DE1522499A1 - Process for the production of offset printing forms - Google Patents

Description

"KALLE AKTIENGESELLSCHAFT ^ 522499

Our sign day sheet

K I660 FP-Dr.Wi-eg May 26, 1966

description
to register the
KALLE AKTIENGESELLSCHAPT
Wiesbaden-Biebrich
for a patent
concerning

Process for producing offset printing forms

The present invention relates to the manufacture of

Offset printing forums under Ver
Halogenated hydrocarbons. ^

Offset printing forums using 'more photosensitive

A copier material is known from German patent specification 737 289, the light-sensitive layer of which contains halogenated hydrocarbons which develop free halogen upon exposure. This causes the creation of a visible image
chemical reaction with starch or agar-agar also contained in the layer. In a special embodiment
the halogen-generating substance and the halogen-sensitive substance are contained in 'different' adjacent layers.

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These materials are used for the production of Flachdruekforinen but not suitable; when exposed to light, color images are formed, there is no differentiation between coloring and hereditary Areas.

However, there are also known copy materials in which the Photosensitivity of organic halogen compounds for the production is exploited by flat printing forces. Their layers In addition to the halogen-releasing substance, they always contain compounds which crosslink under the action of halogen to form oleophilic polymers.

Favorable results are achieved, for example, with a material which contains tetrabromomethane and! ^ - vinylcarbazole. This and similarly structured copier materials used for the production of However, the common feature is that the unexposed areas must be washed off the substrate before printing, so that its hydrophilic water-bearing Surface is exposed. The halogen hydrocarbon is also disadvantageous copier materials containing a material for manufacture offset printing forums mean that their layers only have a limited lifespan. It has therefore already been suggested that the photosensitive layer only shortly before the production of the To bring printing form on the carrier.

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K I66o . FP-Dr.Wi-eg May 26, 1966 /

But is also the shelf life of I & ungen that both Containing halogenated hydrocarbons as well as halogen-sensitive substances, not high., So this method that when using: other light-sensitive substances than "do it yourself method" has found widespread use, prak- ' table is only exercised to a limited extent.

The object on which the present invention is based was. es dalier, a process for the production of offset printing plates to find in the photosensitive halogenated hydrocarbons processed and which does not show the above difficulties.

The inventive method is based on known methods for. Manufacture of off set printing plates by image f bulky exposing the copy material with a material suitable for offset printing Wecke carrier and a layer thereon, .the upon exposure oleophilic φά so that an ink-carrying is, and is characterized in that a flat material water-insoluble with a layer of Polymers with a hydrophilic surface are treated with a dilute solution of at least one halogenated hydrocarbon of all of the above. Formula. . ■ .. '■

R ₁ -C- X

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K l66o FP-Dr.Wi-eg May 26, 1966

where X can stand for chlorine, bromine and iodine and R, R ₁ , R _{2 can be} identical or different and chlorine, bromine, iodine, hydrogen, alkyl, which may be substituted by chlorine, bromine, iodine and / or a member of an aliphatic Can be chain, aryl, aralkyl, alkenyl or a heterocyclic group or an SO R group., Where R. can be alkyl, aryl, aralkyl, and which optionally contains sensitizer, wets, allows the solvent to evaporate and the The layer is then imagewise exposed to ultraviolet light or, in the presence of a sensitizer, also short-wave visible light.

In this process, the surface of the material becomes oleophilic and therefore greasy at the exposed areas, while it remains water-bearing in the unexposed areas without affecting the non-decomposed parts of the light-sensitive Halogenated hydrocarbons through a development process would have to be washed off. It is completely sufficient if you place the exposed printing plate with a moistened pad inks with printing ink, or directly in the offset printing machine clamps and prints with it. The printing ink removes the unreacted halogen compound from the layer, so that the printing form is insensitive to further exposure to light.

The layers used as starting materials in the process according to the invention can be made from pre-hardened gelatin,

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hardened polyvinyl alcohol or cellulose derivatives such as e.g. regenerated cellulose or saponified acetyl cellulose exist. Preference is given to using a hydrophilic polyvinyl

alcohol layer, as described in the German patent specification,

(K 55 279 VIb / 75c - K 1531). Suitable carrier materials are e.g. aluminum, paper or plastic films, with polyethylene terephthalate films are preferred. Layers made from cellulose derivatives do not necessarily require a carrier, they can be self-supporting be.

Within the compound class generally referred to above the halogen compounds which split off halogen on exposure are to be mentioned as being very suitable: a. B. simple halogenated hydrocarbons such as tetrabromomethane, pentabromoethane and Iodoform. Preferred results are obtained with shark hydrocarbons, which are substituted by a longer oleophilic radical "such as tribromoacetophenone and substitution products of which, the further substituents should be as lipophilic as possible. This lipophilicity gets best caused by alkyl substitutions. The same:; applies to that Tribronmethylphenylsulfon and its substitution products, as well as for the 2-tribrorr: methylehinoline. Basically suitable are also tetrabromo- and tetraiodopyrrole, tetraiodothiophene and tetrabromothiophene, as well as Ilexachlorrithan and

Tetraiodomethar). , "^

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All of these compounds can be applied to the hydrophilic surface individually or in a mixture with one another will.

The requirement of the solvents for the halogenated hydrocarbons is that they dissolve in them without leaving any _{residue, in amounts of about 0.5 to 5% 3} based on the solvent, but that they do not dissolve the hydrophilic layer. On the other hand, a certain swelling capacity for the layer is favorable because this is associated with a slight superficial penetration of the halogenated hydrocarbon into the layer and thus an improvement in the adhesion. This property is particularly shown by lower aliphatic alcohols, which are therefore also used with preference. Ethanol is particularly used as a solvent. Acetone is also a cheap solvent, especially when used in a mixture with alcohols.

Increased print run with those produced by the method of the invention, offset printing plates can be obtained when the attached liquid transferred next photosensitive halohydrocarbon approx Io - 5o wt -.%, Based on the content of halogenated hydrocarbon, a condensation product of m-Kresolsulfonaldehydharz with chloroacetic acid, contains. Its addition increases the adhesion

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the exposed areas on the substrate and a hardening these areas. The use of the condensation product for the improvement of offset printing forms is known; it is described in German patent 1 053 93o. There is also a manufacturing process for the condensation product cited.

Because the spectral sensitivities of the halogenated hydrocarbons in the. are essentially in the ultraviolet range of light, it is advisable to add the coating solution Add sensitizers for the photochemical process, that shift the sensitivity to lengthy fringes. Suitable sensitizers are, for example, compounds that have the following chemical structural features:

Compounds with / C = O or ^ C = S groups, sitting on an aromatic system or in its immediate vicinity, such as Anthrachinoii and its substitution products or aromatic or quas! Aromatic sulfur compounds in defi of the closing el ⁿ as -SH group, or occurs as part of a b & erocyclic ring, such as l-phenyl-5-mercaptotetrasol or 2-iierl: aptobben <'zthianol. Acridone, phenylacridone and Ϊί-phenylthioacridöii are also effective as sensitizers. Also benzophenone and ^, ¹ l'-bis-dimethylaminobensophenon are .'- ünstl'g'e sensitizers. All of the mentioned ¹ -stances already have an effect with rerin ^r ; en additives

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noticeable sensitization, but can be used in quantities of up to 5o (weight%, based on the halogenated hydrocarbon content) without damage.

The wetting of the surface of one of the aforementioned suitable Layers with the photosensitive solution can be carried out in a known manner, for example by dipping, wiping over or by machine Roll application happen. The solution can be applied thinly as thick layers do not improve the effect. The evaporation of the solvent should take place in the dark not to. happen at high temperature, evaporation is preferred exclusively through strong ones. Air movement promoted over the layer. The plan weight of the applied The light-sensitive layer should not exceed a few grams per square meter after the solvent has evaporated. ■; -

The copy material produced in this way can then easily. ■■ be exposed immediately. There the places struck by the light oleophilic, so that they become fat-carrying and printing, takes place ■ The exposure primarily through negative originals, because this creates positive images. The exposure times vary depending on the lighting device. you are at unsensitized material the longest, and can maximally. up to Io minutes. They are emitters with a high proportion to be used in ultraviolet light.

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K I660 PP-Dr.Wi-eg May 26, 1966 «0"

Mixed light lamps are preferred for sensitized material. Much shorter exposure times can be used here can be achieved.

The exposed material is ready for printing. It can be injected into the offset printing machine and under the action of printing ink and fountain solution If immediate printing is not intended, it is advisable to use the plate to be colored in the usual way with a protective paint. This step is not strictly necessary if the printing form is kept in the dark. In terms of purpose, however, soon used the printing form. ■

Technical field of application of the method according to the invention Small offset printing with a medium run length is preferred. It can be used with preference in areas in which a regular and short-term delivery with pre-coated so-called presensitized offset printing plates is not guaranteed.

The advantage of the method is that it only requires a cheap carrier and that the step of removing the unexposed area of the photosensitive layer can be dispensed with.

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K I660 +. FP-Dr.Wi-eg May 26, 1966

Often it is desired. Pipes and foils made of hydrophilic To make materials hydrophobic. This can also be done according to the method of the invention; Surface of the molded body exposed to light will.

The invention is further illustrated by the following examples.

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K, 166ο V ■ ;; '... FP-Dr.Wi-eg May 26, 1966

Example 1:

On a 75 / u thick polyester film, known as the trademarked name "Hostaphan", with a thin adhesion-promoting layer made of a polyurethane adhesive became an aqueous solution of foiyvinyiaxitonox riowiox ν 7 => /

88 ^ ^R 'and dimethyl oil urea brought. The polyvinyl alcohol solution was adjusted to a P value between 1 and 2.

The film was dried for 10 minutes at 14o ° C and was then insoluble in water. He was about 10 o'clock thick.

The surface of the layer was then treated with a solution of 2 parts by weight of 2, S-dimethyl - ^^ 'tA-tribromoacetophenone in 100 parts by weight Packaged with ethyl alcohol and allowed to air dry.

The film was then irradiated for one minute under a negative original ₍ q; e with a UV lamp (UV burner Original Hanau Q 25o). The distance between the film and the lamp was approx. 20 cm.,

After exposure, the areas of the layer that were exposed to the Were exposed to UV light. Printing ink on, the unexposed Places remained £ Ut water leading.

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Example 2: "'

On a support with adhesion promoter as specified in Example 1 was an aqueous solution of cellulose ethers (Tylose ^ ^R 'is H 2o p) with 5 parts by weight Ji dimethylolurea, based on the cellulose derivative, and dried 5 minutes at l4o ° C Ψ . The solution was adjusted to a Pu value between 1 and 2 with sulfuric acid. The procedure in Example 1 was also followed. The layer was then strongly oleophilic in the exposed areas.

Example 3

A film made of regenerated cellulose, known by the trademarked name "cellophane" was how | y described in Example 1, with a '2 (Tew .- $ igen solution

from 2,5-dimethyl - ^! ^! ^ - tribromoacetophenone in ethyl alcohol: treated, air-dried and then exposed under a template, as indicated in Example 1. At the exposed areas. the printing ink was accepted well, in the unexposed areas, but Mcht.

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Example 4:.

An approximately 8yu thick layer made of a mixture of 7ο wt ■ * -% aluminum silicate, 2o wt, -% of polyvinyl alcohol with a content of acetelierten hydroxyl groups of 2% (K-value 7o) and Io wt -.% Of a polyvinyl acetate dispersion , which contains polyvinyl alcohol as a protective colloid, was named after the j | Application from aqueous dispersion cured for about 20 seconds at a surface temperature of 125 ° C. In the mixture were 5 wt .- 5? Dimethylolurea, based on the polyvinyl alcohol content, is used as a crosslinking agent and curing is carried out at a value of 2. A 100 / u-thick film made of polyethylene terephthalate, which was provided with a thin adhesive line made of a polyurethane adhesive, served as the substrate. "-

The layer was coated with a 2% strength by weight solution of pentabromoethane tamponized in ethanol and air dried. The dried layer is treated with a UV lamp for 2 minutes, as indicated in Example 1, exposed.

In the exposed areas the layer took on printing ink, while the unexposed areas are still very water-bearing. .

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Example 5:

The procedure was as in Example H, except that carbon tetrabromide was used instead of pentabromoethane. The result corresponded to the example ^ i.

Example 6 :

A water-resistant, cellulose acetate-coated paper, about 3 / u deep saponified on the surface, was treated with a solution of 2 parts by weight of 2, 5- dimethyl-ti), Ul u) -tribromoacetophenone in 100 Vol.TIe.Ethyl alcohol coated.

{After drying, a negative template was used for 7 minutes long under a 30 amp arc lamp exposed at a distance of 60 cm. Then printing ink was applied with a cotton ball moistened with water, which only adhered to the places hit by the light.

Example 7:

On a leo ax thick polyester film ₅ known under the goods.

trademark protected name "lielinex 0", with an adhesion-promoting A layer of polyurethane adhesive was applied to an approx.

lOyU thick hydrophilic layer applied.

The layer was heated to dry and harden for ² 10 seconds at approx

ο
and heated again to approx. 15oC for 2o seconds.

The hydrophilic layer consisted of polyvinyl alcohol (Mowiol N- 70/98) with 5 r: -ow -.- / i- dimethylolurea as crosslinker.

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The polyvinyl alcohol solution was used in the manufacture of the Shift set to a ρ fourth between 1 and 2.

A solution was applied to the layer; consisting of 2 parts by weight of 2 _J 5-dimethyl-tö _i lö.lu-tribromoacetophenone and 1 part by weight of N-phenylacridone applied in loo parts by volume of ethyl alcohol

and dried. ^

It was exposed for 8 minutes through a negative original an arc lamp operated with 18 amperes at a distance of 60 cm and obtained after coloring with a moist Cotton ball with printing ink in the areas hit by the light - black image.

If you use N-phenylthioacridone instead of N-phenylacridone this cuts the exposure time by half.

The sensitizing effects of benzophenone, 5-chloro-l-benzylariinoanthraehinone, l-chloro-S-methyl-anthraquinone, 1-chloro- . *

anthraquinone and!, ^ - dichloro-anthraquinone corresponds approximately that of N-phenylacridone. The exposure time is reduced to 1/2 to 1/3 compared to unsensitized material.

Example 8:

A laminated with aluminum paper was laminated on the aluminum side with an approximately 2o Ax thick 7olie from regenerated cellulose. Then there was a deletion of 2 parts of 2,5-dimethyl- u), w) W-tribronacGtophenonj o ₃ 3 parts of a condensation product from m-cresol formaldehyde resin

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Chloroacetic acid (produced according to "DBP 1 o53 93o) and o, 5 Parts by weight of N-phenylthioacridone in 100 parts by volume of ethyl alcohol applied.

After drying was followed by a negative for 5 minutes Original exposed under a 200 watt mixed light lamp (Philips) at a distance of 30 cm.

Black printing ink was applied to the exposed areas with a moistened cotton tampon.

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Claims (5)

"KALlE AKTIENGESELLSGHAFT" 1522498-. / ξ "^" Our character tag sheet K I660 FP-Dr.Wi-eg 5/26/19/66 Claims l \ Process for the production of offset printing forms by image-wise Exposing copy material with a carrier suitable for offset printing purposes and one thereon Layer which becomes oleophilic around it when exposed to grease, characterized in that one is a flat Material with a layer of water-insoluble polymer with a hydrophilic surface on the layer side with a dilute solution of at least one halogenated hydrocarbon of the general formula. where X can stand for chlorine, bromine and iodine and R, R-j_, R _{2 can be the} same or different and chlorine, bromine, iodine, hydrogen »alkyl, which may be substituted by chlorine, bromine, iodine and / or a member aliphatic chain, aryl, aralkyl, alkenyl or a heterocyclic group or SO "-R ^ group, where P .., alkyl, aryl, aralkyl can be, mean, which may contain sensitizer, wets, allows the solvent to evaporate and then imagewise exposed the layer to ultraviolet or 90983 7/05 5 7 BAD KALLE AKTIENGESELLSCHAFT 1522 * 9 » AU * Our characters tag · sheet K I660 . FP-Dr.Wi-eg May 26, 1966 in the presence of a sensitizer, also short-wave visible light. 2. The method according to claim 1, characterized in that the hydrophilic surface is wetted with a solution _{containing 0.5 to 5 wt .- / £ of halogenated hydrocarbon 3} based on the solvent enthu.lt. 3. Process according to Claims 1 and 2, characterized in that the halogenated hydrocarbon is applied in a solvent - which swells the hydrophilic layer. H. Process according to claims 1, 2 and 3 _S, characterized in that the halogenated hydrocarbon is applied in a lower aliphatic alcohol. 5. The method according to claims 1 to H _s, characterized in that the hydrophilic surface is wetted with a liquid which, in addition to the halogenated hydrocarbon and, if necessary, a sensitizer, still Io to 50% by weight , based on the halogenated hydrocarbon content, a condensation Product made from m ~ cresol sulfonaldehyde resin with chloroacetic acid. according to German patent specification 1053 9 · 3ο. . KALLEAKTIENGESELLSCHAPT ^m ORIGINAL 09837/0557