JPS6389847A - Manufacture of multi-layer photographic material - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of multilayer photographic materials containing certain polymer particles.

It is known that in many cases it is not possible to apply all the layers of a multilayer photographic recording material to a support in one operation, but has to be applied in at least two stages. Each stage requires the application of a single layer or a stack of several layers.

The top layer of the laminate, applied in one step, usually contains a hydrophilic binder such as gelatin, a wetting agent, and optionally an alkali, a softener, a dye, and colloidal silver.

At each stage, the photographic material is dried and rolled up before applying the next layer or laminate. If the intermediate product is rolled up, its surfaces will stick together and create scratches on the material.

It is known that in the finished film this undesirable effect can be prevented by including in the top layer so-called spacers or matting agents, ie solid particles with an average particle size of 1 μm or more. Although this method cannot be applied to the upper layer in one step, it is subsequently removed by other layers since it causes fogging, uneven coating, and reduced breaking strength.

Moreover, it has also been proposed to include a matting agent in the middle layer of acid-treated gelatin, which is the top layer during manufacture. As a matting agent, it is insoluble in water and has an average particle size of 0.2 to 5μ.
m organic or inorganic substances are used. The difference between the refractive index of these particles and the refractive index of gelatin increases the light scattering by these particles, resulting in an increased graininess (DE 25 26 970).

In the first stage of the coating process, in which all the layers are applied in two or more stages with a force t, an intermediate layer is applied which prevents adhesion of the applied top layer and at the same time reduces stiction. It is an object of the present invention to develop this. This interlayer may be used to control other photographic properties of the material, in particular the light-sensitive properties,
must not have any negative impact on

There are now at least two or more layers, characterized in that the top layer of the layers applied in the first stage contains polymer particles that are soluble in alkali and have an average particle size of 0.2 to 5.0 μm. A method has now been found for producing multilayer photographic materials in which the layers are applied in stages, between which the material is dried and rolled up, but which does not have the disadvantages mentioned above.

The particle size is preferably 0.5 to 3.0 μm. Suitable alkali-soluble polymer particles belong to the following chemical groups: 1. Copolymers of alkyl methacrylates and methacrylic acid, acrylic acid or itaconic acid.

2. Copolymer of alkyl methacrylate and maleic acid half ester and half amide.

3. Copolymers of styrene and α, β-unsaturated mono- or di-carboxylic acids or dicarboxylic acid half-esters or half-amides.

4. Glyraft polymer of methacrylic acid/methyl methacrylate to a water-soluble dispersant of maleic anhydride/α-olefin.

5. Dicarboxylic acid half esters of cellulose derivatives, such as phthalate esters and hexahydrophthalates of methylcellulose, hydroxyethylcellulose or hydroxypropylmethylcellulose.

The amount of monomer is chosen such that the particles are insoluble in water below pH 5 and soluble in water above pH 7.

The layer containing the alkali-soluble polymer particles may contain a hydrophilic binder, such as gelatin, especially alkali-treated gelatin, a wetting agent, especially an organic fluorosurfactant, a formalin acceptor, a softener, a colloid, etc. 8 The polymer particles are usually added to the photographic material in an amount of 20 to 20
0 mg/m2, especially 50-120 mg/112
It is applied at a rate of . They are added to the coating solution as an aqueous dispersion.

Surprisingly, by adding the aforementioned particles,
The photographic properties of the multilayer photographic material, especially its graininess and sharpness,
It has been found that it is possible to prevent the occurrence of scratches due to adhesion, reduce the coefficient of static friction, and reduce fog due to discharge of static charges, without affecting the surface of the material.

The method according to the invention can be used for the production of multilayer photographic materials whose layers are applied in at least two or more stages, for example for the production of negative films, universal films and photographic papers, but in particular for the production of color negative films. Suitable for producing color glue universal film. If that layer is 2
When applying in stages or more, the method according to the invention can be repeated as necessary.

The photographic materials produced according to the invention are exposed and processed according to conventional methods.

The matting agent according to the invention is released from the photographic material by the alkaline developer, so that light scattering at the particle surface due to differences in refractive index is avoided. Surprisingly, however, no pores remain in the material, which could have an adverse effect.

Photographic materials, especially color photographic recording materials, to which the method according to the invention is preferably applied are multilayer materials comprising several silver halide emulsion layers or units of emulsion layers, each with a different spectral sensitivity. The emulsion layer units are such that the layers with the same spectral sensitivity do not necessarily have to be adjacent to each other, but may be separated by other layers, especially layers with different spectral sensitivities.
It may be a stack of two or more silver halide emulsion layers having the same spectral sensitivity. The binder of these layers is preferably a protein-based binder containing a free carboxyl group and a free amino group at -m. is gelatin. Besides protein-based binders, the binder layer contains up to 50% by weight of non-protein-based binders, such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and its derivatives, in particular its copolymers and cellulose derivatives. Sometimes it is.

The light-sensitive silver halide emulsion layer or emulsion layer unit contains at least one compound which reacts with it to form a color, generally a color coupler which is capable of reacting with the oxidation products of the color developer to form a non-diffusible dye. Contains. Color couplers are present in the photosensitive layer itself or in the vicinity thereof, and are preferably non-diffusive.Color couplers present in two or more layers in an emulsion layer unit are usually During color development, the light-sensitive halogen emulsion layer develops a similar color that is complementary to the colored light to which it is exposed, but it is not necessarily the same color.

Therefore, the red-sensitive silver halide emulsion layer contains at least one non-diffusive color coupler, usually a phenol or α-naphthol coupler, which forms a corresponding cyan color separation image. There is. US Patent No. 2474293, US Patent No. 2367531,
The cyan couplers described in US Pat. No. 2,895,826, US Pat. No. 3,772,002, EP 0 028 099 and EP 0 112 514 are notable examples.

The green-sensitive silver halide emulsion layer contains at least one non-diffusive color coupler, usually a 5-pyrazolone or indasilone type color coupler, to form a magenta color separation image. Cyanoacetyl compounds, oxacilones and pyrazoloazoles can also be used as magenta couplers. Particularly suitable magenta couplers include, for example, U.S. Pat.
00788, US Patent No. 4383027, German Patent Publication No. 1547803, German Patent Publication No. 1810464
German Patent Publication No. 2,408,665 and German Patent Publication No. 3,226,163.

The blue-sensitive silver halide emulsion layer contains at least one non-diffusible color coupler for forming a yellow color separation image, a color coupler containing a linear ketomethylene group in -m.

Particularly important in this sense are, for example, U.S. Pat.
．． 08194, US Pat. No. 3,933,501, German Patent Publication No. 2329587 and German Patent Publication No. 2456
It is a yellow coupler of the type described in No. 976.

Many color couplers of this type are known and described in numerous patent publications. Other references include, for example, “Agfa Institute Report (Mitte
Forshungs
Laborien der AGF^), a report entitled “Color couplers” by Berb (W, Pe1z) in “Rebelkusen/Munich, Volume 3 (1961), p. 111,” and “The chemistry of synthetic dyes (The chemistry Chemistry of
5 ynthetic dyes),” Volume 4, 341.
There is also a report by Venkataraman, K., p. 387, Academic Press (1971).

The color coupler may be a 4-equivalent coupler or a 2-equivalent coupler.

The latter, as is known, is derived from a 4-equivalent coupler so as to have a substituent at the coupling reaction position that is eliminated during the coupling reaction. Some 2-equivalent couplers are virtually colorless, while others have an inherent strong color that replaces the color of the image dye that disappears during the coupling reaction (masking couplers).
Known white couplers react with the oxidation products of color developers to form substantially colorless compounds, but essentially two
It can be considered as an equivalent coupler. In some two-equivalent couplers, the group released from the coupling reaction site upon reaction with the oxidation product of the color developer is a compound that exhibits certain favorable photographic properties upon release, e.g.
after releasing one or more groups or directly acting as a development inhibitor or accelerator (for example DE 2703145, DE 2855
Examples of such two-equivalent couplers include the DAR and FAR couplers as well as the known DIR couplers.

A suitable DIR coupler is e.g. -1 UK Patent 9
53454, German Patent Publication No. 1800420, German Patent Publication No. 2015867, German Patent Publication No. 2414
006, German Patent Publication No. 2842063 and German Patent Publication No. 3427235.

Compatible DAR and FAR couplers include, for example:
German Patent Publication No. 3209110, European Patent 00
89834, European Patent No. 0117511 and European Patent No. 0118087.

The main purpose of DIR, DAR and FAR couplers is to impart activity to the groups released during the coupling reaction.
Since the color-forming ability of these couplers is of minor importance, it is also appropriate to use DIR, DAR and FAR couplers which yield essentially colorless products during the coupling reaction, as described for example in German Patent Publication No. 1547640. It is.

As described, for example, in U.S. Pat. No. 4,420,556, coupling products, such as dyes, which are diffusible or at least have a slight or limited mobility on reaction with the oxidation products of color developers, The groups released are ballast groups (ballast g).
roup).

High molecular weight color couplers can be used, for example, in German patent D
No. E-C-1297417, German Patent Publication 24075
69, German Patent Publication No. 3148125, German Patent Publication No. 3217200, German Patent Publication No. 3320079
German Patent Publication No. 3324932, German Patent Publication No. 3331743, German Patent Publication No. 3340376,
European Patent No. 27284 and US Patent No. 40802
It is described in No. 11. The high molecular weight color couplers are primarily synthesized by polymerization of color couplers of ethylenically unsaturated monomers, but can also be synthesized by polyaddition or polycondensation.

The layer may also contain further additives other than the aforementioned components, such as curing agents, antioxidants, dye stabilizers and reagents that influence mechanical and electrostatic properties.
In order to suppress or prevent the undesirable effects of ultraviolet light on the color images formed by the color photographic recording material according to the invention, the layer may also contain ultraviolet absorbers.

The curing agent used preferably activates carboxyl groups, in particular in the following general formula RI and R2 are alkyl groups having 1 to 8 carbon atoms, or optionally 1 to 2 carbon atoms. represents an aryl or aralkyl group substituted by an alkyl group or a halogen atom, or the two together optionally substituted by an alkyl group having 1 or 2 carbon atoms or a halogen atom; represents an atomic group necessary to form a heterocycle, R3 represents a hydrogen atom or an alkyl group containing 1 to 2 carbon atoms, and n represents 0 or 2, and the compound formed by preferable.

A color photographic recording material for reversal color development was prepared by applying the following layers in the following order to a transparent support layer of cellulose triacetate: 1 layer 1 and 2;
Layers 3 to 6, layers 7 to 10 and layers 11 to 14 are each applied simultaneously, and then layer 15 is applied in an amount of 0 order per 1 m'', the amount of silver halide used is the corresponding AgN All silver halide emulsions were stabilized with 0.52 of 4-hydroxy-6-methyl-1,3,3a,7-chitraazaindene per 031001 of A g N .

Layer 1 (antihalation layer) flio, 51 and gelatin 1.51 A black lochoidal silver salt that combines

Layer 2 (intermediate layer) Gelatin 0.92, A g N Os (Micrato) 0.333) and octylhydroquinone 0.331° Layer 3 (first red-sensitive light layer) A g N Os 0,982 and gelatin 0.331°. Red sensitized silver iodobromide emulsion (5.5 mole % iodide; average grain size 0.25 μm) prepared from 81jl and coupler C-10,251.

Layer 4 (Second Red Sensitive Light Layer) A red sensitized silver iodobromide emulsion (6.5 mole % iodide; Average particle size: 0.6 μm) Layer 5 (middle layer) Gelatin 1, octylhydroquinone 0.22 and compound WM-1
0.41° Photographic material 1 (according to the invention) Layer 6 (intermediate layer) Gelatin 0.41, (alkali-soluble) hydroxypropylmethyl-cellulose hexahydrophthalate 0.12° with an average particle size of 2.0 μm 2 (not according to the invention) Layer 6 (middle layer) Gelatin 0.4F.

Photographic material 3 (not according to the invention) Layer 6 (intermediate layer) Gelatin 0.42, polymethyl methacrylate (alkali-insoluble) with an average particle size of 2.0 μm and 0.1 F.

Regarding the above-mentioned product 1 (Jill-6), slip properties and surface resistance were measured. Friction coefficient (= tensile force/normal stress xl
OO) is a measure of static friction when it begins to slide under the action of gravity on the back and front surfaces of the same material and on the surface of velvet, with the surface of the material facing down.

Surface resistance was measured at 50% and 20% relative humidity, with an inter-electrode distance of 1 cm and an electrode length of 10 c++.

The layers described below were applied to the above laminate to complete the photographic material.

Layer 7 (First Green Sensitive Light Layer) A green sensitized silver iodobromide emulsion (4.8 mol iodide %; average particle size 0.28 μm).

Layer 8 (Second green-sensitive light layer) A g N Oz 0,941 with gelatin 0.81 and coupler M-10,64,? A green sensitized silver iodobromide emulsion (4.3 mol % iodide; average grain size 0.65 μm) prepared from

Layer 9 (middle layer) gelatin 0.62, ethylene diurea 0.152, Compound WM-10,08&.

Layer 10 (yellow filter layer) Yellow colloidal silver sol containing 2 Ag, 0 gelatin
．． 52 and compound WM-10,122° layer 11 (first blue-sensitive blue-light layer) Iodine prepared from A g N Os 0,769 and gelatin 0.561, coupler Y-10,471 and compound WM-10,47 Silver bromide emulsion (4.9 mol% iodide)
; average particle size 0.35 μm, ) Layer 12 (second blue-sensitive blue light layer) Silver iodobromide prepared from AgNOs 1.39, gelatin 0.71, coupler Y-11,429 and compound WM-10,31 Emulsion (3.3 mol% iodide
; average particle size 0.78 μm).

Layer 13 (Ultraviolet absorbing layer) Gelatin 1.52 Compound UV-10,81° Layer 14 (Intermediate layer) Gelatin 0.92, Ethylenediurea 0.42° Layer 15 (Hardenable protective layer) Gelatin 0.32, Compound HM-10,15F, hydroxypropyl methyl cellulose hexahydrophthalate 0.12, compound Vl-10,031, dimethylpolysiloxane 0.018.9 and a curing agent corresponding to the formula: 0.7.

The breaking strength, graininess and sharpness of the complete laminate were measured. Evaluate the damage visually and record it as a percentage.

The parallel breaking strength was defined using the breaking diameter [W] and the breaking force [N] as parameters. A strip of material 35 mm wide with holes drilled along the transverse line was formed into a loop, and both sides of the loop were sandwiched between the jaws of two parallel scissor tools and continuously compressed toward each other.

The breaking diameter is the inner diameter of the loop, while the breaking force is the force that the two jaws are exerting on the loop at the moment the loop breaks along the line of the hole.

Research Disclosure
25 302, 5/85.

Graininess; Science and Technology of Photography (Photollraphi)
c 5science and engineering)
5PSE Handbook, 1973, page 935, RMS granularity measured with a 48 μm aperture.

Sharpness: The science and technology of photography
5science and engineering)
MTF described in 5PSE Handbook 1973, page 946.

Coupler WM-1 of U.S. Pat. No. 3,933,501 using the following compound:
Commercial aqueous dispersion of anionically modified polyurethane.

yi-x HM-1 CH3 A color photographic recording material for color negative development was prepared by applying the following layers in a certain order to a transparent support of cellulose triacetate. 7111 and 2
, M3-5, layers 6-9 and layers 10-13 were applied simultaneously, with layer 14 being applied last. The amount stated is llI
2 is the standard.

The amount of silver halide applied is the corresponding A g N Oj
is given in the amount of All silver halide emulsions are A
4-hydroxy-6- per g N O3100y
Methyl-1,3,3a,7-thitraazaindene 0.5
It was stabilized by g.

Layer 1 (Anti-halation N) Ag 0.5g, Octylhydroquinone 0.21? and gelatin 1.
Black colloidal silver sol containing 5g.

Layer 2 (middle layer) Gelatin 1.0g Octylhydroquinone 0.05y.

Layer 3 (first red-sensitive light layer) AgNOs 3.5y (80% by weight emulsion containing 5 mol% iodide and having an average grain size of 0.2 μm, and 80% by weight emulsion containing 7 mol% iodide and having an average grain size of 0° 8 μm) A red sensitized silver iodobromide emulsion prepared from a coupler mixture C20,7y emulsified with 1.7 g of gelatin and 0.7 g of tricresyl phosphate (mixture with 20% by weight of emulsion).

Layer 4 (second red-sensitive light layer) AgNO32,0y (20% by weight emulsion containing 0.7 mol% iodide and having an average grain size of 0.8 μm and a narrow grain size distribution)
and 80% by weight of an emulsion containing 10 mol% iodide and having an average particle size of 0.8 μm and a broad particle size distribution), gelatin 2. Red sensitized silver iodobromide emulsion made from coupler mixture C-20,29 emulsified with Og and 0.2 g of tricresyl phosphate.

M5 (middle class) Gelatin 0.7fI and 2.5-diisooctylhydroquinone 0°09g.

Layer 6 (first green-sensitive light N) A g N Os 2 , 21F (65% by weight emulsion containing 5 mol% iodide and having an average grain size of 0.2 μm; and 65% by weight emulsion containing 7 mol% iodide and having an average grain size of 0°8) 1m emulsion 35
Green sensitized silver iodobromide emulsion prepared from coupler M2 0.5y emulsified with 0.5 g of tricresyl phosphate in Matsukami 1.

717 (Second green-sensitive light layer) A g N O31, 5 g (70% by weight emulsion containing 7 mol% iodide and having a narrow particle size distribution with an average grain size of 0.8 μm, and 10 mol% iodide) Including average particle size 0.8μm
A green sensitized meadow odor prepared from 0.2 g of coupler M2 emulsified with 1.7 g of gelatin and 0.2 g of tricresyl phosphate (mixture with 30% by weight emulsion with broad particle size distribution) Silver emulsion.

Layer 8 (middle layer) Gelatin 0.51? and 2.5-diisooctylhydroquinone 0°06y.

Layer 9 (yellow filter N) Ag 0.1y, Gelatin 0.35y and Compound WM-10,2y Yellow colloidal silver sol containing.

Layer 10 (first sensitive blue light layer) 0.6 g of AgNOz (90 wt % emulsion containing 5 mol % iodide and having an average grain size of 0.2 μm, and 90 wt % emulsion containing 7 mol % iodide and having an average grain size of 0.2 μm) Silver iodobromide emulsion prepared from 1.4 g of gelatin and 85 g of coupler Y-20, emulsified with tricresyl phosphate o,s5y.

[11 (Second Sensation Blue 31) A g N O 31, 09 (emulsion containing 7 mol% iodide and having a narrow grain size distribution with an average grain size of 0.8 μm) containing 50% by weight and 10 mol% iodide Iodine prepared from coupler Y-20,311 emulsified with 0.6 g of gelatin and 0.3 g of tricresyl phosphate Silver bromide emulsion.

Layer 12 (UV absorption layer) 1.5g gelatin and Compound UV-10.8g.

Photographic material 4 (according to the invention) Layer 13 (intermediate layer) 0.9 g of gelatin, 45 g of compound WM-10, 0.10 g of hydroxypropyl methyl cellulose hexahydrophthalate with an average particle size of 2.0 μm.

Photographic material 5 (not according to the invention) Layer 13 (middle layer) 0.9g gelatin and Compound WM -10.45g.

Photographic material 6 (not according to the invention) Layer 13 (intermediate layer) 0.9 g of gelatin, compound WM-10,45Li, 0.10 g of polymethyl methacrylate (alkali insoluble) with an average particle size of 2.0 μm.

The following layers were applied and cured to the above laminate (layers 1-13): Layer 14 (curable protective layer) 0.2 g gelatin, 0.152 FI polymethyl methacrylate, 0.1 hydroxypropyl methylcellulose hexahydrophthalate. 15y, compound VI-10,0259, dimethylpolysiloxane 0.063g and photographic material 1
0.7 g of curing agent used in layer 15.

The results are summarized in Tables 1-3.

5% by weight 95% by weight

Claims (1)

Claims: 1. A method for producing a multilayer photographic material, in which the layers are applied in at least two or more stages, and the material is dried and rolled up between these stages, the method being applied in the first stage. A process characterized in that the top layer of the layers contains alkali-soluble polymer particles with an average particle size of 0.2 to 5 μm. 2. The method according to claim 1, wherein the average particle size is 0.5 to 3.0 μm. 3. In an amount of 20 to 200 mg per 1 m^2 of photographic material,
2. Process according to claim 1, characterized in that polymer particles are used. 4. Process according to claim 1, characterized in that the polymer particles are used in an amount of 50 to 120 mg per m^2 of photographic material. 5. The method according to claim 1, characterized in that the polymer particles are hydroxypropylmethylcellulose hexahydrophthalate.