DE2100031A1 - Process for the production of gravure printing plates - Google Patents

Description

W.R. Graee & Co. (Prio 5 January 1970 - 2100031

U, S. 828 - 16148 - 769 ¹ I) 3 »Hanover Square

Hew York, N.Y. / V.SteA. Hamburg, December 28, 1970

Process swr production of engraving printing

The present invention relates to methods sur production of Gfavuräruckplafcten bsw. on the manufacture of printing forms for gravure printing.

In gravure printing, the printing plate, usually as Impression cylinder is present-, sahire-rich grid cells. It There are three basic types of printing plates, namely 1) the conventional printing plates with plates of the same size but of different depths, 2) those for the Benderson processes used grids with different large but equally sized grid cells and 3) the printing plates used for the Dultgen or Hur ■■ "· eton process with different sizes and depths Grid cells. When coloring the printing form, the Color picked up by the grid cells and those between these lying areas are, for example, with a Ink is removed from the squeegee. The printing form is then brought into contact with the paper. With the printing forms 1) and 3) the color becomes stronger the deeper it is

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The shaving bowl is or, depending on the color, e: i picks up. At the Black-and-white printing therefore creates the deeper raster cells sehwärsera tones and the flat tone cells little or no color value. In the event of death of the printing forms 2) and 3) the paper is with large areas 3shv; e.rs3r color printed only through small areas are separated in white, so that the largest raster bowls have a 5 m black impression result, while the smallest raster cells essentially leave an uncolored or white print area. The engraving process or gravure printing process is used for reproduction in such a way that printing plates are produced, which correspond to the image to be reproduced, both halftone images and line screens or generate letter images.

With the gravure printing process one can print Sohwars-White images and make color pictures; in the latter case you need several separate plates for three colors, namely cyan blue, magenta-red and yellow, which are then additive all colors of the visible spectrum result, with mau can still work with black to achieve better details in the shadow areas.

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Zn? Time throw t-s'y.efcro-raen made; _s by performing copper etchings in ä & n eaeepv ^ ec-hendea image areas. During the production of a Tiefdr-uekajrlindera a steel cylinder is electrolytically coated with a st-s: a 1 min-thick copper bar, which is then sanded and polished. Alternatively, a thin d-interribajre can be attached to the steel sylinssa. For the control of the Xtaena phctcchemischresiatente materials are used, which also E.2.S "Pho ^ oresistors"3ei'3isnet were. Diet: wa material usually carbonaceous dare or ^:: Rctof ilxa "heard uiiterechiedlich and speak differently to etching in various Sahwärauno The Photoresiatorenmaterial can weräe.r develops and produces a matrix that would allow lichts aine rest ^ pressure plate by etching.. su obtained in the Phofcoresis ^ orr ^ material upon exposure to an original image comprising: sk su reprcdusieresiden image a latent image eraeugt Eeiin konventicnellen pressure are continuously tinted .- used image templates v in ^{Henderson-Yerfahren:;:..} approximately a halftone Image template is used and in the Hurleton process both continuous tone templates and halftone templates can be used. The exposed resist material is attached to the cylinder, developed and rotated in the solution. The etching itself is critical and time-consuming and it becomes

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bia to six solutions j, paints; Eisan (IIX) -chloria, used in various Kenser-vra ^ ionön -... Usually certain areas are corrected for flaws after the first £ ts5 \ "process after &tsen" When the grid heads are flat "the Zyliuilsr either locally nacageätst ODSR vollefciiriäig. This wi.x-ö the surface carefully geschüfe at. "Too deep geätste Fiästernäpföhsn be corrected, indention is coated electrolytically on dan bodies concerned and AISF the ground dei ^T Näpfehen Laok applies. Anschliaßend wirö the cylinder with electrolytically a 0.005 now thick chrome layer to reduce the wear and tear of the cylinder with large editions.This production of gravure printing plates is extremely laborious and often consuming and requires the use of corrosive chemicals in the etching baths.

According to the invention, there are processes for the production of rotogravure printing plates; hitting, this term including printing plates bearing the image required for gravure printing; ö:, this procedure is based on the fact that nan:

a latent C? forms) avurplatte containing a regular pattern of solid webs and between the webs a fl las strength mixture which can be removed, vn a regular pattern of open

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" ⁵ ~ 2100011

Cups are left behind on the webs, whereby this mixture is curable by actinic radiation and results in a fesfcea product; and from

1) a polyene with at least two non-aromatic unsaturated carbon / carbon bonds per molecule _a

2) a polythioi and

3) there is an HSrtungsbesehelerationigar «whereby the Total number of non-aromatic, unsaturated Carbon / carbon bonds per polyene molecule and the Thiolreete per Polyfchiolmolekül greater than 3 is,

b) the latent engraving plate image-wise on one side with actinic .; Radiation is exposed to add liquid to the exposed areas harden and

c) either 1} the uncured mixture from the unexposed one Seit; - the plate removed and the cell areas left on this side, or

2) the cured mixture removed from the exposed side of the plate and then the remaining one uncured mixture exposed to harden it au.

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The gravure cylinder obtained according to the dsm erf in & un jsgeinää method can be used in order to prevent the use of larger quantities. Each of the three mentioned methods to: Achieve τοπ Tcnwerton can be made possible with the method according to the invention. For the sake of simplicity, the following describes the achievement of the different iTon * reris-3 with rasp bowls, which are the same size but different depths. The usual engraving templates and picture templates can be used.

The mixture usually has a viscosity of 0 to 20 million cP at 130 ^° C. For the sake of simplicity, the uncured mixtures are al "; called photo-curable mixtures.

In the present invention, the polyene and the polythiol react with each other and form a solid product. This reaction is generally referred to as curing. Hardening is a radical reaction that is usually stimulated by ultraviolet radiation. The hardening product is a solid polythioether.

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The polyene compound contains two unsaturated, aromatic carbon / carbon bonds, ie a double bond or an acylene triple bond. The number of such double bonds j: β molecule is referred to as the functionality of the polyene. The polythiol contains at least two SH residues per molecule, the number of which per molecule is also referred to as the functionality of the polythiol is. If the polyene and the Polytfciol both have a functionality of SWEi, the sum of the functionalities (a value of k% corresponds to shower a substantially linear Polytiioäther obtained curing. However, if the sum of the functionality is greater than 4, so A measurement is carried out during hardening, which results in three-dimensional <? arnetste or cross-linked polythioether molecules. The cross-linked polythioether generally has a greater resistance to solvents, a better resistance to aging and, in some cases, a better resistance to deformation than it is the case with linear polythioethers, so the sum of the functionalities should be greater than 4. In general, whoever which the polythiols and polyenes as a precaution - and especially in the range of the lower limits of functionality - are used in such kengen that for each .unsaturated group in the polyene a thiol fraction is present in the polythiol, whereby

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Of course, the total functionality of the system must be greater than 4 legs and the functionality of the thiol and the service must be at least 2 each. If, for example, two moles of a triene are used and a dithiol is used as a hardener, so that the overall functionality has a value of 5, three moles of dithic-1 are preferably used. If much less thiol is used, the rate of hardening drops and the product is in some respects to be considered worse because of the lower proportions of cross-locking in the polythioether. If more than the hemiometric amount of a thiol is used, the rate of cure will be greater than is desirable in some cases, although excessive amounts may result in a plasticized product which does not have the desired properties.

The hardening reaction is caused by actinic radiation of the Daylight or triggered by special light sources that show noticeable deficiencies in light, preferably in a wavelength range from 2,200 to 4,000 S, such as ultraviolet light, radiate. Accordingly, it is possible to use the extruded mixture of an actinic Radiation, preferably in the range from 2,200 to * 1,000% operate in house or in any other way,

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iim a filament made from a solid, alastoiric or resinous product. Di © Härtmigogascfawindigfceifc alt ultraviolet light is increased if one of the mixture eir.

, Acene & phtfcenehlnon, methyl ethyl ketone, valero-hexanopherone, JT'-phenylbutyrophenone, p-morpholine-

Dibensosuberon, Ί-Morpholinbenssophenon, H ⁽ ~ Mo? Pholinodeo3Eybens: oln, p-Diacetylbsnsol, 4-Arainobenzo-! Phemm, H ^% -Methoxyaeetophenon ₉ Benaaldehyd, et -Tetraion, 9-Aeetanthiphenanthren, 1 -Aeetanthiphenanthren, 1 -Aöetypananthenon 3-ethylphenanthrene, I- acatylindole, 9-fluorenone, 1-indanone, i-s5 ₃ 5- ^ riee®tylbeREol. Tiiio2ianthen ~ 9-one, xanthene-9-one »

jde] anthr & een _s-7-one 3. '~ Aaötonaphthon, l-Naphthalde BisCdi -'- ^ ethyl iamincbenaophenon), 2 ^r -Aoetonaphthon and 2.3 ~ butanedione. Di & Köngenenteile of Photoanregere in the mixture Lieger generally between 0, 0005 to SO, usually between 0.0005 to 35, and preferably 0.5 to 25 6@w.£, added to the mixture.

In general, the polyenes have a molecular weight of 50 to 20,000 and a viscosity of 0 to 20 million cP at 70 ° C. They have the general formula [a] - (X) ₈ , where X is a radical of the formula R-CsC - or RC = C-

R R

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and m has a value of at least 2, where R is hydrogen, halogen, aryl _s substituted to aryl, cycloalkyl, substituted cycloalkyl, aralkyl, substituted as alkyl, alkyl or substituted alkyl with 1 to 16 carbon atoms and A is a polyvalent? organic? Rust is. A may contain cyclic and very small manganese heteroatoms, such as N, S, P, or O, but contains primarily carbon-carbon, carbon-dioxide or silicon-oxygen without reactive carbon-carbon unsaturated bonds. Reactive unsaturated multiple bonds are those bonds that can react with £ & n SH-Rostsn of the polythiol3, which includes practically non-aromatic compounds, ie, ethylenic double bonds or an acetylenic triple bond, which can take part in a radical polymerization reaction.

The niehtaroEnatlachen unsaturated carbon / carbon bonds can be at the sndo or near the end of a branched chain, terminal or near terminal (Sews more than 16 carbon atoms away from the end of the main chain) there can be two or more of these unsaturated bonds per molecule. For example, one diene is a polyene that is two non-aromatic Has carbon double bonds. Combinations

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Prior to modernization, double bonds usid triple bonds within its same molecule are also possible, as for example with DSonovinylacetylene; half of the courses. "weri.on all dies® connections al3 "Polyenes" fco

Polyen® tdnd which can be used are described, for example, in German Offenlegungsschrift P 17 20 836-9; In these compounds, the radical A does not contain any reactive carbon / carbon melt bonds and furthermore no unsaturated radicals in conjugation with the carbon fiber bond in the X groups. Allylandate compounds are preferred, alQ at least two -CO-NH-Birs & ungen contained Folyens thesej? Art are also described in German Patent No. P 18 02 559.7. Another group of polymer compounds for the process according to the present invention are unsaturated polymers in which the termination occurs primarily in the main chain of the molecule, such as, for example, conventional elastomers, which are essentially derived from monomeric dienes such as polyisoprene, polybutadiene, styrene / Butadiene rubber, isobutylene / isoprene, polychloroprene, styrene / butadiene / aaryl nitrile rubber and the like, as well as unsaturated polyesters, polyamides and polyurethanes of monomers with reactive multiple bonds,

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such as / idipinaäure / Bu'sendiol _£ fumaric uss 2 ₅ 4-Tolyleri4iisceyanat; / Bi; tt-sndiol, and "who in the form of

A © third group. Ran polyenes which are suitable for the present invention have reactive multiple bonds in condensation to form nearby unsaturated radicals as described, for example, in the German patent application P IS 51 HB3.5 .

Polyenes suitable according to the invention are compounds the (&) the reaction product of i) an organic epo "id with at least two -CH-CH- residues with 2) hydrazine,

a primary or secondary amine or a salt of one tertiary amine, an organic alcohol or thioalcohol or an or && nic acid, where the Compound 2) is polymerizable and at least one contains non-aromatic unsaturated group, or b) the reaction product of 3) an organic epoxide, the at least one pelyiierisable non-aromatic contains unsaturated group, with 4) hydrazine or an organic compound which contains at least two radicals which contain an oxygen atom that can react with an Epo ^ yrest of the compound 3) and the formulas

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-N-, N ⁺ -H, OH, -BH, -SH or -PH possessed «Such H polyenes are described in German patent application P 20 09 620.2. Preferred polyenes of this type are, for example, the reaction products of diglycidyl acetate of bisphenol A with allylarain or diallylamine in a molar ratio of 1: 2 or the reaction product of a diglycidylic acid cup of bisphenol A with diallylamine and mis allylamine in a molar ratio of 2: 2: 1.

The erfindungsgemäfi polyenes employed usually have ein® viscosity of O to 20 million centipoise at 70 ⁰ C, where those compounds are included, with in the presence of an inert solvent, as an aqueous dispersion or with a plasticizer, a solution, a dispersion or a mixture result in a viscosity lying in this range. The molecular weight of the polyenes is usually in the range from -50 to 20,000 and preferably between 50 and 10,000.

Polythiols are understood to mean simple or complex organic compounds which are, on average, two or more branched or terminal -SH - properties per molecule. They typically have "ine viscosity of 0 and 20 million cps at 70 ⁰ C, measured with a BrookfiβId-Viekosimeter. Such polythiols are also used here

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detected with an inert solvent, as an aqueous dispersion or? with buckets of plasticizer in the specified viscosity level. The compounds usually have a molecular weight between 50 and 20,000 and preferably between 100 and 10,000. Suitable polythiols are described in German patent application P 17 20 856.9. Examples of such polythiols, which are preferred because of their relatively low odor, are esters of thioglycolic acid (HS-CH ₂ COOH), <£ -Meroaptopropionic acid (HS-CH (CH -) - COOH) and ß-Mercaptopropionic acid (HS- CHg-CHgCOOH) with polyoxy compounds such as glycols, triols, tetraols, pentaols or hexols. Preferred polythiols are, for example, ethylene glycol bis (thioglycolate>, ethylene glycol bis (a-mercaptopropionate), trimethylolpropane (ti. Ioglycolate), trimethylolpropane (a-mercaptopropionate), pentaarythritol tetrakiscolate (pentaarythritol tetrakiscolate). inercaptopropionate) and polypropylene glycol bis (ß-kercaptopropionate).

"Functionality" is the average of the non-aromatic , unsaturated radicals and thiol radicals per molecule in the polyene btw. Polythiol understood. This is usually expressed in whole numbers »although the actual functionality can also be a fraction. For example, a polyene with a nominal functionality

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2 practically an e ^ which has less functionality; at. Bsi a angenoiuinöntn Synthesis of dienes from einon GXykol is ü: ie functionality at 100 * strength implementation and 100 #ig my Ausgangsrcatsrial 2.0. If every 3 hours the conversion is carried out to 90% , about 10 % of the molecules present only have a single functional group and there may still be impurities in each functional group. About 90% of the molecules have them Desired diene structure, εο that the overall product then has an actual functionality of 1.9. Such a product can be used out in the novel / and bizeichnet to as a product with a functionality of the second

The polyenes and Pclythiols mentioned can optionally are formed in situ and still in the case of the invention Procedure to be hardened quickly.

The polyene / polythiclin mixtures can optionally other additives such as antioxidants, accelerators, Colors, inhibitors, activators, fillers, pigments, antistatic additives, flaron-preventing additives, Thickener, thi;: otropic additives, surface-active Additives, agents for modifying the viscosity, extender oils,

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Contain plasticizers and agents to increase stickiness. These additions should be made against actinic radiation essentially not be opaque »you will get habitual with the polyene or plythiol before or during the miss ohung the polyene κ it the polythiol s set. Suitable Fillers are in the German patent application P 17 20 856 »9 listed. Usually up to 500 parts and preferably 0.005 to 3 (0 parts of additives per 100 parts of polymer used, however, these additives may not be used be so large-quantity that they harden stumble.

The blends will normally contain at least 2 wt.% Einjs polyene and at least 2 ßew.Jf Pclythiol. The weight ratio of the two connections to one another could vary between 9: 1 mi: 1: 9.

The mixing of the ponenfcenes of the photohardenable mixture before irradiation ra;, fc ultraviolet light can act on different Way. For example, in the case of liquid photohesives Mixtures read polyene, the polythiol and everyone other additive, v: 'l © for example the stimulator, under mixed into an inert atmosphere and then into a Aerosol container, in &:> a canister, in a tube or in a The cartridge is filled. Exposure to actinic

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Radiation at room temperature or at elevated temperatures causes the light curing.

Another suitable method for preparing the photohärtbarsn mixtures is that they ein® mixture of the polyene, ainem antioxidant for preventing an in Abwessnheit of aktiniesher radiation with conventional mixing methods: i "spontaneous and auegelösten by oxygen curing olythiol, UV Stimulator? and other accessories. This mixture can be used in closed "

If containers are kept in the dark for a longer period of time, it hardens but in a controlled manner with exposure, e.g. with ultraviolet light, sunlight and the like to a solid polythioether within a very short time

Usual hardening inhibitors or retarders can be used ** if used, such as hydroquinone, p-tert-butylcatechol, 2, ß-di-tert-butyl-p-uethy! phenol,

Phenothiasin and N-Ph ^ nyl-2-naphthylamine, ^

The invention is suitable for engraving plates after exposure by conventional Haster and continuously toned negative or positive To produce artwork. The exposure and the subsequent development or the etching can depending on the

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selected process:.! on the same cder of the other Side of the plate.

In eisiar Au3fühP angSiOi ^f * s; i erfinöiüigiseuiäßen the process, the cured mixture of d "ki exposed areas of the plate is peeled off. This can dursh. be carried out, that one (Si © exploits the fact that * sat your plyene / polythiol mixture in contact with a thin film or some other suitable; οϊι carrier material adheres to the substrate after hardening * One side of the latent printing plate is in contact * with a transparent film exposed to actinic radiation and this side is exposed imagewise through the transparent film, and in process step o) / ird the hardened mixture, which adheres to the film in the exposed areas of the plate, is removed by peeling off the film and the remaining uncured mixture is exposed to light and thereby cured.

The printing plates produced according to the process according to the invention Stage or intermediate areas can be made of metal or of a hardened. ^ olyen / polythiol mixture (a solid Polythioether). The most frequently mentioned type of plate lets see an implementation of the present invention to produce in a simple way that one with the

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In order to produce the latent printing plate, a carrier material that is transparent to! t-sr akfciniseher radiation with a layer of the film / polythiolite is coated at the same time by the carrier film and a negative image grid with ac '; iniacher Strfchlur.,; · exposed, at the process step b) al <$ latent printing plate formed during the process step a) at the same time ■: ^ s ° eh the carrier is exposed to the correct tinted positive image original containing the image and in process step c) the uncured parts of the mixture are removed, and a gravure printing plate or printing form is obtained. In another procedure between Manufacture of a plate with solid polythioether sheets or bridges. In the process step a), a latent gravure plate is formed by making a layered structure from the mixture of poles and folythiols between two carriers, rc « at least eiüisr this support opposite to aktiniachc · radiation is transparent, whereupon © s the mixture simultaneously inischer by eisian transparent support and by a negative raster image akt I radiation exposed and b in process step) the Sciiichtgebilde bildviöise through the same transparent carrier exposed and when Step c) removes the other carrier and removes the uncured mixture from the unexposed side of the plate. The implementation

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these two methods are explained in more detail below.

A uniformly thick layer of the photohardenable mixture is formed between two foil elements, at least one of which is translucent. It is also possible to apply the photohardenable mixture to a base that is translucent without the need for a top layer, which can be the case in particular with highly viscous photohardenable mixtures. In this case, the support transmits actiniaeis radiation and exposure to UV light occurs through the support. The system is exposed longitudinally sufficiently through a suitable grid with bundled UV light so that the exposed areas are cured and empty, namely in the area of the entire layer thickness of the photizable layer. This exposure leads to the formation of itestern cup irons made of uncured, photohardenable material, which are separated by cups made of solidified, light-cured product. The screen is replaced by a screen-free, tone-continuous positive image transparency and the photohardenable layer is exposed through this transparency for a sufficient time so that the tone area of the positive is reproduced by selectively hardening the photohardenable material into a solid product of varying depth. A be-

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exposure of the photosensitive material with UV light This means that the 3 <33 photosensitive material on the FilEi clinging to light source near the act in laughing. if one uses a Mahrsehiöhtgebilöe, becomes the other The film is sucked off on the side away from the light source, daa lichthartoare material and the unhardened Areas of photohardenable material, attached to the plate remain, are made by dissolving in a solvent removed for the light-curable material, so that raster cells with different depths remain in the print.

With buckets another method of making printing plates or printing forms, a metal sleeve is used, which contains a grid or Netzaystein whose holes lead partially or completely through the entire sleeve, which is easily removed from the printing roller or the printing cylinder eu remove is «The holes in the sleeve are photocurable with Mixture is filled and the image is arranged on the grid according to one of the following two systems: f

a) if the holes are not completely through the sleeve enough, the outer surface is opposite with one actinic radiation covered transparent film to which the hunted polyene / polythiol mixture adheres, A negative image is drawn over the film

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applied with continuous tint. After exposure, you will see a negative with sküiniscfcer radiation, for example a bundled oil ^. / ~ Light, the negative is removed, the transparent film and the adhering photogheric t-afce mixture peeled off from the sleeve and the remaining lish-hardenable mixture in the grid is noehmls exposed to bundled UV light or other a'itinisshsn radiation uno cured, so there. ^f i a carrier containing the image for the engraving; > uck aurüok stays »

b) If the Löoh-sr in the Q5.tt@2 "systam go completely through the outer sleeve, cc can work according to the general vex" fafc: * en a) ". In addition to the Ir;. A continuously toned positive image original ienflächa the sleeve arranged and exposed from the Xnnentc.ll sleeve collimated UV light * The 'aste photocured mixture remains in the lattice uiü the uncured portion of the photocurable Miaelv.mg is removed from the outer surface of the sleeve by solvent extraction, so that a carrier protruding from the engraved image remains in the sleeve. In building method a) and b) a redistribution is required; the sleeve with the grid system-possible, and was through complete solvent-

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Use the hardness fairy mixture. Diirfsh the z, \ iii & tzli.®he metal sleeve © of the daa GifcteFßvstsm with this Ve: -; · flags know the image carrier for printing processes for larger editions ves'wenßef. v; e.-rdön "is better suited for this than the real plioto-hardened image carrier.

Another Vcri'ahrei; s? up V "use of the" photo-curable Mixture of he ^ Eteli ^ ug afjies image carriers for the Qravur-

Isafe printing the daily advantage that i

Keina wet chemical; ^ sur production of the plates are he ~ fordarllch and ύε, ίΐ only one ü ¥ -Lich'5-iuelle required is detected to know "This troc-kc'ne" d & a Xtsen a Driscäplette or Ainet Cylinders with a lattice work, so that a multitude of ease-of-use cases and connection bars are obtained. The cells are filled with the light-curable mixture and covered with a film which is permeable to actinic radiation so that

a contact between the surface of the photohardenable ι

Materials produced ^ ird »a continuously toned negative original image is brought into contact with the film and Eait exposed to actinic radiation, for example with bundled UV light. The negative is removed and the film together with the adhered hardened part of the photocurable material from the surface of the plate

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cclsr of the cylinder sucked in. Ώ & 3 remaining photocurable material wii.'d then again exposed to actinic radiation so that this mass solidified through hardening Material remains in the wells, eats proportionally to the quantity of liquid left through the negative. Thus, a clear portion of the negative will not allow the person to cure most of the photo-hardenable material underneath that is removed with the film, so that no photo-curable material remains in the cup. Such a well is completely filled with color during the I); 'ucking process and results in; a deep black print. Conversely, a thin area of the negative creates a white area when printing. Gray areas lead to different depths of the remaining photohardenable material and thus to a correspondingly proportional color absorption. The plates can be reused by treating them with any solvent in which the cured polymers are partially or completely soluble. The surface can be cleaned without damaging the original oitter system.

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The thickness of the layer of photohardenable · Hasse included in a solid polymer is converted is proportional see below the striking light intensity. If the exposure is through a continuously toned negative, so correspond to the brightly transparent areas in the negative the thick areas of the cured polymer, while the optically dense areas in the negative are essentially do not correspond to any polymer and intermediate optical blackening to a corresponding average

Lead thickness of the polymer layer. Although so far *

When talking about exposed and unexposed areas, these terms are to be understood relatively.

The carrier material is preferably a flexible plastic, which after exposure to the photo-curable mixture adheres to this with UV light or awf in some other way, wherein the carrier film is also intended to transmit a substantial amount of UV light. Suitable plastics are Polyethylene, polypropylene, poly-il-methylpentene, polystyrene, Polyethylene terephthalate, cellulose acetate and ' like that. The thickness of the carrier depends on its relative strength and dimensional stability which is required is in order to obtain a corresponding layer thickness of photohardenable mixture. Usually carrier foils are used with a wall thickness of 12 * 5 bis'isfSO ^ u used.

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The molecular weight of the polyenes can be measured in various ways, for example by measuring the viscosity in liquid, by the oarnotic pressure and by gel permeation chromatography. In some cases the molecular weight can be calculated from the known molecular weights of the starting materials. The viscosity of the polyenes and polythiols was measured at temperatures up eu 13O ⁰ C with a Brookfield Viskoaimeter.

The invention is to be explained in more detail below with the aid of examples; sofarn not otherwise specified, All quantities are based on weight.

Preparation of the polyenes example 1

1 mol of diglycidyl ether of bisphenol A with a molecular weight of 370 to 384 (Epon 828} and 2 mol of allylamine were dissolved in 500 ml of benzene in a beaker at room temperature. The exothermic reaction was carried out at a temperature of 80 ° C. for 18 hours, then the benzene was removed in vacuo. The allyl-terminated liquid prepolymer formed is hereinafter referred to as "prepolymer A ⁿ .

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Example 2

The procedure was analogous to Example 1, but now 2 moles of diallylaain were used in place of 2 moles of allylamine; no benzene was used as a solvent. The allyl-terminated liquid prepolymer thus formed is referred to below as "prepolymer B *".

Example 3

1 mole of commercially available tolylene diisocyanate was in a Given a resin boiler, which has a condensation attachment, a A stirrer, a thermometer, and gas supply and / or outlet openings. This cooker was slow with 2 moles of the diallyl ether of triraethylolpropane charged. Then Ί, Ο g of dibutyltin dilaurate were used as a catalyst added and the reaction for 30 minutes at 70 ° C below Nitrogen carried out. The allylendstandtge thus formed liquid prepolymers are referred to below as "prepolymer C".

Production of the photo-hardened gravure form a example H

It became a photo-curable mixture of 10 parts by weight of prepolymer B from Example 2 and 8.5 parts by weight Pentaarythritol tetrakie-i3-mercaptopropionate) and 0.015 parts Dibenzosuberone mixed together and heated by heating

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Degassed under vacuum at 7O ⁰ C and then poured into a black painted glass mold of 10 χ 7 _S 5 x O ₄ I cm. The form was filled and covered with a 25 ^ u thick polyvinyl alcohol sheet. A grid with 16 lines per cm and a ratio of transparent to opaque areas of 1: 2.33 was brought into contact with the emulsion side with the polyvinyl alcohol film. This system was placed in a vacuum table to ensure good contact and then exposed through the line grid to UV light from an Ascorlux lamp, the surface intensity of which was $ 2,000 microwatts / cm ^{2 over} the course of 4 minutes. The grid was removed and the process repeated with a continuous positive artwork with an exposure of 2.75 minutes. The plate obtained with the polyvinyl alcohol backing layer was removed from the mold, washed for 5 minutes in an ethanol solution agitated by ultrasound and post-exposed for 7 minutes on each side for curing with the same lamp and the same intensity. A microscopic examination showed that grid cells of constant size and different depths had been obtained. The flexible intaglio printing form was glued to a roller 73.5 mm in diameter with an adhesive. A cut rubber squeegee with a Shore A hardness of 80 was placed between metal plates and underneath

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applied to the printing form at an angle of 80 °, the sharp Qummikan & e in intimate contact with the surface the printing form was lying. Di® Druckwaise became continuous rotated by a printing ink that is calibrated in one below attached shell. A sheet of white paper from 89 mm width was passed through the gap that see between the printing form and a rubber pressure orphan from 73.5 rom diameter. The paper web was under

Tension held and wound up after printing. the

The prints obtained were of excellent quality. i

Example 5

Example 4 was repeated, but now the The cover of the fora used film was a 0.025 mm thick cellulose acetate film and the grid used 60 lines per cm at a distance to line ratio of 2.5: 1. The prints obtained were of excellent quality.

Example 6 A copper cylinder was exposed through a grid after exposure

with 60 lines per cm and a ratio of distance to

2.5: 1 line etched. A photohardenable mixture of

10 parts of prepolymer A from Example 1 and 5 parts

Pentaerythritol tetrakis-Cß-raercaptopropionate) and 0.2 part " ORIGlNAL BATHROOM

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Benzophenone were mixed after thorough mixing at 70 ° C degassed under vacuum. The recesses of the etched Cylinders were then made with the photographic mix filled in and with a thickness of eiiMr 25 * u, facing UV light permeable cellulose acetate film covered so that the Contact was made on the surface of the photocurable material. A continuously tinted negative image was placed in contact with the cellulose acetate film and exposed to UV light from the @; Insr Ascorlux lamp, which gave a surface intensity of 25,000 microwatts / cm for 3 minutes. The tagative was removed and the cellulose acetate sheet was put together with the light cured part the light-curable Mas-je peeled off the cylinder. Of the The remaining uncured part of the photocurable mass was then exposed to the same light source and the same intensity for 5 minutes, whereby raster cells of different depths resulted. The use of the so educated The gravure cylinder gave excellent prints on a conventional printing press.

Example 7

Example 6 was repeated, but now that Prepolymer A by 10 g of poly (1,3-butadiene) with a Molecular weight of about 2,000 has been replaced. The prints obtained were of excellent quality.

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Example 8

Example 6 was repeated, except that the pre · » polymer A by 2.7 S of the triacrylate of the reaction product of trimethylolpropane with 20 mol of ethylene oxide was replaced. The prints obtained were of good quality.

Example 9

A 75 / U thick copper cylinder was made in the usual manner after exposure through a grid, as in example 6 '

was used, etched clear. The wells in the cylinder were made with a photohardenable mixture 10 parts of prepolymer C from Example 3 and 8.2 parts of pentaerythritol tetrakis-Cß-nercaptopropionate) and 0.02 part of dibensosuberone, and after this mixture had previously been degassed at 70 ° C. under vacuum was. As the cells reach through the copper cylinder, a continuously toned positive artwork was created in the Cylinder placed on the inner surface and exposed to UV light from J

an Ascorlux lamp was exposed for 5 minutes at a surface intensity of 25,000 microwatts / cin ² , so that the photohardenable mixture hardened. The cylinder was then washed for 1 minute in ethanol with the aid of ultrasound to remove the uncured photocurable material.

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The top hat was taken care of by a metal orphan and used as a printing plate. The prints thus obtained were of excellent quality. Using this Cylinders instead of the usual orphans make handling and storage easier.

Example IQ

A 625 / U thick copper cylinder was made up to one Depth of 72.5, u etched in the usual way after he fe beforehand with a line grid, as shown in example 9 used, exposed. The etched cylinder was placed on a metal roller and the grid cells in the cylinder were filled with a photo-curable material, which consisted of 10 parts by weight of prepolymer B from Example 2 and 25 parts by weight of pentaerythritol tetrakis (ß-mercaptopropionate) and 0.015 parts of dibenzosuberone, the mixture previously at 7O ⁰ C had been degassed under vacuum. A 25 / U thick cellulose acetate film was placed over the cylinder in contact with the photohardenable mixture and this was covered with a continuously toned negative image. The system was exposed through the master image to UV light from an Ascorlux lamp, the surface intensity of which was 25,000 microwatts / cm, for 5 minutes. Subsequently was

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the negative is removed and the cellulose acetate film is peeled off the cylinder together with the adhering photocured material. The remaining uncured part of the photocurable material in the cylinder was then exposed again to UV light from the same lamp and intensity for 5 minutes and resulted in a gravure form. The prints obtained were of excellent quality.

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Claims (1)

Claims ft) Process for making an engraving printing plate, characterized in that one a) forms a latent engraving plate that wipes a regular cough from solid webs and "wipes" The ridges have a liquid mixture that can be removed to create a regular pattern of to leave open cells between the bars, this mixture by alctinische Radiation is curable to form a solid product and consists of 1) a polyene with at least two non-aromatic carbon / carbon unsaturated bonds per molecule, 2) a polythiol, the total number of non-aromatic, unsaturated carbon / carbon bonds per molecule of the polyene and of the thiol radicals per molecule of the polythiol being greater than, and 3) a curing accelerator, 109829/1209 b) the latent engraving plate on one side with actinic radiation imagewise exposed to the liquid mixture in the exposed areas harden and c) either 1) the uncured mixture from the unexposed one Side of the plate removed leaving cell areas in this side or 2) the cured mixture from the exposed side the plate removed and then the returned g Remaining unexposed mixture exposed for curing. 2. The method according to claim 1, characterized in that that you have a latent engraving plate with metal bars chooses. 3. The method according to claim 1, characterized in that that nan produces a latent engraving plate, the webs of which consist of a mixture according to claim 1, " that has been hardened. 4. The method according to claim i to 3, characterized in that that one side of the latent gravure plate is in contact with actinic radiation 109829/1209 brings permeable film and that this side is exposed imagewise through the transparent film and that in process step c) the cured mixture that is present in the exposed areas of the plate on the Film has become adhesive, removed by peeling off the film from the plate and the remaining uncured mixture is exposed to further curing. 5. The method according to claim ² I, characterized in that in step a) etching on the outside of a metal cylinder grid cells and fills the cells with the liquid polyene / polythiol mixture, and that in step b) the outer surface of the cylinder in contact with a brings film permeable to actinic radiation and exposes this surface to actinic radiation at the same time through a transparent film and through a continuously toned negative original image, and that in process step c) the cured mixture which adheres to the film in the exposed areas of the plate is passed through The film is removed from the cylinder and the remaining mixture in the cells of the cylinder is exposed to actinic radiation for curing. 109829/1209 6. The method according to claim 1 or 2, characterized in that in process step a) one Metal cylinder etched through the entire wall thickness with grid cells, this is filled with a liquid polyene / polythiol mixture and that in process step b) the inner surface of the cylinder through a continuously toned positive original is exposed to actinic radiation and that in process step c) the uncured parts of the mixture removed on the outer wall of the cylinder sleeve and a " Engraving printing plate forms * 7 * Process according to claim 3> characterized in that in process step a) the latent engraved plate is produced by coating a substrate transparent to actinic radiation with a layer of the polyene / polythiol mixture and this mixture on the same side through the carrier film and through a negative raster image with actinic radiation i exposed, and that in process step b) the latent gravure plate formed by process step a) is exposed simultaneously through the carrier and a continuously toned positive image original and that in process step c) the uncured areas of the mixture are removed to form the gravure printing plate. 109829/1209 8. The method according to claim 3 _S, characterized in that at the process step a) a latent engraving plate is produced by producing a layer structure from the polyene / pelythiol mixture between two supports, at least one support being transparent to actinic radiation, and that the mixture is made exposed simultaneously through the transparent support and through a negative raster image with actinic radiation, and that in process step b) the layer structure is exposed imagewise through the same transparent support and that in process step c) the other support is removed and the uncured mixture is removed from the unexposed side removed from the plate. 9. The method according to claim 1 to 3 and 6 to 8, characterized in that the uncured mixture is through Washing the layer of the mixture with a solvent removed. 10. The method according to claim 1 to 9 »characterized in that the polyene is a® allyl-terminated compound, which contains at least two -CO-NH- bonds. 109829/1209 It ο method according to claim 1 to 9 »characterized in that the polyene is the reaction product of a diglycidyl ether bisphenol A with allylamine or diallylemine in a molar ratio of 1: 2. 12. The method according to claim 1 to 11, characterized in that the polythicl is an ester of thioglycolic acid, OIL -Mercaptopropionäure.oder ß-mercaptopropionic acid old a polyalcohol. 13 · An engraved printing plate showing an image, thereby I characterized in that the image is in cells from one solid folythioether is formed, between which there are solid webs. 14. Gravure printing plate according to claim 13, characterized in that the webs are made of metal or solid polythioether. ue: wy BAD ORJGiNAl 109829/1209