DE2114612A1 - Photosensitive mixt - of polymer and alkaline earth titanate for plates, films and sheets - Google Patents

Abstract

Photosensitive mixt. is based on a polymer (A) and 30-80 wt. % alkaline earth titanate (B), w.r.t. the total wt. of (A) and (B). The mixt canbe used for making photosensitive plates, films or sheets for optical design applications. Ca and/or Ba titanate are pref. and 0.01-10 wt. % phototropic sensitiser can also be added. (A) pref. is poly(di)olefins, esp. butadiene-styrene copolymer contg. 40-80 wt. % butadiene or copolymer of 40-60 wt. % styrene, 50-30 wt. % n-butyl acrylate, 0.5% acrylamide and 5-10% S-vinylthioethanol. (B) content pref. is 40-55 wt. % and its particles size 0.01-10 mu. The compsn. gives reddish-brown, dark brown or brown-black images when exposed with radiation in the 100-500 nm wavelength range.

Description

Photosensitive material The invention relates to a photosensitive material Material made from a polymer and an alkaline earth titanate.

It was a photosensitive mixture, especially in the form of Sheets, foils or films can be applied on the basis (A) of a polymer or copolymers and (B) an alkaline earth titanate found, the content of alkaline earth titanate 30 to 80 percent by weight, based on the total weight of the mixture (A) + (B), amounts to.

The invention is based on the surprising finding that from Mixtures of a plastic with alkaline earth titanates create a photosensitive Recording material, for example in the form of plates, films or foils, produced can be.

As polymers for the light-sensitive plastic mixtures are Polymers of olefinically unsaturated monomers are suitable, especially polyolefins. In particular, polyethylene, polypropylene, polyisobutylene, poly-5-methylpentene- (i), Polystyrene, poly-X-methylstyrene, also polydienes, such as polybutadienes, and polymers Halogenated hydrocarbons such as polyvinyl chloride or polyvinylidene chloride suitable.

As a rule, the polyolefins mentioned are characterized by Intrinsic viscosities @ 1 from 0.5 to 20.0, preferably from R7 1 to 3.

But it can also be mixtures of z. B. polyethylene and / or polypropylene with polyisobutene or graft polymers of acrylonitrile and / or styrene on polydienes, such as polybutadiene can be used.

In addition to homopolymers, graft polymers or polymer mixtures copolymers are also suitable.

Appropriately, copolymers of olefinically unsaturated monomers, such as styrene, acrylates or methacrylates and / or their amides, acrylonitrile or methacrylonitrile, optionally used in combination with S-vinylthioethanol.

For example, those copolymers which in the form of dispersions or solutions containing copolymers between 10 and 6o percent by weight, preferably 40 and 55 percent by weight, based on the Total weight of the mixture that can be processed and how it is for example in Houben-Weyl "Methods of Organic Chemistry", 4th Edition, Vol.

XIV, Part 1.

Dispersions of butadiene-styrene copolymers are particularly suitable with a proportion of polymerized butadiene of 40 to 80 percent by weight, wherein 10 to 40 percent by weight of the butadiene units are preferably copolymerized in the 102-position are, or a copolymer consisting of 40 to 60 wt. Styrene, 50 to 30 wt.% n-butyl acrylate, 0 to 5 wt.

Acrylamide and 5 to 10 wt. S-vinylthioethanol, which is like a lacquer solution can be applied and dried or baked at higher temperatures will.

The above polymers is an alkaline earth titanate in an amount of 0 to 80, and in particular from 40 to 55, percent by weight, based on the total weight added to the mixture.

The alkaline earth titanates are preferably calcium and calcium Barium titanate and mixtures thereof.

They are titanates, as they are, for example, according to the information the monograph "Titanium", J. Barksdale, 1966, Ronald Press, N.Y. can be.

The grain sizes of the alkaline earth titanates used are generally between 0.01 and 10.

Optionally, the photosensitive materials of the present invention are used additionally with phototropic sensitizers in Amounts from 0.01 to 10 percent by weight, preferably 0.5 to 7.5 percent by weight, based on the total weight the mixture. Hydroquinones, for example, are used as sensitizers, Vinyl carbazole, benzotriazole, tungsten or molybdenum oxides, alkali ferrocyanides and others into consideration. Such photochromic sensitizers can be reported on Phototropy in the Angew. Chemie 1964, Vol. 76, p. 465 ff, and in the specified there Can be taken from literature.

The additives according to the invention can be used in the customary manner in the polymers, for example by kneading, rolling or in extruders, at higher temperatures, z. B. at 120 to 260 ° C, are distributed homogeneously.

The photosensitive material can then be made into self-supporting plates, Foils or films, for example, pressed, extruded, calendered, punched or be deformed.

The introduction of additives in polymer dispersions or polymer solutions can be done, for example, by simply stirring or mixing in ball mills.

The dispersions or solutions are expediently thinner Layer applied to a carrier material. The most varied of types can be used as carrier material Materials used are such as glass, paper, wood or textiles. The smears are at normal room temperatures and above or at higher temperatures up to dried to 180 cc. The higher temperatures are applied when mixing for example, to be baked onto the carrier material as a lacquer solution.

The polymers containing alkaline earth titanates are photosensitive and suitable for making optical recordings.

They become smaller than a visible radiation of one wavelength than 500 nm or invisible short-wave radiation up to one wavelength exposed to 100 nm, red-brown, dark-brown or brown-black in particular occur Discoloration.

Conventional mercury vapor lamps, conventional Fluorescent tubes or ordinary light bulbs are used.

The exposure times are generally between 0.1 and 1000, preferably 1 to 100 minutes.

When exposed through an image negative or a grid, the images become sharp Received pictures.

The parts mentioned in the examples are parts by weight. The K value and / or intrinsic viscosities are, unless otherwise stated, in toluene solution measured and determined according to H. Fikentscher, Cellulosechemie 15, 58 (1952).

Example 1 65 parts of barium titanate are combined with 55 parts of polypropylene (£ 47 1.8) at 2200C in a kneader within 100 minutes and then pressed foils with a thickness of 100 ji.

The film is replaced by a writing negative with a commercially available 100 W fluorescent lamp exposed for 5 minutes at a distance of 10 cm. It arises a sharp red-brown typeface.

Examples 2 to 5 As described in Example 1, a light-sensitive film is produced in each case. No. Polymer Titanate Additive Mixing Mixing Mixing Parts parts parts temperature aggregate ° C gat min. -------------------------------------------------- ------------------------------- 2 polyethylene Ba- - 160 kneader 100 30 70 -------------------------------------------------- ------------------------------- 3 Polypropylene Ba- Mo (VI) oxide 220 Schnek- 6 [7] 1.8 k- 65 34 1 extruder -------------------------------------------------- ------------------------------- 4 polyisobutylene Ba- Mo (VI) oxide 80 roller 30 K value 150 20 80 No. Polymer Titanate Additive Mixing Mixing Mixing Parts parts parts temperature aggregate ° C gat min. -------------------------------------------------- ------------------------------- 5 cis-polybutadiene Ca- - 100 roller 25 K value 100 25 75 -------------------------------------------------- ------------------------------- Example 6 100 parts of a butadiene / styrene copolymer dispersion with a dry content of 50% are mixed with 50 parts of barium titanate within 50 minutes by stirring. The butadiene content in the copolymer is 45 percent by weight (10% 1,4-cis, 25 β 1,2-vinyl and 65% trans). A film 200 microns thick is spread on paper. After drying at 80 ° C. for 5 hours, the film is illuminated through a negative with a commercially available 40 watt lamp at a distance of 10 cm.

A sharp copy is created.

Example 7 100 parts of a lacquer solution containing 50 parts of a copolymer made of 35% styrene, 55% n-butyl acrylate, 20% acrylamide and 10% vinylthioethanol contains the K value 54, 50 parts of barium titanate are added and in a Ball mill stirred homogeneously within 5 hours. The mixture is called 250 µ applied thick layer of varnish and dried at 180 ° C for 15 minutes.

Then go through a grid for 5 minutes with a mercury lamp irradiated at a distance of 15 cm. The result is a red-brown, high-contrast copy.

Under the same conditions, but with an addition of 1 part Vinyl carbazole is dark brown when 5 parts of potassium ferrocyanide are added a brown-black, with the addition of 2.5 parts of uranyl acetate a dark brown Image.

Claims (1)

Claims Ö Photosensitive mixture based on (A) a polymer and (B) an alkaline earth titanate, the alkaline earth titanate content being 50 to 80 percent by weight, based on the total weight of the mixture (A) + (B). 2. Photosensitive mixture according to claim 1, characterized in that that calcium and / or barium titanate is added as alkaline earth titanate. 5. Photosensitive mixture according to claim 1 and 2, characterized in that that a photochromic sensitizer in an amount of 0.01 to 10 percent by weight is added.