DE2129086A1 - Development process - Google Patents

Description

* A? E N TAN WAIT E

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MDNCHEN HAMBURG 2129086

TELEPHONE = 55 54 7 «8000 MONKS 15, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

June 11, 1971

W. 40546/71 - Ko / Ne '

Fuji Photo Film Co., Ltd. Ashigara-Kamigun, Kanagawa (Japan)

Development process

The invention is concerned with an improved development process. In particular, the invention relates an improved method for developing a reversal color photographic material.

In the reversal color photographic materials generally an exposed, light-sensitive silver halide material initially of a black and a Subjected to Veiss development and then the remaining Silver halide of a color development to achieve subjected to a color positive image.

The remaining silver halide is made developable for color development by the MateriaD. exposed to light or chemical fog

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educational resources are used. The suspension on Light is simple, but the leakage of light from an exposure device to a poor color rendering, the structure of which becomes complicated and the quality of the exposure is im generally insufficient to achieve a sufficient maximum density.

Therefore, it is generally preferred that the remaining silver halide can be removed by the application of chemical Made mist-forming agents viable

" will.

As such chemical misting agents, use is made of an aqueous solution of an alkali borohydride (B. P. 904 462) known. The aqueous solution of the alkali borohydride gives an effective mist and makes the remaining silver halide developable, however, the alkali borohydride is unstable in aqueous solution. There is another disadvantage with this method in that it is necessary to apply a new bath of an aqueous solution of an alkali borohydride, which results in an increase in treatment levels.

This disadvantage can be avoided by adding a chemical misting agent to the color developer for the Development of the remaining silver halide can be overcome.

For this purpose it is known to use an alkali borohydride to be added to the color developer (B. P. 1 008 015) However, the alkali borohydride has the major disadvantage that it is so unstable in the developer that the chemical misting effect gradually increases over time is lost after the developer is made. ·

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To overcome this disadvantage,?! Was also. already proposed an aminoborane compound to · a color developer to be added (IJSP 3 24-6 98?). However, are ■ known aminoborane compounds for human Body harmful. -.

It is therefore a main object of the invention to provide chemical misting agents to be used in a color developer are stable and not harmful in this way are·

As part of extensive research on this Purpose ^ has been found to be a stable and less harmful chemical misting agent can be obtained when sharing a borohydride compound and an aliphatic amine compound can be used. The invention is also concerned with a method for the development of color photographic silver halide reversal materials, being in the stage of color development subsequent to the development of the first stage the remaining silver halide is treated with a color developer containing an alkali borohydride of the formula (I) and at least one aliphatic amine compound of the formula (II) contains: Formula (I) ZBH., Wherein Z is an alkali metal, such as Na,

E or Li is

Formula (II) XR-NHg, wherein R is a divalent, aliphatic hydrocarbon radical having 1 to 6 carbon atoms, Z is a hydrogen atom or a group -NR ^ R ₂ , where R, - and R _{2 are} each the groups H or -GH. . represent.

Examples of alkali hydrides are NaBH ^, KBH ₇₊ and LiBH ^ and examples of aliphatic amine compounds are CH ₅ NH

₂ ,

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sec-C ₄ H ₉ KII ₂ , tert-C ₄ H ₉ NH ₂ , 11-C ₅ H ₁

BH ₂ CH ₂ CH ₂ HH ₂ , NH ₂ CH ₃ CHEH ₂ , ₂ CH ₂ IiH ₂ , Im ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , (CH ₃ ) - ₂₂₂ and (CH ₃ ^ NCH ₂ CH ₂ NH ₂ .

The color developers used in the invention are the known general color developing agents. These consist of an aqueous ■ solution of an aromatic primary amine, its pH value

Is 10.5 or more, and the pH buffering agents, bromides, . Iodides, organic fog inhibitors, emollients

for hard water, organic solvents such as benzyl) alcohol or diethylene glycol, and auxiliary developing agents, such as polyalkylene glycol, hydroxylamine, 1-phenyl-3-pyrazolidone or N-methyl-p-aminophenol or citrazinic acid may contain.

The borohydride compound and "the aliphatic amine compound are preferably used in proportions of 10 mg to 1 g and 1 g to 20 g per 1000 ml of the paint twicklers used. Alkali borohydrides are unstable in color developers and decompose in the course of the Time and lose the chemical misting effect. On the other hand, it is known to use aliphatic amines to be added to the color developer (TJSP 2 191 037) the addition of an aliphatic amine to the color agent " winder, the speed of development is known to be increased, especially in the interior of the soil layer, however, when an aliphatic amine is used alone, the chemical misting effect is too weak, to produce satisfactory results, if no re-exposure or re-exposure in conjunction with this is applied. The application of a so large a quantity of the aliphatic amine that the renewed E.lighting can be omitted, results in a

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marked increase in the dye mixture and hinders the Color development with lowering of the maximum density due to the dissolving effect for silver halide. Therefore alkali borohydrides and aliphatic ^ amine compounds each unsatisfactory as a chemical misting agent in terms of an additive to a color developer.

_% However, it has now been found that this disadvantage can be overcome, v / hen alkali borohydrides and aliphatic amine compounds are used together. When an alkali borohydride and an aliphatic amine compound are used together, the stability of the alkali borohydride is remarkably improved, and images of good quality free from a mixture of colors and a lowering of the maximum density are obtained since no large one is used Amount of aliphatic amine compound is necessary. Alkali borohydrides are less harmful and cheaper than the previously known aminoboranes. In addition, the color development time is shortened when alkali borohydride and aliphatic amines are used together. This is especially important for high temperature treatments and bapid treatments.

The light-sensitive used in the context of the invention Color reversal materials consist of light-sensitive, multilayer gelatin silver halide materials, which are built up from at least three silver halide emulsion layers, which on one Support, for example a cellulose ester film, polyester film or paper, are attached. The silver halide emulsion layer can be spectral by using common sensitizing dyes be sensitized, cyan, magenta

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and yellow color couplers in the emulsion layers or the Developers to be included. Color reversal photosensitive materials include reversal color papers and Reverse color films where the color coupler is in the emul siönsschicht s are included, d. H. Color reversal films from the. Type of the built-in coupler or the type of coupler in the developer, where the color couplers are in the Developers are included.

Furthermore, photographic silver halide materials, in which one or two silver halide efflusion layers en a color coupler, for example a magenta coupler included with a developer be developed according to the invention with incorporated coupler.

The following examples serve to further illustrate the invention without limiting it.

example 1

A multilayer reversal color photographic film, consisting of a support with a layer of a silver halide emulsion thereon which contained a color coupler and different light sensitivity ranges was exposed by means of a sensitometer and then the following treatments subjected:

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temperature 2129086 1 min. 1 min. treatment 37 ° C Time 4- min. 30 sec. 1 min. 30 sec. Pre-hardening It 2 ItLn. 30 sec. 30 sec. 1 min. Neutralization Il 30 sec. 1 min. First development Il 3 min. 20 sec. First abort Il 30 sec. Water washing Il Color development Il Second demolition Il Water washing ti Bleaching Il Fixation Il Water washing

The composition of the treatment solutions were as follows:

Pre-hardening solution

Concentrated sulfuric acid glutaraldehyde (25% aqueous Solution)

Sodium sulfate (anhydrous) potassium bromide

Formalin (37% J-66 »aqueous solution) Phenazine-2-carboxylic acid

5-Ethy1-3-mercap to 4-phenyl-1,2,4-triazole

Water to 1000 ml neutralizing solution

Hydroxylamine sulfate potassium bromide

Glacial acetic acid

Sodium sulfate (anhydrous) Na t ri umhydrο xi d

1000 ml of water

2.7 ml , 0 ml 4th 6th 150 , Og 2 ml 27 mg 10 mg 5

10.0 g 20.0 g 10.0 ml 50 g

10.0 x g

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First developer

Sodium hexametaphosphate 1.0 g

i-phenyl-J-pyrazolidone 0.3 g

Sodium sulfite 50.0 g

Hydroquinone. 6.0 g

Sodium carbonate (monohydrate) 35.0 g

Potassium bromide 2.0 g

Potassium thiocyanate 1.0 g

Potassium iodide (0.1%, aqueous 10.0 ml solution)

1000 ml of water
First stop solution and second stop solution

Acetic acid sodium acetate

Water to 1000 ml color developer Sodium Hexametaphosphate Benzyl Alcohol

Sodium sulfite Sodium phosphate (tribasic) potassium bromide

Potassium iodide (0.1%, aqueous solution

Sodium hydroxide

4-anlino-3-methyl-N-ethyl-N-methanesulfonamidoethylaniline sulfate

Ethylenediamine Sodium borohydride water to 1000 ml bleach solution

Potassium ferricyanide Potassium bromide water to 1000 ml

25.0 ml 3.0 S. 1.0 S. 6.0 ml 5.0 G 40.0 S. 0.2 G 10.0 ml 4.0 G 10.0 6th 3.0 ml 70 mg 100.0 ε ■ 30.0

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Fixing solution

Sodium thiosulfate Sodium sulfite water to 1000 ml

150.0 g 10.0 g

In the development indicated above, only ethylenedianiine or sodium borohydride became the Color developer added and the same procedures for comparison carried out. The photographic values in development are given in Table I. The photographic values are the Eot, green and blue densities given in the maximum density ranges. Table I also shows the results obtained in the same way with the color developer, which was left for 1 week in a normal reagent bottle »

additions Table I. the , 83 Maximum density d. green 1 week Maximum density Solution after j? arb develops Ethylenedi- Fresh solution 2.87 blue amine sodium red green blue , 40 Red Be borohydride 2.67 drawing Sodium boron 3.45 2.98 2 , 25 3.30 2.51 tion hydride A. Ethylenedi- 2.28 1.92 amine 3.21 2.85 2 2.47 2, 01 B. 3.14 2.51 2 2.63 C.

When developing with color developer A according to of the invention, the highest densities were obtained with the fresh solution, while the densities in the case

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of the color developer s C, which is only ethylenediamine contained, were lower than in the other cases * Of the ear developers, after some time, color developer B, which only contained sodium borohydride, a particularly strong decrease in density and the i'arbentwiekler A, which both jithylenediamine as well as containing sodium borohydride gave only a small one Decrease in density, d. do the best results.

Example 2

A multi-layered color film which, by applying a red-sensitive gelatine-silver iodobronide emulsion layer, a green-sensitive gelatin-superiodobromide emulsion layer, a blue-absorbing gelatin yellow filter layer containing colloidal silver and a blue-sensitive gelatin "silver iodobromide enesion layer" on a cellulose acetate film in this order was exposed by means of a sensitometer, and then the subjected to the following treatments:

Treatment temperature time

Pre-curing 40 ° C 30 sec *

Water wash ". 30 sec *

First development "75 ßek *

Water wash "30 sec.

Reverse exposure

(Red light) from the

Back of the i'olie '"200 GHb

Cyan-i'ai? Development ". 3 Hin» CO oek *

Wasserwänche ^M 30 sec »

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Min. 200 CMS 1 30th Sec. 30th Sec. Mn. 15th Sec. 2 Min. 1 Min. 1 Min. 1 Min. 1

Treatment temperature time

Reversal exposure 40 ° C (blue light) from the
Surface of the film

Yellow color development "

Water wash "

Second black and

Weiss development "

Magenta "
■ winding

Water wash "

Bleaching. "

Fixation "

V / ater laundry "

The following compositions of the treatment solutions were used:

Pre-hardening solution

Sodium hexametaphosphate 1.0 g

Sodium bisulfite 5 ° S

Sodium pyrophosphate 15 ° S

Catalyst sulfate 150.0 g

Potassium brOQid 2.0 g

Sodium hydroxide 0.1 g water to 1000 ml

First Developer '-

N-methyl-p-aminophenol sulfate 5) 0 g

Sodium sulfate 70.0 g

Hydroquinone. 2.0 g

Sodium carbonate (monohydrate) 4-1, above

Kaliuabroraid 4-, O g

Kali tat thiocy ana t 1.6 g

Potassium iodide (0.1 / ye, watery

Lc cuns 1O ₅ CI

'«' Ιss He to 1000 al

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2129Π86

Cyan color developer
Potassium bromide
6-nitrobenziniidazole
Potassium iodide (0.1%, aqueous

Sodium sulfate

lia crium sulfate
Potassium thiocyanate

^ -Amino ^ -methyl-N-ethyl-N-hydroxyethylaniline sulfate

Sodium hydroxide

ψ 1,5-dihydroxy-2,6-dibromo

naphthalene

Monobenzyl-p-aminophenol
p-aminophenol hydrochloride water to 1000 ml
Yellow color developer
Sodium sulfite
Potassium bromide

Potassium iodide (0.1%, aqueous solution)

6-nitrobenzimidazole
Sodium sulfate

N, N-diethy1-p-pheny1endi amine- ^ sulfite

Sodium hydroxide

w -Benzoyl - ^ - Cp-toluenesulfonamide) acetanilide 1.8 g

V / ater to 1000 nil
Second black and white development solution

N-I'iethyl-p-aciinophenol sulfate 1.0 g

lia tri um sulfite 50.0 g

Hydroquinone 1.0g

Sodium carbonate (monohydrate) 41.0 g

Kaliurabrcraid 2.5 pounds of water to 1000 ml

3.0 E. ml 0.03 g ε 10.0 ε 10.0 ε 60.0 G 1.0 ε 2.5 β 3.0 ε 2, ο; ε 0.4- ε 0.1 ε 10.0 ml 0.5 S. 25.0 ε 0.1 ε 60.0 ε 2.5 2.5

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Magenta dye developer Sodium sulfate potassium bromide potassium thiocyanate Sodium sulfate

N, N-diethyl-3-methyl-p-phenylenedi a: ain hydrochloride

Sodium hydroxide 1-phenyl-3- (m-nitrobenzoyl-amino) -5-pyrazolone Ethylenediamine Potassium borohydride

Water to 1000 ml bleach solution

Potassium ferricyanide Potassium bromide

Water to 1000 ml j? Ixi solution

Sodium thiosulfate 150 g

1000 ml of water

As the coupler in the above developer-type reversal development, there have been added ethylene diamine and / or Sodium borohydride was added to the magenta developer and the same procedures followed for comparison. the photographic, characteristic values during development are listed in Table II. The basic density is the photographic characteristic value indicated on the areas of maximum density. Also in Table II are those by like development with the results obtained with the magenta developer are listed, the one at 50 ° G for 5 days in a closed one Test tube was left to stand.

5.0 G 1.0 S. 1.0 S. 60.0 S. 2.5 S. 2.0 G 1.4 S. 4.0 ml 70 ml 100 g 30.0 S.

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Ethyl endi ainin
Potassium borohydride
Potassium borohydride
Ethylenedi amine Table II Maximum density
the solution
after 5 days
(green) Maximum density
the fresh
solution
(green) .. 3.12
2.16 Mapenta developer
Be
drawing accessories 3.38
3.10
2.53 D.
E.
j?

The highest density was obtained in the development with the magenta developer D, fresh solution, while the density in the case of the magenta developer i ¹ , which only contained ethylenediamine, was lower than in the other cases. Of the magenta developers left to stand for some time, the magenta developer E, which contained only potassium borohydride, gave a particularly remarkable decrease in density, while the liagenta developer D, which contained both ethylenediamine and potassium borohydride, only showed a slight decrease in density, ie gave the best results.

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Claims (3)

Claims 1. Process for the development of a multilayer, light-sensitive color reversal silver halide materials, characterized in that after the first black and white development the remaining silver halide with an alkaline color developer, which (1) an aromatic, primary amine developing agent, (2) Alkali borohydride and (3) an aliphatic amine of the general formula X-JR- wherein R is a divalent, aliphatic hydrocarbon radical with 1 to 6 carbon atoms and X is a hydrogen atom, an amino group, a methylamino group or dimethyl amino group represents, contains, is developed. 2. The method according to claim Λ , characterized in that a compound KaBH ₄ , KBH ^ or LiBIL is used as the borohydride. 3. The method according to claim 1 or 2, characterized in that the amine is a compound C ₂ H ₅ KH ₂ , 11-CH ₇ RH ₂ , iso-C H ₇ EH ₂ , ^ C ₄ H ₉ NH ₂ , sec-C ₄ H ₉ NH ₂ , tert-C ₄ HqHH ₂ , nC ^ H ^ KH ^ iso-C 11H ₂ CH ₂ CH ₂ HH ₂ , KH ₂ CH CH ₂ KH ₂ , KH ₂ CH ₂ C CH ₂ HH ₂ , KH ₂ CH ₂ CH ₂ CH ₂ CHpCH ₂ CH ₂ HH ₂ , (CH) - KHCH ₂ CH ₂ KH _p or (CH ₃ ) HCH ₂ CH ₂ KH ₂ is used. 109853/1673