DE1210320B - Photographic opal film - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

G03c

German class: 57b-1

Number: 1210 320

File number: P26231IX a / 57b

Filing date: December 16, 1960

Opening day: February 3, 1966

The present invention relates to an opal photographic film with improved antihalation protection and improved optical resolution properties.

Optically clear and optically cloudy substrates with photographic emulsions are used for many areas of application, z. B. in cartography, as decorative banners, for making tables or maps and used for technical and sales purposes.

Heretofore, in making such films, the photographic emulsion was applied to one side of one applied transparent substrate, the other side of which carried an optically cloudy layer, d. H. one A layer that contains opaque substance and only partially transmits light, which also prevents halation May contain dye. It is also known to have one side of a transparent substrate first to coat with a low light-sensitive emulsion, which opacifiers, such as starch or rubber latex, and then to coat a fairly sensitive silver halide emulsion. On the opposite side can be a simple gelatin layer or a layer with an antihalation Dye can be painted on. Both suggestions leave us with regard to the good resolution and Antihalation properties still leave a lot to be desired. It has also been suggested between applying an antihalation layer to the emulsion layer and the support; however, this one has the Disadvantage that the prints obtained are often color cast or blotchy in an undetectable manner and do not give the white background desired for reflective viewing. This is based on one uneven bleaching or color deterioration during development and is caused by the presence the emulsion layer, which causes the diffusion of the treatment solutions into the antihalation layer and delayed out of this. Furthermore, by installing the antihalation material often the sensitometric properties in a layer adjacent to the silver halide layer influenced by fogging. According to another suggestion, a white, waterproof carrier should be used on one side with a silver halide emulsion and on the opposite side with a tinted one Layer to be coated.

A modified method uses a tinted backing with a white pigment coating coated, on the upper side of which a silver halide emulsion is drawn. These last mentioned Films are opal in their resolution and anti-photographic film

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dr. rer. nat. J.-D. Mr. v. Uexküll, patent attorney,

Hamburg 52, Königgrätzstr. 8th

Named as inventor:

Clifford Edward Milner, Rochester, N.Y.

(V. St. A.)

Claimed priority:
V. St. v. America December 31, 1959
(863 085)

halation properties also unsatisfactory.

A photographic opal film, which consists of the following four layers:

1. a transparent, hydrophobic, polymeric substrate,

2. one that does not contain any bleachable coloring material, optically cloudy binder layer made of water-permeable, macromolecular organic Colloid and finely divided inert, inorganic, white pigment particles from 0.1 to 2.0 μ,

3. A gelatin silver halide photographic photosensitive emulsion layer and

4. an antihalation layer made of the same components as specified for layer 2, but with a pale bear color material,

is, however, according to the invention characterized in that on one side of the substrate 1 only the optically cloudy binder layer 2 and above the light-sensitive gelatin-silver halide emulsion layer 3 are provided, while the antihalation layer is on the other side of the support 4 is located. Preferably the white pigment is in an amount of 1.5 to 3 parts by weight per part Binder present in layers 2 and 4. The bleachable color material, which also acts as an antihalation dye or pigment is preferably manganese dioxide having a particle size from 1 to 100 ΐημ and is generally in a

609 503/364

Amount from 0.05 to 0.10 parts by weight per part of binder is present. -

The support can be any transparent, hydrophobic film, e.g. B. from a cellulose ester, such as cellulose acetate, cellulose nitrate, cellulose butyrate, mixed cellulose esters, or from a vinyl polymer, z. B. polyvinyl acetate,. Polyvinyl chloride, polyvinylidene chloride, polystyrene and mixed polymers the same, or made of a polyamide, e.g. B. Polypentamethylene - sebacamid, Polyhexamethylene - sebacamid, Polypentamethylene suberamidjpolydecamethylene adipamide, or super polyesters, for example made from a high polymer linear polyester of a dicarboxylic acid with a dihydric alcohol, consisting of. Preferred supports are polyester films according to the USA patent 2,465,319, on which a thin and essentially hydrophobic mixed polymer layer according to German Patent 925 032 and German Auslegeschrift 1 095 514 is stacked.

Other polymers can also be used for the support, such as polyethylene terephthalate-isophthalate films, as described in UK Patent 766 290 and Canadian Patent 562 672, or polymers, which by condensation of terephthalic acid or dimethyl terephthalate with propylene glycol, diethylene glycol, Tetramethylene glycol or cyclohexane-1,4-dimethanol (hexahydro-p-xylene alcohol) can be obtained.

When producing a typical film according to the invention, a film made according to Example 4 of German Auslegeschrift 1 095 514 made of polyethylene terephthalate, which may also have a thin gelatin intermediate layer, is coated on one surface with an aqueous gelatin dispersion of about 30 to 50% gelatin and about 50 to 70% % Titanium dioxide (based on the total dry weight) ^{coated with a dry coating weight of about 10 mg / dm 2} gelatin. A gelatin-silver halide emulsion layer is then drawn over this layer, emulsions with a variable gamma avert according to British patent 547 060 being particularly suitable. However, the type of light-sensitive layer depends on how the new opal film is to be used. An aqueous gelatin dispersion with 50 to 70 percent by weight of titanium dioxide and 0.25 to 10 percent by weight of colloidal manganese dioxide as antihalation protection is spread as usual in a dry weight of about 70 mg / dm ² gelatin on the back of the carrier film.

The gelatin can be completely or partially through other water-permeable colloids, e.g. B. by natural or synthetic, hydrophilic polymers such as casein, albumin, interpolyamides, agar-agar, polyvinyl alcohol, and polyacrylamides Polyvinyl acetals; together with gelatin, certain other polymers or polymer mixtures, such as polyvinyl-N-vinyl lactams, butadiene-acrylonitrile copolymers, Vinyl acetate vinyl stearate

in copolymers, styrene-butadiene copolymers, alkyd and acrylic resins.

As a white pigment, titanium dioxide can be used in a wide variety of crystalline forms, however, the rutile crystal form is preferred because of its greater haze for a given weight will. Other white pigments such as barium sulfate, calcium sulfate, and zinc oxide can also be used will. Although colloidal manganese dioxide is under unfavorable because of its greater stability Storage conditions are preferred as the bleachable light-protection color component, others can also be used bleachable dyes or pigments, such as. B. Auramine (Color Index No. 1655), acidic blue black (Color Index No. 1246) and nigrosine (Color Index No. 1864), as well as those described in U.S. Patent 2,203,767 Colors are used.

The layers can contain other conventional additives for a wide variety of purposes, such as. B. optical brighteners included.

To get a retouchable surface or drawing area on the emulsion side of the film, you can add matting agents to the photosensitive emulsions just before they are applied Starch or silica, e.g. B. the extremely porous silica-like compounds according to the United States patent 2 626 867, add.

Furthermore, other emulsions, e.g. B. such as those used for the production of enlargements are common, or emulsions for contact prints on which novel opal films are drawn.

The halation and the other properties of the new films are remarkably good as a result Table 1 below shows a film according to the invention (No. 2) other known Films are compared in comparison. With compatibility there will be both the influence of the antihalation layer on the sensitivity and contrast values of the emulsion layer as well as the influence of the latter referred to the halation.

Table 1

Back layer 4 Intermediate layer 2 Atrium freedom Staining compatibility 1. White pigment
+ bleachable
Color material white pigment
+ bleachable
Color material Well bad inadequate 2. White pigment
+ bleachable
Color material only white pigment Well no Well 3, White pigment only only white pigment inadequate no. Well 4. White pigment only white pigment
- bleachable
Color material inadequate bad inadequate

The above values show that the opal film according to the invention was applied to the opposite side of the film with the white binder layer 2 in an aqueous dispersion which was surprisingly good There was no halation, with a rutile crystal and 0.4 percent by weight containing any incompatibility of bleachable coloring 5 colloidal manganese dioxide. These aqueous materials with the photographic emulsion or dispersion were applied so thickly that there was no staining due to the gelatin dry coating weight of 70 mg / dm ² emulsion layer acting as a barrier in the event of inadequate bleaching.
Problem is more. The obtained photographic film was treated with a

Since the front and back are slightly colored in the usual projection magnification device.

and are visually cloudy, the new opal film is tet. The exposed film was IV at 20 ^° C. for _{2 minutes}

especially good for translucent photographs, in a developer of the following composition

Promotional films, exhibition and wall decorations and develops:

suitable for teaching materials. Compared to products on ,,,,,, "

The paper is based on the flat, non-rolling i ₅ p-methylammophenol sulfate 2.5 g

Opal films much better and can because of their hydroquinone 10.0 g

Shelf life especially for the production of counter-sodium sulfite (anhydrous) 37.5 g

Stands exposed to heavy wear and tear, sodium carbonate monohydrate 44.0 g

such as B. Sales aids and operating tables, KaliiunbromKl ········· 5.0 g

be used. Because of the excellent measure- ₂ o ^{Mlt water topped} up to 1.01

sustainability, they are also for cartographic aerial _{The obi EntwkMer was after} dilution with

recordings and suitable for survey maps. _{2 Teüen water benut / then t} ^ _n J _{6, the film}

In the case of translucent advertising or exhibition _{in the photographic fixer the} following

stucco can achieve a surprising effect Composition fixed:
if one only considers those of the silver halide 25

emulsion layer opposite side with suitable sodium thiosulphate 240.0 g

nice colors. With an exclusive sodium sulfite (anhydrous) 15.0 g

With reflection lighting, the print appears in black glacial acetic acid 47.0 ml

white, while the picture in transmitted light potassium aluminum sulfate 15.0 g

appears colored. For this area of application, 30 are filled with water to 1.01

non-penetrating color materials are particularly suitable.

In the following, the invention is described by means of The fixed film was washed for 30 minutes and

Examples are explained in more detail. dried as usual. The finished film obtained showed

good sensitometric properties without any

For example 35 signs of staining that would otherwise get

becomes when manganese dioxide or other bleachable

A dimensionally stable polyethylene terephthalate film, color substances in a layer between the support which are arranged according to Example 4 of the German Auslegeschrift and the gelatin-silver halide emulsion layer 1,095,514 with a vinylidene chloride-methyl acrylate. The film also had itaconic acid copolymer coated in comparison to the usual, coated with similar emulsions was coated on one surface with an aqueous dispersion of paper supports good antihalation and good optical properties, which - based on the total weight - dissolving properties. In addition, that the dispersion - 3.5 percent by weight gelatin and the print image obtained contained a remarkably superior 7 percent by weight titanium dioxide in rutile crystallinity compared to the previously known and above modification; the dispersion was still one of 45 films written on. The small amount of alkylnaphthalene sulfonate as a wetting agent was investigated with regard to halation formation by applying a small amount of a bis-triazine stilbene device behind a neutral gray step wedge with a compound added as an optical brightener. The density range from 0 to 7 within a dispersion was applied at 17 m / min and resulted in a length of 12 cm and a gradation of 0.3 per one coating weight of dry gelatin of 50 grade. The step wedge was stenciled at 10 mg / dm ² . Over this layer an extremely 1 mm slit with neatly cut and sensitive silver iodobromide emulsion with variable contrast running parallel to the slope of the step wedge was spread, which, relative to the edges, covered. Sufficient exposure was made to produce total solids, 27 weight percent silver- an inversion of the image by solarization behind halide with a silver iodide-silver chloride gel 55 the brightest part of the wedge. At a weight ratio of 3:97 and 73 percent by weight of this degree of exposure, the image of the gelatin is contained. The emulsion was painted on the film as usual with a slit due to halation and dried. The emulsion was framed on each side by two bands, the width of which depends on the thickness of the substrate, produced according to British patent 547 060. The extremely porous silicon dioxide measured is the extremely porous silicon dioxide measured and contained 0.12 g per gram of dry gelatin as the matting ratio of the exposures used by the swelling agent so as to form a retouchable surface. The value of the halo formation and the blackening of the molten emulsion were also the same in front of the tape.

Layer up a small amount of the optical dissolution. The resolution was determined according to the test method of

Heilers bis-triazine stilbene and 140 mg benzotriazole each 65 National Bureau of Standards Circular C 248 »A Test

Moles of silver halide added as an antifoggant. of Lens Resolution for the Photographer «.

The dry weight of the calculated as silver nitrate. The haze was measured as blackness falling through

The silver halide of the coating was 33 mg / dm ² . determined against blue light.

Table 2 shows various properties of the film of the invention (No. 2) compared to other hitherto known films (Nos. 1, 3 and 4), and a film according to the invention in which however, a paper backing was used instead of the mixed polymer backing (No. 5).

Tabel

Back layer 4 Intermediate layer 2 Atrium
protection* Cloudiness Dissolution
capital stains
education 1. White + bleachable
Color material white - bleachable
Color material 44 1.10 122 bad 2. White + bleachable
Color material White 40 1.10 107 no 3. White White 27 1.10 137 no 4. White white + bleachable
Color material 36 1.10 137 bad 5. Simple paper backing simple paper carrier 50 1.30 77 Well

The larger the number, the better the antihalation protection.

Example2

Example 1 was repeated, except that a gelatin-silver chlorobromide emulsion was applied in place of the silver iodobromide emulsion with variable contrast of this example. The silver halide content of the emulsion was about the same as in Example 1; however, the weight ratio of silver chloride to silver bromide was 34:66. The emulsion contained a matting agent in order to achieve a surface that could be retouched as usual. The dry coating weighed 22 mg / dm ² silver halide, calculated as silver nitrate. The back was coated with gelatin with a dry weight of 80 mg / dm ² (instead of 70 mg / dm ^a of Example 1). The properties of the film obtained were similar to those of the film according to Example 1. Due to the warm color of the image and its responsiveness to direct toning, the film was particularly suitable for portrait purposes and photo miniatures, where special effects are required.

Example 3

Example 1 was repeated, but instead of the emulsion of this example, a high-contrast, sensitive contact bromine chloride emulsion with a gelatin content of 73% by weight was coated, the silver halides of which consisted of 30% by weight of silver bromide and 70% by weight of silver chloride. The dry coating weight was 22 mg / dm ² silver halide calculated as silver nitrate. The back was coated with gelatin in an amount of 40 mg / dm ^2. A flat, non-rolling film was obtained which was exposed in a conventional contact frame for 20 seconds with a single arc lamp of 50 amperes at a distance of 4.50 m. The film was developed for 2V ₂ minutes in a developer ^{bath at 20 0} C and the following composition:

p-methylaminophenol sulfate 1.5 g

Hydroquinone 6.0 g

Sodium sulphate (anhydrous) 19.5 g

Sodium carbonate monohydrate 28.0 g

Potassium bromide 0.8 g

Made up to 1.01 with water

The film was then fixed for 10 minutes in the fixing bath according to Example 1 and then showed excellent sensitometric and optical resolution properties as well as freedom from halation.

Example 4

Example 1 was repeated, but instead of the silver halide emulsion of this example, a high-contrast, direct positive silver chloride emulsion with a dry weight of 35 mg / dm ² silver halide, calculated as silver nitrate, was applied. The film was exposed to an extremely powerful mercury vapor lamp through an amber filter. The exposed film was developed for 1 minute in the developer bath from Example 1, which was diluted 1: 1 with water. The film was then fixed in the fixing bath according to Example 1 for 10 minutes. The positive image obtained showed good optical resolution and freedom from halation.

Claims (2)

Patent claims: 1. Photographic opal film composed of the following four layers: 1. a transparent, hydrophobic, polymeric substrate, 2. an optically cloudy binder layer containing no bleachable color material water-permeable, macromolecular organic colloid and finely divided inert, inorganic, white pigment particles from 0.1 to 2.0 μ, 3. a photographic light-sensitive gelatin-silver halide emulsion layer; and 4. an antihalation layer made of the same components as specified for layer 2, but with a bleachable color material, characterized in that the optically cloudy binder layer (2) on one surface of the substrate (1) with the light-sensitive layer (3) above the binder, layer (2), while the halo protective 9 10 layer (4) is on the other surface of the third photographic opal film according to claim 1 Layer carrier (1) is located. and 2, characterized in that the bleachable 2. Opal photographic film according to claim 1, material in the layer (4) having manganese dioxide characterized in that the layers (2 and 4) have a particle size of 1 to 100 microns, 1.5 to 3.0 parts by weight of pigment per part of binder 5 which is contained in an amount of 0.05 to 0.10 Ge, parts of the binder is present per part. 609 503/364 1.66 © Bundesdruckerei Berlin