DE2359376A1 - PRINTING PROCEDURE - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT Attorneys 23593/0

8 MUNICH 86, POST BOX 86 02 45

Attorney File 24 480 November 28, 1973

SUBLISTATIC HOLDING S.A. 8750 Claris, Switzerland

"Printing process"

The present invention relates to a printing method by means of a frame or by serigraphy. Against the conventional processes using liquid inks or colored pastes are related to the present invention a dry printing process characterized in that

Case PRO-11 / E

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(0811) 988272 8 Munich 80, MauerkircherstraBe 45 Banks: Bayerische Vereinsbank Munich 453100

<D89> 98 70 43 Teleflramme: BERGSTAPFPATENT Munich Hypo-Bank Munich 389 2623

3310 TELEX: 05 24 560 BERG d Postscheck Munich 653 43-808

one or more vaporizable substances, preferably dyes, on the to be printed in the gaseous state Material through the design or motif of a printing stencil, 'based on a provisional carrier that can be vaporized with Substances is coated, transferred. It is also possible to obtain 'tints' using this procedure. The printing, The template and the temporary carrier are preferred the same dimensions as the surface to be treated and may be sufficiently flexible to allow desired to be rolled up,

The stencils or clichés used in the present invention are obtained by means of processes which are well known to the person skilled in the art in the field of frame printing and serigraphy. _m

Since the printing is carried out in the vapor phase, it is sufficient that the stencil remains stable at the evaporation temperature of the substances intended for transfer and it should be insensitive to their vapors. It is no longer necessary to increase their resistance to repeated use in the liquid phase, for example by sticking them to a carrier or by tanning. Any porous support is sufficient, whereby it is decisive that it is stable in the heat and permeable to the vapors of the transferred substance and that it ensures the or * dimensional stability of the transferred image.

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represents.

The present invention opens up many possibilities un- _t ter avoiding the disadvantages inherent process in which photomechanical _L order Äussparungen ___ ^ gebndete_kolloi ale;

Hold the images together with the provisional support _L,

without any lack of effectiveness in the method of the invention as a result of poor adhesion and displacement between the temporary support and the colloidal images enter. Because the layer that the vaporizable Substances are not subjected to the coating with the colloid of a treatment in an aqueous phase it is no longer necessary to only use printing inks whose binders are and are insoluble in water Now possible, for the production of printing stencils, the treatment, i.e. developing or washing out rides one Mixture of water and organic solvent, which avoids excessive softening of the cliché and later drying is made easier. The printing stencils of the present invention can be used for numerous transfers and with the temporary vehicles of different vaporizable substances from one use on the other hand used v / earth. Such carriers are known. They are formed by a paper or aluminum sheet, the sublimable dyes, and / or optical brighteners

¹ - ^r

Binding agent that is soluble or insoluble in water and soluble in water and they are, for example, under the trademark

mf the.

4098 24/1) 7.7 4 " ⁴ ~

"SUBLISTATIC '^ on the

μ. if- mm

Brought to market. Any other carrier with the desired dimensions, compared to the evaporation temperature of the evaporable Substances with which it is coated can be considered suitable.

The templates used in the present invention or clichés are formed by a regular or non-regular image or motif that is in one for the Vapors of the substances to be transferred impervious material is formed, whereby, as far as this is necessary, for the motif as a carrier a metal grid or net or textile material or furthermore a sheet, a sheet or Tape made of a material that can be penetrated by these vapors, while ensuring the stability of size and shape the arrangement is used, this arrangement compared to the evaporation temperatures of the intended for transmission Substances is stable.

In order to produce the stencils or clichés according to the invention, One can use a sheet, film or tape with good dimensional stability that is suitable for the vapors to be transferred provided vaporizable substance penetrable and opposite the evaporation temperature of this substance and opposite a soaking with water or the for Be-tI ~ Z .handle the liquid used is resistant, impregnate or coating with a photosensitive preparation, for the vapors of the intended for transmission

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vaporizable substance is impenetrable and in the same way resistant to the evaporation temperature of the latter and you can then dry it, expose this sensitive layer, for which purpose the regular or irregular, äßj, ee. .j intervenes the motif to be cut out, which has been executed on a transparent thin film, and then removes the non-insolubilized photosensitive material by simple washing (treatment) and finally dries it.

The templates of the present invention can be used in other Alternatively, be fabricated on a photomechanical basis, such as by means of one of the numerous known methods the hardening, corresponding to the negative of the image to be reproduced, one that can be crosslinked or polymerized with heat Substance or a preparation (for example based on epoxy or siloxane resins) or better one Substance that by decomposition under the action of heat: becomes insoluble. You can continue to manufacture v / ground durci. the melting, according to the image to be reproduced, of a material responsible for the vapors of the to be transmitted Substances is impermeable (but which is resistant to the evaporation temperature) or that for these vapors made impenetrable by post-treatment.

Those contemplated for use in accordance with the present invention Clichés can also be replaced by a film (from a fü ~

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the vapors of sublimable or vaporizable dyes impenetrable material) be formed with Has provided holes or recesses in accordance with the motif to be transferred or reproduced. You can do that Foils using electronic engraving devices for example, according to the "Rone'otronic" system, in which a stencil or a matrix is used to transfer the

Document carries. The die is "engraved" with the help of a high-frequency spark according to the chosen definition. However, the recesses can also be produced by means of a laser or electron beam. "'" ·

The webs, foils, or tapes that can be used in accordance with the present invention can be quite thin and porous to allow under the. conditions selected for the transfer, to be permeable to the vapors of the substances to be transferred; they can be, for example, a cellulosic material, such as very porous paper similar to the materials used for coloring in the Sptile, or such as porous non-wovens, known as Japanese fabrics, depending on their porosity according to the Gurley test, 'with a nozzle of 0.25 es.inch (1.61 cm ² ), a cylinder of 400 ml and a load of 5 oz. (2.27 kg) preferably less than 50 seconds) or such as materials based on Edgeworthia papyfcra, "Chinese grass fibers", manilla hemp, mulberry brown pulp or "polynosic fibers", for example in

(trons-

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versal network formation, as well as all other materials that have the 'porosity properties specified above, such as metal mesh, the porosity of which is higher than "50 mesh (0.297 mm)." _ ■

It is also advantageous to use a mesh, for example a material made of viscose or acetyl cellulose. fibers, like fine mesh made of triacetyl cellulose, which open up are available on the market. It is sufficient that these materials are stable to the transfer temperature, resistant are against developing without creasing, deforming or tearing and have good dimensional stability have, i.e. that the fibers delimiting the pores do not move against one another or against one another and are not very deformable are. Their dimensions correspond to those of the surface to be treated; their mesh size determines, of course the definition or limitation and accuracy of the image. .

The motif can be produced by a photosensitive material that is intended for the fumes of the intended for transfer Substances are impermeable and stable to the transfer temperature; as a photosensitive material you can use certain monomers or certain photopolymerizable or photocrosslinkable preparations or use certain protein colloids, such as 'gelatin', which are used for the vapors, for example the colorants.

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or'optical brighteners, are impermeable. This photosensitive material should be soluble or dispersible in water or in a mixture of water and an organic solvent, such as an alcohol, in order to facilitate application to the porous film that forms the final cliché and post-drying.

A gelatin, for example bone gelatin, is preferably used. You can also use gelatin of other horizons, such as plastic adhesives, isinglass, "Grenetine", light types of gelatin or albumin, ovalbumin, if necessary even casein, zein and even lecithin. . ·

Methods suitable for forming a latent image include exposing a material sensitized to that effect to light; To be warned is, for example, the insolubilization of gelatine, albumin or chrome gelatine by means of light, among the following

treatment with lukewarm (30 to 50 ⁰ C) or cold water or, in contrast, solubilizing gelatin or casein with light, which was previously made insoluble with ferric chloride of a diazo compound, cellulose glycolate or sodium delluloseoxyethanesulfonate , followed by treatment with acidified water.

In addition to the colloid, preferably bone gelatin in solution in water or a water-alcohol mixture of 5 to 3G # (where the proportion of ethyl or methyl alcohol is for example

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can make up 40 # of the mixture) and in addition to the sensitizer, preferably potassium dichromate with 1 to 10 #, optionally used with traces of ferric chloride (about 0.0025 #), the photosensitive preparation can also contain other adjuvants contain. The percentages are given above or below in relation to the dry weight of the gelatin. The adjuvants may be either the bonding agent counteracting _s fungicides, etc., which are intended to improve the durability and handling of the stencil, with the sensitizer or after de. Treatment can be added, as well as products intended to increase the clarity of the image, as in the case of an image of chromium gelatin, sorbitol (0.25 to Λ ° / α) , which forms a complex with gelatin and oxalic acid (0.5 to 5 ^) or the adjuvants can regulate the hardening process and moisture retention, such as the salts of amphetamine (2 to Q%) or optical brighteners and other light-absorbing substances «

The potassium dichromate can be combined with an iron-II-oxalate v / earth or by ammonium dichromate, quinoline or pyridine or by a diazonium salt of a diphenylamine be replaced. The maximum sensitivity is at the isoelectric point of the gelatin and one works preferentially in the presence of an organic acid or its salt, for example potassium citrate. These last mentioned adjuvants do not necessarily have to be

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temperature must be stable, since they are mostly during loading! ' be removed by hand

The coating can be done with the help of a doctor blade or a roller be performed. The excess liquid can be drawn off with a doctor blade or by blowing and the layer be leveled with an "air knife", i.e. a vortex-free one Air jet, the diagonally over the to be coated Material is directed. The dry sizing can be Thickness of 3 to 10 microns, for example in the case of a gelatin-based layer, Si & should reach be sufficiently thin that the cliché can be developed in a reasonably short period of time; but if it does

is too thin (less than 2 microns in the mile of üeiatine, Kömi. they are no longer impenetrable for the vapors of the substance to be transferred, for example for the dye vapors to be enough. Before exposure, the coated carrier is dried in a darkroom or under red light in order to to avoid premature hardening. Drying can be accelerated by heating and it will not be up carried out for drying, as in general a certain Percentage of moisture that changes with the selected photosensitive material, the sensitivity elevated.

Exposure is made by exposure to daylight or against an actinic light source, for what purpose a transparent or translucent film

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interconnects that creates an opaque image. speaking of the design or motif of the monochrome picture or one of the £ ildel.ement.e, ..die _das · _; Provide a multicolored image, before it is received on the support to be decorated. In the case of a photosensitive layer made insoluble by exposure, the opaque part of the film corresponds to the positive of the motif intended for reproduction. Since the hardening corresponds proportionally to the degree of transparency of the intermediate film, the exposure time depends on this degree of transparency, as well as the distance of the photosensitive layer from the light source, the intensity of this source and the sensitizer used. This time must be controlled fairly precisely. In fact, the exposure should be quite long so that the full thickness of the photosensible layer is hardened; but if it is too long, the reproduction of the details becomes poor, since the contours of the unexposed parts begin to harden in the same way. Generally, the time is on the order of a few seconds to a few minutes, for example from 5 to 1 minute in daylight, with the film in contact with the photosensitive layer. The control of the exposure time can be determined by experiment. It always fluctuates, as does the regularity and density of the photosensitive layer on the occasion of the formation of halftones, which according to this invention can be obtained by using a screened film. The finer the "grid"

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the stencil, i.e. the structure or texture of the porous material that makes up the photosensitive layer the more satisfactory are "the results.

The treatment is carried out according to the usual methods, for example by rinsing with water until all of the: sensitizer that has not reacted has been removed in order to avoid excessive hardening of the remaining parts, which could result in cracking *. You can use the water lukewarm or even warm it or add urea or thiourea "', for example, which also simplifies the treatment. You can also use a suitable mixture of water and organic solvents, such as methyl or ethyl alcohol, to prevent the Do not soften the printing stencil too much and make it easier to dry later.

After the latter, moisture is preferably retained from about $ 14, avoiding the risk of a brittle or brittle layer or reduced shelf life.

The use of a printing stencil produced in this way consists in interposing it between the surface of a support which carries the sublimable substance and the surface of the material to be processed and heating the arrangement to the evaporation temperature of the substance to be transferred for so long that it is Evaporation

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and their penetration into the material to be worked on possible.

The. sublimable or vaporizable substances after can be transferred to the method of the present invention, can colorants, such as certain disperse dyes, certain Vat dyes, optical brighteners, developers or - be sensitizers. One can also use the present invention in conjunction with the above-mentioned colorants or not, transfer any substance that

wherein a porous material throughput T is temperature vaporizable permeable and an impermeable layer photosensitive counter 'is resistant over the vapors of this substance. This substance can react with the surface to be treated or with a chemical agent carried by this surface; likewise, for example, topical products that catalyze, activate, inhibit or retard the polymerization of a coating carried by the surface to be treated, or a chemical agent can be transferred which facilitates the peeling off of a coating, the one Covering the color layer, in order to allow a more colored image to appear.

The surface to be processed can be a textile or other material, whereby it can have an affinity for the substance to be transferred or even react with it; it can be printed with a material or over- '-, ■; ■ ·. '-14-.

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«Be drawn that has these properties. Example _:

wise can be optical brighteners and / or sublimable Disperse dyes, even sublimable basic dyes on non-porous films, surfaces in the form of Loops and meshes, on fabric, npn-woven, felt, etc. transferred from synthetic materials that have a good affinity for the transferred substances (such as linear polyesters, polyamides and polyacrylonitrile) and their density can vary from that of films to veils.

These substances can be used in the same way _; ... sq. well__''

than other sublimable dyes on surfaces

of leather, felt, wool, treated cotton and others

Cellulosic materials, anodized aluminum, etc \ rendered. .

The one applied to the printing stencil. . colloidal motif itself may have a sublimable material layer 'obtained by transmission i _n the vapor phase or obtained by coating. These printing stencils can superficially:

colored, and when used with single-colored embossers, for example, enable two-color printing.

The method of the present invention combines the advantages of printing methods by means of transfer in the gas phase (i.e. processes in the dry phase and therefore without deformation, which is of great interest for ecological reasons earn and which do not require any follow-up treatment after the transfer) with serigraphy or des conventional textile frame printing (au cadre) (where the

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Prints are clear and crisp and made to be very fine Transfer details without applying them to rollers or engraved printing pieces and increased fidelity photographic images compared to, for example matrices obtained therinographically. ) The procedure enables for example in the gas phase, a black and white or

• Transferring color photography onto a polyester surface, for example, without any post-treatment of this surface. In particular, it enables microfilms to be copied, preferably on cellulose triacetate materials, since in this case a “sharpness” of up to 5 microns can be obtained.

Finally, the present invention has important and unexpected Improvements result, both a simplification of the device, as a. Gaining space or the, longer I / = bens-

duration of the printing stencils (although the initial resistance of the latter can be lower than that of traditional printing stencils). In fact, this method suppresses the disadvantage of edge defects that often occur in classic printing stencil printing and are attributable to the frame , on the. the grid, the stencil is stretched. It also makes one end of the bumps

• the Jörucktisches herrührendenNachteilen ■ that are unavoidable in industrial Verfertigungen i these irregularities caused a blemish and even the rupture of the stencil sheet by the scraper. Since the present process is a dry process, the scraper becomes useless - it is no longer

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necessary to use very long printing tables to mechanize the use of flat stencils. If necessary, an extra printing table is no longer necessary. The stencil can be attached while the big carrier "with the" web to be "printed" moves under the stencil, for example by means of an endless path. In addition to the gain in space and time as well as the resulting mechanization, this possibility shows a real economic advantage, due to "the high price of the Printing tables are used in the present process ^w

not necessary anymore . .-. W .- ,,.

In the following, non-limiting examples, unless stated otherwise, some percentages are given and temperatures relate to ⁰ °.

Example 1 · ·

Mix 4 parts of gelatin with 16 parts of water and leave Let the mixture rest for about 1 hour to allow the gelatine to swell * Then, in a lukewarm condition, give 0.04 parts of a 25;?,? - igen sorbitol solution and completed with 20 parts of water. Then add 0.05 parts with vigorous stirring

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Oxalic acid, dissolved in 1.5 parts of warm water, added and allowed to stir for about 15 minutes. Then 0.005 part of a 1% strength iron (III) chloride solution and 0.150 part of ammonium dichromate in 5 parts of water are added.

This preparation is coated over rollers. 0.8 cm wide. A sheet of fine paper that is very permeable to air and vapors and is leveled with an "air knife". After coating, it is dried in the dark at 50 ^° C. to a water content of about $ 15, which takes about 10 minutes. The regular gelatin layer obtained in this way has a thickness of> about 5 / U. The surface is exposed to daylight for 10 minutes one after the other for each motif, for which purpose a film is inserted which has the opaque motif intended for reproduction. It is then developed with a 4-O ^ ethyl alcohol solution in water and. drying, stopping the drying process before it is completely dry when the water content is around $ 14. A printing stencil is obtained which is exposed (or left out) in accordance with the motif to be printed

It is sufficient to place it on a plate heated to 207 ° for 40 seconds to press an overlay, 'the one made from the above!

The printing stencil is composed of one, according to French patent specification 1223330, uniformly printed with a yellow printing ink paper web "SUBLISTATIC ¹ T (this yellow printing ink with the dye of the

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formula

receives), and a fabric web of ethylene polyterephthalate is arranged, whereby one obtains a clear and precise print of the motif on a white background, with faithful reproduction of the finest details and without any adverse effects.
With a red, according to the French patent specification 1.573.698, based on the 'dye of the formula

using the above process, a red motif on a white background is obtained; the following dyes produce blue motifs: UHCH ₁

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where η is 1, 2, 3 or 4.

Example 2

Mix 4 parts gelatin in 10 parts v / water and 6 vol. Parts ethyl alcohol and produces a printing stencil according to the method described in Example 1, wherein one Film used on which opaque and transparent squares are alternately applied. One puts in the In the same way, but by exposure through the previously obtained printing stencil (printing stencil Np. 1) a second one Printing stencil which has openings after the negative image of the first printing stencil. One arranges the printing

stencil no. 1 between a paper web Sublistatic with red and blue stripe patterns and a sheet of hexamethylene polyadipainide fabric with the stripe layer in contact with the stencil. the

■ r

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- 20 -.
blue coloring is produced with the dye

and the red coloring with the dye

OH

The whole is heated at 210 ° for 30 seconds. You then arrange the printing stencil No. 2 between a "SUBLISTATIC" paper with red and blue dots (the colorations being obtained with the same dyes as above) and the already printed fabric web and heats the whole thing for 30 seconds at 210 °. You get one that way Checkerboard print, with alternating dots and stripes in the squares.

Following the same procedure can be sequentially printed from the right "and the left side (front and back) of the surface to be treated, including placing them on the occasion of the transmissions between the two stencil sheets of \ .Φ ■ -19-

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where one is the negative of the other, whereby one the effect of a "reversible fabric" is obtained.

Example 3

Used to print on a surface of 20 χ 13 cm a steel grid USA, the porosity of which is 350 mesh and that on a steel frame 3 cm wide and 0.5 cm Strength is strained, having a surface area of 40 χ 30 a releases. This sieve or grid is degreased and dried and with a squeegee in a dust-free environment coated with a photoresist made from a mixture of 1000 g Photoemulsion 96 D 1833 from the lacquer factory Rosen, Kaldenkirschen (Germany) and 50 ml of a 20 # ammonium dichromate solution consists.

The grid produced in this way is exposed to the irradiation with a Quartz halogen lamp HPR 125 watts exposed by a positive cliché. The unexposed areas of the emulsion are removed with lukewarm water at 30 ° for 10 minutes.

The grid is then dried at normal temperature, always in a dust-free environment, in a heating oven at 180 °.

The grids produced in this way can be used as a printing template in your. Be used- method -was described in the preceding examples _t '. They enable reproduction

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with good page delimitation or sharpness and enable very precise overprinting of monochrome images for Production of multicolored prints.

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Claims (1)

Claims-: on textiles and other materia- ', Lien, characterized in that between the surface of synthetic materials to be printed and a temporary support carrying one or more vaporizable substances to be transferred to the surface to be printed, a printing stencil is placed, which is a thin film (Film) is made of a material that is impervious to the vapors of the vaporizable substance or substances, is stable at temperatures in the region of 220 ° and has recesses corresponding to the motif to be printed, and that the whole is brought to the evaporation temperature of the substance heated for a time sufficient evaporation _r or sublimation of the substances and their fixation or its penetration into the material to be printed to enable. 2 ^ ilradruckverfahröi according to claim 1, characterized in that as a provisional carrier Used paper that is uniformly coated with vaporizable dyes. 3- Filiridruckverfahreii according to claim 1, characterized thereby that recesses in the printing stencil are produced photomechanically. , ■ ■ · ■. · ■ ·. ' -22- 409824/0774 4.Filmdruckverfahren_ according to claim 1 ,. characterized that the vaporizable substances intended for printing are disperse dyes, which sublime between 160 and 220 °. 5-Filndrudroerfahren- according to claim 1, characterized in that the measures provided for printing vaporizable substances are disperse dyes which belong to the class of anthraquinone, methine, quinophthalone dyes or Monoazopyrazol- and that she / een 180 and 210 are ⁰ G sv sublimable. 6. Film printing method according to claim 1, characterized that one as material for the - - '. makeshift carrier holding the vaporizable substances ■ Wear, paper or aluminum used and that are impermeable to the vapors of the substance to be printed Layer is formed by an albumin material. 7. Process according to patent claim 1, characterized in that the layer which is impermeable to the vapors of the printing substances is produced on a gelatin basis and in that the layer contains a very fine metal mesh or a textile material. 8. The method according to claim 1 , characterized in that one successively the stock , » 409824/0774 - -23- parts of a color image is applied in such a way that a faithful copy of the original can be obtained by means of three or Receives four color printing. 9. The method according to claim 1, characterized that the recesses · of the printing stencil -Jinter use of thermal radiation ^ .. manufactures. Ιο «. Method according to claim 1, characterized that holes or recesses are made in the printing stencil in the manner that. one them punctually a laser irradiation, an electron beam or subjected to high frequency irradiation. ·. ... I'ilmdruckverfahrea according to claim 1, characterized characterized 'that the intended for printing vaporizable substances are dyes that 'at Temperatures below 220 ° to at least $ 60 in at least 100 seconds can be converted into the vapor state. 12i'ilnidruckverfahren according to claim 1, characterized characterized in that one as vaporizable, for Printing on intended substances uses basic dyes. 409824/0774 13. Film printing process according to claim!, Thereby marked that one, uniform supports coated with vaporizable dyes and a printing stencil is used, which consists of one or more Microfilming has been made. 409824/077