DE1163672B - Photographic material containing a stabilizer-containing sensitized silver halide emulsion layer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KL: G 03 c

German class: 57 b -8/02

Number: 1 163 672

File number: E 23283 IX a / 57 b

Filing date: July 28, 1962

Opened on: February 20, 1964

The invention relates to new photographic materials, the emulsion layer of which is a new combination of sensitizing additives.

It is known that photographic silver halide emulsions, in order to increase their sensitivity, chemically sensitized with a wide variety of materials. This is done by certain chemical sensitizers believed that they react with the silver halide and act on the On the surface of the same small amounts of silver sulfide or silver or other precious metals form. Also, there may be other classes of compounds that are obviously not related to the silver halide chemically combine, are used to increase the sensitivity of photographic silver halide emulsions to increase. Such sensitization reaches its limit where another sensitizer is added only increases the haze of the emulsion while the sensitivity remains constant or - even - decreasing. ao

It is an object of the invention to provide photographic silver halide emulsions of an enlarged size To develop sensitivity, the veil of which does not reach an objectionable height.

According to the invention, the photographic material contains a sensitizer-containing silver halide emulsion, which is characterized by a content of a sensitizer combination, which from a) a quaternary ammonium salt and b) a developing 3-pyrazolidone compound and / or a hydroquinone developer plus a compound capable of forming a bisulfite ion.

In other words, the emulsions are given sensitizing amounts of a combination of one chemical sensitizer for silver halide and consisting of a quaternary ammonium salt a photographic developing agent for silver halide, such as ζ. B. a hydroquinone developer substance, together with a compound capable of forming a bisulfite ion, or a 3-pyrazolidone compound having developing properties or combinations thereof Incorporated substances.

A whole series of quaternary ammonium salts can be used in the sensitizer combinations according to the invention, and a great number of such sensitizers are also known. Of these, the chemical silver halide sensitizers consisting of bis-quaternary ammonium salts are more generally used, bispyridinium salts, the pyridine nucleus of which is indicated by a photographic, a stabilizer-containing
sensitized silver halide emulsion layer
containing material

Applicant:

Eastman Kodak Company, Rochester, N.Y.

(V. St. A.)

Representative:

Dr.-Ing. W. Wolff

and H. Bartels, patent attorneys,

Stuttgart 1, Lange Str. 51

Named as inventor:

Kenneth Clayton Kennard,

Frederick James Russell, Rochester, N.Y.

(V. St. A.)

Claimed priority:

V. St. v. America 17 August 1961

(No. 132 012)

divalent radical linked to at least 7 carbon atoms are particularly useful. Suitable quaternary ammonium salts are described in U.S. Patents 2,271,623, 2,288,226, 2,419,975, 886 437, 2 940 851, 2 940 855, 2 944 898, 2 944 900 and 2 944 902, etc. With one especially useful class of quaternary ammonium salts are 1-alkyl-1,1-dimethylhydrazinium salts and a, cu-alkylene-bis- (l, l-dimethylhydrazinium salts) the general formulas

CH ₃

RN NH ₂

H ₂ N

CH ₃
CH ₃ CH ₃

N-Ri-N-NH ₂
CH ₃ CH ₃

where R is an alkyl radical with generally 2 to carbon atoms, Ri is an alkylene radical with generally

409 509/350

common 2 to 20 carbon atoms and X is an anion that differs from, for example, p-toluenesulfonic acid, Perchloric acid, hydrochloric acid, hydrobromic acid, etc.

Characteristic quaternary ammonium salts of 5 sensitizer combinations according to the invention are about:

p-xylene-bis-cacetamidodimethylammonium

perchlorate), 10

1,2-ethylene-bis- (1,1 -dimethylhydrazinium-

perchlorate),
1,4-tetramethylene-bis- (1,1-dimethyl-

hydrazinium perchlorate),
1.6-hexamethylene-bis- (1,1-dimethyl- 15

hydrazinium perchlorate),
ln-decyl-Ul-dimethylhydrazinium perchlorate, lauryltriethylammonium perchlorate, N-heptoxymethylpyridinium perchlorate. n-nonylpyridinium perchlorate, 20

n-decylpyridinium perchlorate,
1,2-ethylenebis (dioxymethylpyridinium-

perchlorate),
l, 10-decamethylene bis (triethylammonium

perchlorate), 25

Oxy-bis (methylpyridinium perchlorate), acetcarbohydrazide pyridinium chloride, Malonyldicarbohydrazidopyridinium bromide, N-methyl-2-carbohydrazylpyridinium

p-toluenesulfonate, 30

Decamethylene-u, aj-bis- (oxymethylpyridinium perchlorate),

Lauryl pyridinium perchlorate,
Laurylpyridinium p-toluenesulfonate, decamethylene-bis-ioxymethyl-a-picolinium _i5

perchlorate),

Tetradecamethylene-bis-pyridinium perchlorate), n-myristyl trimethylammonium p-toluenesulfonate. 4,11 -diaza-3.12-dioxotetradecane-1,14-bis-

(pyridinium perchlorate), 40

3,14-diaza-2,15-dioxohexadecane-1,16-bis-

(pyridinium perchlorate),
n-phenylene-bis- (2-aza-3-oxotridecanpyridinium-

perchlorate),
5,12-dioxa-6,11-dioxohexadecane-1,16-bis- ₄₅

(pyridinium perchlorate),
7,18-Dioxa-8,17-dioxotetracosane-l .23-bis-

(pyridinium perchlorate),
7,10,13,16.19-Pentaoxa-6.20-dioxopentacosan-

1,25-bis (pyridinium perchlorate), 50

12-Oxa-l 1-oxod oco san-1.22-bis- (pyridinium perchlorate),
5.12-diaza-3,14-dioxa-4,13-dioxo-hexadecane-1,16-bis (trimethylammonium-

p-toluenesulfonate), ₅₅

7,18-diaza-6,19-dioxotetracosane-1,24-bis-

(pyridinium perchlorate),
6,13-Diaza-4,15-dioxo-5.14-dioxo-octadecane-1,18-bis (N-methyl-pyridinium-

p-toluenesulfonate), 60

9,16-diaza-7,18-dioxa-8.17-dioxotetracosane

1,24-bis (pyridinium perchlorate), 3,10,17,24-tetraza-5,8,19,22-tetroxa-4,9,18,23-tetroxohexacosane-1,26-bis-

(pyridinium perchlorate), 65

3.18-Diaza-5, l 6-dioxa-4,17-dioxoeicosane,

l, 20-bis (pyridinium perchlorate), tetraethoxyethyl bis (pyridinium perchlorate),

Octaethoxyethyl bis-dimethyldodecyl

ammonium perchlorate),
Polypropoxypropyl-fi, (- j-bis- {pyridinium-

methanesulfonate) as well as numerous other quaternary ammonium salts or other onium salts, as described in U.S. Patent 2,288,226.

A wide variety of 3-pyrazolidone developer substances can also be used for silver halide can be used in the sensitizer combinations according to the invention, and there are a large number such developer substances known. Suitable 3-pyrazolidone developer substances are, for example in the USA. Patents 2,289,367, 2,685,516 and 2,772,282.

Characteristic 3-pyrazolidine developing agents have the formula

R ⁴

O = C

HN

CR ³

R ²

χ / I

NR ¹

wherein R is a hydrogen atom, a hydrocarbon radical, such as. B. an alkyl, a heterocyclic or an aryl radical, including phenyl, naphthyl and substituted hydrocarbon radicals and wherein Ri, R ² , R ³ and R ^{4 can be} hydrogen atoms, hydrocarbon radicals, such as alkyl radicals preferably having 1 to 4 carbon atoms, or Aryl radicals, including phenyl, naphthyl and substituted hydrocarbon radicals. However, various other 3-pyrazolidone developing agents for silver halide can be used in the invention. The expression “3-pyrazolidone developer substance for silver halide”, as used here, therefore relates to all such developer substances and their substituted derivatives.

Characteristic 3 - pyrazolidone developing substances which can be suitably used are among other

l-phenyl-3-pyrazolidone,

l-p-tolyl-3-pyrazolidone,

5-phenyl-3-pyrazolidone,

5-methyl-3-pyrazolidone,

1 -p-chlorophenyl-3-pyrazolidone.

l-phenyl-5-phenyl-3-pyrazolidone,

1 -m-tolyI-3-pyrazolidone,

l-phenyl-5-methyl-3-pyrazolidone,

l-p-tolyl-5-phenyl-3-pyrazolidone,

1 -p-M ethoxyphenyl-3-pyrazolidone,

l-acelamidophenyl-3-pyrazolidone,

l-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone,

1-phenyl-4,4-dimethyl-3-pyrazolidone,

l-m-aminophenyM-methyM-propyl-

3-pyrazolidone.

l-o-chlorphenyM-methyM-ethyW-pyrazolidone, ] -m-acetamidophenyl-4,4-diethyl-3-pyrazolidone, 1 - (p-ß-oxyethylphenyl) -4,4-dimethyl-

3-pyrazolidone,

lp-oxyphenyl-4,4-dimethyl-3-pyrazolidone,
lp-methoxyphenyl-4,4-diethyl-3-pyrazolidone,
lp-tolyl-4,4-dimethyl-3-pyrazolidone,

l- (7-Oxy-2-naphthyi) -4-methyl-4-n-propyl-

3-pyrazolidone,

lp-DiphenyMÄdimethyM-pyrazolidon,
l- (p- / S-oxyethylphenyl) -3-pyrazolidone,
lo-tolyl-3-pyrazolidone,

lo-TolyM ^ -dimethyW-pyrazolidone,
1 -Benzothiazolyl-3-pyrazolidone etc.

Finally, a wide variety of hydroquinone developer substances can be used in the sensitizer combinations according to the invention for silver halide together with compounds that are capable of liberating or forming bisulfite ions, to be used. These include hydroquinone itself and substituted hydroquinones with substituents such as alkyl, aryl and the like, as well as hydroquinone derivatives containing carboxyl, acyl, acyloxy and alkoxy radicals. These substituents suitably have 1 to 20 and most often 1 to 6 carbon atoms.

Characteristic hydroquinones which can be used according to the invention include: hydroquinone, p-Toluhydroquinone, 2,5-dioxybenzoic acid and the like.

A particularly useful class of compounds that liberate bisulfite ions are alkali bisulfites such as sodium bisulfite and potassium bisulfite. Other compounds that produce bisulfite ions are sodium and potassium sulfite. Sulfur dioxide can also be used as a source of bisulfite ions. As is well known form sulfur dioxide and hydroquinone clathrates, which is why sulfur dioxide and hydroquinone are preferably added to the emulsion in this form. Such clathrates are from almond corn in "Chemical Reviews", 59, pp. 827-830, October 1959, has been described. Usually she does Compound forming bisulfite ions in weight less than half the sum of the weights of the hydroquinone and the compound which forms bisulfite ions, although larger amounts of bisulfite compounds can be used. Preferably at least about 5 mol percent bisulfite ion, based on hydroquinone. In order to achieve optimal results, the concerned hydroquinone and the compound capable of forming a bisulfite ion prior to incorporation blended or combined into the photographic emulsions, although these compounds can also be added individually to the emulsion.

The sensitizer additives according to the invention are the emulsions in one for the sensitization appropriate amount, as determined in a known manner, added. However, it will generally be about 0.01 to 10 g, preferably 0.1 to 5 g of the quaternary ammonium salt, about 0.01 to 10 g, preferably 0.1 to 5 g of the 3-pyrazolidone developer and about 1 to 100 g of the hydroquinone bisulfite-forming Compound used per mole of silver halide present in the emulsion.

The sensitizer additives according to the invention can be added directly to the silver halide emulsion layer incorporated or they can be used in these adjacent layers.

The preparation of the emulsions containing the additives according to the invention comprises three separate processes Operations: Firstly, the emulsification and ripening of the silver halide, secondly, the liberation of the Emulsion of excess, water-soluble salts, expediently by washing with water and thirdly the second ripening or "post-ripening" in order to obtain a material of increased sensitivity (cf. on this M e s, "The Theory of the Photographic Process", 1954). The additives according to the invention can be applied to the emulsion before the second or last ripening or immediately before coating (des Carrier) are added.

The sensitizer additives according to the invention can be added to the emulsions using any of the in the production of emulsions customary processes can be added. For example, they can dissolved in a suitable solvent and added to the emulsion, or they can be the Emulsion in the form of a dispersion can be added according to a method similar to that used for incorporation of certain types of color-forming compounds (couplers) in a photographic emulsion is used. Techniques of this type are described in U.S. Patents 2,322,027 and 2,811,171. The solvent used should be selected so that it is consistent with normal practice can not exert a deleterious effect on the emulsion, in general Solvents or diluents that are miscible with water should be preferred.

The emulsions can be made up with naturally active gelatin, or they can contain sulfur compounds like those in the USA. - Patents 1,574,944, 1,623,499 and 2,410,689. The emulsions can also be mixed with noble metal salts such as those of the Ruthenium, rhodium, palladium, iridium and platinum are treated.

The emulsions can also be optically sensitized with cyanine and mercocyanine dyes, such as with the US patents 1846 301,

1 846 302, 1 942 854, 1 990 507, 2 112 140, 2 165 338,

2 493 747, 2 739 964, 2 493 748, 2 503 776, 2 519 001, 2 766 761, 2 734 900 and 2 739 149 as well as those in the British Patent 450,958.

The emulsions may contain a suitable plasticizer for gelatin.

The emulsion can be hardened with any suitable hardening agent for gelatin, such as, for example with formaldehyde, a halogenated aliphatic acid, such as. B. that in the U.S. Patent 2 080 019 described mucobromic acid etc.

The emulsions can also contain a coating aid, such as. B. Saponin, a lauryl or oleoyl monoether of polyethylene glycol as described in U.S. Patent 2,831,766.

The emulsions can also be mixed with the mercury compounds of U.S. Patents 2,728,663, 2,728,664, 2,728,665, or those described in U.S. Patent 2,444,608 Triazoles, the azaindenes of U.S. Patents 2,444,605, 2,444,606, 2,444,607, 2,450,397, 2,444,609, 2 713 541, 2 743 181, 2 716 062, 2 735 769, 2 756 147, 2 772 164 and that of B i r r in the »Zeitschrift für Scientific Photographic ", Vol. 47, pp. 2 to 28 (1952), described azaindenes, the disulfides Belgian patent 569 317, the quaternary benzothiazolium compounds of the USA patent 2,131,038, the bis-quaternary salts of U.S. Patent 2,694,716, namely decamethylene bisbenzothiazolium perchlorate etc., and the zinc and cadmium salts of U.S. Patent 2,839,405.

The sensitizer additives according to the invention can be used in various types of emulsions to be used. Except for orthochromatic, panchromatic and infrared sensitive emulsions they can also be used for X-ray and other non-optically sensitized emulsions. You can that Emulsion can be added before or after any sensitizing agents that may be used Dyes are or have been incorporated into the emulsion. As light sensitive Salt, various silver salts can be used, such as: B. silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide, silver bromide iodide, etc. The Additives can be used in emulsions intended for color photography, z. B. in emulsions containing color-forming couplers, or in emulsions containing couplers or other solutions containing color-forming materials are to be developed, furthermore in "Mix pack type" emulsions as described in U.S. Patent 2,698,794, or in emulsions of the "mixed grain type" as described in U.S. Patent 2,592,243. Suitable color couplers usually belong to three most widely known classes, namely pyrazolone couplers, phenolic couplers and open chain ketomethylene couplers, all of which deal with the oxidation products primary, aromatic amine developers for silver halide under formation combine of magenta-cyan and yellow dye images, respectively. When developing such Color emulsions can also contain development accelerators, including polyethylene glycols, their esters and their ethers of the formula

RO (CH ₂ CH ₂ O) _n H

where R is an alkyl radical having 1 to 5 carbon atoms and η = 15 to 100, and related derivatives can be used. The additives according to the invention can also be used in predominantly (latent) surface image-forming emulsions and in predominantly (latent) depth image-forming emulsions, as in the emulsions described in US Pat. No. 2,592,250.

The additives of the invention can also be used in emulsions which are intended for use in diffusion transfer processes, where the undeveloped silver halide in the non- _{image areas of the negative is used to form a 5 U} positive image by dissolving the undeveloped silver halide and on one in the immediate vicinity to the original silver halide emulsion layer is precipitated. Such methods are described in U.S. Patents 2,352,014, 2,584,029, 2,608,236, and 543,181. They can also be used in color transfer processes which rely on the diffusion transfer of an imagewise distribution of developer, coupler or dye from one photosensitive layer to a second layer, the two layers being in close proximity. This type of paint process is described in U.S. Patents 2,559,643, 2,698,798, and 756,142, and Belgian Patents 933, 554,934, 554 212, and 554,935.

For the preparation of the silver halide dispersions used for the silver halide emulsions according to the invention Can be used as a dispersant for the silver halide (in its manufacture) gelatin or another colloidal material such as B. colloidal albumin, a cellulose derivative or a synthetic Resin such as A polyvinyl compound, although gelatin is preferred for this. Colloids that can be used include: polyvinyl alcohol or a hydrolyzed polyvinyl acetate, as in U.S. Patent 2,286,215; a largely hydrolyzed cellulose ester, such as. B. a cellulose acetate hydrolyzed to an acetyl content of 19 to 26%, as in the U.S. patent 2,327,808; a water-soluble ethanolamine cellulose acetate, as in FIG U.S. Patent 2,322,085; a polyacrylamide with a total acrylamide content of 30 to 60% and a specific viscosity of 0.25 to 1.5 or an imidized polyacrylamide of the same acrylamide content and viscosity as described in US Pat. No. 2,541,474; Zein as described in U.S. Patent 2,563,791; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Patent 2,768,154 or the cyanoacetyl groups, such as the vinyl alcohol / vinyl cyanoacetate copolymer described in US Pat. No. 2,808,331 contains; or a polymeric material that is used in the polymerization of a protein or a saturated acylated protein with a vinyl group-containing monomer is formed, as in U.S. Patent 2,852,382. Compatible mixtures can be used if desired Two or more of these colloids are used to make the silver halide in its Disperse manufacture.

The above-described emulsions according to the invention can be used in accordance with common practice to be applied to a wide variety of substrates. Characteristic supports for photographic Materials according to the invention include: cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, Polystyrene film, polyethylene terephthalate film and similar films of resinous materials, as well as glass, paper, wood and metals etc.

The invention is explained in detail below with reference to emulsions, the at least two of the additives listed below I up to and including XVII, with those in the specific examples and the additions used in the tables are numbered accordingly.

No.

additions

I. 7,18-diaza-6,19-dioxotetracosane-1,24-bis-

(pyridinium perchlorate).
II. In-decyl-Ul-dimethylhydrazinium perchlorate.

III. Hydroquinone Sulfur Dioxide Clathrate
(10.6 percent by weight sulfur dioxide).

IV. I-Methyl-1-phenyW-pyrazolidone.

V. 2,5-Dioxybenzoic acid sulfur dioxide clathrate

(7.86 percent by weight sulfur dioxide).
VI. 7,18-Dioxa-8,17-dioxotetracosane-1,24-bis-

(pyridinium perchlorate).
VII. Tetradecamethylene bis (pyridinium

perchlorate).

VIII. 4-n-Octyl-1-phenyl-3-pyrazolidone.
IX. 1,2-ethylene bis (1,1-dimethylhydrazinium perchlorate).

ίο

X. 1,4-tetramethylene-bis- (1,1-dimethyl-

hydr azinium perchlorate).
XI. 1,6-hexamethylene-bis- (1,1-dimethylhydrazinium perchlorate).

XII. p-xylene bis (acetamidodimethylammonium perchlorate).

XIII. 2-chloroacetyl-1-phenyl-3-pyrazolidone.

XIV. 2-chloroacetyl-4-methyl-1-phenyl-3-pyrazolidone.

XV. 4-ethyl-1-phenyl-3-pyrazolidone. XVI. 4-methyl-2-phenoxyacetyl-1-phenyl-3-pyrazolidone.
XVII. 4-benzyl-1-phenyl-3-pyrazolidone.

example 1

Characteristic additives according to the invention were incorporated into samples of a highly sensitive gelatin silver bromide iodide negative emulsion which was sensitized with “gold” and “sulfur” and contained a cyanine dye ao for panchromatic sensitization. The silver halide in the emulsion consisted of about 96 weight percent silver bromide and about 4 weight percent silver iodide. About 200 grams of gelatin per mole of silver halide was present in the emulsion. The emulsion was coated on a cellulose acetate film support in such a way that about 700 mg of silver came to 929 cm ² . The photographic materials thus produced were then exposed in the form of film strips in an Eastman Ib sensitometer, subsequently developed for 6.5 minutes and then fixed, washed and dried in the usual manner. For the sake of comparison, emulsions which did not contain any of the additives according to the invention were also examined. The developer used essentially had the following composition:

N-methyl-p-aminophenol sulfate 2.5 g

Hydroquinone 2.5 g

Sodium sulfite, anhydrous 30.0 g

Sodium borate 10.0 g

Potassium bromide. ' 0.5 g

Filled up to the liter with water.

The results of the sensitometric tests are shown in Table A below Data visible. The sensitivities given in Table A are a function of Exposure required to give a density of 0.3 over background fog and are Expressed reciprocally to the exposure, the original sensitivity of the control material with 100 is used. Otherwise, the additives according to the invention listed in Table A correspond regarding the numbering of the additions listed before example 1. The respective concentration of the Additive is given in grams per mole of silver halide in the emulsion.

Table A.

35

Concentration of per mole of AgX III IV V Relative gamma veil Additions in grams Connection no. 0 0 0 Sensation VTateria II 0 0 0 opportunity 0 0 0 0 0.57 0.09 I. 0 20th 0 0 100 0.61 0.18 a) 0 1 0 1 0 191 0.64 0.13 b) 1 0 0 0 0 209 0.85 0.06 c) 0 0 20th 0 0 112 0.66 0.09 d) 0 1 0 1 0 129 0.61 0.15 e) 0 0 20th 0 0 214 0.68 0.09 0 1 0 0 1 0 289 0.64 0.18 G) 1 1 20th 1 0 269 0.71 0.07 H) 1 1 20th 0 0 257 0.69 0.08 i) 0 0 0 1 0 263 0.77 0.07 j) 0 1 20th 1 0 191 0.69 0.13 k) 0 1 20th 1 0 282 0.66 0.15 1) 1 0 20th 1 0 240 0.73 0.16 m) 1 1 1 23.5 263 0.78 0.10 n) 1 1 347 0.75 0.18 0) 0 1 400 0.90 0.18 P) 1 420 q) 1

40

Example 2

Further sensitizer combinations according to the invention were incorporated into a gelatin-silver bromide iodide emulsion as described in Example 1 and investigated according to the general method also described in Example 1. The sample emulsions after a 1- or 2-week storage at 49 ⁰ C and 50% humidity was also examined. The results obtained can be seen from the data compiled in Tables B, C, D, E and F below.

Table B.

Additives according to the invention
in grams per mole of AgX

Originii
relative
Sensation
opportunity related
gamma material
veil According to Iv
relative
Sensation
opportunity rottier
gamma storage
veil After 2w
relative
Sensation
opportunity ochier]
gamma 100 0.97 0.13 113 0.90 0.13 91 0.80 132 1.08 0.13 138 1.02 0.16 123 0.94 126 0.95 0.14 138 0.94 0.13 115 0.78 132 0.99 0.14 138 0.91 0.14 110 0.70 138 1.00 0.30 105 0.92 0.15 151 0.93 141 1.15 0.38 182 1.04 0.15 159 0.99 132 1.05 0.14 129 1.00 0.11 132 0.97 148 1.11 0.24 141 1.05 0.15 151 0.97 174 1.18 0.28 178 1.26 0.14 162 0.99

veil

Control contains 1.0 g of compound I + 15 g of compound III

Control + 1.0 g of compound IV control + 1.5 g of compound VTII control + 3.0 g of compound VIII Control + 0.5 g Compound XVII Control + 1.5 g Compound XVII Control + 1.5 g Compound XVI Control + 0.5 g Compound XV Control + 1.5 g Compound XV 0.24 0.26 0.24 0.24 0.19 0.23 0.14 0.19 0.24

409 509/350

11

Table C.

12th

Additions according to the invention in grams per mole of AgX

control

Control + 1.0 g compound I + 15 g compound III + 1.0 g compound II

Control + 1.0 g compound I + 15 g compound III + 0.25 g compound XVII ..

Control + 1.0 g compound I + 15 g compound III + 1.0 g compound XVII ...

Control + 1.0 g compound I + 15 g compound III + 0.25 g compound XV ....

Original material

relative

sensitivity

gamma

veil

After a week's storage
relative

sensitivity

gamma

veil

Relative after 2 weeks of storage

sensitivity

gamma

veil

100

135

145

148

141

0.96

1.16

1.03

1.12

1.17

0.13

0.17

0.20

0.22

0.18

120

178

182

186

178

0.78

1.14

1.05

1.10

1.15

0.18

0.15

0.15

0.15

0.15

95

141

166

162

148

0.71

1.05

0.97

0.96

1.07

0.18

0.21

0.18

0.20

0.23

Table D.

Additives according to the invention
in grams per mole of AgX Origin
relative
Sensation
opportunity igliches]
gamma viaterial
veil According to Iv
relative
Sensation
opportunity rottier
gamma storage
veil After 2w
relative
Sensation
opportunity more weeks
gamma storage
veil Control contains 1.0 g of compound I. 100 0.87 0.13 100 0.68 0.15 89 0.71 0.17 Control + 0.75 g of compound II
+ 15 g compound HI 138 1.01 0.09 129 0.90 0.09 110 0.81 0.12 Control + 0.75 g of compound II
+ 15 g of compound III
+ 1.5 g of compound IV 159 1.32 0.12 166 1.07 0.10 159 0.92 0.13 Control + 0.75 g of compound II
+ 15 g of compound III
+ 1.5 g of compound XIII 166 1.22 0.12 166 0.85 0.16 138 0.82 0.22 Control + 0.75 g of compound II
+ 15 g of compound III
+ 1.5 g compound XIV 166 1.26 0.12 174 0.89 0.13 170 0.85 0.13

Table E.

Additions according to the invention in grams per mole of AgX

Control contains 1.0 g of compound I.

Control +10 g compound II + 1.0 g compound IV

Control + 10 g of compound III + 1.0 g of compound IV + 1.0 g of compound II

Control +10 g compound III + 1.0 g compound IV + 1.0 g compound LX

Original material relative

sensitivity

gamma

veil

After a week's storage
relative

sensitivity

gamma

veil

Relative after 2 weeks of storage

sensitivity

gamma

veil

100 166

162 162

0.15 0.14

0.14 0.13

102

151

162

151

0.70

1.0

0.97

0.91

0.15

0.11

0.09

0.11

102
129

151
151

0.66
0.87

0.84
0.86

0.20 0.15

0.16 0.15

continuation

Additives according to the invention
in grams per mole of AgX

Original material

relative
sensitivity

gamma

veil

After a week's storage
relative

sensitivity

gamma

veil

After 2 weeks of storage
relative

sensitivity

gamma

veil

Control + 10 g of compound III
+ 1, above compound IV
+ 5g compound IX

Control + 10g compound III
+ 1.0 g of compound IV
+ 1.0 g of compound X

Control + 10 g of compound III
+ 1.0 g of compound IV
+ 1.0 g of compound XI

Control +10 g compound III
+ 1.0 g of compound IV
+ 1.0 g of compound XII

159

162

162

162

1.14

1.12

1.27

1.30

0.15

0.13

0.14

0.15

155

159

155

0.90

0.13

0.97

0.93

0.11

0.11

174

155

155

159

0.82

• 0.8

0.87

0.85

Table F.

Additives according to the invention
in grams per mole of AgX Origin
relative
Sensation
opportunity related
gamma material
veil According to Iv
relative
Sensation
opportunity rottier
gamma storage
veil After 2w
relative
Sensation
opportunity rottier
gamma storage
veil Control contains 1.0 g of compound I. 100 0.83 0.14 110 0.92 0.13 105 0.70 0.15 Control + 0.75 g of compound II
+ 10 g of compound III
+ 1.0 g of compound IV 174 1.31 0.10 178 1.14 0.11 159 0.99 0.20 0.75 g of compound II
+ 10 g of compound III
+ 1.0 g of compound IV 129 1.19 0.08 123 1.04 0.08 112 0.90 0.15 0.75 g of compound II
+ 10 g of compound III
+ 1.0 g of compound IV
+ 1.0 g of compound VII 195 1.15 0.13 204 1.06 0.14 166 0.98 0.28 0.75 g of compound II
+ 10 g of compound III
+ 1.0 g of compound IV
+ 1.0 g of compound VI 186 1.21 0.14 209 1.18 0.20 145 0.90 0.42

The same results as were apparent from the data in Tables B, C, D, E and F. obtained when a molar equivalent amount of sodium bisulfite was used in place of the sulfur dioxide in the combination with the hydroquinone. Alkali bisulfites in combination with the hydroquinone were used in the present sensitizer combinations as equivalent to hydroquinone sulfur dioxide clathrates, such as the compound III, found.

Example 3

The hydroquinone-sulfur dioxide clathrate (compound III) can be prepared by Hog hydroquinone are dissolved in 700 ml of distilled water at 50 ⁰ C. The resulting solution is then saturated with sulfur dioxide and cooled down to 5 ° C. The clathrate formed separates out of the reaction mixture in the form of yellow crystals, which are filtered off and dried.

It should be added that the development of the sample materials exposed in the sensitometer was carried out at 20 ° C.
As can be seen from the data compiled in the above examples in the tables, a wide variety of chemical tertiary ammonium salt sensitizers for silver halide act with a wide variety of hydroquinone developing agents for silver halide, plus a compound capable of forming a bisulfite ion, or a wide variety of 3-pyrazolidone developing agents for silver halide or finally mixtures of such developers in such a way that they increase the sensitivity of photographic silver halide emulsions. If substantial or very large amounts of quaternary ammonium salt sensitizers for silver halide alone are used as sensitizers in photographic silver

Halide emulsions are used to increase sensitivity Increasing the emulsions in question will result in undesirable levels of fog, such as they are only too well known to those skilled in the art. However, an increased sensitivity according to FIG Invention can be achieved without an undesirable level of fog is achieved by relatively small amounts of quaternary ammonium salt sensitizers with developer compositions can be combined as described above.

Claims (14)

Patent claims: 1. Photographic material consisting of a support and one applied to it stabilizer-containing, sensitized silver halide emulsion layer, characterized, that the silver halide emulsion layer is a sensitizer combination of a) a quaternary ammonium salt and b) a 3-pyrazolidone developer substance and / or a hydroquinone developer substance plus one Has bisulfite ion-forming compound. 2. Photographic material according to claim 1, characterized in that the emulsion layer the quaternary ammonium salt is a 1-alkyl-1,1-dimethylhydrazinium salt contains. 3. Photographic material according to claim 2, characterized in that the emulsion layer Contains 1-n-decyl-1,1-dimethylhydrazinium perchlorate. 4. Photographic material according to claim 1, characterized in that the emulsion layer as the quaternary ammonium salt u, cj -alkylene-bis- (l, l-dimethylhydrazinium) salt contains. 5. Photographic material according to claim 4, characterized in that the emulsion layer 1,2 - ethylene - bis - (1,1 - dimethylhydrazinium perchlorate), 1,4 - tetramethylene - bis - (1,1 - dimethylhydrazinium perchlorate) or 1,6-hexamethylene bis (1,1-dimethylhydrazinium perchlorate). 6. Photographic material according to claim 1, characterized in that the emulsion layer contains a bispyridinium salt as the quaternary ammonium salt. 7. Photographic material according to claim 6, characterized in that the emulsion layer as bispyridinium salt 7,18-diaza-6,19-dioxotetracosane-1,24-bis (pyridinium perchlorate), 7,18-Dioxa -8,17 - dioxotetracosane -1,24 - bis - (pyridinium perchlorate) or tetradecamethylene bis (pyridinium perchlorate) contains. 8. Photographic material according to claim 1, characterized in that the emulsion layer p-xylenebisacetamidodimethylammonium perchlorate contains. 9. Photographic material according to claim 1, characterized in that the emulsion layer a mixture of a 1-alkyl-1,1-dimethylhydrazinium salt or an a, t »-alkylene-bis (l, l-dimethylhydrazinium) salt and a bispyridinium salt. 10. Photographic material according to any one of claims 1 to 9, characterized in that the emulsion layer as a 3-pyrazolidone developing agent 4 - methyl -1 - phenyl - 3 - pyrazolidone, 2-chloroacetyl-1-phenyl-3-pyrazolidone, 2-chloroacetyl-4-methyl-l-phenyl-3-pyrazolidone, 4-ethyl-1-phenyl-3-pyrazolidone, 4-methyl-2-phenoxyacetyl-1-phenyl-3-pyrazolidone, 4-benzyl-1-phenyl-3-pyrazolidone or 4-n-octyl-1-phenyl-3-pyrazolidone contains. 11. Photographic material according to one of the Claims 1 to 10, characterized in that the emulsion layer is a bisulfite ion-forming thickener Contains sulfur dioxide or an alkali bisulfite. 12. Photographic material according to any one of claims 1 to 11, characterized in that the emulsion layer has a sensitizer combination per mole of silver halide of about 0.01 up to 10 g of 7,18-diaza-6,19-dioxotetracosane-1,24-bis (pyridinium perchlorate) and about 1 to 100 g of hydroquinone plus a smaller amount of sulfur dioxide. 13. Photographic material according to any one of claims 1 to 11, characterized in that the emulsion layer has a sensitizer combination per mole of silver halide of about 0.01 up to 10 g l-n-decyl-o. ^ - dioxotetracosane-l ^ l-bis- (pyridinium perchlorate) and about 0.01 to 10 g of methyl-1-phenyl-3-pyrazolidone and about 1 to Contains 100 g of hydroquinone plus a smaller amount of sulfur dioxide. 14. Photographic material according to claim 13, characterized in that the emulsion layer contains 2,5-dioxybenzoic acid instead of hydroquinone. 409 509/350 2.64 Q Bundesdruckerei Berlin