DE2103806B2 - AFTER-TREATMENT BATHROOM FOR DEVELOPED AND FIXED COLOR PHOTOGRAPHIC RECORDING MATERIALS - Google Patents

Description

OH

SO., H

H, C— ■ ''

-CH,

-CO, H

OH

OH

OH

OH

OH

OH

CH = NOH

9. aftertreatment bath according to claims 1 to 6 and 8, characterized by a content of Urea and hydroquinone.

10. aftertreatment bath according to claims 1 to 6 and 8, characterized by a content of Ethylene urea and hydroquinone.

11. Post-treatment bath according to claims 1 to 6 and 8, characterized by a content of parabanic acid and hydroquinone.

OH The invention relates to an aftertreatment bath for developed and bleach-fixed color photographic products Recording materials.

It is generally known that color photographic recording materials with color-forming dyes, for example of the indophenol, indamine or azomethine type, by implementing a development

by means of the aromatic amine type and one Couplers produce images with poor lightfastness. To improve the lightfastness of the images These color photographic systems are generally known to have the following processes:

1. A material that absorbs ultraviolet light is incorporated into color photographic materials, for which reference is made to US Patents 2,632,701 and 2,747,996;

2. a reducing agent or an antioxidant ι ο is incorporated into color photographic materials, including U.S. Patents 2,384,658 and 30 95 302 is referred to.

For incorporating these compounds into the photographic materials, a <n method is the previous addition to the photographic emulsion layers and a method of incorporation of the photographic emulsion layers during processing of the photographic materials the types of the compounds and the properties of the light-sensitive materials are known.

The color photographic light-sensitive materials are usually subjected to the following processing steps after exposure. For example the color photographic material is subjected to the stages of color development, interruption fixing, washing, Bleaching, washing, hardener fixation, washing and stabilization according to "The British Journal of Photography" September 27, 1968, p. 838 or the stages of prebath treatment, rinsing, color development, rinsing, Fixing, soaking, bleaching, soaking, fixing, soaking and stabilizing according to »Journal of the SMPTE ", Vol. 51, No. 12, p. 667 (1963).

It is also known a treatment bath containing a compound having a hydroxyl group, an amino group or a substituted amino group. to improve the stability of the images in the above-mentioned known color photographic processing steps, for which reference is made to US Pat. No. 2,384,658. It is _4C, although the light fastness of the magenta dye of the above patent was treated, even in the color photographic material thereof with a bath containing hydroquinone or a derivative according to, improved, but the problems arise that brown spots significantly to the non-image parts of the form color photographic material upon light development. The ascorbic acid specified in the same patent also improves the lightfastness of the magenta dye itself, but such defects result that brown spots are also formed in the same way and the cyan density is considerably reduced during the treatment. It is also known that bile acid improves the stability of the images, for which reference is made to US Pat. No. 3,069,262. However, the compounds specified above not only slightly improve the lightfastness of the magenta dye compared to the compounds described in US Pat. No. 2,384,658, but also produce strong brown spots. Urea or guanidine or derivatives thereof are also known as agents for preventing light fading, for which reference is made to US Pat. No. 3,095,302. However, as indicated in US Pat. No. 3,201,244, the effects of urea are poor, and guanidine and derivatives thereof also give insufficient effects in preventing light fading.

It is also known that carbohydrazide improves the lightfastness of gastric carbohydrates, for which reason Reference is made to US Pat. No. 3,201,244. Albeit the lightfastness of the magenta color by treating a color photographic material with a bath containing this compound, is improved, the dye bleaches when the resulting color photograph is at high temperatures, for example at 76.7 ° C, is stored considerably. In addition, there are also polyhydroxy compounds according to US Pat. No. 3,095,302. Cysteine according to US Pat. No. 3,201,243 and the like Light fade prevention agents, though the effects of these are insufficient.

The object of the invention is to create an aftertreatment bath for developed and bleach-fixed photographic recording materials with which the fading of color images by light and Heat and the formation of stains are prevented, so that good light-stable color copies are obtained can.

The problem is solved with an aftertreatment bath for developed and bleach-fixed color photographs Recording materials, which are characterized by the combination of the following features is that there is in aqueous solution A at least one water-soluble compound according to the general formula

X X

il ii

NH (CMNHyO ₁₁ R,

X = C

\
NHR ₂

wherein Ri is a hydrogen atom, an alkyl group, an AHyl group, an aryl group or the group NHR3, R2 and Rj is a hydrogen atom, an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an AHyl group or an aryl group, the radicals Ri and R2 with each other to form a 5-membered or 6g! '> third heterocyclic ring can be connected, X the radicals = O or = NH and k and η denote the number 0 or 1, and B at least one water-soluble compound corresponding to the general formula

(Π)

where R4, R5, Re and R? a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group, a sulfonic acid group or a group CH = NOH, ρ the number 2 or 3, q the number 0 or 1 and P + q always the number 3 contains.

As already indicated above, the compounds according to the general formula I or the compounds corresponding to the general formula II so far individually as a means of preventing the Light exhaust used. However, their effect is insufficient and also undesirable Accompanied by side effects. On the other hand, if both

en Compounds used together according to the invention will give extremely unexpected results obtain. It is extremely surprising that the formation of stains when a compound is used corresponding to the general formula Ii by joint application of a compound of the general formula I can be prevented and they thereby have an excellent effect for Prevention of light blowout results.

The benefits obtained by applying the treatment solution that has a compound according to the general Formula I and a compound corresponding to the general formula II according to the invention, can be summarized as follows:

1. The lightfastness of magenta dyes the most diverse lighting materials is significantly improved.

2. The lightfastness of the yellow dye to various types of light is improved.

3. Hardly stains are formed when exposed to various kinds of light.

4. The discoloration and fading of the cyan dye due to heating and the formation of Stains are prevented.

The compounds corresponding to general formula 1 can be used as addition salts, for example as Carbonates, hydrochlorides. Sulfates and the like can be used to increase the water solubility thereof.

Typical examples of the compounds corresponding to general formula 1, which are preferably used in the context of Invention used are the following:

Connection uni; 1

NH,

C) = C

NH ₂

Connection 2
NH,

O = C

NH-

Connection 3
NHCH,

O = C

\
NHCH ₃

Connection 4
NH,

O = C

NHCONH,

Connection 5
NHNH,

O = C

NH,

Compound 6 NHNH,

O = C

NHCH ₅

Compound 7 NHNH,

O = C

O = C

NH -; - ,.

Compound 8 NH -CH ₂

NH-CH,

Compound 9 NH-CH;

O = C CH ₂

NH-CH,

Connection hi

Ij

NH-C

O = C

NH-CO

Compound 11 NH, H-, N

O = C

C =

HN "

Compound 12 NH,

HN = C ^ · HXO ₃ V ¹ H,

Compound 13 NHNH,

HN = C · H ₂ CO,

NH,

2 1 03 806 V 10 9 Connection 2 Connection 14 OH NHCH, COOH

HN = C

NH,

Compound NHCH ₂ CH ₂ SO ₃ H

HN = C

NH,

Typical examples of compounds corresponding to general formula II, which can preferably be used in the context of the invention, are the following:

Connection OH,! - SO, H

OH

Connection OH

Λ- *

OH

Connection OH

CO, H

OH

Connection OH

Y \

Y / - ° ^H

Connection OH

Connection OH

OH OH

Connection OH

OH

Compound ^0H CH,

i :

Yy-C-CH,

y CH,

OH

Connection OH

-T ^ Y-CH,

AY

OH

Connection OH

CH = NOH

OH

The above compounds are all known and can be prepared by known methods. The commercial connections can be used as they are.

The amounts of the compounds according to the general formulas above are as follows:

lot

Optimal amount

General formula I 1 to 100 g / l, 15 to 45 g / l General formula II 0.1 to 10 g / l 1 to 5 g / l

Furthermore, the treatment bath according to the invention can be used with great advantage on photosensitive Materials used are the ultraviolet absorbers according to US Pat. No. 3,352,681 and British Patent 10 26 142 included. It is also effective to make the connection according to the ■ general formula 1 and the compound corresponding to the general formula II for the stabilizing baths

ε measured "The British Journal of Photography" from ptember 1968, p. 838 or "Journal of the SMPTE", id. 61, No. 12, p. 667 (1963) to be added.

Example 1 color developer solution (pH 10.6)

Sodium metaborate 25.0 g

Sodium sulfite 2.0 g

Hydroxylamine (sulfate) 2.0 g

Potassium bromide 0.5 g

6-nitrobenzimidazole (nitrate) 0.02 g

Sodium hydroxide 4.0 g

Benzyl alcohol 15.8 ml

Diethylene glycol 20.0 ml N-ethyl-N- (methanesulfonamido-

ethyl) -p-phenylenediamine 8.0 g

1 liter of water

Tamping fixation solution (pH 4.5)

Ammonium thiosulfate 120.0 g

Sodium pyrosulfite 20.0 g

Glacial acetic acid 10.0 g

1 liter of water

Bleach solution (pH 7.2)

Potassium nitrate 25.0 g

Potassium ferricyanide 20.0 g

Potassium bromide 8.0 g

Boric acid 5.0 g

Borax 2.5 g

1 liter of water

Hardening fixer solution (pH 9.5)

Ammonium thiosulfate 120.0 g

Sodium sulfite 5.0 g

Boric acid 2.5 g

Formalin (35 to 40%) 40.0 ml

1 liter of water

A color photographic photosensitive paper obtained by coating a baryta-coated paper with a blue-sensitive silver iodobromide emulsion layer containing benzoylaceto ^ -chloro-S-dodecyloxycarbonylanilide as a yellow coupler, an intermediate gelatin layer, a green-sensitive silver chloropropionamidocapyl [3- )] - 5-pyrazolone contained as a magenta coupler, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer, the 1-hydroxy-2- [3- (2,4-tert-amylphenoxy) propyl] -naphtamide
contained as a cyan coupler, and a protective gelatin layer in the stated order was prepared, was exposed and sequentially the following treatments at 30 ⁰ C using the above processing solutions, that is, a color development for 7 minutes, a stop fixing for 2 minutes, a rinsing for 2 minutes , lamination for 2 minutes, soaking for 2 minutes, hardening fixation for 2 minutes and subsequent soaking for 4 minutes. Subsequently, the thus treated photographic paper was further treated with each of the following treatment baths for 2 minutes and then dried.

Addition (amount)

Treatment bath 1
Treatment bath 2
Treatment bath 3
Treatment bath 4
Treatment bath 5

35 treatment bath 6

Treatment bath 7
Treatment bath 8

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l (20g)
1 (40 g)
16 (2 g)
16 (4 g)
1 (20 g) and
16 (2 g)
l (20g) and
16 (4 g)
1 (4Og) and
16 (2 g)
1 (40 g) and
16 (4 g)

In the table above, the amount of additive added is the number of grams of additive per liter of the treatment bath.

With the samples specified in each case with the treatment baths specified above, the Stability test of the images carried out under the conditions given in the table below

Final treatment

Fluorescent lamp (10000 lux) fade ratio after exposure during 10 days *)

Yellow Magenta Cyan DY ') (%) (%) (%)

Direct sunlight

Fade ratio after suspension
for 15 days

Yellow magenta cyan DY ')

Without 25 50 10 +0.07 30 50 12 +0.07

Treatment bath 1 23 45 10 +0.06 28 46 12 +0.07

Treatment bath 2 21 43 10 +0.06 26 44 12 +0.06

Treatment bath 3 25 38 10 +0.09 30 37 11 +0.09

Treatment bath 4 25 35 11 +0.12 30 35 11 +0.11

Treatment bath 5 15 15 11 +0.04 15 16 11 +0.04

Treatment bath 6 14 12 10 +0.04 14 12 10 +0.04

Treatment bath 7 12 13 10 +0.04 12 13 10 +0.04

Treatment bath 8 12 12 10 +0.04 12 12 11 +0.04

*) The fade ratio gives the ratio of the reduced color density of the part with one during the test

Initial density of 1.0.

') DY is the value of the increase in density of the unexposed part, which is given by the density of the yellow component

■ f

From the test results given in the table above, the following facts clearly emerge and the effectiveness of the present invention is understandable:

1. The known treatment baths 1 and 2 only showed a slight effect of preventing the light fastness,

2. the known treatment baths 3 and 4 gave remarkable preventive effects for the Fading of the magenta dye, which so far has never happened when using the known Compound 1 or individually.

3. The treatment baths 5 to 8 according to the invention resulted in a remarkable prevention of the Light fading effect of magenta images, which never occurs when using the known compounds 1 or 16 could be obtained individually,

4. The treatment baths 5 to 8 according to the invention gave both a preventive effect for the light fading effect of the yellow images as well as an effect of preventing the formation of spots when exposed to light.

The samples treated with the above treatment baths were at Stored 76.7 ° C under low humidity conditions. The ratios of the color densities that were reduced during the conservation attempt, a part with an initial density of 1.0 and the densities [DY] of the unexposed parts, which are increased with regard to the formation of stains, also result from the following table.

Final

treatment

yellow

Mu cyan
genta

DY of the invention treated samples improved stability of the cyan dye to heat and also had fewer stains on heating.

Virtually the same results were obtained when using color photographic films instead of color photographic films Papers were used.

Example 2

After the color photographic papers specified in Example 1 of color development, plug fixation, the washing, the bleaching, the washing, the hardening setting and the washing according to Example 1 were subjected, the color photographic papers were each in one for 2 minutes the following treatment pictures treated and dried.

0 1 15th + 0.06 Treatment bath 16 Without 0 2 5 + 0.03 Treatment bath 5 0 2 7th + 0.03 Treatment bath 8 The pictures of the a

As can be seen from the above test results, those with the treatment baths according to Addition (grams per Liier)

Compound 16 (2 g) + Compound 1 (30 g) Compound 16 (2 g) + Compound 2 (30 g) Compound 16 (2 g) + Compound 4 (30 g) Compound 16 (2 g) + Compound 5 (30 g) Compound 16 (2 g) + Compound 8 (30 g) Compound 16 (2 g) + Compound 10 (3Og) Compound 16 (2 g) + Compound 12 (30g) Compound 16 (2 g) + Compound 14 (30 g)

were examined under the following conditions with the results in the following table are specified.

Treatment bath 9
Treatment bath 10
Treatment bath 11
Treatment bath 12
Treatment bath 13
Treatment bath 14
Treatment bath 15

Image fluorescent lamp (10,000 lux)

Final fading treatment after exposure during 10 days *)

Yellow Magenta Cyan DY ') Direct sunlight

Fade faucet after exposure for 15 days

Yellow magenta cyan DY ¹ )

Without 25th 50 10 + 0.07 30th 50 12th + 0.07 Treatment bath 2 21 43 10 + 0.06 26th 44 12th + 0.06 Treatment bath 4 25th 35 11th + 0.12 30th 35 11th + 0.11 Treatment bath 9 12th 12th 10 + 0.04 12th 12th 11th + 0.04 Treatment bath 10 15th 15th 10 + 0.04 14th 14th 12th + 0.04 Treatment bath 11 13th 14th 11th + 0.04 14th 14th 11th + 0.04 Treatment bath 12 14th 11th 10 + 0.04 15th 12th 12th + 0.04 Treatment bath 13 12th 12th 11th + 0.04 12th 12th 12th + 0.04 Treatment bath 14 12th 12th 10 + 0.04 12th 12th 11th + 0.04 Treatment bath 15 13th 13th 10 + 0.04 14th 14th 11th + 0.04 Treatment bath 16 13th 14th 10 + 0.04 14th 14th 12th + 0.04

*) The fade ratio is the ratio of the reduced density during the test of the part with an initial

density of 1.0.

') DY is the value of the increase in density of the unexposed part, which is shown by the density of the yellow component

According to the above experimental results, the treatment baths according to the invention clearly exhibited a remarkable effect of preventing light fading of magenta dyes, an effect of preventing light fading of yellow dyes, and an effect of preventing

21 03 8G6

the formation of spots. If, furthermore, those treated with the treatment baths according to the invention Samples stored at 76.7 ° C under low humidity conditions were the Fading of the cyan dye was low and the formation of stains was also as in Example 1. low

When color photographic films were used in place of color photographic papers, were obtained practically the same results.

Example 3

A color photographic positive film obtained by coating an acetate film with a blue-sensitive Silver iodobromide emulsion layer, the benzoylaceto-2-chloro-5-dodecyloxycarbonylanilide contained as yellow coupler, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer. die 1-hydroxy-2- [3- (2,4-tert-amylphenoxy) propyl] naphthamide contained as a cyan coupler, an intermediate gelatin layer. a green-sensitive chlorobromide emulsion layer, which contained 1-phenyl-3- [3- (N-butylcaprylamidopropionamide)] -5-pyrazolone as a magenta coupler, and one The protective gelatin layer that had been sequentially produced in this order was exposed to light and subjected to the following treatments at 21 ° C, namely the steps of a pre-bath treatment during 10 seconds, rinsing for 15 seconds, development for 12 minutes, rinsing for 15 seconds, fixation for 4 minutes, washing for 4 minutes, bleaching for 8 minutes, washing for 8 minutes, fixation for 4 Minutes and soaking for 8 minutes. In the above development process, a developer solution with the following composition is used:

Developer solution (pH 10.65)

Calgon (name) 2.0 g Sodium sulfite 4.0 g N, N-diethyl-p-phenylenediamine (Hydrochloride) 3.0 g Sodium carbonate (monohydrate) 20.0 g Potassium bromide 2.0 g Water too 1 liter

The bath for the pretreatment bath contained sodium hydroxide and the fixer bath contained sodium thiosulfate and the bleach bath contained potassium dichromal. The photographic treated by these methods The film was treated with one of the following treatment baths for 2 minutes:

Addition (grams per liter)

Treatment bath 17
Treatment bath 18
Treatment bath 19
Treatment bath 20
Treatment bath 21

Compound 1 (30 g) +
Compound 20 (2 g)
Compound 1 (30 g) +
Compound 21 (2 g)
Compound 1 (30 g) +
Compound 22 (2 g)
Compound 1 (30 g) +
Compound 25 (2 g)
Compound 1 (30 g) +
Compound 26 (2 g)

Those with the above treatment baths

Treated samples were compared to those in the following table with regard to the stability of the images obtained investigated specified conditions, the results of which are given in the following table.

image Fluorescent lamp (10,000 lux) magenta after suspension Direct sunlight 15 days after suspension Final treatment Fade ratio (%) Fade ratio magenta during 10 days *) 40 Cyan DY ') while (%) Cyan DYi) yellow 35 (O / o) yellow 40 (%) (%) 29 10 + 0.05 (%) 34 13th + 0.05 Without 20th 9 10 + 0.04 24 30th 13th + 0.04 Treatment bath 2 17th 9 11th + 0.10 17th 8th 13th + 0.11 Treatment bath 4 20th 9 10 + 0.03 20th 8th 14th + 0.03 Treatment bath 9 9 10 10 + 0.03 9 8th 14th + 0.03 Treatment bath 17 9 10 10 + 0.03 9 9 13th + 0.03 Treatment bath 18 10 10 10 + 0.03 9 9 13th + 0.03 Treatment bath 19 9 11th + 0.03 10 9 13th + 0.03 Treatment bath 20 9 10 + 0.03 10 14th + 0.03 Treatment bath 21 9 9

*) The fade ratio is the ratio of the color density of the parts with an initial density of 1.0 formed during the test.
') DY is the value of the increase in density of the unexposed part, which is indicated by the density of the yellow component.

From the above test results it is clear that the treatment baths according to the Invention a remarkable effect of preventing light fading of magenta dye, a remarkable light fading prevention of yellow dye and an effect of preventing the formation of spots. Even if those treated with the treatment baths according to the invention Samples stored at 76.7 ° C under low humidity conditions was that Fading of cyan dye was low and stain generation was also low, as in FIG Example 1 shown.

Even when color photographic papers are used in place of color photographic positive film practically the same results were obtained.

Claims (8)

Patent claims: 1. Post-treatment bath for developed and flex-fixed color photographic recording materials, characterized by the Combination of the following features that there is at least one water-soluble solution in aqueous solution A Compound according to the general formula IO X = C X X Ii Il ^ NH (CUNH) _n (C) ₁₁ R ₁
^ NHR, (D Wherein Ri is a hydrogen atom, an alkyl group, »an allyl group, an aryl group or the group NHR3, R2 and R3 a hydrogen atom, an alkyl group, a carboxyalkyl group, a sulfoallcyl group, an allyl group or an aryl group,» Obei the radicals Ri and R2 with each other to form a 5-membered or 6-membered heterocyclic ring can be connected, X is the radicals = O Or = NH and k, m and η are the number 0 or 1, and B is at least one water-soluble compound corresponding to the general formula jo (II) where R4, Rs, R6 and R7 are a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group, a sulfonic acid group or a group CH = NOH, ρ the number 2 or 3, q the number 0 or 1 and P + q always the number 3 mean contains. 2. aftertreatment bath according to claim 1, characterized in that it is 1 to 100 g / liter of Connection of general forms! I contains. 3. aftertreatment bath according to claim 2, characterized in that it is 15 to 45 g / liter of Compound of general formula I contains. 4. aftertreatment bath according to claims 1 to 3, characterized in that it is 0.1 to 10 g / liter of the compound of the general formula H in the treatment solution. 5. aftertreatment bath according to claim 4, characterized in that there is 1 to 5 g / liter of the compound of the general formula 11 in the treatment solution. 6. aftertreatment bath according to claims 1 to 5, characterized in that the connection according to the general formula 1 is one of the following compounds: 35 40 45 O = C NH ₁ NH, 55 60 2
NH ₂ O = C O = C O = C O = C NHCH, ^ NHCH, NH, ^ NHCONH, NHNH, NH,
NHNH, NHCH, NHNH, NH-CH, O = C CH, O = C NH-CH, NH - CH ₂ Il NH-C /
O = C NH-CO NH ₂ H ₂ N / \ O = C C = NH - HN 7. aftertreatment bath according to Ai to 5, characterized in that the according to the general formula I is one of the following compounds: NH ₂ HN = c '· H ₂ CO., NH ₂ NHNH, HN = C · H ₂ CO, NH ₂ NHCH ₂ COOH HN = C \
NH, HN = C NHCH, CH ₂ SO., H NH, 8. aftertreatment bath according to claims to 7, characterized in that the connection of the general formula II is one of the following compounds: OH OH