Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/325—Non-aqueous compositions

Definitions

• the invention relates to a method for producing relief molds crosslinked by photopolymerization, certain developer solvents being used to wash out the uncrosslinked portions of the layers.
• the production of printing forms and photoresists by imagewise exposure of photopolymerizable or photocrosslinkable relief-forming layers with actinic light with crosslinking of the exposed layer portions and subsequent washing out of the uncrosslinked portions of the layers in developer solvents is known.
• Chlorinated hydrocarbons such as e.g.
• Trichlorethylene Trichlorethylene, tetrachlorethylene, aromatic hydrocarbons such as benzene, toluene, saturated cyclic and acyclic hydrocarbons such as hexane, cyclohexane, unsaturated cyclic hydrocarbons such as e.g. terpenoid compounds, limonene, pinene, lower aliphatic ketones such as acetone, methyl ethyl ketone, optionally in a mixture with an alcohol (e.g.
• Butanol with a share of about 20 vol .-%) used.
• the wash-out solution for flexographic printing plates and photoresists which is widely used in the market, consisting of approximately 80 parts by volume of tetrachlorethylene and 20 parts by volume of n-butanol or trichloroethane causes problems in the operation of the washing devices due to its toxicity. Suction is necessary for proper operation and the exhaust air must be freed from the chlorinated hydrocarbons before being released. The disposal of the used washout solution is also problematic. Further problems arise from the high swelling that the exposed layer experiences during washing out. The high swelling of the layer causes damage to the photopolymerized structures (breakouts, detachment of fine elements, etc.) and low resistance to overwashing.
• Terpenoid hydrocarbons such as limonene
• the present invention relates to a process for the production of relief molds crosslinked by photopolymerization by imagewise exposure of layers which can be crosslinked by photopolymerization to actinic light with crosslinking of the exposed layer portions and washing out the uncrosslinked portions of the layers with hydrocarbon solvents or mixtures of hydrocarbon solvents and alcohols, which is characterized in that that hydrogenated petroleum fractions are used as hydrocarbon solvents, which have flash points> 45 ° C. and boiling ranges between 160 and 220 ° C.
• the hydrogenated petroleum fractions generally have an aromatic content according to DIN 51 378 of ⁇ 1%. Such hydrogenated ones are preferred
• DIN 51 378 determined - have between 0.5 and 50%.
• the detergents according to the invention can also contain additives from odor improvers and / or surface-active substances.
• Aromatic hydrocarbon solvents (aromatic content> 10%) are also suitable as a washout agent for printing plates or
• Dearomatized hydrocarbon solvents with a boiling range above 230 ° C are also not suitable as wash-out agents for printing plates or resists due to excessive washout times.
• Hydrogenated petroleum fractions preferred according to the invention are, in particular, those which, in addition to an aromatic content of ⁇ 1% and a flash point of> 45 ° C., have a boiling range of 170 to 220 ° C., in particular 180 to 210 ° C. and have a proportion of naphthenic hydrocarbons of 0.5 to 50, in particular 10 to 40% (according to DIN 51 378).
• flexographic printing plates generally have a multilayer structure (on the approximately 3000 ⁇ m thick relief layer there is often a thin, approximately 5 ⁇ m thick cover layer made of polyamide), it may be expedient to use one of the hydrogenated petroleum fractions to be used according to the invention
• Alcohols with a carbon number of 4 to 8 have proven to be suitable.
• the proportion of the alcohol component should be at least 5% by volume, preferably 20% by volume. The presence of alcohol lowers the
• Flash point of the pure hydrocarbon solvent around 10 to 20 ° C.
• the flash points of the formulated washout solutions are then around 40 ° C.
• the washout solutions can therefore be processed in devices without EX protection.
• the washout solutions can also contain surface-active agents which accelerate the dissolution of the unexposed material and portions of odor-improving substances.
• Suitable surface-active substances are alkyl sulfonates and their salts, alkylammonium salts or ethoxylated fatty alcohols, fatty alcohol ether sulfates and their salts, and fatty alcohol phosphoric acid esters and their salts.
• the surface-active components can usually be added to the washout solution in an amount of 0 to 2% by weight.
• Suitable odor-improving additives are the naturally occurring terpenoid compounds, limonene, pinene, citronellol, etc. Depending on the desired intensity of the aromatic smell, these can be used in the washout solution in a proportion of 0 to max.
• Washout solutions are drastically reduced. This significantly improves the overwash resistance of the structures produced by imagewise exposure, i.e. even if that for a certain relief height
• the outbreak stability of the structures produced by imagewise exposure is also considerably improved by the use according to the invention of the hydrogenated petroleum fractions described above. This is of particular importance for thick, flexible printing plates with a high relief (approx. 3 mm), which are used, for example, in cardboard and corrugated cardboard printing.
• washout solutions to be used according to the invention relates to the surface quality of the imagewise exposed and washed out layers.
• washout solutions to be used according to the invention is the fact that, despite the high boiling range of the hydrogenated petroleum fractions in question, in comparison to the washout solutions with tetrachlorethylene, no longer drying times after washing out are necessary.
• washout agents according to the present invention can be used in non-explosion-protected washout devices. Due to the low intrinsic odor of the hydrogenated petroleum fractions to be used according to the invention, the extraction of the washing devices can be greatly reduced. The relief forms are odorless after completion. Another advantage is the fact that the washout solutions according to the invention can be successfully used on numerous known layers which can be crosslinked by photopolymerization.
• the raw layers used had the following compositions
• 3-block rubber made of styrene / isoprene / styrene-butadiene 87.592%
• Panel type 2 (multi-layer panel)
• Dye Solvent Black (CI 26 150) 0.004% Layer thickness 700 ⁇ m on a 125 ⁇ m thick polyethylene terephthalate film. which was coated with a polyurethane adhesive varnish. A photocrosslinkable layer based on an elastomeric binder (thickness 2000 ⁇ m) was used as the carrier layer.
• a flexo plate (plate type 1) was produced in the usual way.
• the full surface of the flexographic printing plate was first exposed for 65 seconds in a tube imagesetter, then exposed step by step through a negative pad (exposure times per benefit of the negative from 6 to 20 minutes) and at room temperature in a non-explosion-protected brush washer with low air extraction (approx 10 m 3 / h) washed out.
• the washer contained a washout solution of 80 parts by volume of a hydrogenated petroleum fraction (naphthen content 35%. Boiling range 186 to 217 ° C.) and 20 parts by volume of n-butanol.
• the optimal washout time was 6 minutes.
• all test elements of the flexographic printing plate obtained were completely and correctly formed.
• the flexographic printing plate was dried at 65 ° C. for 2 hours, stored at room temperature for 15 hours, subjected to a customary aftertreatment with an aqueous bromine solution and dried again.
• the printing form had a uniformly smooth surface after completion. No orange peel was observed.
• the printing form was odorless after production.
• the post-treated flexographic printing plate was mounted on a printing cylinder in a flexographic printing unit and delivered excellent printing results that showed no loss of information compared to the negative original.
• Example 2 The procedure was as in Example 1, except that the washout solution was added as an alcohol component instead of n-butanol n-pentanol (20 parts by volume). The washout tests were again carried out in a non-explosion-protected brush washer with low suction (approx. 10 m 3 / hour).
• the optimal washout time was 6 minutes. All test elements were completely and correctly formed with an exposure time of 6 minutes.
• the printing plate After the aftertreatment, the printing plate again had a uniform, smooth surface and good printing properties and was odorless.
• Example 2 The procedure was as in Example 1, except that a mixture of 80 parts by volume of tetrachlorethylene and 20 parts by volume of n-butanol was used as the washout solution.
• the washout tests were carried out in a brush washer which was not explosion-proof but provided with a strong air extraction (approx. 100 m 3 / h).
• the optimal washout time was 5 minutes.
• the test elements were only error-free after an exposure time of> 12 minutes. With shorter exposure times, breakouts were found on the test elements, particularly on grid and grid fields.
• Example 2 The procedure was as in Example 1, except that a mixture of 80 parts by volume white spirit (aromatics content 25%, boiling range 187 to 216 ° C.) and 20 parts by volume n-butanol was used as the washout solution.
• the washout tests were carried out in a non-explosion-protected washer with strong suction (approx. 100 m 3 / h).
• the optimal washout time was 5 minutes.
• the printing forms had an unpleasant smell when they were finished.
• Example 2 The procedure was as in Example 1, except that a mixture of 80 parts by volume white spirit (aromatics content 25%, boiling range 155 to 185 ° C.) and 20 parts by volume n-butanol was used as the washout solution. The tests were carried out in an explosion-protected washer with strong suction (approx.
• Comparative Example 4 The procedure was as in Example 1, except that a mixture of 80 parts by volume of a hydrogenated mineral oil (boiling range 220 to 255 ° C., naphthenic content approx. 30%) and 20 parts by volume of n-butanol was used as the washing-out agent .
• the experiments were carried out in a non-explosion-proof
• the washout time for a 700 ⁇ m thick relief was 17 minutes.
• Example 3 The procedure was as in Example 2, except that instead of plate type 1, the multilayer plate type 2 with a defined relief height of 700 ⁇ m was used. The tests were carried out in a non-explosion-protected washer with low suction (approx. 10 m 3 / h). The optimal washout time was 6 minutes. With a 100 Zigen washout, ie with a total washout time of 12 minutes, no damage to the relief structure or missing test elements could be observed. The printing plates were odorless.
• Example 3 The procedure was as in Example 3, except that a washout solution consisting of 80 parts by volume of tetrachlorethylene and 20 parts by volume of n-butanol was now used. The tests were carried out in a non-explosion-protected washer with strong suction (approx. 100 m 3 / h).
• the optimal washout time was 5 minutes. A 100 zig overwash was now noticeable in the absence of critical test elements (free-standing dots and lines) and in breakouts on grids and grids.
• the drying process was determined as a function of time in a circulating air drying cabinet at 65 ° C. on a plate type 1 cliché produced as in Example 1.
• the swelling in weight was 2%. After a drying time of 2 hours at 65 ° C, the swelling in weight had decreased to -0.1% of the initial weight. The extracted fraction determined after a drying time of 24 hours was 0.3%, based on the starting weight.
• Example 5 The procedure was as in Example 4, except that a mixture of 80 parts by volume of tetrachlorethylene and 20 parts by volume of n-butanol was used as the washout solvent. Immediately after washing out, the swelling in weight was 8%. After a drying time of 2 hours, the swelling in weight had also decreased to -0.1%, but the extracted fraction was 1.7%, based on the starting weight.
• Example 5
• Plate type 3 was used as the flexographic printing plate. After the back exposure, the printing plate was exposed imagewise from the front through a test negative (exposure time 20 minutes) and then developed into a cliché in a brush washer. A mixture of 80 parts by volume of a hydrogenated petroleum fraction (naphthen content 35%, paraffin content 65%. Boiling range 186 to 217 ° C., aromatic content ⁇ 1% according to DIN 51 378) and 20 parts by volume n-butanol was used as the washout solution.
• a hydrogenated petroleum fraction naphthen content 35%, paraffin content 65%. Boiling range 186 to 217 ° C., aromatic content ⁇ 1% according to DIN 51 378) and 20 parts by volume n-butanol was used as the washout solution.
• Example 5 The procedure was as in Example 5, except that a mixture of 80 parts by volume of tetrachlorethylene and 20 parts by volume of n-butanol was used as the washing-out agent.
• EXAMPLE 6 The procedure was as in Example 1, except that a mixture of 75 parts by volume of a hydrogenated petroleum fraction (boiling range 160 to 195 ° C., naphthene content 35%), 20 parts by volume of n-butanol and

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Manufacture Or Reproduction Of Printing Formes (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Gas Separation By Absorption (AREA)
• Making Paper Articles (AREA)
• Printing Methods (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 1988
  • 1988-03-10 DE DE3807929A patent/DE3807929A1/de active Granted
  • 1988-10-14 JP JP63257438A patent/JP2577457B2/ja not_active Expired - Lifetime
• 1989
  • 1989-03-03 EP EP89103741A patent/EP0332070B1/de not_active Expired - Lifetime
  • 1989-03-03 DE DE58908989T patent/DE58908989D1/de not_active Expired - Lifetime
  • 1989-04-29 WO PCT/EP1989/000478 patent/WO1990013853A1/de not_active Ceased
  • 1989-04-29 EP EP89905678A patent/EP0470071B1/de not_active Expired - Lifetime
  • 1989-04-29 AT AT89905678T patent/ATE127246T1/de not_active IP Right Cessation
  • 1989-05-03 CA CA000598578A patent/CA1334139C/en not_active Expired - Lifetime
  • 1989-10-20 US US07/425,491 patent/US5061606A/en not_active Expired - Lifetime
• 1991
  • 1991-10-28 NO NO914219A patent/NO179346C/no not_active IP Right Cessation

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