DE1572058A1 - Reprographic process - Google Patents

Description

Dr. Hans-Heinrich Willrath _D _ _{62 WIESBADEN> 7} . _{Aug 1965}

Dr. Dieter Weber 1572058 ^{Postfath 1327}

PATENTANWÄLTE G _U s »vF _rey « _g -St »6 _e 25 IH / gS

Telephone (08121) 37 27 20

Telegram address: WILLPATENT Postal check: Frankfurt Main 6763 Bank: Dresdner Bank AG. Wiesbaden

Account number S76 8O7

P 15 72 058.8 - (K 58 010 IXa / 57b) Case No. 78

Keuffel & Esser Company ——————

Keuffel & Esser Company, Adams and Third Streets, Hoboken, NJ _f USA

Heprographic procedure

Priority t December 30, 1964

corresponding to Japanese application 39-74522

The invention relates to a new reprographic method, in particular to a method in which a photochemical conversion with subsequent toner development is applied will.

The term teprographic used in this description Process "is intended to generally encompass any production process, using various principles including those previously known photographic process can be applied.

Various reprographic processes are already known

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New © documents (Art- 7 SI Para. A No. I Sau 3 of the amendment aea. Of 4.9.19671

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1 ^ 72058

to make a reproduction of an original, for example of handwritten documents, printed matter or there: - same. These processes include diazo processes, silver djf fusion transfer processes, electrophotographic processes, thermographic processes, etc. These known processes however, have drawbacks in that they require the use of copy transparencies containing expensive agents. It also has the image obtained by known methods occasionally shows discoloration or voids. Some of the known procedures must necessarily be done in a photographic darkroom or using means that are strong become corrosive or have an incompatible odor. These disadvantages, as they occur according to the prior art, can be overcome by the method according to the invention will.

According to the invention, a reprographic method is proposed, in which a photosensitive film is exposed through an original bearing the image, a latent Image corresponding to this original is created and the latent image formed Ann as such or after thermal treatment is developed with a toner to obtain a reproduction of the original. The photosensitive sheet includes one Carrier and thereon a coating of a photosensitive Schjdit, which is a usually non-dust-absorbing, Contains thermally non-transferable substance because: by photochemical Implementation alone or after subsequent thermal Treatment can be converted into a dustable mass. ÖÖ9810 / U54

As used herein, "non-dust-accepting" means that the material has little or no dust-holding properties. It should be noted that the term " ^{non-developable with a toner 11} " has the same meaning as "non-dusting" when the former term is used in connection with an image.

The term "thermally not transferable" used here means that a material distributed on a carrier cannot be substantially transferred to a transducer, either then not if the material present on a carrier is combined with your transducer for several seconds on an elevated Temperature is maintained.

The subject of the invention is a new reprographic process, in which a photochemical conversion with subsequent toner development is used. According to a feature of the Invention receives permanent copies with good contrasts from the original. According to another feature of the invention one can economically make multiple copies of the original. Another feature of the invention can be seen Make an original film that you can use for further haste of several copies is suitable for duplication processes. According to the invention, a photosensitive one is used Foil in the new reprographic process.

The method according to the invention is characterized in that that he

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a) imagewise exposed a reprographic material which contains a carrier film with a coating of a photosensitive diazonium salt, which is normally dry and ^{non-adhesive at a given temperature between about 50 0} C and 300 ⁰ C and forms light decomposition products on exposure, which form a much larger one Show adhesiveness than the diazonium salt at the given temperature and in the exposed areas during the coating process at the given temperature result in an image of significantly greater adhesiveness and

b) at least the exposed areas of this type of material treated so that they give a clearly visible image corresponding to the exposed areas.

Heretofore known copying method using the education of dust-binding or dust-developable images include processes which take advantage of the selective distillation of oil is (Japanese Patent 17 166/1962 ^ »that as "Imagic Process" is referred to, and processes in which the supercooling phenomenon is exploited (Japan Printer, Vol. 47, No. 4, page 12 (1964). These known methods in which however, a latent image corresponding to the original is formed by infrared radiation have the disadvantage that one with an ink difficult to absorb IR rays The part described by nature is so insensitive that it is n ± ht transferred to the copy film. In contrast, allowed the reprographic method according to the invention, in which a photochemical conversion of the photo-

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sensitive materials is made, the reproduction of originals with a poorly IR absorbing pattern. The electrophotographic A method is known as a method using toner development. This known method however, it is not satisfactory when the original to be reproduced is a continuous tone photograph or includes a black part of the large area, since the method only makes a copy with poor image quality accordingly the so-called "edge effect". In contrast, can according to the invention, even a continuous tone original or a large black zone becomes a sharp and sharp one reproduce clear image.

Suitable photosensitive substances which can be used according to the invention are usually not dust-binding or not thermally transferable, but can be converted into such a state after photochemical conversion, that they have dust-binding properties immediately or after thermal treatment. The simplest example of such material ien are light-sensitive diazonium compounds that enter into such a photochemical conversion. Suitable materials are, for example, the double salts of 2-: methyl-4-N-diethylamino-benzene-diazonium chloride, p-N-ethyl-H-ß-hydroxyethylamino-benzene diazonium chloride, N-dimethylaminobenzene diazonium chloride, N-diethylamino-benzene diazonium chloride, 4-N-benzoylaraino-2,5-diethoxybenzene diazonium chloride, N-ethyl-N-benzylamino-benzenediazonium chloride and 4-morpholino-benzenediazonium chloride with tin chloride, also suitable are 4-N-diethylamino-

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2-etho: ry-benzenediazonium boron luoride and 1-diazo-2-naphthol-4-sulfonic acid. All of the above-mentioned diazo compounds are usually non-dust-binding and, moreover, are not thermally transferable to such an extent that they can be transferred to a receptor to a significant extent if they

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applied to tracing paper (40 g / m) as a carrier and covered with a transducer and treated from the back of the carrier for a second with a heating roller with a surface temperature of 180 ° C for thermal treatment. After photochemical conversion, these compounds can be thermally transferred under the conditions specified above. The specified compounds can be used alone; two or more of these compounds can be used to achieve increased sensitivity.

When carrying out the reprographic method according to the invention, the photosensitive substances indicated above can be applied in one layer on a suitable support. To prepare such a reprographic element as described above, the following general methods can be used: The photo-sensitive substance, with or without a small amount of a binder, is prepared as a solution or dispersion which is applied to the surface of a support. Suitable supports include paper and metal or plastic foils. Suitable binders are film-forming, hochmolelculu> -o materials with poor heat softening properties, e.g. B. gelatin, polyvinyl alcohol, carboxymethyl cellulose, Vinylchlorld vinylidene chloride

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Mixed polymers, vinylidene chloride-acrylonitrile mixed polymers, Ethyl cellulose, cellulose triacetate, etc. When a carrier with a slightly räoen surface is applied, can optionally rubbed a photo-sensitive substance on the surface to obtain a suitable reprographic element. The photosensitive substance can also optionally either entered into a paper-forming material or applied to the surface of papers to create a reprographic To obtain copier paper that contains an inner layer of the photosensitive substance.

The formation of a latent image on one so produced reprographic element is done by exposing the element by an original having the image. This can be achieved in a suitable manner with the aid of a conventional diazo copier printer used. The use of such a printer is particularly advantageous because the printer is touch-sensitive of the reprographic element with the heated glass drum of the printer both light and heat at the same time supplies. To reproduce microfilms as originals, exposure using an appropriate optical system is sufficient Systems, e.g. B. a magnification device in which an Osram UV lamp-500 is used as a light source. If that reprographic element is exposed, an image-white takes place photochemical conversion of the photosensitive substance through which the corresponding latent image is formed, the dust-binding one Has properties.

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However, there are some cases where the photosensitive components used only give images when exposed to light which are thermally transferable and do not bind dust. In such cases the exposed reprographic element will appear heated to a suitable temperature, whereby an image part, which is formed by photochemical change, is then transformed into a latent one Image is converted, which has dust-binding properties. For your skilled person it is clear that in this description Applied term "thermal treatment" means the direct application of heat and also a thermal transfer to one includes suitable transducer.

According to the invention, the latent image formed on a reprographic element is developed with a toner and a reproduction is thereby obtained. Various methods can be used for this purpose. When only a single reproduction is required , or when an offset pattern or alcohol print pattern is to be obtained, the latent image formed on the remotely reprographic element can be developed directly with a suitable developing toner. According to another embodiment which shows the particular advantages of the invention , the latent image formed, which is thermally transferable, is transferred to one or more receiving foils on which the transferred image is developed with a toner. This design allows a number of copies to be made. Typical processes include the arrangement of the element carrying the latent image on a suitable receiver sheet, face to face, and now guiding them together.

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Settlement over a whale kept at 50 to 300 C or Using the composition together with an infrared absorbent film, e.g. B. black paper, duroh a thermographisohe Kopieranügge, in which an infrared lamp for Application. This thermal transfer technology makes it possible to transfer a latent image onto several receptor foils to reproduce. Each of these transferred images can be developed with toner dust. This method yields great results clear copies with good image resolution, possibly due to the fact that image transfer is in the vapor phase he follows. All papers are suitable as receiving foils, which means the cost of the single copy can be kept very low. Plastic films or - Foils and metal plates are used, and therefore the reprographic process using the thermal transfer technique is used, also suitable for the production of stencils or printed switchboards.

A toner suitable for development is made by mixing in a pigment made into a resin as a binder that melts at a relatively low temperature or in organic Solvent vapors can be easily dissolved, the mixture formed then being reduced to a particle size of 5 is powdered to 100 microns. In general, a toner suitable for an electrophotographic process can be used as such “By choosing a pigment with a suitable color, you can make copies of any color you want. When using a pigment that is resistant to heat, light

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and is resistant to chemical attack, copies can be made that essentially never discolor or empty exhibit. Furthermore, if a suitable resin is selected, a doner suitable for an offset printing pattern can be obtained suitable iBt. If you use a dye that is soluble in an alcohol-like solvent, instead part of the pigment, a toner is obtained which is suitable for alcohol printing patterns.

When developing in the reprographic method according to the invention, the above-described toner in for electrophotographic processes, e.g. B. Cascade method, magnetic brush method, abdominal chamber method, etc. are known used. The developed image can be fixed in a known manner, e.g. B. by applying heat or treatment with a solvent.

The method according to the invention can be used as a so-called "negative-positive method" be considered because the exposed part becomes dust-binding on a photosensitive film. Therefore A negative image should be used as the original if a copy is to be made that has a positive image shows. The original with a negative image can be easily produced by known photographic methods. However, Jsb can also be a positive copy of an original with a positive image if the following procedures are used: It becomes a reprographlsches Element manufactured using a carrier that has a

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has a dark colored HJitergrnnd and this element through a Original exposed with a positive image. The part that is called The result of the photochemical conversion has been converted into a dust-binding state, is treated with a toner, which contains a white pigment such as titanium white or lead white, giving a positive image. It is easier when the reprographic element is exposed through an original and then heated. After that, the total surface of the The film is exposed and a positive image is obtained. If a reprographic element with a white background is used, the part that has become dust-binding after exposure is treated with titanium white or another toner to reduce the dust-binding Property to be completely eliminated, and then the entire surface of the reprographic element evenly exposed to the surface parts of the positive image of the original to convert into the dust-binding state. The element is then treated with a conventional coloring toner to make behave a developed positive copy.

The method according to the invention is a completely new copying process, thereby overcoming several disadvantages encountered in the prior art. In particular, according to of the invention does not require a photographic darkroom, and since it is a drying process, it can be done quickly Dry copies will be received. For the reproduction of documents, the method according to the invention is also one of the most economical copying process and in the production of a number of heads the necessary costs are each one

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single copy compared to the cost of common procedures very low. According to the invention, one also obtains a

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a rough copy that does not discolor / or has voids, as the visible image is formed by treatment with a toner containing a permanent pigment. Another advantage of the invention is that the method allows thermal transfer of an image from a single copy (as a pattern) to several ordinary sheets of paper. Yet another advantage is that, according to the invention, a reproduction of any desired color except black can be obtained when a toner with a suitably colored pigment is selected for development. If negatives separated by color are used in a superimposed state, nan can also produce colored copies.

The invention is illustrated in the following examples. example 1

Finely powdered 4-N-Benzoylamino-2,5-diethoxy-benzenediazonium chloride-zinc chloride double salt is applied to tracing paper with the aid of buffing rollers in the final stage of a papermaking process worn out. The photosensitive reprographic film thus produced is with an original in Brought into contact with a handwritten tracing paper with back to front. This composition is made from the side of the original (front copying) using a commercially available Diazo copier with an 800 watt mercury lamp and a light source

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exposed with a glass drum with a surface temperature of 7O ^{0 C.} The exposed part is now dust-binding. It is then dusted with a powdery toner and heated, and a fixed image is obtained which is negative with respect to the original. Optionally, this part can be dusted with titanium white and then the entire surface of the film can be irradiated with ultraviolet light, which makes the remaining part dust-binding. The film treated in this way is treated with a coloring toner in order to achieve the development of a contrast image which is positive with respect to the original.
Example 2

A powder mixture of pN-dimethylarainobenzene diazonium chloride-zinc chloride double salt and α-methyl ^ -N-diethylaminobenzene diazonium chloride-zinc chloride double salt (in a weight ratio of 7: 7) is rubbed onto sized paper with the aid of buffing rollers. When using the printing machine of Example 1, an appropriate printing time for this mixture is 4 seconds, while ifc the most individual components is about 10 seconds _0. This means that a doubling of the speed is achieved when a mixture is used of two components, "The The latent image formed can be developed as described in Example 1 «,

Example 3

A solution of p- (N-ethyl-ff-benzylaraino) -benzoldiazoniurachlorid-zinc chloride double salt in ÄtlsLalkohol is on a

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glued paper and then dried.

The photosensitive reprographic sheet thus prepared is in intimate contact with a photographic halftone negative brought and then from the front using a diazo printer copied. The negative is removed and the reprographic film is treated with a toner and then heated for fixation. Then the entire surface the slide irradiated with ultraviolet light to the photoerapfindllche Material that was left behind in the light-image pools is to decompose. A copy with a satisfactory continuous tone is obtained.

Example 4

A microfilm negative is printed onto the photosensitive reprographic film of Example 3 with the aid of an enlarger in which an Osram 500 UV lamp is used as the light source. The film is then ^{heated to 70 °} C. for 5 seconds and then processed in the same way as in Example 3, a copy of good quality being obtained.

Example 5

A sand-ground aluminum plate 0.15 mm thick is with a methanolic solution of 0.6? $ 4-M ~ ethyl-If-ßhydroxyäthylamino) ybenzoldiazoniumchlorid-zinc chloride double

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salt coated and then dried.

The photosensitive member formed is similarly exposed as in Example 1 and then treated with a toner for offset pattern printing. After fixing by warming a visible image is obtained on an alurainiura plate. The plate is then washed with water so as not to decompose Remove photo-sensitive component. The one made in this way Plate is suitable as an offset printing pattern and has an oleophi-Ie Image area and a hydrophilic Hchtbildflache.

Example 6

? O g 4- (N-ethyl-N-ß-hydroxyäthylamino) benzene diazonium chloride-zinc chloride-rDouble Sala are with 500 ecm of a 2, above ethyl acetate solution of vinyl / iniBrid-acrylonitrile copolymer (which is commercially available under the name Saran F 220) mixed. The mixture is in a ball mill for 24 hours grind »The resulting dispersion is applied to a polyester film (0.05 ats thick) and then dried. The formed photosensitive film contains the photosensitive

2 components in an amount of 0.9 g / m ".

A usual ·?.? photographisob.es negative placed and the whole with an exposure ::? it of 40 seconds using i ^ v the same slide copier as in Example 1 from the front cop ::: rt. The foil is jet? "* .: for use as a pattern for ther ·: * ·".? Before tJT? Transmission? I finished, Sin unprocessed

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Sized paper is brought into contact with the surface of the film bearing the latent image. From the rear of this composition 0.5 seconds is applied by means of hot rolls having a surface temperature of 12O ⁰ C heat. The photodecomposition product of the photosensitive component is thermally transferred to and forms the receiver paper
corresponding latent image, which is then mixed with a powdery
Toner is developed and fixed with trichlorethylene vapor.
By repeating these procedures, 20 clear copies can be obtained.

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Claims (1)

Dr Hans-Heinrich Willrath icnonRft d-62 Wiesbaden, 7. Aug. 1969 Dr. Dieter Weber '°' ^{L υ 5 q} p «*» * «27 PATENTANWÄLTE * Gustav-Freytag-Str «!« 25 IM phone (0M21) S7 27 20 Telegram address: WHAPATENT - J [ψ » Postal check: Frankfurt Main 67 63 Bank: Dresdner Bank AG. Wiesbaden Account No. 876 807 £ 58 010 IXa / 57b geuffel & Esser Company Case No. 78 Claims 1. Beprographic method, characterized in that one a) imagewise exposes a reprographic material which contains a carrier film with a coating of a photosensitive diazonium salt, which normally dry and non-adhesive at a given temperature between about 50 ° C and 300 ° C and upon exposure to light Forms light decomposition products, which have a substantially greater adhesive power than the diaionium salt in the given temperature and in the exposed area chen in the coating at the given temperature an image of substantially greater adhesion and b) at least the exposed areas of this material are treated in such a way that they form a clearly visible image according to the exposed areas. 2. The method according to claim 1, characterized in that a) the exposure takes place at a temperature which is at least ao high, such as the given temperature and 0 0 9 810/1454 New documents (Art 711 Ab ·. 2 No. I sentence 3 of the Xnderunflset * of 4.9.1967] b) this treatment stage la essentially consists in that a finely divided powder is applied to at least the exposed areas of this seal, which is visibly different τοη the unexposed areas of the coating. 3ο method according to claim 1, characterized in that a) the exposure is carried out at a temperature below the given temperature and b) the treatment consists essentially in that 1) the material uniform to at least the given Temperature heated and Z) at least on the exposed areas of the coating • is applied in finely divided powder which is visibly different from the unexposed areas of the coating. 4. The method, characterized in that a) imagewise reprographic material is exposed which has a carrier film or a coating of a "light-sensitive diazonium salt selected from the group consisting of p-phenylenediamines diazotized on one side and 1-diazo-2-naphthol-4-sulfonic acid, which Diazonium salt usually not adhesive 1st, becomes adhesive on exposure and thus an adhesive image in the coating according to the imagewise Exposure generated, and b) at least on the adhesion lbbildber «ioh · the confessional 00981 Q / H 5 4 a dry, finely divided powder is applied, so that the powder adheres to these adhesive areas of the image and starries the image. 5. The method according to claim 1, characterized in that a) the coated surface of the material is brought into contact with a pick-up foil, b) the material is heated to at least the given temperature, c) the sensor flea removed from the material surface and as a result, part of the coating in the image areas of larger adhesion properties from the material surface is transferred to the transducer height and d) at least on the transferred image areas on the A finely divided powder is applied to the sensor surface, the visible τοη the Aufnehaerflache is different. 6. The method according to claim 1, characterized in that the Attached is carried out at a temperature which is at least as high as the given temperature, and the treatment consists essentially in that a) a finely divided powder is applied at least to the exposed areas of the coating, so that this to the «material adheres in these areas, b) non-adhering powder is removed from the material, o) the reprographic material thus partially treated is uniformly exposed at a temperature at least as high as the given temperature, so that in the 00-98 10 / U 54 -χ- · 1 §72058 to previously unexposed areas of the coating the much greater adhesion damage is achieved and d) a second, finely divided powder is applied at least to the previously unexposed coating areas that is different from the first pudeqeq, 7. Beprographisohes method, characterized in that a) reprographic material imagewise ultraviolet light is exposed, wherein the material la essentially consists of an electrically non-conductive IrÄgerfolle alt a Coating consists of liohteapfindliohea Biazeniuasalz, whereby in the exposed areas of the Sateria-Ies diazoninesalz - light decomposition products are formed that have a much greater adhesive capacity as the SiazonlUBsalz, b) at least on the exposed areas of the material A finely divided powder is applied which essentially consists of a large number of dry, solid pigment particles, the size of which is about 5 to 100 microns so that the powder is at least slightly exposed to the light decomposition products adhering to the exposed areas, c) Powder that does not adhere to the decomposition products removed from the material and d) a substantially direct adhesion of the at least slightly adhering powder to the material is moved. 009810 / U54 ORIGINAL INSPECTED