DE1522483A1 - printing plate - Google Patents

Description

PATENT LAWYERS

DR. W. SCHALK DIPL-ING. PETER WlRTH DIPL-ING. G.E. M. DANNENBERG · DR. V. SCHMIED-KOWARZIK

FRANKFURT AM MAIN CR. ESCHENHEIMER STR. 39

2-48 April 22, 1966

HORIZOIS INCORPORATED
2905 East 79 "fcii Street

Cleveland / Ohio / U S A

P 1 atte "

The invention relates to printing plates for planographic and lithographic printing (for flat and stone printing) and the Manufacture of such items by a completely dry process using light-sensitive preparations. In particular The invention relates to the production of pianographic or lithographic plates for which a suitable one Carrier with a loan-sensitive mixture as below * As described above, it is impregnated or coated and then exposed to form a relief image * whereby a printing form is obtained in which the background is completely hydrophilic and the developed image are oleophilic and hydrophobic *

As in the known processes for the production of photographs the exposed on lithographic or pianographic samples

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Plate must be coated with an insensitive solution and then with a colored varnish in order to achieve the

To make the image visible and to reinforce the weak image so that a long life when pressing, i.e. a larger number of copies (prints) per plate is achieved, a permanent printing plate that does not require such a coating would be
represent an advance in this area.

k In a number of United States patents by Eugene Wainer et al. photosensitive preparations are described that at least
contain the following components:

1 ο An N-vinylamine

2t An organic halogen compound and

3. Various arbitrary components such as a synthetic resin
or another film-forming material in which the two essential ingredients are dispersed or attached. (YgI.e.gο USA patents
3,042,517.00

3,042,518,

3,042,519

3,046,125

3 056 673 and.

3 147 117.)

In addition, it has already been proposed to use aryl compounds of V.
Main groups of the periodic table, such as l'riphenylstibine,

9Ö9835 / ÜBS6. '. "" ³ ~

', -arsin., - "- to add phosphine or -bismuthin to such preparations or to use mercaptobenzothiazole in such preparations" (patent applications H 56 902 IX / 57b and H 58 653 IXa / 57b.)

As already mentioned, the use of N-vinyl compounds for the production of photopolymer images with halogenated hydrocarbons as an activating source for free radicals has already been described in detail in the above-mentioned patents. In these patents, the use is of compounds such as N-vinyl carbazole and carbon letrabromide. described with plastic binders, which are dissolved in organic solvents and applied to a suitable carrier such as paper, glass or plastic films. The plastic ones Binding agents have completely hydrobic properties and cannot tolerate water in any form. With such preparations the image developed by heating takes on color, both on the background and on the image surfaces, when applied to a press. The completely colored master copy obtained is therefore as pianographic or lithographic artwork completely unusable. The invention is now based on the use of hydrophilic colloidal binders in the already known preparations, whereby these on Paper or metal backing can be applied and uniform Coatings without separation of the aqueous and the oily phase deliver"

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With such modification, i.e. "with" inclusion of a hydrophilic binder in the photosensitive preparations that by exposure and subsequent weak heating to Developing and fixing created image receptive to greasy lithographic inks and repels the aqueous liquid from the container. pas background material "is completely hydrophilic Properties, is therefore wetted by the aqueous liquid from the container and repels the greasy paint, whereby a clear white background is achieved. That which takes on the color oleophilic image transfers the color from the image surface to a rubber blanket, which in turn transfers it to the paper used, and with this offset process many copies can be printed. ■

The invention relates to a pianographic or lithographic Printing plate with a photopolymerization of E-vinyl compounds photographic image produced using halogenated hydrocarbon activators, all active ingredients are applied to paper in a hydrophilic binder. The coating obtained is through a A photographic negative, a masking screen, a matrix or a similar object is exposed to visible light. Of the exposed print contains a latent image, which is due to faint Heating is made visible. During heating, dp.r unreacted volatile activator evaporates and the pressure with it progressive development fixed. The developed and fixed print is then used as a lithographic print template in an offset press and copies of them are printed. As well as

Halftone as well as line negatives can be used in the production these templates can be used. The procedure is completely dry. There will be no solutions for making the picture or the desired printing plate "is required.

The aim of the invention is therefore the production of lithographic )

■; i

Print templates with photographic images without any wet ^:

procedures such as desensitization or coloring o After After exposure and subsequent heat development, the original contains a relief image that is used directly for printing can be.

In general, the ingredients required according to the invention brought together by the following procedure: The N-vinylcarbazole or another suitable N-vinylamine and that CBr ^ or other halogen-containing ones in the above-mentioned patents Activators described and applications are dissolved in a suitable solvent such as cyclohexanone or toluene. The resulting solution becomes an aqueous solution of the hydrophilic colloidal binder, which is preferably a suitable one Hetz- or dispersant -contains, added and the mixture introduced into a Waring mixer and until a stable emulsion mixed. The emulsions produced in this way have proven to be stable for weeks without any- ' Lich sign of a separation of the oily and aqueous phase » In addition to the above ingredients, the contains too The solution given to the colloidal binder advantageously contains a sulfur-containing organic compound, such as mercaptobenzene

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thiazole, to improve the sensitivity of the applied Emulsion. The solution advantageously also contains a triphenyl derivative of phosphorus, arsenic, antimony or bismuth. By the presence of these triphenyl compounds and heating sufficiently after exposure to ensure development, a clean, white, non-foggy background is obtained, however the formation of a slight relief image after the heat treatment is a more important reason for the incorporation of the iriphenyl compounds of the elements of Group V of the Periodic Table.

Paper is a preferred base for applying the photosensitive preparation, but aluminum is at least that is anodized on one side, so that it bears a porous, absorbent oxide layer, which easily with the light-sensitive 'Preparation can be impregnated, another and particularly preferred plate material.

Each of the general description of the preparation according to the invention A detailed description of the particular ingredients used now follows and the way in which they can be mixed. For the sake of simplicity, these are typical representatives of each group of components listed in the table below. Of course, other similar materials can also be used in accordance with the invention will. Suitable hydrophilic colloids according to the invention are all natural colloids, such as, for example, starches, gums, polysaccharides and protein material such as casein, or synthetic materials such as polyvinyl alcohol, copolymers of methyl vinyl ether and Maleic anhydride, carboxymethyl cellulose and other synthetic ones

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Cellulose derivatives can be used. In Table I are the Colloids suitable according to the invention are listed and a preferred one Concentration series given for the colloid in water.

Table I.

Hydrophilic colloids colloid Preferred Conc ent rati on fo in H ₂ O Dextrin 20 - 30th Polysaccharides 10 - 25th albumin 10 - VJl Agar Agar 5 - 20th Gum arabic 5 - 20th Dextran. 5 - 10 Casein 2 - 10 Polymethyl vinyl ether halide anhydride 5 - 20th Polyvinyl alcohol (fully hydrolyzed) 5 - 10 Methyl cellulose 5- 20th Ethyl hydroxyethyl cellulose 5 - 10 Carboxymethyl-hydroxyäthylc ellulo se 5 - 15th Carboxymethyl cellulose 5 - 15th Carbapole ' R _ 10 Polyacrylamide 2 - 10 Polyvinyl pyrollidone 2 - 10

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Table II

Suitable solvents for dissolving the photosensitive preparations, which are dispersed in the protective colloid should be o

solvent

benzene

Cyclohexane

Cyclohexanone

toluene

Xylene

boiling point

80.1 '80 ⁰ G 155 ⁰ O 111 ⁰ C 144 ⁰ O

Table III

Triphenylphosphine triphenylstibine triphenylbismuthine Triphenylarsine

Table IV

Mercaptobenzothiazole

Mercaptobenzoic acid

Phenyl mercaptotetrazole

Ethyl mercaptotetrazole

Methyl mercaptotetrazole

All of the materials listed in Table I have proven themselves in accordance with the invention shown to be useful protective hydrophilic colloids. However, some became longer and some became shorter

909835/0656

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Operating times noted when printing, however, all showed the desired and necessary property according to the invention, namely, an effective repulsion of the color from the non-image Background and an assumption of the color on the hydrophobic image area ο Those given for the concentration range in the table Values are extreme values. The best results have been achieved when the concentration of the binder is around the Was midway between the specified extreme values.

To achieve a useful stability of the emulsion with those described above To achieve colloids, an emulsifying agent must be or 'wetting agents are given' A variety of emulsifying agents are commercially available, and many of them (including the following) were used in the preparation of the invention Emulsions used successfully:

The non-ionic agent Triton X-100, an alkyl polyether alcohol from Rohm & Haas, - the anionic butcher agent Tergitol Ur. 7, a sodium heptadecyl sulfate from Union Carbide Corporation, or Nacconol, an alkylaryl sodium sulfonate from the National Aniline Division of Allied Chemical and Dye Corporation, or Hekal, a sodium alkylnaphthalene sulfonate from General Aniline & Film Corp. The preferred concentration of the emulsifying agent is between 1 to 3 fo of the total volume of liquid in the finished emulsion. . ' - '

Suitable solvents for dissolving the U-vinylcarbazole and the Halogen-containing activators are listed in Table II. Of the

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The boiling point of the solvent is a crucial factor in its selection Point of view, If the boiling point of the solvent is too low and its volatility is too great, it will evaporate it suddenly separates from the drying surface of the coating, leaving an irregular surface. On the other hand, if the .The boiling point of the solvent is too high and its volatility too low, the solvent does not evaporate from the coating mixture, and a sticky rubbery remains on the surface Shift back. The solvents given in the table result excellent conditions for kinking, creating smooth, even and non-tacky coatings can be obtained. To adjust the viscosity and for easier application water can be added to the carrier in the finished emulsion. The viscosity can be adjusted to some extent by using a more dilute solution of the hydrophilic colloidal binder be set; however, if the viscosity of the binder is too low, the emulsion will not remain stable, and so will it a separation of the phases occurs. It has been found to be beneficial proven to use a higher concentration of binder and to be diluted after making the emulsion. *

It goes without saying that all processing, coating and drying of the photosensitive mixture are carried out under red light safety conditions carried out.

The invention is illustrated in the following examples;

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909835/0656 ^BA D ofuqinal

Example I. ''.

10 ml of a 7% aqueous solution of polyvinyl alcohol (Elvanol, Type 72-60) were placed in a ¥ aring mixer and then 1 ml Alkyl polyether alcohol (Triton X-100, Rohm & Haas) and 10 ml v / water admitted. A solution of 10 ml of cyclohexanone, 160 mg Mereaptobenzothiazole, 320 mg triphenylstibine, 6.4 g carbon tetrabromide and 8 g H-vinylearbazole prepared and after complete Solution the cyclohexanone solution to the Elvanol solution in the Waring mixer given. The contents were mixed thoroughly for 60 seconds. The emulsion obtained was on 135 g of baryta paper in a thickness (in the wet state) of 0.03725 mm. The dried coating was negative with a photographic a floodlight lamp, whereby üie exposure time (depending on the quality of the negative and the distance from the jLanrpe) 15 to 60 Seconds. The exposed paper was (depending on the exposure time with the Ji'lutlight lamp and the distance from the Ileis lamp) 30 to 90 seconds. Carefully heated under an infrared lamp. By heating with infrared light, the exposed original becomes visible developed and fixed at the same time. After heating with infrared light was the sample on a press, such as a Ditto— ' or an Adressograph-Hultigraph-Duplicating-Offset-Press, applied and prints made according to the operating mode specified for the respective device. The prints were excellent of the artwork received and after making 500 copies no sign of original deterioration was found.

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Example II

In this example, the polyvinyl alcohol used in Example I was used replaced by poly (methyl vinyl ether-maleic acid ai ^^. A TO ^ aqueous solution was used and there were obtained similar results. . ■

Example III

The procedure was as in Example I, except that half of the hydrophilic resin consisted of polyvinyl alcohol and the other half from poly (methyl vinyl ether-maleic anhydride). The master copy obtained was similar to that of Example I.

Example IV

Following the procedure of Example I, a 5% aqueous solution of polyacrylic acid amide was used in place of polyvinyl alcohol. The polyacrylic acid amide used was sold under the trade name Cyanamer Grade P26 by American Cyanamide Corporation.
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Example V

Following the procedure of Example I, polyvinyl pyrollidone was used in place of polyvinyl alcohol. The polyvinyl pyrollidone was a product of General Aniline & Film Corporation; Type E It was used at 5 levels .

Example VI . ·.

Following the procedure of Example I, a 2.5-sequence aqueous solution of methyl cellulose (Methocel, DOW Chemical Company) was used in place of polyvinyl alcohol. _909835/0656 . "_

Example VII

Using the procedure of Example I, a 20% aqueous solution was made Solution of G-uimni Arabicum used instead of polyvinyl alcohol.

The printing plates produced in Examples IV "to VII have proven to be useful for piano and lithographic work Printing proved

As with the preparations described in the Wainer patents becomes one of the general formula as the organic halogen compound A-G-X, used in which X is a chlorine or bromine atom and A is either H, an alkyl, haloalkyl, aroyl, aryl, substituted aryl group or bromine or chlorine.

The relative proportions of vinylamine and organic Halogen compounds are between 10 and 200 - '! Hurry! -Vinylamine-

per 100 parts of organic halogen compound and the amount of hydrophilic Binder in relation to the rest of the preparation is between 10 to 100 parts of binder per 100 parts of the rest Preparation »

The amount required to produce the desired relief image to ary! compound of the element of group V of the periodic Systems is between about 0.625 and 6.25 parts per 100 parts by weight ! -Vinylcarbazole or another! -Vinylamine.

Example VIII

The preparation of this example was as in Example I under a Rotiicht safety lamp manufactured. Also under red light b'e-. '909835/0656

BATH ORIGINAL

conditions was given as & coated photosensitive material high pressure calendered, the pressure exerted by the "roller

2

qm contact point was in the range of 703 kg / cm up to 1758 kg / cm and the rollers used were brightly polished and chrome-plated. A radiant, glossy surface was obtained under these conditions. The exposure time used under the conditions of Example I was reduced by a factor of 5, which is 3 to 12 seconds compared to 15 to 60 seconds in the ψ Example I ₀ The advantage of this calendering process in place of the photographic processing is to increase the lifetime of a master with respect to high-quality prints at least five times and generally ten times.

Example IX

A mixture of 100! Dellen papermaking clay, 18 parts by weight of a 50% polyvinyl acetate emulsion in water and 2 parts of separated soy protein which had been treated with 12% by weight of ammonium hydroxide was prepared, then 20 parts by weight were prepared by weight, is dried at 8O ⁰ C and then calendered on polished rolls, thereby obtaining a highly glossy surface, where parts by water to the mixture and it was applied with a doctor knife on cardboard. A solution of 10 ml of cyclohexanone, 160 mg of mercaptobenzothiazole, 320 mg of triphenylstibine, 6.4 g of carbon tetrabromide, 8 g of K-vinylcärabazole and 1 ml of alkyl polyether alcohol (Triton X 100 Rohm & Haas) was prepared and rolled onto the surface of the calendered cardboard, a thickness in the wet state of about 0.050 mm was obtained o The photosensitive solution was prepared under hot light safety conditions and applied to the cardboard support, and the following

909835/0656 BATHROOM OWGINAL - 15 -

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Dry "., Was performed at 5O ⁰ G .ebenfalls under liotlichtbedingungen wax drying, the 'rager again kalandriort and" re-obtain a plate with long life, their sensitivity _about: how was times the size of a comparable coating VOmJSmulsionstyp fifth The amount of isolated soy protein used in the cardboard can vary from 1 to 10 parts per 100 parts papermaking kaolin and the amount of polyvinyl acetate emulsion from 10 parts to 30 parts per 100 parts kaolin. Casein, or polyaeryl acid amide, can replace soy protein, kg for kg. ■ ■.

Example X _: -

Cardboard was first coated with a 5% solution of polyacrylic acid amide and water to a thickness of 0.075 mm, allowed to dry and calendered ., 320 mg · 'i'riplienylstibin, xmd 6.4 g of carbon tetrabromide, 1 g β-vinylcarbazole, lind 1 ml Alkylpolyätlieralkohol _{(Triton.X-1OP.,:} & Rolim ,. Haas) coated, v / qWhen the coating by Lifintauchyfahren to achieve a thickness in the wet state of Ό, 037: 25 mm. Hapli the Tx'ocknen under emergency lighting3: means: sbediijguiit; eii wux ^ de the product under the same Eotlichtbediit-oP-Hgoii can again - landed, and then - the light-sensitive "material BUi" exposure, development by heat and vendinig, which can be used directly as a lithographic printing plate -

.That. Jialai ^ dration process gives in this way the possibility of also to combine hydrophobic preparations with a hydrophilic carrier

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Muieren, so that (without using an emulsion technology, 'until the photosensitive material has been properly exposed and heat developed) achieves completely hydrophilic behavior will.

Example Xl

The preparation of Example I was anodized onto the surface of a Aluminum plate applied, and (after exposure and development as in Example I) a satisfactory lithographic plate was obtained.

Other documents used for the emulsion described above include polypropylene-coated paper, polyethylene terephthalate or polyester on a polyvinyl butyrate carrier

Example IX illustrates the use according to the invention of a hydrophilic one ! Binder. Polyvinyl acetate, which is completely in eiiioin

Dissolved organic solvent and dried to form a film has a hydrophobic character, but if the polyvinyl acetate is used as an aqueous emulsion in the presence of an EmulsionomittoXr ' has been produced and continues to be by a small 1-ienge of a protective colloid, such as a «13. Soy protein or casein, protected shows the polyvinyl acetate preparation (resulting from such an emulsion), hydrophilic. Character, Hie particles of polyvinyl acetate are likely to be either with hydrogen υαοι Hydroxyl ions coat the. cause the hydrophilic character «.

The difference between one from an organic solution o-jei. - ^ - 909835 / Q856 - ___.

BAD ORIGINAL ^J ''"

Polyvinyl acetate obtained from an aqueous protective colloid emulsion is obvious.

- patent claims -

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Claims (1)

- ■ 18 - Patent talks Dry photosensitive plate for the production of a lithographic printing master, characterized in that it contains at least one of the following components
1 ο H-vinylamine 2. halogen-containing ^ compounds in which at least three halogen atoms are bonded to a single "carbon atom, each of the halogen atoms being Br or O1,
3ο triaryl compounds of P, Bi, Sb or As, contains, these ingredients in a hydrophilic, a minor one Amount of a binder containing emulsifier are dispersed and carried by this. 2. Plate according to claim 1, characterized in that the Preparation 4) at least one sulfur-containing organic compound, in which the sulfur is bonded directly to the carbon atom. 5. Plate according to claims 1 and 2, characterized in that it is applied to a flexible surface. 4ο plate according to claims 1 - 3 »characterized in that for a photosensitive printing plate for planographic and lithographic photolithography with image and ink receptors Surfaces that are non-image and color-repellent 9 0983 5/065 6 SAD OWQlNAt Surfaces by using a liydropli.il en binder β for the ίΓ-vinylamine is made hydrophilic and the halogen-containing one Hydrocarbon and the image areas by entering the Triaryl compound in the flat surface, so that the surface has been emphasized ", 5. Plate according to claim 4, characterized in that it consists of the phot ο chemical conversion products ordered from the : imagewise exposure of a exposure made of H-vinylamine, a halogen-containing hydrocarbon, a sriaryl compound of a lillementes of the V group of the Periodic Table and a sulfur-containing organic compound in which the sulfur is bound directly to a carbon dioxide and by an emulsifying agent into a hydrophilic binder is dispersed, so that the pictorial and architectural structures are identical as a result of the imagewise exposure of the plate and subsequent development by infrared light and heat as a relief formed, which were not previously located areas in color-deviating send are they? Delimitation between image and color recording - in flowing lines and non-image and ink-repellent surfaces permanently through the infrared and viärineeiitviicklimgsstufe been made lot. ':. Process for the production of a photographic plate, culcemiKeiehnet by the fact that one. ■ ^v i ") - -under Dttnfcelteainmeriiedbedingungen a liquid preparation r" * ·· "* ~ applies to a carrier, the most complete of each 909835/0656 .. - -— · ■ »_ ₂ 0 - 'BADOWQiNAL ordered one of the following: a) an N-vinylamine b) an organic halogen compound in which
at least three halogen atoms on a single one
Carbon atom are bonded, each of the
Halogens is Br or Cl, c) a triaryl compound of P, Bi, Sb or As, d) a hydrophilic film-forming binder, e) and a volatile liquid carrier for them
Components and ■ 2) the obtained coated article under darkroom conditions is dried to a photosensitive plate, 7. The method according to claim 6, characterized in that a sulfur-containing organic compound in which the sulfur
is bound directly to a carbon atom, is entered into the preparation. 8. The method according to claims 6 and 7, characterized in that
that the liquid preparation contains a small amount of an emulsifying agent and is emulsified before application to the carrier. 9. The method according to claims 6-8, characterized in that
that the plate is calendered after the preparation has dried, but before the imagewise exposure, 9098 35/065 6 - 21 - 10. The method according to claims 6-10, 'characterized in that a \ dry photosensitive plate according to the. The method of Claims 6-> 9 made ¹ and photographically exposed v; ith and then the entire surface is 8.usgesetzt the plate infrared light and heat. The patent attorney: Allijojno sub-power of attorney according to central department 0 4-25Ö / 64 BAD ORIGINAL 9098 3 5/0656