JPH06208204A - Silver halide material of color photography - Google Patents

Abstract

PURPOSE: To save the application of silver halide insofar as possible without changing the shape and diameter of the grain and the halide composition, to improve sensitivity and to make rapid development possible by decreasing the amt. of chloride and bromide capable of being washed out per mol of silver halide below a specified value. CONSTITUTION: At least one blue-sensitive yellow-coupling silver halide emulsion layer, at least one red-sensitive cyan-coupling silver halide emulsion layer and at least one green-sensitive magenta-coupling silver halide emulsion layer are applied on a carrier. Further, the total amt. of the bromide and chloride capable of being washed out is made smaller than 25 millimols, preferably <=20 millimols, per mol of silver halide, and the application of silver halide is controlled to <=10, preferably <=7, g/m<2> as AgNO3 .

Description

Detailed Description of the Invention

The present invention has improved sensitivity and has more rapid developing kinetics in rapid processing.
Low-silver density color photographic silver halide materials.

The photographic speed of color photographic materials is substantially determined by the silver halide grains, the most influential factors in this regard being the grain size, grain morphology and halide composition. A further important criterion is the coating of silver halide grains with absorbing dyes which sensitize the grains beyond their characteristic sensitivity for the green and red regions of the spectrum. The grain surface is generally only partially coated with a sensitizer, but the sensitivity cannot be increased even if the amount of the sensitizer added is increased. In fact, in many cases this leads to a loss of sensitivity.

The development kinetics of photographic materials are highly dependent on the halide composition in emulsions. For example, emulsions having a high content of silver chloride are remarkable in high development kinetics,
For sensitivity reasons, a relatively large proportion of silver bromide and silver iodide cannot be dispensed with in photographic recording materials. Further, the development kinetics of the photographic layer depends on the amount of emulsion applied to the base. The lower the amount applied, the faster the layer develops. On the other hand, the reduction of silver applied is accompanied by a reduction in gradation and also generally a reduction in sensitivity.

The object of the present invention was to find a material which could save the application of silver halide as much as possible without changing the grain morphology, grain size and halide composition and which showed an increase in sensitivity.

Yet another object of the present invention was to find a recording material that has advantages for rapid development.

Surprisingly, this time both the sensitizer coating and thus the improvement in sensitivity, as well as the development kinetics with rapid development, are reduced by reducing the proportion of halide that can be washed out of the halide contained in the photographic material. It has been found that

The amount of chloride and bromide which can be washed out is 25 mmol or less per mol of silver halide,
Reduction to preferably 20 millimoles or less results above all in both increased sensitivity, especially with increasing sensitizer loading, and more rapid development kinetics.

The amount of chloride and bromide that can be washed out is determined by the following method: Sample preparation The supporting layer present was first mechanically removed and based on the cellulose material of the film material to be investigated. Thereafter, 10 cm ^{2 non-} perforated samples were cut from each.
This sample was mixed with 20 ml of deionized water at 25 ° C. in an airtight Erlenmeyer flask on a vibrator table.
I washed out for an hour. The aqueous extract was then filtered on a chloride-free sterile filter and subjected to ion chromatography with an injection volume of 100 μl.

Anion measurement Conductivity detector (Waters, Mode) under the following conditions:
anion measurement was carried out with an HPLC apparatus using the following: Separation column: IC-PAK-A, 4.6 × 50.
mm, with pre-column (AnionGuard-PAK) from Waters Eluent: Borate-gluconate (conductivity 270 μS) Flow rate: 1.2 ml / min Calibration: Solution A = 1 ppm Cl each
^- and Br ^- Standard: Solution B = 5 ppm each Cl
^- and Br ^- of the solution C = 10 ppm, respectively Cl ^- and Br ^- silver halide application of evaluation examining film material was determined by titration with thioacetamide method.

The anions which could subsequently be washed out were expressed as mmol halide per mol silver halide.

The object of the present invention is ultimately to have a carrier on which at least one blue-sensitive yellow-coupling silver halide emulsion layer, at least one red-sensitive cyan-coupling silver halide emulsion layer and at least one. When the green-sensitive magenta-coupling silver halide emulsion layer is applied, the total amount of bromide and chloride that can be washed out is less than 25 mmol, preferably less than 20 mmol of silver halide per mol of silver halide. A color photographic silver halide material characterized by less than 10, preferably less than 7.5, measured as g AgNO ₃ / m ² .

For this purpose, silver halide is understood to be the sum of light-sensitive and optionally non-light-sensitive silver halide. The latter are, for example, fine grain silver halides (microemulsions not specifically used for dye formation).
)). In a preferred embodiment of the present invention, spectral color sensitivity.
Oxy-, thia-, and imidacarbo- and cyanine dyes from the dicarbocyanine class are used as sensitizers to obtain chromatic sensitivity, and their reduction potentials measured using Ag / AgCl electrodes are It is -0.8 to -1.3V, preferably -0.9 to -1.2V. The amount of sensitizer used in each case is in particular 0.1 to 2 mmol per mol of silver halide it sensitizes, preferably 0.2 to 1 mmol per mol of silver halide, particularly preferably 0.4 per mol of silver halide
~ 1 mol.

Examples of suitable sensitizers are:

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Table 1]

[0019]

[Chemical 5]

[0020]

[Table 2]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Table 3]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

The color photographic material of the present invention has further surprising advantages. They use the same amount of sensitizer and reduced proportions of soluble chloride and bromide and have a faster development kinetics in rapid processing.

The amount of chloride and bromide that can be washed out can be reduced by a number of methods used individually or in combination.

Advantageously, the free halide has already been removed from the silver halide emulsion. This can be done by ultrafiltration, ion exchange or addition of silver salts, ensuring that the equivalence point is not exceeded for the last method.

The silver halide present as a light-sensitive component in the photographic material may contain chloride, bromide or iodide or a mixture thereof as a halide.
The halide portion of at least one layer is, for example, 0 to 15 mol% iodide, 0 to 100 mol% chloride and 0 to
It may contain 100 mol% of bromide. For color negative and color reversal films, brominated-silver iodide emulsions are usually used, and for color negative and color reversal papers, chloride-odor with a high proportion of chloride, which is usually close to that of a pure silver chloride emulsion. A silver halide emulsion is used. The crystals can be predominantly compact, eg regular cubic or octahedral, or exhibit a transition morphology. However, it is preferable that there are tabular crystals having an average ratio of diameter to thickness (aspect ratio) of 5: 1 or more, particularly preferably 7: 1 or more, in which case the diameter of the grains is the same as the projected surface area of the grains. It is defined as the diameter of a circle with an area of. The aspect ratio can also be as high as 20 or higher.

The silver halide grains may, in the simplest case, also exhibit a multi-layered grain structure with different halide compositions in the inner and outer grain regions (core / shell) and / or other modifications such as the doping of each grain region. it can.

The average grain size of the emulsion is 0.2 μm to 2.0 μm.
Is preferable, and the particle size distribution may be uniform dispersion or non-uniform dispersion. Uniformly distributed particle size distribution is 9
This means that 5% does not vary from the average particle diameter by ± 30% or more. In addition to silver halide the emulsions can also contain organic silver salts such as silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions prepared separately can be used as a mixture.

Photographic emulsions can be prepared from soluble silver salts and soluble halides in various ways (eg P. Glaffkides, C.
himie et Physique Photogr
aphique [photographic Chem
istry and physics], Paul M
ontel, Paris (1967), G.S. F. Duf
fin, Photographic Emulsion
Chemistry, The Focal Pres
S. London (1966), V.S. L. Zelikm
ann et al. Making and Coat
ing Photographic Emulsio
n, The Focal Press, London
(1966)).

Precipitation of the silver halide is preferably carried out in the presence of a binder such as gelatin, it can be carried out in the acidic, neutral or alkaline pH range and it is preferred to use a silver halide complexing agent. preferable. Examples of the latter are ammonia, thioethers, imidazoles, ammonium thiocyanates or excess halides. The water-soluble silver salt and halide are optionally continuous either using the single-jet method or simultaneously using the double-jet method,
Alternatively, they are combined using a combination of the two methods. It is preferred to feed at increasing flow rates, ensuring that new "nucleation" does not exceed the "limit" feed rate at which it does not occur. During precipitation, the pAg can be varied over a wide range, keeping a particular pAg value constant during precipitation or following the so-called pAg-, which follows a defined pAg profile.
It is preferable to use the control method. However, in addition to the preferred precipitation with excess halide, a method known as "reverse precipitation" with excess silver ions can also be used. The silver halide crystals can be grown by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent as well as precipitation. Emulsion grain growth can also be accomplished primarily by Ostwald ripening; fine grain emulsions of the type known as "Lippmann emulsions" are mixed with a less soluble emulsion, dissolved and precipitated on the latter. Is preferred.

Cd, Zn, Pb, Tl, Bi, Ir, R
Salts or complexes of metals such as h, Fe can be present during precipitation and / or physical ripening of the silver halide.

Further, the precipitation can be carried out in the presence of a sensitizing dye. Complexing agents and / or dyes can be deactivated at any time, for example by changing the pH or as a result of oxidative treatment.

When crystal formation has stopped, or even earlier, soluble salts can be removed from the emulsion by, for example, conversion to noodle form and washing, flocculation and washing, ultrafiltration or ion exchange. Salts are removed according to the present invention to fall within the upper limits of chloride and bromide concentrations according to the claims.

Silver halide emulsions are generally chemically sensitized under conditions defined with respect to pH, pAg, temperature, gelatin, silver halide and sensitizer concentrations until optimum sensitivity and fog are achieved. Do the feeling. The method is, for example, H.264. Frieser at "Die Grundlage"
n der Photographischen Pr
ozesse mit Silverhalogeni
den ”[Basics of photographi
c processes involvingsilv
er halides], pp. 675-734, Ak
ademische Verlagsgesellsc
described by haft (1968).

In this case the chemical sensitization can be carried out by the addition of compounds of sulfur, selenium, tellurium and / or of metals of group VIII of the periodic table (eg gold, platinum, palladium, iridium); Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazole, azaindene) or spectral sensitizers (eg F. Hamer "Th.
e Cyanine Dyes and Related
Compounds ", 1964 or Ullmann
s Encyclopaedie der techn
ischenChemie, 4th edition,
vol. 18, pp. 431 or lower, and Research
h Disclosure 17643 (Decemb)
er1978), Chapter III) can also be added. Alternatively or additionally, a reducing agent (tin-
II salt, amine, hydrazine derivative, ammonioborane, silane, formamidinesulfinic acid), by hydrogen or with low pAg (eg 5 or less) and / or
Alternatively, reduction sensitization can be performed at high pH (for example, 8 or higher).

Photographic emulsions may contain compounds to prevent fogging or to stabilize photographic function during manufacturing, storage or photographic processing.

Particularly suitable are azaindenes, preferably tetra- and pentaazaindenes, especially those substituted with hydroxyl or amino groups. Such compounds are described, for example, by Birr, Z .; Wiss. Photo. 47 (19
52), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic acids or sulfinic acids such as benzosulfinic acid, or nitrogen-
Heterocycles containing, for example nitrobenzimidazole, nitroindazole, optionally substituted benztriazole or benzothiazolium salts can be used as antifog agents. Mercapto group-containing heterocycle, for example mercaptobenzthiazole, mercaptobenzimidazole,
Mercaptotetrazole, mercaptothiadiazole,
Mercaptopyrimidines are particularly suitable, in which case these mercaptoazoles can also contain water-solubilizing groups, such as carboxyl or sulfo groups. Resea
rch Disclosure 17643 (Dec
Mber 1978), Chapter VI discloses yet other suitable compounds.

Stabilizers can be added to the silver halide emulsion before, during or after ripening. Of course, the compounds can also be added to other photographic layers assigned to the silver halide layer.

Mixtures of the above two or more compounds can also be used.

Preferred stabilizers are among the compounds of the azaindene, imidazole, triazole, tetrazole, thiazole and their mercapto compound classes.

The photographic emulsion or other hydrophilic colloid layer of the light-sensitive material produced according to the present invention may be used as a finishing aid, for example, as an antistatic agent, for improving anti-slip property, for emulsifying a dispersion liquid, or for preventing adhesion. For the purpose of improving the photographic characteristics (for example, acceleration of development, obtaining high contrast, sensitization, etc.), a surfactant can be included. In addition to natural surfactants such as saponins, synthetic surfactants (surfactants) are mainly used: nonionic surfactants such as alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic. Surfactants such as higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds, or phosphonium compounds, anionic surfactants containing acid groups such as carboxylic acid-, sulfonic acid-, phosphorus Acid-, sulfate- or phosphate groups, amphoteric surfactants, such as amino acid compounds and aminosulphonic acid compounds, for example sulfates or phosphates of aminoalcohols.

[0046]

EXAMPLES Example 1 (Comparative) A color photographic recording material was prepared by applying the following layers in the order shown to a transparent cellulose triacetate emulsion carrier. 1 data for quantity in each case
It is the amount with respect to m ² . For silver halide applications, the corresponding amounts of AgNO ₃ are given. 10 for all silver halides
0.5 g of 4-hydroxy-6 per 0 g of AgNO _3.
Stabilized with -methyl-1,3,3a, 7-tetraazaindene.

The following core / shell emulsions having an iodine-rich core and additionally having the following characteristics were used for the material according to the invention:

[0048]

[Table 4] Em1 Em2 Em3 Em4 ─────────────────────────────────── Average diameter (μm) 0. 5 1.2 1.0 1.4 Distribution V (%) ⁺⁾ 15 35 28 38 38 Grain morphology Cube Tabular tabular close packing Aspect ratio 1 4 8 2 I ^(-) (mol-%) 5 10 8 12 Gelatin / AgNO ₃ 0.3 0.3 0.5 0.5 (Value from Cumulative Frequency Curve) Em1 follows European Patent Application Publication No. 152822 and Em4 is European Patent Application Publication No. 6
Prepared according to No. 543. Em2 and Em4 are (a)
Initially at 30-50 ° C. and pBr of 1.2-2.3
A double jet was used to form a nuclear precipitate from 2 to 30 mol% AgI, and (b) silver ions, bromide and iodide were added to the growth phase as AgBrI miscible gap (mi).
(scibility gap), and (c)
At least one more than 20 mol% iodide content
Prepared by precipitating two silver halide layers.

The silver halide emulsions were coagulated and washed in a conventional manner to remove most of the soluble salts and then optimally ripened by chemical methods.

[0050]

Table 5 Layer 1 (Antihalation layer) Black colloidal silver sol (black colloid) having 0.4 g of Ag and 3.0 g of gelatin.
dal silver sol) layer 2 (intermediate layer) 0.5 g gelatin layer 3 (first red-sensitive layer) 1.7 g AgNO ₃ 2.0 g gelatin 0.8 g cyan coupler Em1 / dye S13 (300 μmol / Molar Ag; E _red
= −0.98 V) Layer 4 (second red-sensitive layer) 1.4 g AgNO ₃ 1.7 g gelatin 0.3 g cyan coupler Em 2 / dye 13 (250 μmol / mol Ag) layer 5 (intermediate layer) 1.0 g of gelatin layer 6 (first green-sensitive layer) 1.0 g of AgNO ₃ 1.3 g of gelatin 0.5 g of magenta coupler Em1 / dye S31 (300 μmol / mol Ag; E _red
= -1.21 V) Layer 7 (second green sensitive layer) 1.3 g AgNO ₃ 1.0 g gelatin 0.3 g Magenta coupler Em3, dye S31 (250 μmol / mol Ag) Layer 8 (intermediate layer) 0.3 g of gelatin layer 9 (yellow-filter layer) having 70 mg of Ag and 0.5 g of gelatin Yellow colloidal silver sol layer 10 (first blue sensitive layer) 0.8 g of AgNO ₃ 1.1 g of gelatin 0. 6 g of yellow coupler Em1, dye S39 (400 μmol / mol Ag; E _red
= -1.28 V) Layer 11 (second blue sensitive layer) 1.1 g AgNO ₃ 0.8 g gelatin 0.2 g yellow coupler Em4, dye S39 (300 μmol / mol Ag) layer 12 (intermediate layer) 0.7g gelatin layer 13 (hardened layer) 0.24g gelatin 0.7g formula

[0051]

[Chemical 10]

A curing agent.

The amount of chloride and bromide that could be washed out was determined for each layer and finished material using the method described above. These are shown in Table 1.

Example 2 Example 1 was repeated, but before stabilization according to the method indicated, to the point that the amount of chloride and bromide which could be washed out was below 20 mmol per mol of silver halide. Was treated experimentally. Different methods were used for each color package to show the efficiency of various methods. The washable chloride and bromide contents were again measured for the finished material as well as for each result for the layer package (Table 1).

[0055]

Table 1 Table 1 Washable chloride + bromide (mmol / mol AgX) Example 1 Example 2 Method ──────────────────────── ─────────── Layers 3 and 4 (cyan package) 32 15 1) Layers 6 and 7 (magenta package) 32 15 2) Layers 10 and 11 (yellow package) 30 20 3) Total material 32 16 1) Polysulfone HOLLOW-FIBRE module, 50 ° C. with separation threshold of 50,000 daltons
2) Fluorolide-loaded anion exchanger (Lewati)
t ^R M500, Bayer AG, Leverkuse
n)) at 40 ° C. 3) Addition of silver nitrate solution (1 mol) CN method AP70 / C41 was used and rapid development was performed on the materials of Examples 1 and 2 at 38 ° C. (60, 90, 125
Seconds), sensitivity (0.2 fog) and haze were determined (Table 2). The measured values relating to sensitivity and fogging were equalized by setting the comparative example of the development time of 90 seconds as 100.

[0056]

[Table 6] Table 2 Examples Development time E / S cyan E / S magenta E / S yellow (seconds) Package Package Package ─────────────────────── ───────────── 1 (Comparison) 60 25/90 22/94 37.97 2 (Invention) 60 230/95 166/102 190/98 1 (Comparison) 90 100/100 100/100 100/100 2 (invention) 90 560/120 340/110 390/104 1 (comparative) 125 490/105 355/106 310/103 2 (invention) 125 1620/150 775/120 910/109 E = sensitivity; S = fog; after all, according to the invention, a significant improvement in sensitivity in rapid development was obtained, but only a slight improvement in fog.

Example 3 On the one hand a single coating of layers 4 and 7 (without stabilizer) as described in Example 1 was prepared (comparative), and on the other hand the same emulsion but of washable chloride and bromide was prepared. The amount is AgX
An emulsion film was prepared experimentally by ion exchange to a point of 20 mmol or less per mol. The silver application in each case was 2.5 g AgNO ₃ / m ² .

All the coatings of Example 3 were prepared by CN method AP70.
/ C41 for 195 seconds at 38 ° C., then bleached, fixed, washed and dried in the usual manner. Table 3 shows the measured sensitivity and fog.

Sample 1 was used for the cyan film and sample 7 was used for the magenta film. Sensitivity and fog were 10 in each case.
It was set to 0.

[0060]

[Table 7] Table 3 Samples Layers Washable black sensitizer E / S Lide and bromide (millimeter (μmol / molmol / mol silver halide) silver halide) ────────── ───────────────────────── 1 Cyan 31 (Comparison) 300 100/100 2 Cyan 15 (Invention) 300 100/105 3 Cyan 11 ( The present invention) 300 105/92 4 Cyan 32 (Comparison) 600 67/71 5 Cyan 16 (Invention) 600 115/78 6 Cyan 12 (Invention) 600 155/607 Magenta 30 (Comparison) 200 100/100 8 Magenta 16 (the present invention) 200 100/100 9 Magenta 14 (the present invention) 200 105/95 10 Magenta 11 (the present invention) 200 105/93 11 Magenta 34 ( Comparison) 600 65/95 12 Magenta 17 (Invention) 600 115/88 13 Magenta 15 (Invention) 600 150/88 14 Magenta 12 (Invention) 600 175/53 Decrease in washable halides, chlorides and bromides. Has been found to lead to significant benefits in improved sensitivity and reduced haze, especially when the amount of spectral sensitizer is increased.

A relatively large amount of stabilizer is added to the emulsion processed according to the invention and / or a relatively high p in the coating solution.
Setting H can further improve the preferable results of the present invention with respect to the relationship between sensitivity and fog (Table 4).
See).

[0062]

[Table 8] Table 4 Samples Stabilizer pH E / S mmol / mol Ag ────────────────────────────────── ── 6-6.2 155/60 (See Table 3) 15 Same 6 A; 0.4 6.2 150/43 16 Same 6-8.0 180/80 17 Same 6 A; 0.4 8.0 180/75 13-6.2 150/61 (see Table 3) 18 Same 13 B; 1.0 6.2 175/42 19 Same 13-8.0 190/120 20 Same 13 B; 1.0 8. 0 195/95 Stabilizer: A: Mercaptobenzoxazole B: Hydroxytetraazaindene The main features and aspects of the present invention are as follows.

1. A carrier having at least one red-sensitive cyan-coupling silver halide emulsion layer, at least one green-sensitive magenta-coupling silver halide emulsion layer and at least one blue-sensitive yellow-coupling silver halide emulsion layer; The total amount of bromide and chloride that can be washed out has been applied to the silver halide 1
Less than 25 millimoles per mole, preferably less than 20 millimoles, the application of silver halide is g AgNO
Less than 10 measured as ₃ / m ² and preferably 7.
A silver halide color photographic material characterized by less than 5.

2. Its reduction potential measured with an Ag / AgCl electrode is -0.8 to -1.3 V, preferably -0.
The silver halide color photographic material according to the above item 1, wherein a cyanine dye having a voltage of 9 to -1.2 V is used as a spectral sensitizer.

3. A silver halide color photographic material according to item 1 above, characterized in that the spectral sensitizer is used in an amount of 0.1 to 2 mmol / mol, preferably 0.2 to 1 mmol / mol of silver halide.

4. A silver halide color photographic material according to claim 1 characterized in that the total amount of bromide and chloride that can be washed out is reduced by ultrafiltration or ion exchange of the coating solution or preferably the emulsion.

5. 0.2 to 2 per mol of silver halide
In the above item 1, characterized in that it contains a mmol, preferably 0.4 to 1 mmol, of a stabilizer selected from the group of compounds of azaindene, imidazole, triazole, tetrazole, thiazole and the corresponding mercapto compounds. The described silver halide color photographic material.

6. A silver halide color photographic material according to item 1 above, wherein the pH of the coating solution is> 6.5, preferably> 7.5.

7. Aspect ratio> 5, preferably> 7
2. The silver halide color photographic material as described in the above item 1, wherein the emulsion having tabular silver halide crystals showing is used in at least one silver halide emulsion layer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jörg Siegel Federal Republic of Germany Day 51372 Lef Erkusen Walter-Flexus-Schuttraße 24 (72) Inventor Klaus Bagner Federal Republic of Germany Day 51465 Bergischug Gladbach-Hehebeek 22 ( 72) Inventor Alfred Michiuker, Federal Republic of Germany Day 51519 Odental Le / Holz Amgarten Felt 50

Claims (1)

[Claims] 1. A carrier having at least one red-sensitive cyan-coupling silver halide emulsion layer, at least one green-sensitive magenta-coupling silver halide emulsion layer and at least one blue-sensitive yellow-coupling. silver halide emulsion layer is applied, less than the total amount of 25 mmol per mol of silver halide of the bromide and chloride, which can be rinsed, preferably less than 20 mmol, the application of silver halide g AgNO ₃
/ M less than 10, measured as a ^2, preferably 7.
A silver halide color photographic material characterized by less than 5.