DE2052693A1 - Development of photographic materials - Google Patents

Description

AGFA-GEVAERTAG

LEVERKUSEN 26, OCT. 1970

Development of photographic materials

Priority: Great Britain, October 27, 1969, note number 52 565/69 Gevaert-Agfa N.V., Mortsel, Belgium

This invention relates to photographic development Materials containing exposed silver halide, and refers to I.

on new developer compositions and on photographic materials and solutions containing such compositions

It is known that certain chemical compounds work when alone are poor developers for photographic silver halide emulsions but become more effective in conjunction with other developers; this effect is known as superadditivity. So is e.g., it is known that p-phenylenediamine derivatives and p-aminophenol derivatives show the phenomenon of superadditivity when combined with Developer substances are needed, their ionized forms in alkaline Medium have two or more negative charges, such as hydroquinone, hydroquinone sulfonate, ascorbic acid, etc.

It has now been found that these p-phenylenediamine and p-aminophenol derivatives also show a superadditive character when in connection with the at most simply ionized developer anions of Hydroxylamine and its derivatives are used.

The use of hydroxylamine and its derivatives, their oxidation products have the favorable property, none in the obtained silver picture Leaving residue stains behind has become known, inter alia, from US Pat. No. 2,857,276 hydroxylamine itself and the monoalkyl derivatives are less useful because they can promote haze formation, but the N, N-dialkylhydroxylamines are such as N, N-diethylhydroxylamine and the heterocyclic N-hydroxylamines, such as N-hydroxy

109819/1781

Wjirden published 'aforementioned US Patent, besoüdesfts .- ■ I bear - J morpholine, N-hydroxypiperidine and N-Sydroxypyrrolidin that in j ^ ■ \. Other hydroxylamine derivatives used for silt development *; halides have been proposed., and their development activity ^ t Ι ', igt alk-those of Ν, Ν-dialkyl-hyäroxylaminen, include, for example

^: Hydroxylamine, in particular N, N-DialkylhydroxylaBjine, the I one of the N-alkyl groups intraüneares Aminostickstof fatom> || i, t _^{^:;} ";." V '. .Neither cyclic or acyclic have. Such examples can be ifi-dek "■, -, ■

I U.S. Patent 3,287,125. Also include fsfu.,., '- ■, · "■■. · ■' Vjjl · - · · ■ · ■ ' ^ -,' ■ ". '■■■ .. ■■■■. ■■ ; ■ ■ ' ■ _. ■■■■■■ ■. . ■. ■ '.''"Ί ^ ^.; ' Ν · '> // ·· -. · Γ: ν., V;" ^r : ·

.. ■.;) ■■, alkoxyhydroxylamines, especially Ν, Ν-dialkylhydroxylamines, vc3ü deiien, ■:

; .-, | Γ. '■, ·,' ■. '■' ■■■■ ■■. ■ · ■. '■■ ■ ■ ■ ■, ■. · ■': '·· ■ ·. ■, :: ■■■ - ..,. ■■ (■; ^ ■■ '... ■ / ■ _. "■

■ | ■ _ .. at least one of the N-alkyl groups may be alkoxy or alkoxyalk ^? | Yv-§üb'-. ■ f is established .. Such examples can be found in the USA patent 'scripture;';.; } _: \ 3 293 if found · Furthermore, this includes sulfonylamines, ^v * especially Ν, Ν-dialkylhydroxylamines, which have an intralinear sulfonyl (-SO-) group in at least one of the NI alkyl groups. Examples of this type can be in US Pat. No. 3,287,112. I Furthermore, Ν, Ν-dialkylhydroxylamines have been proposed which have a quaternary ammonium group in at least one of the N-alkyl groups, either cyclic or acjcLic, which are particularly suitable for the Suitable for use as silver halide developing substances, as described in the patent application "New photographic developers" filed at the same time hereby by the applicant (corresponds to British patent application 5256 ^ / 69).

The p-phenylenediamine and p-aminophenol derivatives, the. with hydroxylamine developing agents have a superadditive development effect can be represented by the following general formulas': I.

in which:

E is alkyl or a substituted alkyl such as alkyl substituted with

1098 19/178 1

Hydroxy, carboxy, sulpho, sulphate, acylamino and sulphonamido, e.g. Methyl, ethyl, propyl, butyl, pentyl, "hexyl, 2-hydroxyethyl, 3-hydroxypropyl, ^ f-Hydroxybutyl, ^ - Carboxybutyl, 5-Carboxyhexyl, ^ t - Sulphobutyl, 5-sulphatopentyl, 2-acylaminoethyl, 2-methylsulphonylaminoethyl etc.,

R “alkyl or ethylene, substituted ethylene, propylene or substituted Propylene, which is attached to the ortho carbon atom of the Benzene ring is connected,

E alkyl, and

R. optionally substituted alkyl as under E., with at most one of the substituents E and E. may mean substituted alkyl,

M- ³

in which:

E and Eg are each alkyl or a substituted alkyl e.g. substituted alkyl,

as defined under E, and
X. an electron donating group such as alkyl, alkoxy, amino, monoalkylamino, dialkylamino, acylamino and sulphonamido;

V ^ - ^X 3

in which:

X- and X_ each represent a hydrogen atom, a halogen atom such as chlorine, or a electron-donating group, as defined under X.,

Y hydroxy or amino,

E ₇ optionally substituted ethylene or optionally substituted propylene, which is connected to the adjacent ortho-carbon atom of the benzene ring,

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o a water to ff atom, gwgAeiiQKf'sfl-ls substituted alkyl ,,,: * t

defined under R .., or similar is §l®iqii 1 ", or where E_ 2u@am1n.erb with Bo uad d @ = m Stieksto.f £ ato.m, with which s, i @ · are connected :, , eimeja'ByrrQlidiiariag forms. . · ■ ■

1.Θ the following are representative examples of p-phenylenediamine and p-aminophenol derivatives, which are used in conjunction with Hydroxy Lamin developers. Usable superadditive developing substances are:. a) Compounds according to the general formula I 1. 6-diethylamino-1, 2,3 ", ^ -tetrabydroquinolindishlarhydrat 2» i-Ä-bhyl-6-diethylamiao-1, 2, .3,, A- ^ te-trabydroch .iiiolindiGhlo3 ^! kydxa? t. 3 «1- ( ^z f-Sulphobutyl) -6-d: iä-tliyla _! raira.x3 ~ ^/ l, 2,3, ^ -te-t.ra-bydrochin.olia

hydrate

5 · 1-ethyl-6- (N-ethyl-N-3'-sulphopri? © pylamiao) -1, 2,3., ^ -Tetr-ahyd = roc-ftinoline dichlorohydrate

6. t ~ (3-Sulphopro.pyl) -6 .- (] 5f-ethy.l-N-methylainino) -1,2,3, ^ -tetraiiyäj? Ochiaolindichlorhydra-t

7. 1- (2-Methylsulphonylam.ino.äth.yl) ~ 6-diethylamino-1, 2,3. ', ^ -Tetoala ^ droquinoline dichlorohydrate

8. 1- (3-Carboxypropyl) -6 »-dimet] 3ylamino-1,2,3 ;, ^ -trahydrohydric acid chlorohydrate

9- .. N N-diethyl-N ¹ , N '-dimethyl-p-ph-enylenediamine dichlorohydrate 1 part «Ν, Ν, Ν ¹ , N' ~ tetramethyl-p-phe.nyleadiamine dichloro] hydrate 11 .. N, N, N ¹ , .N'-Tetraeth ^ lp-pihenylendiamiELdiQhloEhyärat 1'2- · N, N-Diethyl-N '-2-13. M, N-diethyl-N: '- ^/ f-sul; ghobutyl-ff ^I ' ~ ethyl-p-phenylenediam ± n

b) Compounds according to the general formula II t%. 2-AmInO - ^ - diethylaanin-o-aniliasulphat

15. 2-MCtMyIaTOInO- ¹ I-diethylajnia © -aia.ilinsulph.at

16. 2-Methylsulphonamide> ©. -4-dd £ ätfiylamißO-anilineulphat 17 · 2-Ethoxy- ^/ i-dieth.ylj

c) Connections_according to ^^^^^ 18. 1 - (* 4-Hydroxyphenyl) ~; gyir: i? Olidin

19 1- (3-chloro- ⁱ + ^{-hydroxyphe <} niyl) -pyrrolidine 20. 1- (3-

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21. 1- (3, ^ - dimethyl - ^ - hydroxyphenyl) pyrrolidine

22. 1- (3-Amino - ^ - hydroxyphenyl) pyrrolidine 23-1- (3-M-ethoxy- * t-hydroxyphenyl) pyrrolidine 2 ^. 1- (3-methylsulphonamido - ^ - hydroxyphenyl) pyrrolidine 25 • i-O-acetylamino- (t-hydroxyphenyl) pyrrolidine

26. 6-Amino-1,2,3, ^ - tetrahydroquinoline ■

27 x 6-hydroxy-1,2,3, ^ - tetrahydroquinoline

28. 1-Sthyl-6-hydroxy-1,2,3, ^ - tetrahydroquinoline chlorohydrate 29 · 1 - (^ - SulphobutylX-ö-hydroxy-i ^^^ - tetrahydroquinoline

30. 9-Amino-Julolidine Sulphate

31 x 1-methyl-6-araino-1,2,3j ^ -tetrahydroquinoline oxalate

32.1 - (2-methylsulphonylamino-ethyl) -6-hydroxy-1,2,3, ^ f-tetrahydro-

quinoline I

33 · 1- (2-hydroxyethyl) -6-hydroxy-1,2,3, ^ - tetrahydroquinoline 3 ^. 1-C ² + -Sulphobutyl) -6-amino-1, 2,3, ^ t-tetrahydroquinoline 35 · 9-hydroxy-julolidine.

The p-phenylenediamine and p-aminophenol compounds which are used according to the present invention can be prepared by methods of the art, for example according to that described in U.S. Patents 3,265,999 and 3,265,502, British Patents 928,671 and 858 hj2 and der Belgian patent 715 500 produce described type.

In accordance with the present invention there is provided a method of making photographic prints. It includes the Behänd- g lung comprising a photographic material, the layers having developable silver salts with an aqueous alkaline solution in the presence of a hydroxylamine-developing agent and a p-phenylenediamine or p-aminophenol compound as described above. The invention also encompasses developer compositions which, in addition to a hydroxylamine developer substance, contain a p-phenylenediamine or p- aminophenol compound as described above. The term hydroxylamine developer is understood to mean both hydroxylamine itself and its derivatives, as described above.

The p-phenylenediamine or p-aminophenol derivatives which are used according to the present invention can be in the developer bath or

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added to the emulsion or both at the same time. you will be however, it is preferably added to the developer bath.

Developer mixtures containing the superadditive developer substances according to of the present invention may additionally include any of the usual ones Contain ingredients that are used in developing mixes, e.g. alkalis such as sodium hydroxide, potassium hydroxide, sodium, carbonate, trisodium phosphate, etc., silver halide solvents, such as sodium thiosulphate, Sodium thiocyanate and cyclic imides such as barbiturates or Uracils, preservatives such as sulfites, hydrogen sulfites, metabisulfites and Acids, such as boric acid and citric acid · Next, the developer composition can Potassium bromide and water softeners, such as polyphosphates and derivatives of ethylenediaminetetraacetic acid, contain antifoggants such as benzotriazole, 5-nitrobenzotriazole and 6-nitrobenzimidazole, and the like Wetting agents and other compounds used in photographic development are known as development retarders or ent "- ' Winding accelerator.

The proportion of the hydroxylamine developing agent to the p-phenylenediamine or p-aminophenol compound in the present invention can be selected so that the combination is useful for the development of all kinds of material including such material as the silver chloride efflulsion layers of low sensitivity as well as material with highly sensitive silver bromoiodide emulsion layers. This quantitative ratio can vary within wide limits and also depends on the type of hydroxylamine developer substance used. In most cases , the quantitative ratio is chosen so that the proportion of hydroxylaein developer substance strongly outweighs that of the p-phenylenediamine or p-aminophenol compound.

A strong, "suparadditive effect is achieved by mixing a quantity of 0.05 Millieol up to 10 Milliaol, preferably from 0.3 millimole of up to 6 Millieol, p-Phenylendiaain- or p-Aeinaphenolderivat added to a Meng · from 10 to 100 su Xilliaol ^^ Hy droxylaeiin — Satüiekl er substance per liter of the ÜntwicklerBueaee * n »* tBung used . Of course, larger amounts of p-phenylenedia- or p-aainophenol compounds can be used, although the superadditive effect that aan ait higher

1098197 1781

BATH ORIGINAL

Concentrations reached, is not even more remarkable.

The reinvented combination of developing agents can be used in ordinary or wet development of silver halide emulsions can be used in diffusion transfer processes in both color and silver such photographic process as stabilization treatment are known, it being desirable to eliminate the need for washing and stabilization operations in liquid baths that prevent the formation of the Follow the silver picture, switch it off or bring it to a minimum,

As is known, in diffusion transfer processes, an exposed Silver halide emulsion containing a liquid developing composition treated while in an interlinked relationship to one Image receiving material is standing.

This treatment turns the exposed silver halide into silver developed, and the unexposed silver halide turns into a complex Silver salt reacted, which is transferred to the image receiving material and there it is reduced to a positive silver image. The developing composition usually contains a solvent for silver halide, such as sodium thiosulfate, sodium thiocyanate and cyclic imides such as barbiturates and uracils, which together with the silver halide form a soluble Complex compound forms, as they are in the production of silver, form by diffusion transfer is known, and it can also be a contain film-forming material, such as sodium carboxymethyl cellulose or hydroxyethyl cellulose, starch or gum, to reduce the viscosity of the To increase the composition, such as in the case of a silver salt diffusion transfer process is necessary within the camera.

In the stabilization treatment, the time-consuming fixation and Washes turned off in order to achieve image reproduction in the shortest possible time by using after developing of stabilizers such as ammonium thiocyanate, the unexposed and the undeveloped The silver halide of the photographic emulsion is converted into colorless, light-insensitive compounds that cannot be removed by washing Need to become.

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The developing agents used according to the invention can be used in solution, or they can be used initially in one layer of the light-sensitive material, e.g., a silver halide emulsion layer or other colloid layer which this is in a water-permeable relationship. In silver salt diffusion transfer process they may also be included in a layer of the image-receiving material which, during the development treatment, is in superposed relation to the photosensitive Silver halide material stands

The following examples illustrate the present invention.

example 1

Strips of photographic material with a photosensitive silver halide emulsion layer, which was applied to a cellulose triacetate carrier are passed through a gray filter with an amount of light E exposed, which corresponds to the shoulder part of the density / log E curve.

Each of the exposed strips is developed at 20 ^° C. in a separate developing bath. One of the strips is developed in a bath A which contains only hydroxylamine chlorohydrate as a developer and has the following composition:

Sodium sulfite 10Og

Sodium hydroxide 10 g

5-nitro-benzotriazole 80 mg

Potassium bromide 1 g

Hydroxylamine hydrochloride 0.06 mole

made up to 1 liter with water

The other strips are developed in baths that have the same composition have the same as bath A, but also contain one of the compounds listed in the table below Quantity are listed.

The densities obtained are shown in the table below.

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Developing bath Obtained densities after an Ent
development time from 20 sec. 1 min. 3 min. 5 min. Bad A
Bad A + 105 mg (0.31 millimoles)
from connection 3
Bad A + 66 mg (0.31 millimoles)
from compound 28 0 sec. 0.05
0.07
0.12 0.3 * l
0.79
0.86 0.95
1.97
2.17 2.68
> 3 0.0 * l
0.0 ^ t
0.0 * f

This example is analogous to example 1 with the only difference that now a development bath B is used, which differs from bath A only in that the hydroxylamine chlorohydrate by 0.06 mol N-methylhydroxylamine chlorohydrate has been replaced.

The following results are obtained:

Developing bath Obtained densities after an Ent
development time from: 20 sec. 1 min. 3 min. 5 min. Bad B
Bad B + 105 mg (0.31 millimoles)
from connection 3
Bad B + 66 mg (0.31 millimoles)
from compound 28 0 sec. 0.05
0.0if
0.0 * f 0;, 07
0.19
0.18 0.60
1.83
1, 66 1.09
2.61
2.72 0.05
0.04
O, o4

Example l _3

This example is analogous to example 1, with the only difference that now a development bath C is used, which differs from bath A only differs in that the hydroxylamine chlorohydrate has been replaced by 0.06 mol of N, N-diethylhydroxylamine oxalate.

The following results are obtained:

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Developing bath Obtained densities after an Ent
development time from: 20 sec. 1 min. 3 min. 5 min. Bad C 0 sec. 0.04 0, ok 0.07 0.37 Bad C + 105 mg (0.31 millimoles)
from connection 3 0.04 0.04 0.11 1.55 2.37 Bad C + 55 mg (0.31 millimoles)
of connection 14 0.04 0.04 0.09 0 49 1.27 Bad C + 66 mg (0.31 millimoles)
from compound 28 0.04 0.04 0.07 0.81 2.03 Bad C + 88 mg (0.31 millimoles)
of compound 34 0.04 0.04 0.05 0.32 1.07 0.04

Example 4

This example is analogous to example 1, with the only difference that now a developing bath D is used, which differs from bath A only in that the hydroxylamine chlorohydrate by 0.06 mol N-methyl-N- (2-hydroxy-3-diethylaminopropyl) hydroxylamine has been replaced

The following results are obtained:

Developing bath Obtained densities after an Ent
development time from: 20 sec. 1 min. 3 min. 5 min.
0.56
2.15
1.97 Bad D
Bad D + 105 mg (0.31 millimoles)
from connection 3
Bad D + 66 mg (0.31 millimoles)
from compound 28 0 sec. 0.04
0.04
O, o4 0.04
0.17
0.12 0.11
1.33
1.01 0.04
0.04
0.04

Example 5

This example is analogous to example 1, with the difference that now a developing bath E is used, which differs from bath A only in that the hydroxylamine chlorohydrate is 0.0b mol hydroxylamine derivative has been replaced with the formula:

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H Π - N-CH ₀ -CH-CH ₀ -N-CH,
-> ^d S ² ϊ ² »3

CH OH OH

according to the patent application filed by the applicant at the same time "New Photographic Developers".

The following results are obtained:

Developing bath Densities obtained after an Ent
development time from: 20 sec. 1 min. 3 min. 5 min. Bath E.
Bad E + 105 mg (0.31 millimoles
from connection 3
Bad E + 66 mg (0.31 millimoles)
from compound 28 0 sec. 0.50
0.06
0.09 0.20
0.95
1.00 1.29
2.50
2.37 2.08
> 3
> 3 0.0 * f
)
0.04
0.0 * f

Example 6

This example is analogous to example 1, with the difference that now a developing bath F is used, which differs from bath A only in that the hydroxylamine chlorohydrate by 0.06 mol Hydroxylamine derivative has been replaced with the formula:

Xl Uli Uli O ₁ -Il-.

₊ * ² 5 ι t ₊ » ² 5

H ^ C ₀ -N-CH ₀ -CH-CH ₀ -N-CH ₀ -Ch-CH _{0 -NC o} H_ 52ι 2 2 _} 2 2 | 25

according to the patent filed by the applicant at the same time registration "new photographic developers".

The following results are obtained:

Developing bath Obtained densities after an Ent
development time from: 20 sec. 1 min. 3 min. 5 min.
> 3 Bad F 0 sec. 0.50 1.13 2.19 0.04

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Bad F + 105 mg (0.31 millimoles)
from connection 3
Bad F + 66 mg (0.31 millimoles)
from compound 28 0.04
0.04 0.71
0.73 1.35
1.35 2.91
2.60 > 3
> 3

Example 7

A photosensitive element was prepared which had a silver bromide iodide emulsion layer on a paper support containing one per kg Contains amount of silver halide equivalent to 60 g of silver nitrate.

After exposure, the photosensitive element and an image-receiving element, which contains a silver-receiving layer on a water-impermeable support which disperses development nuclei, in a matrix of colloidal silica gel, according to the practice described in U.S. Patent 2,823,122 in superimposed relationship between a pair of pressure rollers brought to between the two elements a thin layer of the following composition to distribute:

Water 100 ml

Sodium carboxymethyl cellulose 5 g

Sodium hydroxide 15 g

Uracil 11.25 g

30% ammonium hydroxide 3.5 ml

Ν, Ν-diethylhydroxylamine oxalate 0.06 mol

1-phenyl-2-tetrazoline-5-thione 0.2 g

Compound 3 105 mg

After 36 seconds of contact, the emulsion, along with the layer of this composition, was removed from the image-receiving element to reveal the positive proof. When using the same composition but without Compound 3, the density of the positive print was noticeably lower. In addition, in the presence of Compound 3, better quality diffusion transfer _{images are obtained at lower exposure values compared to the use of N 5} N -diethylhydroxylamine alone.

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Claims (2)

Claims / iJ A photographic development method characterized in that an exposed silver halide emulsion layer of a photographic Material with an aqueous alkaline composition in the presence of a hydroxylamine developer substance and a p-pheny] enediamine- or p-aminophenol derivative according to one of the following formulas I, II and III is developed: IN in which: R ^ optionally substituted alkyl, Rp alkyl or ethylene, substituted ethylene, propylene or substituted Propylene, the one with the attached ortho carbon atom of the benzene ring is connected, R alkyl and R /, optionally substituted alkyl, where at most one of the substituents R- and Ri is substituted Alkyl may mean, g in which: E, _ and Rg each optionally substituted alkyl, and an electron donating group, 109819/1781 X ^ - in which: X and X, each a hydrogen atom, a halogen atom or an electron donating group, Y hydroxy or amino, R ₇ ethylene, substituted ethylene, propylene or substituted Propylene, which is connected to the adjacent ortho-carbon atom of the benzene ring, Rg is a hydrogen atom, optionally substituted alkyl or equal to R ", or where R _n together with R ₀ and the nitrogen atom, bringing them both are connected to form a pyrrolidine ring. 2. A photographic developing method according to claim 1, characterized in characterized in that the method of making images by the silver salt diffusion transfer process is applied 3 * A photographic developing method according to claim 1 or 2, characterized in that the hydroxylamine developer substance and the p-phenylenediamine or the p-aminophenol derivative both in the aqueous composition are present. k. A photographic developing composition for developing an exposed silver halide emulsion layer of a photographic material which, in an aqueous alkaline solution, in addition to a hydroxylamine developer substance, contains a p-phenylenediaein or ρ-aminophenol derivative as defined in claim 1 109819/1781