DE1772924B2 - Color developer for photographic materials - Google Patents

Description

The invention relates to color developers for photographic materials, and more particularly to Color developer, the new, water-soluble leveling developer contain.

In general, a color photographic, light-sensitive material for the reversal process which contains a coupler in one Developer is to be developed after exposure to a customary black and white development and then, after reverse exposure, in one containing a coupler Color developer treated. Usually such a photographic material has a plurality of emulsion layers including three selective, photosensitive emulsion layers. For example such a color photographic element will have a lowermost red-sensitive emulsion layer a green-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer and an uppermost protective layer is formed on a substrate in the order given. A Color developer used for developing such a reversal color photographic light-sensitive material is used usually consists of an alkaline aqueous solution containing a developer of the p-phenylenediamine type with at least one primary amino group. and a color-forming one Couplers and, in general, additives such as sodium sulfite. Sodium bromide or the like. Contains. aside from that usually become a phenolic or naphtholic coupler in such a color developer as a cyan color former, a pyrazolone coupler as a magenta color former and an open-chain ketomethylene coupler used as a yellow color former.

When a reversal color photographic material is cyan development using a color developer, containing a color former or coupler is known to be subjected to suppression the formation of cyan fog in the green-sensitive emulsion layer and the blue-sensitive Emulsion layer of the color photographic element to the cyan developer a leveling developer admitted. As such a leveling developer, N-benzyl-p-aminophenol can be used (DT-AS 11 77 486). It is known that such a leveling developer results in a reduction of the oxidized Color developer to the original developer and a reduction in the exposed silver halide to metallic silver causes. The compensatory developer contributes to the suppression to a very great extent a cyan contamination in the blue-sensitive emulsion layer and particularly in the green-sensitive emulsion layer, and therefore to a correct red reproduction of a photographed Object, since the level developer and the color developer compete with the exposed one Halogen silver react.

The leveling developer practically used in photographic processes must be removed by removal the cyan contamination to increase the red contrast and also to increase the sensitivity the red-sensitive emulsion layer, moreover, the leveling developer may use the maximum Do not lower the density of the red-sensitive emulsion layer as well as that for the cyan color developer do not degrade specific high clarity and moreover the compensation developer may too do not decrease photographic properties without lowering the durability of the cyan developer.

However, when a common color developer that uses a leveling roller for color reversal processing contains, is used, the red contrast and the haze prevention are insufficient, and especially become the decrease in sensitivity with the passage of time as well as the increase in fogging and the Increase in cyan contamination in the green-sensitive emulsion layer is remarkable, and it also, it becomes necessary to increase the amount of the developer to be supplied, thereby reducing the usability of the color development process in terms of photographic suitability as well as economical Respect is significantly reduced.

The object of the invention is therefore to provide a color developer for photographic materials, which has no fog and no cyan contamination in color developing with low aging Caused recording material and ensures a correct red rendering of the subject.

The solution to this problem is achieved by a color developer for photographic materials, which (1) an aromatic primary amine as a color developing agent, (2) a color former, (3) an alkali and (4) contains a secondary p-aminophenol as a leveling developer substance and which is characterized by this is that he has 2 - methyl - 5 - (p - hydroxyaniiinomethyl) coumaran as a compensating developer, 6 - (p - Hydroxyanilinomethyi) - chroman. p-Hydroxyphenylpiperonylamine, 6- (p- Hydroxyanilinomethyi) - 1,4-benzodioxane, 5- (p-hydroxyanilinomethyl) -isocumaran or 6 - (p-hydroxyanilinomethyl) -isochroman contains.

Among the color developers according to the invention, a cyan color developer showing an alkaline one aqueous solution containing a p-phenylenediamine type color developer and a well-known phenolic one or naphtholic cyan color former and a leveling developer according to the invention contains, in particular with regard to the subsequent

standing items compared to common ones Cyan color developers, excellent properties. The cyan color developers are distinguished by the prevention of fog, and cyan contamination and also by a correct red rendering of the object. They also show a low aging.

The concentration of the leveling developer used according to the invention depends on the type and concentration of the color developer and the coupler in the color developer and the pH of the color developer, but generally a concentration of 0.01 to 5.0 g per liter of the developer is preferred. A concentration of OJ to 1.0 g / l is particularly preferred. _1S

The leveling developer is usually used as a salt such as the hydrochloride, which is more stable than the free amine.

The leveling developing agent used in the invention can be effectively used in cyan color developers, magenta color developers and yellow color developers, but it is most effective in cyan color developers. The color developer substance used in the color developer according to the invention is a common p-phenylenediamine derivative, for example Ν, Ν-diethyl-p-phenylenediamine sulfite, N, N - diethyl - 3 -methyl - ρ- phenylenediamine hydrochloride, 4 - amino - 3 - methyl - N - ethyl-N-methanesulfonamidoethylaniline sulfate, 4-amino-3-methyl-N-ethyl-N-hydroxyethylaniline sulfate or _Jo N -ethyl-N-hydroxyethyl-p-phenylenediamine sulfate.

Examples of the color formers used according to the invention are 2,4-dichloro-1-naphthol, 2,4-dichloro-5-tolylsulfonamido -1-naphthol, 1-oxy-2-benzylnaphthamide, 2,6-dibromo-1 , 5-dihydroxynaphthalene, benzoylacetanilide, <»- benzoyl - 4 - (p - toluenesulfonamido) - acetanilide, 1 - phenyl - 3 - (m - nitrobenzoylamino) -5-pyrazolone or cyanoacetylcoumarone.

Examples for the preparation of the new leveling developer substances used in accordance with the invention are given below:

1. Preparation of 2-methyl-5- (p-hydroxyanilinomethyU-coumaran hydrochloride (Connection 1)

A mixture of 16.5 g of p-aminophenol and 24.5 g of 2-methyl-5-formylcoumaran was refluxed in 100 ml of ethanol for 30 minutes, and the product was concentrated to obtain 30 g of a Schiff base. The Schiff base was mixed with 150 ml of methanol, and while stirring the mixture at room temperature, 4.5 g of sodium borohydride was slowly added to the mixture over 10 minutes. Thereafter, the product was poured into 300 ml of ice water containing a small amount of acetic acid, and the crystals thus formed were collected by filtration and recrystallized from benzene, whereby 25 g of 2-methyl-5 - (p - hydroxyanilinomethyl) - coumaran having a melting point from 107 to 109 ⁰ C were obtained. The hydrochloride of coumaran consists of colorless flakes with a melting point of 167 to 170 C (decomp.).

Elemental analysis:

Found ... C 66.12, H 6.41, N 4.57%;
.. C 65.84, H 6.25, N 4.80%.

45

2. Production of p-hydroxyphenylpiperonyl

amine hydrochloride (compound 2)

One prepared by reacting p-aminophenol (14.0 g) with 19.4 g of piperonal in 240 ml of ethanol Schiff base was reduced with sodium borohydride as in the preparation of compound 1, and the amine compound thus obtained was recrystallized from benzene to give 23 g of p-hydroxyphenylpiperonylamine in the form of colorless prisms with a melting point of 83 to 84 ° C. That The compound's hydrochloride consists of colorless prisms with a melting point of 165 to 180 ° C (Dec.).

Elemental analysis:

Found ... C 59.77, H 5.14, N 5.24%;
calculated ... C 59.80, H 5.10, N 5.06%.

3. Production of 6- (p-hydroxyanilinomethyl) -

chroman hydrochloride (compound 3)

23.0 g of a Schiff base, which had been prepared by reacting 10.3 g of p-aminophenol with 15.3 g of 6-formylchroman in the same manner as in the preparation of compound 1, were dispersed in 150 ml of an 18% strength aqueous sodium hydroxide solution and reduced with the gradual addition of 12.0 g zinc dust. The product was neutralized and extracted with ether. The extract was concentrated to give crystals, which were collected by filtration and recrystallized from benzene. There was obtained, 18.0 g of colorless crystals of 6- (p-Hydroxyanilinomethyl) -chroman having a melting point 95 to 96 ⁰ C. The hydrochloride of the compound consists of colorless platelike crystals with a melting point 173-188 ⁰ C (dec.).

Elemental analysis:

Found ... C 65.74, H 6.21%;
calculated ... C 65.84, H 6.25%.

4. Preparation of 6- (p-hydroxyanilinomethyl) -1,4-benzodioxane hydrochloride (Connection 4)

27 g of a Schiff base obtained by reacting 20.1 g of p-aminophenol and 13.4 g of 3,4-ethylenedioxybenzaldehyde was made with

Zinc dust and sodium hydroxide as reduced in the preparation of compound 3. That so educated Product was recrystallized from benzene, whereby colorless crystals of the desired amine with a Melting point of 84 to 84.5 ° C were obtained. in an amount of 20 g. The hydrochloride the compound consisted of colorless crystals with a melting point of 170 to 180 "C (decomp.).

Elemental analysis:

^h0 Found ... N 4.19%;
calculated ... N 4.77%.

The invention is explained in more detail below with reference to examples which show that the Color developers according to the invention containing leveling developer substance over others Color developersi. which contain other common compensating developers, is clearly superior.

1772

Example 1

A multilayer color photographic film comprising a support and a red-sensitive gelatin-iodobromide silver emulsion layer, a green-sensitive gelatin - iodobromide silver - emulsion layer, a blue-absorbing yellow filter layer, the colloidal Contains silver, and a blue-sensitive gelatin-iodobromosilver emulsion layer in the specified Sequence on the support was exposed by means of a sensitometer and the following treatments subject to:

treatment

First development
Water

Reverse exposure (red) at
200 CMS from the surface

Cyan color development
Water

Reverse exposure (blue) at
200 CMS from the back ropes

Yellow color development

Water

Second black and white development watering

Reverse exposure (white light) at 2000 CMS from both sides

Magenta color development

Water

bleaching

Water

Fix

Water

The compositions of the treatment baths used in the above treatments are listed below:

First and second black and white developers

N-methyl-p-aminophenol sulfate ... 2.0 g

Sodium sulfate 9.0 g

Hydroquinone 8.0 g

Sodium carbonate (monohydrate) .. 52.5 g

Potassium bromide 5.0 g

Potassium thiocyanate 1.0 g

Water, rest to 1000 ml

Cyan color developer

Sodium sulfite 5.0 g

2-amino-5-N, N-diethylamino-

toluene hydrochloride 0.6 g

Sodium carbonate (monohydrate) .. 15.0 g

Potassium bromide 0.5 g

Potassium iodide (0.1% aqueous

Solution) 5 ml

l, 5-dihydroxy-2,6-dibromo

naphthalene 1.2 J.

Tem Time 15 temperature CC) (Min. L 24 ⁵ ze 24 2 24 24 2 24 24 2 24 2 24 2 24 5 24 8th 24 2 40 24 2 24 2 24 2

924 Vf

'6

Sodium hydroxide 2.0 g

Water, rest to 1000 ml

Yellow colored wraps

Sodium sulfite 5.0 g

Ν, Ν-diethyl-p-phenylene-

diamine sulfite 2.5 g

Potassium bromide 1.0 g

Potassium iodide (0.1% aqueous

Solution) 5.0 ml

™ -Benzoyl-4- (p-toluenesulfone-

amido) acetanilide 1.2 g

Sodium hydroxide 2.5 g

Water, rest to 1000 ml

Stomach color developer

Sodium sulfite 5.0 ε

2-amino-5-N, N-diethylamino-

toluene hydrochloride 2.0 g

Potassium bromide 0.8 g

l-phenyl-3- (m-nitrobenzoyl-

amino) -5-pyrazolone 1.4 g

Sodium hydroxide 2.0 g

n-butylamine 5.0 ml

Water, rest to! 000 ml

Bleach solution

Potassium ferricyanide HK) g

Potassium bromide 10 g

Borax 20 g

Boric acid 1.0 g

Water, rest to 1000 ml

Fixing solution

Sodium thiosulfate 150 g

Sodium sulfite 10 g

Water, rest to 1000 ml

In the reverse color development process given above, that in the following was used The leveling developing agent listed in Table 1 corresponds to the above-described cyan color developer was added and its effect on photographic properties was measured.

Table I.

attempt

Compensating developer

N-benzyl-p-aminophenol hydrochloride

6- (p-Hydroxyartilinomethyl) -chroman hydrochloride

2-methyl-5- (p-hydroxyanilinomethyl) coumaran hydrochloride

♦) mmol / 10000ml developer.

Menyc *

0.85 0.85 0.85

The photographic properties are shown in Table II below, in which the reversal sensitivity is represented by the reverse logarithm of an exposure amount at which the coupling density obtained is 1.0. The purity of the reproduced red color is determined by the ratio of red filter density to green filter density (DJD ₉ ) of one exposed to red light

Part (referred to as red spot) and represented by the ratio of the red filter density to the blue filter density (DJD ₁ ,) of this part. The ratio is a value representing the color purity of a reproduced color when a red object is reproduced as a color photograph, the lower the value, the better the color purity.

Tabel!!

Try reversing sensitivity

Purity of the produced red color

Cyan

1.13
1.18
1.20

yellow

1.27
1.29
1.30

magenta

1.20 1.25 1.24

15th

0.33 0.27 0.29 0.23 0.28 0.23

These results show that by incorporating the leveling developing agent according to the Invention a high reversal sensitivity and a desired high red purity compared to the usual known N-benzyl-p-aminophenol can be obtained.

After aging for 7 days, the three cyan color developers described above in an open container to induce air oxidation were those described above Treatments using the so aged color developer repeated, with the extent of Deterioration was measured. The results obtained are shown in Table III below listed:

Table III

attempt

Reversal sensitivity

Cyan yellow magenta

0.68
0.77
0.78

yellow

1.07
1.10
1.12

Purity of the red color produced

DJD, D _r D _h

0.92
0.99
0.99

0.38 0.34 0.35

0.34 0.28 0.29

40

45

The above results show that with the addition of those used according to the invention Compensating developer substance of the cyan color developer a constant effect with aging by air oxidation, which is not the case with the addition of a customary leveling developer substance the case is.

Example 2

Using the same procedure as described in Example 1, the three color developments were made replaced by the cyan color development. After soaking for 8 minutes after the cyan development the cyan-developed color film became a bleaching, washing and fixing treatment as in Example 1, whereby cyan-stained images were obtained. The photographic properties of the Color photographs with the leveling developer added were measured, and the Results are shown in Table IV below where the reversal sensitivity is

refers to the red-sensitive emulsion layer and the cyan impurity density by the sum of the Cyan coupling density in the exposed part of the green-sensitive emulsion layer with red light and the cyan coupling density in the part of the blue-sensitive emulsion layer exposed to red light is shown. These two light-sensitive emulsion layers should be used during the cyan color development are not developed, and therefore a cyan coupling in these parts causes undesirable en / winding haze, which lead to a deterioration in the quality of the color photographic images.

Table IV

attempt
No.

Compensating developer substance

lot

(A)

0.85 1.27 0.38 0.85 1.34 0.34

0.85 1.33 0.33

1 N-Benzyl-p-aminophenol hydrochloride

2 6- (p-hydroxyanilinomethyl) -chroman-
hydrochloride

3 2-methyl-5- (p-hydroxyanilinomethyl) -
coumaran hydrochloride

*) mmol 1000 ml developer.
**) Reversal sensitivity.
***) Cyan impurity color density.

These results show that the leveling developing agent used in the invention is a excellent effect compared with a common leveling developing agent, viz with N-benzyl-p-aminophenol hydrochloride.

B e i s ρ i e 1 3

The cyan color developer used in Example 2 inevitably deteriorated by ^{sufficiently developing 2800 cm 2 of} a color film with 1000 ml of the Cyanent curler in a bright room, and thereafter the same procedure as in Example 2 was repeated using the thus deteriorated cyan developer . The results are shown in Table V below. The same amount of starting developer as in Example 2 was used in this experiment

55 -

Table V (Al) (B) " Compensation developer substance search No. 1.05 0.63 1 N-benzyl-p-aminophenol- hydrochloride 1.10 0.58 2 6- {p-hydroxyanilinomethyl) - chromanhydrcehlorid 1.12 0.75 3 2-methyl-5- (p-hydroxyanilino- methyl) coumaran hydrochloride *) Reversal sensitivity. **) Cjanvcrunrciniguncsfarbdichlc.

cno c. λ λ lint)

9 ¹ ^ ίο

In this case, too, the compensation was after the three types of cyan developers

Windersubstanzeri according to the invention containing was exposed to air oxidation for 7 days

Cyan developer excellent compared with that was the same procedure as above

common cyan developer, which indicated the known ones using again the cyan developer

Contained leveling developer substance. 5 color developer repeated, the influence of the

aged cyan developer onto the photographic

Example 4 phical properties were compared. The one with it

The results obtained are in the following

The same procedure as in Example 1 was shown in Table VIII,
repeated, the cyan development during 10
6 minutes at 24 ° C using the cyan developer shown below, Table VIII
became:

Cyan color developer

15 attempt reversal wedge purity of

Sodium sulfite 5.0 g no. Produced red color

Sodium Sulphate 50.0g Cyan Yellow Magenta D, D, D, D _h

Ν, Ν-diethyl-p-phenylenediamine- _

sulfite 2.8 g

Potassium bromide 2.0 g ₁₀ 0.97 1.08 1.10 0.35 0.33

Potassium iodide (0.1% aqueous 2 1.05 1.13 1.15 0.32 0.30

Solution) 5.0 ml 3 1.03 \, \\ 1.13 0.32 0.31

2,4-dichloro-5- (p-toluene sulfone

amido) -l-naphthol 2.0 g

Sodium hydroxide 2.5 g 25 Compared with the well-known compensation development

Hydroxyamine sulfate 0.5 g of intermediate showed the leveling developer substance

Water, rest to 1000 ml according to the invention was also used in this experiment

recorded effects like this from the previous one

The photographic properties which can be seen in the table below.
set of compensating developer substance according to 30
Invention to the cyan developer were obtained,
were compared with those at the addition

a common leveling developer, _R -.

namely N-benzyl-p-aminophenol hydrochloride, obtained Example 5

the amount and type of training 35 °

Same developing agents listed below The same procedure as in Example 1 was followed

^are: repeated, with the leveling developer substance

including a known Table VI level developer substance incorporated into each of the cyan color developers

40, the types and quantities of which are

Comparable balancing developer amount of substance · are given) ^to Table IX,

search
No.

Table IX

1 N-Benzyl-p-aminophenol-0.85 ⁴⁵

hydrochloride "

2 6- (p-hydroxyanilinomethyl) - 0.85 ^Ver 'leveling developer substance amount * chroman hydrochloride ^

3 2-methyl-5- (p-hydroxyanilino-0.85 50

methylj-cuinarane hydrochloride ~

»ImMoI / iooo ml developer. 'N-Benzyl-p-aminophenol-0.85

hydrochloride

2 p-hydroxyphenylpiperonylamine- 0.85

The results obtained are in the post-55 hydrochloride

Table VII below: "3 6- (r> Hydroxyanilinometh _y l) - 0.85

1,4-benzodioxane hydrochloride

Table VII 4 6- (p-Hydroxyanilinomethyl) - 0.85
isochroman hydrochloride

Experiment reverse sensitivity purity of *) mmol / 1000 ml developer.

No generated red color

Cyan Yellow Magenta D _r / D _a D _r! D _h

The multilayer color photographic films

1 1.20 1.31 1.26 0.25 023 ^{& 5} w ™ * ¹⁰¹ . as described in Example 1, treated

-> 174 1-17 nn n? 5 η-η where the above-mentioned cyan color development

ί w 1ä Ii nil nil ler were used. The result obtained thereby

3 1.26 1.36 1.31 0.21 0.20 nits are listed in Table X below

Iabelle: Reversal wedge Purity of attempt 5 Compensation Amount max. Around Cyan generated red color No. developer density sweeping spoiled attempt Cyan yellow magenta D _r D, D _r D _h substance recommend cleaning No. find- Color light-
kcit density

1.13
1.16
1.18
1.16

1.27
1.29
1.30
1.29

1.20 1.24 1.26 1.24

0.33 0.28 0.29 0.30

0.27 0.24 0.23 0.24

These results show that according to the invention used compensating developer substances a high reversal sensitivity and a high Purity of the generated red color in the red-sensitive emulsion layer compared with the usual one Compensating developer substance.

Comparative tests are given below which demonstrate the superiority of the color developers according to FIG Invention about the 11 77 486 described in the DT-AS Show color developer.

The experiments were carried out using the procedure of Example 2. The received Results are summarized in Table XI below.

Table XI

according to
DT-AS
486

attempt
No.

Compensation developer
substance

Quantity Max. Density

Um- cyan dust contamination find- color density speed

N-benzyl

p-amino-

phenol-

hydro

chloride

6- (p-Hy-

droxy

anilino

metrr'l) -

chroman

hydro

chloride

0.85 3.40 1.27 0.38

0.85 3.52 1.34 0.34 2-methyl-

5- (p-hy-

droxy

anilino

methyl)-

coumaran-

hydro

chloride

4-methyl-

amino

2-methyl-

phenol-

sulfate

0.85 3.58 1.33 0.33

0.85 2.83 1.35 0.34

The experiments were repeated after the developer had been stored for 7 days. The results obtained are summarized below.

Table XII

attempt
No.

Max. Density

3.37
3.46
3.51
3.37

Reversal sensitivity

1.05
1.06
1.05
0.92

Cyan

impurity

Color density

0.56 0.51 0.50 0.59

It can be seen from the results that the known compound, 4-methylamino-2-methylphenolsulfai according to the German Auslegeschrift 11 77 486 a lowering of the maximum density when used of the fresh developer and in the experiment carried out after storage of the developer a « There was an increase in cyan impurity color density and a decrease in reversal sensitivity

Claims (2)

Patent claims: 1. A color developer for photographic materials which uses (1) as a color developing agent aromatic primary amine, (2) a color former, (3) an alkali and (4) a leveling developer contains a secondary p-aminophenol, characterized in that it is as Compensating developer subslance 2-methyl-5- (p-hydroxyanilinomethyl) - coumaran, 6 - (p - hydroxyanilinomethyl) -chroman, p-hydroxyphenylpiperonylamine, 6- (p-hydroxyanilinomethyl) -1, 4-benzodioxane, 5- (p-Hydroxyanilinomethyl) -isocumaran or 6- (p-HydroxyaniJinomethy)) - isochroman contains. 2. Color developer according to claim 1, characterized in that the compensating developer substance is present in an amount of 0.01 to 5.0 g per 1 liter of color developer.