMI24.3 hydroÀ7lamine hydrochloride 1.8 g EMI24.4 <tb> <tb> bromide <SEP> of <SEP> potassium <SEP> 2,0 <SEP> g <SEP> <tb> water <SEP> for <SEP> complete <SEP> to <SEP> 1 <SEP> liter. <tb>

Then the film thus developed is treated in the bleaching solution and in the fixing solution having the compositions indicated in Example 2 to obtain a magenta color image.

The density of the color image of the sample thus processed is measured using a green filter. The relative sensitivity thus obtained and the color contamination (haze) are given in Table 4 in which the relative sensitivity is given by assigning a score of 100 to the sensitization obtained with dye 1 (3).

Table 4. EMI24.5 <tb> <tb>

Test <SEP> Colorant <SEP> and <SEP> concentration <SEP> Sensibi- <SEP> Contamination <tb> N <SEP> (g./100 <SEP> g. <SEP> of emulsion) <SEP> ity <SEP> of <SEP> the <SEP> courelative <SEP> their <SEP> (veil <tb> XIV (2.6 <SEP> X <SEP> 10-3) <SEP> 108 <SEP> 0.07 <tb> 1 <SEP> @XV (5.3 <SEP> X <SEP> 10-3) <SEP> 120 <SEP> 0.11 <tb> EMI24.6 , 6 io3 + xv (5.3 10'3> 95 0.09 {I (3) {2.6 X 10-3) 100 0.07 2 XII {5.3 X 10-3) 165 0.08 ! I (3) (2.6 X Io-3) + XII (5.3 X 11-3) 185 0.06 <Desc / Clms Page number 25> Table 4 shows that the sensitivity obtained by the combination of Dye I and Dye XII of the present invention is remarkably higher than that obtained with Dye XIV, Dye XV and their combination, and further that the contamination of the color. is less than that of the latter.

Example 5, fusion by heating at 40 ° C. of the emulsion EMI25.1 negative gelatin-bromo-silver iodide as in Example 4, the emulsion is mixed with a methanoli solution. than the dye listed in Table 5 or a methanolic solution of a mixture of dyes. After maturing for 30 minutes at .0 C, the emulsion is mixed with a solution EMI25.2 0.5 aqueous 4-hydroxy-6-methyl-1,3,3a, 7-tetrazain-dene as stabilizer in an amount of 10 g per 100 g of emulsion. EMI25.3

In addition, 5 g of 1- (2,5-dichlorophenyl) - 3- 3-, 4di.-t.-arnylphenohypropi4nami.do j benzzmido) w..pyra are dissolved. zolone as a magenta coupler in a mixed solvent composed of 10 g of dibutyl phthalate and 10 g of ethyl acetate and the solution is dispersed in 50 g of an aqueous solution of gelatin together with a dispersing agent. In the emulsion prepared above, 12 g of the dispersion is added and the resulting emulsion is applied to a base film as in Example 4 and dried.

By subjecting the film thus obtained to the exposure and development process as in Example 4, an image of magenta color is obtained, The density of the colored image of the sample thus treated is measured using a green filter. Table 5 gives the relative sensitivity thus obtained and the color contamination (haze), in which table the relative sensitivity is given in assigning the rating 100 <Desc / Clms Page number 26> in the test with colorate 1 (3). Table 5. EMI26.1 <tb> <tb> Test <SEP> Colorant <SEP> and <SEP> concentration <SEP> Sensitive <SEP> Contamination <tb> N <SEP> (g./100 <SEP> g.

<SEP> of emulsion) <SEP> unit <SEP> of <SEP> the <SEP> neck- <SEP> <tb> 100 <SEP> mulsion <SEP> relative <SEP> their <SEP> (sail) <tb> EMI26.2 t 'IV (2.6 X 10-) 95 0.28 1 XV (5.3X10) 100 0.34 xzt, 6 X ao' 3) + XV (5.3 X 10-3) 115 0.38 fl (3) (2.6 x 10 "') 100 0.23 2 XII (5e3 X 10-3) 115 0.24 1 (3) (2 @ 6X, 0-3) + XII (5.3 X 10 -3) 210 0.20 zz (2.6 x ao '3) 90 0.22 {II (2.6 10-3) XII (5e3 10-3) 203 oel8 II (2.6 10-3) + XII (5.3 X 10-3) 203 0.18 jflII (2.6X10) 62 0.24 III (2.6 X 10-3) * XII (5.3 X 10-3) 192 0.19 zr (a, 6 X 10-3) 98 0.21 EMI26.3 <tb> <tb> IV (2.6 <SEP> X <SEP> 10-3) <SEP> + <SEP> XII <SEP> (5.3 <SEP> X <SEP> 10-3) <SEP> 147 < SEP> 0.20 <tb> @V (2.6 <SEP> X <SEP> 10-3) <SEP> 95 <SEP> 0.20 <tb> @V <SEP> (2.6 <SEP> X <SEP> 10-3) <SEP> + <SEP> XII <SEP> (5.3 <SEP> X <SEP> 10-3) < SEP> 135 <SEP> 0.16 <tb> Table 5 shows that,

by the combination of the sensitizing dyes of the present invention, much less color contamination and smell is obtained. Higher sensitivity than those obtained by the use of control dyes.

RESELL I C A T I O N S.

1. A light-sensitive silver halide photographic element comprising a support carrying at least one photographic silver halide emulsion layer containing at least one member selected from the benzimidazolo-carocyanine dyes represented by the following formula: EMI27.1 wherein R1 and R2 each represents an alkyl group, R3 and R4 each represents a member selected from the group consisting of an alkyl group and a substituted alkyl group, at least one of these groups R3 and R4 being a substituted alkyl group, X- represents an acid anion and m and n each represent 1 or 2, and at least one member selected from benzoxazolo-carbocyanine dyes represented by the following formula:

EMI27.2 wherein R5 represents an alkyl group, R6 represents a member selected from the group consisting of an alkyl group and a sulfoalkyl group, and A represents a member selected from the group consisting of a polymethylene group and an α-alkylpolymethylene group. <Desc / Clms Page number 28>

2. A light sensitive silver halide photographic element according to claim 1, characterized in that the emulsion layer is an emulsion layer containing a magenta coupler.

3. According to various particular embodiments, the supersensitizing combination indicated according to claim 1, / consisting respectively of: EMI28.1 anhydro-5,5'-6, b'-tetrachloro-.1,1'd.ethyl-, 3 a3 '- di (3-.sulfopropyl) -benzim3dazolo-earbocyanine hydroxide and d-hydroxide 'anhydro-5,5'-diphenyl-9-ethyl-3,3'-di (2-sulfoethyl) -oxacarbocyanine, EMI28.2 - hydroxide of anhydro-5> 5 '-6,6' -tetrachloro-1, 1 'diethyl-3, 3' -di (2- (2- (3-xulfopropoxy) ethoxy) ethyl) -benzimidazolocarbocyanine and anhydro-5,5 '"diphenyl-ethyl-3,3'.-di (2-sulfoethyl) -oxacarbocyanine hydroxide, - 5,5'-6,6'-tetraci bromide. 7. oro-1,3'-diethyl 3 to 3 d.

(- (-cax'boxYethax5 ') thYl i --benzimidazolocarbocyanine and anhydro-5 hydroxide> 5' -diphenyl-9-ethyl..3, 3 '-di (2sulf o ethyl) -oxacarbocyanine, - the 5,5'-6,6'-tetrachloro-l, l'-diethyl, 3'-di (-laydroxyethylj-benzimidazolocarbocyanine and bromide.

]. 'anhydro-.5, 5' ..diphenyl-9-thyl-3, 3 '-di (Z- â ua fo thyl) -oaGarbocyanine hydroxide, - 1' weight of 5,5'-6, ô'-ttrachloro-1,1'-diethyl-3,3 -dâ ('.'- actoxypropylj-benzimidazolocarbocyanine and anhydro-5, 5'-diphenyl-9-ethyl-3, 3' -di (2sulfoethyl) -oxacarbocyanine.