DE2062031A1 - Process for developing color photographic silver halide photosensitive materials at a high temperature - Google Patents

Description

PAiENTANWXUe DR. E. WSEGAND DIPL-ING. W. NIEMANN 2062031 DR. M. KÖHLER .DIPL-IMG. C. GERNHARDT MÖNCHEN HAMBURG TELEPHONE. · 55547 «8000 MÖNCHEN 15, TELEGITAMME = KARPATENT NUSSBAUMSTRASSEIQ

16 December 1970

W. 40 271/70 - Zo / Ke

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

Process for developing color photographic vision, silver halide photosensitive materials

at high temperature.

The invention relates to a method of development of color photographic materials, particularly a hapid development process for color photographic material! - s at high temperature.

Multilayer color photographic materials have at least three superposed silver halide emulsion layers with different spectral sensitivities on a carrier, for example in the case of a typical color photographic material a red-sensitive Emulsion layer, a green-sensitive emulsion layer, a yellow filter layer and a blue-sensitive emulsion layer applied to the support in that order are raised.

A point of view for the progress of the present photographic development work consists of the.

109929/1694

Accelerating the development, by increasing the temperature of the developer (higher than 3O ⁰ C). This is commonly referred to as "high temperature rapid development ^11. One of the troubles with high temperature rapid development of multilayer paint materials is the phenomenon that the top layer is over developed before the bottom layers are fully developed.

It is known that to overcome this disadvantage, a development inhibitor is added to the developer solution will. However, if the previously added development inhibitors, such as 6-nitroiso-indazole compounds, are added to the developer solution are added, the development of not only the uppermost layer but also that of the lower emulsion layers becomes inhibited.

To avoid this error, the addition of an acyl aminophenyl mercaptotetrazole compound to the developer solution or the photographic emulsion layer because the development of the top layer is selective is inhibited by this connection and the balance of the overall development is improved, including on the See U.S. Patent 3,295,976. The mercaptotetrazole compound described in this patent however, it is difficult to manufacture because the raw material for this compound consists of thiophosgene, which is found in the generally difficult to access.

One object of the invention is a high temperature rapid development process for multilayer silver halide color photographic materials using an effective development inhibitor for the top layer.

As part of the study of numerous compounds

109829/1594

2062Q31

it has now been found that the desired effect is obtained Can be grounded if a mercaptotetraazaindene compound, which is easily produced, is added to the developing solution can be added.

According to the invention it is by adding an ileercaptotetraazainden compound to the developer solution or to the bath preceding the development, for example the pre-hardening bath or neutralizing bath, possible, selective development of the top layer of a multilayer color photographic material and prevent the top layer from being excessive is developed so that the overall composition and image quality are improved.

Pre-hardening baths, i.e. aqueous solutions, an aldehyde for hardening the gelatin of the photographic emulsion layer, such as formaldehyde, glyoxal, suecinaldehyde, Glutaraldehyde and the like are used. The aqueous solution also contains a salt, such as sodium sulfate, a pH control agent or buffering agent, like borax, boric acid, acetic acid, ITa-nriumacetat, ITodium hydroxide, sulfuric acid and the like and also Development anti-fogging agents such as alkali halides. The development inhibitor according to the invention can be added to such an aqueous precuring solution will.

If an IT neutralization bath to prevent the discharge of the aldehyde in the pre-hardening bath is used in the developing solution, the development inhibitor can be used according to the invention are added to the neutralization bath. The IT neutralization bath contains an aldehyde

109829/1594

inclusion agents, for example hydroxylamine or
! -Ascorbic acid and may further contain a salt and a pH control agent or buffering agent.

The black and white developing solution for color photographic Reversal film contains at least one developing agent such as hydroquinone, phenyl-3-pyrazolidone and N-methyl-p-aminophenol. The developing solution contains furthermore a salt such as sodium sulfate, a pH control agent or a buffering agent such as borax, boric acid, sodium hydroxide, sodium carbonate and the like and an alkali halide. The development inhibitor according to the invention can also be added to this black and white developing solution be admitted.

As the color developer solution for color negative films or color papers, alkaline, aqueous solutions are usually used which contain a p-phenylenediamine derivative as
Color developing agents contain, for example
N, N-diethyl-3-methyl-p-phenylenediamine hydrochloride,
^ Amino ^ -methyl-N-ethyl-H-methanesulfoamidoethylaniline sulfate, 4-amino-3-methyl-IT-ethyl-II-hydroxyethylaniline sulfate. N-ethyl-IT-hydroxyethyl-p-phenylene-diamine sulfate
and similar connections. The solution further contains a salt such as sodium sulfate, a pH control agent or a buffering agent such as sodium hydroxide, sodium carbonate, sodium phosphate and the like, and common anti-fogging agents such as alkali halides. The development inhibitor according to the invention can also be added to the color developing solution.

The object of the invention is achieved by to
one of the treatment solutions listed above
a mercaptotetraazaine compound according to

109829/1594

general formula

R- -

N,

N,

C-R,

SH

wherein R 1 and R ₂ , which may be the same or different, each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a haloaryl group and R represents a hydrogen atom, a halogen atom or an alkyl group.

Typical examples of compounds which can be used according to the invention and which correspond to the above formula are given below, although the invention is not limited thereto.

Compound Is 1,3,3a, 7-ietraazainden-4-thiol

HC

SH

CH

Connection 2: e-

i ^{H} 0} 1

^! HC

CH

■ I

SH

109829/1894

Compound 3: 6-tert-dutyl-1,3,3a, 7-tetraazainden-4-thiol

S ■ I CH

KC,

1
SH

Compound 4: 6-Oentyl-1,3,3a, 7-tetraazainden-4-thiol

SH

Compound 5: 6-ionyl-1,3,3a, 7-tetraazainden-4-thiol

KC.

I.
SH

Compound 6: 6-Undecyl-1,3,3a, 7-tetraazainden-4-thiol

N-

CH

1 . SH

109829/1594

Compound 7: δ-heptadecyl-1 ^ Sa ^ -tetraazaindet-4-thiol

17th

KC

SH

Compound 8: 6-phenyl-1,3,3a, 7-tetraazaindene ~ 4-tholol

5 ο

CH

SK

Compound 9s 5-Bromo-6-raethyl-1 _r 3,3a, 7-tetraazaindene 4-thiol

C C \.

1 1 CH

p W y.

· V

I SK

Compound 10: 2,6-dimethyl-1,3,3a, 7-tetraazainden-4-thiol

C I

SH

109829/1594

Compound 11: 5-ethyl-6-methyl-1,3,3a, 7-tetraazainden-4-thiol

■ N

SH

Compound 12: S-isobutyl-δ-methyl-1 ^^ a ^ -tetraazainden-4-thiol

H ₃ CC C-— \

SK

The compounds of the above general formulas can generally by reacting an aminotriazole with an acyl acetic acid ester, subsequent reaction of the product with phosphorus oxy / chloride and after the extraction of the extract can be made with thiourea.

Preparation example (compound 3): aminotriazole and an equimolar amount of 4,4-dimethyl-3-oxovaleriacidäthylester were heated for 7 hours in glacial acetic acid and after recrystallization of the crystals obtained from methanol, the 4-hydroxy-6-tert-butyl , 3,3a, 7-tetraazainden with a melting point of 269 ⁰ C obtained. After the tetraazaindene has been reacted with phosphorus oxy ^ chloride at 120 ^° C. for 1 hour

109829/1594

the product was poured into ice water and then extracted with Liethylenehlorid. The obtained crystals of the 4-chloro compound is reacted with thiourea in ethanol and recrystallized, the crystals formed from alcohol, to give sharp, needle-like crystals of 6-tert-Butyll, 3,3a, 7-tetraazaiden having a melting point of 286 ⁰ C obtained .

The other compounds can also be made according to the procedure according to British Patent 893,428.

In British patent specification 893 428 it is described that by adding a compound according to general formula for silver halide the storage stability of the silver halide is improved during storage and the thermal stability of the silver image obtained is increased. However, the application of the compounds according to the invention is fundamentally different from the teachings of the British patent specification. In the case of exposure of a color photographic light-sensitive material to one High temperature development often occurs the phenomenon on that the top layer of the same overdeveloped and the color balance changes. In this case, in the high temperature development in Presence of the compounds according to the invention with a picture be obtained without this Errors occur. The high temperature development for farbphotoßraphio.che, light-sensitive materials can therefore not be effectively carried out in the I'raxin, if not Then the process must be applied. Through each of the above-listed compounds of the general Formula can reduce the excessive development of the surface layer or the top emulsion layer can be prevented and

BAD ORIGINAL 109S29 / 1594

an effective development treatment with good color balance received '. Of these compounds, however, results in the Compound 3 gives the best results.

The amount of the compounds to be used according to the invention varies according to the type of compound, the type of color photographic material and the nature of the composition of the processing solution. In general, however, the amount of the compound 1 mg to Ig per liter of the treatment solution.

The optimal amount of compound depends on numerous factors, such as the compound to be used, the composition of the processing solution, the activity of the processing solution, the processing temperature and the Properties of the multilayer color photographic light-sensitive material.

The following examples serve to further illustrate the invention.
example 1

A multilayer color reversal film made up of three layers of SiI overhalide emulsion existed with different couplers and different spectral sensitivities, v; was exposed by means of a satometer and then the subjected to the following treatments:

treatment

Black and white development. First fixation. Water wash. Color development

Second fixation water wash

rape Time 37 ⁰ C 3 min. Il 30 seconds It 1 min, It 3 min.
and
30 oek. Il 30 oek. It 1 min.

109829/1594 ^BAD original

37 ⁰ C

3TG bleaching 1 min. And 30 sec.

Fixation ". 1 min.

Water wash "1 min.

The compositions of the treating solutions used in the above treatments were the following black and white developing solution

Sodium hexa-metaphosphate l-phenyl-3 ~ pyrazolidone sodium sulfite hydroquinone sodium carbonate (monohydrate) potassium bromide potassium thiocyanate potassium iodide {Ό,! Follow aqueous solution) water

First and second fixing solution

Acetic acid sodium acetate Y / water

Color developing solution Sodium hexametaphosphate Benzyl alcohol Sodium sulfite Sodium phosphate Potassium bromide Potassium iodide (0.1% aqueous solution) Sodium hydroxide

4-Amino-3-methyl-IT-ethyl-N-methanesulfonamidoethylaniline sulfate Ethylenediamine 'water too

1.0 G G 0.3 G ecm 50.0 G G 6.0 G G 35.0 G G 2.0 G ecm 1.0 G G 10 ecm G 1 liter ecm 25 ecm liter 3 g 1 liter 1.0 6.0 5.0 40.0 0.2 10.0 6.5 10.0 8.0 1

109829/1594

100 G β 30th , 0 g liter 1 liter 150 10 1

Bleach solution: fericyanide potassium bromide water to fix solution: sodium thiosulfate sodium sulfite water to

In the above reversal development treatment the compound according to the invention was added to the black and white developer solution. For comparison purposes the same procedure was carried out using the black and white developing solution which is a known common anti-fogging agent, 6-nitro-isoindazole in place of the Compounds according to the invention contained, used.

Trial number Addition to the black amount of the

and -ft'eißrDeveloper addition solution

1 without -

2 Compound 1 2.0xlO ~ ⁵ mol / l

3 connection 3 "

4 6-nitroisoindazole "

5 * 5.OxIO " ⁴ "

The results obtained are summarized in the following table, in which the blue sensitivity (Ε - ^^ χ) and the red sensitivity (Β _Ώ ) of the unexposed

JX- »nietJw

Parts of test tires (parts with maximum density) and the sensitivities for the red and blue exposures are listed to the photographic effect to show.

109829/1594

2.4 3.4 175 115 3.4 3.5 100 100 3.5 3.6 99 98 2.5 3.4 150 105 3.7 3.7 70 72

Trial Numbers Maximum Density Sensitivity '

Blue density. Reddense blue red

'The sensitivity was determined by the relatively

Sensitivity of test sample 2 was assumed to be 100,

As can be seen from the table above, at Addition of the compounds according to the invention a good image quality with a sufficiently high blue density and a get a good balance of blue density and red density, without reducing the sensitivity. On the other hand, in the experiment using 6-nitroisoindazole found instead of the compound of the present invention that if the amount thereof was small, the influence of increasing the The blue density was low, and if the amount was large, the sensitivity was largely lowered although the blue density was increased so that good image quality was not obtained. In other words, the development of the top layer was prevented by the well-known development inhibitor, as well of the lower layers inhibited. On the other hand, in the Pail the application of the connections according to the invention an excessive Development of the top layer in the high temperature development was prevented, development was carried out with a good balance, and no decrease in sensitivity occurred, as can be seen from the table above.

Example 2

A multi-layer color photographic film that is Coating a cellulose triacetate film with a red

109829/1594

sensitive gelatin silver iodobromide emulsion layer, a green-sensitive gelatin-silver iodobronide emulsion layer, a gelatin-yellow filter layer containing colloidal silver and having blue absorption; and a blue-sensitive gelatin-silver iodobromide emulsion layer successively produced v / ar, was exposed by means of a sensitometer and then the following treatments subject.

Procedure temperature time

^ P pre-hardening

v / ater laundry

First black and white development. Water wash Reverse exposure (red light)

from the back of the film

Cyan color development Water washing reverse exposure (blue light)

from the front of the film

Yellow color development water wash

Second black and white development φ magenta color development water washing bleaching
Fixation
Water washing

The composition of the above treatment solutions were the following:

40 ⁰ C 30th Sec. Il 30th ti Il 75 It Il 30th Il 200 CMS 40 ⁰ C 180 Sec. Il 30th Il 200 CMS 40 ⁰ C 90 Sec. Il 30th ti Il 15th It Il 120 Il It 60 Il Il 60 Il Il 60 Il ti 60 It

109829/1594

Hardening solution: ■

Sodium hexametaphosphate 1.0 g

Sodium pyrosulfite 5.0 g

Sodium pyrophosphate 15.0 g

Sodium sulfate 150.0 g

Potassium bromide 2.0 g

Sodium hydroxide "0.1g

Formalin (37 p) 15.0 ecm

vYasser to 1 liter

First Seirarar2- and Weiß 5nt?; Ickler solution: N-methyl-p-aminophenol 5.0 g

Sodium sulfite 70.0 g

Hydroquinone 2.0 g

Sodium carbonate (monohydrate) 41.0 g Potassium bromide 4.0 g

Potassium thiocyanate 1.6 g

Potassium iodide (0.1 $ aqueous solution) 10.0 ecm 1 liter of water

Gyan-J color developer solution;

Potassium bromide __ 3.0 g

6-nitrobenzimidazole 0.03 g

Potassium iodide (0.1 ^c £ ± ge aqueous solution) 10.0 ecm

Sodium sulfite ITodium sulfate Potassium biocyanate

4-Amino-3-πlethyl-lT-ethyl-lί-bydroxyät'.ylaniline sulfate

Sodium hydroxide 1,5-dihydroxy-2,6-dibromonaphthalene Monobenzyl-p-aminophenol p-aminopnenol hydrochloride Water too

109829/1594

10.0 G 60.0 1.0 G 2.5 G 3.0 G 2.0 G 0.4 G 0.1 G 1 liter BATH ORIGINAL

Yellow colors TV / winding

Sodium sulfite potassium bromide

Potassium iodide (0.1% aqueous solution) 6-nitrobenzimidazole Sodium sulfate Ν, Ν-diethyl-p-phenylenediamine sulfite Sodium hydroxide (Cfc) -benzyl-4- (p-toluenesulfoamido) -acetanilide

Water too

10.0 g

0.5 g 25.0 ecm

0.1 g 60.0 g 2.5 g 2.5 g

1.8 g liters

Second black and!, Yiss development solution:

N-methyl-p-aminophenol sulfate 1.0 g Sodium sulfite 50.0 g Hydroquinone 1.0 g Sodium carbonate monohydrate) 41.0 g Potassium bromide 2.5 g Water too 1 liter Gastric color developing solution:

Sodium sulfite potassium bromide
Potassium thiocyanate sodium sulfate

N, N-diethyl-3-methyl-p-phenylenedianine hydrochloride

Sodium hydroxide l-phenyl-3- (m-nitrobenzoylamino) 5-pyrazolone

Ethylenediamine to water

5.0 g 1.0 g 1.0 g

60.0 g

2.5 g 2.0 g

1.4 g 8.0 ecm 1 liter

109829/1594

Bleach solution; Fericyanide potassium bromide V / ater too.

! Fixing solution ; Disodium thiosulphate sodium sulphite. Water too

In the above reverse development, the following compounds of the present invention became the precuring solution added.

100 G G 30th , 0 g S. 1 liter liter 150 10 1

hsnumE tier additive for pre-hardening added Me solution 1 without CVl Connection 2 ■ 5 '. OxKT ⁵ mol / l 3 Connection 4 Il 4th Connection 5 Il 5 Connection 6 Il

The photogr obtained in the development of _a phical characteristics are given in the following table. the

Blue density (D ₁₁ " _n J) and the red density (D _O "") of not jj — max · it — niax

exposed parts of the strip (parts of maximum density) are indicated as photographic properties. The blue density is the density of the top blue-sensitive emulsion layer of the film, which is the yellow color in the There is color development, and the red density is the density of the lowest red-sensitive emulsion layer that the Cyan color results. If the values are large and none show strong difference from one another, this means a good color balance and an image with good color reproduction.

109828/1594

Trial number Blue density Red density

1 2.3 3.5

2 3.6 3.5

3 3.6 3.6

4 3.3 3.6

5 3.2 3.5

As can be seen from the table, when adding the inventive Connections increase the blue density without reducing the red density.

Example 3

In the development treatment according to Example 2, the compounds of the invention of the first black and white developer solution was added, but the compound according to the invention was not added to the pre-hardening solution.

Trial number addition to the first black added

and Y / ice developer solution amount

1 without -

2 connection 7 2 OxKT ⁵ In ο l / l

3 connection 8 "

4 connection 10 "

5 connection 11 "

The photographic properties obtained in the experiments after development are shown in the following table specified. Blue density and red density are listed as photographic properties.

Trial number Blue density Red density

1 2.3 3.5

2 3.5 3.7

3 3.6 3.6

1Q9I29 / 1S9 *

4 3.7 3.6

5 3.6 3.6 "

As can be seen from the table, when the compounds according to the invention are added, the blue density is increased without that the red density is reduced.

Example 4

A multilayer type color photographic picture that of three silver halide emulsion layers with different Couplers (cyan, yellow and magenta) consisted of different spectral sensitivities to one another were exposed with a sensitometer and then subjected to the following treatment:

procedure tempera Color development 35 ⁰ G cancellation dd Water washing η Bleaching Il Fixation Il Water ashes ti

Time Min. 3 Sec. 30th H Min. 1 Sec. 90 Min. 1

The compositions of the treatment solutions were as follows:.

Color development solution

Sodium Hexametapliosphate Benzyl Alcohol Sodium Sulphite Sodium Carbonate Sodium Hydroxide

4-Amino-3-methyl ~ IT-ethyl-IT-methanesulfonamidoethylaniline sulfate Potassium bromide v / ater too

1.0 G 5.0 G 3.0 G 41.0 G 1.0 G 5.0 G 0.5 G 1 liter

109829/1594

20th , 0 g 1 liter 150 G 10 G 1 liter

Demolition solution;

Acetic acid * 25 ecm

Sodium acetate 3 g

Potassium alum 10 g

1 liter of water

Bleach solution

Ferricyanide. 100 g

Potassium bromide water too

Fixing solution sodium thiosulfate sodium sulfite water

In the case of negative color development, compound 3 was used according to of the invention added to the color developer solution in a narrow range of 5 × 10 mol / l.

When the results obtained were compared with those in the case of no addition of the compound, it was found that when the compound according to the invention is added, the topmost blue sensitive emulsion layer does not develop excessively and good color balance between the red, green and blue densities was obtained on development.

Example 5

In the development treatment according to Example 1, a pre-hardening step and an IT neutralizing step were carried out before the first black and white development. The Vorhärtungsbehandlung was carried out for 2 LIinuten and 30 seconds at 37 ⁰ C and the neutralization process was carried out for 30 seconds at 37 ⁰ O. The compositions of the treatment solutions were as follows:

BAD ORIGINAL 109829/1594

Pre-hardening solution

lormalin (37 ' sequence aqueous solution) 2, ■ 5-dimethoxytetrahydrofurane visual acid sodium sulfate potassium bromide borax

Water too

Neutralizing solution

Hydroxylamine sulfate potassium bromide glacial acetic acid Sodium sulfate sodium hydroxide to water

In the above reverse color development, the invention Compounds added to the neutralization solution, as can be seen from the following table:

20th e em 4th ecm CVJ ecm 100 S. CVJ G 5 β ' 1 liter 20th G 20th G 10 ecm 50 G 6th G 1 liter

Trial number

Additive to the neutralization solution

20xl0 " ⁵ mol / l

Amount added

1 without

2 · connection

3 connection 2 "

4 connection 5 "

The results obtained are shown in the following table, where the photographic properties are the blue density and the hot density as the maximum density and also the Reversal sensitivity are indicated.

109829/1594

* J
Reverse density ' Red density Blue density 115 175 100 100 99 199 105 102

Attempt & number maximum density

Blue density red density

1 2.4 3.4

2 3.5 3.6

3 3.7 3.7

4 3.5 3.6

'The reversal sensitivity is called relative sensitivity

indicated, v / obei the sensitivity of test number 2 to 100 was accepted.

As can be seen from the table above, the addition of the compound according to the invention greatly increases the blue density without any influence on the Sensitivity occurs and an image with better color balance of blue and red is obtained.

Example 6

A red-sensitive was applied to an acetyl cellulose film Gelatin silver iodobromide emulsion with a phenolic cyan coupler and further applied an intermediate gelatin layer. Then a green-sensitive gelatin-silver bromide emulsion was made applied to the intermediate layer with a pyrasolone magenta coupler and also a yellow filter layer formed on this layer. Then a blue-sensitive gelatin-silver iodobromide emulsion with a Ketomethylene yellow coupler was applied to the filter layer and finally a gelatin protective layer was formed on the blue-sensitive emulsion layer.

Two kinds of the foregoing color photographic film have been produced. One served as a control sample and

it was not a compound of the invention in any way Contain emulsion layer of the film, especially in the case of the invention Samples 0.5 g / Ag-mol of the compound 3 according to

BATH ORIGINAL

109829/1594

of the invention in the blue-sensitive emulsion layer of the photographic elm.

The produced color photographic film was made using a sensitometer and the color reversal development subjected to the procedure of Experiment 1 according to Example 1. The results are given in the following table.:. '

Maximum density reverse sensitive blue density Red density keif)

; Blue density of eot density

Gliding sample 2.3 3.3 145 According to the invention 3.5 3.5 100

Reversal sensitivity is called relative sensitivity

indicated, the sensitivity obtained with the sample according to the invention being set to 100.

As can be seen from the table above, im If the compound according to the invention is added, the blue density is sufficient, even with high-temperature development and an image with better color balance of blue density and hot density is obtained.

109829 / 15S4

Claims (6)

Claims A development process characterized in that a silver halide multilayer color photographic material is subjected to a high temperature treatment in the presence of a compound represented by the general formula. ·· _N • R ₁ CC ι - I I ! R, C N ~ - SH wherein R ₁ and Rp, which may be the same or different, each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a haloaryl group and R- represents a hydrogen atom, a halogen atom or an alkyl group. 2. A method for developing a silver halide color photographic training layer material, characterized in that that the photographic material is treated at a high temperature with a solution containing a compound appropriately the following formula V-? i R C N ■! 'ι ■. . i SH. wherein R- and Rp, which can be the same or different *, each represent a hydrogen atom, an alkyl group, a Aralky! Group, an aryl group or a haloaryl group 109829/1594 and IU- is a hydrogen atom, a halogen atom or a
Mean aryl group contains. 3. The method according to claim 2, characterized in that the developing solution is used as such a solution will. 4. The method according to claim 2, characterized in that that the pre-hardening solution is used as such a solution. 5. The method according to claim 2, characterized in that an ITeutralisierlösung is used as such a solution will, ' 6. The method according to claim 2-5, characterized in that a temperature higher than 35 ⁰ C is applied. 1Q9829 / 1594