DE1622284A1 - Photographic article and process for its manufacture - Google Patents

Description

DR. MOLLER-BORE DIPL-ING. GRALF8 DR. MANITZ · DR. DEUFEL _fQ

8 MONKS 22, ROBERT-KOCH ^ TR. 1 26.Jun. '"0o

TELEPHONE 225 110 '-

G 16; 66

GLAYEKBEL ₁ 166 Chausee de la Hulpe Watermael-Boitsforb, Belgium

Photographic article and process for its manufacture.

The invention relates to a photographic article with a Peetstoffschioht, for example a material in Plattenfozm and a thin photosensitive layer · The The invention is also directed to a method of manufacture of a photographic article with a plastic hat and a thin light-sensitive layer

There have been known already photographic plates or Filoe that namely when it is a so-called "negativeif carrier consists of a planar substrate made of transparent material" glass or celluloid, or a thin cardboard material, if it is ^w a so-called ⁿ Poeitivkopie -TrSger insist »where a gelatinous gelatin containing photo-sensitive silver halides is sprayed on this support» If these photographic negative films are exposed to light or the effect of a powerful motif, they are necessary «

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Alternatively, it can be developed by means of a chemical product which makes an image of reduced silver appear, it must then be fixed by means of another product which removes the halide which has not been sensitized by the light. But since the process of development is always necessary, the photosensitive layer is easily damaged by mechanical influences (scratching, scratching), thermal effects or atmospheric influences, for example rain, moisture or solar radiation. Di SeIbSt ₁ when applying a glass plate on the photograph, so genfigt * »e not su sohütsen them against the effects of aging uerstöreriachan" or humidity ·

A photographic film with a carrier layer is also known made of polyester and other layers, one of which consists of an organic ctolatin mass and silver halide contains (French patent specification 1 421 101). Auoh is a girder with an organic KoSoldalen coating on it became known, this "layer containing a silver halide. The disadvantages mentioned also apply to this.

According to the invention, these disadvantages are now intended to be overcome.

According to the invention, this is achieved by clicking on dl® The surface of the solid carrier applies at least one film,

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which forms a solid layer that is thin and adheres to, this layer having at least one mineral material in which at least one fetus sensitive material is dispersed9 which, under the influence of height, forms bisociation products, at least one of which modifles the optical characteristics of the thin layer and makes them suitable is, isirevörsibol to remove at least one other product of the dissociation zti. ;

The solid support has, in principle, any shape, but often is used flat or applied curved windows of a preferably transparent material such as glass or acrylic plastic "The one or more films that one anordne on the carrier t _f weräem by known methods, for example AufßtM'jibmng , dipping, brushing, hot or cold ^w Sputteying ", one of this process either alone or in Eombinsitioii since · other applicable? during heat treatment, however, we must, of course, a temperature not th iilaexnchvol in the material of the solid carrier or where appropriate, one δ χ- he would damage the deposited films "Wtnn of or the films deposited in liquid form wivdcm" G® be they can 'into a solid layer by various] !; procedures insbosondere by Tropknen, Brwärmen _s oxidation reshaped · various fotosensible be used, either mineral ©, 'if.fi.o or organic © Subortarisen "Wi © fii © ^ si ^ mt © Im

_009§4 | / 15 43 ^? BATH ORIGINAL

Although the latter phototropic * properties are used as "when they are used in the form of hatred or continuous film®", they only produce photographic characteristics when they are inaccurate Peet fabric layer are suspended »in the case of a layer containing anhydrous polyvinyl alcohol ·

The method according to the invention leads to a very sensitive photographic article which has increased mechanical strength properties, even if the photosensitive material is finely dispersed in the solid layer in the liquid, colloidal or pasty state. The article is also against the impact of atmospheric influence, «belsplele». wise to cherish, very resistant "

After the production of a layer that is thin in the solid state and adheres to the support, the photographic article is advantageously exposed to the effect of an IdLoht motif and, in the following stage, the photographic article is subjected to the effect of a

dl® photosensitive suhetans »the below did not respond, removed *

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Fall produces what is incident on the photographic plate Let me see a partial reduction of every silver halide grain » The reduction must be continued by the action of the developer. "With the KinerelsoMcht according to the invention, on the other hand, the effect of the" ohtaotives ", which can fluctuate between a fraction of a second to a few minutes, allows every dispersed particle of the photosensitive substance to be completely absorbed in the exposed areas opacify. Jet that Image shaped, so you have to put the article »before you can tone it. new exposed to light "the action of a classic fixative expose which is adapted to the nature of the photosensitive substance, wherein, such a fixing agent the. Rope of substance removes "which has not been exposed" which is otherwise without any effect on the dissociation product "which modifies the optical properties of the layer.

At least one PiIm in liquid form is advantageous, the at least one substance contains »which can be transformed into a Let solid mineral substance "and at least one photosensitive substance deposited" then this film is converted into a solid material. convicted. .

In particular, you can create a solution or suspension » which at the same time contains substances "which are in a position" in Tested mineral substances duroh Brwarmungi HirdxOljae Oxidation itself umaiivandelxi * as well as a locates * m & ftgev * fet

^: 009843/1543

Substance® »» -ignfi üim® lüeehung on the solid carrier in the form © feraeheiden, whereby this process is repeated several times by using a pistol or dusting or manure preferably proceed in such a way that a brain dmg @! i dusting of these two types of materials either on the gl @ i © h side or alternatively sifted off.

at least one film is boiled off in liquid form and @ntMlt at least one coat that; Ln (Leu Sage is converted into an intralubstance; at least one photosensitive substance is then given to this film and the film is then converted into a solid soniolite. This is especially The case "if one wants to use margins for the beading of the grains of the photo" sensitive substances · First, therefore, the film forming a solid material is deposited, then this film ₉ is given the photo-sensitive substance in the form of grains, for example by sputtering the desired thickness. It is best to fix it immediately after the film has been built up «

Several are advantageous in at least one process different compositions deposited, the following: .i, ü react differently to form a layer * di. @ ^ snigst © p contains a mineral substance and in de * at least one fc -α «=» Sul) sta3i25 "llapes'giert is" for this "order

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due to the same-sided dusting © der- due to the sputtering processes several films are created @ B0hi®d0 &£> while from a dispersion of a fotoempiiadli <? H © ii in an alcoholic solution of JLthylort & miliMt acetic acid consist "By hydrolysis the films react and form a solid layer »The photo-sensitive substance in silicic acid contains»

Preferably is deposited in at least one Torgang more films of different Zusasimensetsungen from, They are able to "a thin in the solid state layer su form ₄ welehe on the carrier is liable, at least SWEi these films each ewei chemical substances at &fweisan" under implementation of a ^photo-; Form sensitive compounds dispersed in the solid matter * At the same time or alternatively, films are made up of an alcoholic hydrolyzable solution of methyl orthotitanate which contains a soluble silver salt, e.g. Acetic acid mixture - for example dusted on. The carrier can, however, also be thawed one after the other in two baths of liquid, each with a prior axis. Under these
sensitive
one! Dltanosids dispergioEt is «

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By subsequently depositing one or more mineral films, the "sputtering ¹¹ " process can be halted.

When the used photosensitive hatred evaporates in the vacuum it is preferable to separate several films on the Surface of the solid support in at least one doorway ab »by applying at least one mineral and separates at least one photosensitive mass, the « These films form a solid layer. The minerals and Photosensitive masses can also be vaporized one after the other especially if dyes such as oxides of iron, ice cream or manganese are incorporated into the material layer want; But they can also be vaporized at the same time in a single doorway by using several crucibles in the same TakuumbehMlter, which contain the various substances used, namely the minerals and the photosensitive masses; 00 a better homogeneity of the division is obtained photosensitive masses within the minerals

Preferably at least one film is deposited on the support ab, who is capable of »a thin one that adheres to the wearer To form mineral layer, the composition of which differs significantly from that of the wearer · This is particular the value, when one is on a support made of glass oxide * the element " excluding the alkali metals, the alkaline earth metals and SiIi *

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siumdioxid, jtdoch fltas & t® the Ohrome and / or of manganese deposits, Jn this case, different mechanical properties, in particular under the action of temperature which aas iron for the support glass on the one hand and for the deposited layer on the other; this leads to mechanical stresses in the last-mentioned layer, which facilitate the absorption or adsorption or the chemical combination of the diaeotiazion product or products of the dispersed photosensitive haters; each photosensitive colored sub-layer is exposed to the action of a peening agent after each of the photosensitive sub-layers has been colored.

For example, one or more silicon dioxide films are deposited, one or more of these films containing one or more photosensitive compounds and an oxide of iron, in such a way that the underlayer thus formed is colored yellow-brown " This underclass, at least from that in the dark If a moment is stopped where a photosensitive cash register is incorporated, the effect of an Idchtmotiv is exposed, for example, with a slide provided with a slide Projector is generated, which in the rest of the black / white mbgesauged can be! fold exposure over a sufficient period of time If you put the carrier plate with the underlayer in the darkness of the effect of a fixative that the Share of photosensitive haters who are not influenced by light has been removed. A yellow-brown colored photograph is obtained in this way.

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Goal white is increased. fiifc porosity of the layer, by incorporating an agent which increases the porosity of the layer into the absulo-liidoad (s) PiIm (Q). For example, an element such as water or a plastic material is incorporated into a film deposited in liquid form, the boiling point of which is higher than the solidification temperature of the layer. Solidifying the layer, for example in a slightly careworn air stream after calibration has formed a dry and fixed © layer "then suddenly raises the temperature d © rart _f that the eugesetate E3.ement, water or plastics r ves-teipft and that calibration then Clay of the layer is freed while increasing the porosity. If the layer is provided in solid form, the porosity is increased by creating temperature gradients between the carrier plate and the layer in such a way that the layer is divided into an infinitely large number of small parcels adhering to the carrier; it is sometimes also sufficient to heat the support and the layer and, if necessary, to cool them down in several stages.

Torzugweiß converts the layer into the solid! State, in which it is arranged »to irreversibly remove at least one electrical erosion product by removing at least one film is deposited, in which one has built a product that is irreversible with at least one of the Biesosiatlonsprodukte can combine. The kind of combination doesn’t work

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1022284

always determine with certainty that the essential is that at least one diesel product participates in reversible processes, either that it escapes freely in gaseous, molecular or atomic form or that it is adsorbed or absorbed by one of the substances forming the solid layer or that it sees possibly also chemically combined with at least one of these elements. In this way, it has been found i that various so-called photochromic "Products *, ie products which reversibly change their color depending on whether they optionally a Mchtstrahlung exposed, for example, by reversible dissociation, the formation of group A-CiT, or - OH ₉ or - S0 * fi cause a very strong tendency towards irreversibility if they are dispersed in thin, completely moisture-free mineral layers. For example, a cyanide compound of polyvinyl triphenyl methane, which is phototropic in the wet state, is reversible dissociation and generation of - CJJ in the dry state in a mineral layer, for example made of boride or nitride, exclusively photographic, that is, irradiation in it The coloring is irreversibly modified, the dl © - off group no longer recombining with the polyvinyl triphenyl hethane residue in the dark.

At least one PiIm is preferably deposited, which is a compound of one of the elements of groups Ila, ITb, VIb, VIXb ₉

VIII, HZa ₉ XVa, Va of the periodic system according to Mendeleev contains, as well as at least one photoerapindliehe Hasse from the group of photosensitive organic substances containing chlorides, bromides, iodides of silver, mercury, copper and thallium. In particular, compounds of magnesium and calcium are used , Barium, titanium, zirconium, chromium, molybdenum, tungsten, manganese, iron, nickel, cobalt, boron, alltuttinium, silicon, SiBn, lead, nitrogen, arsenic, antimony and bismuth, iodides in particular are used as photo-sensitive hates together with chlorides and / or bromides, as well as chlorides and / or bromides of silver. Halides of mercury * Copper or thallium are used together with halides of silver *

But you can also use organic photosensitive materials such as derivatives of polyvinyl-triphenyl-methane, or spiranes Organometallic compounds, for example the mercury chloride of the monodithiozone, use the following formula:

6 5 j ο 5

Hg Cl

According to the invention, the photographic article has an im solid state thin layer adhering to the carrier consists of at least one mineral substance in which at least one photo-sensitive cash register is diapered, and this one

00 98 4 _{9/154 ^: o} ^, ^ BAD ORfQINAJ.

Layer is capable of irreversibly at least one of the dissociation processes remove su that caused by the exposure with ' an Idchtmotiv was formed, at least one of these Dissoaiationsprodukte the optical properties of the Modified layer. ./. -

In contrast to the usual photographs, this article is extremely l · * - 3 Idle g / egpa Moisture and other atmospheric influences? © r is also safe against high temperatures · The usual © dead movement of the so-called "development" is not necessary? be it directly by means of feann © ines the HÄtur the photoempfindlielien Hasse adapted HxierjHittels fixed · At least QiiiQs dor elements which dissociate under the influence of light forms a * b £ lichtundurohläesiges either sw. opaque product or a colored product that remains integrated i3u ^ .ar schiolite while at least one product of the? Dissociation is removed, either in gaseous form or in a combination iait an element of the layer, for example in absorbed or adsorbed form.

The fuel carrier consists primarily of glass, one on very resistant material on which a deposited Mineral layer essentially. Strongly adheres and its transparency creates special optical effects. You can also get special effects by using a reflective one beforehand

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mirror-like layer of covered glass is used.

The layer preferably consists of several differently colored superimposed mineral layers, of which certain layers contain a photosensitive mass, these colored and photosensitive sub-layers, with the exception of the surface layer, already exposed to the action of a light motif and then to the action of a tixing agent. «In this way you have an item, possibly decorated with a colored pattern. who is ready to take an additional exposure or an additional pressure »by being exposed to a selected light motif. , ■ ^: '■. . . ■ "- ■ ·: ■

The concentration of the photosensitive composition is also preferred over the concentration of the mineral substance variable inside the layer as a function of the distance from the solid support. You get a bigger one Light response speed when the concentration of photosensitive The mass in the surface area of the layer is increased, especially if this layer is highly absorbent if, on the other hand, the concentration of photosensitive If the height is higher near the wearer, then this will hate better protected by the overlaid mineral layer. in the generally one chooses a compromise between the two

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Special features, a Eomproraii3 _s is economical and is often cause "that a concentration gradient is established in the thickness of the layer,

Part of the goal is the concentration at the photosensitive cash register variable over the surface area of the solid support. Photographic degradation effects are thus obtained when the eonsentration is uniformly variable, for example from the middle up to the perimeter of the door frame, or photographic itself sharply distinguishing contours, for example in a medallion » or round image shape. Interesting optisehe effect © can also be used obtained when one has several different colored photosensitive Sublayers superimposed, their photosensitive Hate more concentrated in certain places in the lower classes are·

In the solid state, the layer preferably has superimposed mineral substances, although these substances can sometimes be intimately mixed.With the superimposition of the mineral substances one arrives at a functional selection, that is, the first substance has to adhere strongly to the carrier _p where one or more Substances are favorable for the even division of the dispersed photosensitive mass, others have a specific effect with regard to elimination

0 0 98 49/15 A3

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certain products of sissosis under the action of Light, on the other hand a mechanical increased strength in such a way that the immediately adjacent Hate or protect substances in the best possible way.

The layer is advantageously porous in the solid state, so that a physical "removal of certain dissociation products", especially in gaseous pons _? as well as easy penetration of the 5 ¹ IxIermitteis is possible

The photographic article preferably has an anchoring - Layer between the solid carrier and the solid state layer, especially when the last rer does not allow good adhesion if it is directly on the Carrier is applied; for example becomes a deposit a synthetic resin film that has been oxidized onto the glass adheres more strongly made »if you have a y @ rankerungesohleht on the Baals of a silane derivative is used, the beets. ■ contains "dl" in are able to chemically on the one hand salt the glass, and «- on the other hand, connect with the synthetic resin.

In this case, the photographic article advantageously has a solid support made of glass, one on the solid support secluded VerankgCTngsseMatit on Silanbasia as well as a Sehloht, which is thin in the solid state and looks at the surface of the grain is liable «In the same way you can

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■ certain metallic carriers on the surface are oxidized »sulfated or phosphated to allow a better anchoring of the later deposited schioht,

Sometimes the layer in the solid state has at least one mineral compound of at least one element from one of the following groups of Menä & Leev ¹ its periodic Sys ** · "« eea £ i -lt & _r OTb ₈ VJb, VIII, ZIXa, ItTa, Ta, and at least. © Ine phötoes-sensitive mass from exercising the organic phetoempfi »älieh @ n- masses of iodides ^: combined with the. 0h3.oriden unö / oi © 3f d @ n Bsjoiniden, the chlorides and / or the bromides that sirb & rsι mercury "Eupfers or thallium · in particular, b @ iiutst msn de than Mneralverbindungen borides, Sfitri large Huh ^ te" (hz & AEE of Silisium _p Aluminum, Iitan that are highly adhesive, colored oxides of Msenj manganese, cobalt, wr 1 this on census but on No J ^ tIl should be exhaustive. Six of the zali3.-rich organic photo-apple fairs also include, for example, di @ l @ derivatives of the Poljvinjl tripheny methane, the benzopyrans, a & x spiropyrans or the eobalt koiapleze «

In advance, mmig®t®m »in the Maeralverbinduag also consists of a Cte.iä; The oxides, apart from their property "can easily be deposited in the form of thin layers in the most varied of directions", are generally strongly adherent

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the supports and often porous. In addition, they practice a vahrscheixtilch catalytic «effect on the speed of reaction the photosensitive mass added to this. The exposure time can therefore be reduced considerably will. It also appears that the oxides are able to coalesce of the grains oppose the photosensitive composition, which means that the grain fineness of the photo is retained.

At least one advantageously differs in the layer Existing 'mineral deposits from the composition of the festival * material carrier, you differences in the behavior of the carrier on the one hand, and the layer on the other hand with different loads such as temperature changes, degree of fire resistance etc, probably cause micro-hair cracking of the layer, which is favorable for dl® removal of one or more disosation products the photosensitive mass and for the subsequent wrestling of a fixative is

A photographic article "as described above "was can easily be named after one or more of the above Embodiments of the method are produced.

The following examples explain the invention without it limit, referring to the accompanying drawings.

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noaimen, in tenim

Figures Ia and Ib sections through a flat solid support during the treatment or through a finished one are photographic articles; ~

Figure Ha is a section through a photographic article ;; -. . '..' V. ■. ■■ '-' -

Pigur Hb shows the graphical representation of the royal tration of photosensitive material as a function of thickness the deposited layer;

Figure HX is a section through a photo-graphic article, which is composed of a flat question and several sub-layers ».

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FIG. Ia shows in section a planar solid carrier “fixed to the treatment; the support 1 consists EUSI a glass Platt © ordinary window glass on Eiesolsäurebasis having a thickness tone 3 mm · The atomizer 2a and 2b directed against the carrier 1 rays 3a or · 3b in the form of cones with 60 ° opening angle, said shot peening 3a and Va in Eontakt with the carrier 1 a fluidity film 4 layers.

Using this procedure, one makes two solutions A and B each. TSm. to get the solution A, one desires

009 849/15

14 grams of AgffO- ίη 20 com of distilled water and mixes them '. Solution with a liquid made up of 22 cm of glacial acetic acid. Then one brings the volume by dilution with ethyl alcohol on 1500cem; so a solution A is obtained, which after a Allowing it to stand in the dark for about a day was completely okay is.

Solution B is prepared by dissolving 2 g of NaCl in 50 ecm of distilled water, the volume is brought to 500 ecm by adding ethyl alcohol} this solution B is transparent *

The solutions A and B are distributed simultaneously by atomizers 2a and 2b in such a way that the conical jets 5a and 3b strike the same area of the? Estatoffträger's 1. The solutions A and B are fed at a pressure of 3 kg / cm. Solutions A and B have a temperature of 20 ⁰ C while the solid carrier 1 has a temperature of 80 ⁰ C. "The atomizer 2a and move 2b susammen parallel to the plane of the carrier 1 'in such a manner that uniform, the solutions A and B on its surface are distributed "at such a speed" SaJ every square meter of surface after four back and forth movements of the atomizers 2a and 2b - these movements increase the thickness of the deposited film 4 - 21 com of solution A and 7 cc of solution B absorbs "The process takes place in the dark.

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T622284

Figure It) is a section through the photographic object, which is composed of the solid substrate 1 from $ lae, on the surface of which there is a thin layer 5 of five micron beading, which consists of an essentially mineral substance 6 and disperses Silver chloride crystals 7 consists of the photographic composite discoid consisting of solid carrier 1 and simmer Sählibt 5 was obtained after the Yerfaiteen obtained from clay figure Xa, after which the thickness of the flüselgkeltsfilms from 4 to about 25 is obtained by atomization Microns and then allowed to air dry at 80 ° C for 10 hours so that a thin layer (Fig. 1b) of 5 microns thick was obtained. It can be seen that the thin splint 5 adheres strongly to the question .1 and that it has great mechanical and chemical resistance; ** <% "This ^ mrde" corroborated by © inen äreiisionatigen Tersuqh in a chamber with accelerated Iriaation where the photographic products alternatively atmosphere of 100 -jt Peuchtlgkelt at 40 ° _p © iner dry JltmosphSre at 80 ° and then a trockeneji atmosphere was exposed at minus 25 °: no harmful or corrosive effect .know, be attached to the article »The thin layer 5 consists of a transparent glass structure 6, which is probably made of kie, hydrofluoric silicate and undoubtedly non-stoichiometrically isohem kffi; by evenly dispersing silver chloride crystals over the entire thickness.

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The photographic article comes with a slide equipped projector exposed for 10 minutes / connection - SeM the article is immersed in a sodium thiosulphate solution, as it is normally used in photography. Simply an immersion time of 30 minutes with subsequent Drying shows the photographic article a black / white reproduction of the idohtmotlves of the! slide.

The thin layer 5 adheres strongly to the microporous carrier 1 and has great resistance to mechanical and chemical attack agents.

Figure IZa shows a photographic article 10 in section, in which some layer thicknesses are exaggerated in the figure in order to make it easier to understand. The photographic article 10 consists of a solid or solid carrier H ₉ that is flat and made of copper with a 2 mm bead and consists of a thin, compact sub-layer 12 of 500 angstroms.

iand AgGl is formed , and a layer

So Dioke of TiO and AgCl * The 12 IMD 13 contain finely in the Ii w ä 13 © ingea £ beit @ t # © md dispergi "RTE silver

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? igur Ub are the concentration (in #) of des on the abscissa photosensitive silver chlorides and on the ordinate die corresponding thicknesses of the sub-layers 12 and 15 of the figure Ha, expressed in angstroms "plotted.

You now proceed: as follows

The carrier 11 made of copper is cleaned by dipping "during 5" Hinuten in concentrated phosphoric acid, danneorgfültig rinsed under distilled water and then for one hour in dry liuft dried at 110 ⁰ g G ©. The carrier 11 is then placed horizontally in a comb above three cells "each containing SiO", TiO and AgOl _9, all three of great purity. A vacuum of 10 Torr is produced in the chamber / then the temperature of the SiO is rapidly increased to 150 ° C. in such a way that 15 Angstroms per second are applied to the surface of the support; during this operation, DER · 5 Msmten dausrfe, the temperature äes AgCl irird of 75O ⁰ C to 8So ⁰ O progressively increased "Hack 5 minutes you interrupt plStslieh the SiO" Suf fer ^ _f by placing a screen over the Mpfehen. Bag @ g @ n is now the that Mpfehön- abdeokend® · Sohiral removed; " ₉ um w® £ 2000 ⁰ O erwlCTit @@ TiO © ntliiltj whereby- dlee'ee see ataf des ^ ifi &terQohi'dht 12 100 seconds' long, abiagerti during: * äi @ i) © S-1Ö0 Süküafi ^ a ver

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reduces the temperature of the AGPLs sunäohst plötslioh up to 810 ° σ, then gradually from 810 ° to 75O ⁰ O. It will be noted a thickness of the layer 13 of about 200 angstroms.

The photographic article is after printing by a light motif, Fixing by a chemical photographic fixing agent, In the present -Sail Shiosulfate, with subsequent drying sufficiently resistant to be exposed to rain without any damage; turn, "aw; know.. The one in contact with the Eupf bearer 11 st @ B @ nS @ € © ii / ä @ 2? Layer 12 contains practically no AgOl; 'his ~ Htftwm% @ n -sie i'rägsr is .. excellent. The strenght Ag01 ~ K @ mi®atmti @ a im. Contact with the. two phases SiO and ■ TiO "des ®a, te3? © dM, © liten 12 and 13 increases the sensitivity fies

10, .the by being a second, he ^R & may be rucldn. The SiO ₉ containing the thickness variable proportions

13 have Hikrp hairline cracks that. Sas fisJL <§ «itteXs as well as rinsing in distilled

is @ £ & -Stiboitt through a photographic article

from «@iaem bottles carrier 21 m <3 ■

! © sylkunststoff, © iner MineralsoMcht 22

009BA3 / 1 B- 3
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consisting of an underlayer 23 based on rid and an organic so-called photoenroisatiscliesi ^w dsri "vat", an underlayer 24 made of polynylMtsrralkunstetöff and "an underlayer 25 made of glass.

The carrier 21 consists of a sheet of transparent polymethacrylate plastic of 5 ram thickness; the sub-layer 23 'consists essentially of chromium chloride and p ^f p-dimethylaminocy & notriphenylmethane with the following structural formula s

- C - (JgH ^ Ή

(CH ₅ ,)

V 2

To prepare these backsheet 23 of genanntsn compound was 5 $> dissolved in a mixture of equal parts of clay Xthylacetat and methanol; 20 cc of Xösung so included are 205 com a solution mixed, the 20 cc Yimylaee "did" 30 cc chloroform, 100: '© em water and 5 fi a> QHT @ m *> compound contains, the latter following © iOssiel aufseistg

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& MB characters (§)

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& m ifetlmerylB & urecoordinated with chromium deals «SeIiSg v © n205 ose one puts NH ₄ OH until one gets ®iaen. '^ E-fferfc * 5"

If-.file ... to- obtained total solution is dusted onto a surface of the carrier 01, dried to harden and then again 5 ml dusted and dried, an underlayer 25 with a thickness of 125 microns is obtained. .Anschließend is dried in perfect as possible ¥ ice in the dark, by 25 a stream of dry air at 60 ⁰ exposing the backsheet C. for 24 hours "in not more than 1 f £ relative humidity contained" The backsheet 24 of a thickness of 100 microns «consisting of transparent polyvinyl butyral is immediately after the drying of the underlayer 23? which is still in the dark »upset with light support» while the general order amf GO ⁰ Q is kept. Finally, one brings the

Section length of 5 mm thickness, which was previously set to 80 ⁰ C

and h & S: '£ ot strong on support 21 in the 17nt®reohief

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849/154 3
ORIGtNÄL BATHROOM

when exposed to darkness and radiation, It should also be pointed out that in this example the cyanide derivative of triphenylmothane annihilates a green warning after exposure to sunlight for one minute. which does not go away when the article 20 is back in. the Darkness is brought in; this article can be aleo ° pho ~ tograflecher article * and no longer has the Phototropic character on. The photographic character of a generally photochromic hatred stems from the Small, weakly bound molecules are produced by raking, for example from HgO and BH- »after the lower layer 23 is formed on the surface of the carrier 21. The photographic article 20 can be used as a colored over-eye plate, inside or outside of buildings, or as a radiation integration element in comparison with similar calibration plates.

However, a transparent polyvinyl butyral can also be used as the underlayer 24, which is slightly yellow when inserted is colored in the FegO ^ mass "

In this case the green coloration obtained is the photografi sohen article 20 after being exposed to sunlight became, very, much weaker as the ultraviolet rays were eliminated by the Ohtereohicht 24 “But one can also a limitation insofar as one can subtract the audio

00 9 84 9/1543

23 We «χι readsiamtm places ata carrier 21 aTascheläet. If you now leave itiohii © iaffekteii _s, you get the entepreoiiende pho-

Patent application

009849/1543

Claims (1)

.-. si - 1) 1.) PMtogrsf isolates teti & el with a , - exampleveiäe in üOsm one of one düsmefi XichteMpfinäliehen M one in the solid gustaad b © fia & licSs® oiläim © tiaä ^ haftesj.de Sshleht (5) »Tsestestand mxm ^ enigsteug; buckets of fabric (6) j, intlem at least one ph © toe © nsi "bl® bass © .. pergiert tat» «fobei the slip is right, i # at least one of the" formed upon exposure by a power factor JDiBBOBiationsproducts irreversibly to remove _e iä3id at least one § @ ^ Bisso ^ iationsprodüktd the optical of the damage 2 ») Piiotog3? A £ iecher article according to claim 1> Sadureh ge that the test substance carrier? (1) au @. 3 ») Piiotografischer iSftikel mae & denotes, ate the sweet stuff. 0 09849 / .f-5'4 3. BATH ORIGINAL . · .'-.... ■ "■■■ - 32—.-._- ^v 4 ») Photographic article according to claim 1, characterized in that that the concentration of the photosensitive Mass compared to the concentration of the mineral inside it . the layer as a function of its distance from the solid carrier is variable. 5 «) Photographic article according to claim 1, characterized in that the concentration of photosensitive The cash register is variable over the surface area of the solid carrier is, 6.) Pliotograflecher article according to claim 1, characterized in »that the layer in the solid state consists of several superimposed minerals 7.) Photographic article according to claim I _9, characterized in that the layer in the solid state is porous « 8 “) Photografisoher article according to claim 1, characterized by an anchoring layer between the solid support and fixed layer " 9 ») JÄntogiTafischer article according to claim 1, characterized aurc .- 'i" äi.ä! Poal'Btoffträger from' 01ae and .eine Terankerunga- OÜ90 A 9/1 ύΨΨ ^{] ΐ} ~ - "' ^uv ' ^ ^: '/ --- ■;': _ ■■ '" ■ BAD ORIGINAL - 33 - ■. '■' "." ■■. ' . '; ■■ - Silane-based layer deposited on the solid support 1st, is thin and adheres to the latter 10.) Photographic article according to claim 1, characterized in that »the layer which is in the solid state at least one mineral compound of at least one of the elements of groups Ha, IYb, TIb, TIIb, VIII, IHa, HTa, Ya des periodic Mendeleev * see system as well as a photosensitive hater from the group of organic photosensitive Kassen, of chloride, bromide, iodide of silver »mercury Having copper, thallium. 11.) Photografi cal article according to claim 10, characterized in that * indicates that at least one mineral compound is an oxide. 12 «) Photographic article according to claim 10, characterized in that at least one mineral compound (25) differs substantially from the composition of the solid carrier (21). 13.) Ancestors for the production of a photographic article consisting of "a solid carrier or test material carrier, for example in the form of a plate, and" liier illlmmeu llöhfe "eiap-f Lridl lohoa" Schi .chb, iimhimomlin'r: after οΐινωι ύητ i BATH ORIQINAL. ■ ο - 54 - the claims, characterized gekennseiohnet that the! is deposited in Piim solid carrier least © on the surface, which is capable in the solid state to form a thin and adherent to Sräger layer, wherein the layer comprises at least one mineral _y at least one phötoempfindliohe in the It is dispersed, which under the action of light leads to dissociation products "of which at least one codifies the optical properties of the thin layer" whereby this is capable of irreversibly eliminating at least one other product of dissociation. H.) Procedure neon Inspruoä 13, denoted by it, dad by Here division; A solid soil is located and thin and adherent vision the photografisohe irtiScel of the exposure is exposed by a LiohtmotiT and that subsequently the photographic article is exposed to the action of a fixative that nib. <; converted photosensitive mass removed. 15) The method according to claim 13, characterized in that that in liquid form at least one film that at least a layer that can be converted into solid oil and at least one photo-sensitive mass is deposited, and that the Hlsi is then converted into a solid layer, BATH ORIGINAL V 35 - "■ ■ - 16 ·) Method according to claim 13 # characterized in that that in the liquid pore there is at least one filament of at least one ine has a substance that is convertible in mineral matter »deposited is, and that then in the film at least one photosensitive Hasse is incorporated and the film is then converted into a solid layer. 17.) The method according to claim 13, characterized in that that Sm wünlgsteaas Girnjim work process several films of different beginnings from | g @ separated, theunt @ ^ # inanäie2? react to form a layer containing at least one mineral substance, ix ^ Stnvvönigffteae 'a photosensitive mass is dispersed. 16 ') The process according Ampm®h 13 _»9 characterized in that in at least one operation m®hx> @re elm untersohiedli- € fusammensetisungen ° deposited who ®n € that is capable sindp eime in the solid state thin and T em rager adhesive layer to form, at least gw @ i this. Films each have two chemical substances that form a photo-sensitive compound that is dispersed in the substance-alcoholic substance. 19.) The method according to claim 13, characterized in '', that on the surface of the pestilent under 0 U 9 ίΠ 9 / ΪΆ 4 3 162228A At least one mineral material is attenuated, the film forming a moisture material layer, which is thin and adheres to the carrier, is deposited, iiraem at least one photosensitive cash register is dispersed. 20.) Method according to claim 13, characterized in that that several films on the surface of the solid carrier in at least one Yorgang be deposited by under Vacuum at least one mineral substance and at least one photoeapfIndllohe mass evaporated or vaporized, wherein these films form a solid layer. 21.) The method according to claim 15 »characterized · that at least one film is deposited on the support which is capable of a thin mineral layer adhering to the support Jeu, the composition of which is essentially different from that of the Carrier differs. 22.) The method according to claim 13, characterized in that that successively several films that are able to form a mineral layer consisting of several sublayers, are deposited, each sub-layer at least one Mineral material of one color different from that of another sub-layer, with several differently colored sub-layers one in the dispersed state photo-sensitive 009849 / 1S43 BATH Flindllche have mass, and that each colored photosensitive submits a light motif - and then the action a fixative is exposed after each of the eliigsf & rb- » th photo-sensitive sub-layers built 1st 23.) The method according to claim 13, characterized in that the layer in the solid state is in the laying ▼ replaces, irreversibly, at least one product of the association "u remove »by increasing the porosity of the layer. 24 «-) Method according to claim 23 * characterized in that that the porosity of the layer is increased »by going into the film, which one separates, incorporates a means »that is able» increase the porosity of the layer *. 25.) The method according to claim 13 »characterized in that that the layer in the solid state is put into position vsrsetst, irrereraibel at least one Disaoaiationeprodii j su remove by "abaoheidet at least one film" in the let a product incorporated which is capable of irreversibly with at least one of the bending association products associate. 26.) The method according to claim 13, characterized in that that at least one connection of an element of the groups 0098 49/1 5 A3 ■ - 38 - IXa ₉ ZTb, TIb ₉ TIIb ₉ TIII ₉ IHa ₉ ITa ₉ Ta of the periodic Hendeleer ¹ see system containing TiIa and a photo-sensitive mass from the group of photosensitive organ! » see masses of "chloride * bromides, iodides of silver, mercury, copper and thallium being deposited" 27.) Photographic article, made like after a Method according to one or more of claims 15 - 26 « 009049/154 3 BATH ORIGINAL