BE596376A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  New photographic emulsion with silver halides, chemically sensitized.



   The present invention relates to a novel photographic silver halide emulsion and, more particularly, to such a chemically sensitized emulsion.



   A number of methods have already been described for increasing the sensitivity of photographic emulsions to silver halides which differ from spectral or optical sensitization methods which involve the incorporation of certain color compounds or dyes into the emulsions. The incorporation of such dyes into emulsions increases the optical range of sensitivity and, for this reason, dyes of this type are commonly referred to as all but not optical sensitizing dyes or spec-.

 <Desc / Clms Page number 2>

 traux.

   It is also well known to increase the sensitivity of photographic emulsions by the addition of sulfurizing compounds which are capable of reacting with silver salts to form silver sulfide, or by the addition of reducing agents (compounds of this type are naturally present in gelatin), salts of gold or other noble metals, or combinations of two or more of the above compounds, generally known as chemical sensitizers. It is believed that such chemical sensitizers react with silver halides to form minute amounts of silver or silver sulfide or other noble metals on the surface of the silver halide grains. The sensitivity of the emulsions giving images by development can thus be multiplied by very large factors.

   Chemical sensitization, however, has a definite limit, beyond which further additions of sensitizers or subsequent curing in the presence of the sensitizer only increases haze of the photographic emulsion as the sensitivity remains constant or decreases.



   A method of increasing the sensitivity of photographic emulsions has now been found which can be applied while ordinary chemical sensitization methods have been pushed to their effective limit for the particular photographic emulsion used. The process according to the invention is distinguished from hypersensitization, which is obtained by soaking the finished layer in water or in solutions of ammonia, healthy or silver salts. Processes of this kind act primarily on optically sensitized photographic emulsions and tend to increase the concentration of free silver ions in the emulsion and considerably decrease the stability.

   The process according to the invention is also distinguished from hypersensitization by mercury vapor, which produces a transient effect which disappears during storage of the product.

 <Desc / Clms Page number 3>

 movie. The compounds used according to the invention do not appear to constitute chemical sensitizers in the usual sense, because they increase the sensitivity by their presence during the exposure and the treatment, and do not require any maturation of the photographic emulsion for to produce this increased sensitivity; chemical behavior does not indicate either that they are able to react with the silver halides under the normal conditions of the emulsion.



   The new sensitizers according to the invention are quite exceptional in that the effects produced are additive in photographic emulsions which have already been sensitized to the optimum value or close to the optimum using conventional chemical sensitizers, such as compounds containing labile sulfur. However, the novel sensitizers according to the invention can be used if desired to sensitize phoographic emulsions to silver halides containing no other sensitizers. The novel sensitizers according to the invention are not, strictly speaking, sensitizers. chemical, because the latter do not generally give the additive effects indicated above.



   The objects of the invention are therefore in particular - a photographic silver halide emulsion which is sensitized by various non-polymeric compounds containing sulfone groups and quaternary ammonium groups, - a process for increasing the sensitivity of ordinary photographic emulsions to silver halides. silver that have already been sensitized by chemical sensitizers, such as compounds containing labile sulfur atoms or gold compounds.



   It has been observed, according to the invention, that the sensitivity of a usual photographic emulsion to silver halogdnurea can be significantly increased by incorporating in it compounds not

 <Desc / Clms Page number 4>

 polymers consisting of bis-quaternary salts containing a sulfone group.



   The sensitizing compounds useful for the implementation of the invention comprise the compounds of the following general formula
 EMI4.1
 where R and R1 each represent an alkylene group, such as ethylene, trimethylene, tetramethylene (butylene), ethylene substituted with a methyl group, trimethylene substituted with a methyl group, j pentamethylene, tetramethylene substituted with an ethyl group, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc.

   (for example, a hydrocarbon alkylene group containing from about two to ten carbon atoms), a number # # between about 1 and 3, QN and NQ each an organic ammonium group such as pyridinium, picolinium, collidinium, N- methylpiperidium, N-ethylpiperidium, triethylammonium, diethylmethylammonium, tripropylammonium, diethylbutylammonium, N-methylmorpholinium, etc. and X an acidic one such as perchlorate, paratoluenesulfonate, benzenesulfonate, methylsulfate, ethylsulfate, bromide, etc.



   A particularly useful group of sensitizing compounds of formula (I) is that which can be represented by the following general formula
 EMI4.2
 where QN, NQ, X and d have the above meanings and m and n each represent an integer between about 2 and 10.



   A useful group of compounds according to the invention containing heterocyclic quaternary ammonium radicals is that which can be represented by the following general formula
 EMI4.3
 

 <Desc / Clms Page number 5>

 where d, m, n and X have the above meanings and Q1 represents the non-metallic atoms necessary to complete a monoazine tertiary heterocyclic ring, such as pyridine, picoline, collidine, etc.



   Another group of useful sensitizing compounds of formula (Ià) is that which can be represented by the following general formula
 EMI5.1
   where ± n, m and X have the above meanings and R2, R3 and R4 each represent a lower alkyl group such as methyl, ethyl, propyl, butyl, etc.



   The compounds of formulas (I) to (Ic) can advantageously be prepared according to processes which have already been described previously. For example, the compounds of formula (Ib) can be prepared by condensation of the hydroxyl compounds described in the Belgian patent application filed on September 28, 1960 and entitled; "New photographic silver halide emulsion", with an organic sulfonyl chloride, then by condensation of the sulfonic ester obtained with a heterocyclic tertiary amine, such as pyridine, picolines, collidines, etc. The thioether obtained can then be oxidized to a sulfone by treatment with hydrogen peroxide in solution in acetic acid or with another oxidant, such as hypochlorous acid, etc.

   The compounds of formula (Ia) where Q represents the non-metallic atoms necessary to complete a piperidine or other ring can be prepared by quaternization of a compound of the following formula
 EMI5.2
 (II) QN - (CH2) a-LS- (CH2) n-! DS (CH2) m- NQ where QN, NQ, d, m and n have the above meanings, with an aromatic sulfonic ester such as dimethyl sulfate , sulfate
 EMI5.3
 diethyl, methyl banzenesulphonate, methyl para-toluenesnl-fonate, etc. The thioether obtained can then be oxidized by

 <Desc / Clms Page number 6>

 sulfone by treatment with hydrogen peroxide, in solution in acetic acid, or with another oxidizing agent, such as hypochlorous acid, etc.

   Likewise, the compounds of formula (Ie) can be prepared by internizing a compound of the following general formula
 EMI6.1
 where R2, R3, d, m and n have the above meanings, with an organic sulfonic ester, such as dimethyl sulfate, diethyl sulfate, methyl benzenesulfonate, methyl paratoluenesulfonste, etc. The thioether obtained can then be oxidized to a sulfone by treatment with hydrogen peroxide in solution in acetic acid, or with another oxidant, such as hypochlorous acid, etc.



   Another useful group of sensitizers of formula (I) and (Ia) is that which can be represented by the following general formula
 EMI6.2
 where R2, d, m and n have the above meanings and J and J1 together represent the non-metallic atoms necessary to complete a pyridine ring which may bear substituents, such as methyl, ethyl, chlorine, etc. For the compounds of formula (Id), it may be noted that the quaternary nitrogen atom is not attached to the terminal carbon atoms of the intercyclic chain, unlike the nitrogen atoms of the compounds of formula (Ib) which are attached to these carbon atoms.

   The compounds of formula (Id) can be prepared in a manner analogous to that indicated above, for example, these compounds can be prepared by condensation of a dihalogenated alkane or of a thiaalkane with a pyridyl-

 <Desc / Clms Page number 7>

 alcenethiol of the following general formula
 EMI7.1
 where J, J1 and a have the above meanings. The thioether obtained can then be quaternized with an organic sulfonic ester such as those indicated above, then the product obtained can be oxidized with an aqueous solution of hydrogen peroxide and acetic acid, or with another oxidizing bath such as illustrated below. -above.



   The following non-limiting examples illustrate the invention.
 EMI7.2
 



  N # XPLJL. 1.18dra-toluèriesulfonoxy-4.15-dithiaoctadecane.



  (p) CH3-C6H4S03 (CH2) 3S (CH2) 10S (CH2) 303SC6H4-CH3 ()
A mixture of 31.2 g (0.1 mole) of 4,15-dithiaoctadecane-1,18-diol and 100 ml of pyridine is treated with 39.4 g (0.23 mole) of para-toluenesulfonyl chloride . After maintaining the mixture for 1 hour below 20 ° C., 150 ml of concentrated hydrochloric acid in one liter of water are added thereto. The oil is extracted with chloroform, washed with dilute lucid, then with saturated brine, and dried over magnesium sulfate. By removing the solvent under reduced pressure, 41 g of a light brown oil are obtained.
 EMI7.3
 



  EXAMPLE 2. 4,15-Dithiaoctadecare-1,18-bis-O (pyridinium) Tidinium perchlorate.



  C5H5 (CH2) 3S (CH2) lOS (CH2) 3 5H5 2C10
A solution of 21 g of the product of Example 1 and 10 g of pyridine is heated to the boil for ten minutes, cooled and poured into ether. The solid is filtered off, dissolved in water and treated with excess sodium perchlorate. The yield of colorless solid is 13 g. We can
 EMI7.4
 also use the para-toluenesulfonate directly in the following test.

 <Desc / Clms Page number 8>

 
 EMI8.1
 EXAMPLE 3. Del, 4,515-tetroxo-1,15-ditYiaoctadecane perehlorate-
 EMI8.2
 ¯1,18-bis- (nyridiniun).



  C5H5N (CH2) 3S02 (CH2) lOS02 (CHz) 3NC5H5 '2CJO4
13 g of the product of Example 2 are dissolved in 500 ml of acetic acid, heated to 60 ° C. and 15 g of a 30% solution of hydrogen peroxide are added. After twenty-four hours at 60 ° C., the solvent is removed under reduced pressure and the product is recrystallized from acetone. 4 g of a product, melting at 86 ° C., is obtained.
 EMI8.3
 



  Analysis: Calculated for cz6x4zc1zN2olzsz C: 44.0%; H: 5.9; N: 3.9A Found C: 44.4%; H: 6.0%; N: 3 EXAMPLE 4. 4.4.10.10-Tetroxo-4,10-dithiatridecane- perchlorate
 EMI8.4
 6 / .13-b1S-lDvr1d1n1umJ. d9 C5H519 (CH2) 3so2 (CH2) 5so2 (CH2) 3NC5'5y 2C104
By operating as in Examples 1 to 3, the desired product is obtained which melts at 235 ° C., with decomposition.
 EMI8.5
 



  Analyze Calculated for C21H32C12N2012S2 C: 39.4%; H: 5.0%; N: 4.4, b Found C: $ 3.5; H: 5.1%; N: 3, 6, 1X.Lg 5.ro 0-7 18-dithiatetracosane- 1.2-biB- (oyrldinium).
 EMI8.6
 



   By operating as in Examples 1 to 3, the desired compound is prepared which melts at 125 -130 C.
 EMI8.7
 



  Analyzes Calculation for C'6H61H2010S 'C: 60.0%; H: 7th3%; N: 3eO%; S: 13e7% Found C: 58e4%; H: 7.6%; N: 3.19; S: 13.5 tXLK 6. PerchloMte dei..8.8-totroxo-.8-dlthiaundëcanekXlLI 6. 8-t6trQXQ-4.8-d1th1aundécane-
 EMI8.8
 This compound, prepared as in Examples 1 to 3 and
 EMI8.9
 r.crl.t.11t. in nitromethane melts at 2030-2050C.



  Analyzes Calculated for C19H2SCl2 "20l2S2 C: 37,; H: 4.6; N: 4.6% Finds C: 38.1%; H: 4.9; N: 4.6%

 <Desc / Clms Page number 9>

 
 EMI9.1
 EXAMPLE 7. 7.7.10910133-hexoxo-7.10.13- perchlorate, trithianonaàecane-1,19 = bis-pyridinium).
 EMI9.2
 



   This compound, prepared in the usual manner, melts with decomposition at about 160 C.
 EMI9.3
 



  Analysis: Calculated for Cz5H4zC1zN2014s3 C: 40.3; H: 5.4ti; N: 3.6; 52.4: Found C: 39.2; H: 5.6 m; N: 3.00; S: 12.0? EXAMPLE 8 - 7 7 13 13-tetroxo-7 1 dithianonadecane-1,19-bis- (Dylinium) toluenesulfonate.
 EMI9.4
 



   This compound, prepared as in Examples 1 to 3, melts at 187-190 C.
 EMI9.5
 



  Analysis: Calculated for C41H58N2O10S4 C: 56.7%; H: 6.7%; N: 3.2; 5: 14.7, Found C: 56.0%; H: 6.7%; N: 3.4%; s: 15.1Si EXAMPLE 9 p-toluene sulphate of 7.13-dithianonadecane-1.19-bis- (pyridinium).
 EMI9.6
 WCH3-C6B4S02 (CH2) 6S (CH2) SS (CH2) 603SC6H4 -CH3 W
The intermediate used in Example 8 is prepared by operating as follows. A solution of 34 g of 7,13-dithia-
 EMI9.7
 1,19-nonadecanediol in 100 ml of pyridine per 50 g of para-tolu..ulton11e chloride, at -20 ° C. and kept cold overnight. The mixture is treated as in Example 1, and the oil obtained is boiled for fifteen minutes in an excess of pyridine.

   The solution was cooled, and poured into ether to obtain a colorless hygroscopic solid, melting at 130 ° -132 ° C after drying in vacuo.
 EMI9.8
 



  Analyzes Calculated for C4135gNZ8406 c: 61.3%; H: 7.39; N: 3> 5%; S: 15.9% hole, C: 6110%; H: 7p3%; N: 3.2%; S: 15th6% JZR2MH &. .13-tr1 th1anonadecane-b1s- (bvridinium).
 EMI9.9
 
 EMI9.10
 The interm'd1a1re used in Example 7 is prepared by

 <Desc / Clms Page number 10>

 operating as follows. The para-toluenesulfonate, obtained
 EMI10.1
 starting from 7,10,13-trithia-1,19-nonadecanediol as indicated in Example 9, in aqueous solution with excess sodium perchlorate. Removal of the solvent and recrystallization from ethanol gives a crystalline solid melting above 235 ° C. with decomposition.
 EMI10.2
 



  EXAMPLE 11 7.18-Dithiatetracosane-1.24-bis-pyridinium toluenesulfonate.



  WCH) -C6H4SO) (CH2) 6S (CH2) IOS (CH2) 60) SC6H4-CH) Ú2.)
The intermediate used in Example 5 is prepared by operating as follows. The procedure is as in Example 9 and the product obtained is recrystallized from an ether-ethanol mixture to finally obtain the desired product which melts at 143 -145 C.
 EMI10.3
 



  EXAMPLE 12. 7.7.13.13-tetraoxo-7.13thiaonad cane-1.19-is-2-picolinium p-toluenesultonate.
 EMI10.4
 



   By operating according to the procedure described in Examples 9 and 3 and using 2-picoline in place of pyridine, the desired compound is prepared which melts at 85 -90 C.
 EMI10.5
 SXSKPLE 13. 7.7,13,1-tetraoxo-7,13-4lthietn4nadcAne-1.19-bis-picolinium p-toluenesulfonate.
 EMI10.6
 



   This compound is obtained in the form of a non-crystallizable oil by operating as in Examples 9 and 3 and using 3-picoline.
 EMI10.7
 



  V ± XPU 1.4 ,. 7.7.13.13-tetraoxo-7.13- 9-¯b1s-4-oi p-tpluenesulfonate, colinium.
 EMI10.8
 This compound ', obtained by operating as in Examples 9 and 3
 EMI10.9
 and using 4-picoline, melts at 790-800C.



  1XEKPL! l. fifioo - to (u) 1,18-di-Raoeuarid 1- 4.15-dithiaoctadecangL sulfonate.

 <Desc / Clms Page number 11>

 
 EMI11.1
 



   A solution of 44.4 g of 1,18-di-gamma-pyridyl-4,15-dithiaoctadecane and 37.2 g of methyl para-toluenesulfonate in 200 ml of ethanol is refluxed for four hours. . By evaporation of the solvent and recrystallization from acetone, colorless crystals are obtained, melting at 100 -102 C.
 EMI11.2
 



  EXAMPLE 16 Bi-smetho-p-toluene sulphate of 1.18-di-gamma-pyridyl-4.4.15.15-tetraoxo-4,15-dithiaoctadecane.



   (General formula (Id) where R2 represents a methyl group, J and J1 the non-metallic atoms necessary to complete a 4-pyridine ring, m the number 3, n the number 10, d the number 1 and X a para-toluenesulfonate radical) .



   A solution of 15 g of the sulphide of Example 15 and of 5 g of a 30% solution of hydrogen peroxide in crystallizable acetic acid is heated at 60 ° C. for twenty-four hours. The solvent is removed under reduced pressure, the residue is dissolved in methanol, decolorized with activated carbon and the solvent is removed to obtain the oily sulfone, light amber in color.



    Analysis: Calculated for C42H60H2S4O10 C: 57.3; H: 6.8; N: 3.2; S: 14.5
Found C: 56.4; H: 7.0; N: 3.1; S: 14.3
 EMI11.3
 üP, '7. 14-Dithiahexadecane-1.16bis (N-methylpiperidinium) 0-toluenesulfonate.
 EMI11.4
 Is brought to reflux for sixteen hours, a solution of
 EMI11.5
 ± 8.7 g of 1,16-bis- (1-piperidyl) -3,14-dithiahexadecane and 53 g. due

 <Desc / Clms Page number 12>

 
 EMI12.1
 Methyl p.ra-tolu nesulfon3te, the solvent is removed and the residue dissolved in ethanol. By precipitation with ether,
 EMI12.2
 86 g of a crystalline 3oll is obtained, melting at 155 -157 C.



  Anal ".1 Calculates for C4,116, N2s 406 C: 60, O; H: 8.5- N: 3.5; S: 16.0 Found C: 59.0; H: 8.5; N: 3.1; S: 16.3 7CiPLFr 18 p-% Mfopa de 3,14..dithia-3,3 14,14-tetraxo, q, tē- 6 s-Nm th, ylpio ridinium.



  (Fortuitous (Ia) where QN and NQ each represent an N - Ilp1p'r1d1n1um nucleus, n the number 2, g the number 10, d the number 1 and X a para-toluenesulfonate radical).



   A 60 1 solution of the sulphide of Example 17 and 36 ml of a 30% solution of hydrogen peroxide in acetic acid is heated to 50 -60 C for sixteen hours. The solvent is removed under reduced pressure, the residue is dissolved in ethanol and precipitated with ether, and then recrystallized from ethanol to obtain a product melting at 175 -178 C.
 EMI12.3
 



  Analysis: Calculated for C40H6gN2S4O10 C: 55.7; H: 7.9; N: 3.2 ;. S: 14.8 Found C: 54.7; H: 7.9; N: 2 ,; S: 14.4
 EMI12.4
 EXAMPLE 19. 3 1 -dithia-3 3 1 1 -tetraoxohexad cane-1,1 -bis- p-toluenesulfonate (diethylmethylammonium.



   (General formula (Ic) where R2 represents a methyl group, R3 and R4 each an ethyl group, m the number 2, n the number 10, d the number 1 and X a para-toluenesulfonate radical.



   This compound is obtained in the form of a viscous oil by operating as in Examples 17, 18 and 20, starting from beta-diethylamino-ethanediol.



   Examples 20 and 21 illustrate the process for the preparation of two intermediates useful for the preparations described in Examples 15 and 17.
 EMI12.5
 



  EX] 2 {PLE 20. 1s18-di-gamma-oyridvl-lt, l5-ditr.iaoct2decane.
 EMI12.6
 

 <Desc / Clms Page number 13>

 



   16.6 g of gamma-3-mercaptopropylpyridine are added to a solution of 9.2 g of sodium in 500 ml of absolute methanol, followed by 60.2 g of 1,10-dibromodecane. After two to three hours of reflux, one liter of water is added, the mixture is extracted with chloroform, the extracts are decolorized with decolorizing charcoal, dried over magnesium sulfide, and the solvent is evaporated to obtain a m @ yellow crystalline dryness.
 EMI13.1
 iP 21. A, 16-bis (1-nineridYl) -3.14-lithiahexadecane.
 EMI13.2
 



   This compound is prepared according to the procedure of Example 20, using 9.2 g of sodium, 50 u ml of methanol,
 EMI13.3
 58 g of beta-1-piperidino-1-6thanediol and 60 g of 1,10-dibromo-decane. 62 g of product are obtained in the formula of an oil.



   The sensitizers according to the invention can be added to the usual photographic silver halide emulsions to increase their sensitivity, as indicated above.



   The preparation of silver halide emulsions involves three distinct operations (1) emulsification and maturation of silver halides, (2) removal of excess soluble salts from the emulsion, usually by washing with l water, (3) the second digestion, or re-melting maturation, which increases
 EMI13.4
 sensitivity (Mees, The Theory of the Photography Process, 1954).



  The sensitizers according to the invention can be added to the emulsion before the recasting maturation, or they can be added immediately before coating. The new photographic sensitizers do not require any special overhaul.



   The particular amount of sensitizer to be used for a given emulsion can vary depending on the effects desired, the degree of ripening, the silver content of the eclision, etc.



  The amount used also depends on the particular stage at which the sensitizer is added when preparing the emulsion.

 <Desc / Clms Page number 14>

 



   It has been found that, generally, it is quite suitable to use from about 0.05 g to about 5 g of sensitizer per mole of silver halide to achieve the desired sensitization.



   The sensitizers according to the invention can be added to the photographic emulsions by any well known technique for preparing the emulsions. For example, the sensitizers can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion, according to a technique analogous to that which makes it possible to incorporate certain types of dye-forming compounds (couplers) in a photographic emulsion. Techniques of this kind have been described in Belgian patent 470,936, applied for on February 3, 1947, and in Belgian patent 543,745, dated December 17, 1955.

   As indicated above, the solvent should be chosen such that it has no adverse effect on the emulsion, and in general, solvents or diluents which are miscible with water should be preferred.



  Water and dilute alkaline solutions constitute dispersion media for some of the sensitizers according to the invention. In a preferred embodiment, the sensitizer can be dissolved in a solvent such as ethanol, acetone, pyridine, N, N-dimethylformamide, etc., and added in this form to the emulsion. If desired, some of the sensitizers can be prepared in finely divided form, and dispersed in water alone or in the presence of a suitable dispersing agent, (such as the alkali metal salts of aromatic or aliphatic sulfonic acids). and add them in this form to the emulsion.

   It is obvious that the sensitizers according to the invention must have a sufficient dispersion capacity in water so that they can be adsorbed on or associated with the silver halide grains present in the emulsion.

 <Desc / Clms Page number 15>

 sufficient amount to sensitize said emulsion. It is helpful that the optimum amount for each of the sensitizers will vary somewhat from emulsion to emulsion and from compound to compound, n can determine the optimum amount for a given sensitizer and for a particular emulsion, by performing a series of tests in which the amount of sensitizer is varied within a given range.

   Exposure of the treated emulsion in a conventional photographic tester, such as a variable intensity sensitometer, will reveal the most desirable concentrations for that sensitizer in that particular emulsion. These tests are well known to those skilled in the art.



   The photographic emulsions used for the implementation of the present invention are obviously of the type giving images by development.



   The emulsions used according to the invention can be chemically sensitized by any of the conventional methods. The emulsion can be subjected to maturation in the presence of a gelate which is active by nature and sulfurizing compounds can be added, as mentioned in Belgian patent 327,252 applied for on June 4, 1925.



   The emulsions can also be treated with salts of noble metals such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are, for example, ammonium palladichloride, potassium platinichloride and sodium palladochloride which is used for sensitization in amounts less than those which significantly inhibit haze, as described in Belgian patent 476.363 applied for on 27 September 1947 and as haze inhibitors, in larger quantities, as described in Belgian patent 470,282, applied for on January 2, 1947 and in improvement patent 476,364 of September 27, 1947.

 <Desc / Clms Page number 16>

 



   It is also possible to chemically sensitize the emulsions with gold salts or to stabilize them with gold salts as described in Belgian patents 498, 286 and 498,287; requested September 22, 1950. Suitable compounds are, for example, potassium aurochloride, potassium aurithiocyanate, potassium aurichloride, gold chloride and 2-aurosulfobenzothiazole methochloride.



   Emulsions can also be chemically sensitized by reducing agents such as the stannous salts described in Belgian patent 490.198 applied for on July 15, 1949, polyamines such as diethylenetriamine, described in Belgian patent 492.214, applied for on November 16, 1949, polyamines such as than spermine, described in Belgian patent 492,214, applied for November 16, 1949, or bis- (beta-amino-ethyl) sulfide and its water-soluble salts described in Belgian patent 492,188, applied for November 15, 1949.



   The emulsions according to the invention are optically sensitized by cyanines and merocyanines, such as those described in Belgian patent 378,117 applied for on March 11, 1931, in Belgian patent 385,331 applied for on December 30, 1931, in Belgian patent 380,472, applied for June 10, 1931, to French patent 741,572 applied for August 27, 1932, to French patent 808,598, applied for July 4, 1936, to Belgian patent 466.

   676 applied on July 16, 1946, in Belgian patent 531,257, applied in August 19, 1954 and in Belgian patent 481,343 applied in March 20, 1948, in Belgian patent 480,616, applied in February 24, 1948, in Belgian patent 517,099 applied in January 22, 1953, in Belgian patent 534,443 applied for December 27, 1954, to Belgian patent 526,524, applied for February 16, 1954 and to French patent 793,722, applied for August 10, 1935.



   It is also possible to stabilize the emulsions by mercury compounds such as those described in the Belgian patent.

 <Desc / Clms Page number 17>

 524,117, applied for on November 7, 1953, in Belgian patent 524,119 applied for on November 7, 1953 and in Belgian patent 524,120 applied for on November 7, 1953 by triazoles, by azaindenes, for example those described in Belgian patent 530. 062 applied in July 1, 1954 , to Belgian patent 530,063 applied for on July 1, 1954 and by Birr in "Zeitschr. für Wiss.

   Phot. "47, 2 (1952), by certain disulfides described in Belgian patent 569,317 applied for on July 10, 1958, by the benzothiazolium compounds, described in French patent 851,912, applied for September 26, 1958 or in Belgian patent 514,796 of 13 October 1952 (for example, tetramethylene-bis-benzothiazolium perchlorate), or by zinc and cadmium salts described in United States Patent No. 2,839,405, filed March 8, 1955, and by the compounds carboxymethylmercapto described in Belgian patent 554. 210 applied for February 21, 1957.



   The emulsions used according to the invention can also contain compounds which increase the sensitivity of the type of quaternary ammonium salts, described in Belgian patent 466,375, applied for July 2, 1946 to Belgian patent 463,680 applied for March 7, 1946, to Belgian patent 467. 068 applied for August 3, 1946, or the quaternary ammonium and polyethylene glycol salts, described in US Pat. No. 2,886,437, applied for December 1, 1955, and the polyethylene glycols described in Belgian patent 537,789, applied for April 29, 1955, or thiopolymers as described in Belgian patent 588,242 applied for on March 3, 1960.



   The emulsions used according to the invention may contain a gelatin plasticizer, such as glycerin, a dihydroxyalkane, such as 1,5-pentanediol, an ester of an ethylene-bis-glycolic acid, such as ethylenebis- (methyl glycolate), bis- (ethoxydiethylene glycol) succinate, described in French patent 1,200,094 applied for on September 6, 1956, or a resulting polymeric hydrozol

 <Desc / Clms Page number 18>

 of the emulsion polymerization of a mixture of an amide of an acid of the acrylic series, of an acrylic ester and of a compound of the styrene series, as described in Belgian patent 522,869 applied for September 17, 1953 .

   The plasticizer can be added to the emulsion before or after the addition of a sensitizing dye, when one is used.



   The emulsions can be tanned with an appropriate gelatin tanning agent, such as formaldehyde, a halogenated aliphatic acid, such as mucobromic acid, described in French patent 826,492, applied for on September 9, 1937, a compound comprising several anhydride groups of acid such as 7,8-diphenylbicyclo- acid dianhydride
 EMI18.1
 (2.2.2) -7-tetene-2,3,5:

  6-tetracarboxylic, or a dicarboxylic or disulfonic acid chloride, such as tetraphthaloyl chloride, or naphthalene-1,5-disulfonic acid chloride, a cyclic 1,2-diketone, such as cyclopentane-1,2- dione, a bis-ether of methanesulfoni-
 EMI18.2
 that, such as 1.2-di- (methanesulfonoxy) -ethane, as described in Belgian patent 515,924, applied for November 29, 1952, 1,3-dihydroxymethylbenzimidazole-2-one, as described in French patent 1,088,876, applied for December 2, 1953, a dialdehyde or a sodium bisulfite derivative of an aldehyde, the aldehyde groups of which are separated by two or three carbon atoms, such as the disodium bisulfite derivative
 EMI18.3
 blta-m4thy1llutaraldehyde, described in French patent 1.

   169,616, applied for on December 28, 1956, a bis-aziridinecarboxamide, such as trimethylene-bis- (aziridinecarboxaide), or also 2,3-dihydroxydioxane.



   The emulsions according to the invention may also contain a coating adjuvant such as saponin, a lauryl or oleyl amino ether of a polyethylene-elycol, as described in Belgian patent 538,152 applied for.

 <Desc / Clms Page number 19>

 May 13, 1955, a salt of a sulfated and alkylated polyethylene glycol ether, an acylated alkyltaurin, such as the sodium salt of N-oleyl-N-methyltaurine, as described in Belgian patent 530.

   382 applied for July 14, 1954., the reaction product of a tetracarboxybutane dianhydride with an alcohol or an aliphatic amine containing eight to eighteen carbon atoms which has been treated with a base, for example the sodium salt of the monoester of tetracarboxybutane, a water-soluble maleopimarate or a mixture of such a maleopimarate and a substituted glutamate, as described in Belgian patent 553,743 filed on December 27, 1956, an alkali metal salt of a substituted amino acid, such as N - (carbo-paratertio-octylphénoxypentaéthoxy)-disodium glutamate, as described in French patent 1,205,155 applied for on July 29, 1957 or a sulfosuccinamate, such as N- (1,2-dicarboxy-
 EMI19.1
 ethyl)

  -N-octadecylsulrosuccinemate tetrasodium or N-laurylsulfosuccinamnte disodium.



   The adjuvants described above can be used in the various types of photographic emulsions.



  In addition to their utility in x-ray emulsions and other non-chromatized emulsions, they can be used in orthochromatic, penchromatic and infrared sensitive emulsions. They can be added to emulsions before or after sensitizing dyes. Various silver salts, such as bromide, iodide, silver chloride, or mixed silver halides, such as silver chlorobromide or bromoiodide, can be used as photosensitive salts.



  The agents can be used in emulsions intended for color photography, for example in emulsions containing color couplers or other emulsions to be developed by developers containing couplers or other color-forming substances, mixed pack emulsions, such as described in the Belgian patent

 <Desc / Clms Page number 20>

 
502,544, applied for April 13, 1951, or in emulsions of the mixed crack type, as described in the Belgian patent
491,769, requested October 20, 1949.

   These agents can also be used in emulsions in which the latent images form predominantly on the surface of silver halide crystals or in emulsions in which the latent images form predominantly on the surface. interior of silver halide crystals, such as those described in French patent 966,221, applied for
May 13, 1948.



   They can also be used in emulsions for diffusion inversion transfer processes, which use the undeveloped silver halides in a negatively imaged layer, to form a positive by dissolving these undeveloped silver halides. , and precipitation on a receiving layer placed in contact with the original silver halide emulsion layer.



  Such methods are described, for example, in Belgian patent 557,693 applied for May 21, 1957. They can also be used in color reproduction methods of inversion-transfer by migration of a developer, a coupler or a. dye forming an image from a photosensitive layer to a second layer when these two layers are in close proximity to each other. Color processes of this type are described, for example, in Belgian patent 525,871, applied for January 20, 1954, and in Belgian patent 578,470 applied for May 6, 1959.



   In the preparation of the silver halide dispersions intended for the preparation of the silver halide emulsions, it is possible to use, as a dispersing agent for the silver halides, gelatin or any other colloidal product, such as albumin. , a derivative

 <Desc / Clms Page number 21>

 cellulose or a synthetic resin, for example a polyvinyl compound.

   As a particular example of useful colloids, mention may be made of polyvinyl alcohol or a hydrolyzed polyvinyl acetate, as described in French patent 869,973, applied for on February 12, 1941, a highly hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed up to 'to an acetyl content of
 EMI21.1
 $ 19 to $ 26 # a water soluble ethaiolaminecellulose acetate, a polyacrylamide with a combined acrylamide content of 30% to 60%, and a specific viscosity of 0.25 to 1.5, or an imidized polyacrylamide with the same acrylamide content and same viscosity, as described in Belgian patent 476,083 applied for September 16, 1947 zein, as described in French patent 1.

   000,682, applied for September 1, 1949, a vinyl alcohol polymer containing urethanecarboxylic groups, or containing cyanoethyl groups, such as a copolymer of vinyl cyanoacetate and vinyl alcohol, as described in Belgian patent 548,911 applied for on 22 June 1956, or a polymer product resulting from the polymerization of a protein or an acylated protein saturated with a monomer having a vinyl group, as described in Belgian patent 543,746, applied for December 17, 1955.



   If desired, compatible mixtures of two or more of these colloids can be used for the dispersion of the silver halides in this preparation.



  Combinations of these haze inhibitors, sensitizers, tanners, etc. can be used.



   The sensitizers according to the invention can be used in emulsions intended for black and white photography or in those intended for color photography. In the latter case, the sensitizers according to the invention can be incorporated into emulsions containing

 <Desc / Clms Page number 22>

 dye formers or color couplers, or to emulsions intended for color development by developers containing such couplers. In each of these cases, the particular couplers react with the oxidation products of the color developers (in particular, the phenylenediamine type developers) to give subtractive color images.

   The couplers can be of ordinary types used in color photography, such as pyrazolone type couplers, for magenta image formation, phenolic type couplers, for blue-green image formation, and blue-green images. Open chain compounds containing a reactive methylene group, for the formation of the yellow image. Such couplers can be dispersed in a high boiling point crystalline compound which can serve as a vehicle for incorporating the coupler into the photographic emulsion, or the couplers can be of the chain ballast group type. oily (see in particular FIAT Final Report No. 721), which can be dispersed in photographic silver halide emulsions.

   These two types of couplers have the property of not migrating out of the silver halide emulsions into which they are incorporated. The couplers can be incorporated into the silver halide emulsions by any of the usual methods known to those skilled in the art.



   Couplers which are useful for color photography according to the present invention include the following bodies:

 <Desc / Clms Page number 23>

 
 EMI23.1
 COUDler giving blue-green images 3- (p-ssrylphenox, ybensèneaulfonamino) -1-naphthol 5- (K-bonzyl-N-naphthalenesulfonanino) -1-naphthol 5- (N-bon²1l-Xn-vnl'rylam1no) -l -naphthol 5-caproylsmino-1-naphthol -ehloro-5- (Nn-valâryl-Yp-isopropylbenzylamino) -1-naphthol 2, -dichloro-;

  - (p-nitrobet.zoyl-beta-o-hydroxyethylalmir.o) -1-naph to1 2 # 4-dichloro-5-palmitylamino-1-naphthol 2.2e-dihydroxy-5,5P-dibromostilbene -diphnylétharsulronamido-1-naphthol 1-hydroxy-2- (N-isoamyl-N-phenyl) -naphthxmide 1-hydroxy-2- (Np-soa, amylphenyl) -naphthxnide 8-hydroxy-1-alpha-naphthoyl-1,2,3,4- tetrahydroquinolinp
 EMI23.2
 2-lauryl-4-chlorophenol l-naphthol-2-carboxylic-alpha-naphthalide 1-naphthol-5-sulfo-cyclohexylamide
 EMI23.3
 5-phinoxyacetamino-1-naphthol 5-beta-phenylpropionylamino-1-naphthol Monochlor-5- (N-gamma-phenylpropyl-N-p-sec.amylbenzoylamino) -1-naphthol
 EMI23.4
 2-acetylamino-5-methylphenol 2-benzoylamino-3,5-dimethylphenol 2-alpha- (p-tert.amylphenoxy) -n-butyrylamino-5-methylphenol
 EMI23.5
 6- {gamma- 4 gamma- (2, / + - di-tert.

   amylphenoxy) -butyramid-phenoxyacetamido -2,4-dichloro-3-m thylphenol 1-hydroxy-2-delta- (2,4-di-tert.amylphenoxy) -nb, zty> -naphthamide 2-alpha- (p- tert.amylphenoxy) -n-butyrylamino-4-chloro-5-methylphenol 2- (p'-terit. amylphenoxy-p-benzcyl) -amino-4-chloro-5-methylphenol 2- (4tt-tert..amyl- 3'-phenoxybenzoylamino) -3,5-dimethyl-1-phenol
 EMI23.6
 2-phenylacetylamino-4-chloro-5-methylphenol
 EMI23.7
 2-benzoylamino-4-chloro-5-methylphenol
 EMI23.8
 2-anilinoacetylamino-4-chloro-5-methylphenol
 EMI23.9
 2- 4 'alpha- (4-tert.amylph; enoxy) -n-butyrylamin benzoylamino -4-chloro-5-nethyl #enol

 <Desc / Clms Page number 24>

 
 EMI24.1
 z-C4 ', 3 n- (4 "L te r t. amylphenoxy) -benzoylamin-henzo;

  l a.nino-4-
 EMI24.2
 chloro-5-methylphenol 2-p-nitrobenzoylamino-4-chloro-5-methylphenol 2-m-aminobenzoyl-4-chloro-5-methylphenol
 EMI24.3
 2-acetamino-4 - ch-oro-5-methylphenol 2- (l'sec, amylbenzamino) -4-chloro-5-methylphenol 2- (4'-n-amyloxybenzalnmo) -4-chloro-5-methylphenol 2 - (4y-phenoxybenzoylamino) -phenol
 EMI24.4
 2- (4 "-tert.amy '?' - phenoxybenzoylamino) -phenol
 EMI24.5
 2-alpha- (4'-tert.butylphenoxy) -propionylamino> -phenol 2- * alphtt - ('- tert.anyl) -phënoxypropionylaminp7-phenol 2- "1-mdthyl-H- (b'" -tert.amyl -3'-phenoxybenzoylar.inoy-phenol 2- (4 "-tert. Amyl-3'-phenoxybenzoylamino) -3 -methyl-1-phenol 2 - (;" - tert.amyl-3'-phenoxybenzoylamino) -6- methyl-1-phenol 2- (± "-tert. anlyl-3'-phenoxybenzoylamino) -3,6-dimethylphenol 2, 6-di- (4" -tert, amyl-3'-phenox;

  benzoylamino) -1-phenol 2-alpha- (4'-tert.amy1phenoxy) -butyrylamino-1-phenol 2- ("-tert.amyl-3'-phdnoxybenzoylamino} -3,5-âimethyl-1-phenol -L alpha- (4'-tert.amylph6noxy) -n-butyrylamin> -5-methyl - 1-phenol 2- "-tort.amyl-3'-Phenoxybenzoylamino) -4-chloro-1-phenol 3-alpha- ( 'tert.amylphdnoxy) -n-butyrylamin> -6-chlorophenol 9 - ("- ttrt.nayl-3'-phdnoxyben2oylamino) -phenol 2-alpha - (' - tert.amylphenoxy) -n-butyrylamin> -6-chlorophenol -alpha - ('- tart.amylph6noxy) -n-butyrylamin> -4-chlorophenol -alpha- (ert.amylphdnoxy) -n-butyrylaminç7-5-chlorophenol alpha - (' - tort.amylphenoxy) -n..butyrylaminç- 2-chlorophenol -slpha - (.'- tert.amylphdnoxybutyrylamino) -5-chlorophenol 2 - ("- tnrt.amrl-3'-phdnoxrbenzoylamino) -3-chlorophenol 5-bonsene mlfonamino-1-naphthoi Z ,, - rdichloro- 5-ben:

  enesulfonamino-1-naphthol 2,4-dichloro-5- (p-toluenomlfonamino) -1-naphthol 5- (102p3 # 4-titrahydronaphthalene-6-sulfamino) -l-naphthol 2, -diohloro - ('- bronodiphdnyl- 4-sulfonamino) -1-naphthol 'u1nol'1n.-'-, ulram1no) -1-naphthol

 <Desc / Clms Page number 25>

 



   All the couplers of the acylaminophenol series indicated in French patent 951,540, applied for on December 31, 1946, can be used as couplers to form the blue-green image, for example:
 EMI25.1
 

 <Desc / Clms Page number 26>

 
 EMI26.1
 Couplers giving magenta 1-p-sec. Amylphenyl-3-n-amyl-5-pyrazolone images
 EMI26.2
 2-cyanoacetyl-5-B-sec.anyibenzoyiamino) -coumarone 2-cyanoacetylcoumarone-5- (n-amyl-n-sec.amyisulîanilide) 2-cyanoacetylcoumarone-5- (N-n-amyl-p-tert.amylsulfanilide)
 EMI26.3
 2-cyanoacetylcoumarone-5-sulfon-N-n-butylanilide
 EMI26.4
 2-cyanoaacetYl-5-benzoylamino-coumarone
 EMI26.5
 2-cyanoacetylcoumarone-5-sulfondimethylamide 2-cyanoacetylcoumarone-5-sulfon-N-methylanilide 2-cyanoacetylnaphthaler sulfon-N-methylanilide
 EMI26.6
 2-cyanoacetylounarone-5- (N-gamma-phenylpropyl)

  -B-tert.amylsultonanilide 1-p-laurylphenyl-3-methyl-5-pyrazolone 1-bata-naphthyl-3-amyl-5-pyrazolone 1-p-nitroph% y1-3-n-amyl-5-pYrazoione 1 -a-phhoxyph'nyl-3-n-amyl-5-pyrazolone 1-ph'nyl-3-n-nyl-5-pyPazolone 14-phnrlnt-bis-3- (1-Phenyl-5-pYrazolone) 1- phenyl-3-àa'tylanmo-5-pyrazolone 1-phenyl-3-propionylamino-5-pyrazolone l-ph) <nyl-3-nv <LKrylamlno-5-pyrazolone 1-ph6nyl-3-oh1oroaa'tyismmo-5- pyrazolone 1-phityl-3-dichloroacetylamino-5-pyrazolone 1-phnyl-3- & n3uiamino-5-pyrazolone l-ph <ayl-3- (a-) MinobMMyl) -amino-5-pyrazolone 1-gh = 9- ( p = sae.aahrlbtazoylamino) -5-pyrazolone 1-PhMyl-3-diamylbonzoylacLino-5-pyrazolone 1-phhl-3-bita-naphtoylasino-5-pyrazolone l-ph <nyl-3-ph <nylc <trbMylamino-5- pyrazolone l-ph <ayl-3-p * l * ityl <mino-3-pyr <zolone 1-phenn-3-bonzénesulfonyiammo-5-pyrazoione 1-p-phqrphial) -3- (p-tart.amyloxybenzoyl) - amino-5-pyrazolone 1- (2 ', 4', 6'-tr1br080pb4nyl)

  -3-benzamido-5-pyrazolone

 <Desc / Clms Page number 27>

 
 EMI27.1
 1 - (-. ', 4', 6'-trichlorophenyl) -3-benzamido-5-pyrazolone 1- (2-1,41,6-1-tr-lchlorophenyl) -3-phenylacetamido-5-pyrazolone
 EMI27.2
 1- (2 ', 4', 6'-tribromophenyl) -3-phenylacetamido-5-pyrazolone
 EMI27.3
 1- (2 ', 4'-dichlorophenyl) -3 "- (2"', 4 "'- di-tert.amylphenoxyacetamido) -benzamido -5-pyrazolone 1- (2', 4 ', 6'-trichlorophenyl) 3 "- (z '', 4 '' -di-tert.amylphenoxy acetamido) -benzamido -5-pyrazolone l- (246'-tribromophënyl) -3-Z" 3 "- (2" * '-di-tert .amylphenoxyacetamido) -benzamidil-5-pyrazo1one 1- (2 ', 4', 6'-trichloro henyl) -3 L beta (2 "; 4" -di-tert. amylphenox:

   propionamid. 2 / -5-pyrazolone 1- (2 ', 4', 6 '-tribromophenyl) -3-beta- (2 ", l,' -di-tert. amylphenoxy, propionamido7-5-pyrazolone 1- (2 '5'-dichloro) -3-3 "- (4"' - tert.amylphenoxy) -benzamid-
 EMI27.4
 5-pyrazolone
 EMI27.5
 1- (2P, 4ye6l-tribromophenyl) -3- ± -3 "- (4" -tert.amylphenoxy) benzamld-5-pyrazo10ne 1- (25'-dichlorophenyl) -3- "- (2", 4 "- di-tert.amylphenoxyacetamido) -benzamido-5-pyrazolone.
 EMI27.6
 



  Couplers giving Yellow images
 EMI27.7
 N-amsyl-p-bonzoylacetaminobenzenesulronate N- (4-anisoylacetaminobenzenesulronyl) -N-benzyl-m-toluidine
 EMI27.8
 N- (4-benzoylacetaminobenzenesulfonyl) -N-benzyl-m-toluidine
 EMI27.9
 N - ('- benzoylac6taminobenzenesulfony1) -Nn-amyl-p-toluidine N- (4-bonzoylacitaminobenzenesulfonyl) -N-benzylaniline 084CI- (p-blnzoylbenzoyl) -nc6tanllide om6a-bensoylacet-ail-oichloride benzlacet-ail-oichloride p-lec.acylacetanlide 1t, it'-di- (oe6a-boazoylacetyl) -p-phenyl ened iamine 1, l '-di- (àc'Eoa'tamino) -diphenyl alpha- 3-alpha- (2 4-di -tert.amylphenoxy) -butyramid> -benzoyl -2-sdthoxyacetenilide ¯lphA- 3-falha- (2 4-di-tert.amylphenoxy) -acetamid-benzoyl -2-m't .oxyaoàtanilido i4'-di- (ac6toac6tamino ) -33'-dimethyldiphenyl p, p'-d1- (ac'toac'tamtno)

  -dlphenylmethane Kth71-p-blnzo1Iac'tam1nobenznesu1fonate Nonyl-p-bonzoylacitaminooenzenesulfonate

 <Desc / Clms Page number 28>

 
 EMI28.1
 l-pb'n71-1 - (p-oc6toacetam1nophenyl) -urea n-ProP71-p-benso1lncetaminobenzenesulonate-acetoacetopiperidine oa4ca-btnzo11ac'top1per1dine 1t- (oa6a-bentoylinolactyl) -1,2 oaéaa-benzo1lacÓtyl) -morphol1ne.



   The: aforementioned couplers give colored images by development of the emulsions exposed by color developers, such as color developers with phenylenediamines.



  Particularly useful developers are those which derive
 EMI28.2
 para-phenylenediamines containing at least one primary amine group, such as N, N-dimethyl-para-phenylenediamine, Ii, N-diethyl-para-phenylenediamine, N-carbamidoethyl-N-methylpara-phenylenediamine, N4¯ carbamidomethyl-N4-tetrahydrofurfuryl- 2-methyl-para-phenylenediamine, N4¯ethyl-N4-carboxymethyl-2-methyl-para-phenylenediamine, N4-carbamidomethyl-N4¯ethyl-
 EMI28.3
 2-methyl-para-phenylenediamine, N 4¯ethyl-N / + - tetrahydrofurfuryl- 2-methyl-para-aminophenol, 3-acetylamino-4-aminodimethylaniline, N-ethyl-N-beta-methanesulfonamidoethyl-4- aminoaniline,

     the
 EMI28.4
 N-ethyl-N-beta-methanesulfonamidoethyl-3-methyl-4-aminoaniline, the sodium salt of N-methyl-N-beta-sulfoethyl-para-phenylenediamine, etc.



   Given the large number of sensitizers forming part of the invention and the large number of couplers that can be used, it is possible to use a large number of combinations of sensitizers and color couplers. It has been found that one can use, to quickly determine the effectiveness of a particular combination, the technique described by Pontius and Thompson in "Phot. Science Eng." Volume 1, pages 45 to 51, and thus have an idea of the potential effectiveness of a given combination when used in a color photographic material containing a coupler.

   This technique does not require the preparation

 <Desc / Clms Page number 29>

 ration of coupler dispersions, but the sensitizers can be added to the usual photographic silver halide emulsions intended for black and white photography, such as gelatin silver bromoiodide emulsions, expose the emulsions in a sensitometer to variable intensity, at daylight type radiation, for a fraction of a second (usually 1/25), and develop them, for about fifteen minutes, by a chromogenic developer with phenylenediamine, to which 10 g per liter of Acid H. The pH of this developer is usually adjusted to 10.8 by the addition of sodium hydroxide.

   A suitable developer composition for use in the Pontius and Thompson method is as follows:
 EMI29.1
 Bonzyl alcohol ................: ...... 10 cm Sodium hexametaphosphate .............. 2.0 g Sulfite sodium ........................ 2.0 g Sodium hydroxide .................. .... 3.4 g Acid H (1-amino-8-naphthol-3,6-disulfonic acid) ................... 10.0 g
 EMI29.2
 4-Amino-3-methyl-N-ethyl-N- (b3ta-methylsulfonamidoethyl) aniline sulfate .... 8.0 g
Sodium carbonate monohydrate .......... 40.0 g
Sodium bromide 1.5 g
Sodium thiocyanate ................... 0.2 g
Benzotriazole ............................ 0.03 g
Water ............................ q.s.p.

   1 liter pH 10.8 ¯ 0.1 The relative sensitivity, gamma and haze of the emulsion layers treated in this way were recorded in the following table.



   The following technique was used to determine the effectiveness of the compounds according to the invention as sensitizers of photographic silver halide emulsions intended for black and white photography.



   A customary silver bromoiodide photographic emulsion containing a sensitizing dye and a sulphurizing sensitizer, and sensitized to gold as described in Belgian patent 476,363 mentioned above, is divided into several fractions. The sensitizers obtained are then added as a

 <Desc / Clms Page number 30>

   described above, and identified by the numbers of the corresponding examples, in the form of solutions in an organic solvent, such as ethanol or N, N-dimethylformamide, and in the amount indicated in the following table. It is then coated on transparent supports, such as cellulose acetate, the divergea fractions of emulsions, and then they are dried.

   The dried samples obtained are exposed, for about 1/25 of a second, to daylight type radiation in the Eastman type Ib sensitometer. The samples are then developed for about five minutes by the photographic developer of the following composition
N-methyl-para-aminophenol sulphate .......... 2.5 g
Hydroquinone 2.5 g
Anhydrous sodium sulphite .................... 30.0 g
Sodium borate ............................. 10.0 g
Potassium bromide 0.5 g
Water ................................... q.s.p. 1 litre
The relative sensitivity is then measured by comparison with a fraction of the same batch of emulsion not containing a bis-quaternary salt containing a sulfone group, as well as the gamma and haze of each of the samples.

   The results were recorded in the following table.

 <Desc / Clms Page number 31>

 



  BOARD
 EMI31.1
 
<tb>
<tb> Sample <SEP> Compound <SEP> Concentration <SEP> in <SEP> Sensitometric <SEP> results
<tb> g / at.-g <SEP> Ag <SEP> Sensitivity <SEP> Veil
<tb>
 
 EMI31.2
 I6 & Oin 100 14 TéMin - 100 0.14
 EMI31.3
 
<tb>
<tb> b <SEP> 6 <SEP> 3.0 <SEP> 129 <SEP> 0.15
<tb> c <SEP> 5 <SEP> 0.75 <SEP> 148 <SEP> 0.38
<tb> d) <SEP> 5 <SEP> 3.0 <SEP> 178 <SEP> 0.39
<tb> (g) <SEP> Witness <SEP> - <SEP> 100 <SEP> 0.15
<tb> (f) <SEP> 0.75 <SEP> 142 <SEP> 0.16
<tb> (g) <SEP> 3 <SEP> 3.0 <SEP> 162 <SEP> 0.17
<tb> h <SEP> Witness <SEP> - <SEP> 100 <SEP> 0.16
<tb> 1 <SEP> 7 <SEP> 0.75 <SEP> 159 <SEP> 0.17
<tb> (j) <SEP> 7 <SEP> 3.0 <SEP> 174 <SEP> 0.22
<tb> k <SEP> 8 <SEP> 0.75 <SEP> 155 <SEP> 0.20
<tb> (l) <SEP> 8 <SEP> 3.0 <SEP> 170 <SEP> 0.20
<tb> (m) <SEP> Witness <SEP> 100 <SEP> 0.11
<tb> n <SEP> 4 <SEP> 0.75 <SEP> 142 <SEP> 0.16
<tb> (o) <SEP> 4 <SEP> 3,

  0 <SEP> 162 <SEP> 0.17
<tb> p <SEP> Indicator <SEP> - <SEP> 100 <SEP> 0.16
<tb> q <SEP> 12 <SEP> 0.75 <SEP> 178 <SEP> 0.21
<tb> r <SEP> 12 <SEP> 3.0 <SEP> 240 <SEP> 0.25
<tb> s <SEP> 13 <SEP> 0.75 <SEP> 174 <SEP> 0.22
<tb> t <SEP> 13 <SEP> 3.0 <SEP> 263 <SEP> 0.24
<tb> u <SEP> 14 <SEP> 0.75 <SEP> 166 <SEP> 0.18
<tb> v <SEP> 14 <SEP> 3.0 <SEP> 224 <SEP> 0.22
<tb> (w) <SEP> Indicator <SEP> 100 <SEP> 0.13
<tb> (x) <SEP> 16 <SEP> 0.75 <SEP> 214 <SEP> 0.21
<tb> (x) <SEP> 16 <SEP> 0.75 <SEP> 214 <SEP> 0.21
<tb> (z) <SEP> Witness <SEP> - <SEP> 100 <SEP> 0.12
<tb> (a ') <SEP> 18 <SEP> 3.0 <SEP> 155 <SEP> 0.14
<tb> (b ') <SEP> Witness <SEP> - <SEP> 100 <SEP> 0.11
<tb> (c ') <SEP> 19 <SEP> 0.75 <SEP> 123 <SEP> 0.11
<tb> (d ') <SEP> 19 <SEP> 3,0 <SEP> 141 <SEP> 0,

  11
<tb>
 
The effect of the sensitizers according to the invention on customary photographic silver bromoiodide emulsions has been illustrated above, although it is understood that it is also possible to advantageously use other silver halide emulsions.



   While it has previously been suggested to add various thioether type sulfur compounds to photographic silver halide emulsions to increase sensitivity, it has however been found that the sulfone group compounds according to the invention have marked advantages over sensitizers

 <Desc / Clms Page number 32>

 of the aforementioned type. For example, although the compound of Example 5 increases the sensitivity of a usual photographic silver halide emulsion from 100 to 178 at a concentration of 3.0 g per gram atom of silver, the corresponding thioether decreases. the sensitivity of the same emulsion from 100 to 55, at the same concentration, gives a haze of 0.48.

   Likewise, although the compound of Example 7 increases the sensitivity of a conventional photographic emulsion to silver bromoiodide from 100 to 174, at a concentration of 3.0 g per. gram atom of silver, the corresponding thioether decreases the sensitivity of the same emulsion from 100 to 79, at the same concentration, and gives a haze of 0.32. Finally, although the compound of Example 8 increases the sensitivity of a usual photographic emulsion to silver bromoiodide from 100 to 170, at a concentration of 3.0 g per gram atom of silver, the corresponding thioether decreases. the sensitivity of the same emulsion from 100 to 76, at the same concentration, and gives a haze of 0.34.



   Of course, the invention is not limited to the embodiments described, which have been chosen only as examples.


    

Claims (1)

ABSTRACT The objects of the invention are in particular 1 - a photographic silver halide emulsion which is remarkable in particular by the following characteristics considered separately or in combinations a) - it contains, as sensitizer, a non-polymeric compound of the following general formula EMI32.1 wherein R and R1 each represents an alkylene group, an integer of between about 1 and 3, QN and NQ each an organic ammonium group and X an acid radical; <Desc / Clms Page number 33> b) - it contains a sensitizing amount of a compound of the following general formula EMI33.1 where R and R1 each represent an alkylene group containing from two to ten carbon atoms, of an integer between EMI33.2 E9 0 about 1 and 3, QN and NQ each an organic ammonium group and X an acid radical; c) - it is a silver halide emulsion giving images by development which has been sensitized by a gold compound and by a sulfurizing compound; d) - according to an embodiment of 1 b), it contains a sensitizing amount of a compound of the following general formula EMI33.3 where is a number from about 1 to 3, m and n is an integer from about 2 to 10, X is an acidic radical and QN and NQ each is an organic ammonium group; e) - it is an emulsion giving images by development which is sensitized by a compound of the following general formula EMI33.4 where 1 represents a number between about 1 and 3, m and n each an integer between 2 and 10, Q1 the non-metallic atoms necessary to complete a monoazine tertiary heterocyclic ring and X an acid radical; f) - according to a variant of 1 e), it contains a sensitizing amount of a compound of the following general formula EMI33.5 where R2, R3 and R4 each represent a lower alkyl group, <Desc / Clms Page number 34> d an integer between approximately 1 and 3, m and n each a positive integer between approximately 2 and 10 and X an acid radical; g) - according to another variant of 1 e), it contains a sensitizer of the following general formula EMI34.1 where R2 represents a lower alkyl group, J and J1 together are the non-metallic atoms necessary to complete a pyridine ring, an integer of between about 1 and 3, m and n each an integer of between about 2 and 10 and X a acid radical; h) - according to various particular embodiments, it contains a sensitizing amount of a compound of one of the following formulas EMI34.2 2 - photographic products comprising at least one emulsion layer as defined under 1 and the photographic images obtained on said product.