US3732104A

US3732104A - Silver halide emulsions containing azaindene and amide stabilizing agents

Info

Publication number: US3732104A
Application number: US00084489A
Authority: US
Inventors: H Vandenabeele; Munck J De; R Thiers; R Pollet; R Florens; J Willems
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1969-11-03
Filing date: 1970-10-27
Publication date: 1973-05-08
Anticipated expiration: 1990-05-08
Also published as: CH568581A5; JPS5021088B1; DE2053714A1; GB1325878A; BE758341A; DE2053714C2; FR2068912A5

Abstract

PHOTOGRAPHIC MATERIALS COMPRISING A LIGHT-SENSITIVE SILVER HALIDE EMULSION ELEMENT CONTAINING AN AZAINDENE EMULSION STABILIZING AGENT IN CONTACT WITH AS AN ADDITIONAL STABILIZING AGENT AN AMIDE HAVING THE FORMULA:

R3-CO-N(-R1)-R2

WHEREIN EACH OF R1 AND R2 STANDS FOR HYDROGEN, LOWER ALKYL, LOWER ALKYL CARRYING A HYDROXYL GROUP, LOWER ALKYL CARRYING THE GROUP R3CONH-, OR A PHENYL GROUP, R1 TOGETHER WITH R2 STANDS FOR THE ATOMS NECESSARY TO CLOSE A PYRROLIDONE, PIPERDINE OR MORPHOLINE NUCLEUS, R3 STANDS FOR LOWER ALKYL OR THE GROUP

-N(-R''1)-R''2

WHEREIN EACH OF R''1 AND R''2 HAVE THE SAME SIGNIFICANCE AS R1 AND R2, R''1 AND R''2 BOTH BEING DIFFERENT FROM HYDROGEN, OR R3 MAY REPRESENT HYDROGEN WHEN R1 OR R2 IS SUBSTITUTED ALKYL, OR R3 TOGETHER WITH R2 STANDS FOR ALKYLENE. A SYNERGISTIC EFFECT IS OBTAINED WITH REGARD TO FOG INHIBITION PARTICULARLY UPON STORAGE OF THE ELEMENT.

Description

United States Patent 3,732,104 SILVER HALIDE EMULSIONS CONTAINING AZAINDENE AND AMIDE STABILIZING AGENTS Hubert Vandenabeele, Wilrijlr, Joseph Louis De Munck, Heide-Kalmthout, Robrecht Julius Thiers, Brasschaat, Robert Joseph Pollet, Vremde, Raymond Leopold Flor-ens, Edegem, and Jozef Frans Willems, Wilrijk, Belgium, assignors to Gevaert-Agfa, N.V., Mortsel, Belgium No Drawing. Filed Oct. 27, 1970, Ser. No. 84,489 Claims priority, application (7622; Britain, Nov. 3, 1969,

Int. Cl. G03c 1/34 US. Cl. 96-109 12 Claims ABSTRACT OF THE DISCLOSURE Photographic materials comprising a light-sensitive silver halide emulsion element containing an azaindene emulsion stabilizing agent in contact with as an additional stabilizing agent an amide having the formula:

R1 R -C ON wherein each of R and R stands for hydrogen, lower alkyl, lower alkyl carrying a hydroxyl group, lower alkyl carrying the group R CONH, or a phenyl group, R together with R stands for the atoms necessary to close a pyrrolidone, piperidine or morpholine nucleus, R stands for lower alkyl or the group wherein each of R5 and R have the same significance as R and R R and R' both being different from hydrogen, or K, may represent hydrogen when R or R is substituted alkyl, or R together with R stands for alkylene.

A synergistic effect is obtained with regard to fog inhibition particularly upon storage of the element.

This invention relates to improved photographic materials comprising light-sensitive silver halide emulsions, more particularly to photographic materials having less tendency to fog formation and showing no appreciable desensitization upon storage.

It is well known that light-sensitive silver halide materials comprising gelatin silver halide emulsion layers are subject to fogging. Fogging in general and chemical fogging in particular may be defined as the formation of a uniform deposit of silver on processing which is dependent on a whole series of circumstances and factors namely on the nature of the emulsions, on their age, on the conditions under which they have been stored, on the processing conditions, etc. For particular processing conditions the fog tends to be greater as the time of storage and the temperature and relative humidity of the atmosphere, in which the emulsions are stored, are increased.

Addenda to the photographic material known as stabilizers or antifoggants protect the light-sensitive silver halide emulsions against formation and growth of fog particularly in high-sensitive emulsions and in emulsions which are stored under adverse conditions of temperature and humidity as is for instance the case in tropical countries. Among these addenda the azaindene stabilizing agents are widely used because of their unique properties in stabilizing the emulsions against the development of this general fog without giving rise to an appreciable desensitization.

It has now been found that the stability of light-sensitive silver halide emulsions comprising azaindene stabilizing agents against growth of fog can still be improved by the use of amide compounds corresponding to the formula:

R1 Ra-OON or polymers comprising recurring units of the formula:

wherein each of R and R stands for hydrogen, alkyl preferably comprising at most 5 C-atoms including substituted alkyl such as hydroxyalkyl and the group R OONH- alkyl, or aryl including substituted aryl,

or R together with R represent the atoms necessary to close a pyrrolidine, piperidine or morpholine nucleus,

R stands for alkyl preferably comprising at most 5 C-atoms, for the group as additional stabilizing agents, the sensitivity not being influenced to a noteworthy extent.

Thus, in accordance with the present invention photographic emulsions are provided which are stabilized with azaindene and additionally stabilized with amide compounds corresponding to the above general formulae.

Exemplary compounds corresponding to the above general formulae that are suitable for use with azaindene stabilizing agents in light-sensitive silver halide emulsions are:

acetamide H30 0 ONE;

/0 H dimethylacetamide H 0 0 ON CHzCHzOH dihydroxyethyl acetamide H 0N CHaCHzOH /CH3 NC ON tetramethylurea HaC propiouamido CHgCHzC ONE:

butyramide CHsCHz CHzC ONH:

CHz-CHz-C O e-cap rolactam H: C

C H:- C Hr-NH (8) poly(N-acrylmorpholine) having recurring units of the formula:

acetanilide mo 0 0 N110 OHCNHCHz CHzNHCHO The amide compounds of use according to the present invention are preferably incorporated into the silver halide emulsion layer comprising azaindene stabilizer of the light-sensitive material. The way in which the azaindene and amide compounds of use according to the invention are added to emulsions is not critical and the addition may occur during no matter what step of emulsion preparation.

The preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, and (3) the second digestion or after ripening (chemical ripening) to obtain increased sensitivity.

The azaindene and amide compounds of use according to the present invention can be added before or after the emulsion has been optically sensitized, preferably just before coating of the emulsion on a suitable support such as for example paper, glass or film such as cellulose triacetate and polyethylene terephthalate.

Instead of incorporating the amide compounds of the invention into the emulsion layer comprising azaindene stabilizer they can also be incorporated into another layer of the photographic material, e.g. a gelatin antistress layer or intermediate layer, which is in waterpermeable relationship with the said emulsion layer or into one of the processing baths for said photographic material.

The amide stabilizers of use according to the present invention may be used in conjunction with azaindene stabilizers in any type of light-sensitive material e.g. spectrally sensitized or non-sensitized silver halide material, silver halide material of use in diffusion transfer processes for the production of silver images, and X-ray material. They may be used in high speed negative materials as well as into rather low speed positive materials. Various silver salts may be used as light-sensitive salt e.g. silver bromide, silver iodide, silver chloride, or mixed silver halides e.g. silver chlorobromide or silver bromoiodide.

The silver halides are dispersed in the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., gelatin being, however, favoured.

The amount of amide compound employed in the lightsensitive silver halide material depends on the particular type of emulsion and the desired effect and can vary within very wide limits. The optimum amount of amide compound to be added is best determined for each partioular type of emulsion by trial. Generally, the most suitable concentration is between 0.5 g. and 20 g. of amide compound per mole of silver halide.

The azaindenes are used in the silver halide emulsions in concentrations as known in the art which are of the order of from 0.02 gram to 10.0 grams, preferably from 0.1 and 5 g. per mole of silver halide.

Azaindene stabilizing agents for use in light-sensitive silver halide material are widely known in the art. Examples of azaindene stabilizing agents can be found in literature amongst others in US. Pat. 2,944,902 and the patent literature referred to therein for that purpose. They include amongst others the hydroxy tetraazaindenes corresponding to the formula:

wherein:

each of R and R stands for hydrogen, alkyl, aralkyl and aryl, and R stands for hydrogen, alkyl, carboxy or alkoxycarbonyl.

By way of example, S-methyl-7-hydroxy-s-triazolo [1,5-a] pyrimidine, 6-carboxy-7-hydroxy-s-triazolo[1,5-a] pyrimidine, 6 carbethoxy 7 hydroxy-s-triazolo[1,5-a] pyrimidine and Z-B-hydroxyethyl-5-rnethyl-7-hydroxy-striazolo[1,5-a]pyrimidine can be mentioned as suitable hydroxy tetraazaindenes.

The light-sensitive emulsions may be chemically as well as optically sensitized. They may be chemically sensitized by any of the accepted procedures. The emulsions may be digested with naturally active gelatin or sulphur compounds may be added such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in our British patent specification 789,823 and by means of small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium. Representative compounds are ammonium chloro palladate, potassium chloroplatinate, potassium chloroaurate and potassium aurithiocyanate. These sensitizers can be added during no matter what step of emulsion preparation e.g. before, during or after the chemical ripening.

Other addenda such as hardening agents e.g. formaldehyde, dialdehydes, halogen substituted aldehyde acids such as mucochloric and mucochromic acid, etc., Wetting agents, plasticizers, colour couplers, developing agents and optical sensitizers can be incorporated into the emulsion in the usual way.

The azaindene and amide compounds of use according to the present invention are particularly suitable for use in conjunction with compounds which sensitize the emulsion by development acceleration for example alkylene oxide polymers. These alkylene oxide polymers may be of various type. Various derivatives of alkylene oxides may be used to sensitize the silver halide emulsions, e.g. alkylene oxide condensation products as described among others in United States patent specifications 2,531,832 and 2,533,990, in United Kingdom patent specifications 920,637, 940,051, 945,340 and 991,608 and in Belgian patent specification 648,710. Other compounds that sensitize the emulsion by development acceleration and that Development occurred for 6 min. at 20 C. in a developing bath having the following composition:

are suitable for use in combination with the azaindene Water 800 and amide compounds of use according to the invention 5 p-Moflomeihylamlflo Phenol Sulphate 4 are the onium derivatives of amino-N-oxides as described Sodium sulphite (anhydrous) g 65 in United Kingdom patent specification 1,121,696. Hydroquinone g 10 The emulsions may further comprise other known Sodium carbonate (anhydrous) g 45 antifoggants or stabilizers for instance heterocyclic nitro- Potassium bromide g 5 gen containing thioxo compounds such as benzothia- 10 Water to make 1000 ml.

TABLE Fresh material Stored material Compound(s) added per kg. Relative Relative emulsion Fog speed Fog -y speed 0.600 g. of azaindene (a) 2. 30 100 0.15 l. 93 105 (a plus (b) 2.46 102 0.11 2.12 107 (a plus a? 2.63 102 o. 11 2. 30 110 8 g. of compound 3(d)... 2. 34 200 3. 15

(a) pl 2.62 105 0.13 2. 126

8 g. of compound 5(e) 2. 43 123 2.51

(a) p e) 2.60 100 0.12 2. 110

s .of 2.00 81 2.15

(85131 2. so 123 o. 11 2 49 11s 1 The azaindene stabilizer used in the above materials is 5-methyl-7-hydroxy-s-triazolo [1, 5-a] pyrimidine.

From the above results appears that when using in azaindene stabilized emulsions the amide compounds according to the invention fog formation is still reduced, especially upon storage, though these compounds, when used alone, give high fog values upon storage.

EXAMPLE 2 Example 1 is repeated with the difierence, however, that development now took place for 20 sec. at C. in the tanning 1 phenyl 3-pyrazolidinone/hydroquinone developer G 137 marketed by Gevaert-Agfa N.V. Belgium.

The sensitometric results attained are listed in the table are particularly suitable for use in emulsions ripened 40 below.

Fresh material Stored material Compound(s) added per kg. Gra- Relative Gra- Relative emulsion Fog dation speed Fog dation speed 0.600 g. of the azaindene compound of example 1(a) 0. 05 1. 87 100 0. 12 1. 29 63 (a) plus 8 g. of compound 1-. 0.03 2. 01 102 0. 09 1. 33 71 (a) plus 8 g. of compound 0.03 1. 95 102 0.08 1. 59 93 (a) plus 8 g. of compound 5.- 0.02 2. 08 105 0. 09 1. 41 72 (a) plus 8 g. of compound 6.- 0.03 2.19 107 0. 09 1. 47 76 (a) plus 8 g. of compound 8 0.06 1. 77 73 0.07 1. 59 60 with noble metal compounds or reducing agents and are,

unlike the sulphinic acids, fully compatible with hardening by means of mucochloric and mucobromic acid.

The following examples illustrate the present invention.

EXAMPLE 1 An orthochromatic ammoniacal silver bromoiodide emulsion (2.75% of iodide), for photography of the green fluorescent screen, which comprises per kg. an amount of silver halide equivalent to 180 g. of silver nitrate and 72 g. of gelatin, was divided into several portions. To each of these portions the compounds listed in the table below were added in the amount given, prior to coating on a conventional film support.

The values of speed, gradation and fog of the materials formed were determined shortly after preparation and after having been stored for 36 hours at 57 C. and 34% relative humidity.

These values are listed in the table below. The values of the speed are relative values with respect to the speed of the material comprising only 5-methyl-7-hydroxy-striazolo[l,5-a]pyrimidine to which the value 100 is given (fresh material).

From these results too it appears that the amide compounds of the invention reduce fog formation in azaindenestabilized emulsions.

EXAMPLE 3 A gelatino silver bromoiodide emulsion (2 mole percent of iodide) comprising per kg. an amount of silver halide equivalent to 180 g. of silver nitrate and 72 g. of gelatin was divided into several portions. To each of these portions the compounds listed in the table below were added in the amount given, prior to coating on a conventional film support.

The values of speed, gradation and fog of the materials formed were determined shortly after preparation and after having been stored for 36 hours at 57 C. and 34% of relative humidity by exposure to X-rays with an X-ray radiation source of kv. and development for 4 min. at 20 C. in a common X-ray developer having the composition given in Example 1.

The values attained are listed in the table below. The values of the speed are relative values with respect to the speed of the material comprising only 5-methyl-7- hydroxy-s-triazolo[1,5-a]pyrimidine to which the value is given (fresh material).

Fresh material Stored material Oompouud(s) added per kg. Gra- Relative Gra- Relative emulsion Fog dation speed Fog dation speed 0.000 g. of the azaindene compound of Example 1 (a) 0. 11 2. 88 100 0. 24 2. 16 128 2 g. of compound 1 (b 0. 10 2. 59 128 2. (a) ll O. 07 2. 96 104 0. 12 2. 32 162 10 g of compound 2 (c). 0. 16 2. 52 114 2. 00 0. 07 3. 00 110 0. 16 2. 29 132 10 g of compound 4 (d) 0.15 2.42 128 2. 00 plus 0.09 2. 78 112 0. 20 2 10 126 10 g. of compound 5 (e). 0.09 2. 57 128 2. 00 (a) plus 0) 0. 03 3. 117 0. 13 2 41 144 EXAMPLE 4 E l 3 eat d w th th dfieren 8 however that 15 with the said emulsion layer as an additional stabilizing l? 1S rep 6 1 e 1 c a ent an amide com ound corre's ondin t th development took place for sec. at C. in the g p p g o e formula tanning 1 phenyl 3 pyrazolidinone/hydroquinone de- El veloper G 137 marketed by Gevaert-Agfa N.V., Mortsel, R C Belgium. 5

The results attained are listed below. 20 R1 Fresh material Stored material Compound(s) added per kg. Grada- Relative Grada- Relative emulsion Fog tion speed Fog tion speed 0.600 g. of azaindene compound of Example 1 (a) 0.28 1. 90 100 0. 1. 112 2 of compound 1 (b)- 0. 28 1. 112 3. 00 (a 0. 13 1. S7 100 0. 21 1. 46 100 10 g of compound 2 (e). 0. 36 1. 50 78 3. 00 (a) 0. 13 1. 90 98 0. 26 1. 44 98 10 g of compound 4 (d) 0. 29 1. 50 100 3. 00 (a) plus ((1) 0.18 l. 85 107 0. 1. 34 88 10 of compound 5 (e) 0.37 1. 48 78 3. 0 (a) plus (e) 0. 07 2. 00 107 0. 23 1. 42 100 EXAMPLE 5 wherein: Examples 3 and 4 are repeated and the results attained r each of 1 and 2 Stands hydrogen, lower l yl, o er are listed in the following tables. alkyl carying a hydroxyl group, lower alkyl carrying 1. After development as described in Example 3 Fresh material Stored material Oompound(s) added per kg. Grada- Relative Grada- Relative emulsion Fog tion speed Fog tion speed 0. 00 g of the azaindene compound of Example 1 (a) 0 20 3. 52 100 0.30 2. 74 142 10 g. of compound 1 (b) 0. 2 3. 50 76 1. 70 (a) plus (1)) 0.09 3. 35 96 0.18 2.62 142 10 g. of compound 9 (c). 0. 1 3. 35 81 1.80 (a) plus (0) 0. 13 3. 30 102 0. 20 2 54 152 2. After development as described in Example 4 0.600 g. of the azaindene compound of Example 1 (a 10 g. of compound 1 (b) (a) plus (h) 10 g. of compound 9 (c) (a) plus (0) i R together with R stands for the atoms necessary to 1. Photographic material comprising a light-sensitive, close a pyrrolidone, piperidine or morpholine nucleus,

developing-out, silver halide emulsion layer containing R stands for lower alkyl or the group an azaindene emulsion stabilizing agent having the formula: l

OH N

N R: R C; \N/ C R wherein each of R and R' have the same significance I 4 as R and R R and R' both being different from R -c /C:N hydrogen, or R may represent hydrogen when R or R is substituted alkyl, or

R together with R stands for alkylene. 2. Photographic material according to claim 1, wherein said amide compound corresponds to the formula:

RaCON wherein:

each of R and R stands for hydrogen, alkyl, aralkyl and aryl, and R stands for hydrogen, alkyl, carboxy or alkoxycarbonyl,

said material comprises in the said emulsion layer or in another colloid layer in water-permeable relationship R2 wherein: R stands for hydrogen, and R together with R stands for alkylene.

3. Photographic material according to claim 1, wherein said amide compound corresponds to the formula:

RsCON a wherein: R stands for hydrogen or lower alkyl, R stands for lower alkyl carrying the group R CONH,

and R stands for hydrogen or lower alkyl.

4. Photographic material according to claim 1, wherein said amide compound is present in the azaindene stabilized emulsion layer.

5. Photographic material according to claim 1, wherein said azaindene is 5-methyl-7-hydroxy-s-triazolo pyrimidine.

6. Photographic material according to claim 1, wherein the said emulsion layer comprises a development ac celerator of the polyoxyalkylene type.

7. Photographic material according to claim 1 wherein said amide compound corresponds to the formula:

RsCON R2 wherein: each of R and R stands for hydrogen, lower alkyl, hy-

droxy-substituted lower alkyl, or phenyl, and R stands for lower alkyl, or

each of R and R' being lower alkyl, hydroxy-substituted lower alkyl or phenyl.

8. Process for inhibiting fog-formation in photographic silver halide materials comprising a support carrying Water-permeable colloid layers including a silver halide emulsion layer, which comprises an azaindene emulsion stabilizing agent having the formula:

R1 Rs--CON R2 wherein: each of R and R stands for hydrogen, lower alkyl group,

lower alkyl carrying a hydroxyl group, lower alkyl carrying the group R 'CONH, or a phenyl group,

10 R together with R stands for the atoms necessary to close a pyrrolidone, piperidine or morpholine nucleus, R stands for lower alkyl or the group wherein each of R and R' have the same significance as R and R R and R' both being different from hydrogen, or R may represent hydrogen when R or R is substituted alkyl, or R together with R stands for alkylene.

9. Process according to claim 8, wherein said amide compound corresponds to the formula:

RBCON/ RSOON wherein: each of R and R stands for hydrogen, lower alkyl, hy-

droxy-snbstituted lower alkyl or phenyl, and R stands for lower alkyl, or

each of R and R' being lower alkyl, hydroxy-substituted lower alkyl or phenyl.

References Cited UNITED STATES PATENTS 3,333,959 8/1967 Hayakawa et a]. 96109 3,486,901 12/1969 KarlsOn 96-109 FOREIGN PATENTS 350,996 6/1931 Great Britain 96-109 NORMAN G. TORCHIN, Primary Examiner W. H. LOUIE, 111., Assistant Examiner U.S. Cl. X.R. 96-66.5

Patent No. 3,732, 104 Dated May 8, 1973 Inventor(s) HUBERT VANDENABEELE ET AL P 1 f 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, lines 15 18, the formula should appear as follows:

R -CON Column 3, line 16, "poly(N-acrylmorpholine)" should read poly(N- acryloylmorpholine) Column 3, line 27, "0.134 d]... /g. should read 0.134 dlg Column 5, line 30, "525,121" should read 524,121 Column 6, lines 12 25, in the Table, column 1, compound 5, "(a) plus (d)" should read (a) plus (c) Column 6, lines 12 25, in the Table, column 1, compound 7, "(a) plus (b)" should read (a) plus (d) Column 7, lines 36 45, in Table 1, column 1, compound 1, "0. 00 g" should read 0. 600 g Column 7, lines 36 45 in Table 1, column 2 under Fog, line 2, 00 2" should read 0, 26 Column 7, lines '36 45, in Table 1, column 2 under Fog, line 4, "0.1' should read O. 16 Column 7, line 74, claim 1, "comprises" should read comprising Column 10, lines 3 8, claim 8, the formula should appear as follows:

FORM PO-105O (10-69) USCOMM-DC 60376-P69 US, GOVERNMENT PRINTING OFFICE: I969 0"366'334,

v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 732, .1 04 I)ated IVL'IX 073 Inventor(s) HUBERT VANDENABEELE ET AL Page 2 of 2 It is certified that error appears in the aboveidentifi-ed patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 32, claim 11, after stands for" insert lower alkyl carrying Column 10, lines 46 50, claim 12, the formula should appear as follows:

Column 8 line 35 "carying" should read carrying Same line 35, after "carrying", second occurrence, ,insort the group R CONH-, or a phenyl group,

Signed and sealed this 17th day of September 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR.

C. MARSHALL DANN Attesting Officer Commissioner of Patents 'ORM PO-105D (IO-69) USCOMM-DC 60376-P69 Yr u.s. GOVERNMENT PRINTING OFFICE: 1969 0-366-334,