DE1447929A1 - Process for the production of relief forms for printing purposes - Google Patents

Description

BADISCHB ANILINE & SODA FACTORY · ««!

144792S

_Λ Our sign; OZ 23 8θ4 Buc / Wn

Ludwigshafen am Rhein, August 12, 1965 Process for the production of relief forms for printing purposes

It is known to produce "relief forms for printing purposes" by a plate consisting of a mixture of 70 to ^ O % of a soluble synthetic linear polyamide, 30 to 60 % of a compound and at least two unsaturated double bonds and 0.001 to 5 % of an activator through a The original is exposed and the unexposed areas of the plate are then washed out. The polyamides used for this purpose are copolyamides, such as a copolyamide made from hexamethylenedlammonium adipate, hexamethylenediaomonium sebacate and caprolactam, or polyamides which have been modified by reacting with formaldehyde and then etherifying the N-methylol groups. When using unsubstituted copolyamides, it has hitherto been impossible to add so many photopolymerizable monomers with at least two double bonds that the relief forms have sufficient strength for printing purposes after exposure and washing out. In addition, the contour definition of the relief was insufficient for most printing purposes. If, on the other hand, polyamides which have been modified by reaction with formaldehyde and subsequent etherification are used, the proportion of monomers with at least two double bonds in the mixture can be increased. When such a mixture is compressed at elevated temperature, undesired crosslinking and side reactions with the bifunctional monomers often occur

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It has been found that relief forms for printing purposes can be advantageously produced by exposing plates, films or foils from a mixture of polyamides, compounds having at least two photopolymerizable double bonds, one or more initiators and, if appropriate, an inhibitor and then washing out the unexposed areas by plates, films or sheets used, 69.5 to 25 weight percent soluble mixed polyamide, 30 to 60 wt.% of compounds having at least two photopolymerizable double bonds and 0.5 to 15 weight percent of compounds represented by reacting polyamides, carboxylic acids, acid amides or hydroxyl compounds with a compound of the formula (A)

R ₁ - CH - CH - R ₀

^{£ 1}

are prepared, where R, Rp = hydrogen or lower alkyl radicals with up to 3 carbon atoms and X - means oxygen or a = NH group. The weight data relate to the total mixture.

Preferred compounds of type (A) are ethylene oxide and Ethylenediamine.

Those used according to the invention in a mixture with polyamides and compounds having at least two photopolymerizable double bonds Reaction products have the general formula (B) to (E):

Polyamide chain - N - CO - ... polyamide chain

¹ HC- R ^
HC-Ro
. X, < ^Β )

R-CO-O Λ— CH-CH-X -4— H, _rN

it IW L R ₁ R ₂ Jn

+ CH-CH-X -4- H

¹ 'fD ^

R, R ^ 'Jn ^ν " ^λ

R-CO-NH

R-O

CH-CH-X t ι

R ₁ R ₂ ^J n

The relief forms produced according to the invention for printing purposes have excellent definition and strength.

The reaction products of polyamides, carboxylic acids, hydroxyl compounds or acid amides with compounds of the formula (A) are in a known manner by single, or repeated Addition of (A) to the component carrying the reactive hydrogen atom.

Homopolymers or copolymers of the compounds can also be used of type (A), e.g. those made of propylene and ethylene oxide which still contain reactive epoxy groups with React polyamides, carboxylic acids, hydroxyl compounds or acid amides and these reaction products with the carrier substance Mix the soluble polyamides used and, after adding the other additives, press the mixtures to form sheets.

As polyamides with the compounds of formula (A) or whose polymers can be implemented, both oligomers and low or high molecular weight polymers are suitable Laotams with 4 to 12 carbon atoms, for example caprolactam or Caprylic lactam.

Polycondensates of aminocarboxylic acids or are also suitable

809812/0718 ORIGINAL INSPECTED

those from salts of the diamine / dicarboxylic acid type, such as hexamethylene d i ammoni umad i pat.

Reaction products of alkylene oxides, such as Ethylene oxide, or alkylene imines, such as ethylene imine with acid amides; such as acetamide, propionic acid amide, etc., or with compounds that Contain ureas or urethane groups, such as ethylene urea or ethyl urethane.

Finally, reaction products from compounds containing carboxyl groups, such as mono-, di- or polycarboxylic acids, as well as polymers containing carboxyl groups or compounds containing hydroxyl groups, such as acetic acid, adipic acid, Polyvinyl alcohol and its half esters with dicarboxylic acids with compounds of the formula (A) or their polymers are suitable.

The "carrier substance" for the mixture are linear synthetic mixed polyamides, which are available in amounts of 69.5 to 25 percent by weight, based on. the total mixture, are used, e.g. those that are conventionally produced by polycondensation or Prlymerization of a mixture of two lactams with 4 to 12 Carbon atoms are made. Such lactams are, for example, caprolactam, oenanthlactam, capryllactam, laurolactam or corresponding C-substituted lactams, such as C-methyl- ε-caprolactam, t-ethyl-C-caprolactam, ^ -ethylönanthlactam or the aminocarboxylic acids on which the lactams mentioned are based. At least three are also suitable Mixed polycondensates made up of various components from customary diamines and dicarboxylic acids, customary dicarboxylic acids are for example adipic acid, suberic acid, sebacic acid,

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Dodecanedioarboxylic acid, *, * - diethyladipic acid or (t-ethylkorkic acid or dloarboxylic acid containing cycloaliphatic or aromatic ring systems, such as phthalic acid or cyelohexyldicarboxylic acid. Suitable diamines are, for example, pentethylenediamine, hexamethylenediamine, ”heptamethylenediamine or these substituted diamines, or octamethylenediamine derivatives. such as N-methyl-, N-ethyl, hexamethylenediamine, 1,6-dimimo-3-methylhexane, cycloaliphatic or aromatic diamines such as m-phenylenediamine, m-xylylenediamine or 4,4'-diaminodlphenylmethane, the bridge members between the two amino groups Mixed polyamides which are produced by polycondensation of a mixture of one or more laotams and at least one salt of the diamine / dicarboxylic acid type, such as the salt of adipic acid / p, p ^f -diaminodicyclohexylmethane, are particularly suitable.

The polyamides used as "carrier substances" and for the production of the additives used according to the invention are soluble in solvents or solvent mixtures. Suitable Solvents are, for example, aliphatic alcohols such as Methanol, Xthanol, propanol, alcohol-water mixtures, benzene-alcohol-water mixtures or alcohol-aromatic mixtures, such as e.g. methanol-water, ethanol-water, propanol-water, benzene-methanol-water, toluene-propanol etc.

Particularly suitable photopolymerizable monomers with at least two double bonds are those which contain no ald groups in addition to the double bonds - e.g. methylene-bis-acrylic-

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809812/0718

ORIGINAL INSPECTED

amide, methylene-bis-methacrylamide, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene-bis-acrylamide and methacrylamide; Diacrylates or dimethacrylates of glycols, such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol or cyclic diols. Monomers that contain urethane groups in the molecule, eg *, are equally suitable. the reaction products of glycol monoacrylates or glycol monomethacrylates with diisocyanates, or monomers which, in addition to amide groups, also contain urea groups, such as reaction products of hexamethylene acrylamide with isocyanates. Other customary photopolymerizable monomers, such as triacryl formal, triallyl cyanurate, and substituted acrylates or methacrylates of polyols or phenols are also suitable.

Vicinal ketaldonyl compounds, for example diacetyl or are suitable as activators for the photopolymerization Benzil; «T-ketaldonyl alcohols, such as benzoin, pivaloin; Acyloin ether, e.g. benzoin methyl or ethyl ether, oC-hydrocarbon-substituted aromatic acyloins such as t-methylbenzoin or tf-ethylbenzoin.

The photosensitive plates, sheets or films from the Mixtures used according to the invention are made by customary methods manufactured for the production of plates and foils. The plates are then prepared in a known manner by means of a template. exposed, and after exposure, the unexposed areas are removed with a solvent. This can happen, for example, by spraying, brushing, brushing or in a bath with the exposed plates with the solvent rinses the solvent.

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The relief forms are suitable for letterpress printing of flat and curved printing forms, for indirect letterpress printing as well as for autotypical gravure printing. According to the invention, both rigid as well as flexible forms »if desired with rigid or flexible carrier foils or plates made of metal » Paper, wood or plastics can be firmly bonded, can be produced

The parts mentioned in the example are based on weight. example

97 parts of a mixed polyamide, produced in conventional catfish from a mixture of equal parts of caprolactara, hexamethylenediammonium adipate and the salt of 4,4'-diaminodicyclohexylmethane and adipic acid, are mixed with 12 parts of a reaction product of polycaprolactam with about 3 parts of ethylene oxide (LUROTEX A 25) in 500 ml of benzene-methanol-water (2: 7: 1) dissolved. Parts of hexaethylene-bis-acrylamide and 1.5 parts of benzoin methyl ether and 0.00} parts of hydroquinone are then mixed in. The viscous solution is poured into containers with the exclusion of daylight and dried at room temperature for 24 hours. The product is then crushed and a further 12 hours under reduced Druok (20 mm Hg) dried at about 50 ° C · The material is granulated and pressed at 160 to 170 ⁰ C to form a clear transparent plate. In a copy frame, the plate is exposed for 5 minutes using a combined line-raster negative with 4 fluorescent tubes, which have a particularly high UV component and are arranged at a distance of ~ *> cm from the plate. After exposure, it will be on a

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Metal plate glued on polyamide plate in a bath Benzene! Methanol: Water (2: 7: 1) brushed out for 7 minutes. To after drying, a relief printing form with excellent Contour sharpness and the best reproduction of details. The relief is 0.6 mm deep at the deepest points.

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Claims (1)

Claims 1. A method for producing relief forms for printing purposes -—- ^ by exposing plates, films or foils made of a mixture of polyamides, compounds with at least two photopolymerizable double bonds, one or more initiators and optionally an inhibitor and then washing out the unexposed areas, thereby contained in that plates, films or sheets used, 69.5 to 25 weight percent soluble copolyamide, from 30 to 60 percent by weight of compounds having at least two photopolymeri- sierbaren double bonds and 0.5 to 15 percent by weight of compounds of Ver, by reacting Polyamides, carboxylic acids, acid amides or hydroxyl compounds with a compound of the formula (A) R ₁ -CH - CH - R ₂ (A) have arisen, where R ₁ , R ₂ = hydrogen or lower alkyl radicals with up to > C atoms and X = oxygen or an = NH group and the weight data relate to the mixture as a whole. 2. The method according to claim 1, characterized in that compounds are used as nonoaere diacrylates and / or dimethacrylates of diols or Diaainen. 5. The method according to claim 1, characterized in that as ~ ² ~ 809812/0718 -ίο- U47929 Monomeric triacryl formal is used. 4. The method according to claim 1, characterized in that ethylene oxide adducts of polyamides are added. 5. The method according to claim 1 to 3j, characterized in that ethylene oxide polymers are added. 6. The method according to claim 1 to 3 *, characterized in that polymers of ethylene imine are added. Badische Anilin- & Soda-Fabrik AG 809812/0718