DE1571832A1 - Process for making copies - Google Patents

Description

DR. E. WIEGAND 8000 MÖNCHEN 15, February 18, 1966

MÖNCHEN NUS6BAUMSTRASSE10 _{Λ r n Λ Λ} «-

DIPL-ING. W. NIEMANN phone * 55547 «10/1832

HAMBURG

PATENT LAWYERS

Expl.

W. 12463/66 13 / Pe

i Shashin. Film Kabushiki Kaisha Kanagawa (Japan)

Process for making copies

The invention relates to a "method for Making copies and in particular to a method for making a number of copies ordinary papers.

According to the invention, a copying method is provided in which one with a photosensitive or heat-sensitive material coated sheet or web-shaped intermediate material exposed, images from transferable material, which has a tendency to Has formation of a metastable liquid "if its melt on the intermediate sheet or the intermediate web in the corresponding to the position of the images on the original sheet Areas is cooled, part of the image of transferable material on a recording sheet or a Receiving web, for example on ordinary papers and films, transfers and then the transferred image subjected to powder development and fixation.

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The image copied in this way is so stable that the discoloration which occurs with ordinary copier materials with silver salt and deterioration in quality does not take place. This represents a first feature of the invention. A second feature of the invention can be seen in that the above-described transfer operation can be carried out several tens of times, i.e. h »that from one Intermediate material a number of copies or reproductions can be obtained.

In the method according to the invention, any original can be used, provided that it is a Is original, the image parts of which have a selective absorption factor against infrared or ultraviolet rays. This represents a third feature of the invention.

A fourth feature of the invention is that the incorporation of any special chemicals in a receiving sheet is no longer necessary and also a dark room and the use of any Liquid is unnecessary, d. H. the treatment or processing to produce copies is a dry system represent.

According to a fifth feature of the invention is Provision is made for a cheap and simple method of copying or reproducing. -

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The "method of making copies according to the invention is characterized in that one Placing copy material on an original to be encoded, wherein the copy material by applying a coating or by vacuum deposition on a '-'rager Material that releases crystallization water when heated, this arrangement has a » Transmission or reflection co ^ ieren by means of infrared exposure subjects the formed image with powdery solid material that is normally hard and not sticky at temperatures in the region of 70 ° to l? 0 ° C melts and the formation of a metastable Liquid tends to develop as the melt cools, dap hard, non-sticky material on a receiving sheet under the influence of «/ poor transfers, the recording sheet Developed and fixed with a developer powder.

ti) Sheet or sheet intermediate material - 1 A sheet or web-shaped intermediate material is produced according to the invention by that on a carrier applies a material which is capable of releasing at least a portion of the water of crystallization contained therein with heating. The bound crystal! -, Material containing satine water is preferably made of

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one which the water of crystallization in a Temperature in the range of 40 ° to 200 ° C can release. Examples of such materials are compounds, such as sodium acetate trihydrate, tribasic Sodium phosphate 12 hydrate, sodium sulfate 10 hydrate, Lead acetate trihydrate, potassium alum 24'-hydrate, ammonium alum 24-hydrate, .ammonium ferrosulfate-6-hydrate and minerals such as clay and bentonite. These compounds and minerals can be on a carrier, e.g. B. on natural or synthetic resin films, paper or the like. In the form of a »Aqueous solution, suspension or dispersion, applied will; they can also be subjected to vapor deposition Vafcuuö be subjected or they can be in the paper or rub a roughened surface of the support uniformly after being finely divided.

In the manufacture of the intermediate sheet or the intermediate sheet according to the invention, a natural or synthetic resin can be used as the bathing agent. For example, an aqueous solution or suspension of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, or polyvinyl butyral can be used as the binder. When using a polymer WässcrunlÖßliöhen! · 'Gate as binder, a polymer is preferably used the j _f Where this is water permeable

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Polymer in the form of a solution in a suitable organic solvent is used. For example can be a -ßenzollösung of a copolymer of methyl methacrylate and methacrylic acid, an ethyl alcohol solution of N-methoxymethyl-polyhexamethylene-adipamide or a benzene solution of ethyl cellulose for use reach.

In this solution, the material containing bound crystal water is in the form of a fine powder in an aqueous concentrated solution or dispersed in a suspension. The solution or suspension becomes applied to the carrier, which then dried will «When using a suspension will be more advantageous .Veise a surfactant to improve the Suspension effect added. On the other hand, the material containing bound water of crystallization can be applied to a Carrier by means of vacuum abs before id ung are applied. In this case, the crystalline water can evaporate during the application of a coating under vacuum; if however, the vacuum coated material for a longer period of time, especially for a period of at least 10 minutes, left to stand in the air, the vVapor in the air the separated compound or absorbed the deposited mineral as crystal water

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The excess surface of the sheet produced in this way or baunenförwigen intermediate material is approaching copying original placed and exposed to infrared rays »The copying that takes place can be performed using a transmission copying process however, flexion copying is preferred, the exposure taking place from the side of the interleaf sheet or web and the formation of fog can be recycled and clear images are obtained can.

To make the flexion copying process effortless, It is necessary to select a support for the intermediate sheet or intermediate brace that is opposed to infrared rays is transparent or translucent.

The image parts of the original absorb the infrared rays to a greater extent than the non-image parts and are heated by infrared rays during exposure. Accordingly, the interleaf is attached to the Parts of the image are heated and the crystals are heated the compound containing crystal water or the mineral containing crystal water set the crystal water free, which wets the surface of the interleaf at these points. 7 / hen this interleaf with a powder developer of the type shown below Composition is developed§ results in a different

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Different adhesion of the powder developer between the parts on which the water of crystallization has been released is, and the hurry, where no such jirscuein occurred, whereby the Fulverentv / ickler stronger at the; the former parts adheres to form an image.

". When copying an interleaf after the previous end described fieflexion copying process is carried out an image of the powder developer that is symmetrical to the original results, i. h "a so-called mirror image" This is particularly desirable in the method according to the invention.

If the exposure time to infrared rays is long, the crystals of the intermediate material corresponding to the image parts of the original first release crystal water in order to wet or moisten the parts of the intermediate material and, if the infrared exposure is continued, will '" ater evaporated, whereby the adhesive property WiM reduced to a powder developer ₄ Meanwhile give the crystals of the ISS Zwischeßuaterials

of the original / the non-image parts / corresponding parts ifrrrristallwasser due to the long-term exposure to infrared rays afc »which increases the adhesiveness of the powder developer. Hence, a negative conflict material

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BATH

from a positive original with a long-lasting one Exposure can be obtained (negative mode of operation).

The length of time between the infrared exposure process and the development process is preferably as great as possible in short »The in, development inside of, for example, 10 Seconds after the infrared exposure can result in a good intermediate material; when IG Li Minuten has passed or more after the exposure, however, a good picture will be made with a strong contrast due to the decrease in the difference the adhesion of the powder developer is no longer maintained. However, if the exposed intermediate material in air for 24 hours or more after exposure is left to stand without development, the intermediate material can again as such in a manner similar to an intermediate material that does not expose to infrared rays has been used. This is due to the fact that the crystals from which the crystal water is released had been, at the Stenen in air again the "moisture in absorb the air and convert back to the crystals containing water of crystallization.

(2) Intermediate sheet or sheet material - 2

Another sheet or sheet-like intermediate material is produced according to the invention in that

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BATH

one is a photosensitive diazonium salt or one solution containing photosensitive azide compound applies a carrier and dries the coated carrier. In particular, on the same carrier as described above, an aqueous solution of an isophthalic acid-triethylene glycol-ethylene glycol condensate, Polyvinyl butyral, maleic anhydride-vinyl acet-at-mixed pol-vmeriBats or a mixed dispersion of gelatin and a resin or resins, or an aqueous solution of gelatin as sub or Intermediate layer (subbing layer) applied and then dried »A solution of a light-sensitive diazonium salt or a photosensitive azide compound and dried.

vVenn. the direct application of a solution of the diazonium salt or the azide bond to an iräger possible the intermediate or underlay coating can of course be omitted. In this i'all there can be a suitable Coating agent of the coating solution for improvement the coating properties of the solution are added "

The photosensitive diazonium salts which are useful in accordance with the invention include those generally in US Pat Conventional diazo papers ver ended salts, for example the diazonium salts of p-phenylenediamine or their

0 0 9 8 U / 0 9 0 0 ' _8A D ORIGINAL

- ίο -

Derivatives, or of p-aminodiphenylamine, the diazonium salts of p-monoalkyfniline Pjp-tetrazodiphenyl or its derivatives or double salts, sulfates, fluoroborates thereof or the substances used for lithographic printing materials, ζ = B. High molecular weight compounds represented by the formula given below:

CH

-NH-

CH,

-NH-

CH ₂

-N ⁺ Cl ⁷ ZnCl.

^CH

-? ^H In

CO

NH

ZnCl,

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BATH

Used as photosensitive azide compounds according to the invention those used for common uiazo paper, such as phenylazide, naphthylazide or theirs Derivatives, preferred "

As a solvent for applying the solution is in the case of - ^ iazonium salt water and in the case of azide compounds Dimetriylformanide commonly used. the Solution of the diazonium salt "or the azide compound also contains gelatin or one or more synthetic heaters as indicated above

The j ^ räfeeroberflüchseite (back side) of the so produced sheet or web-shaped intermediate material is on a translucent or translucent original that is to be copied, and one with light Wavelength to which the diazonium salt or the acid salt is sensitive, exposed by the original, for example using a mercury lamp, the transmission copying process from the back of the original is followed. On the other hand, the overdone Surface side of the leaf-shaped or thimble-shaped intermediate material placed on a transparent or translucent original, turned over a transparent support and then with a mercury lamp after the transmission

the

Copying process exposed from / top side of the original.

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If this sheet or web-shaped measure; crial with a powder developer having the composition shown below is developed, sicn results from a detention submission of the powder developer against the exposed and unexposed parts of the intermediate material of the powder developer. Auen in this case is the picture of the powder developer symmetrically or a mirror image the original »

(^) Powder developer for developing an exposed Intermediate material

after exposure is / Powder developer zur- ^ evelopment / the sheet-

or sheet-like material, as described in (1) or (2), is formed from a transferable fluid that tends to form a metastable liquid when the melt cools down. In addition, an infrared ray absorption material can be incorporated into the powder processor . In this i'all a sheet of the intermediate material can be transferred to an Λ-sheet by means of infrared heating. There are various transferable materials, some of which are described in detail in Belgian patents 631,304 and 644,239. In the method according to the invention, such transferable materials should in particular be selected so that they are non-adhesive at room temperature, but after melting at a

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Temperature in the range of? O ° to 170 ° C to become tacky and a iioh.es Unterkmilungsvermagen have ie _s "that it is in a metastable -tf'lUssigkeitsphase ia eiüea? remain at room temperature for a few or more ten minutes after melting and cooling »

Typical examples of such transferable materials are plasticizers, "Santicizer 9" and "Aroclor 1268" (sold by Monsanto Chemical Company), benzotriazole, Tribenzylamine, Vanillin, Fhthalophe # Qö. ·., 2,4-Dihydroxybenzopnenone, Benzyl, benzoin, sulfur, acetanilide, benzoic acid and phthalic anhydride.

A finely divided inorganic or organic pigment is used as an infrared ray absorption material used. Special examples are Huss, iron oxides, Chrome green, ultramarine blue, cobalt blue and indigo.

The winding of an exposed intermediate material Powder curler used in the method according to the invention is made according to the procedure given below Prepared: One part by weight of a transferable material is mixed thoroughly with 0 to 0.1 part by weight of a finely divided, infrared rays absorbing material mixed and heated. When the transferable material -.- melted is, the molten vision becomes sufficient

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mixed further and cooled to fiorial temperature => After the molten mixture has completely solidified it is finely pulverized by suitable means and then to a grain size of 0.1 to IOC microns in diameter grains A mixture of a powder developer used in common • c-electrophotography (called "Toner") and finely divided transfer material can be used in the method according to the invention used as a powder developer for • developing an exposed intermediate material will"

(4) Transfer of a sheet or web-shaped Intermediate material on a sheet or web-shaped Recording material

After a mirror image on the sheet or tree-shaped intermediate material described under (1) or (2) of an original was formed by the powder developer described under 0), becomes the intermediate material heated by suitable means to raise the temperature to the melting point of the transferable material, whereupon it is cooled to Räumepperatur; that will Powder image of the original on the sheet or web-shaped Intermediate material fixed. The coated side of the sheet or web-shaped intermediate material treated in this way is applied to a recording sheet or web, e.g. B,

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Paper, film, glass, cloth or the like. laid and heated. That Heating is carried out by placing the assembly between two hot plates or using infrared radiation On the other hand, the surface of the intermediate material can be heated by infrared radiation, whereupon a recording "sheet is placed over it and the arrangement is pressed ο

A part of the image part of the sheet or web-shaped intermediate material is placed on a receiving sheet or transfer a receiving sheet. When infrared ray heating is used, the transfer material is preferably made an infrared ray absorbent Material added

In this way, the transferable material is transferred to a receiving sheet or web. This transferable material with the supercooling properties has the effect that when the powder development is immediate after the transfer is carried out, the powder developer is only applied to that part due to the adhesiveness or tackiness of the transferable material adheres to form an image.

As a powder developer for developing a recording sheet can be any fine powder with a suitable grain size to melt at a transferable

material

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to adhere, to be used »Suitable powder developer werien generally by dispersing in one

Molded thermoplastic resin, e.g. B. a pheno-1-saldehyde resin, a molten mixture of chlorinated naphthalene and polystyrene, or a lipophilic polymer of vinyl chloride and vinyl acetate, a carbonaceous iuaterials, such as soot or asphalt powder, an inorganic pigment, such as basic bicarbonate, zinc oxide, titanium dioxide, antimony trioxide, iron oxide, cadmium sulfide, basic chromate, Molybdenum orange, cadmium yellow, chrome green, ultramarine blue, or an organic pigment such as benzidine yellow, indigo, and alizarin, and granulation or graining of the dispersion prepared in this way ηε-ch a suitable process to cores with a diameter of 0.1 to 50 Micron made. E ".n for the gebräucalicae - ^ lekterophotographie the toner used is used in the method according to the invention. The color of such - ^ ntwic ler should be in accordance with the color of the recording material to get voted.

Powder developer, the surface of which has an upper surface active agent has been treated as described in the applicant's patent application .... can be used in the Methods according to the invention can be used.

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If the material is heated after development or treated with the vapor of an organic solvent such as trichlorethylene (trichlene), freon, acetone, chloroform or benzene, a visible copy image which is not affected by light and moisture and is durable and can be obtained can be stored permanently ₀

The transfer of a transferable material to a sheet or web-shaped recording material from a sheet or sheet-like intermediate material can be some tens of times be repeated.

The invention is explained in more detail below with the aid of examples.

example 1

(1) Manufacture of powder developer for development of the intermediate material

(a) 20 g of a powdered plasticizer on the basis of a mixture of o- and p-toluene sulfonamide (Santicizer 9) and 1 g of carbon black were geaischt and heated to 110 ⁰ C to melt the mixture · The molten mixture was stirred and mixed in the molten state, cooled to room temperature and, after solidification, granulated or granulated to a size of less than 74 microns in diameter.

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(b) 20 g of powdered benzotriazole and 1 g of carbon black were mixed and ^{heated to about 100 °} C. to melt the mixture 7 ^ microns or less in diameter granular »

(2) Manufacture of the intermediate material

5 g of gelatin were dissolved in 200 ml of v / water. 5 S sodium acetate trihydrate were dissolved and mixed with 40 ml of ethyl alcohol while stirring. The stirring was continued during further Continued for 2 minutes «(Ethyl alcohol serves to promote the favorable growth of sodium acetate crystals and their drying). A mixture of 10 g zinc palmitate (to reduce fogging) and 100 ml ethyl alcohol was treated in a ball mill for 24 hours "to give a dispersion; 10 ml of the obtained dispersion were added to the above solution. The resulting mixture was after thorough stirring on a cellulose triacetate film backing applied to give a coating at a rate of 60 ml / m, and under Formation of an intermediate material dried

The side of the intermediate material provided with the coating was applied to an original and subjected to a reflection copying process by copying the reverse side of the

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sheet or web-shaped intermediate material was exposed with infrared rays. "The infrared exposure was carried out using a Thermofax Model 4-6 Secretary copier (manufactured by Sumitomo-3M Co ₀ ) ) described powder developer. After the powder development, heating was carried out by means of infrared rays and the image was fixed, whereby an intermediate image or an intermediate copy was obtained.

Then a recording sheet was stuck on the picture surface of the intermediate material and placed by means of a heater or heated by infrared radiation from the back of the intermediate material to form part of the transfer material to melt and transfer this to the receiver sheet. The receiver sheet then underwent powder development using a toner for Xerox 9Ί4-Office Oopier (from Fuji-Xerox GoI, Ltd «,) subjected to what was fixed in trichlene vapor. About 30 sheets of prints or copies were obtained

Example 2

10 g of gelatin were dissolved in 200 ml of water x 10 g of sodium acetate trihydrate were dissolved and 20 ml of ethyl alcohol was added with stirring. Stirring was continued for an additional 2 minutes. A mixture of 10 g of barium

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BAD OPJGMAL

stearate and 100 ml of ethyl alcohol were treated in a ball mill for 24 hours to obtain a dispersion. After adding 30 ml of the dispersion with stirring to the above solution, the obtained mixture was applied to an oil triacetate film support, whereby a coating of 75 ml / m was formed; after drying, an intermediate material in the form of a sheet or web was obtained. The intermediate material placed on an original was exposed and developed in a corresponding manner as described in Example 1. The powder developer described in (1) - (b) from Example Λ described in (1) - (b) was used to develop the intermediate material irradiated and the image was fixed, whereby an intermediate image was obtained «

The transfer, development and fixing of the intermediate image was carried out in a similar manner to that described in Example 1 executed »

Example 5

The procedures and treatments described in Example 1 were carried out with the modification that the sheet or sheet-like intermediate material was produced by pulverizing ammonium ferrous sulfate-6-hydrate «a4 and that through a sieve with a mesh size of about 0.074 200 mesh sieve (mm) powder rubbed uniformly into tracing paper.

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Example 4

A 4% ethyl alcohol solution of polyvinyl butyral was made applied to a polyester film base and dried. A 2% strength aqueous solution of the condensation product of formalin and the zinc chloride double salt of diazotized p-aminodipher.ylamine was then applied to give a coating at a thickness of 70 ml / m, followed by the formation of a sheet or web-shaped intermediate material has been dried «

The carrier surface side of the intermediate material thus produced was applied to a transparent one to be copied Original placed and using transmission copy-dyeing exposed from the back of the original using a mercury lamp transparent

/ Original placed and turned over against a transparent carrier, and then according to the transmission copying process from the top of the original by means of a mercury lamp exposed · After exposure, powder development was carried out using the method described in (1) - (b) Powder developer of Example 1 carried out eiafewiek-elfc, with Irradiated infrared light and fixed the image to form an intermediate image.

The transfer of the intermediate image to a recording sheet, development and fixing were carried out in a manner similar to that described in Example 1.

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~ 22 -

Example 3

A 2% aqueous solution of sodium 2,1-diazonaphthol-5-sulfonate was applied to a polyester film support to form a coating with a thickness of 30 ml / m 2 and dried, with an interleaf or an interlayer was obtained.

The interleaf placed on an original was exposed and developed as described in Example 4-. To the Development of the interleaf became that described under (i) - (a) Powder developer from Example Ί Used. After the powder development, infrared light was irradiated and fixes the image to form an intermediate image

The transfer of the intermediate image to a recording sheet, the development and the fixing were carried out in a similar manner Way as described in Example 1.

^BATH

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Claims (1)

Pat complies Ίο "Procedure for listening to copies, characterized in that that he (1) A copying material obtained by applying a coating of a water of crystallization which releases water of crystallization with heating Material is produced on a carrier by coating or vacuum deposition onto a material to be copied hangs up, (2) subjects this arrangement to transmission copying or reflection copying by exposure to infrared light, (3) the image formed is developed with powdery, normally hard and non-sticky or adhesive material, which ^{melts at a temperature in the range from 70 to 170 °} C. and tends to form a metastable liquid when the melt cools down, (4-) transferring the hard and non-sticky material onto a receiving sheet under the influence of heat, (5) Developed the recording sheet with the powder developer and (6) fixed. BATH 0098U / 0900 Process according to claim 1, characterized in that a photosensitive material is placed on the original to be copied, which is produced by applying a coating of a solution containing a photosensitive diazonium salt or a photosensitive azide compound to a support, and with light of one wavelength
exposed to which the light-sensitive diazonium salt or the azide compound is sensitive and further process using the powder developer 0098 1 A / 0900