DE2056340A1 - Process for applying colored or color-emitting materials - Google Patents

Description

47 429

A r? Nelr! He j_ A.5J. Stale * ¹ / Narrufacturin ·· * · Comr>ar> v

State nf Delaware, United States of America Illinois , United States

j Procedure for applying τοπ colored or color-emitting ¹ materials

The invention relates to methods of making ceramic materials. In particular concerns the Invention of a method of making screens for Color television tube ^ in which uniform layers of a Phosphor can be deposited on the tube surface as an intermediate stage in the manufacture of these screens.

Screens for cathode ray tubes dos type that are suitable for use in color television sets usually a transparent faceplate, the numerous, separately formed on it, the same pattern having. Each of the patterns can consist of series of stripes, lines or dots made of red-emitting, green-emitting and blue-emitting cathodoluminescent materials exist, which are capable of color fluorescence when bombarded with electron beams »A multicolored one The screen of a cathode tube of this type can be Other subsequent photo printing operations can be made by separately applying a photosensitive Materials or readsist or covering material ^

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is used to apply each of the special ■ color emitting fluorescent materials to the inner concave front surface of the lens. To produce a dotted color screen by this method, for example, a thin layer of a negative-acting photosensitive substance and one of the fluorescent materials is deposited on the concave surface of the faceplate and separately irradiated with light that is incident through a suitable negative or perforated mask. This causes the photosensitive substance struck by light to harden and adhere to the plate in the form of numerous point-like areas. The unexposed areas of the screen are practically not hardened and are then removed by dissolving the unhardened substance with a suitable solvent and washing it off the surface of the plate. In this way, the unexposed, radiation-sensitive binding agent and the luminescent substance adhering to it are removed, with numerous individual elements remaining on the screen. This means that well over two thirds of the luminous substance are removed together with the non-exposed photosensitive binder. This process is repeated to form the second and third color-emitting cathodoluminescent areas, in that a new layer of the photosensitive material, a different color-emitting fluorescent substance and a differently oriented light source are used in each case. As a result, numerous three-color elements arranged next to one another are achieved, which make up the screen of the glass plate of the three-color picture tube. The order in which the various proportions of the color- emitting luminous substances are applied is not critical. A subsequent annealing or

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Heating removes the volatile components and leaves the screen, which - the luminous substance in the form of a Has pattern as a complete element.

In the past, the photosensitive masking material was deposited and the corresponding phosphor particles by first applying a film of the photosensitive material the plate was applied and the phosphor in the form of a powder was arranged on it, "for example by the "known processes of dusting or precipitation or by applying a suspension of the phosphor in the light-sensitive material, "for example by the usual slurry method. The layer was im substantially dried "before subjecting it to a different exposure.

The evenness of the screen and the color balance require that the dots of the various color areas be of the same size, free from color contamination from adjacent color-emitting phosphors and suitable adhesion to the plate surface demonstrate.

The size and adhesion of the individual points depend on several factors, such as the size of the mask openings, the density of the phosphor particles contained in or on the photosensitive layer and the length of exposure, which is directly related to the curing rate of the photosensitive Layer stands.

The hardening of the material in the known, negative-acting sensitized layer is a function of

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BAD ORJGlNAt

Time accelerated by heat and light, essentially in the ultraviolet range. The drying of the negative-acting, sensitized layer can therefore have a duration of 6 to 10 minutes at a temperature in the range from about 27 to 38 ° C. and initiates a so-called "dark hardening reaction" over the entire process
Screen area, which tends to apply the phosphors in the image areas and the non-image areas uniformly to the sensitized layer
to tie. This process is not a rapid conversion, but is a continued reaction, although the temperature is lowered after drying. It should be noted that a lesser degree of continued reaction is initiated and effected even at room temperature and for the usual duration. After exposure, curing is greatly accelerated in the exposed areas. The continued reaction therefore proceeds in the separately covered areas of the screen during exposure and is directly related to the length of time of exposure. If the exposure is of short duration during exposure, the associated continued curing will be of such a degree that
less hardening of the one carrying the phosphor
Masking material enters the covered areas. The sensitized material is therefore easier to read
Remove from covered areas during the appropriate development stage of the screen formation process.

In this description and the claims
the term "continued curing reaction" in the
Sense of the previously known literature for the hardening of the cover material used by the dark reaction
is initiated during the drying of the cover layer

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and which continues during the exposure of the screen in the covered areas, i.e. for one continued reaction initiated in the dark.

The natural color of the fluorescent material is a major factor which determines the duration of the exposure in the formation of the corresponding I color screen pattern. This important The property of cathodoluminescent phosphors relates to the degree of transparency or opacity of the color emitting material in question Fluorescent crystals. Phosphors that are essentially are transparent are usually classified as having a desirable white intrinsic color, which facilitates the passage of light during the manufacture of the screen. The different color emitting cathodoluminescent phosphors, which according to the state of the Technique commonly used have representative intrinsic colors with different degrees of transparency, which, when used for screen production, require an appropriate exposure range. If the resist or cover material is assigned a blue phosphor, such as zinc sulfide, essentially has a white intrinsic crystal, a relatively short exposure time is required to achieve the desired to harden punctiform areas of the photosensitive layer and to achieve a hardening depth, which causes the dots to adhere to the plate surface. A green phosphor, such as zinc cadmium sulfide, has a slightly yellowish tinge due to its cadmium sulfide content Intrinsic color; a slightly longer exposure time is therefore required in order to allow the phosphor to penetrate and to achieve the desired degree of hardening of the colored dot area in the cover layer. There the continued reaction in the darkened area of the screen that occurred during the drying of the

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sensitized cover layer was initiated, turns white .ter during the period of the pattern-shaped exposure continues, a higher degree of hardening of the darkened cover or resist material is effected. This requires a longer stage of development to partially remove hardened material from the darkened area of the screen. For example, the blue area require a development time of nearly four minutes, while the green area will require approximately six minutes can.

The hardening of the covering material in connection with the deposition a red fluorescent substance, such as zinc cadmium sulfide, requires an even longer exposure time because these fluorescent particles, which have a yellow-orange color of their own and because of the higher cadmium sulphide content have a lower transparency than the green particles, noticeably slow down the passage of light radiation and the resulting hardening rate of the covering material. Therefore, in order to achieve the degree of hardening that is necessary for the proper adhesion of the red colored dots is, therefore a much longer exposure time is required than for the other Parbleuohtstoffe that to be used in the approaches for the screens. The openings in the perforated mask remain constant, however, the longer duration of the exposure tends to form larger dots than he wishes. The ultraviolet radiation that images the red dots reaches a duration necessary for training a diffusion value is sufficient in connection with the continued hardening reaction in the darkened areas the hardening of the Resistina Lerial assigned to the red lamp toff beyond the desired limits of the

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red points in the edges of the already previously deposited neighboring Parbpunkt continues into, creating a disturbing Adhesion of red phosphor forming impurities to these adjacent colored points will. This cross-contamination with red phosphor reduces the purity of the fluorescent color of the neighboring ones green and blue phosphors. In addition, this longer exposure time extends the continued curing reaction in the covered or darkened ones Areas of the resist material, which makes the corresponding removal of the resist material difficult. It can therefore be seen that the continued reaction in the darkened areas in view of various aggravating problems both on quality and on reconditioning. In summary, these difficulties express themselves in the form of larger than desired color dots, as cross contamination of color-emitting phosphors, that previously processed te portions of the luminescent screen exposed to prolonged development and that as a result a long manufacturing period is required.

With the known methods of "damming up ¹¹ " on fluorescent screens, difficulties occasionally occurred which adversely affect the finished tube. These difficulties manifested themselves as so-called "pick-outs", i.e. areas in which the phosphor did not adhere well to the screen and as a result fell away, leaving free spaces and in an uneven light emission, which was caused by uneven distribution of the phosphor and the resulting different thicknesses of the individual elements.

It is a general object of the invention to provide a method of manufacturing screens for color television

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made available to be arranged in the dry phosphor particles uniformly in imagewise configuration on a front plate or front plate and the mentioned disadvantages are avoided "A further aim of the invention is a method for producing \ screens for color television, uniform in the dry phosphor particles in imagewise configuration be deposited on a front plate after 'the front plate has been exposed to actinic radiation in an image-wise arrangement. The aim of the invention is also a method for producing screens for color television tubes using a positive-acting sensitizer.

In the following description the term ⁿ is powder-receptive, solid, photosensitive organic layer "used to describe an organic layer, the black after exposure to actinic light and by embedding powder particles of a predetermined size in a single layer on the surface of this organic layer of a predetermined contrast or a reflection density (R _d) is capable of forming. the value of R _d of a photosensitive layer, which is explained in more detail later, a photometric measurement of the difference of the blackening is not developed areas, and with black powder developed areas. The terms "physically embedded" or "physical force" are used to indicate that the powder particle is subjected to an external force other than an electrostatic force or the gravitational force resulting from the dusting or spraying of powder particles onto a substrate or the like that of an additional force to these forces

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is subjected. The terms "mechanically embedded" or "mechanical force" are used to indicate that the powder particle is a manual or mechanical force, such as a lateral, reciprocating or circular rubbing or scrubbing effect. The term "embedded" is used to indicate that the powder particle has at least a portion of the photosensitive layer is displaced and held in the recess thus formed, that is, that at least a portion of each particle is below the surface of the photosensitive layer.

These objects can be achieved by the method according to the invention in that the front plate of a cathode tube is coated with a solid, light-sensitive organic layer which is used to form a value R, from 0.2 to 2.2, preferably an R, from 0.4 "to 2.0 is capable of exposing the light-sensitive organic layer in an image-recording manner to actinic radiation, so that a potential R ^ of 0.2 to 2.2 is generated, on the layer of organic material free-flowing phosphor particles (phosphor particles) are applied whose diameter is at least one axis is at least 0.3 microns but less than 25 times the thickness of the organic layer, the phosphor particles are physically embedded as a single layer in a layer on the surface of the photosensitive layer at a temperature of the layer below the melting point of the phosphor powder and the organic layer so that an image is obtained the B-rich _e of each part vary in density in proportion to the exposure, and that the non-embedded particles are removed under · development of an existing particulate phosphor pattern of the organic layer. The front panel ^ is exposed

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can be fired to make the solid, photosensitive to volatilize the organic layer and at the same time to fuse the phosphor with the front panel. The front panel is then again covered with additional solid, light-sensitive organic layers with or without Burning coated and processed in the same way to produce phosphors or phosphors with different To deposit colors in the appropriate arrangement and / or the first phosphor image with additional Reinforce fluorescent of the same color. After all "phosphors have been deposited in an image-wise arrangement, the faceplate is fired to remove all organic material from the face of the faceplate.

Because according to the invention the phosphors after exposure are embedded in the photosensitive layer, the inventive method has the obvious advantage that far less phosphor is required to manufacture a cathode tube and that the exposure time each light-sensitive layer independent of the inherent color of the phosphors used is, creating a more uniform size of the phosphor dots is achieved. Furthermore, the preferred, positive-acting photosensitive layers of the invention the additional advantage that the so-called "continued" occurring in the known processes Curing reaction "neither degrades the sharpness of the phosphor dots nor cross-contamination caused by fluorescent dots. Instead, slight overexposure makes the according to the invention used, positive-acting, light-sensitive layers increases the sharpness of the phosphor dots and eliminates any possibility of cross-contamination.

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The invention provides a method for forming a phosphor deformation image, in which the deformation image is developed by embedding phosphor particles of a predetermined size in a layer on the surface of a powder-receptive, solid, photosensitive organic layer. This process makes use of the discovery that numerous solid organic layers, when applied in thin layers, partly in their naturally occurring or synthetically produced form, partly with the addition of additives, reduce the powder absorbency and / or sensitivity to actinic radiation to regulate, can have surface properties which can be varied by exposure to actinic radiation within a critical range between a form which is receptive to particles and a form which is not receptive to particles. As will be explained below, are the absorption capacity for particles and the Niehtaufnahmefähigkeit for particles of the solid, thin layers of the size of the particles, the thickness of the solid thin film and the developing conditions such as the S _c hichttemperatur dependent.

In general terms, the inventive method for forming phosphor images differs from known methods in various, ingenious and unpredictable ways. For example, the an image-forming phosphor or phosphor particles not only prior to exposure of the photosensitive ones Layer dusted with actinic radiation, rather on the other hand, under wet physical force after exposure of the photosensitive layer to actinic Radiation on the surface of the photosensitive. borrowed organic layer applied. the

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The photosensitive layer has a relatively soft or particle-absorbent character, so that essentially a single layer of phosphor particles or individual small agglomerates of a predetermined size is at least partially embedded on the surface of the photosensitive layer under the action of moderate physical force. The surface quality in the area capable of absorbing particles is at most only slightly soft, but not fluid, as in known methods. The nonabsorbable relatively hard or particles B _e integrity of the photosensitive surface in the non-image areas is formed such that detaching when applying phosphor particles of a predetermined size at the same moderate physical force few or no particles are sufficiently embedded to removal by moderate Effect of resisting the blowing of air against the surface. Particles remaining in the non-image-bearing areas are easily removed by rubbing the surface with a soft sponge. Hence, the developed images, and consequently the further processed screens, are by practical lack of "pick."

out "and show substantially uniform brightness over the entire screen the previous wasteful application of the fluorescent material is eliminated by the method according to the invention Avoided on both image-bearing and non-image-bearing areas, since the phosphors only apply to the desired ones Image areas are applied.

For the purposes of the invention, the solid, light-sensitive, organic layer consisting of an organic material naturally occurring or

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synthetically produced form or from a mixture this organic material with plasticizers and / or photoactivators to adjust the powder absorption capacity and sensitivity to actinic radiation may exist, the ability to have a predetermined Contrast or Ra using an appropriate one black developing powder under the developing conditions to train. The powder-absorbing areas of the layer (unexposed areas of a positive-acting light-sensitive material or exposed areas of a negative-acting light-sensitive material) must have such a degree of softness that suitable particles can be moved in by mild physical forces a layer can be embedded on the surface of the photosensitive layer. The shift should but be so hard that film slides can be pressed against the surface without damaging the surfaces stick to each other or be damaged, even if slightly heated by high-intensity light radiation will. The film should also have such a degree of toughness that it will remain intact during development remain. If the R i value of the photosensitive layer is below about 0.2, it is the photosensitive layer Layer too hard to absorb fluorescent particles in a suitable concentration. If the value R, on the other hand is over about 2.2, the photosensitive layer is so soft that it is difficult to to keep the film intact during physical development and that the layer tends to stick Slides to adhere, so the use of a vacuum frame or contact exposure device is excluded. If the value R ^ is above 2.2 furthermore, the photosensitive layer is so soft that more than one layer of the phosphor particles is deposited

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can be and as a result the faithful image reproduction is lost and that the layer by mechanical forces can be shifted, which leads to a distortion or destruction of the image. Therefore, for the sake of-. The light-sensitive layer has the ability to use a suitable black developing powder under the developing conditions, a value of R-, within the range of 0.2 to 2.2, preferably 0.4 to 2.0.

κ The value R. of a positive-acting photosensitive Layer called R is a photometric one Measurement of the reflection density of a photosensitive layer developed with black powder after a positive-acting, photosensitive layer was exposed to actinic radiation, which is sufficient to the exposed To convert areas into a form that is essentially not receptive to powder (lightening of the background, clear the background). The value R-, a negative-acting photosensitive layer called R ^, is a photometric reading of the reflection density of an area developed with black powder after a negatively acting, light-sensitive layer with actinic

f shear radiation was exposed, which is sufficient to convert the exposed area into a powder receptive area.

The reflection density of a solid, positive-acting, light-sensitive layer ( ^R _dt) ) is determined by applying the light-sensitive layer to a white substrate and exposing it imagewise to sufficient actinic radiation to brighten the background of the solid, positive-acting, light-sensitive layer black powder (made from 77% Pliolite VTL and 23%

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Neo Spectra carbon black was produced) on the "exposed Layer is applied, the black powder under developing conditions as a single layer in a layer on the surface of this photosensitive layer physically is embedded and the non-embedded

\ Particles are removed from the photosensitive layer. The developed organic layer, the image-trans-

Having \ constricting portions and substantially powder-free, non-image-carrying areas is placed in a standard Photoraeter with a graduated scale for O to 100 fo reflection of the incident light or with an equivalent density scale. The instrument is set to 0 (density 0; reflection 100%) on a powder-free, non-image-bearing surface of the light-sensitive organic layer and an average reading R of the powder-developed area is then determined. The reflection density is a measure of the degree of blackening of the developed surface, which is related to the concentration of particles per unit area. The reflection density of a solid, negatively acting, photosensitive layer (R (J _n ) is determined in the same way, with the exception that the negatively acting, photosensitive layer is exposed to sufficient actinic radiation to convert the exposed area into one for powder If, under the development conditions, the value R- is between 0.2 (63.1 1 ° reflection) and 2.2 (0.63 # reflection) or preferably between O.4 (39.8 $> reflection) and 2.0 (1.0 $> reflection), thus the solid, photosensitive organic material coated in the form of a layer is suitable for the purposes of the invention.

Although the value R ^ of all light-sensitive layers * with embedded black powder.,

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was determined using the aforementioned black developing powder and a white substrate R, just a measure of the suitability of a photosensitive Layer for the purposes of the invention.

As the value of R-, any photosensitive layer apart from the chemical composition of the light-sensitive layer, it depends on numerous other factors, the photosensitive layer becomes best by its value R, under the developing conditions the intended use. The positive-acting, solid, light-sensitive ones suitable according to the invention organic layers must be receptive to powder in the sense that among the predetermined ones Development conditions the aforementioned black developer powder as a one-part layer in a layer on the surface the unexposed layer can be embedded and a value R ^ from 0.2 to 2.2 (preferably 0.4 to 2.0) and they must be photosensitive in the sense that after exposure with actinic radiation most of the exposed area iu. uen under the predetermined development conditions

for particles not absorbable state (lightened background) can be transferred. Different Expressed, the positive-acting, photosensitive layer must have a certain powder absorption capacity of its own and have photosensitivity. The positive-acting, light-sensitive layers are evidently through a light-catalyzed curing effect, such as photopolymerization, photocrosslinking or photooxidation, in the transferred for powder non-absorbent state. Some of these photo-curing reactions are dependent on the presence of oxygen, such as the photooxidation of ethylenically unsaturated acids and esters with

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internal unsaturation, while others are inhibited by the presence of oxygen, such as reactions based on the photopolymerization of vinylidene or polyvinylidene monomers alone or together with polymeric materials. For this reason, solid, positive-acting, film-forming organic materials are preferably used which have no terminal ethylenic unsaturation. As already mentioned, positive-acting, solid, light-sensitive organic layers are preferred, as the so-called, known "Continued curing reaction ¹¹ neither degrades the sharpness of the phosphor dots nor causes mutual contamination or cross-contamination of phosphor dots.

The negative-acting, solid, light-sensitive organic layers suitable according to the invention must be in the Sense that being photosensitive by exposing with that actinic radiation most of the exposed areas of the photosensitive layer from one of the predetermined ones Developing conditions for powder into a non-absorbent form under the predetermined developing conditions be transferred for powder absorbent form. In other words, it must be negative effective, photosensitive layer has a certain minimum value of the photosensitivity and the potential Have powder absorbency. The negative-acting, light-sensitive layers are evident through a light-catalyzed emollient effect, such as by photo-depolymerization, in the receptive to powder Porm convicted.

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In general, the positive-acting, solid, light-sensitive layers that are suitable for the purpose comprise of the invention, a film-forming organic material in natural or synthetic form or a mixture of this organic material with plasticizers and / or photoactivators to adjust the powder absorbency and sensitivity to it actinic radiation. To suitable positive-acting, film-forming organic materials, which by Oxygen are not inhibited, include ethylenically unsaturated acids with an internal double bond, such as abietic acid, resin acids, partially hydrogenated resin acids, v / ie those under the name "Staybelite resin" distributed compounds, tree resin, esters of ethylenically unsaturated acids with internal double bonds, Methylolamides of maleic oils, such as soy lecithin, partially hydrogenated lecithin and dilinolenyl-alpha-lecithin, partially hydrogenated resin acid esters, as sold under the name “Staybelite-Ester”, resin-modified ones Alkyds, polymers made from ethylenically unsaturated monomers, such as vinyltoluene-alpha-methylstyrene copolymers, Polyvinyl cinnamate, polyethylene methacrylate, vinyl acetate-vinyl stearate copolymers and polyvinylpyrrolidone, coal tar resins such as coumarone-indene resins, halogenated Hydrocarbons such as chlorinated waxes and chlorinated polyethylene. Too positive-looking, light-sensitive Materials that are inhibited by oxygen include blends of polymers such as polyethylene terephthalate / sebacate or cellulose acetate or acetate / butyrate with polyunsaturated vinylidene monomers, like Ethylem; Lykoldiaerylat or -dimethacrylat, Tetraethylene glycol diacrylate or dimethacrylate.

Although many have a positive, film-forming effect

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organic materials have the required sensitivity to light and powder absorbency at predetermined Developing temperatures generally preferably, the film-forming organic materials with one or more photoactivators and / or plasticizers to mix in order to optimize the photosensitive layer To give powder absorbency and photosensitivity. In most cases, the photosensitivity of an element can be increased by several times by incorporating it a suitable photoactivator, which is capable of forming free radicals, which catalyze the photosensitive reaction and the amount of Lower photons that cause the desired physical change is required »

Suitable photoactivators capable of forming free radicals include benzil, benzoin, Michler's ketone, diacetyl, phenanthraquinone, p-dimethylaminobenzoin, 7,8-benzoflavone, trinitrofluorenone, deoxybenzoin, 2,3-pentanedione, dibenzyl ketone, nitroisatin, di - (6-dimethylamino-3-pyradil) methane, metal naphthenates, N-methyl-N-phenylbenzylamine, pyridil, 5,7-dichloroisatin, azodiisobutyronitrile, trinitroanisole, chlorophyll, isatin and bromoisatin. These compounds may be used in a concentration times the 2-0.001- to the G _e Klobuk the film-forming organic material corresponding to (0.1 i> 56 to 200 by weight of the film-forming material). As in most catalytic systems, the best photoactivator and its optimal concentration depend on the film-forming organic material. B _e agreed Phctoaktivatoren respond better to one type of F: ibildners and can within a fairly. .. _b s concentration range to be effective, while others are all film-forming agents are suitable within wide concentration ranges in combination with substantially.

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The active as photoactivators acyloins and vieinalen Diketones, especially benzil and benzoin, are preferred. Benzoin and benzil are within wide concentration ranges effective with essentially all film-forming, water-sensitive organic materials. Benzoin and benzil have the additional advantage that they act on film-forming photosensitive layers exert a softening or emollient effect and thereby the powder absorption capacity of the light-sensitive Increase layers. If benzil is used as a photoactivator, it should preferably be in an amount of at least 1 percent by weight of the film-forming organic Material (0.01 times the weight of the film former).

Dyes, optical brighteners and light absorbers can be used alone or preferably in connection with the named, photoactivators that form free radicals (primary Photoactivators) are used to increase photosensitivity the photosensitive according to the invention Increase layers by converting the rays of light into rays of light with longer wavelengths. the end For reasons of expediency, these secondary photoactivators (dyes, optical brighteners and light absorbers) referred to as "super photoactivators". For suitable dyes, optical brighteners and light absorbers include ^ -Methyl-V-dimethylaminocoumarin, Calcofluor yellow HEB, Calcofluor white SB Super 30080, Calcofluor, Uvitex W cone, Uvitex TXS cone, Uvitex KS (described in Textil-Rundschau 8 (1953), 339), Uvitex WGS cone, Uvitex K, Uvitex CF cone, Uvitex W (described in Textil-Rundschau 8, (1953), 340), Aclarat 8678, ulancophor OS, Tenopol UWPL, JIDAC S-8844, Uvinul 400, Thilflavin TGN cone, aniline yellow - S (nied.cone) »

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Setoflavine T 5506-140, Auramine 0, Calcozine yellow OX, Calcofluor RW, Calcofluor G-AO, Acetosol yellow 2 RIiS-PHF, Eosine "bluish, Chinoline yellow-P cone, Ceniline yellow S (high cone), Anthracene blue violet fluorescence , Calcofluor white MR, Tenopol PCR, Uvitex GS, Acid-yellow-T-supra, Acetosol yellow 5 GIS, Calcocid OR. Y. Ex. Cone, Diphenyl-brilliant-flavine 7 GPP, Resoflorm fluorescent yellow 3 GPI, Eosin yellowish, Thiazol fluorescor G, Pyrazalone orange YB-3 and National PD & C yellow. Individual super photoactivators may respond better to one type of photosensitive, organic mushroom builder and photoactivator than others. Furthermore, some photoactivators work better in conjunction with certain classes of brighteners, dyes and light absorbers, but the most advantageous combinations and proportions of these materials can usually be determined by simple experiments.

As already indicated, plasticizers can be used to give the photosensitive layer optimal powder absorption to rent. With the exception of lecithin, most of the film-forming ones are photosensitive organic materials that are suitable for the purposes of the invention, not capable of absorbing powder at room temperature, but capable of absorbing powder above room temperature. It is therefore desirable to have a sufficient Amount of a plasticizer to be added in order to give the photosensitive layers powder absorbency at room temperature (15 to 30 ° C) or ambient temperature and / or the R. range of photosensitive Layers to expand.

Although numerous softening agents, such as dimethylsiloxanes, Dimethyl phthalate, glycerin and vegetable

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Oils are suitable as plasticizers, but benzil and benzoin are preferred, as these materials, as already indicated, have the added benefit of the photosensitivity of the film-forming organic materials to increase. Benzoin are used as plasticizer photoactivators and benzil .. preferably in a concentration of 1 percent by weight to 80 percent by weight of the film-forming, solid organic material is used.

Among the preferred, positive-acting, light-sensitive Film imaging that does not have a conjugated terminal ethylenic Have unsaturation, include unsaturated acids with internal ethylenic unsaturation and their Esters, in particular phosphatides, resin acids, partially hydrogenated resin acids and partially hydrogenated resin esters. If these materials are combined with suitable photoactivators, preferably acyloins or vicinal diketones mixed with super photoactivators, less than 2 minutes of exposure is required to achieve the The background of light-sensitive layers can be brightened and the layers can form fluorescent patterns can be developed with the desired arrangement.

In general, the negatively acting photosensitive layers suitable according to the invention comprise a film-forming layer organic material in natural or synthetic form or a mixture of the organic Materials with plasticizers and / or photoactivators to adjust the powder absorption capacity and Actinic Radiation Sensitivity. To suitable negative-acting, film-forming organic materials include N-benzyl-linoleamide, dilinoleyl-alpha-leci thin. Castor wax (glycerin-12-hydroxysteara t), alkyl uglycol monohydroxystearate, Polyisobutylene and Polyvinyi; :: tearat.

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Among these compounds are castor wax and other hydrogenated esters of ricinoleic acid (hydroxystearate) preferred. These materials can be used in the same way as the positive-acting, light-sensitive, film-forming organic Ilaterialien are mixed with plasticizers and / or photoactivators.

Some solid, photosensitive organic film former may be used, "to produce either positive or negative working light-sensitive layers. Thus, for example a layer resulting from poly (n-butyl methacrylate) containing 20 ψ benzoin contains (20 G _e weight parts benzoin per 100 parts by weight of the polymer ) to good positive acting images. By increasing the Benzoingehaltes to $ 100, the poly (n-butylmethacrylate) -S hicht _c is converted into a good negative acting system.

The support to which the screen is applied, and preferably the inner or concave surface the faceplate of a cathode tube is first cleaned thoroughly. This cleaning can be done by successive washing carried out with alcohol followed by rinses with distilled or deionized water. Douching with a mild one alkaline solution and a subsequent rinse with a weakly acidic solution are also effective, However, each of the specified operations should be thoroughly washed with distilled or deionized water follow. If an acid bath containing halogen ions is used, sufficient rinsing should be provided ensure that they are removed, as these are extraordinary reactive ions tend to be applied later Poison fluorescent substance.

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BATH

Those for forming a value K, or R, O ₀ 2 - ?. _A capable, solid, light-sensitive, film-forming organic layer can be applied to the front panel, for example by spraying on, vortex bleaching from a solution in a solvent or by coating the front panel with a solution in a solvent. That

Photosensitive material is preferably sprayed upwards applied to the carrier and the coating gradually by successive spraying operations and not built up by a single process. Multiple spraying allows one to be applied ™ more uniform coating. Unlike other procedures, which are dependent on a certain degree of tack being maintained, this coating process can can be done at almost any temperature and humidity.

The photosensitive layer must be at least 0.1 micron and preferably at least 0.4 micron thick in order to hold the phosphor powder in place during development. If the thickness of the photosensitive layer is less than 0.1 micron or if the diameter of the phosphor powder is more than 2.5 times the thickness of the layer, the photosensitive layer does not hold the phosphor with the required strength. In general, the light-sensitive layer can hold larger phosphor parts as the layer thickness increases. If, however, increases the thickness of the Ii chi sensitive Soli layer, v / es ird increasingly Schwi (rigor, while uvu ENLWI ekelnr to maintain the film intact. Therefore muli di ο Di before <ä <.r photosensitive layer 0.1 to 40 U]. Ton, v <) r: -, Ui'.f; weiij (; O.4 to 10 HiJtron, be.

Photosensitive, layers with over; ti mini er Dicla;

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BATH ORIGINAL

are preferably made of an organic solvent (a hydrocarbon such as hexane, Heptane or benzene, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, 1,1,1-trichloroethane or trichlorethylene) applied. Generally will Hydrocarbons "preferred to the possibility of one Eliminate contamination of the phosphor with halide ions. The thickness of the photosensitive layer can be used as a puncture of the concentration of the in the solvent dissolved solids can be varied.

After the front plate has been coated with a suitable solid, photosensitive organic layer, a latent image is generated by exposing the element in a manner suitable for image recording to actinic radiation for a period sufficient to generate a potential R. , from 0.2 to 2.2 (lightening the background of the positive-acting, light-sensitive layers or building up a potential R ^ _n from 0.2 to 2.2 in the case of negative-acting light-sensitive layers). The photosensitive elements can be exposed to actinic radiation through a photographic positive or negative.

As mentioned, the latent images in positive-acting, photosensitive layers are generated by the The element is exposed in a manner suitable for image acquisition for a period sufficient to cover the background lighten, that is, to make the exposed areas non-powder-absorbent. Varies to some extent the amount of actinic radiation required to brighten the background, depending on the Size of the developer powder and the development conditions. Because of these fluctuations, it is often desirable

109825/2077 " * ⁶ ~

slightly overexposed for full brightening to ensure the background and the dimensions of the luminaire toffpunkt sharper and the pollution to avoid the fluorescent dots. Generally, overexposure will result in negative-looking, photosensitive ones Elements preferred for maximum contrast.

After the photosensitive element has been exposed to actinic radiation for a time sufficient to brighten the background of a positive-acting photosensitive layer or to build up a potential R ^ _n of 0.2 to 2.2, a phosphor powder with a diameter or dimension of at least microns physically applied along an axis with a suitable force, preferably mechanically, in order to embed this phosphor in the photosensitive layer. The phosphor developer powder can have virtually any shape, such as spherical, needle-like or plate-like shape, provided that it has a diameter of at least 0.3 microns along at least one axis.

The phosphor powder can be in practically pure form or can be applied from a suitable carrier. Carrier, such as resinous or polymeric materials can be used to adjust the particle size of the phosphor rules and / or a larger one at each stage of development Amount of fluorescent material to apply. The phosphor can mill with the polymeric carrier in the ball mill in order to coat the support with the phosphor or the phosphor can be customized at a temperature above the melting point of a Resin-type Lgcn Trügdrs mixed in, to a suitable size be married and classified.

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BATH ORIGINAL

The fluorescent particles could-; η from numerous conventional color-outer phosphors are formed, such as Sulphides, Uzyden, v / clframaten, Alumina ten, Eoraxen, Selenide oil silicates of one or more metals, such as Zinc, Cadr.s.iuEi, beryllium, magnesium, manganese, calcium and Strontium. Mece materials can be replaced by metals, such as Silver, copper or manganese.

The for determining the value ¹ R, a light-sensitive layer used black developing powder is formed by about 77 $> Pliolite VTL (vinyltoluene-butadiene Copolyneres) and 23 <?> Heo Spectra-soot at a temperature above the melting points clers haraartigen carrier heated, nibbled for 15 minutes in a rubber mill and then ground in a Hikro-Atomiser.

Formulations suitable for the invention kweeire ¹ Leuchtetofi powders contain particles whose Durclimpssei ¹ or dimension läiifre 0 .;) bit 40 microns mjndestena an axis is preferably 0.5 to 10 microns. Powder kits with a diameter on the order of 1 to 15 microns are best suited for light-sensitive layers with a size of 0.4 to 10 microns. The maximum particle size int depends on the thickness of the photosensitive layer, while the minimum particle size is independent of the layer thickness. Elel ^r tronenrnikroBko> pii3che Untercu en Chung have shown that powder whose diameter is; ; <5-j'a ° iH the thickness of the light-sensitive layer Iu tr ^ gt «not uamrhaft in Ii oil: · lunrd ' i.ndl i ο layers v? .Nr <A < i 1 -vi v / (- rd !. (} - 1 ;;: · ηη Allgeriei.n be the best Ei'i, e ->i;:!? iro crt ;? 1, \ n-mx is Durck ^t .h .. '·. . ':> he qpb RiI distribute i-jj ^ i) .'- ν /..- ΐϋ; ·! ;; civ; a dn ;; 10 times the thickness of the lent · <- :: ι i iiu i .f »Lon i'.oni (? h1 betrögt. Jn drn liieint'-n Fäl Iv-U stcr» .- n L- \ .ch \ -st aiii c-.i Ί eh t ^j n .eiiK 'ürö !, t von wehr

1 0 9 3; ^J B / 2077 " _r . ₈ "

6AD

than 40 microns will not develop the image, provided that the developer powder is an appropriate concentration of powder particles less than 40 microns, less than 25 times in size, and preferably is less than 10 times the thickness of the photosensitive layer ".

Although phosphor particles larger than 40 microns in size do not interfere with the development of the image, the presence of particles can contribute
less than 0.3 microns in diameter along all axes. In general, it is preferred to use phosphor developer powder in which virtually all of the powder particles are longitudinally at least
of an axis have a diameter of not less than microns, preferably more than 0.5 microns, since particles less than 0.3 microns tend to be in
to be embedded in non-image areas. As the particle size of the smallest phosphor particles in the developer increases, there is less exposure to it
actinic radiation is required to lighten the background.

For best results, the phosphor developer powder should consist practically exclusively of particles (at least 95 percent by weight), their
Diameter along an axis is greater than 1 micron and preferably 1 to 15 microns when this powder
in connection with light-sensitive layers a
Thickness of 0.4 to 10 microns is used. In this way, maximum powder embedding is achieved in image-bearing areas.

Described in more detail is the phosphor developing powder directly onto the photosensitive layer

109825/2077 ~ ²⁹ "

applied, while the powder receptive areas of this layer are at most slightly soft state and this layer at a temperature below the melting point of the layer and the powder. The powder is v / ied over the Area to be developed is distributed and physically incorporated into the layer on the surface of the photosensitive layer embedded, which is preferably done mechanically by a force with a lateral component, such as by a

reciprocating and / or circular rubbing or scrubbing action using a soft pad or Pillow, a fine brush or an inflated balloon. If desired, the powder can be used separately applied or contained in the pad or brush. The amount of powder is not critical, provided that there is an excess of what is required to fully develop the area, because the development mainly depends on the mutual action of the particles and not on the forces between brush and surface or pad or pillow and surface seems to be dependent on a layer of powder particles, which are essentially the strength of a Has particles (particle single layer) to embed in a layer on the surface of the photosensitive layer. Only a simple layer of powder particles penetrates into the powder-receptive areas of the photosensitive layer, even if the photosensitive layer Layer is several times thicker than the diameter of the developer particles.

The developing pad or burete is critical only in that it should not be so stiff that, when used under moderate pressure with the preferred amount of powder, it will scratch or scratch the film surface in developing the film.

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205 θ

Particularly suitable for this purpose is ordinary- .: -.,. _: Cotton wadding loosely compressed into a wad about the size of a baseball and weighing van - .. · .. · about 3 to 6 g. Which during development on; -sign ■:, .- .: -.:ΐ Bausch exerted developing movement and force is "·: · not critical. The speed of the polishing action. is not critical, apart from the fact that it influences the time required, since a rapid movement is a The preferred mechanical movement used consists essentially of a lateral action, such as occurs when fine polishing a wooden surface by sanding it by hand or by working with steel wool.

Brushing by hand is completely satisfactory and if so it is carried out under the above conditions, it leads in a reproducible manner to the highest possible Density that can be achieved with the material. This means that the maximum concentration of ropes. per unit area is deposited under the conditions described, which depends on the physical properties of the material, such as softness, elasticity, plasticity and adhesion. Essentially the same Results can be achieved when a mechanical device is used to apply the powder. To the A rotating or rotating and oscillating cylindrical one can achieve the coating effect described Brush or pillow or pad can be used, all of which produce substantially the same end result.

After the phosphor has been applied, excess phosphor, which has not been sufficiently embedded in or connected to the front plate, remains on the surface. This phosphor can be in anyone

- 31 109825/207 7

BATH ORIGINAL

removed by suitable means, for example by Wipe with a clean pad or brush, usually using a slightly stronger force than mechanical Developing is applied by applying vacuum, by vibration or by stripping with Help of an air jet. The excess phosphor can be won. For the sake of simplicity and for the smoothness of the results, the excess Powder is usually blown away with the help of a blowgun, which has an air-line pressure of about 1.4 to 2.8 kg / cm (20 to 40 psi). The gun is preferably at an angle of 30 to 60 ° in a distance of 2.54 cm to 30.5 cm (1 to 12 inches), preferably 7.6 to 20.3 cm (3 to 3 inches) from the Surface held. The pressure at which the air hits the surface is around 0.007 to 0.21 kg / cm, preferably 0.017 to 0.14 kg / cm (0.1 to 3 »preferably about 0.25 to 2 psi). The cleaning with The help of the air jet can be carried out for a few seconds or longer, until no further, loosely held particles are removed. The remaining Powder should adhere so firmly that it can be easily wiped off with moderate force or some other suitable method Abrasion effect is not removed.

The front panel, which is a first phosphor in image-wise Arrangement is then covered with a second solid, photosensitive organic layer coated while the first phosphor is held in its pictorial arrangement, and the second Layer is treated in the same way to deposit phosphors with different colors and / or the pattern of the first phosphor with additional Reinforce fluorescent of the same color.

- 32 109825/2077

The process steps described are repeated as often as necessary, usually three times by three different phosphors for the currently used, customary tube. After all phosphors were deposited in a pictorial arrangement, the faceplate is either before or after assembling the Tube burned to remove and not remove all organic material from the face of the faceplate to fuse fused phosphors with the surface of the front panel. For the purposes of the invention it is it is essential that each solid, light-sensitive organic layer on the first phosphor or the first front plate carrying phosphors is applied without affecting the pictorial arrangement of the previously deposited Phosphors is disturbed.

For applying one or more solid, light-sensitive organic layers on an image-bearing faceplate, while the first or the first phosphors are kept in a pictorial configuration, numerous methods can be used. Some of these methods, such as the methods in which the light-sensitive organic material consists of a ^ Liquid carriers are deposited to some extent by the solubility properties of the photosensitive organic layer limited. For example, the image fidelity of the phosphor image can be lost, when the front plate, which carries a first, photosensitive organic layer, which is a single layer of fluorescent particles, with a second photosensitive layer made of a support, which is a good solvent for the first photosensitive layer is flow coated. The difficulty can be minimized or overcome in a number of ways. For example, the image fidelity of the

109825/2077 " ⁵³ "

Phosphor image generally good if the second or a subsequent light-sensitive organic Layer or layers can be applied from a support that is a good solvent for the photosensitive represents organic layer or layers which hold the phosphor (s) in place when this layer is applied by spraying up onto the faceplate. If desired, a dry light-sensitive Layer of an aerosol may be deposited, kept at a sufficient distance from the faceplate so that practically all of the abrasive evaporates can before the solid organic;) layer is deposited on the front panel. On the other hand, the second or subsequent solid, photosensitive organic Layers on the front plate, which carries the first phosphor (s), without destroying the pictorial Arrangement of this or these first phosphors are deposited when the subsequent photosensitive organic layers are applied from a carrier which is a relatively poor solvent for the previously deposited, solid, light-sensitive represents organic layers.

Numerous methods can be used to change the solubility properties of the solid, photosensitive organic layer which holds the phosphor particles in an imagewise arrangement and / or to change the adhesion of the phosphor particles to the front panel. For example, various polyfunctional compounds, which are known to react with the solid, light-sensitive organic layer, can act on the one provided with the phosphor image. S _c hicht be applied and reacted with it before the application of the second light-sensitive organic layer,

- 34 109825/2077

Suitable polyfunctional compounds include polyvalent metal salts, dimethylolurea, urea-formaldehyde resins, and melamine-formaldehyde resins. In some cases it may be desirable to treat the first image with diethylenically unsaturated, polymerizable vinylidene monomers or with dichromate and to convert the layer into an infusible form with actinic radiation. In some cases the solubility properties of the originally photosensitive layer can be changed after development by uniform exposure. For example, the P can not exposed areas of solid, photosensitive ¹ organic layers diäthylenisch unsaturated polymerizable it contained Vinylidenmonomeres be a thermoplastic polymer and a converted by uniform actinic radiation in a · thermally cured form.

In some cases it is advantageous to cover the layer provided with the phosphor image with an insulating layer coat to the solubility properties of the surface of the substrate to which the second photosensitive layer is applied. If bye For example, both in the first and in the second layer a hydrocarbon-soluble, water-insoluble, light-sensitive organic material is used, a hydrophilic layer, such as polyvinyl alcohol, can act as an insulating layer between the two photosensitive ones Layers are deposited. If desired, the insulating layer can be treated using one treated with dichromate Colloids can be tanned into an infusible form, such as dichromate-treated polyvinyl alcohol or gelatin and by irradiating the layer with uniform actinic radiation, which the Insulating layer tanned.

- 35 109825/2077

In other cases it may be desirable to use the phosphor particles melt into the surface of the faceplate. For example, if "is in both the first and also the second layer is a hydrocarbon-soluble, water-insoluble, light-sensitive organic material is used, a hydrophilic carrier for the phosphor particles such as polyvinyl alcohol, corn starch or rice starch can be melted with the surface of the front panel with the aid of steam, whereby the fluorescent particles fused to the front panel will. According to a particularly preferred method, each deposited phosphor pattern is cleaned prior to application fired a new photosensitive organic layer. The firing makes all of the organic Material removed from the surface of the faceplate and the phosphor particles become more precisely pictorial The arrangement is fused to the faceplate so that the fluorescent pattern is invulnerable to the effects of the Support materials which are used for applying the light-sensitive organic layers.

The invention is, though primarily, to manufacture directed by screens for color television tubes, however, it can also be used to make ceramic items such as black and white television tubes and pottery with different "designs-be applied. At this modification of the method according to the invention is a suitable ceramic material comprising a solid, photosensitive organic layer with a value of R-, from 0.2 to 2.2, preferably 0.4 to 2.0, in a manner suitable for image recording with actinic radiation exposed to form a potential R- from 0.2 to 2.2. Be on top of this organic layer

- 36 ~

109825/2077

_BATH

free-flowing powder particles applied a meltable pigment whose diameter along at least one axis but less is at least 0.3 micron, than 25 times the thickness of the organic layer, while the S _c hicht at a temperature below the melting point of the powder and the organic layer is held. The powder particles are, as a single location in a layer on the surface of the S hicht _c physically embedded in order to obtain an image whose areas vary in density according to the intensity of the exposure of each area, are ^CNEN not embedded T _e il from the organic layer removed and the ceramic article fired to fuse the pigment to the article. In this method, a single pigment can be applied to the ceramic article and fired, or two or more pigments can be applied to the ceramic article, with a firing process being carried out after each application of the pigment or after application of all pigments.

In general, any of the methods already described in relation to the manufacture of color television tubes can be used. In addition, the ceramic objects can be exposed through negative or positive master images of line images, halftone images or halftone images, with excellent line images, halftone images and halftone images being produced.
As in the German disclosure documents 20 03 764, 20 03 761 and 20 03 762

is explained, the deformation imaging technique can be advantageous can be used to form line, halftone and halftone images.

The invention is illustrated by the following examples.

109825/2077 -57-

example 1

1 1/4 g of Staybelite-Sster No. 10 (partially hydrogenated rosin acid ester of G-lycerin) and 0.25 g of benzil, dissolved in 100 ml of hexane, are applied to the concave surface of a cleaned front plate by spraying upwards onto the front plate, whereby a 2 micron thick photosensitive layer is formed. A slide with a suitable pattern capable of producing the desired arrangement of strips, lines or dots (in this pail of dots) is then placed over the faceplate and the faceplate is exposed through the slide for about 3 minutes to the light radiation of a carbon arc . The front plate is developed in a room kept at 24 ° G and 50 fo relative humidity room, by rubbing with a cotton swab from the front panel, the green phosphor longitudinally (with silver activated zinc cadmium sulfide) having a diameter of about 1 to 40 microns of the major axis contains. The green phosphor is embedded in the unexposed areas of the photosensitive layer by rubbing the cotton ball back and forth across the photosensitive layer with the aid of a force which is used to polish wooden surfaces. Excess phosphor is removed from the photosensitive layer by blowing air at an angle of about 30 ° against the surface until the surface is essentially free of phosphor particles. The front panel is then rubbed with a fresh cotton ball, which creates a faithful reproduction of the fluorescent dot pattern on the front panel. By burning the front panel, the fluorescent particles are fused with the front panel and the light. sensitive organic layer volatilized.

- 38 109825/2077

The front plate is re-sensitized with the Staybelite-J ^ ster sensitizing solution used to produce the first phosphor pattern. A slide provided with a suitable pattern is then arranged in a second layer opposite the front plate and the front plate is exposed through the slide to the light rays of a carbon arc for about 3 minutes. The faceplate is developed using a blue phosphor (silver activated zinc sulfide) having a particle size of about 1 to 40 microns along the largest axis in the manner described in the previous paragraph. After embedding of the blue phosphor in the non-exposed areas of the photosensitive layer of the excess phosphor is removed and fired the F _r ontplatte.

The process is repeated a third time to produce a red-emitting phosphor (activated with silver Zinc cadmium sulfide) with a particle size of 1 to 40 Embed microns along the largest axis. After embedding the red fluorescent and removing it of non-embedded phosphor from the faceplate, the faceplate is reburned, leaving a screen is generated, the innumerable triples of green, blue and red colored luminous points, all of which are perfect are round and have the same size.

Example 2

Example 1 is repeated with essentially the same results, except that the Staybelite ester No. 10 as the sensitizer is replaced by a sensitizer containing 5 g of the ethanol-insoluble fraction of soy lecithin and 0.2 g of benzil dissolved in 100 ml of hexane, and that the exposure time is reduced to 60 seconds.

109825/2077 - 39 -

BATH ORIGINAL

205B340

Example 3

Example 1 is presented with the same results with the exception that the faceplate was repeated only after developing the third phosphor pattern is fired and that the first and second phosphor patterns with a 5% aqueous solution of polyvinyl alcohol sprayed and thereby a hydrophilic polyvinyl alcohol insulating layer is formed after drying.

Example 4

Example 3 is repeated with substantially the same results, and with the exception that the PoIyvinylalkohol-Isolierschiehteii be replaced by dichromatbehandelte polyvinylalcohol and that the polyvinyl alcohol layers by uniformly exposing the entire S Liicht _c tanned with ultraviolet light.

Example 5

Example 1 is repeated with the exception that the front plate is only after the embedding of the third phosphor is burned. Essentially the same results are achieved.

Example 6

Example 1 is repeated with essentially the same results, except that the Staybelite ester No. 10 used as a sensitizer is replaced by a sensitizer solution, the 0.64 g Staybelite ester Mr. Contains 10 and 0.16 g of benzil dissolved in 100 ml of hexane.

Example 7

Example 1 is repeated, the Staybelite ester No. 10 being used as a component of the sensitizer B by (1) Abietic acid, (2) Staybelite resin (partially hydrogenated,

109825/2077 -40-

Resin acids) and (3) Staybelite-Ester Hr. 5 (partially hydrogenated glycerol rosin ester) is replaced in the same weight concentration. In doing so, iin essential achieved the same results.

Example 8

Example 1 is repeated except that each exposure to actinic radiation using An electron beam is carried out after the faceplate is inserted into a precisely evacuated tube became. Essentially the same results are achieved.

Example 9

This example illustrates the use of a negative-acting photosensitive coating for manufacture the faceplate of a cathode tube. Example 1 is repeated with the exception that the Staybelite ester Hr. containing coating solution is replaced by a solution consisting of 1.5 g Paracin 15 (ethylene glycol monohydroxystearate), 0.2 g of benzil and 0.2 g of 4-methyl-7-dimethyl-aminocoumarin in 100 ml of 1,1,1-triehloroethane and that instead A shadow mask is used for a slide.

Example 10

This example illustrates the production of a three-color ceramic hot plate. 0.96 g Staybelite ester No. 10, 0.24 g benzil and 0.144 g 4-methyl-7-dimethylaminocoumarin, dissolved in 100 ml of chlorothene were flow-coated onto a glazed 0.635 cm thick

ρ applied ceramic tile with a size of 38.71 cm, while the plate was inclined at an angle of about 60 ° to the horizontal. After air drying for about a minute it became photosensitive

- 41 109825/2077

Element in a vacuum frame in contact with a cyan-blue color separation slide of the reproduction to be copied and used for about 60 seconds exposed to a point-shaped mercury light source. The photosensitive element was removed from the vacuum frame removed and developed by using a cotton ball, the Blue Overglaze No. 6341 from B.F. Drakenfeld & Company was rubbed over the item. The blue overglaze was in the unexposed areas The photosensitive layer is embedded and excess overglaze by blowing air underneath an angle of about 30 °. removed against the surface until the surface was essentially free of particles. The reproduction was rubbed with a fresh cotton ball, creating a faithful reproduction of the slide was obtained. The blue overglaze was in a muffle furnace for one hour at 982 ° C the ceramic tiles fused, removed from the furnace and cooled.

After the ceramic tile with the picture has cooled down at room temperature this was flow-coated with the same sensitizer solution that was used to prepare the blue overglaze had been used, air-dried, brought into conformity with the yellow color separation positive (color separation), in the manner described above exposed, developed with yellow overglaze (Yellow Overglaze No. 6286 from B.P, Drakenfeld and Company) and melted the overglaze onto the ceramic tile in the manner previously described.

After the image-bearing ceramic tile has cooled down At room temperature, this was coated with the same sensitizer solution that was used to prepare the blue and

109825/2077 "'^"

yellow overglaze was used, air-dried, in accordance with your magenta color separation (color separation positive) brought, exposed, with blood-red overglaze * (Blood Red Overglaze No. 6344 by B.F. Drakenfeld & Company) and fired in a muffle furnace at 982 ° C for one hour. The glazed tile put represents an exact reproduction of the reproduction from which the color separation transparencies were made.

Essentially the same results are obtained if the first two firing stages are omitted and a primer is applied to the developed overglaze about 5% aqueous polyvinyl alcohol is applied before the fresh sensitizer solution is applied.

Example 11

A single-color glazed ceramic hot plate was used in the manner described in Example 10 of the blood red overglaze (Blood Red No. 6344 Overglaze), with the exception that the applied Image was fired at 538 G in a muffle furnace. After one hour at 538 ° C, the muffle furnace was turned on switched off and the tile left in the muffle furnace allowed to cool slowly. There' drawn monochrome image obtained.

Let the tile cool down slowly. An excellent

- 43 109825/2077

Claims (1)

205B340 - 45 Patontans examine M. Process for applying colored or colored ~ "" sending materials onto the surface of a glass— or ceramic object, characterized in that one a) the surface of the glass or ceramic object, which is a solid, light-sensitive organic Layer contributes to the formation of an R. value from 0.2 to 2.2 is capable of image-wise actinic Radiation exposed, b) the exposure is carried out until a potential R, from 0.2 to 2.2 is reached, c) free-flowing particles of the colored or color-emitting material on the layer of organic material Material applies that along at least one axis has a diameter of at least 0.3 Microns but less than 25 times the thickness of the organic layer, d) while the object is at a temperature below the melting point of the colored or color-emitting Particles and the organic layer is held, the particles as a single layer in one Layer embeds on the surface of the organic layer, creating an image of which individual parts have varying density depending on the exposure, e) removing non-embedded particles from the organic layer, f) all organic by burning the item Material removed from the surface of the object and the particles with the surface of the object merges and - 44 109825/2077 205R340 g) optionally before or after the firing in a second stage, the surface of the object as well a second layer of the same or a different photosensitive organic material that to develop a R.-value of 0.2 to 2.2 bed capable of being at least 0.1 micron thick coats the process steps while the previously applied particles are held in place a) to f) using the same or a different colored or color-emitting material and by firing the article, all organic material is removed from the surface and the particles merge with the surface of the object. 2. The method according to claim 1, characterized in that the concave surface of the front panel is used as the glass object a cathode tube and applies a screen to this, the groups of individual elements contains at least two different colored, light-emitting phosphors by following the process steps a) and b) on the first layer of organic material free-flowing phosphor particles has a diameter of at least 0.3 microns along at least one axis, however less than 25 times the thickness of the organic layer (c); d) while the faceplate is at a temperature below the melting point of the phosphor particles and the first organic layer is held, the phosphor particles as a single layer in a Layer embeds on the surface of the organic layer, creating an image of which individual parts have varying density depending on the exposure, - 45 _ 109825/2077 e) non-embedded phosphor particles under formation of a fluorescent pattern from the first organic layer removed, f) the faceplate, which has the first fluorescent pattern contains, with a second solid, light-sensitive organic layer which forms an R -, - value from 0.2 to 2.2 is capable of coating to a thickness of at least C.1 microns, while the first fluorescent pattern in its pictorial arrangement is held g) after repeating process steps a) and b) phosphor particles of a second color flowing freely onto the second layer of organic material has a diameter of at least 0.3 microns along at least one axis but less than 25 times the thickness of the second organic Have layer, h) while the faceplate is below the melting point of the second organic layer and the second Phosphor particles are held, the phosphor particles as a single layer in a layer on the Embedded surface of the second photosensitive layer, creating an image, its individual Parts have varying density depending on the exposure, i) non-embedded phosphor particles from the second organic layer is removed to form a phosphor pattern and k) all organic material is removed from the surface of the faceplate by firing the faceplate and the phosphor particles fuse with the surface of the faceplate. - 46 - ■ 109825/2077 BATH 205R340 Process according to Claim 2, characterized in that solid, light-sensitive layers are used as organic layers Organic layers are used which enable the formation of an R, value of 0.2 to 2.2 and that these layers are up to lighten the background of the photosensitive organic Layer to be exposed. Method according to Claim 2 or 3, characterized in that the front panel is removed after it has been removed non-embedded phosphor particles from the second organic layer with a third, solid, light-sensitive organic layer capable of developing an R, value of 0.2 to 2.2 is coated to a thickness of at least 0.1 micron on the photosensitive organic layer imagewise exposed to actinic radiation to remove the background of this photosensitive organic Lighten the layer, on the exposed layer free-flowing fluorescent particles of a third color has a diameter of at least 0.3 microns, but less, at least along one axis than 25 times the thickness of the organic layer that, while the layer is at a Temperature below the melting point of the phosphor particles and the third organic layer is held, the phosphor particles as a single layer embedded in a layer on the surface of the photosensitive layer, whereby an image is obtained whose individual parts vary in density depending on the exposure of each part and the non-embedded particles from the organic layer to form groups of three removed from three differently colored, light-emitting phosphors. 109825/2077 -47- 205R340 ~ 47 - 5. The method according to claim 2 to 4, characterized in that nan nacli the removal of non-embedded Phosphor particles from the first organic layer in process step e) by firing the The first organic layer was removed from the front panel and the first fluorescent particles were out- . ^ ₁ plate fuses. 6. The method according to claim 2 to 4, characterized ™ net that after removing non-embedded * -v. Phosphor particles from the first organic layer in process step e) cover the front plate with an insulating layer made of a hydrophilic colloid. 7. The method according to claim 6, characterized in that that one adds a tannin to the insulating layer and the insulating layer by exposure to actinic Radiation tanned equally. 8. The method according to claim 2 to 4, characterized in that the second, light-sensitive layer Applied from a liquid carrier medium that is a poor solvent for the first photosensitive represents organic layer. 9. The method according to claim 1, characterized in that colored material is applied to a ceramic object applied by, after performing method steps a) and b) in method step c), on the layer of organic material free-flowing, meltable pigment particles having a diameter along at least one axis of at least 0.3 microns but less than 25 times the thickness of the organic layer, • - 48 - 109825/2077 _ßA0 original d) while the ceramic object is at one temperature is kept below the melting point of the pigment particles and the organic layer, the pigment particles embedded as a single layer on a layer on the surface of this organic layer, wherein an image is generated whose individual parts vary in density depending on the exposure own, e) removing non-embedded pigment particles from the organic layer to form a pigment image and f) by firing the ceramic article, the organic material is removed from the surface of the article and the fusible pigment fuses to the surface of the ceramic article. 10. The method according to claim 9, characterized in that after removing non-embedded pigment particles in process step e) a second, solid, light-sensitive organic layer with the specified Properties and the process steps a) to e) performs again. 11. The method according to claim 9 or 10, characterized in that there is the first and second organic layer a solid, photosensitive organic layer used to form an R ^ fourth from 0.2 to 2.2 is capable and this layer up to the lightening of the background of the photosensitive organic Layer exposed. 12. The method according to claim 1 to 11, characterized in that that a film-forming organic material is used as the photosensitive organic layer which 109825/2077 BAD ORJGINAL carries no terminal ethylenic unsaturation and contains at least one photoactivator. 13. The method according to claim 12, characterized in that there is used as a solid, film-forming organic material \ an unsaturated acid with internal ethylenic unsaturation is used. 14. The method according to claim 13, characterized in that the solid, fUmbildende organic material partially hydrogenated resin acid contains. 15. The method according to claim 12, characterized in that that the solid, film-forming organic material is an ester of an unsaturated acid with internal Contains ethylenic unsaturation. 16. The method according to claim 15, characterized in that the ester is a partially hydrogenated carz ester is. 17. The method according to claim 15, characterized by, that the ester is a phosphatide. 109825/2077 _eAD