DE1060710B - Photographic film for phototechnical purposes - Google Patents

Description

GERMAN

kl. 57 b 1

INTERNAT. KL. G 03 C

PATENT OFFICE

A26298IVa / 57b

REGISTRATION DAY! 3L DECEMBER 1956

NOTICE
THE ANMELÖUNÖ
AND ISSUE OF THE
AUSLEGESCHRlt "f:

JULY 2, 1959

In addition to the requirements for the substrate that apply to all phototechnical materials, such as sufficient mechanical strength, resistance to aging, etc., film bases must be suitable for Photo-technical emulsions also have very special properties «For everyone phototechrtischen, preferably used in copying technology Film material, the most important thing is excellent dimensional accuracy. if this is not guaranteed, compliance is ίο Accurate register for line and screen combinations and for multi-color prints that are created by overprinting colored partial panels come about, impossible. Also the use of correction masks of any kind is bound to the satisfactory fulfillment of these requirements. Another area of application Finally, cartography represents with very high demands on dimensional accuracy.

In addition, any film material used in reproduction technology must be used in processing often necessary, sometimes considerable temperature increases (e.g. when used in a copier, during assembly on the light table, during the fluoroscopy in the slide attachment of the repro camera) tolerated without changing the size.

These extremely high requirements have not been met by any of the previously common film materials realized in a satisfactory manner. For a lot of work in repro technology is therefore also today nor prefers the glass plate, although film is more convenient to use in all respects.

Film bases based on cellulose ester, as they are generally introduced for photographic purposes, have too high a climate dependency of their dimensions, which is due to their too high water sensitivity is due. Even their dimensional accuracy at elevated temperatures does not meet all requirements.

An improved dimensional stability at room temperature, in particular a significantly reduced dependency the mass of the climate, show phototechnical films on plastic substrates, such as polyvinyl chloride, Copolymers of vinyl chloride and other polymerizable components, polystyrene and films made from polyesters of terephthalic acid and glycol. A disadvantage of all these foils is, however, that they change their dimensions when they are exposed to elevated temperatures, but the practical processing can certainly occur.

It has now been found that these disadvantages are avoided if you use high-molecular thermoplastic substrates for phototechnical films Polycarbonates used.

Head of photography for photographic purposes

Applicant:

Agfa Aktiengesellschaft,

Leverkus en-B ay er work,

Kaiser-Wilhelm-Allee

Dr. Armin Ossenbrunner, Dr. Heifried Klockgether,

Dr. Julius Geiger, Leverkusen,

and Dr. Hermann Schnell, Krefeld-Uerdingen,

have been named as inventors

With the help of these polymers one has the possibility completely transparent clear, colorless, mechanical and to produce optically homogeneous films that meet the extremely high requirements of phototech'iiik suffice. Layer base made of high molecular weight thermoplastic Polycarbonates are characterized by the highest dimensional accuracy, high tear resistance, which is for the durability of the perforation in the case of motion picture film 'and 35mm film is important, as well as by high 'stretching and shock resistance. Furthermore, these films show high resistance to aging, especially with Irradiation with visible and ultraviolet light and under the influence of heat. The persistence of the Films against all types of treatment solutions j the good adhesion for photographic erriül sions or for intermediate layers as well as the VeT ^ compatibility with haloget silver and the additives used in photography, such as Z < B. color components, sensitizers or stabilizers, result in the particular suitability of the polycarbonate films also for all other photographic purposes.

Suitable high molecular weight thermoplastic polycarbonates can, for. B. by implementing aromä ^ tables dioxy compounds, e.g. B. hydroquinone or resorcinol, but especially of di-moilooxyäfylalkanen, alone or in a mixture with aliphatic or cycloaliphatic dioxy compounds, with aliphatic or aromatic 'diesters of the carbon

909 559/368

acid or with phosgene or by reacting bis-chlorocarbonic acid esters of aromatic Dioxyverbindüngen with free aromatic or aliphatic or cycloaliphatic dioxy compounds, e.g. B. according to the procedures described in Belgian patents 532 543, 546 375; German patent specification 959 497 and German Auslegeschrift 1 011 148.

Particularly suitable polycarbonates are obtained using, for. B. the following di-monooxyaryl-alkanes: 4,4'-Dioxydiphenylmethane, 4,4'-Dioxydiphenyldimethylmethane, 4,4'-Dioxydiphenyl-l, l-cyclohexane, 4,4'-Dioxy-3,3'-dimethyldiphenyl-l, l-cyclohexane, 2,2'-dioxy-4,4'di-tert-butyl-diphenyl-dimethylmethane and 4,4'-dioxydiphenyl-3,4-n-hexane, 2,2- (4,4'-dioxydiphenyl) -butane, 2,2- (4,4'-dioxydiphenyl) -pentane, 3,3- (4,4'-Dioxydiphenyl) -pentane, 2,2- (4,4'-Dioxydiphenyl) -3-methyl-butane, 2,2- (4,4'-Dioxydiphenyl) -hexane, 2,2- (4,4'-dioxydiphenyl) -4-methyl-pentane, 2,2- (4,4'-dioxydiphenyl) -heptane, 4,4- (4,4'-dioxydiphenyl) -heptane and 2,2- (4,4'-dioxydiphenyl) tridecane.

The highly melocular polycarbonates based on 4,4'-di (monooxyaryl) alkanes correspond of the following general formula:

R 'R'

R 'R'

0 -C O

R 'R' R 'R'

where X is the groupings
R ₁

- C - or --Ο
Ι
R ₂

R ₁ and R ₂ hydrogen atoms, branched and unbranched, monovalent hydrocarbon radicals with not more than 10 carbon atoms, monovalent cycloaliphatic radicals, monovalent araliphatic radicals, phenyl and furyl radicals, Z the atom groupings required to close a cycloaliphatic ring, R 'hydrogen atoms, monovalent, branched and unbranched aliphatic hydrocarbon radicals with up to 5 carbon atoms, monovalent cycloaliphatic and aromatic hydrocarbon radicals, and "is an integer greater than 20, preferably greater than 50.

The processes of the following publications can also be used to produce the polycarbonates mentioned: Patent Specification 1 031 512, Belgian Patent Specification 553 614, Patent Specification 1020184, Patent Specification 1026 958, German Auslegeschrift 1046 311, Patent Specification 1024 710.
Further suitable high molecular weight polycarbonates can be obtained by reacting dioxydiarylsulfones or mixtures of dioxydiarylsulfones with other bifunctional dioxy compounds according to German Auslegeschrift 1 007 996 and from dioxydiaryl ethers or dioxydiarylthioethers or from mixtures of the compounds mentioned with other dioxy compounds according to Belgian patent 560 610. Such polycarbonates are obtained, for example, using the following dioxy compounds: 4,4'-Dioxydiphenylsulfon, 2,2'-Dioxydiphenylsulfon, 3,3'-Dioxydiphenylsulfon, 4,4'-Dioxy-2,2'-Dimethyl-diphenyl-sulfone, 4,4'-dioxy-3,3'-dimethyldiphynyl-sulfone, 2,2'-dioxy-4,4'-dimethyldiphenyl-sulfone and 2,2'-dioxy-l, r-dinaphthyl-sulfone, 4,4 '-Dioxydiphenylether, 4-4'-Dioxy-2,2'-dimethyldiphenylether, 4,4'-Dioxy-3,3'-dimethyldiphenylether and its homologues, 4,4'-Dioxydiphenylsulnd, 4,4'-Dioxy-2 , 2'-dimethyldiphenyl sulfide, 4,4'-dioxy-3,3'-dimethyldiphenyl sulfide and their homologues,

Since the polycarbonates to be used according to the invention The films can be used if they are readily soluble in a number of low-boiling solvents Manufacture using the usual casting process on a belt or drum machine, with the advantages this process, namely, achieving uniform thickness and optical clarity in see-through and surface, come into their own. The well-dried raw material is in an agitator, am best a high speed mixer, z. B. in methylene chloride to a solution with a viscosity of about

ao 50,000 cP solved. There can also be small amounts of higher-boiling solvents, which are not necessarily Good solvents for the plastic needing to be (such as chloroform, propyl acetate, and butyl acetate) are added will. Depending on the desired quality, small amounts of plasticizers can also be added recommendable. The solution is after removal of the air on a casting machine depending on the desired Starch poured at the same speed as is usual for acetyl cellulose films. Possibly the polyesters to be used according to the invention can also be obtained in a manner known per se from the Melt flow can be processed into films. Of course, the solutions or melts dyes or pigments are also added to the polycarbonates prior to shaping.

Before applying the photosensitive layers, in particular halogen silver emulsion layers or photographic auxiliary layers, their binders made of gelatin or other natural or synthetic film-forming hydrophilic colloid layers consist, the support is generally provided with suitable adhesive layers, which are produced by various methods can.

It can e.g. B. the substrate prior to the application of hydrophilic colloid layers with a solution treated, which is a mixed acetal of polyvinyl alcohols and aldehydes with water-solubilizing agents Contains groups and aldehydes without water-solubilizing groups. This mixed acetal is in organic Solvent-soluble and has a strong swelling capacity in water. Treatment with the solution mentioned can be done either alone or in combination with other intermediate layers.

The above-mentioned films can be made with this artificial resin layer without an additional intermediate layer can be produced directly. In some cases, the use of an intermediate layer may be desirable in order to achieve a good adhesive effect. For the production of these intermediate layers have Vinyl chloride copolymers, such as. B. those made of vinyl chloride and vinyl acetate, proven.

Mixed acetals can be obtained by a conventional method, e.g. B. by moving the components Heated for several hours in methanolic solution with sulfuric acid as catalysts. Examples of aldehydes with water-solubilizing groups are aromatic aldehydes, which in the aromatic Nuclei are substituted by carboxyl, sulfonic acid or oxy groups, e.g. B. Benzaldehyde-2-sulfonic acid,

Benzaldehyde-2,2-disulfonic acid and p-oxybenzaldehyde. Examples of aldehydes without water-solubilizing groups are araliphatic and aliphatic Aldehydes, e.g. B. benzaldehyde, tolylaldehyde, p-chlorobenzaldehyde and hydrocinnamaldehyde.

For the adhesive effect that is to be achieved, it is of crucial importance that both the hydrophilic and the hydrophobic components are used. The degree of acetalization can vary widely Limits vary, but the best results are obtained with products in which 50 to 60% of all hydroxyl groups of the polyvinyl alcohols are acetalized. The most favorable ratio between aldehydes with water-solubilizing groups and those without water-solubilizing groups on the type of aldehydes. However, it has been shown that in general a molecular excess of aldehydes without water-solubilizing groups for the production of a sufficient degree of solubility in organic solvents is required.

To produce the intermediate layer, the mixed acetals are expediently used in an amount of 0.75 to 1.25% in a mixture of methanol and one or more other organic solvents, e.g. B. acetone, tetrahydrofuran or dioxane dissolved. To improve the adhesive effect, it is advisable to use a small part of a partially saponified copolymer of vinyl chloride and an organic vinyl ester, e.g. B. vinyl acetate, vinyl propionate, vinyl butyrate, e.g. B. a partially saponified copolymer of vinyl chloride and vinyl acetate to add. These partially saponified copolymers are produced by known processes by saponification in methanol solution with sulfuric acid as a catalyst, only the organic ester groups being partially saponified. Suitable saponified copolymers contain approximately 45 to 70 percent by weight vinyl chloride, 5 to 30 percent by weight hydroxide and 10 to 40 percent by weight vinyl acetate or another organic vinyl ester. Copolymers of vinyl chloride and α, ^ -unsaturated carboxylic acids or partially saponified copolymers of vinyl chloride and esters of the aforementioned acids are also suitable for the present application. The coating is advantageously produced by one of the conventional dipping processes.

Furthermore, the substrate can be provided with a thin intermediate layer of polyvinyl chloride copolymers and nitrocellulose or organic cellulose esters, another thin layer arranged above it Intermediate layer made of cellulose esters and a thin layer containing gelatine as a third layer will.

The vinyl chloride copolymers used for the first layer are expediently a Copolymer of about 40 to 70 parts by weight vinyl chloride with about 30 to 60 parts by weight more copolymerizable Components, e.g. B. lower alkyl esters of unsaturated carboxylic acids and vinyl esters lower fatty acids, such as methyl, ethyl, propyl, butyl esters of acrylic acid, methacrylic acid, crotonic acid, Maleic acid, also vinyl acetate, vinyl propionate, vinyl butyrate. Suitable cellulose esters are e.g. Mixed esters of cellulose with acetic acid and fatty acids containing 3 to 4 carbon atoms, e.g. B. Cellulose acetopropionate and cellulose acetobutyrate.

For the production of the first layer, the cellulose esters are advantageously used in quantities of 30 up to 70 percent by weight, calculated on the total amount of the polymers and cellulose esters, applied.

For the preparation of the layer support, you can also use auxiliary layers, which essentially consist of Gelatin and a partially hydrolyzed copolymer of 40 to 60 parts by weight of vinyl chloride and 60 to 40 parts by weight of vinyl acetate, this copolymer advantageously 45 up to 70 percent by weight vinyl chloride, 5 to 30 percent by weight vinyl hydroxide and 10 to 40 percent by weight Contains vinyl acetate. The ratio of gelatin to the copolymer can be within further limits fluctuate; advantageous however, a ratio of 2 to 3 parts by weight of gelatin to 3 to 2 parts by weight of the copolymer is used. Hardeners for gelatin can also be used in this auxiliary layer, e.g. B. formaldehyde, glyoxal are incorporated. The above components are used in the usual organic

Solvents dissolved and the solutions applied to the carrier by one of the known dipping processes.

Other suitable auxiliary layers exist, for. B. from nitrocellulose and from an epoxy resin, what about a second layer of gelatin is applied. Another layer of nitrocellulose can be placed between the layer of nitrocellulose epoxy resin and the gelatin layer are applied. It is advantageous to use epoxy resins that are Settlement of epichlorohydrin with the di (monohydroxyarylene) alkanes are obtained, which for the production of the polycarbonates of the support can be used. Instead of the epoxy resin can a polycarbonate ester from a di (monohydroxyarylene) alkane is also used use, also mixed with nitrocellulose. For the order of Interlayers can use the usual devices

to be used. _:

The films prepared in this way for coating with a hydrophilic colloid layer are coated with a photographic silver halide emulsion by one of the customary methods.
. An examination of the film material coated with phototechnical emulsion shows that it is characterized in particular by very good dimensional accuracy and can therefore also meet the high requirements of repro technology mentioned at the beginning.

The pronounced hydrophobicity of the film results in an extremely low water absorption capacity and results in such a low climate dependency of the film material that it is practically neglected can be.

During a change in relative humidity by 10% at 20 ° C (in a range between 30 and 85% r. F.) for phototechnical films Acetyl cellulose leads to a change in length of the film dimensions of about 0.10%, this is at of the polycarbonate film only 0.02%.

For the same reasons, the change in length caused by wet processing is also very small. This so-called processing shrinkage occurs with film material on a polycarbonate base also below 0.02%,

It should also be emphasized that in comparison with photographic films on others Substrates extremely little change in dimensions with temperature increases.

The measurements listed in the following table were made after the film had been stored for 24 hours.

Claims (2)

materials at the relevant temperatures. Temperature 40 ° C SO0C 600C 700C Change in length in ° / o of a photographic film material based on acetyl cellulose I polycarbonate -0.02 -0.18 -0.33 -0.50 ± 0 -0.02 -0.02 -0.02 Shorter time the film can also be exposed to even higher temperatures without having to fear shrinkage, which is of the greatest importance for practical processing. In the same way, the dimensional accuracy of the film material can be described as very good when stored for a long period of time. The shrinkage measured over longer periods of time was also below ao 0.02 «/ 6. Another noteworthy property is that at kinks, which cannot always be avoided, especially when processing large formats, there is no clouding, so that disturbances are not to be expected with a5 of the copy. The production of the film material can be carried out without difficulty in such a way that in all processing stages a flatness that meets all requirements is guaranteed, which is maintained even under 3 different climatic changes. The application possibilities of the phototechnical film on a polycarbonate base are very diverse. For example, the foils prepared in this way for casting with a hydrophilic celloid layer are coated with the emulsions of steep and overdivided gradations customary in reproduction technology for the production of line and raster images. The emulsions used for reproduction technology to reproduce halftones can be high-contrast, brilliant or normal. All emulsions mentioned can be unsensitized, orthochromatic or panchromatic. The new film base is also suitable for so-called assembly films, especially for gravure and offset printing, because good register accuracy is also important here. 5 Pa TENT A NSl 'Η Ο cat ": 1. Photographic film for phototechnical purposes, characterized by a layer support, the layer-forming substance, which is high-molecular, ίο Contains thermoplastic polycarbonates. 2. Photographic film according to claim 1, characterized in that as high molecular weight thermoplastic polycarbonates those based on di (monooxyaryl) alkanes, in particular of 4,4'-di- (monooxyaryl) -alkanes of the general formula are present: R 'R' R 'R' O — C —O - X R 'R' R 'R' in the X the groupings - C - or - C R ₁ and R _{2 represent} hydrogen atoms, branched and unbranched, monovalent hydrocarbon radicals with not more than 10 carbon atoms, monovalent cycloaliphatic radicals, monovalent araliphatic radicals, phenyl and furyl radicals, Z the atom groupings required to close a cycloaliphatic ring, R 'hydrogen, means monovalent, branched and unbranched aliphatic hydrocarbon radicals with up to 5 carbon atoms, monovalent cycloaliphatic and aromatic hydrocarbon radicals and η is an integer greater than 20, preferably greater than 50.