DE1522478B1 - Presensitized, positive working planographic printing plate - Google Patents

Description

The invention relates to a presensitized, positive applies, but * as was found that adhere

working planographic printing plate described by a diazo in USA.-Pateiitscfiiift 3 046120

oxide resin has been made photosensitive. Connections bad on the aluminum plate, like that

Such planographic printing plates and their processing that the mechanical strength of the image is reduced.

are detailed in U.S. Patent 2714066-5.

described. Diazonium compounds can also be used. There are also light-sensitive layers for the

genes that are known when exposed to alkali-soluble carboxylic acid photomechanical reproduction, the water-

derivatives of five-membered carbocyclic rings insoluble, resinous esters of the sulfonic acids of

can be converted into an organic quinone- (l, 2) -diaziden, especially of condensa-

Solvent dissolved, ionization products of naphthoquinone (l, 2) -diazidesulfo- on a hydrophilic carrier

apply, and after exposure and development with acidic and alkali-soluble phenol-formaldehyde-resins

an alkaline solution, the exposed parts will have zen as photosensitive substances. As

dissolved away and leave a positive image. Such-found can be done when using with these

Flat printing plates a are not high planographic printing plates produced in the USA patent layers

Writings 3,046,122 and 3,046,123. 15 print runs sufficient to meet the requirements of

The connection-free prints applied to planographic printing plates are achieved
fertilize are according to the aforementioned United States patent object of the invention is to create rules for esters or amides that are sensitized by benzene or. positive-working planographic printing plates are derived from naphthalene diazooxides; however, of the type mentioned, which enable almost all of the compounds described above to be obtained in a particularly high number of copies, of perfect quality, low molecular weight, and if they allow without printing and which can be easily developed, corresponding additional compounds have been applied. if they have a tendency to crystallize, printing plate according to the invention, the photosensitivity of which leads to a reduction in mechanical strength, the layer has a 2-diazo-1-naphthol-4-sulfonic acidity of the resulting image, so that no 25 or 2-diazo l-naphthol-5-suh onsäureester ⁱ can be obtained in which large number of copies. In order to esterify the sulfonic acid group with a phenol polymer in the photosensitive layer, it is characterized in that it prevents and improves the mechanical strength from acetone and pyrogallol phenol-formaldehyde resin, shellac or a styrene-30 obtained resin.

Maleic anhydride resin used. However, if the planographic printing plates according to the invention show

Substances other than light-sensitive compounds, as experiments have shown, are not just better

for the highly sensitive layer, the number of copies used is compared to known, commercially available

the differences in the solubles, presensitized, positively working flat

between the exposed and unexposed printing plates, but can also be done with substrates

Areas in development. of various kinds, especially plastic

There are also known copier layers that adhere to metal substrates, are etch-resistant or have plastic surfaces and are made of light. The planographic printing plates according to the sensitive substances naphthoquinone- (1,2) -diazide- invention can be present as a layer support both mecha- (2) -suh ° onic acid esters and in addition to 40 nically roughened aluminum plates as well as acid-resistant, alkali-anodic ones due to the photosensitive substances Have plates prepared for oxidation. A soluble resin of the non-curable phenol type - another advantage, which is particularly advantageous for non-metallic formaldehyde resin novolaks as chemically non-layer substrates, is that they contain bound admixtures in such amounts that the plates can be developed particularly easily and that that the proportion by weight of alkali-soluble resin is at least as great as the proportion of light-sensitive alkaline solutions that can develop in the exposed plates.
sensitive substance. The phenolic polymer is a product that is characterized by, metallic substrate, ζ. B. aluminum or the implementation of acetone with pyrogallol in counter-zinc, use. In addition, a catalyst, such as phosphorus oxychloride, has been obtained in particular for the production of printing forms intended for light, preferably at room temperature. sensitive layers known to have at least one It contains free phenolic hydroxyl groups. Whether a free hydroxyl group-containing naphtho- well the structure of this polymer is not exactly known bequinone- (l, 2) -diazidesulfonsäureester of optionally, it is probably obtained by the same substituted hydroxyl compounds of the diphenyl, mechanism that leads to the formation of bis-naphthalene or Contain dinaphthalene and lead to phenol A from acetone and phenol,
if necessary mixed with alkali-soluble resins. The acetone-pyrogallol polymer is soluble in ketones. According to USA.-Pa, alcohols or alcohols serve as a layer support and has a molecular weight of 2,534,588. from about 1000 to 1800. When it is applied as a coating on a

Even when these materials are used, the aluminum plate is formed from a solution in methylethyl The difficulty that arises from the presence 60 ketone is applied, it forms a solid, smoothness from substances other than the photosensitive film.

borrowed compounds in the light-sensitive layer The esterification of the polymer can thereby

th result. follow that the sulfonic acid chloride derivative one

In order to overcome these difficulties, in the diazo oxides under consideration and the US Pat. No. 3,046,120 to use 65 polymer in a solvent such as dioxane or of a photosensitive material, the tetrahydrofuran, dissolves and then to the solution even a high molecular weight compound is a weak alkali such as an alkali bicarbonate or alkali. If an aluminum plate is carbonated as a layer support, it clogs. The reaction ratio of acid

3 4

cWorid to the phenol polymer can be phthalocyanine blue, or eiji ©! soluble dye, such as range from 1: 0.6 "to 1: 2 Hegen, with preferred Ver Malachitgiüa,

Mean ratios 1 ί 1 to 1: 1.8 are. The sulfonic acid chloride Furthermore, azo dyes such as p-dimethylamino-

Can be made from the relevant diazooxysulphonic acid and azobenzene or p-benzolazodiphenylamine suitable, a chlorosulphonic acid according to known methods qv- 5 A phenol-formaldehyde resin or a sty can be obtained. The diazooxide resin is incorporated into a layer support suitable for egg-borrowing in the form of a solution in a sensitive layer in order to increase its resistance to a solvent such as ethylene glycol monomethyl resistance to subsequent treatment baths, ethylene glycol ethers, dimethylformamide, di-ether on a roller-painter's acid anhydride copolymer. If such a resin of the photosensitive oxane, methyl ethyl ketone or butyl acetate, is incorporated on a layer of surface printing points, it is necessary. The weight of the photosensitive layer with the addition of a plasticizer such as dioetyl phthalate is best kept at 500 to 700 mg / m ⁸ ; It is triphenyl phosphate or o-phenylphenol, however, in order to be able to improve the film quality of the photosensitive printing plates, which are also satisfactory, if the weight is ^{advantageously 50 to 3000 mg / m a} layer. The light-sensitive layer is used in the usual 15

Way z. B. by a diving inspection or with example 11

With the help of air knives, nozzles or reversing rollers

upset. Suitable supports consist of an aluminum plate in an aqueous solution

Aluminum, zinc, magnesium, copper, plastic, from trisodium phosphate immersed to from the z. B. polyester, paper and glass; However, aluminum has 20 surface oils removed from it by rolling preferred. adhere, e.g. B. 5 minutes in a 5- to 10% aqueous

The aluminum plate is said to be washed first, then trisodium phosphate solution at 70 ^? With sodium phosphate and then with the treatment of nitric acid, an etching occurred which increased the absorption properties of the water * acid or a sulfuric acid-chromic acid mixture. After rinsing with treated water and finally rinsed with water, the aluminum plate was turned into an aqueous one. If desired, they can also be a Si 7O ⁰ /, ^ nitric acid solution and then immersed Licat, as rinsed in USA. Patent 2,714,066 loading well with water; the aluminum plate is written on, or a zirconate, as described in US Pat. No. 2,946,683, was then dipped for 2 minutes in a 2% aqueous potassium USA.-Patent 2,946,683, treated fluorine zirconate solution at 85 ⁰ C, whereupon delts or electrolytically roughened as did another water rinse. The treated is described in British patent specification 223 994. The aluminum plate was then coated with the diazooxide resin by printing 5 parts by weight of the polymeric diazooxide plate is placed under a transparent or very penetrating phenol ester resin in 80 parts by weight of cyelohexane with a casual positive original and covered with a sheet of yellow light. The coating weight is exposed to light. For example, it takes about 2 minutes to ^{carry 500 mg / m 3} and the drying temperature with an arc lamp of 35 A at a distance of 85 ⁹ C (for 1 minute). The plate prepared in this way is exposed for 70 cm. After that, the photosensitive is very suitable for use as a presensitized plate layer on the aluminum plate with a sponge; after storage for a year or a tampon in a 2 to 5 ° / ₀ aqueous at a dark and cool place their properties were 'solution was dipped of trisodium phosphate, 40 transactions yet satisfactory. The plate was rubbed in, whereupon the exposed parts of the layer, which was sensitive to light under a transparent positive original, were dissolved away for 2 minutes. A 35 A arc lamp produces a positive image at a distance of. The image obtained in this way is solid and 70 cm exposed. After that, the exposed plate can be used for a long time on a lithograph! - with a tampon that can be seen in an aqueous solution of press. In a comparison 45 trisodium phosphate was immersed, rubbed in until the phenol-formaldehyde resin, as it is in the USA.- the surface was colored purple-brown. According to Wa patent specification 3 046 120 is described, with the diazo see with water, the plate with an overoxide resin according to the invention was found that borrowed aftertreatment agent by means of a cellulose with the printing plate according to the invention rubbed a lot of sponge. The exposed parts were larger print runs can be achieved. It is not dissolved away in order to expose the hydrophilic water-absorbent capacity, clearly why such a remarkable undersheet. The unexposed parts differed in the printing life, possibly - served during printing for color guidance, wise it is due to the presence of many non- The po-

reacted hydroxyl groups in the diazooxy resin polymeric ester had been prepared as follows: caused. Since the esterification product of the poly 55

meren phenol with the diazooxide film-forming egg production of phenol polymer

has properties, there can always be printing plates

deliver with high quality while the presence 50 g of pyrogallol were dissolved in 350 g of acetone. 5 g

of additional substances (as in known processes) Phosphorus oxychloride were used as condensation catalysts, which can lead to a reduction in image quality. 60 lysator was added, and the solution was left overnight. To use the solution in such an amount that the image quality was added dropwise to water with stirring, but then pressure was applied, whereby a tarry resin was precipitated. Get the panels that have other advantages. In the case of resin was dissolved in a small amount of acetone, for example, a dye of the photosensitive 65 and the solution in a large amount of water can be layered to form a visible image, to precipitate a solid which can be obtained by fiI development. Suitable dyes for trieres were removed and dried. The melting for this purpose are blue organic pigments, as point of the product was 200 to 215 ⁰ C.

5 6

Making ^ ^e * ^m example! exposed. The exposed parts

2-Diazo-l-naphthol-5-s _U lfon _S äureester TT'Z ^ S ^^ r ^ ST * ^ f ^ T

the Phenolpolymerisats ^eng * ^{ldl of} f ⁿ mchtbehchteten parts to decision

^{v J} winding was a 5% aqueous Trmatnum-

100 g of 2-diazo-1-naphthol-5-sulfochloride and 62 g of 5-phosphate solution were sprayed onto the plate in order to dissolve the phenol polymer in 500 g of dioxane and to dissolve exposed parts. After washing with and then a 10% aqueous solution of water, a gum arabic solution of 7 ° Be potassium carbonate was applied to the resulting solution in a thin layer, added sam with stirring until the solution was completely neutralized; the temperature of the solution was kept at 30 ^° C. After the addition was complete, the mixture was stirred for a further 30 minutes. A 0.127 mm thick sheet of polyethylene tere- After cooling, the solution was made into 2500 ml of phthalate film was sandblown to give a fine water, and the precipitated solid was roughened. The sheet was collected by filtration with a and dried. The 15 5 ° / _o solution of trichloroacetic acid in toluene beSchmelzpunkt of the product was 25O ⁰ C. These. The slide was then made with the following

Mixture coated;

B e i s ρ i e 1 2 1 part titanium dioxide,

5 parts epoxy resin,

Both surfaces of an aluminum plate were ² ° 97 parts of methyl ethyl ketone, by sandblasting using grains 3 parts of cyclohexanone,

grained fused alumina with a particle size of 250 mesh and then into a Drying of the be-20 as described above ° / ₀ aqueous solution of trisodium phosphate at acted this film was immersed with a coating of 70 ⁰ C for 1 minute. Thereafter, the plate 25 was provided with a layer of the following mixture: 2 minutes in a 2% aqueous solution of Na 13.6 kg starch carbonate, trium silicate (the SiO ₂ : Na ₂ O ratio was 2.45 272 kg water, up to 2.55: 1) immersed ^{at 80 to 85 ° C.} 5 parts by weight \ 79 w titanium dioxide, parts of the 2-diazo-1-naphthol-4-sulfonic acid ester of 214 kg china clay, polymeric phenol, which after the 30 '

an example! The following method was prepared for this purpose, just before use

were added with 2 parts by weight of an oil mixture: soluble phenol-formaldehyde resin, 1 part by weight ^ 07 g oxalic acid,

Phthaloeyanine blue and 20 parts by weight methyl 2520 cm ³ water '

Ethyl ketone ground in a ball mill for 18 hours, 35 3 ^ 4 _{g of} melamine-formaldehyde resin, and the resulting mixture was with 60 Ge η \ _cm 3 of sodium alkyl sulfate.

most importantly diluted methyl ethyl ketone and

as described above, treated aluminum plate After exposure and development of the printing plate,

upset. The surface of the plate with the layer according to Example 2 lifted the image parts of photosensitive material was glossy green. 40 clearly (in green) against the underground of the poly-die Plate repelled water droplets, and no ethylene terephthalate support became peeled off. Water drop pattern on the surface after the

Making the printing plate left behind what example

is often seen on common presensitized planographic printing plates. The plate was exposed using a copy template similar to that in Example 4. For example, the would hold up when used as a substrate instead of the paper Plate was used for 2 minutes with a 35 A arc lamp in a polyethylene terephthalate film, with Exposed from a distance of 70 cm. The paper according to US Pat. No. 2,766,688 was then prepared exposed surface under light pressure with a beTampon to apply the light-sensitive layer, which had been acted in a 5% aqueous solution of 50. Trisodium phosphate had been immersed, an "R" 1 6

rubbed. The parts of the picture appear clearly in green color

compared to the milk-white background of the alumi- A thin aluminum sheet with a copper-

-ö / umplatte out. plated surface was made with a uniform

55 layer of about 2.5 g / m ^{2 of} the light-sensitive ingredients

Example 3 Composition according to Example 2 on the copper top

surface by coating at 40 rpm in one

In 70 parts by weight of ethylene glycol monomethyl ether provided with a centrifuge. The plate was then exposed to 5 parts by weight of the 2-diazo-1-naphthol-5-sul-speaking Example 2 and developed. Thereafter Fonsäureester the phenol polymer, which after the 60 was the copper in the non-image-bearing areas in connection with example 1 described method with an iron (III) nitrate solution of 30 Be etched away, had been produced, 1 part by weight of an oil solution to the underlying aluminum in this area borrowed phenolic resin and 0.8 parts by weight p-benzene to expose. The unexposed and the undeveloped azodiphenylamine dissolved, and the resulting Lö resin diazo layer was with Ethylenglykolmonosung was removed by spraying as a coating on a 65 methyl ether, the plate was then with Aluminum plate washed with a hydrophilic layer on water and used as a bimetal printing plate for brought the verMethode according to the printing of fine, clear, sharp copies described in Example 1 had been made. The plate was turned.

Claims (7)

7 8 patent claims estertis ’, characterized in that the polymer component of the ester 1. Presensitized, positive working flat from one by acid condensation of acetone printing plate, the sensitive layer of which consists of a resin obtained and pyrogallol. 2-diazo-1-naphthol-4-suh ° onic acid or 2-diazo-5 2. Planographic printing plate according to claim 1, characterized l-naphthol-5-sulfonic acid ester, in which the sulfone denotes that the layer support is an aluminum acid group with a phenolic polymer. 109531/281