DE1547651C3 - Use of a recording material containing crystalline compounds with several acetylenic bonds for the production of microscopic or electron microscopic images and processes for the production of such images - Google Patents

Description

where mean:

X is a hydrogen or halogen atom or a hydroxyl, nitrile or COOY group, where Y is a hydrogen or alkali metal atom or an alkyl group with 1 or 2 carbon atoms,
η is an integer of at least 2 and
/ πι, / Π2 whole, preferably the same numbers between 6 and 9.

3. Use according to claim 2, characterized in that the connection with several acetylenic bonds consists of a diacetylene compound with 16 to 26 carbon atoms, which contains two terminal alkyl ester groups

4. Process for the production of microscopic or electron microscopic images, in which a Recording material is exposed imagewise, characterized in that a recording material with a radiation-sensitive layer, which is a crystalline compound with several acetylenic Contains bonds, imagewise exposed and then heated or with a solvent for the unirradiated crystalline compound is treated.

5. The method according to claim 4, characterized in that a recording material with a radiation-sensitive layer, which is a liquid compound with several acetylenic bonds contains, cooled to crystallization, then exposed imagewise and then to a temperature is heated, at which the unexposed crystals become liquid again.

6. Process for the production of microscopic or electron microscopic images, in which a Recording material is exposed, characterized in that a recording material with a radiation-sensitive layer, which is a crystalline compound with several acetylenic Contains bonds, insensitive to radiation of a certain wavelength range is made that an imagewise pressure is exerted on the recording material and that immediately thereafter the recording material is uniformly irradiated.

7. Process for the production of microscopic or electron microscopic images, in which a Recording material is exposed imagewise, characterized in that a recording material with a radiation-sensitive layer, which is a crystalline compound with several acetyleniDie The invention relates to the use of a recording material with one on a layer support firmly adhering radiation-sensitive layer, the crystalline compounds with several acetylenic Contains bonds, for producing microscopic or electron microscopic images, and relates to them also a method for producing microscopic or electron microscopic images, in which a Recording material is exposed imagewise.

In conventional, known photographic recording materials based on silver halide, a latent image is produced on exposure, which is made visible by development and then fixed. Also known are copy-out materials based on silver halide, in which a visible silver image f is produced directly in situ. In both cases, the entire exposed silver halide crystal is converted into the silver particle forming the visible image, so that the resolution of such recording materials is limited by the crystal size, even if the wavelength of the radiation energy used for exposure is small compared to the crystal size. A satisfactory solution to this problem cannot be achieved with the "grainless" or exceptionally fine-grained Lippmann emulsions, in which the silver halide crystals are apparently smaller than the wavelength of visible light, but larger than the wavelength of the electron beams used in conventional electron microscopes, since these Lippmann- Emulsions are usually too insensitive for the intended use.

A high image resolution can be achieved with known recording materials that do not work on the basis of silver halide, but a time and _{ξ is required for the direct production of copy-out images}

expensive chemical or physical post-treatment of the exposed recording material. So z. B. in known diazo processes, unexposed diazo compounds are later coupled, the blue copying process requires the reduction of an iron (IH) salt, the reaction of the reduction product with ferricyanide and the washing out of unreduced iron salt with water, recording materials with photosensitive glass systems must are heated, and in the known bichromate-albumin process it is necessary to make the unexposed soluble material insoluble by exposure to remove part of the image that has become. A particularly simple way of producing high-quality direct copy images Resolution is therefore not achievable with known means.

It has also been known for a fairly long time that certain compounds with several acetylenic Bindings are sensitive to the effects of radiation and visibly discolour in the process. Reference is z. B. on corresponding publications. gen in Fette und Seifen 54 (1952) 544-549; 55 (1953)

· .. 95-97; Annalen der Chemie 543 (1940) 104-110; 589 (1954) 222-238; Chemical Reports 84 (1951)

785-794; 1953, 86, 657-667; 87 (1954) 712-724; 89 (1956) 1276-1287; Angewandte Chemie 65 (1953) 385-389; Arch. Pharm. 292 (1959) 519-528; Acta Chemica Scandinavica 6 (1952) 893; J. Chemical Soc. (1952) 1993-2013; (1952) 2883-2891; (1953) 1785-1793; (1963) 2048-2064; (1964) 1998; J.Am. Chem. Soc. (1957) 5817-5820, 6263-6267; Pure Appl. Chem. 2 (1961) 569-586; Proc. Chem. Soc. (June 1960) 199-210; Russian Chemical Reviews (May 1963) 229-243.

These compounds with several acetylenic bonds, hereinafter, for the sake of simplicity, polyynes called, contain at least two conjugated acetylenic bonds of the formula

and can belong to a wide variety of chemical classes, e.g. B. hydrocarbons, acids, esters or Be diols. A particularly important class of such compounds, which are found in crystalline form Visibly discolour exposure to radiant energy are diynes with two terminal carboxyl groups and their ester derivatives.

So is z. B. the 2,4-hexadiyne diacid from the cited literature Angew. Chemie 65 (1953) 385 known, and the red coloration of crystals thereof on the exposed side of the crystal is described in the cited literature reference Fette und Seifen 54 (1952) 544. Of the 4,6-decadiyne-dioic acid is known from the cited reference in fats and soaps and in Annalen der Chemie 589 (1954) 222, that it is slowly red when heated to 130 ⁰ C, that it at the irradiation with an UV - The lamp immediately turns red at room temperature and that it turns red when heated. The 5,7-dodecadiyne diacid is obtained according to the cited reference in the Annals, depending on the speed at which the methanol solution containing it cools, in two different forms, one of which forms colorless prisms which quickly take on a reddish-purple color under light, whereas the other shape consists of needles that turn blue on exposure. 9,11-eicosadiyne diacid and 10,12-docosadiyne diacid are from the cited literature reference J. Chem. Soc. (1953) 1787, 1790 and 1791, and the eicosan derivative is known from Fette und Seifen 55 (1953) 95 that it turns deep dark blue when exposed to light, and the docosan derivative is known from the same reference and from the above-mentioned Annalen 589 (1954 ) 222 that it turns deep dark blue slowly in the dark and quickly in the light, and that its color changes from blue to red when heated. In the above-cited literature reference Fette und Seifen 54 (1952) 546 it is stated that such photosensitivity to derivatives of the formula

R-CH ₂ -C = CC = C-CH ₂ -R

Seems to restrict and only 2,4-hexanediyne diacid is an exception to this rule, although various diynes are photosensitive.

The photosensitivity of various esters of dunes with two terminal carboxyl groups is ζ. Β. known from the cited reference Acta Chemica Scandinavica 6 (1952) 893, where it is reported that that the dimethyl ester of 3,5-octadiyne diacid with Standing takes on a beautiful purple-red color and that the discoloration is accelerated in the light, but that some crystals remain colorless and therefore obviously have some catalyzing impurities for this are responsible. There is no change in color of the dimethyl ester of 4,6-decadiyne diacid reported. The preparation of 3,5-octadiyne diacid is also described in the reference Chem. Reports 87 (1954) 712, whereby it is emphasized that the colorless needles are sensitive to light and in a short time Time to turn pink. The same observation is also described in Annalen der Chemie 589 (1954) 2264. Out

, o Chem. Abstr. 54 8624b (where via Arch. Pharm. 292 [1959] 519-528) the dimethyl ester of 10,12-docosadiyne diacid is known.

The radiant energy to which polyynes of the specified type respond is not just a matter of to actinic radiation and infrared radiation, but also to electron beams such as those from cathode emitters generated, namely gamma rays, x-rays, beta rays, electronic corona discharges and other types of corpuscular and / or wave-like radiant energy. Usually speak the polyynes partly rapidly and partly slowly selectively for one or more forms of radiant energy on, but mostly only within narrowly limited ranges and wavelengths of the electromagnetic spectrum.

The object of the invention is to provide ways and means with the aid of which visible copy-out images with extremely high image resolution by exposing a recording material to radiation energy directly can be produced without the need for additional chemical and / or physical treatments.

The invention is based on the knowledge that the specified object can be achieved by making it usable the properties of compounds with multiple acetylenic bonds shown.

In addition to the specified use of such a crystalline compound, the invention provides with recording material containing several acetylenic bonds for the production of microscopic or electron microscopic images also a process for producing microscopic or electron microscopic images, in which a recording material is exposed imagewise and that is characterized by

That a recording material with a radiation-sensitive layer which contains a crystalline compound with several acetylenic bonds is exposed imagewise and then heated or treated with a solvent for the unirradiated crystalline compound, or
that a recording material with a radiation-sensitive layer which contains a crystalline compound with several acetylenic bonds is made insensitive to radiation of a certain wavelength range, that an imagewise pressure is exerted on the recording material and that immediately thereafter the recording material is uniformly irradiated, or

that a recording material with a radiation-sensitive layer which is a crystalline compound containing several acetylenic bonds, imagewise exposed, then with a mineral acid is brought into contact until an image becomes visible, and that it is then uniform

is exposed.

The invention achieves that by simple Radiation exposure to a recording material

under quantum yields greater than 1 microscopic or electron microscopic images ir.it extraordinary high image resolution can be achieved, although the resolution is not limited by the size of the Polyine crystals, but only determined by the radiation impinging on them and what is formed Copy image from visibly color-changed parts of crystals, but not from whole crystals, the one Are subject to change or implementation.

The polyynes which can be used according to the invention for most practical purposes are in solid crystalline form in which the adjacent molecules in the crystal are oriented and structurally arranged relative to one another in such a way that incident radiation induces polymerization. Without wishing to be bound by any particular theory, it is believed that upon interaction with a discrete unit of radiant energy, a photo-induced reaction takes place involving several molecules. In a crystal of hundreds of photosensitive oriented molecules, this photochemical reaction causes a visible change in color of only part of this multitude of oriented molecules, and it has been found that an average of 8-16 polyyne molecules are directly influenced by each quantum of light. The exposed, color-changed portion of the crystal or the initial photoproduct has an unchanged empirical ratio of the components, but has a higher molecular weight than a single, unexposed molecule, indicating that photopolymerization has occurred. The initial photo product has a distinctly different color than the unexposed polyine crystals, which are colorless to white or pale yellow under transmitted light. It usually has an intense blue, purple or bluish-purple color and occasionally a reddish-blue purple color. When exposed to intense radiation, a bronze-metal-like color is created that appears to be stable to further exposure to the same radiation that caused it to form. The initial photo product shows no discernible EPR (electron paramagnetic resonance) signal. Its color will last as long as the original polyine structure is retained. Destruction of the crystal structure by heating or the action of a solvent for the unexposed polyyne causes the conversion or conversion of the initial photo product into another colored reddish product. In most cases, this second product is ^{relatively insoluble in organic solvents at about 20 °} C. and somewhat soluble at an elevated temperature.

In any solvent, the second product is usually less soluble than his initial photosensitive form. The reddish product is thermochromic and shows at a higher level Temperature range a reversible color change usually to a bright yellow, and at at higher temperatures it becomes rubbery and darkens at even higher temperatures. Both the red and the yellow product is also piezochromic and turns dark blue at a pressure of 10-20 kilobars. Possibly the structure of this second polymeric product consists of recurring conjugates Units with alternating olefinic and acetylenic bonds and non-acetylenic components from the initial polyyne structure as side chain substituents and end groups of the recurring Units. This polymeric product is relatively stable at room temperature and has little chemical reactivity, however, it is decomposed by concentrated sulfuric acid and can be obtained via Raney-Nicke! at elevated temperatures and printing are slowly hydrogenated.

Numerous crystalline polyines are sensitive to radiation and are well suited according to the invention. The production and use of preferred radiation-sensitive polyynes is described below. For determination

ίο the special radiation sensitivity and suitability For a specific purpose, samples of the polyine to be tested are a specific Radiant energy exposed, preferably using an opaque one provided with openings Mask or stencil so that only part of the sample is exposed. After exposure will determined whether a satisfactory visible color change occurred in the exposed image areas Not all polyynes are sensitive to all types of radiation, but there is a wide scope for the selection of suitable polyynes for specific uses.

For the polyynes which can be used according to the invention, their direct color change on exposure to a effective type of radiant energy, whereby the color shift creates an image that resembles the direct copying when using another form of radiant energy is capable. It is also typical the discrete character of the color change in the crystals exposed to radiant energy, after which the Color change occurs only in limited parts of partially exposed whole crystals. Since only the irradiated part of the crystal and the directly adjacent part of that struck by the discrete radiant energy Crystal undergoes a color change, an exceptionally high resolution can be achieved, and it is not necessary to use crystals of smaller size, especially in peripheral areas and boundary lines of exposed and unexposed image areas can be observed.

Suitable processes for the preparation of polyynes which can be used according to the invention are in addition to the cited references z. B. also in US-PS 28 16 149, 29 41014 and 30 65 283 described. For example Oxidative coupling reactions or oxidative dehydrogenation-condensation reactions may be mentioned with numerous terminal acetylene compounds to produce symmetrical or asymmetrical ones Polyynes and dehydrohalogenations for the production of compounds with acetylene bonds, as well as conventionally known variations, modifications and combinations of such basic reactions., Wenn If certain functional groups are to be introduced into the polyynes, these can be terminated in the acetylenic reactants that are coupled or in those subjected to dehydrohalogenation Compounds exist, or they can be in the form of other functional groups or as blocked functional groups may be present in the reacted components and at the end of the reaction be formed or released.

According to the invention, radiation-sensitive crystalline acid derivatives of the polyines and in particular are preferred certain esters and salts thereof with two terminal carboxy groups of the formula

in which π is an integer of at least 2 and

is preferably 2 (ie that it is a diacetylene compound) and m 1 and m _{2 are} integers, preferably equal numbers, which are greater than 5 and less than 10. The preferred acid derivatives include the mono- and diesters of these diacids and in particular the symmetrical diacetylenic diacids, preferably lower alkyl esters and especially those in which the alkyl ester component contains less than 3, preferably only 1, carbon atom. The alkali salts and acid derivatives of these diacids and their half-esters, preferably the potassium salt of the methyl half-ester of the particularly preferred symmetrical diacetylenic diacids, are also preferred. Examples of suitable radiation-sensitive crystalline compounds are:

Dimethyl ester of 11,13-tetracosadiyne diacid;
Dimethyl ester of 4,6-decadiyne diacid;
Diethyl ester of 11,13-tetracosadiynedioic acid,
Dibenzyl ester of 10,12-docosadiyne diacid,
Dimethyl ester of 7,9-hexadecadiyne diacid,
Dicyclohexyl ester of 10,12-docosadiyne diacid;
Dimethyl ester of 9,11 -eicosadiyne diacid,
Monomethyl ester of 4,6-decadiyne diacid;
Monocyclohexyl ester of 10,12-docosadiyne diacid;
Monobenzyl ester of 10,12-docosadiyne diacid;
Monoethyl ester of 11,13-tetracosadiyne diacid;
Monomethyl ester of 10,12-docosadiyne diacid;
Monoethyl ester of 10,12-docosadiyne diacid;
Monomethyl ester of 11,13-tetracosadiyne diacid;
Monosopentyl ester of 10,12-docosadiyne diacid;
Methyl potassium 10,12-docosadiyne dioate;
Methyl potassium 7,9-hexadecadiyne dioate;
Methyl barium 4,6-decadiynedioate;
Dipotassium 7,9-hexadecadiyne dioate;
Dipotassium 10,12-docosadiyne dioate;
10,12-docosadiine dichloride;
10,12-docosadiine dibromide;
10,12-docosadiyne dinitrile.

Other polyynes in crystalline form are also sensitive to radiation and can be used well according to the invention. Examples are:

2,4-hexadiyne; 7,9-hexadecadiyne; 9, ll-eicosadiyne;
11,13-tetracosadiine; 12,14-hexacosadiyne;
ll.lS-hexacosadiin ^ .ig-hexatriacontadiin;
4,6-decadiyne diacid; 7,9-hexadecadiyne diacid;
9,11-eicosadiyne diacid; 10,12-docosadiyne diacid;
11,13-tetracosadiyne diacid,
12,14-hexacosadiyne diacid,
12,14-octacosadiyne diacid,
17-octadecen-9, l 1 -diyne acid,
2,4-hexadiyne-diol, 3,5-octadiyne-diol;
10,12-docosadiyne diol; 11,13-tetracosadiyne diol;
Dioluene-p-sulfonate of 2,4-hexadiyne-diol;
2,4,6-octatriine; 2,4,6,8-decatetrain diol;
3,5,7, g-dodecatetrain ^ .S.10.lo-octadecatetrain;
9,11,13,15-tetracosatetrain;
1,6,8,13-tetradeca tetrain;
1,8,10,17-octadecatetrain.

Each of these polyynes is at least somewhat sensitive to one type of radiation. In those cases where the If polyynes are liquid at normal temperature, they are cooled to a temperature at which a suitable temperature Crystal form is obtained, whereupon the crystalline form is exposed to radiation energy. With some Polyynes, the color change after exposure is almost spontaneous, i. i.e., it takes place in fractions of Seconds, while others have a longer exposure time of z. B. some hours is required to bring about a noticeable visible change in color. With some polyynes, the color change is right conspicuous, e.g. B. from transparent or white to an intense purple or a vivid red others quite monotonous, e.g. B. of transparent or white

ίο to brown, dark brown or black. Apparently affects the number of acetylene bonds, in the polyyne compound the specific color change, the The triines, tetraine and higher polyynes turn brown or black.

In addition to the polyynes listed, z. B. also suitable the following polyynes:

1,7,9,15-hexadecatetrain; 1,5,7,11 -dodecatetrain;
. 1,9,1 L.ig-Eicosatetrain ^ AöÄlO-Dodecapentain;
1,3,5,7,9-tridecapentaine;

2,4,6,8,10,12-tetradecahexaine;

1,3,5,7,9,1 1,13,15-hexadecaoctaine;

1,6,8,13,15,20,22,27-octacosaoctaine;

1,9,11,19,21,29,31,39-tetracontaoctaine;
Dimethyl ester of 3,5-octadiyne diacid,

4-pentynyl ester of 10,12-tridecadiyne diacid,

Ichthyothereol acetate, isanolic acid,

2,4-hexadiyne diacid; 5,7-dodecadiyne diacid;

1,8-dichloro-2,4,6-octatriyne;
l.lO-dichloro ^ Aö.S-decatetrain;

3,5-octadiyne-2,7-diol; 2,4,6-octatryn-1,8-diol;

1,3,5-nonatriin-8,9-diol; 4,6,8-nonatriine-1,2-diol;

eS-triin-1 oil;
n ^ AS-triine-1 oil;
4,6-decadiyne-1,10-diol; 4,6,8-decatrien-1,2-diol;

2,4,6,8-decatetrain-1,10-diol;

3,5,7,9-dodecatetrain-2, ll-diol;

5,7,9,1 l-hexadecatetrain-4,13-diol and the
Diurethane-4,6-decadiyne-l, 10-diol.

The following examples explain the production of polyynes which can be used according to the invention:

B e i s ρ i e I A

Dimethyl ester of 10,12-docosadiyne diacid

200 g of commercially available 10-undecylic acid or undecylic acid are heated to 60 ° C. in 600 ml of boron trichloride / methanol solution (10% by weight / volume). Ten minutes after clearing of the solution it is poured into 1 liter of ice-water and three times with 400 ml of petroleum ether - extracted (bp 30 ° 6O ⁰ C.). The combined petroleum ether extracts are washed twice with 200 ml of water each time and dried over magnesium sulfate. After filtering and removing the petroleum ether under reduced pressure, a yield of 213 g of a colorless liquid, namely methyl 10-undecylinoate with a boiling point of 106-107 ° C. at 2.5 mm Hg, is obtained.

20 g of copper (I) chloride, 24 g of Ν, Ν, Ν ', Ν'-tetramethylethylenediamine (TMEDA), 2400 ml of methanol and 213 g of the 10-undecylinoate produced are placed in a 5-1 three-necked flask. The reaction mixture is stirred vigorously while oxygen is bubbled through. The temperature of the reaction mixture is kept ^{below 45 °} C. by occasional cooling in an ice bath during the first hour of the reaction.

709 524/322

After about 12 hours, the flow of oxygen is interrupted and the methanol in a rotary evaporator removed under reduced pressure. The residue is four times with 300 ml of petroleum ether (Bp. 30-60 ° C) extracted and the resulting bluish solution five times with 100 ml of an aqueous 4% Hydrochloric acid solution and then washed twice with 200 ml of water each time. The resulting colorless petroleum ether solution is dried over magnesium sulfate. The magnesium sulfate is removed by filtration and the filtrate concentrated to 800 ml and cooled. The resulting white crystalline product is filtered off collected and dried, a yield of 185 g of dimethyl ester of 10,12-docosadiyne diacid with a melting point of 41-42 ° C is obtained.

Nuclear magnetic resonance spectrum;

CH ₃ OS

220 cPs, singlet (6.1)
O

-CH ₂ CO-
and

-CH ₂ -C = C-

136 cPs, multiplet (7.8)

-C-CH ₂ -C-

80 cPs, wide singlet (24).

The nuclear magnetic resonance spectrum was measured with a spectrometer in a deuterichloroform solution determined. Chemical shifts are expressed in periods per second (cps) below the internal Standard tetramethylsilane at 60 Mc / sec. specified. The numbers in brackets indicate this relative resonance field.

Example B.
Dimethyl ester of 11,13-tetracosadiyne diacid

A mixture of 100 g of commercially available lithium acetylide-ethylenediamine complex and 400 ml Dimethyl sulfoxide in a dry 1-1 flask stirred under an atmosphere of dry nitrogen. After one hour, 40 g of Ω-bromodecanoic acid are added dissolved in 100 ml of dimethyl sulfoxide and added dropwise to the flask while the The temperature of the reaction mixture is maintained at 35 ° C by means of an ice bath.

After the addition is complete, the mixture is stirred further and the temperature maintained for approximately 14 Maintained at 32 ° to 36 ° C for hours. The resulting dark-colored reaction mixture is cooled to 10 ° C, acidified with aqueous 6N HCl and extracted three times with 300 ml of ether each time. The combined ether extracts are washed with aqueous 1N HCl, water and aqueous, saturated sodium chloride solution and then dried over magnesium sulfate and activated charcoal. After filtering, the ether is under removed under reduced pressure and the resulting syrupy liquid from petroleum ether (b.p. 30-60 ° C) crystallized. The product is distilled under vacuum, the fraction collected between 155-161 ° C, 1 mm Hg and recrystallized from petroleum ether (b.p. 30-60 ° C.). The yield is 20 g of 11-dodecylic acid with a melting point of 44 ° -46 ° C. Small amounts of unreacted ß-bromodecanoic acid, 10-dodecylin- and 11 docosain diacid are still in the product

ίο included.

20 g of the 11-Dodecylinsäure thus prepared are dissolved in 100 ml Bortichlorid-methanol solution (10 wt .- / vol .-%) and the solution heated to 6O ⁰ C. After 10 minutes, the solution is poured into ice water and extracted three times with 50 ml of petroleum ether (boiling point 30-60 ° C.) each time. The combined extracts are washed with water and dried over magnesium sulfate. After filtering and removing the solvent, a yield of 10 g of a colorless liquid, methyl 11-dodecylinoate, with a boiling point of 49-50 ° C. at 0.3 mm Hg is obtained.

Oxygen is passed through a mixture of 3 g of methyl 11-dodecylinoate, 0.4 g of copper (I) chloride and 0.5 g of tetramethylethylenediamine in 60 ml of isopropyl alcohol, which is kept ^{at 40 ° C. for 14 hours.} The alcohol is removed under reduced pressure and the residue triturated with ether and filtered. The filtrate is treated with activated charcoal to remove any residual color and then cooled. The resulting crystalline product is collected by filtration and dried, and a yield of 2.8 g of dimethyl ester of 11,13-tetracosadiynedioic acid is obtained (melting point 39.5-40.5 ° C.).

Nuclear magnetic resonance spectrum;

CH ₃ OC-220 cPs. Singlet (5.8)
O

-CH ₂ CO-
and

-CH ₂ -C = C-

136 cPs, multiplet (8.0)

-C-CH ₂ -C-77 cPs, broad singlet (28)

Example C
Dimethyl ester of 4,6-decadiyne diacid

4,6-decadiyne diacid is produced by a known process (Annalen 589, page 234 [1954]). A solution of 6 g of this 4,6-decadiyne diacid in 50 ml of boron trichloride / methanol (10% by weight / volume) is brought to the boil for 15 minutes, then poured into ice water, filtered and washed with cold water. The solid diester is dissolved in ether and successively with Water, dilute sodium carbonate solution and water

water washed and then dried over magnesium sulfate. After evaporation of the solvent becomes a yield of 6.1 g of dimethyl ester of 4,6-decadiinedioic acid was obtained, which after recrystallization Petroleum ether (b.p. 60-110 ° C) melts at 34 - 35 ° C.

Nuclear magnetic resonance spectrum;

CH ₃ OC-219 c Ps, singlet (6.0)

and

—CH, C — O-

-CH ₂ -C = C-

151 cPs, singlet (8.0)

Example D
Dimethyl ester of 7,9-hexadecadiyne diacid

8.6 g of 7,9-hexadecadiyne diacid are dissolved in 25 ml of boron trichloride / methanol solution (10% by weight / volume). The reaction mixture is heated for 20 minutes under reflux and then poured into ice water and extracted with petroleum ether (bp. 30-60 ⁰ C). The ether extract is washed with water, dried over magnesium sulfate and filtered. After evaporation of the ether, 9.4 g of an oil are obtained from crude dimethyl ester of 7,9-hexadecadiyne diacid, which is used to prepare the monomethyl ester of 7,9-hexadecadiyne diacid and methyl potassium 7,9-hexadecadiyne dioate can be.

Example E.
Diethyl ester of 11,13-tetracosadiyne diacid

50 g of 11-dodecylic acid are dissolved in 165 ml of boron trichloride-ethanol solution (10% by weight / volume). After half an hour boiling the solution, it is poured into 700 ml of ice water and extracted with 200 ml of petroleum ether (bp. 60- 110 ⁰ C). The petroleum ether solution is dried over magnesium sulfate. After removal of the solvent under reduced pressure, a yield of 55.7 g of a colorless oil is obtained from crude ethyl 11-dodecylinoate, which is not purified further, but directly in an oxidation-coupling reaction to produce the diethyl ester of 1! •, 13- Tetracosadiyne diacid is used.

Oxygen is stirred through a mixture of 4.0 g of copper (I) chloride, 4.8 g of ethylenediamine and 600 ml of ethanol passed for 15 minutes. Then 55.7 g of the crude ethyl 11-dodecylinoate produced added and stirring and oxygenation continued. The temperature of the reaction mixture is kept below 45 ° C by an ice bath.

After 6 hours the ethanol under reduced pressure with a rotary evaporator is removed The residue is extracted with 1500 ml of petroleum ether (bp. 60-110 ⁰ C) The petroleum ether solution is washed three times with 100 ml of aqueous 4% hydrochloric acid solution and then twice with 200 ml Washed water and dried over magnesium sulfate. After filtering off

the magnesium sulfate is concentrated by evaporation, the petroleum ether solution to about 150 mL in vacuo and - cooled to -20 ⁰ C. The colorless crystals obtained from the petroleum ether solution are removed by filtration and dried, a yield of 42.8 g of diethyl ester of 11,13-tetracosadiynedioic acid (melting point 29-30 ° C.) being obtained.

Nuclear magnetic resonance spectrum;

CH, -

75 cPs, triplet *)

-CH ₂ OC-248 cPs, Quartet (3.9)
O

C / Γ12 C * O

and

-CH ₂ -C = C-

134cPs, multiplet (8.3)

78 cPs, wide singlet (36)
*) Integral signal in which

I I

-C-CH ₂ -C- value
included, as there was an overlap of the "peak".

Example F
Dicyclohexyl ester of 10,12-docosadiyne diacid

A solution of 25 g 10,12-Docosadiin-dioic acid and 1 g of p-toluenesulfonic acid in 100 g of cyclohexanol was stirred for about 20 hours at 100-110 ⁰ C and allowed to stand for about 72 hours at room temperature. The solvent is removed by distillation, the

The residue was dissolved in ether and washed successively with water, aqueous potassium hydroxide solution (2%) and water washed. After drying over magnesium sulfate and

Filtering, the ether is removed by distillation.

The resulting product is recrystallized twice from petroleum ether (bp. 30-60 ⁰ C) and once from petroleum ether (bp. 60 to 110 ⁰ C). The yield is 18 g of a product with a melting point of 39-40 ° C.

Nuclear magnetic resonance spectrum;

and

-CH ₂ CO-

-CH ₂ -C = C-

134 cPs, multiplet (8.1)

-C-CH ₂ -C

and

Cyclohexyl — CH ₂ -

79 cPs. wide singlet (43.9)

Cyclohexyl, CHO-C -
284 cPs, wide singlet (2.0)
Example G

Nuclear magnetic resonance spectrum;

-CH ₂ CO-

and

-CH ₂ -C = C-

133 cPs, multiplet (8.2)

78 cPs, wide singlet (24.0)
O

Il

-CO-CH ₂ -O

306 cPs, singlet (4.0)

H H

■ Η

M Μ

441 cPs, singlet (9.5)

Example H
Monomethyl ester of 4,6-decadiyne diacid

A solution of 21 g of dimethyl ester of 4,6-decadiyne diacid in 100 g 0.93 n-barium hydroxide in absolute methanol 19 hours at 40 ⁰ C stirred. The precipitate is filtered off, washed with methanol and dispersed in an approximately equal volume of chloroform and aqueous 4% hydrochloric acid for about 5 minutes and filtered. The solid becomes again

40

45

dispersed and filtered as above. The two filtrates are combined, the aqueous layer is discarded and the organic phase is washed with water until neutralization and dried over magnesium sulfate. The solvent is removed by distillation under reduced pressure, and the residue from a mixture of chloroform and petroleum ether (bp. 60 to 11O ⁰ C) recrystallized, and 11g are obtained of a product with a melting point of 103 to 104.5 ⁰ C.

Nuclear magnetic resonance spectrum;

Dibenzyl ester of 10,12-docosadiyne diacid

A solution of 6 g of 10,12-docosadiynedioic acid and 1 g of ₅ n-toluenesulfonic acid in 100 g of benzyl alcohol is stirred at 102 ° C. for 18 hours. The solvent is removed by distillation under reduced pressure and the residue is ^{extracted with hot petroleum ether (boiling point 60-HO 0} C). The extract is washed with aqueous potassium hydroxide solution (2%) and then with water, dried over magnesium sulfate and filtered, and the solvent is removed by distillation under reduced pressure. The residue is recrystallized twice from petroleum ether (b.p. 60-110 ° C.) and a yield of 4.2 g of the desired product with a melting point of 40-41 ° C. is obtained.

CH ₃ OC-

215 cPs, singlet (3.3)

and

Il

-CH ₂ CO-

-CH ₂ -C = C-

148 c Ps, Düblet (7.6)

—C — OH

720 c Ps, wide singlet (1.0)

Example I.
Monocyclohexyl ester of 10,12-docosadiyne diacid

A solution of 9.2 g of 10,12-Docosadiin-dioic acid, 13.3 g of 10,12-Dicyclohexylester Docosadiin-dioic acid and 1 g of p-toluenesulfonic acid in 300 g dimethylsulfoxide are for 18 hours at 100-105 ⁰ C and then Stirred at about 20 ^° C. for 24 hours. The reaction mixture is poured into ice water and filtered. The filtrate is extracted with ether, the solution dried over magnesium sulfate and the solvent removed under reduced pressure The residue is combined with the solids of the initial filtrate, freed from the diacid by stirring with hot petroleum ether (bp. 30-6O ⁰ C), and filtered . The filtrate is then extracted with aqueous potassium hydroxide solution (2%) in order to separate the diester from the monoester of the diacid. The basic solution is acidified with aqueous 10% hydrochloric acid and extracted with chloroform Monoester of the diacid, 6.0 g being obtained, melting after recrystallization from petroleum ether (bp. 60-110 ⁰ C) at 52 -53 ° C .

Nuclear magnetic resonance spectrum;

-CH ₇ -CO-

and

133 cPs, multiplet (7.7)

I I

-C-CH ₂ -C-

and

Cyclohexyl — CH ₂ -

79 cPs, wide singlet (33.6)

Cyclohexyl CHO-C -
285 cPs, wide singlet (1.4)
O

Il

—C — OH
550 cPs, wide singlet (1.4)

Example J
Monobenzyl ester of 10,12-docosadiyne diacid

A solution of 37.7 g of 10,12-docosadiyne diacid in 100 g of thionyl chloride is refluxed for 1 hour and then unreacted thionyl chloride removed by distillation. The residue is dissolved in chloroform, washed with water, filtered and dried over magnesium sulfate. After the solvent has been distilled off, 33.7 g of an oil are obtained. The infrared spectrum shows no absorption in the range of 3.0 μ, which is in agreement with the 10,12-docosadiyne-1,22-dioyl dichloride.

A solution of 4 g lO ^ -. Docosadiin-l ^ -dioyldichlorid in 6 g of benzyl alcohol and 25 g of pyridine is stirred for 18 hours at about 20 ⁰ C, poured into water and extracted with ether. The ether solution is washed successively with water, dilute hydrochloric acid and water and dried with magnesium sulfate, and the solvent is removed under reduced pressure. The residue is extracted by stirring with hot petroleum ether (bp. 60- 110 ⁰ C). After partial distillation of the solvent and cooling, brown-colored crystals are formed. After two further recrystallizations, 1.8 g of the monobenzyl esters with a melting point of 54-56 ° C. are obtained. (The dibenzyl ester is not obtained in this process.)

Nuclear magnetic resonance spectrum;

and

-CH ₂ -C = C-

133 cPs, multiplet

-C-CH ₂ -C-

79 cPs, wide singlet
O

Il

-CO-CH ₂ -306 cPs, singlet

Il

—C — OH

525 cPs, wide singlet

Example K
Mononeopentyl ester of 10,12-docosadiyne diacid

A solution of 20 g 10,12-Docosadiin-dioic acid and 1 g of p-toluenesulfonic acid in 50 g neopentyl alcohol is stirred for 17 hours at 107-118 ° C, diluted with petroleum ether (bp. 30-60 ⁰ C) and washed with water . About 3 g of solid are obtained in the boundary layer,

'5 separated by filtration and as a raw starting product by infrared spectrum and the melting point identified from 104-117 ° C. The organic phase will Washed with aqueous potassium hydroxide solution (2%), acidified with dilute hydrochloric acid and treated with petroleum ether (bp.

30-60 ⁰ C) extracted. After drying with magnesium sulfate, the petroleum ether is concentrated to a small volume and cooled. The resulting precipitate is recrystallized twice from petroleum ether (bp. 30-60 ⁰ C) and a yield of 0.15 g of Mononeopentylestern obtained. The organic phase is washed with aqueous potassium hydroxide solution (2%), the solvent is removed by heating and 21 g of crude dineopentyl ester which could not be crystallized is obtained.

Nuclear magnetic resonance spectrum;

CH ₃ -

55 cPs, singlet (8.7)

225 cPs, singlet (2.0)

Il

CH ₂ CO-

and

135 cPs, multiplet (3.9)

/ ^ O

79cPs. wide singlet (12.5)
Example L
Monoethyl ester of 11,13-tetracosadün diacid

42 g of diethyl ester of 11,13-tetracosadün diacid, 450 ml of 0.206 n-barium hydroxide-ethanol solution and 300 ml of absolute ethanol are placed in a 1-1 flask, which contains a glass-covered stirring magnet and a sodium hydroxide asbestos as an absorbent for carbon dioxide The solution is ^{stirred at about 20 °} C. for 5 days. The ethanol is then

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Nuclear magnetic resonance spectrum;

CH, -

74 cPs, triplet *)

-CH ₂ OC-248 c Ps, Quartet (2.4)
O

and

-CH ₂ CO-

-CH ₂ -C = C-134 cPs, multiplet (8.2)

78 cPs, wide singlet (31)
O

Ii

-COH
533 cPs, wide singlet (1.3)

*) Integral signal in which

I I

-C-CH ₂ -C value
included, since the "peaks" overlap.

Example M
Monomethyl ester of 11,13-tetracosadiyne diacid

40 g of dimethyl ester of 11,13-tetracosadiynedioic acid are dissolved in 60 ml of methanol and placed in a 1-1 flask which contains a glass-covered stirring magnet and is equipped with a drying tube containing sodium hydroxide-asbestos as an absorbent for carbon dioxide 97 ml of 0.928 n-barium hydroxide methanol solution are added. The stirring is continued for 20 hours at room temperature continued The precipitated barium salt of Monoesters is washed and removed by filtration with petroleum ether (bp. 60-110 ⁰ C). The white solid is triturated in 500 ml of ether and 200 ml of aqueous 5% hydrochloric acid until all of the solid is dissolved. The ethereal layer is washed with water until neutralization and dried over magnesium sulfate. The ether is removed under reduced pressure and the residue from petroleum ether (bp. 30-60 ⁰ C) to give a yield of 20 g of the 11,13-Monomethylester Tetracosadiin-dioic acid having a melting point of 71-72 ° C is obtained.

Removed tem pressure and the residue extracted with ether until about 17 g of unreacted diethyl ester are removed. The remaining residue is acidified with aqueous 4% HCl and the mixture extracted with ether, the ether extract washed with water and dried over magnesium sulfate the ether is removed and the remaining residue from petroleum ether under reduced pressure (bp. 30-60 ⁰ C) recrystallized, a yield of 20 g of monoethyl ester of 11,13-tetracosadiynedioic acid with a melting point of 60-61 ° C. being obtained.

Nuclear magnetic resonance spectrum;

CH ₃ OC-

219 cPs, singlet (2.9)

and

O
-CH ₂ CO-

- CH, -C = C-

■ 5 135 cPs, multiplet (8.0)

-C-CH ₂ -C

77 cPs, wide singlet (28)
O

Il

-COH

536 cPs, wide singlet (1.2)
Example N

Monomethyl ester of 10,12-docosadiyne diacid

2 liters of methanol are placed in a 5-1 flask and 185 g of dimethyl ester of 10,12-docosadiyne diacid are added. The mixture is stirred until the diester has dissolved. 509 ml of 0.928 n-barium hydroxide-methanol solution are added to the solution. The reaction mixture is stirred at room temperature for 24 hours. The precipitated barium salt is removed by filtration and washed with methanol. The methanol filtrates are concentrated and filtered until no more barium salt can be obtained. The barium salt is triturated with 500 ml of 1N HCl and the mixture is extracted three times with 300 ml of ether each time. The combined ether extracts are washed with 200 ml of water and dried over magnesium sulfate. After removing magnesium sulfate by filtration, the ether is distilled off under reduced pressure and the resulting solid from petroleum ether (bp. 30-6O ⁰ C) recrystallized. The crystalline product is collected by filtration, washed with cold petroleum ether and dried. A yield of 118 g of monoethyl ester of 10,12-docosadiyne diacid is obtained (melting point 61 ° -62 ° C.).

Nuclear magnetic resonance spectrum;

and

CH ₃ OC—
220 cPs, singlet (3.1)

Il

-CH ₂ CO-
-CH ₂ -C = C-137 cPs, multiplet (7.9)

80 c Ps, wide singlet (24)
O

Il

-COH

619 cPs, wide singlet (1.1)

In addition, 18 g of unsaponified dimethyl ester and 8 g of the corresponding diacid are isolated and won.

The infrared spectra of the di-diester and half-ester of the previous examples show the expected absorption bands. Show all UV spectra obtained a particularly characteristic absorption of the dine group

(-C = C-C = C-)

with maxima at 215, 225, 240 (ε-380) and 254 πιμ (ε-230).

Example O
Methyl potassium 10,12-docosadiyne dioate

To the monomethyl ester of 10,12-docosadiyne diacid with an acid number of 150-160, which is produced from the corresponding diester by hydrolysis has been, aqueous potassium hydroxide solution is used in a stoichiometric amount to neutralize the half-ester admitted. The resulting clear solution is filtered. The filtered, methyl potassium 10,12-docosadiin-dioate containing solution is practically evaporated to dryness on paper. That while drying on the Crystalline methyl potassium 10,12-docosadiin-dioate precipitated on paper surface Visibly changes its color when exposed to UV rays.

Example P
11,13-tetracosadiine

About 1.25 moles of bromine are added dropwise to a cooled solution of about 1.13 moles of 1-dodecene in 11% carbon disulfide. After all the bromine has been added, a small amount of 1-dodecene is added which is sufficient to remove the red color due to the small excess of bromine. The carbon disulfide is removed by distillation and the remaining yellow liquid is taken up in ether, washed with aqueous 10% ethanol and dried over magnesium sulfate. The ether is removed by distillation, leaving about 1 mole of crude 1,2-dibromodecane, which is used for dehydrobromination. The crude 1,2-dibromodecane is mixed with 5.3Mol potassium hydroxide in aqueous solution and under a nitrogen atmosphere for 3 hours 170-200 ⁰ C heated the first half hour was refluxed, and during the last 2 '/ 2 hours, about 200 ml of a condensate in the form of a cloudy, colorless liquid collected Now, ether and water were added to the distillate, and after thorough Mixing the ether layer is separated and dried over sodium sulfate. The dry ethereal solution is then freed from the ether by vacuum distillation and 19.4 g of a fraction between 43-50 ⁰ C at 0.5 mm Hg and 68.3 g of a fraction between 49-62 ° C at 0.6 to 1.2 mm Hg collected. Each fraction is identified as crude 1-dodecine by infrared spectroscopy.

2 g copper (I) chloride and 2.4 g Ν, Ν, Ν ', Ν'-tetramethylethylenediamine are mixed with 400 ml of isopropanol, and oxygen is passed through the for 15 minutes

ίο Mixture passed Then about 24 g of raw 1-dodecine are added. Stirring and the addition of oxygen continues while the first reactant 14 hours at 35 ⁰ C and are heated to about 50 ⁰ C then 19V ₂ hours. The isopropanol is then separated off ^{at 40-5O 0 C under reduced pressure.} The remaining residue is repeatedly mixed with aliquots (200 ml) of petroleum ether (boiling point 30-60 ° C.), which are then filtered off, until a colorless filtrate is obtained. The filtrates are combined and washed several times with aqueous 10% hydrochloric acid. The washed petroleum ether solution is then freed from petroleum ether in vacuo and a slightly yellow liquid product is obtained. The product is mixed with ether and at about 0 ^° C. for 16 hours

ditched. The crystalline material that forms in the ethereal solution is quickly filtered through the cold solution separated and dried under magnesium sulfate, 19.4 g being obtained. The ether filtrate is concentrated in vacuo and filtered to give a second batch of precipitated crystals weigh about 7.1 g after drying under magnesium sulfate. So the total yield is 26.5 grams of 11,13-tetracosadiine.

Each polyyne compound described in the above examples is sensitive to radiation and shows at Exposure with at least one type of radiation, in particular with UV radiation of a wavelength of predominantly about 2537 Ä, a visible change in color. A semi-quantitative determination and a comparison of the Radiation sensitivity of various polyynes can be carried out as follows.

The polyyne compound dissolved in an organic solvent is applied to a white surface, e.g. B. white filter paper or a white index card is applied and the solvent is evaporated, leaving behind an adhering precipitate of crystalline polyyne compound, which is then emitted with radiant energy is exposed. A short-wave ultraviolet lamp with a maximum

Radiation component of wavelength 2537 Å used at a distance of 57 cm. After 30 seconds long exposure to this lamp, the precipitate of the crystalline monomethyl ester changes 10,12-docosadiindioic acid (preparation according to example N) visible on the white base from a white to a purple-blue color, which roughly corresponds to the Munsell designation system 7.5 PF 4/2 corresponds. Using this color as a comparison standard you can Precipitation of other crystalline polyynes by exposure to the same lamp from the same distance are irradiated with visual determination of the formation of a color similar to the standard color required time

The ultraviolet sensitivity of a number of crystalline polyyne compounds determined in this way, the preparation of which is described in the above examples is shown in the following table reproduced.

Example crystalline polyyne compound

UV exposure
Time (seconds) *) to
Achieving a color
of about 7.5 PB 4/2
after Munsell

N monomethyl ester of 10,12-docosadiyne diacid 30

M monomethyl ester of 11,13-tetracosadiyne diacid 80

B dimethyl ester of 11,13-tetracosadiynedioic acid 180 (a)

L monoethyl ester of 11,13-tetracosadiynedioic acid 120 (b)

J Monobenzyl ester of 10,12-docosadiyne diacid 600

I Monocyclohexyl ester of 10,12-docosadiyne diacid 420

K mononeopentyl ester of 10,12-docosadiyne diacid about 900 (b)

F Dicyclohexyl ester of 10,12-docosadiyne diacid 195

*) For each specific polyine, the sensitivity can vary depending on the purity, crystal size,

Crystal form and the like of the polyyne compound differ considerably from these values, (a) and (b) It is difficult to get the exposure time required to achieve approximate color uniformity to be specified exactly, since the resulting photo product (a) is a little greenish blue and the resulting photo products (b) have a slightly different purple color than the purple blue standard color. Other polyynes, which are not specifically designated, achieve only roughly the color of Munsell standard 7.5 PB 4/2, as pale red and yellow products can be found in it.

According to the invention, a recording material is used which contains a carrier material which is used for solid anchoring of the polyine crystals is used, so that the unexposed and exposed material in the required Wise can be handled without changing the arrangement of the crystals relative to each other.

As a rule, the carrier material consists of a binder, e.g. B. natural or synthetic Plastic, resin, colloid or gel in which the polyine crystals are dispersed. In these cases it will Polyine as a lacquer, solution, emulsion, dispersion and the like. Mixed with the binder and then resistant Films, plates, coatings and the like. Processed. According to another embodiment, a Support used on top of a layer, film or coating of the binder with the therein dispersed polyine crystals is applied. Typical suitable supports are e.g. B. sheets of paper, glass plates, Plastic sheets and other known ones commonly used for photographic purposes Support. According to a further embodiment, a binder-free coating is on the layer support firmly adhered from polyine crystals. Furthermore, a coating of a suitable radiation-sensitive Coating material are present on one or more surfaces of various carrier materials.

Examples of materials that can be used as a component for the substrate are: vitreous materials, preferably glass itself, glazed ceramics, porcelain, etc .; Fiber materials such as cardboard, fiber sheets, Paper such as binding paper, resin-sized and clay-sized paper, paper made transparent with wax or otherwise, Paperboard, etc., cloths and fabrics such as those made of silk, cotton, viscous rayon, etc .; Metals like Copper, bronze, aluminum, tin, etc .; natural polymers and colloids, such as gelatin, polysaccharides; natural and synthetic waxes such as paraffin, beeswax, carnauba wax; synthetic resins and Plastics, especially polyethylene, polypropylene, polymers and copolymers of vinylidene and monomeric vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinyl acetate, vinyl acetate / acrylate. Vinyl acetate / methacrylate, vinylidene chloride / acrylonitrile, Vinylidene chloride / vinyl acetate, vinylidene chloride / methacrylate polystyrenes, polyvinyl acetals, such as polyvinyl butyral, polyvinyl formal (polyvinyl dimet

hoxymethane), polyvinyl alcohol, polyamides, such as polyhexamethylene adipamides, N-methoxymethyl-polyhexamethylene adipamide, natural and synthetic rubbers such as butadiene-acrylonitrile copolymers, 2-chloro-1,3-butadiene polymers, polyacrylate polymers and copolymers, such as polymethyl methacrylate, polyethyl methacrylate, polyurethanes, polycarbonates, Polyethylene terephthalate copolymers of polyethylene terephthalate / isophthalate and others Esters formed by condensation of terephthalic acid or its derivatives with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane-1,4-dimethanol, cellulose ethers such as Methyl cellulose, ethyl cellulose and benzyl cellulose, cellulose esters and mixed esters such as cellulose acetate, Cellulose triacetate cellulose propionate cellulose nitrate and cellulose diacetate; and not thermoplastic either Materials such as cellulose, phenolic resins, melamine-formaldehyde resins, alkyl resins, curable acrylic resins, Epoxy resins and numerous other synthetic resins and plastics that are known.

The substrate can be transparent, almost transparent or opaque to the type of radiation, to which the polyyne compound used is sensitive Purpose of the image material and the specific type of radiation and with regard to the specific Image recording method selected If, for example, the recording method ultraviolet transmission Requiring radiation through the substrate material to expose the polyacetylene crystals should be the substrate have such permeability and can be a cellulose acetate-butyral cellulose acetate-polyvinyl alcohol, polyvinyl butyral or another suitable transparent material.

The material of the support or substrate can be used directly with the binder-free or in one Binder dispersed photosensitive crystals firmly bonded or optionally be indirectly connected by an intermediate layer or a coating on the substrate, especially with special application forms, e.g. B. to the radiation permeability of the substrate or the radiation reflection of the substrate to change the adhesion of the

To modify substrate material and for other purposes. Similar to the material for the substrate or The substrate is the intermediate layer, taking into account the specific type of radiation and the Image recording method chosen technology applied.

Examples of suitable binders as components for the carrier are: natural and synthetic Plastics, resins, waxes, colloids, gels and the like., such as B. preferably photographic gelatin, various polysaccharides such as dextran, dextrin, hydrophilic cellulose ethers and esters, acetylated starch, natural and synthetic waxes such as paraffin, Beeswax, polyvinyl lactams, polymers made from acrylic and methacrylic esters and amides, hydrolyzed Copolymers of vinyl acetate and unsaturated and polymerizable compounds such as maleic anhydride, Acrylic and methacrylic esters and styrene, vinyl acetate polymers and copolymers (and their derivatives z. B. fully and partially hydrolyzed products of the same) such as polyvinyl acetate, polyvinyl alcohol, Polyethylene oxide polymers, polyvinylpyrrolidine, polyvinyl acetate such as polyvinyl acetaldehyde acetal, Polyvinyl butyraldehyde acetal, polyvinyl sodium-o-sulfobenzaldehyde acetal, Polyvinyl formaldehyde acetal and numerous other known photographic binders and also a large number of the named suitable plastic and resin substrate materials, which can be brought to the polyin in the form of varnishes, solutions, dispersions, gels and the like to add, after which these are brought into solid form, which then contain the dispersed crystals of the polyine. As is known in the manufacture of such smooth, uniform, continuous coatings from binders is, you can use a small amount of well-known coating aids, such as agents for regulating the Use viscosity, leveling agents, dispersing agents, and the like. The special binder comes with Consideration of the specific type of radiation used in the particular imaging process and technology chosen, which is always created so that it is opposite to the specific type of radiation used is practically permeable. The binder is preferably not a solvent or has only limited properties Solubility properties for the photosensitive polyyne so that the polyyne is in its crystalline form preserved.

Known light sources, lenses, optical systems, camera equipments, focusing and projection systems and the like are used for the various types the radiation energy used to expose the recording material.

Transillumination and reflex exposure methods can be used. Therefore, stencils made of one are practically impermeable to radiation Material placed on the recording material or arranged so that the stencil does not come with the Recording material comes into contact. The recording material can be by contact or Projection processes are exposed through a two-tone image or a transparency, e.g. B. by a so-called lines or halftone negative or slide, or a continuous tone negative or positive. Reflex exposure methods are particularly useful for copying of sheets that are printed or written on on both sides and for the illustration of patterns and objects Materials that are opaque to radiation are suitable.

The following examples are intended to explain the invention in more detail.

example 1

A small amount of 11,13-tetracosadiynedioic acid containing about 20 to 30% of its monoethyl ester (Mp. 118 ° C) is dissolved in alcohol and under added vigorous stirring to aqueous polyvinyl alcohol. In the aqueous polyvinyl alcohol one forms

ίο Suspension of finely divided crystals. By pouring and / or spreading this suspension onto various substrates, e.g. B. a sheet of white paper, and drying by gently heating to evaporate the water and alcohol from the nasseti coating, a material is created which consists of a paper substrate to which a polyvinyl alcohol binder with dispersed colorless crystals of diyne diacid adheres is located. After exposure of a material produced in this way to ultraviolet rays from a radiation source with a main wavelength emission of 2537 Å, the irradiated diyne preparation changes to a deep blue to purple-colored product and, after prolonged exposure, shows a bronze color, which is durable in the absence of further ultraviolet radiation and temperatures below 50 ° C is. By heating the exposed material to a temperature above about 120 ⁰ C, which are to bronze color in red. The blue to bronze colored product can also be by 5 minutes of exposure to warm Äthanoldämpfen converted to a red product blue changed.

When a fine-meshed metal wire grid is placed over a material produced in this way and the arrangement is exposed to ultraviolet rays, a colored negative image of the screen is produced on the exposed material. The color negative can then be converted to a temperature above about 12O ⁰ C in a red negative by heating the exposed material. Heating above 120 ^° C. and converting the blue into a red image can also result in lightening of unexposed parts of the material.

Example 2

A small amount of 11,13-tetracosadiyne diacid (melting point about 118 ° C.) containing some monoethyl ester is dissolved in ethanol or, if appropriate, in acetone and the solution is added to aqueous polyvinyl alcohol. The resulting dispersion is ground with glass beads up to a degree of fineness of 7 (North Shore Gage). With a knife Mikroskopobjekträger of glass is coated with the dispersion, and water and alcohol is evaporated from the wet coating by drying in an air oven at about 50 ⁰ C. The resulting material consists of a glass substrate with a smooth, permanent film about 0.01 mm thick made of polyvinyl alcohol binder with dispersed colorless crystals of the diyne derivative.

The resulting material is used as photosensitive material in electron microscopy instead known materials, namely a glass plate with a silver halide gelatin emulsion, used; The electron microscope used is a model in which the electron source is a hot tungsten cathode with an accelerating potential of 80 kV and with a current intensity of the beam of 60-80 μΑ is used with an exposure time of 10-15 seconds, using wire mesh in 2500 to

709 524/322

4500x instrument magnification. After removing the exposed material from the electron microscope a visibly blue electron microscope negative image of the object is obtained.

Example 3

7,9-hexadecadiyne diacid having a melting point containing a small amount of its monomethyl ester from 117-119 ° C becomes an average Particle size of 5-10 microns pulverized in a jet mill. The powder is then using from glass beads to a dispersion containing approximately 10% solids in aqueous polyvinyl alcohol processed. As in the previous example, the dispersion becomes a recording material a glass substrate on which a smooth, solid film of polyvinyl alcohol binder with dispersed white Crystals is applied, produced. This material is used in electron microscopy as in the previous example used, whereby a longer exposure time should be selected. It was found that the exposed material had a visible blue-colored negative image of the object.

The blue color image of the exposed material is reversibly converted by heating to a temperature between 50-60 ⁰ C in red, and the red image returns to a blue after cooling to below 50 ° C. However, when the image is heated to about 100 ° C, the blue image becomes a red image that is persistent even after the image is cooled to 20-50 ° C

Example 4

Monomethyl ester of 10 ^ - docosadiyne diacid (melting point 60 ° C.) is heated slightly above its melting point and slowly and dropwise added to rapidly stirred, warm, aqueous polyvinyl alcohol. After cooling, small particles of the diyne diacid monoester dispersed or emulsified in the aqueous polyvinyl alcohol are obtained. The mixture is applied as a wet film to the surface of glass plates and dried slowly and carefully to produce a photosensitive material from a glass substrate with an adherent, smooth, solid film of polyvinyl alcohol binder and white monoester crystals dispersed therein , the crystals having a size of have about 10 μ . During drying, the wet film tends to separate from the corners of the glass plate and cover only part of the glass surface. The addition of small amounts of glycols and / or additional vinyl alcohol and ethanol to the applied dispersion reduced such an appearance. Likewise, a suitable intermediate layer on the glass substrate can weaken this. The resulting material can record an image that is immediately visible when it is used in an electron microscope that has already been described.

Example 5

Monomethyl ester of 11,13-tetracosadiyne diacid (Mp. 71 ° C) is used in place of the monoester from the previous example to a similar To manufacture material. This can record an immediately visible image if it is in one of the preceding Examples described electron microscope is used.

Example 6

Monomethyl ester of 10,12-decosadiyne diacid is pulverized to a fine particle size and then stirred in aqueous hydroxyethyl cellulose. The emerging Dispersion is applied as a coating to microscope glass slides and the water from the wet coating evaporates. The resulting material is a glass substrate on which a solid coating is made Hydroxyethyl cellulose with fine, white crystals of the polyyne compound dispersed therein firmly adhering is upset. The material changes after or when exposed to ultraviolet rays, which have a strong effect The proportion of rays with a wavelength of 2537 A contain immediately the color to blue. The material is for Image formation using electron beams or ultraviolet rays is suitable

Example 7

The monomethyl ester of 10,12-docosadiyne diacid is in water / methanol, water / ethanol or preferably water / acetone with glass beads at about Grind to fine, crystalline particles at 15 ° C. the Glass beads are removed from the resulting finely ground slurry and the slurry in aqueous gelatin dispersed by careful mixing. An approximately 0.25 mm thick wet coating of the Combination gelatin / polyine compound is applied to a glass plate and the coating becomes one resistant film about 0.008 mm thick dried in a warm air oven. Another wet one Coating from the dispersion of gelatin / polyin compound

manure is applied and this coating is also dried to a solid film in the hot air oven, after which the total thickness of the two coatings is about 0.015 mm

The resulting material consists of a glass substrate and two coating layers of a gelatin binder in which finely divided white crystals of the polyyne compound are dispersed. When the material is exposed to ultraviolet rays, a blue-colored product is produced immediately. The material is also suitable as a recording material for electron microscopy and this creates a visible blue-colored negative of the object imaged with the electron microscope.

Example 8

Crystalline dimethyl ester of 11,13-tetracosadiinedioic acid (melting point 39.5 ° -404 ° C.) is ground in a mortar with a pestle in a cold room and the resulting, finely ground material is commercially available on the side provided with an adhesive Available cellophane film ("scotch tape" for office use) is sprayed on. The coated film is rubbed with the ground material, then shaken and turned over to remove any loose material that does not adhere to the adhesive layer. The resulting material consists of a cellophane substrate, an intermediate layer of a sticky coating and finely crystalline polyyne compound adhering to it. The surface of the material with the polyyne compound is exposed to ultraviolet radiation from a source with a predominant wavelength of 2537 A, the crystalline polyyne compound rapidly changing color from white to deep blue-violet

Example 9

A small amount of n.lS-octacosadiine crystals, which has been produced as a mixture with a melting point of about 40 ⁰ C from two obviously different crystal forms, of which only has a practical photosensitivity to ultraviolet rays, is dissolved in ether and a filter paper is saturated with this solution The filter paper is then left under the conditions of the laboratory room until the ether has evaporated.After the filter paper, which now contains crystals of the diyne compound, is exposed to ultraviolet rays with a main wavelength of 2537 Å, shortly after its production, the irradiated diyne components quickly acquire a blue color.

A saturated filter paper produced in the same way is kept in the laboratory for a week Left in the absence of visible light, and after exposure to the same ultraviolet ray source Up to about 1 minute no visible color change is found the UV exposure of this aged filter paper exerts a slight pressure such as scratching with a Pen or action of a letter-shaped surface, then appears with the following Ultraviolet exposure to the location of the filter paper being pressure applied or scratched became a deep blue color.

Example 10

A small amount of 11,12-Tetracosadiin which is liquid at about 2O ⁰ C and from about 170-190 ⁰ C (0.1 mm Hg) has a boiling point is added to the liquefied paraffin wax, the well fluid by heating over a steam bath with sufficient agitation to disperse the small spheres of liquid diyne in the liquefied paraffin. The liquid mixture is then poured onto a solid surface and ^{cooled to 0} ° C., whereupon the paraffin solidifies and the thin beads crystallize. After exposure of the cooled to 0 ⁰ C preparation of paraffin wax and dispersed Diinkristallen with ultraviolet rays from a radiation source having a principal wavelength of 2537 A white Diinkristalle change color to a deep blue. After the preparation, which has been exposed to ultraviolet rays, has been heated to about 20 ° -25 ° C., the blue-colored radiation product turns red

Example 11

About 0.45 g of aqueous 50% potassium hydroxide solution are added dropwise to a mixture of about 4 g of water and about 1 g of the monomethyl ester of a 10,12-docosadiyne diacid product given with an acid number of about 166. The resulting solution is filtered and 1 g of the filtered solution with stirring to 0.86 g of aqueous, 20% strength polyvinylpyrrolidone (commercially available Polyvinylpyrrolidone with a medium viscosity grade) given. The resulting solution with about 20% Solid is added to coat a surface of glass microscope slides and dried The photosensitive material consists of about 47% polyvinylpyrrolidone binder, the 53% finely crystalline methyl potassium 10 ^ - docosadiindioate contains dispersed

These photosensitive materials are used as image recording materials in electron microscopy suitable whereby a visible, blue-colored image of an electron microscope image is obtained.

Example 12

An acetone solution of the monomethyl ester of 10,12-docosadiyne diacid is slowly added dropwise with stirring to water and 12 hours with

ίο Grind ceramic balls. The balls are removed and the acetone is removed from the ground product in vacuo. 5 g of the aqueous, 20% monomethyl ester of 10,12-docosadiyne diacid are mixed with 5 g of aqueous, 20% polyvinyl alcohol (commercially available, hydrolyzed polyvinyl acetate [88-90%] of medium viscosity). A wet coating of the resulting mixture is applied by a Baker-knife on a thin film of polyethylene terephthalate and in a forced air oven at about 50 ⁰ C dried after or during exposure of the resulting material with ultraviolet rays, the color of the crystalline diyne in the coating of polyvinyl alcohol is blue.

Example 13

Crystalline monomethyl ester of 10,12-docosadiyedioic acid is ground to fine particles in an aqueous 50% methanol solution. The ground Product is dissolved with an aqueous, 10%, water-soluble Ethylene oxide polymer mixed and stirred for about 30 minutes. The mixture is then mixed with Grind glass beads and, after removing them, apply them as a layer to a glass surface.

In this way, photosensitive materials of glass substrate after coating twice each with 0.15-0.18 mm thick Naßüberzügen and after drying at 50 ⁰ C obtained on which the polymer binder with the disperse fine crystalline particles of the Monomethylesters 10.12 -Docosadiyne diacid is firmly adhering

When used in electron microscopy imaging processes, these materials give visible blue colored images. Also, when ultraviolet rays are used, visible blue ones become visible Received pictures.

Example 14

In this example, the binder used is an emulsion copolymer of ethylene and vinyl acetate (sometimes also called acetoxylated polyethylene because of its practically linear copolymer structure), in which 20 to 50% of the carbon atoms in the chain are acetoxy, and which has an average molecular weight of I. Million owns .Etwa 038 g of an aqueous 48% emulsion of this ethylene / vinyl acetate copolymer are mixed with 0.48 g of water and the resulting emulsion with about 1 g of a filtered solution of methyl potassium 10,12 docosadiin-dioate mixed, which was prepared as described in Example H. A Naßüberzug from the mixture is applied to the surface of glass plates and dried at about 50 ⁰ C. The resulting material is used for image recording method After exposure to ultraviolet rays or the electron beam of the electron microscope, the irradiated methyl-potassium-10,12-docosadiin-dioate change Crystals in the copolymer binder turn blue in color.

Example 15

An acetone solution of the monomethyl ester of 10,12-docosadiyne diacid is mixed with water and ground with ceramic balls. The ground product is decanted from the ceramic balls and treated with aqueous 20% polyvinyl alcohol (as in previous examples) mixed. The mixture is freed from acetone in vacuo. The emerging Dispersion of the polyine crystals in aqueous polyvinyl alcohol solution has a solids content of about 20% (Total amount of dispersed polyynes and dissolved polyvinyl alcohol), being 50% of total solids does not apply to the polyine. To 1.25 g of this dispersion, 0.1 g of practically complete hydrogenated monomethyl ester of 10,12-docosadiyne diacid (i.e. monomethyl ester of docosacid) and applied layers to glass surfaces and dried at about 50 ° C.

When the material of the glass substrate with adhered coating of polyvinyl alcohol binder, dispersed polyine crystals and small amounts of hydrogenated polyine is used for ultraviolet imaging, a visible image of blue color is obtained. After heating the exposed material to about 60 ^° C. for a short time, the blue-colored image becomes a red image. The unexposed parts of the exposed and heated material are now remarkably insensitive and have at least a greatly reduced sensitivity to further ultraviolet radiation. Likewise, the red image, ie the converted blue image, is remarkably insensitive to further ultraviolet radiation, which can be assessed with the naked eye.

Instead of the hydrogenated monomethyl ester of docosadiyne diacid, other hydrogenated polyyne products can be used can be used and the same result of greatly reduced sensitivity unexposed Part of the material is preserved. Other suitable materials in place of the hydrogenated polyyne products are Dicyclohexyl phthalate, benzophenone, and generally similar materials that are unexposed when heated Solubilize polyynes and keep them in soluble form after heating.

Example 16

To an aqueous dispersion of 7,9-hexadecadiinedioic acid 50% potassium hydroxide solution is added in an amount sufficient to dissolve the polyine, with an aqueous solution of dipotassium 7,9-hexadiyne-dioate is obtained. The aqueous solution of the dipotassium salt is mixed with aqueous polyvinyl alcohol and placed on a glass surface as in previous examples described, applied. The resulting material is a glass support on which a dry film is formed made of polyvinyl alcohol, which contains dispersed crystals of the dipotassium salt, is firmly attached.

A grid is placed over the coating and exposed to ultraviolet rays. No visible image is obtained on exposure. The exposed material is then dipped for about 10 sec. In concentrated hydrochloric acid and dried at about 50 ⁰ C. A faint image now becomes visible, and when the acid-treated material is exposed to total ultraviolet radiation, a blue-colored positive image of the grating is produced.

Instead of hydrochloric acid, other strong mineral acids such as sulfuric acid and the like can be used and instead of immersion, acid steam treatment is also suitable.

Example 17

Monomethyl ester of 10,12-docosadiyne diacid is dissolved in acetone and a solution containing about 20 wt .-% dissolved polyyne compound prepared. The solution is slowly added to a 20% by weight aqueous polyvinyl alcohol solution with vigorous stirring

ίο and the acetone removed in vacuo. The polyvinyl alcohol consists of approximately 88-90% hydrolyzed polyvinyl acetate (commercially available). The resulting dispersed precipitation of the polyyne compound in the polyvinyl alcohol solution is ground with glass beads, until the dispersed particles have a particle size of approximately 5 to 12 μ, which is usually after 5 hour marriage is the case. The glass beads are then removed from the dispersion. One Sufficient water is added with mixing and one containing about 10 to 12% solids Dispersion obtained. The dispersion is then applied as a layer on a glass plate and left in the air dried at temperatures not exceeding approx. 50 - 55 ° C. It arises from a wet coating of 0.17-0.255mm, a photosensitive material with a dry layer about 0.012mm thick that sticks to the glass plate.

Example 18

A monomethyl ester of a 10,12-docosadiyne diacid product with an acid number of about 155 - 160 (the theoretical acid number of the monoester is about 149; this product is made from its diacid and contains monoesters and diacids in such an amount that the product has an acid number of 155 - 160) is mixed with 10,12-docosadiynedioic acid in such an amount that a polyyne mixture with the acid number from about 170 originated. To this mixture in water, dilute, aqueous potassium hydroxide solution is added in a very small amount

Added excess to neutralize the mixture and dissolve most of the polyyne compound. The neutralized aqueous solution of the potassium salt is filtered and the filtrate is mixed with about 12% by weight aqueous polyvinyl alcohol (about 88-90% hydrolyzed polyvinyl acetate, commercially available). This mixture is then applied as a coating to a glass plate and air-dried at about 45 ° C. The dispersed potassium salt in the dry layer has an approximate size of 0.5 to 1.5 μ. The amount of potassium salt and polyvinyl alcohol in the applied dispersion is in the dry layer about 60% crystalline polyine potassium salt and 40% polyvinyl alcohol. A second coating of the dispersion is applied and air dried. The image receiving material essentially consists of the glass plate as a layer support and a dry, clear coating of about 0.1 g / 6.5 cm ² of polyvinyl alcohol binder applied to it, the dispersed crystals of methyl potassium 10,12-docosadiin- contains dioate

In the present example, diacid is added to bring the monoester product to an acid number of about 170 to bring and produce a practically clear polyvinyl alcohol coating. At lower acid numbers and those that are close to the theoretical value for monoesters arise with the photosensitive Potassium salt a coating of polyvinyl alcohol that is not clear but translucent. With acid numbers above 170

or for those in which the diacid content is above about 7 1/2% and more of the polyyne blend, the potassium salt in the resulting dry coating is not as photosensitive to electron beams as a coating made from a monoester product having an acid number below 170

In the resulting materials from the dry, photosensitive layer on the glass plate, the Polyine potassium salt content can be up to about 75% by weight. If the amount is higher, there is not enough polyvinyl alcohol binder exists to firmly bind all the crystal particles to the glass plate and some crystals are relatively easy to wipe off. For films with a layer of less than 0.012 mm after drying, a Potassium salt content of less than about 40% by weight is undesirable because it is not sufficiently photosensitive Substance is present to form an image of suitable density after brief exposure to an electric beam to manufacture.

An image receiving material prepared by following the procedure of Example 17 is X-rayed exposed image by image to produce immediately visible copy images. With chrome-K-a-X-rays one With a strength of 40 kV for 5 seconds, a visible copy-out image is obtained directly. In the same way are also used with iron-K-ct and other X-rays Obtain visible copy images.

Image receiving materials according to Examples 17 and 18 are used in electron microscopy to produce visible print-out images. With latex spheres on a carbon support in an electron microscope, a hot tungsten cathode electron source, an acceleration potential of 80 kilovolts and a radiation current of 70-80 μ and an instrument magnification of 4500 times, a suitable exposure time is about 10 seconds for a sweep of the photosensitive material according to Example 17 and about 30 seconds for the material according to Example 18. With other types of exposure, the exposure times are varied accordingly. To illustrate the versatility of the materials for imaging purposes; Images are electron beams having an accelerating potential of 50, 80 and 100 kilovolts of: recording a variety of items such as latex beads, mica flakes, pork liver parts Jodkaliumkristallen, "Hampster" - tissue and through transmission and diffraction electron microscope method.

The electron-irradiated image materials produced in this way show directly visible copy-out images of a clearly visible different color than the non-irradiated image parts. Therefore, such images can easily be viewed, studied and checked immediately after the image material has been removed from the electron microscope, since no prior development is necessary Background Equivalent sharpness cannot be obtained with commercially available glass plates coated with silver halide emulsions under normal exposure and development conditions after an electron microscope image has been recorded. When comparing a polyine image material with a known silver image by optical enlargement processes, whereby the crystals and grains forming the image become visible, it is found that the boundaries or outlines between image areas and background in the known silver images are relatively odd and irregular, since whole Silver crystals stick out and distort the real image outlines. In contrast, the boundaries and outlines of the image recorded in this way on the polyine image material are unusually sharp and show clear details, since the boundary lines and outlines pass through individual crystals of the image material and there are clearly discrete parts of individual crystals located in the image field clearly differ from the unexposed parts of the individual crystals in the image field.

A similar comparison can be made with a straight-edged, opaque object, that is placed on a part of the photosensitive material of Examples 15 and 16, and with ultraviolet rays is irradiated. Here, too, a copy-out image of unique sharpness is recorded directly, and that The enlarged image shows that the straight lines or outlines between image areas and non-image parts pass through the individual, discrete crystals of the polyyne compound. In contrast, this becomes with the same, straight-edged opaque object and the same photographic The method of using a silver halide emulsion for image recording is a conventional photographic one Silver picture produced, in which the border line (and outlines) between the picture surface and the background is jagged and irregular, and deviates from a straight line because the silver crystals are irregular across the border or the outline of the field of view protrude.

In order to clearly explain the unique sharpness and clarity of the image borders and outlines with the image material according to the invention, discrete crystals of the monomethyl ester of 10,12-docosadiyne diacid in ethanol and acetone are produced under controlled conditions Approximately 3.2 mm to 12.7 mm picked up by hand and carefully tied with a clear tape. the surface of a microscope glass slide is glued and secured in this way. A wire mesh or net is set up in such a way that strands of wire cross various individual crystals and thus cover parts of them. This arrangement is then exposed to an 80 kV electron beam for about 1-2 seconds. In this way , the uncovered crystal parts are irradiated and the covered parts receive practically no irradiation. The wire screen is then removed and the irradiated and non-irradiated parts of the crystals examined with a microscope

SS found that the irradiated crystal parts have acquired a visibly different color (in this case a deep blue to purple color), while the covered, unexposed parts of the same crystals have retained their initial color (in this case

water-white to transparent-white). .

An important property of most of the exposed materials according to the invention using Ultraviolet or electron rays, consists in their good resistance and lack of photosensitivity

ability against visible light The directly produced, visible copy can therefore be used for a certain length of time, in some cases even days or weeks, under visible light without or with

709 524/322

a barely noticeable change in color of the photosensitive crystals of the image background of the material copied, handled and checked. This property also enables it to be used known photographic processes with silver halide materials, prints and copies, Produce negatives or positives and enlargements of the captured image. A special The advantage of the material according to Example 18 is the clarity of the binder and the unexposed parts of the image unchanged polyine crystals. In order to produce copies of such images on the materials according to the invention, can do this in practically the same way as known, exposed silver halide negatives and Films are processed. If the material, as in Example 17, is in the unexposed polyine areas whitish or translucent are used for copying copies by known silver halide photography techniques various known color filters and papers are preferably used for the To increase the contrast between the image and the background on the copies made of the image, e.g. Are a 4-64 Kodak green filters suitable

A particular advantage of the image produced in the electron microscope on polyine material is that the image can be optically enlarged to a much greater extent without loss of detail than known silver halide images produced in the electron microscope. In electron microscopy, when choosing the most suitable maximum magnification, one must consider the smallest detail to be examined in the recorded image. The maximum magnification is the product of the instrumentation magnification and the photographic optical magnification of the recorded image. Because of the limitation of the maximum image size in ordinary electron microscopy, the field of view is inversely proportional to the square of the instrument magnification. In the known silver halide materials exposed by electron microscopy, a magnification greater than 10 times, usually only 4 to 5 times, is seldom usable because the details are indistinct because of the grain size. Because of the limited optical magnification, the instrument magnification must be sufficiently high that the desired final magnification can be achieved. Therefore, a corresponding limitation of the maximum field of view is provided. Now that the polyine material can be optically magnified several orders of magnitude more - without loss of detail - a smaller instrument magnification can be used to produce the equivalent final magnification, and therefore a much larger field of view can be examined and studied.

If the exposed materials are to be kept for a long period of time, they are preferably stored in an envelope or a radio-opaque container so that stray radiation or other radiation to which the material is sensitive is eliminated. The initially exposed materials can also be converted to a more permanent form or fixed. When fixing, the unexposed photosensitive crystalline polyine is brought into a form in which it is practically no longer photosensitive, as by its solution in the

Conversion from the crystalline to the liquid form or washing out of the material and binding agent The like. When converted, the color induced by the initial radiation becomes one another, distinctly different color implemented compared to exposure with the initial one, the image creating radiation is relatively stable

In a particularly convenient way, the color conversion is effected by carefully heating the image material to a suitable elevated temperature, usually between 5 - 20 ° C, below the melting point of the non-irradiated, crystalline, photosensitive polyine. The color of the crystalline or crystal parts induced by the initial radiation changes to a different, visible color. For materials in which z. B. Monomethylester the 10,12-Docosadiin-dioic acid or 11,13-dioic Tetracosadiin the photosensitive polyyne is used, a quick heating is preferably from a few seconds up to about one minute, preferably at temperatures between 50 ° to 60 ⁰ C, not made higher than 60 ⁰ C, the color conversion to another, different color effect (ie, from initial radiation-induced blue to purple to red to reddish orange color). Other photosensitive crystalline polyynes also have preferred temperatures for this color conversion by heating, the preferred maximum temperature being below the melting point of the unirradiated photosensitive polyynes.Temperature which are around the melting point of the unirradiated photosensitive polyynes or even higher cause a color conversion of the initial radiation-induced polyynes Tinting, but there may be a loss of sharpness, blurring and blurring the image boundary or outlines. This can be prevented or at least reduced to a minimum if the crystals are held in a fixed position at these temperatures by the binder, in such a way that the image-forming crystals are not in molten, unexposed! Polyin can be dissolved or coated with this.

Another way to effect the color conversion of the blue-colored image is to treat the unexposed polyine with a solvent. A treatment for about 10 to 15 seconds at elevated temperatures which are about 5 to 10 ^° C. below that used for fixation by the action of heat is usually sufficient. Methanol, ethanol, toluene, diethyl ether, butyl acetate, carbon tetrachloride, acetone, 2-butoxyethanol and similar solvents are suitable for the material according to Example 15 and steam and aqueous solutions such as aqueous hydrochloric acid are suitable for the material according to Example 16. Other suitable solvents can easily be selected will.

The advantage of a material with an image in a completely different color than that of the radiation-induced Picture is that this other color is better Can provide hard copies with good contrast, if prints, negatives and the like of this picture with known silver halide photography processes.

Claims (2)

Patent claims: 1. Use of a recording material with a radiation-sensitive one adhering firmly to a layer support Layer containing crystalline compounds with multiple acetylenic bonds, for the production of microscopic or electron microscopic images. 2. Use according to claim 1, characterized in that the compounds with several acetylenic bonds correspond to the following formula contains chemical bonds, exposed imagewise, then in contact with a mineral acid for so long until an image becomes visible and that it is then evenly exposed.