CH633115A5 - Process for photographic image generation and photosensitive polymeric substrate for carrying out the process - Google Patents

Description

The present invention relates to a method for photo-graphic image generation which is suitable for diverse applications in the graphic arts industry and which is based on the production of viable latent images in a polymeric substrate by direct photooxidation of organic sulfur functions in the polymer. The invention is also directed to the polymeric substrate for carrying out the method according to the invention.

Photographic imaging on polymeric substrates such as e.g. on films, by selective exposure to effect localized crosslinking or vulcanization, is known. The mechanism involved often depends on free radical polymerization or crosslinking that requires the presence of a peroxide or other free radical source. The exposed areas of the polymer film generally become relative

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insoluble compared to the unexposed areas and lie- e.g. by coating a support with the polymer solution to form a latent image which can be developed by washing with a solvent-containing solvent suitable for this invention. any polymer that contains a sufficient amount of pho-

Photooxidative methods for imaging on polymer-oxidizable organic sulfur function, so that filming is disclosed in a number of published U.S. Patents 5 by selectively exposing a portion of a body from e.g. 3,790,389 (Heimisch et al.), 3,801,320 (Erickson), 3,847,609 polymer, a latent, developable image and 3,926,642 (Breslow et al.), And 3,846,266 (Duynstee et al.) .

have been described. Satisfactory polymers can be applied to any of the following

imaging by photooxidation of -C = C double- the types can be produced:

Bonds in polymer films by exposure in the presence of io 1. Polymerization of monomers in the presence of one of oxygen and a photosensitizer. From the photo thiols or disulfide. Useful starting materials for oxidation result in the generation of hydroperoxides which include such polymerization of any of the following mono-

Bound the location of the allylic unsaturation to the polymer chain, which are the basis for the production of either homopolymers. The latent hydroperoxide polymer image can then be used or suitable copolymers can be used:

reinforced by a number of different methods and / is rol, methyl methacrylate, butyl acrylate, butadiene, isoprene, acrylic

or be developed. The present invention for generating nitrii, ethylene, propylene, etc.

Image is not of the hydroperoxidation of If the polymerization in the presence of a thiol compound

-C = C double bonds dependent, but the sensitivity is usually carried out, a crosslinking

of the films is due to the additional presence of -C = C-, such as divinylbenzene or trimethylolpropane trimethacry-

Double bonds in the polymer substrate increased. In embodiment or another for the methods of polymer crosslinking modes of the invention where high sensitivity is a well known crosslinking agent.

worth seeing property is the coexistence of photo- While other polymerization meth-

Oxidizable sulfur function and -C = C unsaturation which could be used is the emulsion polymer

a preferred embodiment is particularly suitable because individual networked parts

It has now been found that the photographic products result from products made from a benzene or similar dispersion.

of images by selective exposure of certain ions can be applied as a coating in order to produce polymer materials containing film material-photooxidizable sulfur functions.

Substrates in the presence of oxygen and a suitable example of thiols used in this process

Photosensitizer can be achieved. alkyl mercaptans, e.g. n-dodecylmercap

The tan, tert-dodecyl mercaptan, n-butylthioglycolate, octyl-β-mer

The polymeric films must contain photooxidizable sulfur radio captopropionate, p-thiocresol, pentaerythritol tetrakis (ß-mercap-

ions, preferably sulfide functions (i.e. sulfur functions topropionate) and thioglycerin.

of the type -C-S-Ç-, included. Suitable polymers can be based on the introduction of organic sulfide functions in predetermined

many ways are obtained, the following of which serve to illustrate the polymers by adding a thiol to an unsaturated tertiary: 35 site, e.g. a -C = C site, or other reactive a) polymerization of a monomer in the presence of a site in the polymer. Suitable polymers include e.g. Butadiene, thiols or disulfides, isoprene polymers or copolymers with main chain-standing b) addition of a thiol to a preformed polymer, and side chain-standing types of unsaturation. Polymers produced by suitable reaction sites such as carbon-carbon-dop- can contain active and soluble pel bonds. Be 40, i.e. it is not necessary for them to be crosslinked, in contrast to c) polymerizing or copolymerizing an organic monomer containing the photo-sulfide functions prepared by the previous method. polymers. Crosslinked polymer starting materials are

Other related types of sulfur-containing polymers, reversible, are not required.

which are also expected to be effective are poly- It is believed that the fact that such polymers have -S- or -S-S units in the main chain. 45 mers are useful for the invention, related to that, the poly used in the process according to the invention that in the polymers produced by this method can be saturated or unsaturated, and the latter more than one point in the polymer (chain or particle) sul generally have a higher sensitivity. fidfunctions are introduced.

The photosensitizer is preferably used with the poly- Representative of these types of polymers are styrene-

mer by mixing before film formation, but can 50 butadiene and methyl methacrylate-butadiene copolymers.

can also be incorporated after film formation. The photosensi- 3. Polymerization or copolymerization of sulfur

bilizer must be able to absorb photons and then holding monomers, e.g. Vinyl sulfide, ethylthioethyl

Oxygen from a triplet into a highly active singlet methacrylate and styrene with sulfide substituent on the ring.

Condition in which the oxygen with the resulting polymeric substrates, the photooxidized

Sulfur function in the polymer reacts. The photosensitizer 55 bare sulfide function, for example, poly-

is generally regenerated at the end of the cycle. olefins such as polyethylene, polypropylene, polymers of diolefin

The exposure of the films according to the invention can be achieved by known methods, such as polybutadiene, polymers of α, β-unsaturated carbon. acid esters, acrylate or methacrylate esters, addition poly

The development of polymer films which have been exposed according to the invention by unsaturated hydrocarbons, vinylidene-poly can be carried out by the action of 60 mers, condensation polymers such as phenol-formaldehyde-poly solvents, in order to remove the relatively soluble mers, polyamides such as nylon etc., and to remove various parts of the film, or by methods which include copolymers of the foregoing types of materials, depending on other changes in film properties.

are. It is believed that other than those described above

The polymer mass, which is usually mixed with 65 polymers and other similar types of sulfur polymer.

If the photosensitizer is incorporated, it can be converted into a film in the same photooxidation / photoimaging process.

or another should be useful for graphic arts applications such as the following: Polymers with -S-

Useful structural configuration, or -S-S- as units in the polymer backbone, e.g.

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Poly (ethylene sulfide), poly (propylene sulfide) or thiocol polysulfide, as can be produced by condensation of certain organic dihalides with Na2S, SCI2, S2CI etc.

With regard to the concentration of the photosensitizer or better photooxidation sensitizer, the appropriate amount will depend on the specific polymer / sensitizer / exposure system to be used and will have to be worked out empirically for each case. In general, enough photooxidation sensitizer is added to generate so much singlet oxygen that a developable image is formed by reaction with the sulfur function of the polymeric substrate. When using e.g. Tetraphenylporophorin (TPP) would generally be used in an amount in the range of about 0.01 to 10 mg / g polymer, with about 1.0 to 5.0 mg / g polymer being preferred.

Any suitable photosensitizer can be used. TPP and other porphyrin and 1,8-dinaphthylene thiophene type sensitizers are preferred.

Many of the following types of photooxidation sensitizers are expected to be useful, and it would be a matter of routine and simple experimentation for those skilled in the art to select additional, satisfactory sensitizers from the following categories:

1. The aromatic meso-substituted porphin compounds. Among these aromatically substituted porphins are the ms-tetraarylporphins (ms-meso). These compounds are those porphins in which aryl groups having 6 to 24 carbon atoms are present as substituents on the bridging carbon atoms of the porphine ring structure, which contain four pyrrole nuclei connected to one another by four bridging carbon atoms in a circular pattern to form a large ring. Examples of aryl groups which may be present as substituents in the meso position of these compounds are phenyl, chlorophenyl, dichlorophenyl, methylphenyl, N, N-dimethylaminophenyl, hydroxyphenyl, naphthyl, biphenylyl, anthracyl, phenanthryl, etc., besides those mentioned above Substituents in the aryl group, the aryl groups can be any or a combination of such substituents as alkoxy (1 to 20 carbon atoms), for example Contain methoxy, ethoxy, isopropoxy, butoxy, hexoxy, etc., as well as any other substituents that do not change the fundamental aromatic character of the group. These porphine sensitizers, which include the aryl porphins exemplified above, may contain various other substituents, particularly in the β and β position of the pyrrole rings, e.g. such substituents as alkyl (1 to 20 carbon atoms), alkenyl such as vinyl or allyl, or alkane carboxylic acid groups such as methyl carboxy or ethyl carboxy.

Examples of porphin compounds which are expected to serve as photochemical sensitizers in the practice of this invention are aryl porphins such as tetraphenyltetraazoporphins and complexes thereof such as diamagnetic complexes e.g. Magnesium tetraphenyltetraazoporphine, tetraphenyltetraazoporphine acetate, tetraphenyltetraazoporphine sulfate, zinc tetraphenyltetraazoporphine, and the meso-arylporphins including a-, ß-, y, 8-naphthyl-porphine and the diam. Tetraphe-nylporphin, Tetrakis (2,4-dichlorophenyl) porphin, Tetrakis (2-furyOporphin, Tetrakis (4-methoxyphenyl) porphin, Tetrakis (4-methylphenyl) porphin, Tetrakis (2-thienyl) porphin, Tetraphe-nylporphin Complex, T etrakis (4-nitrophenyl) porphine, Tetrakis (4-dimethylaminophenyl) porphine the tetrabenzomo-noazo- and tetrabenzodiazoporphins, which like 1,2,3,4,5,6,7,8-octa-phenylporphine and -azoporphine Octaphenylporphyrazine, the tetrabenzoporphins, for example tetrabenzoporphine and the zinc complex of tetrabenzoporphine.

2. Other types of photosensitizer materials include chlorophyll such as a-chlorophyll and β-chlorophyll, hemin, the tetraazoporphins, chlorophyllin salt derivatives such as the reaction product of an alkali metal chlorophyllin salt with sodium bisbisulfite, hematoporphin, mercury proto- and -hemato-borphine its derivatives and tetrakis (l-naph-tyl) porphin.

3. Related porphine-type materials include phthalocyanine and metal complexes such as zinc and magnesium complexes of phthalocyanine, as well as phthalocyanine derivatives such as the barium or calcium salt of phthalocyanine sulfonic acid, acety-lated phthalocyanine, alkoxy- and aryloxybenzo-substituted phthalocyanines, 5,5 ', 5 ", 5" 'tetraamino-metal phthalocyanine-4,4', 4 ", 4" 'tetrasulfonic acid, magnesium tetra (4) methyl thiophthalocyanine, aryl thioethers of phthalocyanines, vinyl group-containing tetraazoporphins and polymers thereof, mercaptoaminophthalocyanine derivatives and Phthalocyanine.

4. Other photosensitizers include fluorescein-type dyes and light-absorbing materials based on the triarylmethane core. Such compounds are known and include crystal violet, malachite green, eosin and rose bengal and the like.

Paths 1 and 2 in polymer production can in fact occur side by side during the emulsion polymerization or copolymerization of butadiene or isoprene.

Suitable polymer substrates can contain different amounts of sulfur function. Thus, the photographic imaging process of the invention can be limited to relatively low levels of sulfur, e.g. at as low as 1 mole of sulfur per 2500 moles of monomer units. For typical thiols, this corresponds to approximately 25 mg per 40 g of polymer. Even lower levels are possible. Higher levels, e.g. 1 mole of sulfur per 1 mole of monomer unit has been found to be useful and it is believed that even higher levels are possible. Roughly speaking, higher levels result in higher sensitivities, but the image quality is also affected by the sulfur content, so it is necessary to adjust a number of complex variables for each system.

Film materials can be made from the photosensitive polymer substrates defined above by any suitable method. Depending on the nature of the polymer, film formation by coating from an emulsion, dispersion, solution or melt of the polymer may be preferred. It may serve to explain that films can be formed by coating a suitable carrier substrate, such as polyethylene, polypropylene or polyester film, with the polymer / photosensitizer mixture.

The exposure can be achieved by any suitable means, such as using an "Ascorlux" 4 kilowatt xenon pulse lamp at a distance of 76.2 cm for about 1 s to 100 s. The nature of the light source, the distance of the source from the film, the photopolymer sensitivity, the sensitizer content and other factors will influence the exposure time required to fix an image. The exposure can take place through any target with different light transmission. The use of a mask of the silver type is typical.

The image development can be effected after many working methods. For example, development can be accomplished by using a solvent to either expose exposed or unexposed areas from the film surface due to different solubility resulting from exposure under photooxidation conditions. Organic developing agents such as trichloromethane, trichloroethane, methyl chloroform, methyl chloroform / ethanol, benzene, toluene have been used successfully.

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Aqueous, alcoholic, acidic, and alkaline developing areas of the photoactive layer again, while the exposure baths are believed to be just as effective and useful. remain in place (negative manufacturing process). This

As a basis for the development of the latent image development process generally takes about 15 to 20 s. This can also be seen on changes in the color receptive polypropylene / polyester substrate film, on which the development, adhesion or adhesive strength and other changes of 5 celtic image is located, is then removed from the bath and properties between exposed and unexposed areas briefly air-dried.

build.

If desired, the developed image can be transferred to supports such as cardboard, fabric, leather, metal, plastic, glass, etc. A polymer was prepared by emulsion polymerization. io using 40 g styrene, 2.0 g trimethylolprop

It was found that the sensitivity in the presence of pantrimethylacrylate, 0.2 g of n-butylthioglycolate, 83 g of oxygen — from unsaturation in the polymer chain or laterally to free water, 1.2 g of sodium lauryl sulfate, 0.1 g of ammonium per — was significantly improved . The reason could be that sulfate and 0.1 g sodium sulfite. As in Example 1, the unsaturated function as superior pigment binder and / or was stabilized, with the exception that magenta pigment was used or serves as a "comonomer" in order to achieve the image-fixing crosslinking <5. A good image was obtained after 15 s exposure.

in addition to promoting the dimerization of radicals that may result from photooxidized sulfur. Example 3

The present invention should come in handy. Example 1 was repeated except that none was used for color proofs, contact films, masking varnishes, projection dodecyl mercaptan. After 50 s exposure films, photo prints and other applications in the graphic 20 no image was obtained.

Business.

Compared to previous systems, which rely on Example 4 photooxidation of polymer unsaturation to give a 34 g styrene, 6 g butadiene, 0.5 g bromoform, 83 g oxygen latent hydroperoxidized image, this allows the free water , 1.2 g sodium lauryl sulfate, 0.1 g ammonium-permeable system. Photographic imaging in about a 25 sulfate and 0.1 g sodium sulfite were emulsion polymerized. up to two orders of magnitude shorter (or with a corresponding time). The product was tested as in Example 1 and formed an image after 50 s exposure, less exposure, less sensitizer, etc.).

than for early hydroperoxide imaging. It was necessary to use a higher hydroperoxide system using the above formulation. It also requires the latex material to be manufactured that has not been exposed to the air. To present system less oxygen for image fixation, what was 30 1 g of n-butylthioglycolate, 0.1 g of ammonium persulfate is important where the exposure step is given under limited and 0.1 g of sodium sulfite. The mixture was carried out under oxygen conditions such as 18h at 50 ° C under nitrogen after which the polymer is isolated when exposure was made in a vacuum frame. A satisfactory yellow pigmented image will appear. was developed in benzene using this material

The following examples serve to explain the inventions that are applied for 15 s with the radiation source of Example 1. was exposed, but also when using a neutral

Black filter, which only allowed 0.09 of the incident light quantity example 1 to reach the film. «1 / 2A» 5% coverage points

A polymer was made by emulsion polymerisation and 95% coverage "M" points were open using the following components: 40g Sty-40 when using a halftone silver mask.

rol, 2.0 g 55% divinylbenzene, 0.2 g n-dodecyl mercaptan,

83 g of oxygen-free water, 1.2 g of sodium lauryl sulfate, 0.1 g of example 5

Ammonium persulfate and 0.1 g sodium sulfite. From the dry- An emulsion polymerization was carried out while a powdery product, a dispersion was prepared by rend 18 h at 50 ° C using 32 g of styrene, 1.6 g of mixing 8 g of polymer with 92 g of benzene. To this dispersion, 45 55% divinylbenzene, 0.5 g bromoform, 8 g butadiene, 83 g acidic were added 40 mg (5 mg / g polymer) tetraphenylporphin (TPP) anhydrous water, 1.2 g sodium lauryl sulfate, 0.1 g ammonium. For the flask, an aluminum cover was made of persulfate and 0.1 g of sodium sulfite. The polymer was provided by When the sensitizer was dissolved, cases in methanol were isolated and dried. 7.2 g were dispersed in 84 g about 1 g of cyan pigment powder per 15 g of photosensitive benzene. Then 0.6 g of n-butyl thioglycolate and polymer dispersion were added and shaken. 50 0.1 g of recrystallized azobisisobutyronitrile were added and the mixture was kept at 50 ° C. for 18 hours from the sensitized, pigmented dispersion. The Polymerpro film was cast on a film consisting of a 0.5 ml product and isolated and a cyan pigmented film was laminated in a polypropylene laminated 76.2 µm film made of polyester under a darkened photo chamber using a red safe-using a wire-wound rod Size 8x16 light cast as in example 1. The film was dimmed for 3 seconds. After air drying in the dark 55 exposed using the light source of Example 1, a photoactive film of about 1 µm in thickness was formed. a black filter to reduce the incident light

The desired image to be copied, a slide or tes by a factor of 0.09. When developing in benzene silver negative, a good image was obtained on the photosensi- prepared as above.

bilized film placed. In order to ensure good contact between the photoactive film and the target, the two examples 60

which are placed in a vacuum frame made of glass. The emulsion polymerization was carried out under

Compilation was then the rays of an "Ascorlux" using 34 g of methyl methacrylate, 1.5 g of trimethyloltri-4 kilowatt xenon pulse lamp at a distance of 76.2 cm methacrylate, 6.0 g of butadiene, 83 g of oxygen-free distilled for about 20 s exposed (this is mainly see water, 1.2 g sodium lauryl sulfate, 0.1 g ammonium persulfate bare radiation in the 360-800 nm range). After exposure to 65 and 0.1 g of sodium sulfate. The polymer product was isolated, the pigmented photoactive film had the same appearance and was cast as a cyan pigmented film as in Example 1 as before. When placed in a dish and covered with methyl chloroform after exposure to 50 s and subsequent development, the unexposed image was dispersed.

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The same mixture as above was prepared except that 0.2 g of tert-dodecyl mercaptan was also added before the polymerization was initiated. Using this product as in Example 1, images were obtainable using 10 s exposure with the light source of Example 1 weakened to 60% of its full value by a filter.

Example 7

A cyan pigmented film made of poly (ethylthioethyl methacrylate) was prepared and exposed as in Example 1. A visible image was obtained after 20 s exposure and development in either methyl chloroform + 5% ethanol or in toluene, although the image quality, in terms of fidelity and resolution, was not as good as that with the systems explained by the examples above.

Example 8

Emulsion polymerization was carried out using 34 g of styrene, 1 g of ethylthioethyl methacrylate, 6.0 g of butadiene, 0.1 g of n-dodecyl mercaptan, 83 g of oxygen-free water, 1.2 g of sodium lauryl sulfate, 0.1 g of ammonium persulfate and 0.1 g Sodium sulfite. The resulting polymer was isolated and cast as a pigmented film using the procedure of Example 1. An image was obtained after exposure for 5 s with the light source of Example 1 weakened by a factor of 0.09 through a black filter and after development in methyl chloroform + 5% ethanol.

Example 9

An emulsion polymerization was carried out as in Example 8, except that 34 g of methyl methacrylate was used instead of styrene. An image was obtained when developed after 45 s exposure to the light source of Example 1 without any attenuation.

gated polymer was cast as a sensitized pigmented film as in Example 1. A satisfactory image was obtained by developing after 15 s exposure with the light source of example 1 weakened by a factor of 0.09.

Example 11

An emulsion polymerization was carried out using 25 g of ethylthioethyl methacrylate, 5.0 g of butadiene, 10 g, 2 g of trimethylolpropane trimethacrylate, 0.1 g of n-dodecylmercapitanium, 83 g of oxygen-free water, 1.2 g of sodium lauryl sulfite, 0.1 g of ammonium persulfate and 0. 1 g sodium sulfite. The isolated polymer was cast as a sensitized pigmented film as in Example 1. A high quality image was obtained after i5 2s exposure with a luminous flux of 4x 104 erg / cm2 / s. The sensitization was carried out with 0.1 percent by weight tetraphenyl-porphin. In this example, a photometer was used to measure the exposure intensity.

2o Example 12

An emulsion polymer was prepared using 29 g styrene, 1.6 g trimethylolpropane triacrylate, 7.6 g ch2 = ch- © -ch2-s-ch2-c-o-ch2ch2ch2ch3

O

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0.7 g of n-dodecyl mercaptan 6.0 g of butadiene and the water emulsifier and the initiators as in Example 11. A good image was obtained after 2 s exposure with a visible luminous flux 3o of 4.0 x 10 "erg / cm2 / s and obtained with 0.1% by weight of tetraphenylporphyrin.

Example 13

An emulsion polymer was prepared using 29 g methyl methacrylate, 5.9 g ch2 = ch- -ch2-s-c- (ch3) 3,

Example 10

An emulsion polymerization was carried out using 29 g of methyl methacrylate, 5 g of ethylthioethyl methacrylate, 2.0 g of trimethylolpropane trimethacrylate, 4.2 g of buta- 6.0 g of butadiene, 1.6 g of trimethylolpropane triacrylate and 0.2 g of diene, 0.2 g of n-dodecyl mercaptan, 83 g of oxygen-free water, n-dodecyl mercaptan as in Example 11. The same 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite. The iso behavior during image generation as observed in example 10.

Claims (34)

633115 PATENT CLAIMS 1. A method for photographic imaging, characterized in that a polymer substrate containing photooxidizable sulfur functions is selectively exposed to an exposure in the presence of oxygen and a photooxidation sensitizer, and thus a latent image is generated by oxidation of the exposed areas and the latter is developed. 2. The method according to claim 1, characterized in that that the polymeric substrate also contains -C = C double bonds. 10th 3. The method according to claim 1, characterized in that the sulfide functions are introduced into the polymeric substrate by polymerizing the monomeric material in the presence of a thiol or disulfide and a crosslinking agent. 's 4. The method according to claim 3, characterized in polymerizing the monomeric material by emulsion polymerization to produce a polymer in the form of individual, cross-linked particles. 5. The method according to claim 1, characterized in that one introduces the sulfide functions in the polymeric substrate by adding a thiol to the reactive sites of a pre-formed polymer. 6. The method according to claim 5, characterized in that the reactive sites have -C = C double bonds- 25. 7. The method according to claim 5, characterized in that the pre-formed polymer is cross-linked. 8. The method according to claim 1, characterized in that the polymeric substrate is produced by polymerizing or copolymerizing sulfide-containing monomeric material. 9. The method according to claim 8, characterized in that at least one sulfide-containing monomeric material is selected from the group consisting of vinyl sulfides and ethylthioethyl methacrylates 35. 10. The method according to claim 1, characterized in that the polymeric substrate contains a polymer with -S- or -S-S units in the main chain of the polymer. 11. The method according to claim 10, characterized in that the polymeric substrate contains polyethylene sulfide or polypropylene sulfide. 12. The method according to claim 1, characterized in that that the polymeric substrate contains a polyfin. 13. The method according to claim 12, characterized in that the polymeric substrate contains a polyethylene or polypropylene. 14. The method according to claim 1, characterized in that that the polymeric substrate contains a polydiolefin. 15. The method according to claim 14, characterized in 50 that the polymeric substrate contains polybutadiene. 16. The method according to claim 1, characterized in that the polymeric substrate contains a polymer of an α, β-unsaturated carboxylic acid ester. 17. The method according to claim 16, characterized in that the polymeric substrate contains a polyacrylate polymer or a polymethacrylate polymer. 18. The method according to claim 1, characterized in that the polymeric substrate contains an aromatic polyvinyl polymer. 60 19. The method according to claim 18, characterized in that the polymeric substrate contains polystyrene. 20. The method according to claim 1, characterized in that the polymeric substrate contains a polyvinylidene polymer. 21. The method according to claim 21, characterized in 65 that the polymeric substrate contains a condensation polymer. 22. The method according to claim 21, characterized in that the polymeric substrate contains a phenol-formaldehyde polymer. 23. The method according to claim 1, characterized in that the polymeric substrate contains a polyamide polymer. 24. The method according to claim 23, characterized in that the polymeric substrate contains nylon. 25. The method according to claim 1, characterized in that the photooxidation sensitizer is selected from the group consisting of porphine photosensitizers such as tetraphenylporphine, dinaphthylene thiophene and mixtures thereof. 26. The method according to claim 1, characterized in that one selects the polymeric substrate so that the exposed and unexposed areas have different solubility in at least one solvent, and that the latent image with this solvent by removing the more soluble areas from the exposed polymer Substrate developed. 27. The method according to claim 1, characterized in that one selects the polymeric substrate so that the exposed and unexposed areas have different adhesion to at least one other substrate, and that the latent image is developed by selective transfer of one of these areas to the other substrate . 28. Polymeric substrate for carrying out the method according to claim 1, characterized in that it contains sulfur functions and a photooxidation sensitizer, these being present in a sufficient amount to give a developable latent image in the polymeric material after exposure in the presence of oxygen if the exposure is of insufficient intensity to produce a latent image in the absence of sulfur functions. 29. The substrate according to claim 28, characterized in that it contains -C = C double bonds. 30. The substrate according to claim 28, characterized in that it is produced by polymerizing monomeric material in the presence of a thiol or disulfide and a crosslinking agent. 31. The substrate according to claim 30, characterized in that it is produced by emulsion polymerization and contains individual, crosslinked particle shapes. 32. Substrate according to claim 28, characterized in that it contains a polymer with -S or S units in the main polymer chain. 33. Substrate according to claim 32, characterized in that it contains polyethylene sulfide. 34. Substrate according to claim 32, characterized in that it contains polypropylene sulfide.