DE19640208A1 - Photographic material useful for colour photographic paper - Google Patents

Abstract

A photographic material with a base and light-sensitive silver halide (AgX) emulsion layer(s) on one side has back coating(s) containing (a) conductive organic polymer(s) (I), (b) colloidal silica (II), (c) organic polymeric binder(s) of formula (A) and (d) hardener(s) (IV). In (A), a = 30-60 wt.%; b = 0-60 wt.%; c, d = 1-20 wt.%; R<1> = hydrogen (H) or 1-4 carbon (C) alkyl; R<2> = optionally substituted 1-18C alkyl; R<3> = H, methyl (Me) or ethyl (Et); R<4> = H or COOH; R<5> = H, Me or -CH2-COOH; and L = a chemical bond or a linking group.

Description

The invention relates to a photographic recording material with a support, on the one hand at least one photosensitive silver halide emul sionsschicht and on the other side (back) at least one back layer, which is characterized by the following properties:

Conductivity before and after processing, good printability, dirt-repellent Properties, especially with strongly oxidized developer baths and high adhesion assets on the pad.

The carrier is preferably reflective.

Above all, photographic materials should have a sufficiently high conductivity have disturbances due to flashes as well as sticking or dust exclude attraction due to electrostatic charge.

Photographic materials with reflective supports, such as those used for supervisory pictures used should also be printable on the back.

Type printers, dot matrix printers, thermal printers, ink jet printers are used and electrophotographic printing systems. The printing is usually done before processing. Rapid absorption is required, furthermore high retention and smudge resistance for the applied Print media so that the printed image is still legible after processing.

On the other hand, soiling of the photographic material, e.g. B. by oxidized developer components can occur, can be avoided or can be easily removed.

A sufficiently high adhesion of the layer to the base is also required, to detach layers and thus contaminate developing baths avoid.

The object of the invention was to provide such a material.  

It has been found that this task is determined by the combined use ter substances in the back coating can be solved.

The invention therefore relates to a photographic material of the introduction named type that in the back layer at least one connection according to the Substance classes listed above contain:

• (A) a conductive organic polymer,
• (B) colloidal silica,
• (C) an organic polymeric binder of the formula (I) below and
• (D) a curing agent.

wherein
a 30 to 60% by weight,
b 0 to 60% by weight,
c 1 to 20% by weight,
d 1 to 20% by weight,
R¹ H, C₁-C₄-alkyl, preferably H or CH₃,
R² straight-chain or branched, optionally substituted C₁-C₁₈-alkyl, preferably C₁-C₈-alkyl,
R³ H, CH₃, C₂H₅,
R⁴ H, COOH,
R⁵ H, CH₃, -CH₂-COOH and
L represents a chemical bond or a connecting member such as alkylene, arylene, carboxyalkylene, carbonamidoalkylene.

Examples of L are p-phenylene, p-benzylene, -CONHC (CH₃) ₂-CH₂-, -COOCH₂-CH₂-, -COO (CH₂) ₃- and -CONH- (CH₂) ₄-.

The application amount of binder C can be 10 to 100 mg / m². An application amount between 20 and 60 mg / m 2 is preferred. The binders of the formula I in particular have a molecular weight M _n of 50,000 to 2,000,000, preferably 100,000 to 700,000.

The polymers, preferably polymer latices, can include, for example, the following Have composition:

C-1 a = 52% by weight; b = 26% by weight; c = 5% by weight; d = 17% by weight; M _n = 250,000;
C-2 a = 52% by weight; b = 21% by weight; c = 10% by weight; d = 17% by weight; M _n = 340,000;

C-3 a = 60% by weight; b = 30% by weight; c = 5% by weight; d = 5% by weight; M _n = 470,000
C-4 a = 57% by weight; b = 28% by weight; c = 5% by weight; d = 10% by weight; M _n = 160,000
C-5 a = 54% by weight; b = 26% by weight; c = 5% by weight; d = 15% by weight; M _n = 620,000
C-6 a = 52% by weight; b = 23% by weight; c = 5% by weight; d = 20% by weight; M _n = 510,000.

As a curing agent such. B. suitable polyfunctional compounds that as Reactive groups have at least two epoxy or aziridine units. The like compounds are described for example in EP-030 352, EP-191 302, DE 22 42 394, GB-2 283 332.

The application amount of the hardening agent can be 0.1 to 20 mg / m². Before an order quantity between 1 and 10 mg / m² is added.

The following compounds can preferably be used:

The backside layer can also be an anionic or nonionic Contain wetting agents. Suitable wetting agents are fluorosurfactants, alkyl sulfonates, Alkylarylsulfonates, succinic acid half esters, sulfosuccinic acid esters, saponin, Alkylarylalkyl ethers, the selection not being based on the classes of compounds mentioned must be limited.  

Suitable wetting agents are e.g. B.

The organic conductive polymers can be used in an amount of 1 to 100 mg / m² can be used.

Suitable organic, conductive polymers are e.g. B. ionically conductive polymers or copolymers containing a carboxyl, phosphonate, sulfo or sulfato group. These can exist both as free acid and as salt. For crosslinking, the polymer chains can also contain functional groups, e.g. B. epoxy or aziridine groups. The average molecular weights (M _n ) can be in the range from 1000 to 2,000,000, preferably 2500 to 100,000. The application amount can be 5 to 100 mg / m². An application amount between 20 to 60 mg / m² is preferred. The following connections are suitable.

Suitable organic, conductive polymers are, for. B. Polymers that a permanent conductivity, d. H. a constant before and after processing Conductivity, enable. Organic compounds that are high are suitable possess conjugated binding system and thus an electronic conductivity exhibit. Such antistatic agents are described, for example, in EP-440 957 and EP- 593 111. Certain thiophenes can be in the presence of poly Acids polymerize and can be used as stable preparations in water for users be used. With the help of these connections, transparent, from humidity-independent antistatic coatings on substrates  be put. The application amount can be 1 to 50 mg / m². Prefers an order quantity of 5 to 20 mg / m².

The mixtures of 3,4-polyethylene-dioxythiophene and, for example, are suitable Polystyrene sulfonic acid in the ratio 1: 2.5 (A-15).

Suitable colloidal silicas are e.g. B. colloidal silica sols with Alumi nium are modified. Such products are known and for example in fol described patents: EP-421 764, EP-558 138, DE-37 00 183. The spec Fish surface can be 50 to 500 m² / g. Can be used for. B. Han Products like the Levasil types from Bayer or the Ludox types from the Du Pont company. The application amount can be 10 to 100 mg / m². An application amount between 20 and 60 mg / m 2 is preferred.

Examples are the following commercial products

B-1 Levasil 200 A (Bayer)
with a specific surface area of 200 m² / g
B-2 Ludox AM (DuPont)
with a specific surface of approx. 210 m² / g.

In addition to the additives mentioned, the antistatic layer can also contain other additives included: e.g. B. inorganic and organic spacers, lubricants, optical Brighteners, pigments, adhesive compounds.

The front of the material can be any, for photographic materials usual structure of photosensitive silver halide emulsion layers and optionally contain further layers.

It is preferably a conventional layer structure for a color material.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the sil over color bleaching process.  

Color paper is preferred.

Thin films and foils are particularly suitable as supports. An overview of Backing materials and auxiliary layer applied to their front and back ten is shown in Research Disclosure 37254, Part 1 (1995), p. 285.

The color photographic materials usually contain at least one red sensitive, green-sensitive and blue-sensitive silver halide emulsions layer and, if necessary, intermediate layers and protective layers.

Depending on the type of photographic material, these layers can vary be arranged. This is shown for the most important products:

Fire photographic films such as color negative films and color reversal films show in in the order given below on the support 2 or 3 rotsensit liche, cyan-green coupling silver halide emulsion layers, 2 or 3 green temp sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow-coupling silver halide emulsion layers. The layers same spectral sensitivity differ in their photographic emp sensitivity, with the less sensitive sub-layers usually closer arranged to the carrier than the higher sensitive sub-layers.

Between the green sensitive and blue sensitive layers is more common a yellow filter layer, which prevents blue light from entering the to get layers below.

The possibilities of the different layer arrangements and their out effects on photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193.

Color photographic paper, which is usually much less sensitive to light as a color photographic film, points in the order given below usually a blue-sensitive, yellow-coupling silver halo on the carrier genide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion layer and a red-sensitive, cyan-coupling silver halide emulsion layer on; the yellow filter layer can be omitted.  

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low sensitivity layers to another layer package in a photographic film be summarized to increase the sensitivity (DE 25 30 645).

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectrals sensitizers can be found in Research Disclosure 37254, Part 3 (1995), pp. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain Sil berbromide iodide emulsions, which may also contain small amounts of silver chloride can contain. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxidation Product-formed dyes are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photography films, to improve sensitivity, Graininess, sharpness and color separation are often used in compounds Reaction with the developer oxidation product release compounds, the photo are graphically effective, e.g. B. DIR couplers that have a development inhibitor columns.  

Information on such connections, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

Mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm through knife) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the layers of a photographic material and other methods, chemical Introducing connections into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve the stability of dyes, couplers and whites and to reduce the color fog, plasticizers (latices). , Biocide and others included.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.  

The layers of color photographic materials are typically hardened, i.e. H., the binder used, preferably gelatin, is by suitable che mixed processes networked.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.

After imagewise exposure, color photographic materials become their character ter processed according to different procedures. Details of the Procedures and chemicals required for this are in Research Disclosure 37254, part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff. Published together with exemplary materials.  

Experimental part Test criteria

The test was carried out with a color negative paper, the carrier of which is a paper coated with polyethylene on both sides. After exposure processing (development, bleach-fixing, stabilization and drying) according to the standard procedure AP 92.

Antistatic properties

The surface resistance was determined. Measuring electrodes were used of 10 cm in length at a distance of 1 cm. The surface resistance is given stood per cm, hereinafter indicated with Ω /. The samples were pre-24 hours Room temperature (20 to 23 ° C) at 50% r. F. conditioned. The measurements were carried out before and after processing the test samples.

Dirt-repellent properties

The test medium was a strongly oxidized developer (AP 92) with about 10 g of tar-like Developer oxidation products, in finely dispersed form in 700 g Ent winder solution templates. The photographic material was at 40 ° C for 50 seconds in this Approach treated. The back of the sample was then covered with a Hand shower rinsed and the degree of contamination of the layer surface visually judged. Grading system 1 to 5 according to increasing pollution: Grade 1 none, grade 5 very heavy pollution.

Printability

The tests were carried out with a dot matrix printer and a thermal printer. Judged was the printed image before and after processing. Grading system 1 to 5 ent descending pressure density: grade 1 highest, grade 5 lowest pressure density.  

example 1 Baste of the antistatic layer

The back of a paper coated on both sides with polyethylene became too next subjected to corona irradiation. Subsequently, from aqueous Medium the following substances applied to the base. Order quantities see overview table below:

Table 1

Comparative compounds

V-1: polymer of 63% by weight butyl acrylate, 32% by weight styrene and 5% by weight Methacrylic acid.

V-2: polymer of 63% by weight styrene, 33% by weight butadiene and 4% by weight Acrylic acid.

V-3: polymer of 14% by weight styrene, 50% by weight butadiene, 30% by weight Acrylonitrile and 6% by weight methacrylic acid.

V-4: polymer of 86% by weight butyl acrylate, 9% by weight methyl methacrylate and 5% by weight methacrylic acid.

V-5 :. Polymer of 90% by weight methyl methacrylate and 10% by weight methacrylic acid sulfoisopropylamide.

The test results are recorded in Table 2;
u = unprocessed, v = processed.

Table 2

Samples 1 to 6 according to the invention are notable for conductivity, Dirt repellency and printability by a quality level that the Er meets requirements in practice. Furthermore, the samples have a high Layer strength on. Long-term tests in a processing machine left nothing Detect delamination.

The comparative samples 7, 9, 10, 11, however, left deficits in the dirt recognize repellent properties. In the comparison samples 8, 11 occurred all defects in printability.  

Example 2

In the same way as in Example 1, materials with the following rear faces were layering made:

Table 3

The test gave the result of Table 4.

Table 4

Sample 12 (according to sample 2 according to the invention) has a sufficiently high one Conductivity and good printability with sufficient dirt repellency the properties.

In sample 13 (comparison) without additive A-1 there is a significant decrease in Conductivity and a sharp increase in dirt absorption can be observed.

In sample 14 (comparison) without the addition of compound C-3 there is a clear ver deterioration in printability.  

Example 3

In the same way as in Example 1, materials with the following rear sides were used layering made:

Table 5

The test gave the result of Table 6.

Table 6

In contrast to the above samples, samples 15, 16 are drawn all characterized by permanent conductivity. That means the conductivity remains before and after processing at the same level.

Sample 17 is intended to show that combinations of ionically conductive Polymers with electronically conductive polymers are possible.

Claims (4)

1. Photographic recording material with a support which has on one side at least one photosensitive silver halide emulsion layer and on the other side (rear side) at least one back side layer which contains at least one compound each of the substance classes listed below:

• (A) a conductive organic polymer,
• (B) colloidal silica,
• (C) an organic polymeric binder of the formula (I) below and
• (D) a curing agent. wherein
  a 30 to 60% by weight,
  b 0 to 60% by weight,
  c 1 to 20% by weight,
  d 1 to 20% by weight,
  R¹ H, C₁-C₄ alkyl,
  R² straight-chain or branched, optionally substituted C₁-C₁₈ alkyl,
  R³ H, CH₃, C₂H₅,
  R⁴ H, COOH,
  R⁵ H, CH₃, -CH₂-COOH and
  L represents a chemical bond or a connecting link.

2. Photographic recording material according to claim 1, characterized characterized in that (A) in an amount of 1 to 100 mg / m², (B) in one Amount of 10 to 100 mg / m², (C) in an amount of 10 to 100 mg / m² and (D) are used in an amount of 0.1 to 20 mg / m². 3. Photographic recording material according to claim 1, characterized in that (A) have an average molecular weight (M _n ) of 1000 to 2,000,000 and (C) have an average molecular weight (M _n ) of 50,000 to 2,000,000. 4. Photographic recording material according to claim 1, characterized records that (B) has a specific surface area of 50 to 500 m² / g.