DE1772590C3 - Photographic recording material and its uses - Google Patents

Description

From DE-AS 11 89 850 a recording mat is π rial for the production of relief images or printing forms known that in the light-sensitive layer Contains monomers, such as acrylic monomers, that are subject to the presence of certain photosensitizers Light exposure to be photopolymerized. The development of this material occurs because the not exposed and thus not photopolymerized monomers dissolved out with the help of a solvent be, whereby a relief image from the polymer formed during the photopolymerization back- 4> remain. The disadvantage of this is that only image areas on the one hand and non-image areas on the other hand and none Intermediate tones can be formed so that it is not possible to take pictures with fine gradation and a to train continuous change in color depth, w Furthermore, it is only possible to remove the unexposed areas and this is another disadvantage Recording material can be seen in the fact that it is considerably heavier due to the monomers used to be handled and stored. v>

From DE-AS 12 39 940 a light-sensitive recording material for reproduction purposes is known, that of a support and a layer containing a photosensitive aromatic nitro compound consists. When imagewise exposing this recording wi The exposed parts of the image are usually discolored darker than the unexposed parts of the image. To the It is possible to transfer the image-wise exposed recording material into planographic printing forms with a Treat washing solution thereby reducing the exposed tr> Parts of the image are detached from the support, while the unexposed parts of the image are not attacked lag behind. Here, too, there is the disadvantage that it is not easily possible to use arbitrary intermediate tones train and target either the exposed areas or the unexposed areas for the To use the creation of the visible image. Furthermore, this recording material can be improved insofar as and the unexposed parts of the image are mostly yellowish in color.

Finally, DE-PS 6 56 956 discloses a method for producing photographic images ceramic plates made of titanium dioxide-containing masses known, in which the contrast by treating the The photosensitive surface of the image carrier is improved with a starchy iodine-potassium solution. Of the The disadvantage of this prior art is to be seen in the fact that the only dyes used are essentially those with iodine and Starch formed colored compound can be relied upon and it is not possible to target either to use the exposed areas or the unexposed areas for imaging, and to stain or remove.

In the graphic industry, when using photographic, photolypie or collotype, photolithography or lithographic printing, glue printing, etc. silver halides and diazo compounds as photosensitive materials to absorb the energy of the light spectrum in processes for Production of photographic images and used in reprography. These photosensitive Means usually require close control of the chemicals used, a long treatment time and a significant effort to develop images of objects on the photosensitive Surface can be reproduced. These procedures are both expensive and impractical when there is is required numerous copies or replicas of an object or a picture on a cheap Surface, such as a cellulosic fabric, e.g. B. cellulose films, sheets of paper or cardboard and tightly woven Cellulose webs. In addition, those required for developing and fixing the photosensitive Silver halide or diazo surfaces have precise control over the chemicals used Temperature and concentration or use of aqueous solutions to be acceptable To effect reproduction on the photosensitive surface.

It is also known that the ver for most photographic and reproduction processes turned silver is difficult to obtain, so it is desirable. via a photographic recording material grouting that is cheap and does not require the application of silver.

The object of the invention is therefore to provide a photographic recording material which neither Silver halides, nor diazo compounds, is easy, simple and problem-free to handle, whose photosensitive layer adheres better to the substrate and is therefore more abrasion-resistant than that after light-sensitive materials used in the prior art, and images with fine gradation and provides continuous intermediate tones and enables in a targeted manner either the image areas or to selectively color the non-image areas and / or to detach them with the formation of a relief image.

This object is achieved by a photographic recording material having a support and a photosensitive layer containing a photo-oxidizing agent and an oxidizable compound,

solved, characterized in that the light-sensitive layer as a photo-oxidizing agent a porphine and as an oxidizable compound a solid one Contains polymer with carbon-carbon double bonds

The photosensitive layer of the photographic recording material according to the invention absorbs due to the presence of porphine, which acts as a photo-oxidizing agent or oxidation photosensitizer is used to radiate energy from the parts electromagnetic Spectrum between and including the near infrared and the ultraviolet, creating a Oxygen transfer from the environment to the solid polymer used as the oxidizable compound takes place with carbon-carbon double bonds. As a result, there is now no photopolymerization, but causes a selective photo-oxidation of the oxidizable polymer, so that a latent image thereby results in the oxygen being selectively bound to certain image areas and to other image areas is not bound. By treating with a dye that has a selective affinity for this has oxidized or non-oxidized areas, this latent image can be developed. There no Photopolymerization takes place, this can be done according to the invention polymer used as desired and according to the selection of the solvent from the exposed or unexposed areas are removed. In this way it is easy to To create reproductions that are true to the original with fine gradation and much better intermediate tones than it is is possible with the conventional recording materials. A nuance succeeds in doing this having an image on a flat surface, such as on a film or picture print, and if desired to produce colored relief images. The recording material is convenient and quick to handle and shows high flexibility in that, depending on the dye and / or solvent used either the positive image or the negative image can be developed with the Development can be done with either a dye or, if desired, a solvent can, whereby either the exposed or the non-exposed areas are selectively dissolved out can. Furthermore, the exposed areas of the recording material according to the invention can be seen well further treatment so that they can be transferred to other substrates, since they are not through a Polymerization or be made insoluble by a crosslinking process. Furthermore it is not required to resort to special facilities such as darkrooms, expensive control facilities regarding the exposure line and the type of developer and the concentration of the applied Pay special attention to developer solutions.

The support of the photographic recording material according to the invention can be a glass or Metal plate, a solid plastic or a plastic film, a sheet of paper or a cardboard surface.

The solid polymer with carbon-carbon double bonds, that as an oxidizable compound in the photosensitive layer of the invention photographic recording material is contained; can be natural or synthetic be polymeric material that contains unreacted carbon-carbon double bonds having. These

Carbon-carbon double bond can be present in the chain, as is the case with vinyl compounds formula

-CH ₂ -CH = CH-CH ₂ -

is the case or can be terminal, such as, for example, in the case of vinyl compounds of the formula

-CH ₂ -CH = CH ₂

or in the case of vinylidene compounds with the group of the formula

CH ₁ = C

CH ₂

CH-,

The groups connected to the units mentioned can be straight-chain or branched. in the In general, the polymer structure comprises a hydrocarbon chain, the associated halide, Can carry ester, ether, hydroxyl, nitrile, phenyl groups or other groups.

It can be seen that the vinyl compounds are a special type of vinylidene compounds since they _{contain characteristic CH 2} = CH groups, the specified free carbon valence being saturated by any atom in the polymer molecule. The term "vinylidenes" is therefore used to include both vinylidene and vinyl-type unsaturated bonds.

Examples of such olefinically unsaturated polymers are natural rubbers and homopolymers. Copolymers and polymers of three or more monomers derived from diolefins such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, chloroprene, bromoprene, 2-acetoxy-butadiene-1,3, 2-methyl-pentadiene or 2-ethylhexadiene are produced, and polymers, those made from diolefins such as those of the type described above and compounds containing a vinyl or vinylidene group, such as:

(A) vinyl ethers, for example vinyl alkyl ethers such as vinyl ethyl ether, vinyl butyl ether, vinyl octyl ether, Vinyldotlecyl ether, vinyl tetradecyl ether, vinyl hexadecyl ether ". Vinyloctadecylether and vinylalkenylether, for example vinylether, Vinyloctenyläther, Vinyl tetradecenyl ether, vinyl octadecenyl ether;

(b) vinyl esters, for example vinyl acetate, vinyl butyrate, vinyl caprylate, vinyl caprate, vinyl laurate. Vinyl myristal, Vinyl palmitate, vinyl stearate;

(c) vinyl halides, for example vinyl chloride, vinyl bromide;

(d) vinyl ketones, for example vinyl methyl ketone;

(e) vinyl sulfides, vinyl sulfoxides and vinyl sulfones, for example vinyl ethyl sulfide, vinyl propyl sulfoxide, vinyl tert-butyl sulfone;

(f) vinylidene compounds. for example vinylidene chloride;

(g) Acrylic, methacrylic acids or crotonic acid !! and their derivatives, for example acrylic acid, acrylonitrile. vlethaerylamid.crotonamid;

(h) Acrylic acid, methacrylic acid esters or crotonic acid esters, for example methyl methyl acrylate, ethyl acrylate, Propyl acrylate, amyl acrylate, heptyl acrylate,

Octyl methacrylate, nonylacrylate, undecyl acrylate, Tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, Ethenyl acrylate, hexenyl methacrylate, dodecenyl acrylate, Octadecenyl acrylate, ethyl crotonate; (i) allyl esters, for example allyl acetate, allyl butyrate, Allyl caprylate, allyl caprate, allyl laurate, allyl myristate, Allyl palmitate, allyl stearate;

(J) Allyl alkyl ethers, for example allyl ethyl ether, AlIyI octyl ether, Allyl dodecyl ether, allyl tetradecyl ether, allyl hexadecyl ether, allyl octadecyl ether and vinyl alkenyl ether, for example allyl octadecenyl ether, allyl ethenyl ether, allyl octenyl ether, allyl tetradecenyl ether;

(k) cycloaliphatic vinyl compounds, for example vinyl cyclohexane;

(I) aryl vinyl compounds, for example styrene, vinyl toluene, Vinyl biphenyl, vinyl naphthalene, and the ar-chlorine substituted styrenes;

(m) heterocyclic vinyl compounds, for example vinyl pyridine and vinyl dihydropyran;

(n) Alpha-olefins, for example ethylene, propylene, Butene-1, octene-1, dodecene-1, tetradecene-1, hexadecene-1 and 1-heptadecene, dichloroethylene, tetrafluoroethylene; and

(o) Branched olefins, for example isobutylene, isoamylene, 2,3,3-trimethyl-1-butene.

20th

25th

It should be noted that the unsaturated polymers which are used in the practice of this invention can also be prepared by copolymerizing two or more different diolefins, for example from a mixture of butadiene and piperylene, either in Presence or absence of one or more non-diene copolymerizable monomers.

The preferred vinyl or vinylidene monomers have at least one with an electronegative Group connected valence such as a carbon in a double or triple bond, for example a Vinyl, propynyl or other groups such as phenyl, nitrile, carboxy and the like are the preferred vinylidene comonomers are represented, for example, by the classes of the preceding in (a), (b), (c), (d), (g), (h), (k), (1), (m) and (o) specified monomers. Hydrocarbon vinyl monomers of the monomers of Classes (1) and (o) are particularly preferred. The amount of copolymerized diolefin monomer in one Copolymer of diolefin monomer and vinyl monomer is generally about 0.1 to 99% by weight. However, if polymers of copolymerized diolefin monomer and vinyl monomer are used, it is preferred that they contain at least about 1% by weight copolymerized diolefin monomer.

The physical properties of the olefinically unsaturated polymers, which according to the present Invention can be photooxidized, can be in a range of lower polymer oils Molecular weights containing relatively few olefinic bonds up to high rubber and resins Molecular weight wiv. those that result from the e> o Polymerization or copolymerization of diolefins in the presence or absence of one or give several non-dienic copolymerizable monomers.

The photooxidants or photosensitizers b5 Ren, as they are sometimes called, which are a further component in the light-sensitive layer of the photographic recording material according to the invention are contained; subject in general no permanent chemical change. The porphins used for this are made by absorbing Photons are excited and join in a series of with the oxygen present in the atmosphere chemical reactions, resulting in oxidation of the solid polymer with carbon-carbon double bonds leads, the sensitizer generally regenerating again at the end of the cycle will.

In the present invention, a porphine is used as the photo-oxidizing agent, which is any Compound with porphine structure acts, that is, a compound in which 4 pyrrole rings through individual ones Carbon or nitrogen atoms are linked, the term related compounds such as Includes porphyrazines, phthalocyanines, or chlorophylls

Particularly suitable photo-oxidizing agents are those meso-substituted with an aromatic group Porphine compounds. These include the meso-tetraarylporphines, i. H. Porphins attached to the bridging Carbon atoms of the porphine ring structure substituted with aryl groups of 6 to 24 carbon atoms are, these compounds containing 4 pyrrole nuclei arranged in a circular pattern through four Bridging carbon atoms are linked together to form a large ring. Examples of aryl groups in the meso position as Substituents that may be present are phenyl groups, chlorophenyl groups, dichlorophenyl groups, methylphenyl groups, Ν, Ν-dimethylaminophenyl groups, hydroxyphenyl groups, naphthyl groups, biphenylyl groups, Anthracyl groups, phenanthryl groups and the like. In addition to the substituents in the above defined aryl groups are contained, the aryl groups can be further or a combination of further Have substituents, for example alkyloxy groups with 1 to 20 carbon atoms, such as methoxy groups, ethoxy groups, isopropoxy groups, butoxy groups, Hexyloxy groups and the like, as well as other substituents that give the basic aromatic character of groups do not change. These porphine sensitizers including the aryl porphines noted above may have various other substituents, especially in the beta and beta 'positions of the Pyrrole rings, for example substituents such as low molecular weight alkyl groups with 1 to 20 carbon atoms, Vinyl groups, allyl groups or alkanoic acid groups such as methyl carboxy groups or ethyl carboxy groups.

Examples of porphines which are suitable as photo-oxidizing agents are the aryl porphines such as Tetraphenyltetrazoporphine and the metal complexes thereof, for example magnesium tetraphenyltetrazoporphine, Copper tetraphenyl tetrazoporphine, tetraphenyl tetrazoporphine acetate, tetraphenyl tetrazoporphine sulfate, Zinc tetraphenyl tetrazoporphine, nickel tetraphenyl tetrazoporphine and cobalt tetraphenyl tetrazoporphine; the meso-arylporphins, including alpha-, beta-, gamma-, delta-naphthylporphine and the metal chelates of it, for example

Tetraphenylporphine

Tetrakis (2,4-dichlorophenyl) porphine

Tetrakis (2-fury I) -porphine

Tetrakis (4-methoxyphenyl) porphine

Tetrakis (4-methylphenyl) porphine

Tetrakis (2-thienyl) porphine

Tetraphenylporphine zinc complex

Tetrakis (4-nitrophenyl) porphine

Tetrakis (4-dimethylaminophenyl) porphine

Zinc complex:

the tetrabenzomo ·> azo and tetrabenzodiazoporphine, the 1,2,3,4,5,6,7,8-octaphenylporphine and _azo porphine such as octaphenylporphyrazine, the tetrabenzoporphine, for example tetrabenzopoiphine and the zinc complex of tetrabenzoporphine.

More porphines, which can be according to the invention used as a photo-oxidizing agent, chlorophyll include, such as chlorophyll a and chlorophyll b, hemin, the Tetrazoporphine, Vanadiumtetraphenylporphin, Chlorophyüinsalzderivatc how the Rcaktäonsprodukt a Alkalimetallchlorophyllinsalzes with sodium bisulfite, Hämatoporphin, Quecksilberproto- and Hämatoporphine, vitamin _{B] 2} and its derivatives, tetrakis (lnaphthy!) -porphine and cobalt-protoporphin.

Related porphine type materials that can be used include both phthalocyanines including metal-free phthalocyanines and metal complexes of phthalocyanine such as copper, zinc, Magnesium-. Tungsten, manganese, iron, nickel and cobalt complexes of phthalocyanine, as well as phthalocyanine derivatives such as copper phthalocyanine sulfonic acid, or the barium or calcium salts of the same acid, acetylated phthalocyanine, alkoxy- and aryloxy-benzo-substituted ones Phthalocyanine, 5,5 ', 5 ", 5"' - tetraamino copper phthalocyanine-4,4 ', 4 ", 4'" - tetrasulfonic acid, Copper and magnesium tetra (4) methylthiophthalocyanine, aryl thioether of phthalocyanines. Containing vinyl groups Tetraazoporphine and polymers thereof, mecaptoaminophthalocyanine derivatives and phthalocyanine.

The terms »photooxidizing«, »photooxidation«, »photosensitizing« and so on, as used in the Description and as used in the claims are to be understood as true photosensitized Cover oxidation reactions in which light in the presence of a sensitizer causes oxygen, to oxidize the photooxidizable polymer having carbon-carbon double bonds; the Designations are not to be understood in such a way that they autooxidaiionen generated by a free radical mechanism be triggered, include, in which the radiation with light is used to initiate free radicals. The true photosensitized oxidation reactions are characterized by the fact that they occur at Use of light can drain with wavelengths that are ineffective for auto-oxidation can, and further that, in general, ordinary antioxidants do not delay the reaction can.

The light necessary in the practice of this invention may vary depending on the photooxidant vary considerably in wavelengths. The light can be monochromatic or polychromatic be. Light with wavelengths in the range of 3600 to 8000 Å has been found to be very suitable.

According to one embodiment of the invention, the porphine used is preferably an aryl porphine and more preferred tetravinylporphine. According to a further preferred embodiment, this comprises Recording material a layer support made of a cellulose fabric, which as porphine tetravinylporphine and as a polymer with a carbon-carbon double bond contains an unsaturated styrene-butadiene copolymer. These embodiments are insofar particularly advantageous, as it is possible with the help of extremely cheap layer supports to create an extremely sensitive, photographic material that is easy to handle and provides images with finely graded intermediate tones provide.

The invention also relates to a method for producing an image in which a recording material imagewise exposed and then treated with a solvent, characterized in that is that a recording material of the type defined above and a solvent that one the exposed or the unexposed parts of the image containing dye which stains the image in a dissolved state, can be used.

In this case, the photographic recording material according to the invention is exposed imagewise, as a result of which oxidation reactions take place on the treated surface when exposed to light, which are dependent on the light intensity. The photochemical reaction is then stopped by removing the intense light. The extent of the oxidation achieved depends largely on the oxidizable compound and photo-oxidizing agent used. For example, a polyisoprene polymer used as a solid polymer with carbon-carbon double bonds, with which a desired surface is coated, requires stronger oxidation to produce a clear image than is the case with a solid polymer made from 60 parts of styrene and 40 parts of butadiene because of the difference is the case in the color absorption properties of the two oxidizable compounds. In the case of styrene-butadiene polymers as oxidizable compounds, which are composed of about 60 parts of styrene and about 40 parts of butadiene and possibly small amounts of other functional monomers, such as itaconic acid or itaconic anhydride, an oxidation is sufficient, about 10 ~ ⁹ to about To cause 10 ~ ⁷ mol of oxygen per cm ^{2 of} the coated surface to give an intense image after treating the surface with a dye. Are generally obtained can recognizable images, when the oxidation is carried out to an extent sufficient to ensure the absorption of about 10 ^-2 to about 10 ^"10 moles of oxygen per cm ^{2 of} substrate surface.

The depth of oxidation in the substrate is not known. However, in the case of the above-mentioned styrene-butadiene ^{polymer, for example, the oxidation to the extent of 10 ~ 8} to 10- 'mol oxygen / cm ² uptake by the polymer corresponds to a minimal coating

depth of about 250 to 500 Å if all of the double bonds in the polymer turn oxidized. It can be seen that in this application of the photo-oxidation reaction the weight concentration of the photo-oxidizing agent in proportion to the weight concentration of the solid polymer with carbon-carbon double bond for the the desired purpose only has to be quite minor. It is not necessary to oxidize all available To bring about double bonds in the polymer. It is sufficient that an oxidation takes place which causes the Noticeable latent image formation is enabled by treating the oxidized surface with a Can be made visible by dye or by other methods.

The photo-oxidizing agent and the oxidizable compound can be used separately or as a single Preparation can be applied to the desired surface by conventional methods, such as by

Incorporation by means of a suitable diluent according to the emulsion technique. You can do the same with Suitable pigments are applied, in which the oxidizable compound is not only considered to be oxidizable Compound acts, but also as a component of a pigment binder or adhesive. A typical one An example of a polymer which can be used for this purpose is an aqueous styrene-butadiene latex emulsion with 48% solids content, either alone or in combination with materials made from starch or Casein types as pigment binders in the coating of paper surfaces for the production of printing papers high quality. Within the scope of the invention is a coating preparation that does so is made so that it contains a small amount of photo-oxidizing agent, for example tetraphenylporphine, a pigment or mixture of pigments, typically a kaolin clay, titanium dioxide and a binder or glue, for example an aqueous latex one Styrene-butadiene copolymer, the total solids content in such a preparation is in the range of about 10 to 70% by weight. the Coating preparation can be on a suitable sheet of paper or cardboard, on a metal, plastic or Glass object applied, used immediately, or stored and for future use for Photocopying are packaged according to the invention.

It will be clear to those skilled in the art that the choice of diluent or others will be related to the photosensitive Preparations of the agents used of the type jo of the substrate to be treated and the one to be applied Depends on photooxidant in order to obtain complete surface coverage.

Examples of diluents that r alone or together with the photosensitive compositions of this invention can be used are chlorinated hydrocarbons such as ethyl chloride, methylene chloride, chloroform, carbon tetrachloride, Tnchlorpropan, monochlorobenzene, trichlorethylene, perchlorethylene, difluoro-dichloromethane, ortho-chlorobenzene, chlorinated polyphenyls , chlorinated paraffins and the like; Hydrocarbons such as heptane, hexane, cyclohexane, eicosane, octadecene, benzene, xylene, toluene and the like; Polyethylene glycols, butyl cellosolve; Esters such as methyl acetate, ethyl acetate, carbitol acetate, di-2-ethylhexyl phthalate, dimethyl phthalate, dimethyl cellosolve phthalate, di-tetrahydrofurfuryl phthalate and the like; Acetone, methyl ethyl ketone, cyclohexanone, undecanone and so on; Dibutyl stearate dimethyl sulfoxide and the like

When the photo-oxidation reaction is desired for the photo-reproduction purposes of this invention Extent has progressed, the reaction can essentially be removed by removing the photographic Recording material, d. H. the combination of the photo-oxidizing agent and the oxidizable Connection from which intense light is halted. Usually an exposure of around 10 is Seconds up to about 60 seconds with light energy, 1000 watt white light all in one Distance of about 30 cm from the rotor production eo element arranged is sufficient to produce a clear print of the copied object induce suitable photochemical reaction.

The dyes used in this invention for b5 Fixation or development of the images produced in the photo-oxidation step of this invention be any dye that has an affinity for the oxidized or the unoxidized sites of the through Has exposure treated surface. Dyes generally considered useful in this invention were found to be the dyes that are soluble in organic solvents or oil, such as kerosene or Alcohol-soluble dyes, for example of the triphenylmethane type, Azo dyes and disperse dyes. It was found to be dissolved in a solvent Colorants, such as deodorized or highly refined kerosene, generally on the unoxidized Area and the dyes that are dissolved in an alcohol such as 2-ethylhexanol, mainly due to the oxidized areas of the exposed surface act. The special place where the Dye settles, seems to be due to the selective swelling properties of the solvent used, the effect of the dye on the solubility parameter of the solvent and on the polarity of the To depend on the dye. Although these factors appear to control the direction of the dye, that is actual chemical or physical mechanism of response and image deposition by the Dye not completely cleared.

The solvents or dispersants that are used for the dye can be any organic material that can dissolve or disperse the dye and selectively direct the dye to the oxidized or non-oxidized areas of the exposure treated surface, so that the differences in the photo-oxidation in the various surface areas can easily be made visible in this way. Suitable solvents or diluents for the dyes that can be used include, low melting point, molten waxes, liquid alkanes, cycloalkanes, alkanes mixed with aromatic compounds such as benzene, toluene, xylene, chlorobenzene and so on, aliphatic fatty acids with from 6 ■ up to 24 carbon atoms, molten, unsaturated fatty acids such as palmitic acid, higher liquid aliphatic alcohols with from 6 to about 20 carbon atoms and those higher alcohols that are mixed with up to about 50% lower alcohols, aliphatic esters that are liquid or low-melting (below 100 ⁰ C) are solids at room temperatures, such as triacetin, ethylhexanoate, methyl oleate. The dyes can be used in any desired concentration in the solvent or diluent, but a solution containing from about 0.1 to about 6% dye based on the weight of the solvent selected is generally for most fixing or developing purposes this invention is sufficient. The dyes can also be used as a solid.

Examples of color index dyes used to enhance or develop latent images those with a positive image-forming object, for example a typewritten one, are useful opaque white sheet, used include Sudan Brown (Cl. No. 12 020), Sudan Red. (C.I. No. 26 100) or Calco Oil Red (CI. No. 26 125), dissolved in deodorized kerosene. Examples of dyes that are used for amplification or development latent images useful are those associated with a negative image-forming article such as a photographic Negatively related include crystal violet (CI. No. 42 555), melachite green (CI. No. 42 555), melachite green (CI. No. 42 555) 42 000), Victoria Blue (CI. No. 44 040) or Nigrosine B

(C.I. No. 50 420) dissolved in 2-ethylhexanol.

The point at which the dye responds or acts depends on both the dye and the Solvent off. For example, Sudan Brown, dissolved in kerosene, preferably goes to the non-oxidized, Areas. A strongly basic dye such as crystal violet (CI. No. 42 555) goes preferably to oxidized ones Areas, except for areas where higher levels of oxidation have occurred. In such areas In the case of higher oxidation, an inversion appears to occur with the dye, which is from excessively oxidized Areas is repelled.

The dyes can in a simple manner on the exposed photo-oxidized recording material, such as with a rag or brush, painted on or sprayed on, or other conventional methods and then by wiping the surface treated with the dye with a dry Tissue to be wiped off. The result is a clear, usable print or copy of what is to be copied or reproducing item.

Chelates, graphite, metal oxides and similar materials can also be compared to the exposed photo-oxidized surfaces to produce the desired Products are used.

The photo-oxidizing agents used in the practice of this invention can be used alone or in combination to achieve more effective use of the irradiation of the light spectrum, so long as the combined sensitizers do not attenuate or neutralize each other's light absorbency. For example, Rose Bengal and Methylene Blue can be used as sensitizers together with the porphine-type sensitizers such as tetraphenylporphine. Suitable base or support materials include metals, for example steel, aluminum plates, zinc, copper, magnesium sheets or foils, glass, wood, paper, composite plates, fabrics, cellulose esters, for example cellulose acetate, cellulose propionate, cellulose butyrate and so on. Films or plates which are composed of various film-forming synthetic resins or high molecular weight polymers, such as addition polymers, including those mentioned for use in the photooxidizable 4 ^r ) layer and in particular vinyllidene polymers, for example vinyl chlorocopolymers with vinyl chloride, vinyl acetate, styrene , Isobutylene and acrylonitrile; the linear condensation polymers such as the polyesters, for example Polyäthylente-, 0 rephthalate; the polyamides, for example polyhexamethylene sebacamide. Polyester amides; for example polyhexamethylene adipamide / adipate and so on. Fillers or reinforcing agents can be present in the synthetic resin or the polymer base materials, such as the various fibers (synthetic, modified or natural) for example cellulose fibers, for example from cotton, cellulose acetate, viscose silk, paper; Glass, wood, nylon and the like. These reinforcement materials can be used in laminated form.

The method of this invention, the visible light, a photo-oxidizing agent and an oxidizable compound used as a styrene-butadiene copolymer is used to produce a latent image under Use of reflective, light-transmitting systems suitable- The latent image thus produced is visible through suitable dye systems for the production of continuous high quality tinted images made.

The latent image can also be used for selective deposition of finely divided solids, metals and / or Metal oxides and chelates can be used. If graphite is used, it can be used as a conductive material can be used for electrodeposited metals. When natural rubber is used as a substrate is used, the unexposed area can be selectively dissolved to form a relief image. Multicolor images are also possible according to the invention.

The photographic recording materials of the present invention have a wide range of uses and are generally useful in graphic work where a reproduction of a drawing, a model, a plan and so on. So are used in the manufacture of Copy models used in the manufacture of parts for airplanes, automobiles, boats, radios and electrical equipment and so on, the materials intended for use are used, such as steel, aluminum and so on, with the photosensitive preparations of this invention coated, dried, exposed over the model drawing and developed. The produced print is a exact reproduction of the original and adheres firmly to the metal or other materials. Stencils or Described transparencies can also be used to reproduce instructions, identification numbers and so on further, to be used on parts of the manufactured items. The photographic recording materials of the present invention can also be used as printing blocks for the production of black and white white imprints can be used.

The photosensitive layer is generally coated by a transparency method; H. a negative one or positive process exposed (whereby an image-bearing transparent structure consisting essentially of opaque and essentially transparent surfaces, the opaque Areas have essentially the same optical density, so that a so-called line or halftone negative or positive).

It is possible to cover the photosensitive layer through paper or other translucent materials expose. In this case, however, a stronger light source or longer exposure times must be used will. Reflective exposure can also be used, for example when copying paper or translucent Films, can be used.

Light sources useful in the practice of this invention include carbon arc lamps, Tungsten and mercury vapor arc lamps, fluorescent lamps, argon incandescent lamps, electronic flash units, photographic headlights and sunlight

The invention is further illustrated by the following examples, which cover the scope of the invention in in no way intended to limit.

Photosensitive preparations used for coating paper and other suitable substrates are suitable are prepared so that they are (A) a solvent or carrier, (B) a photo-oxidizing agent and (C) a solid polymer with carbon-carbon double bonds, which in the treatment is photo-oxidized with light. Such preparations are explained in Example 1 below, wherein

the preparation A and R applied to a paper coated with a styrene-butadiene copolymer are. All parts are parts by weight unless otherwise specified. In the following In the examples, the photo-oxidizing agent is also referred to as a sensitizer.

Example 1 Preparations A to R

Constituent ii

Preparation ABC

chloroform

Di-2-ethylhexyl phthalate
Tetraphenylporphine
Tall oil (acid number 170-180)

Formaldehyde modified
Resin (rosin)
(Acid number 18 to 20)
Reinforced resin adduct
(Acid number about 200)
Meleopimaric acid

300

300

100

300

300

100

300

300

100

300 300

component

Preparation E F

Chloroform 300 300 300

Di-2-ethylhexyl phthalate 300 300 300

Zinc chelate from Tetra- 2 - -

phenylporphine

2,4-dichlorotetraphenyl- - 2 -

porphine

3,4-dichlorotetraphenyl- - - 2

porphine

Gum resin 100 100 100

(Acid number 160-170)

component preparation I. J H 100 100 chloroform 300 100 100 Di-tetrahydrofurfuryl phthalate 300 - - Chlorophyll 3 2 2 Tetraphenylporphine - - - Maleopimaric acid 100 100 - Gum resin - (Acid number 160-170) - 100 Pinene -

100

component

Preparation KLM

Chloroform 15

Di-tetrahydrofurfuryl 25
phthalate

Octadecene -

Chlorinated paraffin -

Undecanon -

Tributyl tin stearate -

Dimethylfuran -

Tetraphenylporphine 0.1

2,4-dichlorotetraphenyl-0.1
porphine

Naphthyltetraphenyl-
porphine

Maleopimaric acid 2

Gum resin (acid number 160-170)

1.0

12 2

4.4 3.5

0.1 3.5 0.1 0.1

0.3 -

0.5 0.6

component

Preparation O P

chloroform

Di-2-ethylhexyl phthalate

Tetraphenylporphine

Chlorinated paraffin

Maleopimaric acid

Tung oleoresin

Pinene

300
300

300

300

100 100

700

700

200 100

Preparations A to R described above are used on coated cardboard. It become exact positives from positive transparencies used to cover the substrate produced when the light-sensitive preparations exposed through the transparency and further with a Kerosene solution of the dye DuPont Brown N (C.I. No. 21 010).

Example 2

A solution containing 9 parts of Ditetrahydrofurfurylphthalai and 1 part contains acetophenone, is coated on a previously with a styrene-butadiene copolymer latex Cardboard applied. A suitable positive transparency is placed over the coated paperboard The cardboard is then exposed to ultraviolet light (85 watts) for 15 minutes Cardboard is coated with an odorless kerosene solution containing 0.4% of the dye DuPont Brown N (C.I. No. 21 010) contains, wiped On the cardboard will be a clear picture of the banner received.

Similar results as in Example 2 are obtained when acetophenone is replaced by benzophenone, Benzoin. Benzil or TriDhenvlen is replaced.

Example 3

A cardboard previously coated with a styrene-butadiene copolymer latex is mixed with preparation A from Example 1 coated. The exposure of the cardboard to a fluorescent light is about 10 Minutes carried out. The picture is made with a kerosene solution of the dye DuPont Brown N (C. I. No. 21 010).

Example 4

Example 3 is with a 300 watt white headlight lamp used as the light source was repeated.

Example 5

An opaque sheet of paper coated with a styrene-butadiene copolymer latex, is treated with a solution of the following composition:

Levopimaric acid formaldehyde

adduct 100 parts

Chloroform 400 parts

Chlorinated paraffin 250 parts

Ditetrahydrofurfuryl phthalate 600 parts

Tetraphenylporphine 3 parts

The resulting coated sheet is useful for receiving an image of an object to be copied, like a typewritten letter on lightly glued paper, one being 1000 watts Light source is aimed at the sheet of paper for about 30 seconds at a distance of 35 cm and the Object is placed between the light source and the treated paper. The picture comes with a 0.4% solution of the dye Crystal Violet-Basic Violet 3 (C.I. No. 42 555) in dodecane.

Example 6

Following the procedure of Example 5, similar results are obtained when levopimaric acid or dihydroabietic acid instead of the levopimaric acid-formaldehyde adduct is used.

Example 7
Preparation S.
The following solution is made:

Chloroform 600 parts

Chlorinated paraffin 500 parts

Di-tetrahydrofurfuryl phthalate 1200 parts

Levopimaric acid formaldehyde

adduct 50 parts

Gum resin 100 parts

Maleopimaric acid 50 parts

A large number of sensitizer solutions are prepared by adding 5 parts of the following! specified photo-oxidizing agent to 1000 parts of the solution S. Each resulting photosensitizer solution Solution is based on a styrene-butadiene copolymer latex coated cardboard applied. The cardboard is then covered with a banner and with a 300 watt light source located approximately 25 cm away; is arranged, exposed for four minutes A kerosene solution of the dyes DuPont Brown N (C. No. 21 010), Crystal Violet-Basic Violet 3 (C. I. Ni 42 555), Violet BN (C 1. No. 37 165) or Nigrosin B (C. No. 37 165) used.

The results are set out below.

Photo-oxidizing agents

Assessment of the resulting developed image

Tetraphenylporphine
Methoxytetraphenylporphine
Zinc tetraphenylporphine
Hydroxytetraphenylporphine
Naphthyltetraphenylporphine
3,4-dichlorotetraphenylporphine

2,4-dichlorotetraphenylporphine
Chlorophyll

good picture weak picture weak picture dark background good picture good background and border good background and border good picture and weak limit

Example 8

A mixture of 3 parts of 2,4-Dichlortetraphenylporphin, 400 parts of chloroform, and 1600 parts of eicosane and is heated to a temperature of about 40 to 50 ⁰ C is applied to a surface coated with a styrene-butadiene Copo lymerisatlatex cardboard. An excellent picture is produced if the cardboard is covered with a transparency, exposed to a 300 watt lamp and treated with a solution. Dye DuPont Brown N (CI. No. 21010 is being developed.

Examples 9-12

Following the procedure of Example 8, but using the sensitizer solutions described below for the sensitizer solution of Example 8, excellent reproduced images are obtained.

component

Example number
10

Parts by weight

12th

2,4-dichlorotetraphenylporphine
Polyethylene glycol (1000)
Polyethylene glycol (4000)
Chlorinated polyphenyl (54% chlorine)
Eicosan

3.5

400
1600

3.6 1000

030 233/2

continuation

component

Example number 9

Parts by weight

12th

Chlorinated polyphenyl (12% chlorine)

Paraffin wax (melting point 65 Q

chloroform

Butylated hydroxytoluene

Examples 13-18

These examples illustrate the incorporation of both the photo-oxidizing agent and an oxidizable one Connection in the surface coating of a cellulose web. A standard coating will be like prepared as follows: 1.25 g of tetrasodium polyphosphate are dissolved in 300 g of water and a mixer admitted. While this mixture is being stirred, 450 grams of clay and 50 grams of titanium dioxide are added. That resulting mixture is stirred for 10 minutes 129 g of a 60/40 styrene-butadiene polymer latex containing 48% 1400 700

250 4.6

15th

Contains 20 solids and 11 g of water, 200 g of the standard coating are added and the mixture is stirred gently for 15 minutes.Equivalent parts of this coating solution are mixed with the photosensitizer solution, as indicated in each example below, and applied to a sulfite cardboard.The results of the evaluation of each treated Cardboard as photographic substrates after exposure through a transparency with an exposure time of 1 to 2 minutes using a 1000 watt lamp and subsequent development with dye are given below.

Ex.
No. Parts of the
default
coating Parts
Sensibi
lizer Sensitizer preparation 13th 7th 3 1% 2,4-dichlorotetraphenyIporphine
in dimethyl sulfoxide 14th 7th 1.5 as in example 13 15th 8th 2 2% dichlorotetraphenylporphine
in chloroform 16 8th 2 1% 2,4-dichlorotetraphenylporphine
in carbitol acetate 17th 9 1 as in example 16 18th 30th 2 0.5% 2,4-dichlorotetraphenylporphine
in butyl cellosolve

BiM results

clear picture yellow background

clear picture yellow background

clear picture good picture

good picture clear picture

Example 19

The styrene-butadiene copolymer latex coating material! is replaced by a natural rubber latex. The sensitizer solution of Example 8 is added to the rubber latex. The resulting solution is applied to a sulfite cardboard Es the resulting surface is found to be an image when covered with a transparency, exposed with a 1000 watt lamp for 1 to 2 minutes and developed with a suitable dye.

Example 20

A standard cardboard is made using the slot nozzle application process double-coated with a styrene-butadiene copolymer latex, the clay / titanium dioxide pigment (90/10) contains, in a ratio of 2 parts 1 part styrene-butadiene copolymer pigment. A sensitizer solution containing 83.8 mg of tetraphenylpoiphine, 6.5 g of chlorinated polyphenyl, 13.5 g of mineral oil and 8 g of chloroform is applied to the coated cardboard wiped. A negative transparency is placed on the cardboard and approx. 1 with a 1000 watt lamp Minute exposed. The cardboard is dusted with activated charcoal, after which the excess is brushed off. on The cardboard creates an image because the carbon adheres to the unexposed areas.

Example 21

A standard cardboard is coated with a pigmented styrene-butadiene copolymer latex. the Sensitizer solution from Example 20 is applied to the coating. The coated cardboard will exposed through a photographic negative transparency. The image on the cardboard is made using a solid dye solution of crystal violet (C.I. No. 42 555) developed in a petroleum wax with a melting point of 47 ° C.

Example 22

A standard cardboard coated with a pigmented styrene-butadiene copolymer latex (2: 1 pigment to Binder) is with a solution of 320 mg of tetraphenylporphine, 50 g of chloroform and 90 g of one 1: 1 mixture of Qe hydrocarbon and chlorinated Polyphenyl Sensitized Specific areas of two sets of the above; Cardboard boxes are exposed. The first cardboard box is included

Graphite wiped off The unexposed areas become darker than the exposed areas. The scored The resistance of each surface is shown below.A second box is first wiped with kerosene, then with a kerosene solution of the dye Calco oil red BMC (C. I. No. 26 125) and then with a 2-ethylhexanol solution of the dye Victoria Blue R (C.I. No. 44 040). The surface is finally wiped with dry graphite The resistance obtained for each area is shown below.

Box no.

Box No. 2

Unexposed area.Exposed area

300,000 ohms / cm 40000-50000 ohms / cm

A surface is obtained
Conductivity on every cardboard.

with different

Example 23

A standard cardboard, coated and sensitized as described in Example 22, is replaced by a negative exposed. The image is first developed with a Sudan Brown kerosene solution (C 1. No. 12 020) and then the surface is polished with a kerosene solution from Victoria Blue R (C I. No. 44 040) to form of a bronzed picture. so

Example 24

A standard cardboard which has been coated and sensitized as described in Example 19 is used according to Laying of an aluminum foil strip exposed, r, After 5 to 10 minutes of exposure, the coated surface is rubbed with kerosene and graphite. That Graphite is selectively deposited on the non-oxidized surface. The cardboard is then electroplated underneath Use of 1.5 volt dry cells and a copper sulfite-sulfuric acid bath coated with copper. The copper is deposited on the graphite surfaces.

A piece of brass strip backing is made in a similar fashion to the cardboard box given above coated with copper using the same process. The <r> Copper is deposited on the graphite surface.

Example 25

The sensitizer solution from Example 24 is applied to a cardboard which has been coated with a natural rubber latex. The coated plate is exposed through a transparency. The surface is then wiped with kerosene, giving a relief image. γ,

Example 26

A sulfite-bleached carbon pad comes with a 0.1016-0.1270 mm thick top layer is coated tet, the 2 parts pigment (90:10 clay titanium dioxide) and 1 part vinyl acetate latex with a dye content of 50 contains up to 60%. The carton is sensitized with a solution containing tung oil, tciraphenylporphine, chloroform and contains octadecane. After exposure through an hour transparency, the image is made with a 0.5% solution of the dye DuPont Brown N (C.I. No. 21 010) developed in kerosene.

Example 27

Similar results as in Example 26 are obtained when an ethylene / vinyl chloride copolymer latex with a solids content of 50 to 60%, is used in place of the vinyl acetate latex.

Example 28

The procedure of Example 26 is repeated using a butyl acrylate latex containing 50 to 60% solids is used in place of the vinyl acetate latex. An excellent picture is obtained.

Example 29

Example 26 is repeated using polyethylene terephthalate as the support instead of Cardboard pad.

Example 30

The procedure of Example 26 is followed using a polyvinyl chloride latex in place of the vinyl acetate latex is used.

Example 31

A sheet of tracing paper is made with a styrene-butadiene copolymer latex coated, which contains finely divided polyvinyl chloride.

A sensitizer solution consisting of 2 parts of tetraphenylporphine, 100 parts of maleopimaric acid, 300 parts Chloroform and 300 parts of di-2-ethylhexyl phthalate is applied to the coated surface of the paper. The coated paper is made with the coated side is applied to a printed sheet of paper, the pressure being applied through the coated Paper can be seen. A light source of 300 watts is placed approx. 25 cm above the coated paper and the printed paper is exposed for 15 seconds, creating a latent image of the print on the translucent paper is obtained. The latent image is made with a solution of 0.4% Sudan Brown (C.I. No. 12 020) developed in kerosene. A reproduction of the print of the printed paper is made on the translucent Received paper.

Example 32

In this example, a cardboard with the The sensitizer solution of Example 31 coated. That Light from a 500 watt lamp is reflected from and through a black image onto a white background convex lenses guided. The rays of light are for

focused on the photosensitive paperboard which is 106 cm from the Image is located away. The resulting latent image is made with a solution of 0.5% of the dye Brown N (C. 1. No. 21 010) developed in kerosene

Example 33

A standard cardboard made with a styrene-outadiene copolymer latex is coated is treated with the sensitizer solution from Example 22 and exposed through a negative transparency. The picture is made with an ethanol solution of S-hydroxyquinoline and with Iron (IIl) nitrate dissolved in water, developed. A black positive image is obtained.

Example 34

Following the procedure of Example 33, the developed image is further treated with a solution of Potassium hydroxide in ethanol, with the formation of iron oxide on the oxidized part of the substrate.

Example 35

Following the procedure of Example 33, the exposed substrate is coated with a solution of silver nitrate in a mixture of ethanol, isopropanol and octanol. The treated area will then vaporize hydrogen chloride and exposed to light to form a brown image.

Example 36

Following the procedure of Example 33, the exposed area is made by applying the following Solutions developed in the order presented.

(1) potassium hydroxide in ethanol and octanol,

(2) hydroquinone in octanol

(3) Silver nitrate in water and a mixture of ethanol and methanol.

An image is obtained in which the metal is selectively deposited on the oxidized surfaces.

Example 37

The procedure of Example 33 is followed and iron (III) sulfate is replaced by iron (III) nitrate; under education of a yellow positive image.

Example 38

The procedure of example! 33 is repeated ', with the difference that copper sulphate takes the place of Iron (III) nitrate is used. A positive image is obtained.

Example 39

A cardboard made with a pigmented styrene / butadiene copolymer latex is coated is with the sensitizer solution of Example 33 with a vinylidene copolymer film covered, which adheres impermeably to the surface in some areas and wrinkles the other surfaces. The assembly is exposed and the surface is then coated with a solution of crystal violet (C.I. No. 42 555) in 2-ethylhexanol developed. The areas under the folds selectively absorb the dye. The areas on which the Film stuck, show no color recording.

B ε i s ρ i e I 40

The procedure of Example 39 is followed with drops of water on the coating of the plastic film be applied. After exposure and development with a solution of Victoria Blue R (C.I. No. 44 040) in 2-Ethylhexanol are the areas under the water droplets especially as light areas in a dark one Background detectable. The Victoria Blue R dye solution (C.I. No. 44 040) is selective from the oxidized Surfaces absorbed.

Example 41

The procedure of Example 40 is repeated except that a solution from Sudan Brown (CI. No. 12 020) in kerosene is used to develop the exposed surface. The surfaces under the water droplets appear as dark areas on a light background. The solution of the dye Sudan Brown (C.I. No. 12 020) is selectively absorbed by the non-oxidized areas.

From the preceding general description and the individual specific examples it can be seen that the invention provides photographic recording materials which are suitable for a variety of copying, Printing, decorative and manufacturing applications are suitable. The advantage lies in the cheap, fast ones and simple methods of general applications of the materials of the invention.

Claims (4)

Patent claims: 1. Photographic recording material with a support and a light-sensitive Layer which contains a photo-oxidizing agent and an oxidizable compound, characterized in that that the photosensitive layer is a porphine as a photo-oxidizing agent and a solid polymer as an oxidizable compound with carbon-carbon double bonds. 2. Recording material according to claim 1, characterized in that it is a porphine Arylporphine, preferably tetraphenylporphine, contains. 3. Recording material according to claim i, characterized in that it is a layer support from a cellulose fabric, as porphine tetraphenylporphine and as a polymer with a carbon-carbon double bond contains an unsaturated styrene-butadiene copolymer. 4. A method for producing an image, in which a recording material is exposed imagewise and is then treated with a solvent, characterized in that a recording material according to claim 1 and a solvent which is one of the exposed and the unexposed Parts of the image containing staining dye can be used. «Ι