CH628747A5 - Colour-photographic material containing two red-sensitive silver-halide emulsions - Google Patents

Description

The present invention relates to color photographic material which is cast onto a photocarrier and comprises at least one green-sensitive silver halide colloid emulsion layer 60 and at least one blue-sensitive silver halide colloid emulsion layer, together with a red-sensitive silver-halide colloid emulsion of high sensitivity and a red-sensitive silver halide emulsion of lower sensitivity, which are used in separate layers or in a single layer. 65 gene layer may be mixed, and is characterized in that the sensitivity maximum of the red-sensitive emulsion high sensitivity in

The range from 635 to 675 nm and the maximum sensitivity of the red sensitive low sensitivity emulsion is in the range from 600 to 640 nm, with a difference of at least 10 nm between the maximum sensitivity of the high sensitivity emulsion and the maximum sensitivity of the low sensitivity emulsion.

The maximum sensitivity of the high sensitivity layer is preferably in the range from 650 to 660 nm. The maximum sensitivity of the low sensitivity layer is preferably in the range from 610 to 630 nm;

For the photographic sensitivities of the emulsions, the terms high and low sensitivity are only relative. In this connection, however, the photographic sensitivity of the red-sensitive emulsion of high sensitivity is preferably at least twice that of the photographic sensitivity of the red-sensitive emulsion of low sensitivity, the sensitivities relating to the arithmetic scale.

It is already known that, in order to achieve high light sensitivity of the color photographic material tripack, it is desirable to sensitize the layers for a broad wavelength range, including wavelengths for which the human eye is relatively insensitive. When using normal spectral sensitizing dyes, however, the maximum of this sensitivity is usually reached in the range from 635 to 675 nm and in particular between 640 and 655 nm. However, if both red-sensitive layers have a sensitivity maximum in the range from 635 to 675 nm, it was found that this leads to two disadvantageous phenomena:

(1) With light sources of low color temperature, the red-sensitive layers give high densities in the color negative, and the filtration densities in the copying process are therefore high and the copying times are relatively long. Similarly, in the direct positive or reversal method, the color reproduction of the copy or the slide is unacceptably warm unless a correction filter is used for the exposure.

(2) Certain blue flowers and some synthetic blue textile dyes not only reflect strongly in the blue part of the spectrum and therefore appear blue to the eye, but also reflect light at the extreme red end of the spectrum, where the sensitivity of the human retina is very low.

628747

4th

If the color film has a high sensitivity in this external red wavelength range, it registers the red tones of the flower or the textile dye too strongly, and the blue color is therefore reproduced as purple or even pink.

However, when the wavelength of this sensitivity maximum was shortened considerably, which is sufficient to overcome the above two disadvantageous phenomena, it was found that a significantly reduced sensitivity in the red was obtained in the red-sensitive layers, together with an increased sensitivity to green light, which consequently produced the green worsened.

The photographic material of the invention overcomes these two categories of adverse phenomena.

In the photographic material according to the invention, no high sensitivity is required for the less sensitive emulsion component, and somewhat increased sensitization to green light is of no consequence because of the low intrinsic sensitivity. The advantages of spectral sensitization in the range from 655 to 675 nm are therefore low for the emulsion of low sensitivity.

On the other hand, good color rendering over those exposure areas to which the low-sensitivity emulsions respond (i.e., medium and highlight densities of the object) is of particular importance. It is therefore advantageous if the sensitivity maximum of the emulsion of low sensitivity is at a shorter wavelength than that of the emulsion or emulsions of high sensitivity. Of course, maximum resistance to the effects of changes in color temperature of the light source is obtained when all red-sensitive emulsions have their maximum sensitivity at such short wavelengths, but a certain valuable resistance to the effects of changes in color temperature is obtained if sensitization to short wavelengths is only in the emulsion low sensitivity.

The photographic material according to the invention, in which the maximum sensitivity of the high-sensitivity emulsion is in the range from 635 to 675 nm and that of the low-sensitivity emulsion in the range from 600 to 640 nm, with a difference of at least 10 nm between the two, is thus overcome the disadvantageous phenomena that occur when only dyes with a high sensitivity maximum or only dyes with a low sensitivity maximum are used in the red emulsions of a multilayer material.

An additional advantage arises from the reflection density of the low-sensitivity emulsion when it is poured in a mixture with the high-sensitivity emulsion or poured into a layer that is either directly below it or that is underneath only through a layer that does not absorb light e.g. an intermediate gelatin layer) is separated. If sensitization for a relatively short wavelength is applied to this emulsion or emulsions, the degree of reflection for red light, to which the emulsion is sensitive, is relatively higher. The real sensitivity of the high sensitivity emulsion is consequently increased.

Any single spectral sensitizing dye that has a maximum sensitivity within the range of 635 to 675 nm, or any mixture of dyes that together give a maximum sensitivity in this range, can be used in the high sensitivity red-sensitive emulsion. Any single sensitizing dye that has a maximum sensitivity within the range of 600 to 640 nm, or any mixture of dyes that together produce a maximum sensitivity in this range, can be used in the low-sensitivity red-sensitive emulsion.

Dyes of the general formula are particularly useful as sensitizing dyes which have a maximum sensitivity within the range from 635 to 675 35 nm

(l)

wherein X and Y, S and Se, Ri and R2 alkyl and aralkyl optionally substituted by hydroxyl, alkoxy, carboxylic acid or sulfonic acid and Ra to Rio are hydrogen, alkyl, aralkyl,

Aryl, hydroxyl, alkoxy and halogen are, Rs and Re and / or R7 and Rs can complement one another to form a benzene ring, R11 55 is lower alkyl, preferably ethyl, Z is an anion and n is 2 or n is 1 if both Ri and R2 a carboxyl group or entÏ1-I

neither Ri or R2 contain a sulfonic acid group.

It is sometimes advantageous to use mixtures of such dyes, for example the mixtures described in British Patent 1,333,270.

Dyes of the general formula are particularly useful as sensitizers which have a maximum sensitivity within the range from 600 to 640 nm

(2) R.

= CH -

? 21

C = CH

zP 1

n-1

5 628747

wherein Xi and Y are O, S, Se or NR12, wherein R12 is lower alkyl 557 178,558 710 and 560 082) and of the polyethylene glycol type or aralkyl, optionally containing R 1 and R 2 by hydroxyl (US Pat. No. 2,866,437).

Alkoxy, carboxylic acid or sulfonic acid substituted alkyl and The photographic support can be any normal aralkyl and R13 to R20 are hydrogen, halogen, alkyl, aralkyl, such as supports used for photographic negative films aryl, hydroxyl and alkoxy, Ris and Ri «and / or R17 and 5, for example a cellulose triacetate, cellulose acetate buter ris can add up to a benzene ring and, if xi rat or a polyester that has been pretreated so that one and / or Y1NR12 are, Rh, Ru, Ris and Ris trifluoromethyl or hydrophilic cast thereon can adhere.

Can be chlorine, R21 hydrogen or lower alkyl, Z on An antihalation layer can be on the back of the carrier.

Anion and n is 2 or n is 1 if both Ri and R2 cargers have been cast. Otherwise, the material may contain an anti-bono group or either Ri or R2 sulfonic acid halo underlayer under the bottom cast sensitive group. chen emulsion layer.

If only one dye is used, Xi is preferred. The following example is selected for illustration under O or NR12 and Y1 stands for Se. One can of the invention.

however, use dye mixtures, especially if broad spectral sensitization is required. If a dye-15 sample mixture is used, at least one dye corresponds to three tripack coatings 1, 2 and 3 are coated with the following

in a mixture of the general formula (2), in which Xi O or NR12 basic structure is prepared:

and Yi is S or Se and both Xi and Y1NR12 can be layer 8 containing a yellow-forming coupler. The other dye (s) in the mixture is a blue-sensitive emulsion.

Chen of formula (1), wherein X and Y are S or Se. 20 Layer 7 yellow filter layer.

Preferably, in the photographic layer 6 according to the invention, green- containing a purple-forming coupler is

the red sensitive emulsion layer of high sensitive emulsion.

Sensitivity is poured over (i.e., farther away from the support) the red-sensitive layer 5, which contains a magenta-forming coupler, and contains a sensitive sensitive green emulsion layer, sensitive emulsion of lower sensitivity.

The photographic material according to the invention can, in layer 4, contain a cyan-forming coupler containing the various layers of the structure, 2- and 4-equivalent red-sensitive emulsion.

colorless and / or colored couplers, DIR couplers, anti-fog layer 3, a cyan-forming coupler containing agents, crosslinking agents, leveling agents and further additives customary in photoresponsive emulsions of low sensitivity, tographic emulsion layers, including layer 2 antihalation underlayer. 30 layer 1 carrier.

The light-sensitive layers are preferably each a gelatin silver halide emulsion layer and in particular further gelatin layers may be required, preferably an iodide bromide layer. However, they can be used as a protective agent against abrasion during casting, for the silver halide any synthetic or or to separate emulsion layers, however, these are the naturally occurring hydrophilic colloid or a 35

Mixture of such contain, for example albumin, casein, sen.

Polyvinyl alcohol or a cellulose ester or ether. Layer 8 of this material contains a yellow one

The emulsions used in the preparation of the photogra coupler of the benzoylacetanilide or pivaloylacetanilide type, phical material, according to the invention, can be either 2-equivalent or 4-equivalent. The well-known methods can be chemically sensitized. One 40 layers 5 and 6 contain a 4-equivalent pyrazolone - the emulsions can mature with natural active gelatin coupler. Layers 3 and 4 contain a 4-equivalent or sulfur compound, such as that found in British phenol couplers.

Nos. 235 211 and 544 812. Furthermore, the layer 4 is a silver iodide bromide emulsion, the emulsions can be treated with noble metal salts such as those of (8.8% iodide) with an arithmetic sensitivity of 100. ruthenium, rhodium, palladium, iridium and platinum. 45 Layer 3 is in each case a silver iodide bromide emulsion. The emulsions can contain sensitizing amounts of reductant which contains a smaller proportion of iodide (7.5% iodide) and a detergent such as tin-II salts (British Patent No. arithmetic sensitivity of 25).

658 592) or polyamines such as diethylenetriamine. Both red-sensitive layers in tripack 1 are included

The emulsions can sensitize a mixture of 1 part of dye of the formula (101) and 2 partial bonds of the quaternary type (British Patent No. 50 len dye of the formula (102) sensitized.

(101)

C = CH -

C = CH

^ CH

/ Se ^ v 3

- c ^ ©

(k) 3 io ©

65

628747

6

(102) CH

I2 "5 /

C = CH - C = CH - C ^

(çh2) 2

CH-CH,

I e:

SQ, V

The sensitivity maximum of this layer is 650 is. Both red-sensitive layers in tripack 2 are with nm. A mixture of 2 parts of dye (102) and 1 part of dye

(103) sensitized.

(103)

C2H5

ch -c = ch - \ © X1.

N *

(ch2) 3

0

©

OCH,

30th

The sensitivity maximum of this layer is 660 dyes (102) and (103) as was used in both red-sensitive nm layers in tripack 2. Layer 3 contains

Layer 4 in tripack 3 contains the same mixture of the dye of formula (104).

(104)

^ 2H5 "

C = OH - C = CH -

<9H2} 3 SO P

OCH,

OCH,

The sensitivity maximum of this layer is 615

nm.

After exposure as detailed below, the tripacks are processed as follows:

Develop 3.25 minutes at 37.8 ° C

Bleach for 6.5 minutes at 35 to 40 ° C,

Soak for 3.25 minutes at 35 to 40 ° C,

Fix for 6.5 minutes at 24 to 41 ° C,

Soak for 3.25 minutes at 35 to 40 ° C,

Stabilize for 1.5 minutes at 24 to 41 ° C and dry for 10 to 20 minutes at 32 to 49 ° C.

Bleaching solution water

Ammonium bromide so iron III ammonium EDTA solution (1.56 molar) acetic acid water to pH

55

Fixer bath water

Ammonium thiosulfate solution (50%)

6500 ml 150 g

175 ml 10.5 ml 1 liter 6.00 ± 0.2

800 ml 162 ml

Developer solution

EDTA disodium salt

1.25 g

water

800 ml

60 sodium bisulfite

12.4 g

Potassium carbonate

37.5 g

Sodium hydroxide

2.4 g

Sodium sulfite

4.25 g

Water on

1 liter

Sodium bromide

1.3 g pH

6.50 ± 0.2

Hydroxylamine sulfate

2.0 g

4-amino-3-methyl-N-ethyl-N-

65

(2-hydroxyethyl> aniline sulfate

4.75 g

Water on

1 liter

pH

10.00 ± 0.3

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Stabilizer solution water

Formalin (37% formal

dehyde solution)

Water on

800 ml

5.0 ml 1 liter

(EDTA stands for ethylenediaminetetraacetic acid)

(I0i>)

The negatives are then copied onto conventional color copy paper.

Each tripack is used to photograph a color chart containing a normal gray patch and a blue patch consisting of a sheet of fabric dyed with the textile dye of the formula. The light sources are simulated daylight (normal sunlight) and tungsten light (photo floodlight). The reflection spectrum of the bruise is shown in the attached drawing. Each negative is carefully copied so that the reproduction of the normal gray stain is identical as measured with a Macbeth RD-519 reflection densitometer. The following table shows the

NH-

CH3 / ^ Br would give the bruise and the sensitivity required in logarithmic exposure units to give a density of 0.10 over the veil. The response given is expressed as the total density and the difference between the purple and blue green densities on the copy as measured by the reflection densitometers; the more positive this difference is, the more the reproduction is purple.

Sensitivity of the red- blue rendering sensitive layer

Without With selection daylight tungsten light

Filter red filter

Tripack 1 3.52 3.14 -0.07 at +0.03 at

Density 1.00 Density 0.99

Tripack 2 3.62 3.31 +0.08 at +0.16 at

Density 0.94 density 0.96

Tripack 3 3.66 3.36 - 0.05 at - 0.02 at

Density 1.24 Density 1.06

Experiments show that the preferred reproduction of this blue textile dye is obtained with a copy density of 1.0 to 1.3 and a difference between the magenta and cyan copy densities between 0.0 and -0.10. The playback with Tripack 1 is only within this acceptable range in daylight. With Tripack 2, the sensitivity is higher, but the blue rendering is unacceptable. With Tripack 3, however, the sensitivity is even higher and the reproduction is within the acceptable range in both daylight and tungsten lighting.

G

1 sheet of drawings

Claims (9)

628747 1. Color photographic material cast on a photocarrier at least one green-sensitive silver halide colloid emulsion layer and at least one blue sensitive silver halide colloid emulsion layer, together with a red-sensitive silver halide colloid emulsion of high sensitivity and a red-sensitive silver halide emulsion of lower sensitivity, which are mixed in a separate layer or in separate layers , characterized in that the sensitivity maximum of the red-sensitive emulsion of high sensitivity is in the range from 635 to 675 nm and the sensitivity maximum of the red-sensitive emulsion of low sensitivity is in the range from 600 to 640 nm, with a difference of at least 10 nm between the sensitivity maximum of High sensitivity emulsion and the maximum sensitivity of the low sensitivity emulsion. 2. Color photographic material according to claim 1, characterized in that the sensitivity maximum of the layer of high sensitivity is in the range from 650 to 660 nm. 5 3. Color photographic material according to claim 1 or claim 2, characterized in that the sensitivity maximum of the low sensitivity layer is in the range of 610 to 630 nm. 4. Color photographic material according to claim 1, characterized in that the photographic sensitivity of the red-sensitive emulsion of high sensitivity is at least twice the photographic sensitivity of the red-sensitive emulsion of low sensitivity, the sensitivities relating to the arithmetic 15 Get scale. 5. Color photographic material according to claim 1, characterized in that the sensitizing dye used in the red-sensitive emulsion layer of high sensitivity of the general formula R 11 X \ I C - CH-C = CH - C N ^ 'P n n ~' where X and YS or Se, Ri and R2 optionally substituted by hydroxyl, alkoxy, carboxylic acid or sulfonic acid groups alkyl and aralkyl and Rj to Rio are hydrogen, alkyl, aralkyl, aryl, hydroxyl, alkoxy or halogen or Rs and R 1 and / or R7 and Rs can complement each other to form a benzene ring, R11 is lower alkyl, Z is an anion and n 2 or n is 1 if both Ri and R2 contain a carboxyl group or either Ri or R2 contain a sulfonic acid group. 1 6. Color photographic material according to claim 1, characterized in that the sensitizing dye of the general formula used in the red-sensitive emulsion layer of low sensitivity 45 = CH - ^ 21 C = CH n-1 in which Xi and Yi, O, S, Se or NR12, where R12 is lower alkyl or aralkyl, Ri and R2 alkyl and aralkyl optionally substituted by hydroxyl, alkoxy, carboxylic acid or sulfonic acid groups and Ru to R20 hydrogen, halogen, alkyl , Aralkyl, aryl, hydroxyl and alkoxy, R15 and Ri «and / or R17 and Ris can be combined to form a benzene ring and, if Xi and / or Yi are NR12, Ru, Ris, Ri8 and R19 can be trifluoromethyl or chlorine, R21 is hydrogen or lower alkyl Z is an anion and n is 2 or n is 1 if 60 contain both Ri and R2 carboxylic acid groups or either Ri or R2 sulfonic acid groups. 7. Color photographic material according to claim 6, characterized in that X: O or NR12 and Yi Se. 8. Color photographic material according to claim 6, which contains a dye mixture, characterized in that that Xi in one dye is O or NR12 and Yi S or Se and both Xi and Yi are NR12 and that the other dye (s) of the formula 3rd 628 747 R, R / Rr L X I. R. R 11 C ■ = CH — C = CH - C R. R? ii-1 where X and YS or Se, Ri and Rz are optionally substituted by hydroxyl, alkoxy, carboxylic acid or sulfonic acid groups alkyl and aralkyl and Rs to Rio are hydrogen, alkyl, aralkyl, aryl, hydroxyl, alkoxy and halogen, Rs and Rs and / or R? and Rs can form a benzene ring, R11 is lower alkyl, Z is an anion and n 2 or n is 1, if both Ri and R2 contain a carboxyl group or either Ri or R2 contain a sulfonic acid group. 9. Color photographic material according to claim 1, characterized in that the red-sensitive emulsion layer 20 of high sensitivity is poured over the red-sensitive emulsion layer of low sensitivity. Color photographic material mostly belongs to the so-called tripack type and contains at least one emulsion layer that is only sensitive to blue light, a filter layer that absorbs blue light, and cast under it at least one emulsion layer that is suitable for green light (but not for red light) ) is sensitive and at least one emulsion layer that is sensitive to red light (but not to green light). By appropriately selecting either the dyes or the color couplers in each layer, a color representation of an image can be obtained. In order to achieve sufficient exposure latitude, it is customary to use at least two emulsions in that part of the color film material which absorbs red light and in that 40 part of the material which absorbs green light, one emulsion in each of these parts of the material having a lower sensitivity than the other . You can mix these emulsions together and pour them as a mixture, or you can pour them in separate layers. In the latter case, the emulsion layer of highest sensitivity in each part of the material is usually poured directly over the emulsion layer of lower sensitivity, the layers possibly being separated only by a gelatin layer, but this is not necessary. 50 So far it has been common in practice to use the same spectral sensitizing dyes in the red sensitive emulsions of both high and low sensitivity in such a tri-pack. However, it has now been found that advantageous results can be achieved if the spectral sensitivities of the red-sensitive emulsions of high and low sensitivity are different.