EP0262504A2 - Preparation of a multilayered photographic material - Google Patents

Abstract

In the material, the layers are applied in at least two steps, between which the material is dried and wound up; sticking of the semi-finished products is then avoided if the topmost layer of the step carried out first contains alkali-soluble polymer particles of a mean particle diameter of 0.2 to 5.0 mu m.

Description

The invention relates to the production of a multilayer photographic material with an intermediate layer which contains certain polymer particles.

It is known that photographic recording materials which consist of several layers can often not be produced in one operation, but that the layers are applied to the support material in at least two operations. You can apply single layers as well as layers of layers from several layers in one step. The top layer of each layer package applied in one operation usually contains a hydrophilic binder, for example gelatin, a wetting agent and, if appropriate, alkali, a plasticizer, dyes and colloidal silver.

After each operation, the photographic materials are dried and wound up before they are provided with the next shift or the next shift package. The rolled-up semi-finished products tend to stick to one another and thus cause stains on the recording material.

It is known to avoid this undesirable effect in a finished film by introducing so-called spacers or matting agents into the top layer, i.e. solid particles with an average particle diameter of at least 1 µm. This measure cannot be taken for the upper layers of an operation, which will later be inner layers, since this leads to the formation of fog, unevenness in the casting and deterioration of the breaking strength.

It has also already been proposed to incorporate matting agents in intermediate layers with acid-treated gelatin, which are top layers during the manufacture, organic or inorganic materials with a particle size of about 0.2 to 5 μm being insoluble in water. Since there are differences in the refractive index between these particles and the gelatin, there is increased light scattering on this particle, which leads to increased granularity (DE-A-2 526 970).

The invention is therefore based on the object of developing intermediate layers in which the top layer of a first coating step is avoided when all layers are applied in at least two coating steps, and also the static layer Friction is reduced. The other properties important in film technology, in particular the sensitometric properties, should not be adversely affected.

A process has now been found for producing a multilayer photographic material, in which the layers are applied in at least two work steps and the material is dried and wound up between the work steps, in which the aforementioned disadvantages are avoided, which is characterized in that the top layer of the first step contains alkali-soluble polymer particles with an average particle diameter of 0.2 to 5.0 µm.

The particle diameter is preferably 0.5 to 3.0 μm.

• 1. Copolymerisate von Alkylmethacrylaten mit Meth­acrylsäure, Acrylsäure oder Itaconsäure.
• 2. Copolymerisate von Alkylmethacrylaten mit Malein­säurehalbestern oder Maleinsäurehalbamiden.
• 3. Copolymerisate von Styrol mit α,β-ungesättigten Mono- oder Dicarbonsäuren, Dicarbonsäurehalbestern oder Dicarbonsäurehalbamiden.
• 4. Pfropfpolymerisate von Methacrylsäure/Methylmeth­acrylat auf wasserlösliche Dispergatoren von Male­insäureanhydrid und α-Olefin.
• 5. Cellulosederivate von Dicarbonsäurehalbestern, z. B. Phthalate und Hexahydrophthalat von Methyl­cellulose, Hydroxyethylmethylcellulose oder Hy­droxypropylmethylcellulose.

Suitable alkali-soluble polymer particles are those of the following chemical classes:

• 1. Copolymers of alkyl methacrylates with methacrylic acid, acrylic acid or itaconic acid.
• 2. Copolymers of alkyl methacrylates with maleic acid half-esters or maleic acid halamides.
• 3. Copolymers of styrene with α, β-unsaturated mono- or dicarboxylic acids, dicarboxylic acid half-esters or dicarboxylic acid halamides.
• 4. Graft polymers of methacrylic acid / methyl methacrylate on water-soluble dispersants of maleic anhydride and α-olefin.
• 5. Cellulose derivatives of dicarboxylic acid half-esters, e.g. B. phthalates and hexahydrophthalate of methyl cellulose, hydroxyethyl methyl cellulose or hydroxypropyl methyl cellulose.

The compositions are selected so that the particles are insoluble in water at pH below 5 and soluble in water at pH above 7.

The layer containing the alkali-soluble polymer particles can also contain conventional additives such as hydrophilic binders, for example gelatin, preferably alkaline-ashed gelatin, wetting agents, preferably surface-active organic fluorine compounds, formalin scavengers, plasticizers, colloidal silver and dyes.

The polymer particles are usually applied in an amount of 20 to 200 mg / m² of photographic material, in particular 50 to 120 mg / m² of photographic material. They are added to the corresponding casting solution as an aqueous dispersion.

Surprisingly, the addition of the polymer particles mentioned avoids the adhesive spots, a reduction in the static coefficients of friction and a reduction in the exposures caused by static discharges, the photographic properties of the multilayer photographic material, in particular grain size and sharpness, not being influenced.

The method according to the invention can be used for the production of all multilayer photographic materials, in which the layers are applied in at least two work steps, for example for the production of negative and reversal films and photo paper, but in particular for color negative film and color reversal film. If the layers are applied in more than two work steps, the measure according to the invention can be used several times.

The photographic materials produced according to the invention can be exposed in the manner customary for them and processed using the processes customary for this.

The alkali-soluble matting agents to be used according to the invention are dissolved out of the photographic material by the alkaline developers, so that it thereafter light scatter from these particles can no longer occur due to different refractive indices of polymer and gelatin. Surprisingly, no pores remain in the material, which in turn could cause negative effects.

Photographic, in particular color photographic, recording materials to which the method of the present invention can advantageously be applied are preferably multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity. Emulsion layer units are understood to mean laminates of 2 or more silver halide emulsion layers of the same spectral sensitivity. Layers of the same spectral sensitivity do not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity. The binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin. However, in addition to the proteinaceous binder, the layer binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives.

The light-sensitive silver halide emulsion layers or emulsion layer units is at least one coloring compound, usually assigned a color coupler, which is able to react with color developer oxidation products to form a non-diffusing dye. The color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it. The color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.

The red-sensitive silver halide emulsion layers are consequently assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or α-naphthol type. Particularly noteworthy are, for example, cyan couplers as described in US-A 2,474,293, US-A 2,367,531, US-A-2,895,826, US-A 3,772,002, EP-AO 028 099, EP-AO 112 514.

The green-sensitive silver halide emulsion layers contain at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Of particular note are, for example, purple couplers as described in US-A-2,600,788, US-A-4,383,027, DE-A-1,547,803, DE-A 1,810,464, DE-A 24 08 665, DE-A- 32 26 163.

Finally, the blue-sensitive silver halide emulsion layers contain at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. Yellow couplers, as described in US-A-3 408 194, US-A-3 933 501, DE-A-23 29 587, DE-A-24 56 976, are particularly noteworthy.

Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications "Color Coupler" by W. Pelz, "Messages from the Research Laboratories of AGFA, Leverkusen / Munich", Volume III (1961) p. 111, and by K. Venkataraman in "The Chemistry of Synthetic Dyes" , Vol. 4., 341 to 387, Academic Press (1971).

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. As is known, the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that the Color coupling disappears or is replaced by the color of the image dye generated (mask coupler). In principle, the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation products. The 2-equivalent couplers are also those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and which either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( eg DE-A-27 03 145, DE-A 28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

Suitable DIR couplers are described, for example, in GB-A-953 454, DE-A-1 800 420, DE-A 20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.

Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-O 089 834, EP-A-0 117 511, EP-A-O 118 087.

Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, are also such DIR, DAR or FAR couplers are suitable which, when coupled, result in essentially colorless products, as described, for example, in DE-A 1 547 640.

The cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products coupling products e.g. Dyes can be obtained which are diffusible or at least have a weak or restricted mobility, as described, for example, in US Pat. No. 4,420,556.

High molecular weight color couplers are described for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A- 33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are generally produced by polymerizing ethylenically unsaturated monomeric color couplers . However, they can also be obtained by polyaddition or polycondensation.

In addition to the constituents mentioned, the layers can contain further additives, for example hardening agents, antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties. In order to reduce or avoid the disadvantageous effect of UV light on the color images produced with the color photographic recording materials according to the invention, the layers can also contain compounds absorbing UV light.

worin
    R¹ und R² eine Alkylgruppe mit 1 bis 8 Kohlenstoff­atomen oder eine gegebenenfalls mit einer Alkyl­gruppe mit 1 oder 2 Kohlenstoffatomen oder mit einem Halogenatom substituierte Aryl- oder Aral­kylgruppe, oder zusammen die zur Vervollständigung eines gegebenenfalls mit einer Alkylgruppe mit 1 oder 2 Kohlenstoffatomen oder mit einem Halogenatom substituierten heterocyclischen Ringes erforder­lichen Atome,
    R³ ein Wasserstoffatom oder eine Alkylgruppe mit 1 oder 2 Kohlenstoffatomen und
    n 0 oder 2 bedeuten.Carboxyl group-activating curing agents are preferably used, in particular those of the general formula

wherein
R¹ and R² are an alkyl group having 1 to 8 carbon atoms or an aryl or aralkyl group optionally substituted with an alkyl group with 1 or 2 carbon atoms or with a halogen atom, or together to complete an optionally with an alkyl group with 1 or 2 carbon atoms or with a halogen atom substituted heterocyclic ring required atoms,
R³ is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms and
n is 0 or 2.

A color photographic recording material for reverse color development was produced by the on a transparent layer of cellulose triacetate following layers were applied in the order given, namely layers 1 and 2, layers 3 to 6, layers 7 to 10, layers 11 to 14 together and then layer 15. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 1

(Antihalation layer)
Black colloidal silver sol with
0.5 g Ag
1.5 g gelatin.

Layer 2

(Intermediate layer)
0.9 g gelatin
0.33 g AgNO₃ (micrate)
0.33 g octyl hydroquinone

Layer 3

(1st red-sensitized layer)
red-sensitized silver bromide iodide emulsion (5.5 mol% iodide; average grain diameter 0.25 µm) from 0.98 g AgNO₃, with
0.81 g gelatin and
0.25 g coupler C-1

Layer 4

(2nd red-sensitized layer)
red-sensitized silver bromide iodide emulsion (6.5 mol% iodide; average grain diameter 0.6 µm) from 0.85 g AgNO₃, with
0.7 g gelatin and
0.58 g coupler C-1

Layer 5

Intermediate layer
1 g gelatin
0.2 g octyl hydroquinone
0.4 g connection WM-1

Material 1 (according to the invention)

Layer 6

Intermediate layer
0.4 g gelatin
0.1 g hydroxypropylmethyl cellulose hexahydrophthalate (alkali-soluble) with an average particle diameter of 2.0 µm.

Material 2 (not according to the invention)

Layer 6

Intermediate layer
0.4 g gelatin

Material 3 (not according to the invention)

Layer 6

Intermediate layer
0.4 g gelatin
0.1 g polymethyl methacrylate with an average particle diameter of 2 µm (insoluble in alkali)

The described partial layer structures (layers 1-6) were tested for sliding properties and surface resistance. The coefficient of friction (coefficient of friction = tensile force / normal force × 100) is a measure of the static friction when the material with the coating side begins to slide under the action of a tensile force over the back and layer side of the same material or over a surface made of plush.

Surface resistance measured at 50 and 20% relative humidity RF.
Electrode distance 1 cm
Electrode length 10 cm

The partial structures described were further developed with the layers listed below.

Layer 7

(1st green-sensitized layer)
green-sensitized silver bromide iodide emulsion (4.8 mol% iodide; average grain diameter 0.28 µm) from 0.94 g AgNO₃, with
0.77 g of gelatin and
0.30 g coupler M-1

Layer 8

(2nd green-sensitized layer)
green-sensitized silver bromide iodide emulsion (4.3 mol% iodide; average grain diameter 0.65 µm) from 0.94 g AgNO₃, with
0.87 g of gelatin and
0.64 g coupler M-1

Layer 9

(Intermediate layer)
0.6 g gelatin
0.15 g ethylene diurea
0.08 connection WM-1

Layer 10

(Yellow filter layer)
yellow colloidal silver sol with
0.2 g Ag
0.5 g gelatin and
0.12 g connection WM - 1

Layer 11

(1st blue sensitive layer)
Silver bromido emulsion (4.9 mol% iodide; average grain diameter 0.35 µm) from 0.76 g AgNO₃, with
0.56 g gelatin
0.47 g coupler Y-1
0.4 g connection WM-1

Layer 12

(2nd blue sensitive layer)
Silver bromide iodide emulsion (3.3 mol% iodide; average grain diameter 0.78 µm) from 1.3 g AgNO₃, with
0.76 g gelatin
1.42 g coupler Y-1
0.3 g connection WM-1

Layer 13

(UV absorber layer)
1.5 g gelatin
0.8 g of compound UV-1

Layer 14

(Intermediate layer)
0.9 g gelatin
0.4 g ethylene diurea

Layer 15

(Hardening protection layer)

0.3 g gelatin
0.15 g of compound HM-1
0.1 g hydroxypropyl methyl cellulose hexahydrophthalate
0.03 g of compound VI-1
0.018 g dimethylpolysiloxane
0.7 g of curing agent of the formula

The breaking strength, granularity and sharpness of the finished layers were measured. In addition, the stain load was assessed visually and given in percent load.

The parallel breaking strength was characterized by the parameters breaking diameter [mm] and breaking strength [N]. Here, a 35 mm wide strip of the material in question, which was perforated along a transverse line, was formed into a loop and pressed together between two parallel, continuously approaching jaws. Breaking diameter is the inner diameter of the loop and breaking force is the force with which the two jaws act on the loop at the moment when the loop breaks along the perforation line.

Method described in Research Disclosure 25 302, 5/85.

Granularity: RMS granularity described in SPSE Handbook of Photografic science and Engineering 1973, p. 935, measuring aperture 48 µm.

Sharpness: MTF described in SPSE Handbook of Photografic science and Enginieering 1973, p. 946.

M-1 Kuppler 7 aus US-A-2 000 788

Y-1 Kuppler 16 aus US-A-3 933 501

WM-1 handelsübliche wäßrige Dispersion eines anioni­schen modifizierten Polyurethan

The following connections were used:

M-1 coupler 7 from US-A-2,000,788

Y-1 coupler 16 from US-A-3,933,501

WM-1 commercially available aqueous dispersion of an anionic modified polyurethane

A color photographic recording material for the color negative development was produced by applying a transparent layer of cellulose triac did the following layers were applied in the order listed; namely layers 1 and 2, layers 3 to 5, layers 6 to 9, layers 10 to 13 together and finally layer 14 were applied. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 1

(Antihalation layer)
Black colloidal silver sol with 0.5 g Ag, 0.2 g octylhydroquinone and 1.5 g gelatin

Layer 2

(Intermediate layer)
1.0 g gelatin
0.05 g octylhydroquinone

Layer 3

(1st red-sensitized layer)
red-sensitized silver bromide iodide emulsion from 3.5 g AgNO₃ (mixture of 80% by weight of an emulsion with 5 mol% iodide and average particle diameter of 0.2 µm and 20% by weight of an emulsion with 7 mol% iodide and average particle diameter of 0.8 µm), 1.7 g gelatin and 0.7 g coupler mixture C2, emulsified with 0.7 g tricresyl phosphate

Layer 4

(2nd red-sensitized layer)
red-sensitized silver bromide iodide emulsion from 2.0 g AgNO₃ (mixture of 20% by weight of an emulsion with 7 mol% iodide, average particle diameter of 0.8 µm and narrow particle size distribution and 80% by weight of an emulsion with 10 mol% iodide, average Particle diameters of 0.8 µm and wide particle size distribution),
2.0 g of gelatin and
0.2 g coupler mixture C2, emulsified with
0.2 g tricresyl phosphate

Layer 5

(Intermediate layer)
0.7 g gelatin and
0.09 g of 2,5-diisooctyl hydroquinone

Layer 6

(1st green-sensitized layer)
green-sensitized silver bromide iodide emulsion from 2.2 g AgNO₃ (mixture of 65% by weight of an emulsion with 5 mol% iodide and average particle diameter of 0.2 µm and 35% by weight of an emulsion with 7 mol% iodide and average particle diameter of 0 .8 µm),
1.7 g gelatin and
0.5 g of coupler M2 emulsifies with 0.5 g of tricresyl phosphate

Layer 7

(2nd green-sensitized layer)
green-sensitized silver bromide iodide emulsion from 1.5 g AgNO₃ (mixture of 70% by weight of an emulsion with 7 mol% of iodide, average particle diameter of 0.8 µm and narrow particle size distribution and 30% by weight of an emulsion with 10 mol% of iodide, average particle diameter of 0.8 µm and broad particle size distribution), 1.7 g gelatin and 0.2 g coupler M2, emulsified with 0.2 g tricresyl phosphate

Layer 8

(Intermediate layer)
0.5 g gelatin and
0.06 g of 2,5-diisooctyl hydroquinone

Layer 9

(Yellow filter layer)
yellow colloidal silver sol with 0.1 g Ag
0.35 g gelatin and
0.2 g connection WM-1

Layer 10

(1st blue sensitive layer)
Silver bromide iodide emulsion from 0.6 g AgNO₃ (mixture of 90 wt .-% of an emulsion with 5 mol% iodide and an average particle diameter of 0.2 microns and 10 wt .-% of an emulsion with 7 mol% iodide and an average particle diameter of 0.8 µm), 1.4 g gelatin and 0.85 g coupler Y2 emulsified with 0.85 g tricresyl phosphate

Layer 11

(2nd blue sensitive layer)
Silver bromide iodide emulsion from 1.0 g AgNO₃ (mixture of 50% by weight of an emulsion with 7 mol% iodide, an average particle diameter of 0.8 µm and narrow particle size distribution and 50% by weight of an emulsion with 10 mol% iodide, an average particle diameter of 0.8 µm wide particle size distribution),
0.6 g gelatin and 0.3 g coupler Y2, emulsified with 0.3 g tricresyl phosphate

Layer 12

(UV absorber layer)
1.5 g gelatin and
0.8 g of compound UV-1

Material 4 (according to the invention)

Layer 13

(Intermediate layer)
0.9 g gelatin
0.45 g connection WM-1
0.10 hydroxypropylmethyl cellulose hexahydrophthalate with an average particle diameter of 2.0 µm.

Material 5 (not according to the invention)

Layer 13

(Intermediate layer)
0.9 g gelatin
0.45 g connection WM-1

Material 6 (not according to the invention)

Layer 13

(Intermediate layer)
0.9 g gelatin
0.45 g connection WM-1
0.10 g of polymethyl methacrylate with an average particle diameter of 2 µm (insoluble in alkali).

The layer structure described (layers 1-13) was hardened by overlaying as follows:

Layer 14

(Hardening protection layer)
0.2 g gelatin
0.152 g polymethyl methacrylate
0.15 g hydroxypropylmethyl cellulose hexahydrophate halate
0.025 g of compound VI-1
0.063 g of dimethylpolysiloxane
0.7 g of curing agent such as material 1, layer 15.

The results are summarized in Tables 1-3.

Claims (5)

1. A process for the production of a multilayer photographic material, in which the layers are applied in at least two work steps and the material is dried and wound up between the work steps, characterized in that the uppermost layer of the first work step carried out alkali-soluble polymer particles with an average particle diameter of 0, Contains 2 to 5.0 µm. 2. The method according to claim 1, characterized in that the average particle diameter is 0.5 to 3.0 microns. 3. The method according to claim 1, characterized in that the polymer particles are used in an amount of 20 to 200 mg / m² of photographic material. 4. The method according to claim 1, characterized in that the polymer particles are used in an amount of 50 to 120 mg / m² of photographic material. 5. The method according to claim 1, characterized in that the polymer particles consist of hydroxypropylmethyl cellulose hexahydrophthalate.