DE1080398B - Sensitized silver halide emulsion - Google Patents

Description

The invention relates to a highly sensitive silver halide emulsion, which one with the oxidation products of a primary aromatic amino-halosilver developer substance contains reactable coupler compound.

It is known to use photographic emulsions with various onium compounds such as surface active agents cationic quaternary ammonium, phosphonium and ternary sulfonium salts, for example with such from U.S. Patents 2,271,623, 2,275,727, 2,288,226, and 2,334,864. Furthermore it is known that the emulsions sensitized with the onium compounds are used in color photography can be developed by developing the emulsions with developer solutions containing coupler compounds will. The couplers react with the color developing agents and produce dyes. It can the couplers can also be contained directly in the emulsions sensitized with the onium compounds.

Furthermore, the sensitization of photographic emulsions with various nonionic polyalkylene oxides, e.g., polyethylene oxide, known from U.S. Patents 2,423,549 and 2,441,389.

According to the invention, it has now been found that in emulsions containing coupler compounds and with nonionic polyalkylene oxide compounds are sensitized, no improvement in sensitivity occurs. There may even be a loss in the photosensitivity of the emulsion.

However, if instead of the nonionic polyalkylene oxide as the sensitizing substance, the coupler compound containing emulsion with an ionic, d. H. a cationic polyalkylene oxide salt, e.g. B. a quaternary ammonium or phosphonium polyalkylene oxide salt or a ternary sulfonium polyalkylene oxide salt, e.g. tetraethoxylethyl bis-pyridinium perchlorate, or an anionic polyalkylene oxide compound, e.g. the carbamic acid, glutamic acid or sulfuric acid salts given below, is sensitized, the photosensitivity of the emulsion containing the coupler is substantially increased. This improvement in photosensitivity occurs regardless of the genus for development the developer substance used with the ionic polyalkylene oxide salt sensitized emulsion. The increase in sensitivity is achieved with both black and white developers as well as with color developers. About the mechanism underlying the phenomenon is little known. However, it was observed that the effect was of the kind used in the emulsion Coupler is independent, since the sensitizing effect is both in the presence of coupler compounds the phenol-hydroxyl genus as well as the reactive methylene genus is achieved.

Although through the use of the Polyalkylene Oxide Sensitized Halpgen Silver Emulsion

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America 10 December 1956

Burt Haring Carroll, Herbert Samuel Elins,
James Leo Graham, Charles Vernon Wilson,

Rochester, NY (V. St. A.),
have been named as inventors

salts in the coupler-containing emulsions the indicated increase in sensitivity is achieved this sometimes from an increase in general fogging, especially on storage of the emulsions under unfavorable temperature and humidity conditions. It can accordingly It may also be desirable to use reducing substances in the emulsions, as they are in the following examples are explained to use.

According to the invention, photographic silver halide emulsions are to be provided, the coupler » compounds included. The emulsions are made with ionic polyalkylene oxide compounds, e.g. the cationic ones quaternary ammonium and phosphonium polyalkylene oxide salts,. the ternary sulfonium polyalkylene oxide salts or -the ^ ihionischen Polyalkylenoxydverbindungen, e.g. the polyalkylene oxide carboglutarnic acid salts, polyacylene oxide bis-N-carboxymethyl carbamate salts, Polyalkylene oxide - bis - sulfuric acid salts etc., sensitized. Furthermore, according to the Invention corresponding means for reducing any obfuscation are proposed in the Use of the ionic polyalkylene oxide salt sensitizers could occur. .

According to the invention, the ionic polyalkylene oxide compounds in the silver halide photographic emulsions containing the coupler compounds immediately stored.

909 787/354

The cationic poly used in the emulsions, for example aliphatic or aromatic radicals, e.g. B. alkylene oxide salts are characterized in that they are methyl, ethyl, propyl, benzyl or phenyl,
a divalent polyalkylene oxide radical, e.g. -g _

- (CH ₂ CH ₂ O) _n CH ₂ CH ₂

CH,

CH ₃

- (CHCH ₂ O) ₇₁ CHCHg-

- (CH ₂ CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ - and

R ₄ O- (CHgCH ₂ O) ₇₁ CH ₂ CH ₂ -N ⁺ -R ₁

X " _R

where X-, η, R, R ₁ and R _{2 have} the meanings given above and R _{4 is} an alkyl or an aromatic ίο radical, ζ. B. methyl, phenyl or p-tert-octylphenyl means.

C. A structure similar to A and B, but where N is replaced by an —S ⁺ = or —P ~ = atom.

corresponding to the polyethylene oxide, polypropylene oxide and polybutylene oxide residues, to which at least one onium salt group, e.g. B. a quaternary ammonium, phosphonium or a ternary sulfonium salt group is attached. In the formulas, η denotes a positive integer of at least 4, corresponding to the smallest number of alkylene oxide units occurring in the polyalkylene oxide radical of the salt.

The quaternary and ternary polyethylene oxide salts are particularly useful as sensitizers for the emulsion effective.

These have the structure

15th

N ⁺ - (CH ₂ CH ₂ O) ₇₁ CH ₂ CH ₂

20 in which X and η have the meanings given above and Q is used to complete an organic heterocyclic nucleus, e.g. B. a pyridyl, α-picolyl or γ-picolyl ring, means required non-metallic atoms.

A. R

R ₄ O - (CH ₂ CH ₂ O) J ₁ CH ₂ CH ₂ - + N = C

R ₁ -? N ⁺ - (CH ₂ CH ₂ O) ₇₁ CHgCH ₂ - N ⁺ ς- R ₁

² in which R ₄ , n, Q and X have the meanings given above

to have.

where η is greater than 3 and X ~ is an anion or a particularly suitable cationic quaternized and

acidic radical, for example a halide, an alkyl sulfate, p-To- 35 ternary polyalkylene oxide salts, which this formula denotes luenesulfonate or perchlorate, R, R ₁ and R ₂ are:

₇ - N ⁺ - (CH ₂ CH ₂ O) ₄ - CH ₂ CH ₂ - ⁺ N -

ClO ₄

CIOI

t — C ₈ H ₁ , -

Tetra (ethoxy) ethyl bis (pyridinium perchlorate)

• O - (CH ₂ CH ₂ O) _n - CH ₂ CH ₂ - ⁺ N - ζ

"OSO ₉ CH,

pt-octylphenoxypolyethoxyethylpyridinium methanesulfonate
Derivative of an ethylene oxide and p-tert-octylphenol, in which η has an average value of 4)

/ SN ⁺ - (CH ₂ CH ₂ O) ₈ -CH ₂ CHg- + N

I I

cior

cio;

Octa- (ethoxy) -ethyl-bis- (pyridinium perchlorate)

(CHg) ₃ N ⁺ - (CH ₂ CHgO) ₈ - CH ₂ CH ₂ - + N (CH ₃ ) ₃

j

cior cior

Octa- (ethoxy) -ethyl-bis- (trimethylammonium perchlorate)

Pia "" C ₁₂ H ₂₅

(CH ₃ ) ₂ N ⁺ - (CH ₂ CH ₂ O) ₈ - CH ₂ CH ₂ - + NiCH ₃ ).,

cior cior

Octa- (ethoxy) ethyl bis (dimethyldodecylammonium perchlorate) (CH ₃ J ₂ S ⁺ - (CH ₂ CH ₂ O) ₄ - CH ₂ CH ₂ - + S (CH ₃ ) ₂

cior cior

Tetra (ethoxy) ethyl bis (dimethylsulfonium perchlorate)

-C ₈ H ₁₇ -

> - O - (CH ₂ CH ₂ O ₁₁ CH ₂ CH ₂ - + S (CH ₈ ),

~ oso _a

pt-Octylphenoxypolyäthoxyäthyldimethylsulfonium-p-toluenesulfonat (where η has an average value of 4)

> ^{- N +} - (CH ₂ CH ₂ O) ₅₁ CH ₂ CH ₂ - + N- <VIII

cior cior

Poly (ethoxy) ethyl bis (pyridinium perchlorate)

(in which the polyethyleneoxy chain is derived from a polyethylene glycol, which has a molecular weight

of about 300 has)

The quaternized polyalkylene oxide monoethers having the formulas B and E given above are used produced by corresponding poryalkylene oxide monoethers, e.g. B.

35

t CrH ₁

> - O (CH ₂ CH ₂ O) ₄ CH ₂ CH ₂ OH

or methoxypolyethylene oxide with alkyl sulfonyl halides, e.g. B. methanesulfonyl chloride, ethanesulfonyl chloride or p-toluenesulfonyl chloride. Then with tertiary bases, z. B. pyridine, picolines or trialkylamines, e.g. B. trimethylamine, Trimethylbenzylamine, drimethyllaurylamine, etc., quaternized. The quaternary salts so prepared can be converted into salts of other anions, e.g. B. in the perchlorate, can be converted to make cleaning easier.

The bis-quaternary compounds of the above-mentioned Formehi A and D are by reaction of Polyalkylene oxides of various molecular weights with the sulfonyl halides just mentioned above and subsequent quaternization prepared as above. Accordingly, polyalakylene oxides such as the polyethylene oxides having an average molecular weight of the order of about 200 to 1500 or above are used to denote the polyalkylene oxide radical to get the sensitizers.

The cationic, quaternary and ternary polyalkylene oxide sensitizers can be used in the emulsion with useful results in concentrations on the order of about 0.1 to 6.0 grams per mole of halosilver be used.

40

45 The syntheses of the following cationic materials, which can also be used in the emulsions, are given in Belgian patent 562,591

3,6,9,12,15,18,21 ^ Octoxahexacosan-l ^ o-bis- (pyridiniümmethansulfonatj.

3,6,9,12,15,18,21,24-octoxahexacosane-1,26-bis (pyridinium perchlorate).

3,6,9,12,15,18,21,24-octoxahexacosane-1,26-bis (trimethylammonium perchlorate) (Compound IV).

Polypropoxypropyl-a.cü-bis-ipyridinium methanesulfonate) - "With about 16 isopropoxy units".

Polypropoxypropyl-a, ra-bis- (pyridmium methanesulfonate) - "With about 6 isopropoxy units".

The ionic polyalkylene oxide sensitizers can be of the various genera, including e.g. B. the polyalkylene oxide-carboglutamic acid aca, N-carboxymethylcarbamate aca and polyalkylene oxy-sulfuric acid salts. These anionic materials are characterized in that they contain at least four and preferably at least thirteen divalent polyalkylene oxide radicals, z. B. Pölyäthylenoxyd, Polypropylenoxyd- and Polybutylenoxydreste contain to which at least one anionic group is attached. the

The following compounds are anionic polyalkylene oxide sensitizers, as they are useful according to the invention.

Na ⁺ -O-CH ₂ NHCO (CH ₂ CH ₂ O) ₃₅ CH ₂ CH ₂ O-CO ₂ CNHCH "Na ⁺

Poly (ethoxy) ethyl bis (N-carboxymethylearbamate) (Di-Na-Sak)

7 8

H + O- ₀

A - \ Il

Cl- / V-NHCO- ^ V-NHCOCH ₂ (OCH ₂ CHj) ₃₄ -OC-CH ₃

CH ₃ -I ) 1

γ ο

it V

Cl A ^X

C ₅ H ₁₁ (t)

C ₅ H ₁₁ (t)

Na ⁺ ^ 0OCCH ₂ NHCOO (CH ₂ CH ₂ O) ₇₅ CH ₂ CH ₂ O - CONHCH ₂ COO- Na ⁺ XI

Poly (ethoxy) ethyl bis (N-carboxymethyl carbamate) (Di-Na salt)

H ⁺ 'O ₃ S - O (CH ₂ CH ₂ O) ₇₁ CH ₂ CH ₂ O - SO ^ H ⁺ XII

Poly (ätiioxy) -äthyl-bis-sulfuric acid
{η = 35 or 75 or 8)

Na ⁺ "OOCCHNHCOO (CH ₂ CH ₂ O) ₃₅ CH ₂ CH ₂ O-CONHCHCOO ^- Na ⁺

1 I xnr

Na + ~ OOC (CH ₂ ) ₂ (CH ₂ ) ₂ COO "Na ⁺

Poly (ethoxy) ethyl bis carboglutamic acid (Na salt)

C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₂ CH ₂ CH ₂ O-CONHCH-C00 ~ Na ⁺

I xiv

Na ⁺

N-CarboIauroxypoly- (ethoxy) -äthylglutammäure (Di-Na-Salt)

Na ⁺ "SO ₃ 'SOr Na ⁺

COO (CH ₂ CH ₂ O) ₃₅ CH ₂ CH ₂ O-CO

Na ⁺ SO ₃ SOiT Na ⁺

Poly (ethoxy) ethyl bis (3,5-disulfobenzoate) (tetra sodium salt)

C ₁₈ H ₃₅ -O- (CH ₂ CH ₂ O) ₁₂ CH ₂ CH ₂ O-CONHCh-COO "" Na ⁺

i XVI

(CH ₂ ) ₂ COO "Na ⁺

N-carbooleyloxypoly (ethoxy) ethylglutamic acid (di-Na salt)

C ₁₆ H ₃₃ - O - (CH ₂ CH ₂ O) ₂₇ CH ₂ CH ₂ O - CONHCH - COO "Na ⁺

I XVII

(CH ₂ ) ₂ COO "Na ⁺

N-carbocetyloxypoly- (ethoxy) -ethylglutamic acid (di-sodium salt)

t-C ₈ H ₁₇ - /; - O (CH ₂ CH ₂ O) ₃₀ CH ₂ CH ₂ O - CONHCH - COO "Na ⁺

\ / I XVIII

CH ₂ CH ₂ COO "Na ⁺ N-Carbo-p-octylphenoxypoly- (ethoxy) -ätliylglutamic acid (Na-Salz)

O
t-C ₈ H ₁₇ - <^ ^) - O (CH ₂ CH ₂ O) ₁₂ CH ₂ CH ₂ OS-O "Na ⁺ 'χΐχ

p-tert-octylphenoxypoly (ethoxy) ethyl sulfate (Na salt)

9 10

The above anionic polyalkylene oxide (88.5%). The product solidifies on cooling Connections can be made as follows: a white wax.

Connection XII («= 8) Connection XIX

Nonethylene glycol-a ^ -disulphonic acid, 5,104 g (0.14MoI) disodium salt, nonethyleneglycol-a, copper dichloride £ q jj / \ __ (QCH CH) OH

103.5 g (0.25 mole) of nonethylene glycol were in 40 g

(0.5 mol) dissolved anhydrous pyridine and the solution were dissolved in 400 ecm dichloromethane and the solution Chilled to 0 ° C. 59.0 g io were cooled to 0 ° C. with rapid stirring. Then 16.0 g (0.14 mol) (0.50 mol) thionyl chloride slowly added, adding chlorosulfonic acid, with a strong nitrogen die Maintains temperature between 0 and 10 ° C. While the inflow was blown through the solution, which the If there were, a thick sludge forms. The slurry removes generated hydrogen chloride gas. The solution was was left overnight at room temperature and stirred for 3 hours at 10 ° C under a stream of nitrogen, then poured into 400 ecm of ice water. The product 15 The dichloromethane was under reduced pressure at 40 ° C was extracted three times with 250 cc portions of benzene. removed, leaving 115.0 g of a brown viscous syrup The extracts were dried over sodium sulfate. remain (99% yield). After removing the solvent, 65.0 g of λγτττ remain

of a dark yellow oil. The oil was fractionated. The compound XIIl

desired proportion could be at 237 to 243 ° C and 0.1 to 20 A mixture of 137 g of polyethylene oxide with a 0.2 mm print with a weight of 26.0 g (23% molecular weight of 1540 and 36 g of dimethyl isocyanate yield) to be collected. Glutarate was heated to 70 ± 5 ° C for 24 hours.

Analysis for C H O Cl · During heating, the mixture was turned against

^{18 W} _n l (-X _o , atmospheric moisture protected. The product

Calculates U IbO J ₀ ; ^ was placed in a beaker and treated by treatment

Result .... U 16, U / ₀ . _{with 4 molar parts} (^ _{5 g} ) sodium hydroxide in 35 ecm

9 g (0.02 mol) of nonethylene glycol dichloride were selectively hydrolyzed in water. The alkaline solution was 175 ecm of ethanol dissolved. 4.9 g of this solution were stirred in in portions, the temperature increasing to 60 to (0.04 mol) sodium sulfite in 100 ecm water was added. 70 ° C was maintained. The mixture then became 3 stun-man the mixture is heated to 60 to 70 ° C. for 18 hours with vigorous stirring, with occasional water boil on the reflux condenser. The aqueous ethanol was added so that the material became liquid removed, leaving a waxy solid. The material was put on a with water remains behind. This was diluted in 100 ecm hot, absolute 48% solution, which was nitrated. Dissolved ethanol. The inorganic salt was filtered off

and the filtrate was concentrated to dryness, yielding 35 compound XI

a cream-colored, waxy solid in one

Weight of 8.5 g (73%) is obtained. The absence of 80 g of polyethylene oxide with a molecular

Chloride ion was with a solution of silver nitrate weight of 4000 with 6 g of ethyl isocyanate acetate for 4 hours

checked. heated on a steam bath, with the material against

Compound XII (n = 35) was ^{protected from 4} ° atmospheric humidity. That

the product obtained from this was treated with 1.6 g of sodium

144 g (0.093 mol) of polyethylene oxide treated with a mol- xyd, which dissolved in about 5 ecm of water A weight of 1540 was in 400 ecm dichloromethane. One continues with the heating on the steam bath dissolved and the clear solution cooled to 0 ° C. Continued through a 2 hour period, with additional amounts of water sintered over Glass tip has been placed under the surface of the 45 to keep the product in a liquid state A constant stream of nitrogen is blown into the liquid. It became water until a while 21.6 g (0.185 mol) of chlorosulfonic acid was slowly added, total weight 150 g. Such a one were admitted. The solution is kept for 2 hours. The solution contains an estimated solids content of 0 ° C, with the strong nitrogen flow at around 85 g (57%).

Settlement drives out hydrogen chloride gas formed. 50 compound XVI

the solution stand overnight. The dichloromethane was

removed under reduced pressure at 45 ° C. On cooling, there were 87 g of the oleyl ether from polyethylene solidifying get 156 g (97%) of an amber colored glycol with a molecular weight of 525 and 22 g Liquid to a waxy, cream-colored solid dimethyl isocyanate glutarate for 20 hours at 60 to 70 ° C body. When left standing, the double sulfur 55 darkens while keeping away atmospheric moisture acidity slowly, but more rapidly when heated. An aqueous heated. The product obtained in this way was treated with 9 g of sodium solution the double sulfuric acid shows treated with a silver hydroxide in 25 ecm of water. The mixture nitrate solution no presence of chloride ion. was held at 60 to 70 ° C for 2 hours, with water

_ in quantities added to the mixture in

Compounds {n = / b) to keep 60 liquid state. The material was

To 200 ecm of dichloromethane, 33.5 g (0.01 mol) were finally added with water until a 42% strength was achieved Polyethylene oxide with an average molecular aqueous solution (111 g of solids with a total weight of 3000 to 3700 were added. The solution was weight of 262 g) of a product which essentially ' cooled to 0 ° C. While in the mix a strong look

When a nitrogen stream was bubbled in, 2.33 g (0.02 mol) of 65 C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) _m CONHCHCOONa

Chlorosulfonic acid was added with stirring. After 2 hours

the solution is allowed to stand at 0 ° C. in the stream of nitrogen. CH CH COONa

warm to room temperature. Remove the slide ^{a 2}

chloromethane under reduced pressure at 45 ° C. The product consists, diluted. In the formula, η has a softness that was a light amber oil, weighed 31.0 g 70 average value of 12.

OH link X The amine / - .. Cl- ' -NHCO- '' \ CH ₈ -L

11 12

Compounds XVII and XVIII Compounds for use in the emulsions

° ■ together with the ionic polyalkylene oxide compounds

Similarly, the cetyl ether from poly-fertilizer to reduce the haze on normal ether glycol and the dimethyl isocyanate glutarate the density are most effective, the azaindoles, N-carbocetyloxypolyäthoxyäthylglutamic acid (sodium 5 e.g. a 4-oxy-6-alkyl- l, 3,3a, 7-tetrazaindole, especially salt). The p-tert-octylphenyl ether of polyethylene-4-oxy-6-methyl-1,3,3a, 7-tetrazaindole, as well as 5-carbglycol and dimethyl isocyanate glutarate yielded N-carbooxy-4-oxy-1,3, 3a, 7 - tetrazaindole (USA. - Patent p-tert.-octylphenoxypolyethoxyglutamic acid (sodium 2,576,147), 1,2-bis (4-oxy-6-methyl-1,3,3a, 7-tetrazaindole salt). In the first case, the average molecule contained 5-yl) -ethane, 1,2,3,4-tetrakis- (4-oxy-6-methyl-1,3,3a, 7-th section 27 CH ₂ CH ₂ O units. In the latter case, io trazaindol-2-yl) -butane, 2-amino-5-carboxy-4-oxy-1,3,3a, an average of 30 units. 7-tetrazaindole, 4-oxy-2 - /? - oxyethyl-6-methyl-1,3,3a, 7-te-

trazaindole, 5-carbethoxy-4-oxy-1,3,3a, 7-tetrazaindole (U.S. Patent 2,576,147), 7-oxy-l, 2,3,4,6-pentazaindole, 2,4-dioxy-6-methyl-1,3a, 7-triazaindole, 4-oxy-2y-15 oxypropyl-6-methyl-1,3,3a, 7-tetrazaindole and 4-oxy-2- (4-pyridyl) -6-methyl-1,3,3a, 7-tetrazaindole.

Other azaindole compounds which can be used for this purpose are disclosed in U.S. Patents 2,716,062, NH ₂ 713 541, 2,735,769, 2,743,181, 2,835,581, 2,756,147,

20 2 743 180 as well as from the »Zeitschrift für Wiss. Phot. «47., pp. 2 to 28 (1952), known. Furthermore, according to the invention still a number of azaindole compounds. . which have not yet been presented

⁵ ti \> has been described, for the same are in the following

25 section gives some examples. (However, the increase in sensitivity will nonetheless be achieved with the Use of the ionic polyalkylene oxide compounds even in the absence of such antifoggants was dissolved in absolute acetone. An equivalent of that obtained.)

acidic chloride CH ₃ COO (C ₂ H ₄ O) ₃₄ CH ₂ COCl became 30 4-oxy-6-methyl-1,3,3a, 7-tetrazaindole

added to the solution at room temperature. It was

Stirred for 10 minutes. Then 1 equivalent was a mixture of 108.8 kg (800 mol) of aminoguanidine

Quinoline added. The reaction mixture was stirred and refluxed for 1.5 hours under bicarbonate and 44.8 kg (877 mol) of formic acid (90%). The reaction was cooled in a jacketed mixture overnight. The quinoline hydrochloride, 100 gallon, glass-lined, refluxed vessel was filtered off. The acetone was heated with cooling. The vapor pressure was removed to 1.75 atmospheres reduced pressure. The residue was turned off. In the morning the reaction mixture was diluted 60:40 benzene-ligroin (boiling point 100 to 110 ° C.) with 60 liters of hot water. Furthermore, they crystallized out. The product, slowly reaching 10.4 kg (98 mol) of anhydrous sodium carbonate in the form of white needles, had a melting point of 49 to 50 ° C. 40 added. The batch was for 3 hours at 90 to 100 ⁰ C. The amine is heated from the USA. Patent 2,688,544, and then concentrated under reduced pressure until no known. Water more distilled over (about 4 to 5 hours). Of the

The acid chloride was produced in that the excess residue was a mushy white solid. He A shot of the polyglycol with metallic sodium was cooled under reduced pressure overnight. Deals became. The sodium salt was mixed with chloroacetic acid- 45 then 144 kg of glacial acetic acid and 150 kg (1150MoI) acid and then added with acetic anhydride and ethyl acetoacetate. The mix was Thionyl chloride implemented. Heated under reflux for 3 hours. The run

was cooled to room temperature and placed in a

Compound X Analysis: 150 gallon stainless steel tank dripped.

C ₁₀₂ JJ ₁₇₆ Cl ₂ N ₂ O _40:50 The liquids were separated by filtration and

TiWrWt ΓΏ =! ti «? ΓΠί ΝΠ »ί · ^{canceled for} recovery. The solid became

ürrecimet .... LW ₁ S ₁ Ά &, ζ, (Λά, ό j> \ lä / _0> ^ _{30 GaUonen} alcohol slurried, nitrated and

found .... C56.7, H8.5, Cl3.4, N 1.5 "/". centrifuged. Washing with fresh portions

Alcohol was repeated until the color stopped

Compound II _gg changes and the acetic acid odor becomes minimal. the

A solution of 42.6 g (0.1 mol) of white to yellow-pink needles, cooled to 0 ° C., was dried on paper trays in p-tert-octylphenoxytetraethoxyethanol and 11 g in a warm air oven. The melting point (0.109 mol) of triethylamine (anhydrous) in anhydrous is 285 to 287 ^° C. The yield was 98 kg. This is ethyl ether were in portions 11.5 g (0.1 mol) of methane 81.5% of the theoretically achievable amount of 120 kg.
sulfonyl chloride added. The mixture became thoroughly 60

shaken and stand for 3 days at room temperature- 7-oxy-l, 2,3,4,6-pentazaindole

calmly. The triethylamine hydro-

chloride was removed by filtration. When removing a solution of 50 g (0.22 mol) 4,5-diamino-3-oxy-

of the ether remain 50 g of a clear, colorless liquid pyrimidine sulfate (J. Am. Chem. Soc, 74, p. 411, 1952) and return. 65 18 g sodium nitrite in 300 ecm 10 "/ jiger sodium hydroxide

A mixture of 5.03 g (0.01 mol) of the above liquid solution was slowed down by adding acetic acid speed and 0.8 g (0.01 mol) of pyridine was acidified on a steam. The mixture was left on for 30 minutes bath heated for 18 hours. The steam bath, which is fairly soluble in water, is stirred and left in a refrigerator overnight The resulting liquid is essentially p-tert.-octyl-cooled. The solid was on a Büchner funnel phenoxytetraethoxyethylpyridinium methanesulfonate. 70 collected and from 5% hydrochloric acid and

then recrystallized from water, 30 g being refluxed. The hot solution was

(99%) of the product achieved.
Analysis for C ₄ H ₃ N ₅ O:

Calculated .... C 35.0, H 2.7%;

Result C 35.0, H 2.7%.

2,4-Dioxy-6-methyl-1,3a, 7-triazaindole

filtered and then cooled. A white solid with a melting point of 257 to 260 ° C. is obtained in a yield of 12 g. A second recrystallization from water gives 6.5 g (10%) of the pure anhydrous material with a melting point of 262 to 263 ^° C.

A solution of 18.4 g (0.8 mol) of sodium in 500 ecm analysis (C ₈ H ₁₀ N ₄ O ₂ , 194); 23.4 g (0.2 mol) of io guanidoacetic acid were added to anhydrous methanol. Then 52 g (0.4 mol) of ethyl acetoacetate were added. The mixture was heated 20 hours under reflux, concentrated, washed with ether and added ° / _o hydrochloric acid in 5 until the solution has a _pH value of 15 is 1 (about 600 cc of acid). The insoluble material was collected and recrystallized from water, 5 g of the product having a melting point of 310 ^° C. being obtained.

Calculated .... C 49.4, H 5.2, N 28.9%:
Result C 49.7, H 4.9, N 27.2%.

1,2,3,4-tetrakis- (4-oxy-6-methyl-1,3,3a, 7-tetrazaindol-2-yl) butane

20 1,2-bis-4-oxy-6-methyl-1,3,3 a, 7-tetrazaindole-

5-yl-ethane

A mixture of ethyl a, a'-diacetyl adipate (29 g) (H 518-20) and 3-amino-1,2,4-triazole (17 g) in 100 ecm acetic acid was refluxed for 4 hours. The solid was collected and digested with 800 ecm boiling dimethylformamide, then filtered while hot and washed with ethanol. ^{A product with a melting point above 310 °} C. is obtained in a yield of 20 g (plus 2 g from the filtrate).

Analysis for C ₁₄ H ₁₄ N ₈ O ₂ :

Calculated .... C 51.5, H 4.3, N 34.4%;

Result C 51.5, H 4.7, N 34.5%.

35 195 gl, 2,3,4-tetrakis- (carbohydrazido) -butane (prepared by reacting 1,2,3,4-tetracarbomethoxybutane with hydrazine), 340 g 2-ethylmercapto-4-oxy-6-methylpyrimidine, 100 1 cm glacial acetic acid and water were refluxed for 24 hours and then filtered.

This crude 1,2,3,4-tetrakis- (4-oxy-6-methyl-2-pyrimidylhydrazino) butane was refluxed with 11 glacial acetic acid and 50 ecm of concentrated hydrochloric acid for 24 hours, then cooled to ^{0 ° C. and} filtered. After recrystallization from water, 39 g of solid 6-methyluracil with a melting point are obtained

with that of an authentic sample 6096 AE). the combined mother liquors were evaporated and recrystallized from water. One obtains in this way if necessary 18 g of a white solid with a melting point of 263 to 265 ° C. The infrared spectrum of this solid differs from that of 6-methyl-uracil and of 2,6-dimethyl-4-oxy-1,3,3a, 7-tetrazaindole. The analytical numbers agree pretty well with that Tetrahydrate. However, there will be a slight incomplete

2-Amino-5-carboxy-4-oxy-1,3,3a, 7-tetrazaindole

A mixture of guanazole (25 g) and diethyl ethoxymethylene malonate (56 g) in 150 ecm acetic acid

Heated under reflux for 4 hours. The 2-amino- 4 ° _{constant conversion of the} carboxyl to the tetrazaindole-5-carbathoxy-4-oxy-l, 3,3a, 7-tetrazamdol was collected on a portion of the supposed Büchner funnel and dried (46.5 g, 83%) .

The ester
acid

45

(25 g) and 250 ecm of 1N hydrogen chloride heated under reflux for 4 hours. The solid was collected and recrystallized from water, 9 g of the acid being obtained (melting point above 300 ^° C.).

Analysis for C ₆ H ₅ N ₅ O ₃ :

Calculated .... C 37, H 2.5, N 35.9%;
Result C 37.9, H 2.8, N 35.6%,

4-Oxy-2- / 3-oxypropiohydrazido-6-m ^ ethylpyrimidine

A mixture of 246 g / 9-oxy-propiohydrazide (267MoI, 50% excess) (JACS, 73, p. 3168), 300 g of 2 - ethyl mercapto - 4 - oxy - 6 - methyl - pyrimidine (1.77 mol) (Ber., 86, p. 1403), 11 ethanol and 11 water were refluxed for 18 hours. The crystallization begins after about 15 hours, after which you cook for another 24 hours (a total of 42 hours). It is cooled to 25 ° C and nitrided 212 g (57%) of a product having a melting point 223-226 ° C. After recrystallization from water, the melting point rises to 233-234 ⁰ C. Ss

4-Oxy-2- / S-oxyethyl-6-methyl-1,3,3a, 7-tetrazaindole
63 g of hydrazide were analyzed for 20 hours in 500 ecm glacial acetic acid (C ₂₈ H ₂₆ N ₁₆ O ₄ 4H ₂ O, 772):

Calculated .... C 46.5, H 4.7, N 31.0%;
Result C 48.9, H 5.0, N 27.5%.

The production of halogen silver emulsions generally involves three separate operations:

1. the emulsification and digestion or ripening of the halogen silver,

2. the removal of aqueous soluble salts from the Emulsion generally by washing,

3. the second digestion or subsequent ripening to achieve increased sensitivity (cf. Mees, "The Theory of the Photographic Process," 1942, p. 3).

The sensitizing substances can now be added in any of these stages. Preferably they will added after the final digestion.

The photographic emulsions used in accordance with the invention are generally those which can be developed Genus. The best results are achieved with gelatine-bromiodide-silver emulsions. It can however, emulsions of the most diverse halogen

acid and 50 ecm concentrated hydrochloric acid 70 types of silver can be used.

15 16

The emulsions can by themselves complement one of the usual sensitivities of the emulsion layers Process in addition to creating awareness with the color. With a standard color film, you can do so ionic polyalkylene oxide compounds chemically sensitive one or more of the differentially sensitized be bilized. The emulsions can be made with natural emulsion layers with the ionic polyalkylene oxide active Gelatin to be digested. Sulfur salts can also be sensitized. The emulsions can contain compounds For example the one from the USA. Patent for example for the red area, green area and Writings 1 574 944, 1 623 499 and 2 410 689 known blue region of the spectrum and sensitive in this Sulfur compounds are added. The Emul order arranged one above the other on a carrier Sions can also be mixed with salts of precious metals, e.g. B. be. The emulsions then contain a blue-green, those of ruthenium, rhodium, palladium, iridium and purple or yellow dye-producing couplers Platinum. These precious metals include bonds. Between the blue-sensitive emulsion all the VIII. Group of the Periodic Table of the layer and the green-sensitive emulsion layer Elements and have an atomic weight over 100. preferably a yellow filter layer, ζ. Β. from yellow Typical such compounds are ammonium chloro-colloidal silver, arranged.

palladate, potassium chloroplatinate and sodium chloropalladite, 15 As those with the ionic polyalkylene oxide salts of the the invention-sensitized emulsion layers used for sensitization in lesser amounts become couplers can contain veil connections worth mentioning, they can by means of the known protective effect required, as z. B. from the USA.- Process easily for the immediate achievement of color patent specification 2,448,060 is known. The compounds negative or positive images according to the known ones however, they can also be treated as antifoggants in reverse procedures. After the first bigger one Quantities are used, as from the USA.- the emulsion is thinned out by means of a template Patents 2,566,245 and 2,566,263 are known. a p-phenylenediamine type developer a colored one

The emulsions can still be produced with gold salts, such as negative according to the original. In a similar way known from U.S. Pat. No. 2,399,083, chemically becomes when the development of the emulsion layer be sensitized or with gold salts, as from the USA - 25 first with a non-dye-producing patent specification 2 597 856 and 2 597 915 known, stabilizing winder with subsequent reverse exposure of the remainder be. Suitable compounds are potassium chloraurite, borrowed halogen silver and subsequent color developing potassium aurithiocyanate, Potassium chloroaurate, auritrichloride treatment is carried out, a colored positive is achieved, and 2-aurosulfobenzothiazole methchloride. The ones with the ionic polyalkylene oxide derivatives

The emulsions can also contain couplers used with reduction sensitized emulsion layers agents, e.g. stannous salts (USA.-Patent No. 2,487,850), are the usual known color couplers which are produced with the Polyamines, e.g. B. Diethylenetriamine (U.S. Patent Specification of the oxidation product of primary aromatic amino-2 518 698), polyamines, e.g. B. Spermin (USA.-Patent halogen silver color developing agents attributed to dyes 2 521 925), or bis- (jS-aminoethyl) sulfide or collected. Such couplers are, for example their water-soluble salts (USA.-Patent 2521926) 35 phenol derivatives according to USA.-Patents 2266452, be chemically sensitized. 2 362 598, 2 589 004, 2 474 293, 2 521 908, 2 423 730 and

As already mentioned, the use of the German patent 1 003 586; Pyrazolone ionic Polyalkylene oxide derivatives for sensitizing derivatives according to US Patents 1 969 479, of the emulsions any undesirable obscuration under- 2 369 489, 2 600 788, 2 618 641, 2 511231 and the and to normal density by using reactive methylene couplers with open chain according to the various compounds, e.g. the mercury salts USA patents 2,298,443, 2,652,329, 2,407,210, U.S. Patents 2,728,663, 2,728,664,2271,238, and 2,875,057 and 2,728,665. Furthermore, emulsions can also contain colored, dye-producing couplers the organic mercury compounds known to contain, as they are from the USA patents 2,521,908, made German patent application E 8089 IVa / 57b 45 2 706 684, 2 455 169, 2 694 703, 2 455 170 and 2 453 661 be used. are known.

Furthermore, the polyalkylene oxide salts can be The couplers can be used in the emulsion layers by means of

holding emulsions other stabilizing substances, an oily coupler solvent according to the method e.g., cadmium chloride, cadmium nitrate, cobalt nitrate, according to U.S. Patents 2,304,940 and 2,322,027 Manganese chloride, manganese sulfate, zinc chloride, zinc nitrate 50 are distributed. If, however, as may be the case, or zinc sulfate, can be added. the couplers solubility enhancing groups, e.g. B.

The chemical sensitizers and the other SO ₃ groups, which make them alkali-soluble, can be omitted in the most varied of sets of the oily coupler solvent. The photographic emulsions can be used. These couplers can then be added to the emulsion from aqueous emulsions as photosensitive compounds. Solutions in the form of their alkali metal salts. B. the bromide, iodide, are.

Chloride or halosilver mixtures, e.g. B. Chlorobromine- The following examples serve to further illustrate

silver or silver bromide. the invention.

The dispersant for the halogen silver can be Example 1

Gelatin or other hydrophilic material, e.g. B. 60

Collodion, egg white, cellulose derivatives or a synthetic resin, this example illustrates the well-known chemical

be. Sensitization effect of non-quaternized poly-

Since the alkylene oxides with the ionic polyalkylene oxide salts.

sensitized and coupler-containing emulsions A negative bromiodide-gelatin emulsion based on

particularly suitable for color photographic purposes, 65 optimum speed with a mixture of one they will generally form the emulsion layers of a labile sulfur compound and a soluble gold salt multilayer color films. These layers have been set in, were divided into two parts, the usual way to the basic areas of the visible. Each part was sensitized at 40 ⁰ C the same amount of a spectrum differentiated. They contain optical sensitizing dye added, which coupler compounds, which dye images one of the 70 sensitize the emulsion in the range of 5000 to 6000 AU

sated. Each part was then put on one before being potted appropriate carrier as indicated below.

a) Control sample: no further treatment.

b) Before casting 1.69 g per mole of silver halide of the oleyl ether of a polyethylene oxide of a molecular weight of about 1500 added.

The cast layers were tested sensitometrically by exposing them for ₅₀ seconds through a green filter using a lamp of the studio type on a sensitometer with an intensity scale (e.g. "Eastman Ib") and for 10 minutes at 23.9 ° C in an Elon hydroquinone -Developers were developed with discontinuous stirring. The following results were achieved:

The negative developer had the following composition:

Water at 32 ° C 1.0 1

Sodium hexametaphosphate 2.0 g

N-methyl-p-aminophenoIsulf at 6.0 g

Dried sodium sulfite 50.0 g

Hydroquinone 6.0 g

Sodium carbonate monohydrate 35.0 g

Potassium bromide 2.0 g

Sodium thiocyanate 1.5 g

0.5% solution of 6-nitrobenzimidazo nitrate 12.0 ecm

O, l ° / _O by weight solution of potassium iodide 10.0 cc

sample Sensitivity* Minimal
optical density a)
b) Control sample
+ 10 0.06
0.09

The color developer solution had the following composition:

Water from 21 to 27 ⁰ C 1.0 1

Benzyl alcohol 6.0 ecm

Sodium hexametaphosphate 2.0 g

Dried sodium sulphate 5.0 g

Trisodium phosphate 40.0 g

Potassium bromide 0.25 g

* The sensitivity is expressed in the system of measurement 100 (1 - log E) , where E is the exposure in meter candle seconds necessary to achieve a silver blackening of 0.2 above the

minimal blackening is required in the treated film. 25 0.1% solution of potassium] 'odide 10.0 CCm

Sodium hydroxide 6.5 g

A similar effect is achieved when the development of 4-amino-N-ethyl-N - [^ - methane-sulfonamido-

ethyl] m-toluidine sesquisulfate monohydrate 11.33 g

Ethylene diamine sulfate 7.8 g

- 1.5 g

is carried out with a developer of the p-phenylenediamine type.

The developer used above had the same composition as citrazinic acid (2,6-dioxyisonicotinic acid) as that in Example 2 below
mentioned negative developer.

Example 2

35

This example illustrates the mentioned effect of sensitizing a coupler-containing emulsion with a non-ionic polyalkylene oxide.

A silver bromide gelatin negative emulsion, which is optimized for sensitivity with a mixture of a unstable sulfur compound and a soluble gold salt, was divided into two portions. Everyone Portion was added at 40 ° C an equal amount of a dye that the emulsion to the area of 5000 to 6000 AU sensitized. Furthermore were the same Amounts of a purple dye-forming color coupler of the pyrazolone genus, namely l- (2,4,6-trichlorophenyl) - 3 - [3 '- (2 ", 4" - di -1 - amyl - phenoxy - acetamido) benzamido] -5-pyrazolone added, which was dispersed in a high-boiling lyophobic solvent. Each portion was then treated as indicated below prior to potting on a suitable support.

a) Control sample: no further treatment.

b) 1.69 g per mole of silver of the oleyl ether indicated above of polyethylene oxide were added before potting.

The layers produced in this way were tested sensitometrically by using them in the same way as the layers The above silver bleach solution had the following composition:

Water at 32 ° C 1.0 1

Potassium dichromate 5.0 g

Potassium ferricyanide 70.0 g

Potassium bromide 20.0 g

The above fixing baths had the following composition:

Water at 27 ° C 1.01

Sodium thiosulfate 150.0 g

Sodium bisulfite 20.0 g

The following Results were achieved: sample Sensitivity** a)
b) Control sample
4th Maximum
optical density Control sample
+ 0.10

** The sensitivity is in the measurement system. 100 (1 - log E) , where E is that exposure in meter candle seconds which is necessary to achieve a total dye density of 1.0 with suitable lighting after handling.

From the above data of the list it can be seen

exposed according to Example 1 and on a color positive below 6o that sample b) has a higher maximum optical density

Using a commercially available paint process carried out at 23.9 ° C, developed:

1. Negative development 10 minutes

2. Reverse light exposure

3. Color development 15 minutes

4. Silver bleach 8 minutes

5. Fixate 3 minutes

than the sample a), since the lower sensitivity of b) is due to the fact that in the negative development less halogen silver was developed.

Example 3

In this example, this is achieved by sensitizing the coupler-containing emulsions with cationic polyalkylene oxide salts the increase in sensitivity achieved in accordance with the present invention.

909 787/354

A silver bromide gelatin negative emulsion, which had been adjusted for optimum sensitivity with a mixture of a labile sulfur compound and a soluble gold salt, was divided into three portions. An equal amount of an optical sensitizing dye, which sensitized the emulsion in the range from 5000 to 6000 AU, was added to each portion at 40 ^{° C.} Furthermore, equal amounts of a magenta dye-forming coupler of the pyrazolone type (such as Example 2), which was dispersed in a high-boiling lyophobic solvent, were added. Each portion was then treated as indicated below prior to potting on a suitable support.

a) Control sample: no further treatment.

b) Before casting, 2 g per mole of halosilver were polyethoxyethyl bis-pyridinium perchlorate (the above indicated compound VIII, wherein the carbon chain had a molecular weight of over 1500) was added.

c) Before casting, 2 g per mole of halogen silver were tetra (ethoxy) ethyl bis (pyridinium perchlorate) (the Compound I) given above was added.

The layers obtained in this way were checked sensitometrically by exposing them to form one Color positive in the same way as the layers according to Example 2 were treated further. The following results were achieved:

sample Sensitivity*** Maximum
optical density a)
b)
c) Control sample
+ 10
+ 16 Control sample
-0.04
-0.16

and developed into a color negative in a developer SD-30. Its composition is in the »Journal of the Society of Motion Picture and Television Engineers ", Vol. 61, No. 6, p. 674, December 1953. Following Results were obtained:

*** The sensitivity is in the same system of measurement as given in Example 2.

The increased sensitivity of samples b) and c) clearly shows the effect of the polyalkylene oxide salt sensitizers according to the invention when taken together can be used with the coupler compound.

Example 4

A silver bromide gelatin negative emulsion, which had been digested for optimal sensitivity with a mixture of a labile sulfur compound and a soluble gold salt, was divided into two portions. The same amount of an optical sensitizing dye, which sensitizes the emulsion in the range from 5000 to 6000 AU, was added to each portion at 40 ^{° C.} Furthermore, equal amounts of a magenta dye-forming coupler of the pyrazolone type which was appropriately dispersed in a high-boiling iyophobic solvent were added. Each portion was then treated as indicated below prior to potting on a suitable support.

a) Control sample: no further treatment.

b) Before casting, 2.0 g per mole of halosilver were added the compound III given above was added.

The layers produced in this way were tested sensitometrically by exposing them for ¹ Z ₅₀ seconds through a yellow filter using a studio lamp (3150 ° K) on a sensitometer with an intensity scale (eg "Eastman Ib")

sample Sensitivity* Minimal
optical density a)
b) 215
254 0.27
0.44

* The sensitivity is expressed in the measurement system 100 (1 - · log E) , where E is the exposure in meter-candle seconds which is necessary to achieve a purple dye density in the treated film against green light of 0.20 above the minimum optical density for green light .

In the list, the comparatively higher minimum optical density value of 0.44 can be seen, that the use of an anti-fog agent in the sensitized with the polyalkylene oxide salts Emulsions to reduce fogging, as indicated, is useful.

Example 5

A bromoiodine over gelatin negative emulsion made with a mixture of a labile sulfur compound and a soluble gold salt digested to optimum sensitivity was divided into two portions.

The same amount of an optical sensitizing dye, which sensitizes the emulsion in the range from 5000 to 6000 AU, was added to each portion at 40 ^{° C.} Furthermore, equal amounts of a magenta dye-forming coupler of the pyrazolone type (Example 2), which was appropriately dispersed in a high-boiling lyophobic solvent, were added. Before being poured onto a suitable carrier, each portion was further treated as described below:

c) Control sample: no further treatment.

d) 2.0 g per mole of halosilver of compound III were added.

The layers produced in this way were ^{exposed for 1} hour ₅₀ seconds using a 500 watt tungsten filament lamp in a sensitometer with an intensity scale. The light was attenuated by a green filter and a 0.6 neutral density filter. The exposed layers were treated as follows:
50

1. 10 minutes development at 23.9 ° C with discontinuous Stir in the negative developer according to Example 2.

2. Fixation in an acidic thiosulphate solution for 5 minutes. 3. Wash in running water for 10 minutes.

4. Rehalogenization 10 minutes in a bath that is out 70 g potassium ferricyanide and 20 g potassium bromide per liter of distilled water.

5. Wash in running water for 10 minutes.

6. Further treatment to a color negative, as described for the layers in Example 4.

The following Results were achieved: 65 sample Sensitivity* c)
d) Control sample
+ 24 Minimal
optical density 0.07
0.27

* The sensitivity is given in the same measurement system as in example 4.

As in Example 4, the comparatively higher minimum blackening of 0.27 indicates that the use an anti-fog agent appears to be appropriate in the emulsion.

Example 6

A silver bromide gelatin negative emulsion was made with a mixture of for optimal sensitivity a labile sulfur compound and a soluble gold salt and digested with an optical sensitizing dye treated, which sensitizes the emulsion in the range of 6000 to 7000 AU. Farther became a cyan dye-forming coupler at 40 ° C, namely (6- [a- (4- [a- (2,4-Di-t-amylphenoxy) butyramido] -phenoxy) -acetamido] ^^ - dichloro-S-methylphenol) added appropriately dispersed in a high-boiling lyophobic solvent. the The emulsion was divided into two equal parts and treated further as follows.

e) Control sample: no further treatment before Shed.

f) Before casting, 4.0 g per mole of halosilver of the abovementioned compound III were added.

The layers produced in this way were tested sensitometrically by exposing them for ¹ Z ₅₀ seconds through a yellow filter using a light source of daylight quality on a sensitometer with an intensity scale (e.g. "Eastman Ib") and using the reverse color method given in Example 2 to a positive were developed.

The following Results were achieved: Maximum
optical
density Minimal
optical
density sample Sensitivity * * * 2.58
1.9 0.05
0.05 e)
f) relation
+ 38

*** The sensitivity of the layers treated in the reverse process is expressed in the system of measurement 100 (1-log E) , where E is the exposure in meter candle seconds which is required to achieve a total color density of 1.0 with suitable lighting after the layers have been treated is.

sample Sensitivity * * * Maximum
optical
density Minimal
optical
density G) Control sample
+ 58 2.34
1.70 0.05
0.05

Example 8

In the same manner as in Example 6, emulsions were prepared as follows:

i) As for emulsion e) in Example 6.

j) As emulsion f) in Example 6 plus 8.0 g per mole of halosilver 4-oxy-6-methyl-1,3,3a, 7-tetrazaindole and 4.0 g per mole of halogen silver 1,2-bis (4-oxy-6-methyl-1,3,3a, 7-tetrazaindol-5-yl) ethane, which were added before potting.

The layers produced in this way were exposed and further treated similarly to those in Examples 6 and 7. The following results were achieved:

sample Sensitivity*** Maximum
optical
density Minimal
optical
density 20 Ϊ)
i) relation
+ 58 2.20
1.60 0.07
0.07

*** The sensitivity values were determined as in Example 6.

Layers e), f), g), h), i) and j) of Examples 6, 7 and 8 were _{incubated in a sealed metal foil container for 7 days at 49 ° C. and 50 ° / 0} relative humidity. After exposure and development as described in Example 6, the following results were obtained:

Sensitivity * * * Maximum Minimal sample optical optical Control sample density density 35 ⁶ < ^e ) 2.50 0.05 6, f) Control sample 0.20 0.05 7, g) + 60 2.08 0.06 7, h) Control sample 1.62 0.05 8, i) + 55 1.91 0.07 40 8, j) 1.50 0.06

The relatively low value for the maximum density of 1.9 indicates that this is due to the fogging a larger amount of halogen silver was developed in the negative developer, so that less Halogen silver remains to achieve the dye image.

Example 7

In the manner described in Example 6, emulsions were prepared as follows:

g) Emulsion, similar to emulsion e) according to Example 6

without antifoggants,
h) Emulsion, similar to f) from Example 6, but with 16.0 g per mole of halosilver of 4-oxy-6-methyl-1,3,3a, 7-tetrazaindole.

The following results were obtained after exposure and after further treatment, as described in Example 6, achieved:

*** The sensitivity was determined on the same basis as in the example 6 determined.

The data in the tables show pronounced evidence of the use of the cationic polyalkylene salt sensitizer The increase in sensitivity that can be attributed to storage at elevated temperatures and moisture is retained. No sensitivity values were found for samples 6, e) and f) indicated in the list as none of the emulsions contained an anti-fog agent. Emulsion 6, f) developed accordingly, a rather high fog upon incubation, so that the sensitivity does not could be determined. Samples 7, h) and 8, j), which contain both the polyalkylene oxide salt sensitizer and containing the azaindole antifoggant had sensitivity values 60 and 55 units higher than control samples 7, g) and 8, i).

Further stabilizing compounds such as the mercury compounds given above can be used in a similar manner and azaindole compounds to reduce fogging of the sensitized emulsions normal density can be used.

Example 9

A silver bromide gelatin negative emulsion was made with a mixture of for optimal sensitivity a labile sulfur compound and a soluble gold salt and digested with an optical sensitizer that sensitizes in the range of 6000 to 7000 AU. Then at 40 ° C it became a cyan dye generating compound 6- [a- (4- [a- (2,4-di-t-amylphenoxy) -

butyramido] -phenoxy) -acetamido] ^ y phenol added, which in a high-boiling lyophobic solvent was appropriately dispersed. The emulsion was divided into several equal parts and treated as follows before potting:

a) Control sample: no further treatment.

b) Before casting, 4.0 g per mole of halosilver polyethoxyethyl-γ , ca - bis - carboglutamic acid (disodium salt, compound XIII) were added.

c) Before casting, 4.0 g of compound XIII and 4.0 g of oxy-6-methyl-1,3,3a, 7-tetrazaindole were added at 40.degree (AZA) was added per mole of halogen silver.

d) Before casting, 4.0 g Polyäthoxyäthyly, w-bis-N-carboxymethylcarbamate, Disodium salt (compound XIII) was added per mole of halosilver.

e) Before potting, 4.0 g of Compound XI and 4.0 g of AZA were added per mole of halogen over.

f) Before casting, 4.0 g of polyethoxyethyl-co-double sulfuric acid were added (Compound XII) was added per mole of halosilver.

g) Before casting, 4.0 g of compound XII and 4.0 g of AZA were added.

The layers produced in this way were tested sensitometrically in that they were exposed for ¹ Z ₅₀ seconds through a red filter using a lamp of daylight quality on a sensitometer with an intensity scale ("Eastman Ib") and developed.

Method A: To a silver negative in the first developer of the procedure of Example 2. Procedure B: To a reversal color positive in the procedure according to example 2.

The following results were obtained: Method A

sample sensitivity Minimal
optical density A. relation relation B. - - C. + 12 + 0.04 D. + 08 + 0.06 E. + 16 + 0.07 F. + 04 + 0.04 G + 16 + 0.04

40

45

Procedure B

sample sensitivity Maximum
optical density A. relation relation B. + 23 - 0.28 C. + 30 - 0.30 D. + 35 - 0.44 E. + 38 - 0.50 F. + 06 - 0.24 G + 26 - 0.24

The following results were achieved: sensitivity Maximum
optical density sample relation relation A. + 04 - 1.08 B. + 40 - 0.08 C. - 08 - 1.72 D. + 51 - - 0.36 E. + 20 - 0.53 F. + 36 + 0.17 G

The data demonstrate the effectiveness of the anionic polyalkylene oxide sensitizers in increasing sensitivity and in combination with Azaindole compound in terms of maintaining maximum optical density upon incubation.

Example 10

A silver bromide gelatin negative emulsion was made with a mixture of for optimal sensitivity a labile sulfur compound and a soluble gold salt. At 40 ° C it became a yellow dye generating couplers N-4-benzoylacetamidobenzene- (sulfonyl) -N- (γ-phenylpropyl) -p-toluidine added which was suitably dispersed in a high boiling lyophobic solvent. The melt was divided into three equal parts and treated as follows.

a) Control sample: no further treatment.

b) Before potting, 1 g per mole of halogen was added over the pyridinium compound TII at 40 ° C.

c) Before casting, 1 g per mole of halogen over compound III and 4 g of 4-oxy-6-methyl-1 were added at 40 ° C , 3,3 a, 7-azaindole added.

The layers produced in this way were tested sensitometrically in the same way as in Example 4. The following Results have been achieved.

sample sensitivity Δ minimum
optical density a)
b)
c) Control sample
+ 24
+ 20 Control sample
+ 0.12
+ 0.04

The layers were sealed in metal foil containers and incubated for 7 days at 49 ° C and 50% relative humidity and then turned into a color negative in the above indicated manner (Example 4) developed. The following results were achieved:

sample sensitivity Δ minimum
optical density a)
b)
c) Control sample
- 46
+ 44 Control sample
+ 0.46
+ 0.01

The layers were kept in sealed metal foil containers for 7 days at 49 ° C and 50% relative humidity and then tested again in method B.

55

So

The values of +44 and -0.01 show that the

Sensitivity is retained and that at the

Incubation of the stabilized sample c) a slight haze occurs.

Example 11

An emulsion melt was prepared as described in Example 6. The melt was in three divided equal parts and treated as follows:

a) Control sample: no further treatment.

b) Before casting, 4 g per mole of halosilver of compound III were added.

c) Before casting, 4 g per mole of halogen silver of compound III and 4 g per mole of halogen silver were added 1,2-Bis- (4-oxy-6-methyl-1,3,3a, 7-tetrazaindol-5-yl) -ethane was added.

These layers were exposed in a manner similar to Example 6 and developed into a colored positive. The following results were obtained:

a) Control sample: no further treatment.

b) Before casting, 2 g per mole of halosilver polyethoxy - α, ω - bis - pyridinium perchlorate (VIII, η = 35) were added.

c) Before casting, 2 g per mole of halosilver of bis (pyridinium perchlorate) I were added.

The layers were tested sensitometrically in the same manner as those in Example 6. The following Results were achieved:

sample sensitivity Δ maximum
optical density a)
b)
c) Control sample
+ 15
+ 23 Control sample
- 0.50
- 0.50

sample sensitivity Δ Maximum density a)
b)
c). Control sample
+ 10
+ 16 Control sample
-0.16
-0.04

The layers were incubated for 3 days at 49 ° C and 50% relative humidity and in the same manner as treated the fresh layers. The following results were achieved:

sample sensitivity Δ Maximum density a)
b)
c) Control sample
+ 0.32 Control sample
- 2.10
-1.0

Example 14

The above anionic coupler compound X was made into samples of one prepared as in Example 2 Emulsion without coupler added in the amounts given below. The samples then became one colored positive according to the method given in Example 2 and a colored negative according to the Procedure according to Example 4 further treated with the following results:

Example 12

Emulsion melts similar to Example 6 were used manufactured and divided into several equal parts and how. follows further treated:

a) Control sample: no further treatment.

b) Before casting, 2 g per mole of halosilver were p-t-octylphenoxydiäthoxy - äthylpyridiniummethansulfonat (II) added.

c) Control sample for d).

d) Before casting, 2 g per mole of halogen silver were added to polypropylene glycol-a.cü-bis-pyridinium methanesulfonate derived from a polypropylene glycol with a molecular weight of 425.

These layers were exposed in the same manner as in Example 4 and developed into a colored negative. The following results were achieved:

Procedure according to Δ log E Procedure according to Δ log .E Example 2 modification Example 4 modification gX / mole AgX sensitivity +15 log E. sensitivity +08 Log E Δ £> + 18LogE ΔΖ> + 08LogE maximum minimal 2 - 0.16 0.02 4th -0.20 0.12

Example 15

The ionic compounds XI and III were added to emulsions prepared as in Example 2 and containing the couplers as disclosed in U.S. Patents 2,706,685 and 2,694,718 are.

After treatment according to the procedure of Example 1, those were given in the following table Results obtained:

sample sensitivity Δ Minimum density a)
b)
c)
d) Control sample
+ 8
Control sample
+ 16 Control sample
no change
Control sample
+ 0.32

-0.30-0.24

Example 16

The layers were also exposed in the manner described in Example 6 and formed into one colored positively developed. The following results were obtained:. ■ '",

sample sensitivity Δ Maximum density a)
b)
c)
d) Control sample
+ 6
Control sample
+ 6 Control sample
-0.10
Control sample
- 0.20

60

65 Example 13

An emulsion melt similar to that described in Example 5 was prepared, in three equal parts divided and treated as follows:

Two tri-color reversal films were made as follows: -... '. "

1. The following were poured onto a suitable film one after the other: _: .._ ;. ".

a) A red- and blue-sensitive silver bromide emulsion and a cyan dye-forming emulsion Link.

b) An intermediate gelatin layer.

c) A green- and blue-sensitive silver bromide emulsion and a purple dye-forming emulsion Link.

d) A Carey-Leafl-Süber-Blue-Elder-Layer.

e) A blue-sensitive silver bromide emulsion and a yellow dye-forming compound.

f) A protective gelatin layer.

909 787/354

2. A multilayer material similar to 1, but with layers a), c) and e) before casting on 1 mol of halogen silver 4 g of 4-oxy-6-methyl-1,3,3a, 7-tetrazaindole and 4 g of compound XI were added.

The layers were exposed in the same way and colored positives with the same contrasts as in Example 2, with the result that the following increases in speed of the last specified shift compared to the first specified ίο shift:

1. Compared to red light, there was an improvement in the threshold exposure (expressed in candlestick-meter seconds) of 0.22.

2. The gain in threshold sensitivity to green light was 0.12.

3. Against blue light, it was 0.15.

20th

35

Example 17

A three color reversal film was made similar to Film 1 of Example 16 except that layers a) and e) 3,6,9,12,15,18,21,24-octahexycosane bis (pyridinium perchlorate), 4-Oxy-6-methyl-1,3, 3a, 7-tetrazaindole and 6-methyl-4-phenylmercapto-1,3, as 3 a, 7-tetrazaindole contained. This film was treated as indicated in Example 16 with the following speed gains over film 1 of Example 16 which did not contain an ionic polyalkylene oxide compound observed:

1. A threshold exposure gain of 0.34 (log of candlestick-second) versus red light.

2. Against green light, the same was 0.15.

3. Against blue light, it was 0.34.

Emulsions which are chemically sensitized in the manner indicated in the above examples and for the basic regions of the spectrum are optically sensitized and the coupler compounds continue to be generated Subtractively colored color images contained in the color development can be superimposed on a support be arranged so as to achieve multi-layer color plume that leads directly to a negative or indirectly to a colored positive using the procedures given in the examples can.

Claims (10)

Claims ·. 1. A photosensitive silver halide emulsion containing a coupler compound which reacts with the Oxidation products of a primary aromatic aminohalosilver developer substance to achieve of a dye, characterized in that the emulsion with ionic polyalkylene oxide is sensitized, the polyalkylene oxide radical of which contains at least 4 alkylene oxide units. 2. Halogen silver emulsion according to claim 1, characterized in that the emulsion with an anionic Polyalkylene oxide is sensitized. 3. Halogensüberemulsion according to claim 2, characterized in that it is with a polyalkylene oxide glutamic acid salt, with a polyalkylene oxide carboxymethyl carbamate and / or with a polyalkylene oxide sulfate is sensitized. 4. Emulsion according to claim 1, characterized in that it is treated with a cationic polyalkylene oxide salt is sensitized. * 5. halogen silver emulsion according to claim 4, characterized in that it is with a quaternary Ammonium polyalkylene oxide salt, preferably mil is sensitized to a quaternary ammonium polyethylene oxide salt. 6. Halogen silver emulsion according to claim 5, characterized in that it is associated with a quaternary Ammonium polyethylene oxide salt is sensitized, the polyethylene oxide residue of which is a molecular weight has over about 300, preferably with a corresponding poly (ethoxy) ethyl bis (pyridinium per chlorate.) 7. Emulsion according to claim 5 or 6, characterized in that it is with octa- (ethoxy) -ethyl-bis (pyridinium perchlorate) and / or tetra (ethoxy) ethyl bis (pyridinium perchlorate) is sensitized. 8. Halogen silver emulsion according to one of the claims <1 to 7, characterized in that the emulsions additionally contains an azaindole stabilizer, preferably a tetrazaindole. 9. Emulsion according to claim 8, characterized in that it is 4-oxy-6-methyl-1,3,3a, 7-tetrazaindo contains, especially in combination with the sensitizers according to claim 5, 10. Halogen silver emulsion according to claims, there characterized in that it contains at least one of the following stabilizers: 4-oxy-2 - /? - oxyethyl-6-methyl-1,3,3 a, 7-tetrazaindo] 1,2-Dioxy-1,2-bis (4-oxy-6-methyl-1,3,3a, 7-tetraza indol-2-yl) ethane, 6-oxy-4-methyl-1,2,3 a, 7-tetrazaindole, 4-Oxy-2- (4-pyridyl) -6-methyl-1,3,3a, 7-tetrazaindole 4-Qxy-2y-oxypropyl-6-methyl-1,3,3a, 7-tetrazaindole, S-carbethoxy-4-oxy-1,3,3 a, 7-tetrazaindole, 2,4-Dioxy-6-methyl-1,3,3 a, 7-triazaindole, 1,2,3,4-tetrakis- (4-oxy-6-methyl-1,3,3 a, 7-tetraza- indol-2-yl) butane,
1,2-bis- (4-oxy-6-methyl-1,3,3 a, 7-tetrazaindole- 5-yl) ethane,
6-oxy-3- (4-pyridyl) -4-methyl-1,2,3,3a, 7-tetrazaindole, S-carbethoxy- ^ oxy ^ -methyl-1.S.SaJ-tetrazaindo 2-Amino-5-carboxy-4-oxy-l, 3,3 a, 7-tetrazaindole, 7-oxy-1,2,3,4,6-pentazaindole. A priority document was displayed when the registration was announced. © 909787/354 4.60