DE1196505B - Process for the production of a photo-polymerizable plate for the production of printing plates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN Mftim PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

G03f

German class: 57 d- 2/01

1196 505
P 23157IX a / 57 d
14. JuH 1959
July 8, 1965

Photopolymerizable ones suitable for the production of printing plates Plates are z. As described in U.S. Patent 2,791,504. Own these panels a photopolymerizable layer comprising a polymeric binder, a photo-activatable Contains initiator for addition polymerization and an olefinic, addition-polymerizable compound, which, in the presence of such an initiator, form a high polymer by photoinitiated addition polymerization can form. The layer is on a suitable layer support. The plates also contain usually a fabric that avoids halos, generally a layer below the relief-forming material Part of the photopolymerizable layer. The substrate usually consists of one Foil, sheet metal or plate, in particular made of metal.

Most of the time, these have photopolymerizable plates between the photopolymerizable layer and the support an anchor layer, which the adhesion of the photopolymerizable Layer on the substrate improved.

In the case of the plates described in the above-mentioned USA. Patent there is the photopolymerizable Layer directly on the anchoring layer, with which it is essentially through physical Adhesion is connected.

According to the invention, however, between the anchoring layer and the photopolymerizable Layer another thin barrier layer through polymerization of the unsaturated component on the underside of the photopolymerizable layer formed after its application to the anchoring layer. That gives several advantages. Once you achieve a stronger connection between the photopolymerizable Layer and the anchoring layer due to the chemical bonds between the photopolymerizable Layer and the barrier layer on the one hand and between the barrier layer and the anchoring layer on the other hand; this is particularly the case with relief panels important with small raised spots. On the other hand, the anchoring layer is through the barrier layer protected from the action of solvents, which is particularly advantageous if the anchoring layer, as is preferred for many reasons, contains an adhesive which is particularly suitable for solvent used to develop the relief is sensitive. It is especially true for the polyester adhesives described below. In other words, since the barrier is over the Extending the entire surface of the plate, attack by the solvent serving as the developer will occur the edges of the junction smaller, more individual

Method of making a photopolymerizable plate for the production of
Printing clichés

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dipl.-Ing. E. Prince and Dr. rer. nat. G. Hauser,

Patent attorneys,

Munich-Pasing, Ernsbergerstr. 19th

Named as inventor:

Marion Burg, Metuchen, N. J. (V. St. A.)

Claimed priority:

V. St. v. America July 25, 1958

Prevents image areas and the anchoring layer during the production of a printing plate.

According to the invention, the photopolymerizable plates are produced in such a way that, with the application of heat and pressure at a temperature not exceeding 185 ° C., a layer support, a photopolymerizable, photosensitive layer (in which the initiator for the addition polymerization is thermally inactive at temperatures below these ), and from a one layer structure produces between the layer support and the photosensitive layer in direct contact with at least the latter located anchoring layer, wherein the anchoring layer includes a thermally active at temperatures below 185 ° C, addition polymerization initiator, of but below 6O ⁰ C thei is mixed inactive. The initiator is preferably present in an amount of 0.5 to 10% (based on the weight of the anchoring layer).

The binder in the photopolymerizable layer is expediently an ester of cellulose with a Carboxylic acid.

The adhesive used to form the anchoring layer preferably contains at least 66.5 percent by weight a linear polymeric compound which is either (1) a polyester of the esterification product of (a) hexahydroterephthalic acid and (b) a glycol having 2 to 10 carbon atoms and zero to four

509 599/248

Ether bonds or (2) at least one mixed poly known. A preferred catalyst combination is

ester corresponding to the esterification product of (a) calcium acetate and antimony trioxide.

at least one saturated aliphatic dicarbonate. The dialkyl hexahydroterephthalate is best

acid by hydrogenation of dialkyl terephthalate via Raney

HOOC - (CHa) ₁ , - COOH, ^{5 nickel} produced.

The adhesives can be made simply by mixing the

where η is 4 to 8 and the total amount of these aliphatic desired amounts of the polyester or mixed poly dicarboxylic acid is 50 mol percent of the mixed polyester or mixtures of the esters obtained as above, (b) terephthalic acid, isophthalic acid mixed polyester with the thermally sensitive ini or both, where the Total amount of aromatic ¹⁰ tiator for the addition polymerization and given-dicarboxylic acids 50 mole percent of the mixed polyester if with other ingredients, e.g. B. an olefinic is, with (c) a glycol with 2 to 10 carbon addition polymerisable, a polymerization atom and zero to four ether bonds or (3) a hibitor and a halo avoiding substance, eg. B. mixed polyesters according to the esterification process, a dye or pigment, are prepared in a suitable product of (a) hexahydroterephthalic acid in an amount of> 5 solvents,
up to 100 mole percent and preferably 20 to 80 mole- The anchoring layer does not necessarily have to be included

percent of the mixed polyester, (b) a saturated aluminum substrate is in surface contact, phatic dicarboxylic acid. B. the sheet-like carrier has a coating

have a halo-avoiding substance that

HOOC - (CHa) _n - COOH, ^ao can be in a suitable binder

and then in turn the anchoring layer

wherein η is 4 to 8 is applied in an amount up to 50 mole percent. In another embodiment and preferably 10 to 40 mole percent of the mixed poly- may include the adhesive forming the anchoring layer, (c) terephthalic acid, isophthalic acid, or both agents themselves as a halo-avoiding substance an amount up to 50 mole percent and preferably * 5 can be left and good results are obtained. 10 to 40 mole percent of the mixed polyester with (d) in an exemplary method of preparation

a glycol with 2 to 10 carbon atoms and zero of the plates according to the invention becomes a steel plate until there is four ether bonds. with an adhesive of the type described above

All "parts" and "ratios" in the description type in a suitable solvent, e.g. B. are methyl Parts by weight or weight ratios, if 3o ethyl ketone, coated. The coating is dried not stated otherwise. and you press on the coating layer on the steel

If the adhesive used to form the anchoring layer for about 3 minutes under a pressure of 14kg / cm ^{a is} the above-defined mixing in a hydraulic press a foil made of a polyester (3), it preferably contains the same rolled, photopolymerizable mixture of cellu proportions of components (b) and (c). An inventive succinate, triethylene glycol diacrylate according to preferred mixed polyesters, which has excellent adhesive strength in the inventive and anthraquinone with formation of a layer structure. The plates of the hydraulic press are heated to about plates containing the reaction product of 150 ° C (or above the sensitivity temperature of ethylene glycol and dimethylhexahydroterephthalate, thermal initiator). During the pressing dimethyl sebacate and dimethyl terephthalate, the 4 <>, the activated thermal initiator in the adhesive causes three reactants in a molar average that a part of the photosensitive, photopoly ratio of 8: 1: 1 are present. merizable layer, which is with the adhesive

The adhesive also contains conveniently up to the anchoring layer in contact, undissolvable 33% an olefinic, addition polymerizable is borrowed and cures.

Compound with a polymerization inhibitor. 45 At the interface between the adhesive and

A specific preferred adhesive contains (1) the photopolymerizable layer thus forms about 75 parts of the mixed polyester, corresponding to a thin barrier layer made of a solvent-transesterification product of ethylene glycol and dimethyl-stable polymerized material. The thickness of hexahydroterephthalate, dimethyl sebacate and dimethyl sebacate of this barrier layer is only a small fraction of ethyl terephthalate, with the latter three reaction parts - 50 of the total thickness of the photopolymerizable, light-sensitive layer in a molar ratio of 8: 1: 1 to the sensitive layer, and advantageously less, ( 2) about 2.4 parts of benzoyl peroxide as thermal as about 0.051 cm. Their exact strength depends, among other things, on the initial concentration of the thersation and (3) about 22.5 parts of triethylene glycol diacrylate mix initiator, the aging time for the photopoly as an olefinic, addition polymerizable compound 55 merizable plate and the particular plate used, with about 0, 1 part of p-methoxyphenol as polymerisation components. This barrier layer prevents ion inhibitor. These components are most effective in the passage of solvent or in solution in a common solvent, e.g. B. other substances, which the adhesive bond of the methyl ethyl ketone, which is appropriate in an amount of anchoring layer with the support and about 311 parts, mixed. 6o can weaken the photopolymerizable layer, the one essential component of the adhesive without, however, an unfavorable influence on the photo-forming polyester or mixed polyester can be exercised according to the polymerizable layer and the known process contained therein by alcoholysis with the highly sensitive material,
the desired glycol of a dialkyl ester (e.g. the diminic- When using the photopolymerizable

ethyl ester) of the acid component (s). 65 bare layer of the plate in a pneumatic pressure die Reaction is preferably in the presence of frame by a negative with an actinic one or more esterification catalysts through radiation of about 1.5 to 7.8 watt seconds per quage. Suitable catalysts are exposed to a person skilled in the art within a few centimeters. Not to the picture

5 6

belonging areas are with an aqueous quinone and p-methoxyphenol (as an inhibitor). Other

Solution, preferably with dilute sodium photopolymerizable layers of the German

droxyd, washed away. In the unexposed areas patent specification 1 031 130 type described can

a thin layer of polymerized material remains, also to form the solid, photopolymerized

material (the barrier layer), while the layers that can be exposed are used. More suitable

there is a thick layer of the image. As a result of compositions, among other things, the N-meth-

the formation of this thin barrier layer from polyoxymethylpolyhexamethylene adipamide mixtures, which

merized material, the printing types are fixed with the mixtures of polyester, polyacetal or mixed

Carriers connected and show an exceptional polyesters and acetals, the polyvinyl alcohol derivatives

Stability of their dimensions. io according to DAS 1 121 928 as well as layers of 60 genes

Although, as stated, the preferred composite weight percent is cellulose acetate, 40 weight percent

Settlement of an essential component of the adhesive triethylene glycol diacrylate, 0.1% «based on the

by means of polyester forming the transesterification product photopolymerizable material, anthraquinone and

from ethylene glycol and dimethylhexahydroterephtha- 0.1%> based on the photopolymerizable material

lat, dimethyl sebacate and dimethyl terephthalate in 15 rial, p-methoxyphenol, which is described in the USA patent

a molar ratio of the latter three of 8: 1: 1, 2,927,023 described water-soluble cellulose

but polyesters from other acids and after- and ester compositions, which the German

Glycols can be used. see interpretation document 1 104 825 corresponding poly-

Suitable saturated, aliphatic dicarboxylic acids vinyl acetate with extra-linear vinylidene groups, the

are, among other things, besides sebacic acid adipic acid, 20 described in Belgian patent 569,759

Pimelic acid, suberic acid and azelaic acid. 1,3-butadiene compositions and the linear poly

Typical glycol amide compositions to be used according to the invention with extra-linear N-acrylyl

include: 1,2-ethanediol (ethylene glycol), oxymethyl groups.

1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-Bu- Practically every initiator for an addition poly-

tanediol, 1,4-butanediol, 1,2-pentanediol, 2,3-pentanediol, 25 merisation, which under the influence of light a

2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 2,3-He polymerization sets in motion and at temperatures

xanediol, 3,4-hexanediol, 1,6-hexanediol, 1,2-heptanediol, not noticeably thermally activatable below 185 ° C

1,2-Octanediol, l ^ -NonandioLl ^ -Decanediol ^ -Methyl- can be used in the photopolymerizable layers

propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2,2-di-can be used. It should be used in the photopolymer

thylpropane-l ^ -diol, ^ 2-methoxymethyl-2,4-dimethyl- 30 baren mixture so far be dispersible that the

pentane-l, 5-diol, 2-ethylhexane-l, 3-diol, diethylene glycol- desired polymerization under the influence of

Kol, triethylene glycol, dipropylene glycol, tripropylene-absorbed amount of light energy in proportion

glycol, tetraethylene glycol, pentaethylene glycol, is set in motion for a short time,

1,2-Cyclopentanediol, 1,3-Cyclopentanediol, 1,2-Cyclo- A preferred class of initiators for the

hexanediol and 1,3-cyclohexanediol. 35 addition polymerization are the substituted and

As a thermally sensitive initiator for the addi- unsubstituted polynuclear quinones, d. H. Vertion polymerization In the adhesive, preference is given to bonds with two benzoyl peroxide sitting on ring carbon atoms used, which also has more or the intracyclic carbonyl groups in a konweniger activated by actinic light. Another jugated six-membered, carbocyclic ring, where suitable initiators include tert-butyl- 40 the ring carrying the carbonyl groups with a minimum peroxide, tert-butyl hydroperoxide, cumene hydroper- stens an aromatic, carbocyclic ring, Succinic acid peroxide, methyl ethyl ketone per- melted. Examples of such initiators are oxyd ^ auroylperoxydjp-Chlorbenzoylperoxyd ^^ - Di- among other things: 9,10-anthraquinone, 1-chloranthrachlorobenzoyl peroxide and cyclohexanone peroxide. quinone, 2-chloroanthraquinone, 2-methylanthraquinone,

As olefinic, addition-polymerizable compounds 45 2-tert, -butylanthraquinone, octamethylanthraquinone,

dung, which is useful in the adhesive of the l ^ -naphthoquinone ^ lO-phenanthrenequinone ^ -Benz-

Anchoring layer is contained, a large anthraquinone, ^ -Benzanthraquinone ^ -Methyl-l / l-naph-

Variety of compounds can be used. Before thoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethyl-

Triethylene glycol diacrylate is added. Other suitable anthraquinone, 2,3-dimethylanthraquinone, 2-phenyl

Compounds include ethylene glycol anthraquinone, 2,3-diphenylanthraquinone, sodium

dimethacrylate, diethylene glycol diacrylate, a Mi- anthraquinone-w-sulfonate, S-chloro ^ -methylanthrachi-

mixture of triethylene glycol diacrylate and acrylamide, non, retenquinone, 7,8,9,10-tetra-hydronaphthacene

Triethylene glycol dimethacrylate, diacrylates of polyquinone and 1,2, 3, 4-tetra-hydrobenz - [«] - anthracene

Ethylene glycols with molecular weights of about 300 to 7,12-dione.

500, and esters of α-methylenecarboxylic acids, e.g. B. 53 A suitable thermal polymerization inhibitor

Methyl methacrylate. Each of the above mono- is not only the preferred p-methoxyphenol, but

Meren can be partially through N - (/ S-hydroxyethyl) - also hydroquinone as well as alkyl and aryl substituted

methacrylamide, N, N-bis (/ 3-hydroxyethyl) acrylamide, hydroquinones, tert-butylcatecbol, pyrogallol, copper

ß - acetoamidoethyl methacrylate and β - methacrylic resinate, naphthylamine, / ^ - naphthol, cuprochloride,

amidoethyl propionate or a mixture of a 60 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, Ni

Olefins with an ethylenic α. / 3-dicarboxylic acid trobenzene and dinitrobenzene. Other suitable inhibi-

or an ester thereof, e.g. B. styrene diethyl fu tors are z. B. p-ToIuchinon and Chloranil, and

marat, styrene diethyl maleate or thiazine dyes by an ester, e.g. B. Thionin (Color Index No. 920),

vinylbenzoic acid, e.g. B. methyl vinyl benzoate or thionine blue G (color index No. 926), methylene blue B

ß-Hydroxyäthylvinylbenzoat be replaced. 65 (color index No. 922) and toluidine blue 0 (color index

Appropriate is the photopolymerizable, light no. 925).

sensitive layer a mixture of celluloseace- The fabric avoiding halos can become in the

Actual succinate, triethylene glycol diacrylate, anthracite support or in one on the surface of the

7 8

The solution was then left in the dark for 2 days.

layer or in the photopolymerizable, light vapor. The clear, tough, flexible film obtained was

sensitive layer. It is said to have as much actini-

absorb light that no more than 35% of the carrier is cut to size and to form a incident actinic light from the carrier reflects 5 sandwiches on the covered with the adhesive

be animalized. In the patent specifications listed above, layer supports are laid,

suitable substances are described. This sandwich then went into a hydraulic one

The adhesive is advantageously applied in a solvent press whose plates were preheated to 150 ⁰ C, and medium-solved onto the support. Suitable for 3 minutes under a pressure of 14 kg / cm ² Nete solvents are methyl ethyl ketone, methylene io pressed. The plates were allowed to cool and the chloride, chloroform, methyl isopropyl ketone and the layer structure were removed from the press,
ethyl isobutyl ketone. The solution may prior to application of the photopolymerizable plate thus obtained of the remaining layers was coated or sprayed under a 1800 Watt high pressure mercury vapor, lamp at 7.8 Ws / cm ² exposed to actinic radiation,

However, the adhesive can also be used in its absence, with an area of 5 x 5 cm in the middle

a solvent applied in the form of a film remained exposed. The unexposed polymer was then

or painted on with a trowel. by brushing in 95% ethanol for 5 minutes

Instead of being on the backing, it can also be removed on the. Although the unexposed area is not poly-

light-sensitive, photopolymerizable layer was merged and could easily be washed away,

to be brought. There was no thin layer (the barrier layer)

The photopolymerizable platinum polymerized material of the invention. The photopolymer

th are particularly suitable for the production of printed material in the exposed areas

clichés according to the solvent in the German patent specification are not attacked.

1 031 130 described method. The printing plates The plate obtained thus consisted of a thick one

are suitable for types of printing where a pronounced 25 image layer on each side and a thin barrier

Height difference between printing and non-layer of polymerized material in the middle,

printing area is required. where the unpolymerized material brushed away

In addition to the improved adhesive strength, they were invented. The plate was attached to the connecting

plates according to the invention also more practical in that one of the photopolymerized image areas and

due to the thin, polymerized barrier layer, the 30 of the brushed, unexposed area strongly bent,

a coherent carrier for the relief image to determine whether the carrier metal from the back

det, this will get better support. One side of the polymerized material can be peeled off

Another advantage of the plates according to the invention lies could. Good adhesive strength was found; H.,

in that the adhesive its elasticity over a the photopolymerized material stood out from the

maintains a wide temperature range. 35 metal girders did not come off at all.

The invention is illustrated by the following examples.
explained in more detail. Parts and percentages are as far as ü e 1 s ρ 1 e ι ζ
not otherwise indicated, parts by weight or weight- An aluminum foil was coated with an anchoring percentage, layer according to Example 1, but with the example ⁴ ° layer ^of the adhesive to a thickness of

0.095 mm was dried.

100 g of a reaction of an excess of from a solution of 75 g of polyvinyl alcohol (27 mol

Ethylene glycol with dimethylhexahydroterephthalate, percent), polyvinyl acetate (42 mol percent) -acid ma-

Dimethyl sebacate and dimethyl terephthalate in a leat (31 mol percent), which is prepared according to the in Example 4 of

The molar ratio of the latter three of 8: 1: 1 is obtained from German Auslegeschrift 1 121 928

tenen mixed polyester, 30 g of triethylene glycol diacrylate was prepared, 25 g (i.e. 25% of the total

with a p-methoxyphenol content of 0.1% and solids) 1,2-bis (3-methacrylamidopropoxy) ethane

3 g of benzoyl peroxide were formed in a mixture of 37% and 0.25 g of benzoin methyl ether

Solids-containing solution in methyl ethyl ketone 170 g of ethyl alcohol and 35 cm ^{3 of} water were added

solved. 50 cast a photopolymerizable film. Man

An aluminum foil measuring 5 x 15 cm evaporated the solvents at room temperature and a thickness of 0.038 cm was with this under subdued light and cut the obtained, Mix to form a 0.051 cm thick film about 0.051 cm thick to the size of the support Anchoring layer covered. Adjust the aluminum foil, whereupon it was sanded to form a previously "alodised" (i.e. with a very thin wank-like structure on the coating with the adhesive laid from an amorphous mixture of mixed opaque carriers.

Metal oxides with chromates). The sandwich then came into a hydraulic press,

Adhesive layer was then preheated to 120 ° C for 60 minutes in air, and was

Dried room temperature, their layer pressed for 10 minutes at 14 kg / cm ^2. The obtained plate

thickness on the carrier decreased to about 0.0089 cm. 60 was, as described in Example 1, with actinic

Exposed to light from a filtered solution of 30 g of N-methoxy. The unexposed areas were

methylpolyhexamethylene adipamide and 30 g of glycerol - 5 minutes with a solution of 1 part by volume of ethanol

dimethylacrylate in 160 ecm hot ethanol and 1 part by volume of water was brushed during which

a photopolymerizable, photosensitive layer except for the adhesive layer

manufactured. To this end, the solution was mixed with 0.45 g of a thin barrier layer of polymerized layer covering it

Benzoin methyl ether and poured it onto a glass plate material was washed away. At the exposed

from which on their edges a small elevation remained a thick layer of photopolymeric

owned to keep the solution from running down. backed material.

Tests carried out as in Example 1 showed that benzophenone was excellent as an agent to prevent halos Adhesion strength that had been photopolymerized. The adhesive solution was like th layer on the substrate. described in Example 1, dried, and obtained

an anchoring layer 0.0076 cm thick.

Example 5 From 60 g of cellulose acetate with 0.4 g of benzoin and

40 g of triethylene glycol diacrylate had been added,

A photopolymerizable film was produced using that according to Example 2 with the. Anchoring layer of coated aluminum foil as The mixture obtained was mixed with 120 ecm of ethanol The substrate was moistened with a photopolymerizable plate, and the alcohol was allowed to incorporate for 3 days. ίο pull. The material was then rolled for 12 minutes

A photopolymerizable film was made from one at 110 ° C on a rubber mill, whereupon it was Mixture of 680 g cellulose acetate acid succinate, in a layer press, the plates of which are heated to 145 ° C before-320 g of triethylene glycol diacrylate with a content of heated were pressed. The obtained photopolymeri-0.32 g of anthraquinone as a phthalene initiator, 0.32 g of mucosable film was adjusted to the size of the support chloric acid as a stabilizing agent and 6.5 g of triethy- 15 cut to size and on the one covering the support made in latnin. The mixture was applied to an anchor layer to form a sandwich Brought 150 ° C heated rubber roller mill and placed 30 mi.

grooves rolled. The material obtained was taken from the This sandwich was placed in a hydraulic press,

Rubber roller mill was taken and preheated at 140 ° C to one of its plates to 120 ° C, and film was pressed. This was pressed to the size of the aluminum for 2 minutes under a pressure of 21 kg / cm ² , the substrate was cut to size and the photopolymerizable plate was then exposed to form a sandwich with the adhesive with 3.1 Ws / cm ^{2 of} actinic light , as in Example 1 covered layer support laid. wrote and removed the unexposed polymer

This sandwich then came into a hydraulic one by brushing it out with acetone. After the non press whose plates were heated to 15O ⁰ C before, and 25 exposed areas were washed out, a remained was pressed for 3 minutes at 14 kg / cm ^2. The resulting thin barrier layer of thermally polymerized plate was as in Example 1 with actinic light material, while one exposed in the exposed areas, whereupon the plate was with a 0.08-solder thick image layer,

Sodium hydroxide solution for 7 minutes. Since tests carried out as in Example 1 gave a

The unexposed areas were washed out, there was good adhesive strength, and the connection between the but remained a thin barrier layer of thermal adhesive and the photopolymerizable material polymerized material. The exposed one was so firm that the latter was more likely to tear.
Spots were not caused by the solvent wash
influenced. Example 6

Tests carried out as in example 1 resulted in a test pretreated as described in example 1 Good adhesive strength without interrupting the connec- Aluminum backing was with a 0.051 cm formation between adhesive and polymer, d. H. the thick layer of an adhesive solution coated, photopolymerized material did not come off from the material whose true viscosity was 0.69. The solution was carrier off, but rather tore. was composed of 50% solids dissolved in methyl ethyl ketone

40 substances, and the solids in turn consisted of

Example 4 15g of a mixed polyester obtained by transesterification

an excess of ethylene glycol with dimethyl

Example 3 was repeated, except that the phototerephthalate (33 mol percent), dimethyl isophthalate (17 polymerizable plate through a letter negative mol percent) and dimethyl sebaeate (50 mol percent) were obtained in a pneumatic copy frame of 4-5, as well as from 4.5 g Triäthylenglykoldilichtet were, so that a close contact with an acrylate content of from 0.1 ° / ₀ to p-Methoxyzwischen the photopolymerizable film and the phenol had as a polymerization inhibitor, and from 0.45 g negative. The plate was then, as described in Example 3, benzoyl peroxide as thermal initiator and 0.045 g, washed out, with the unexposed benzoin as photoinitiator. The adhesive polymer was allowed to be removed. 50 dry the solution as in Example 1, using the

The printing form obtained was used as a 0.0076 cm thick connector for printing on an aluminum substrate Flat die press used. A good potting layer was obtained.

Results, and the adhesive strength of the carrier on the As in Example 3 was then the photopolymer

photopolymerized material was excellent. produced film, to the size of the layer

55 cut to size on the carrier with the

Example 5 layer covered carrier laid to a plate

pressed, exposed and the unpolymerized material

In this example, a 0.0634 cm thick steel al was washed out. Also as in example 3 The photopolymerized material could be used on the substrate with dimensions of 5 × 15 cm det, do not wash away the areas previously exposed with a phosphate surface film. That not covered ("Bonded"). Thinned, unpolymerized material was discarded.

The steel backing was washed with a 0.038 cm, leaving a thin barrier layer of poly-thick Layer of adhesive solution coated merized material over the adhesive layer from a mixture of that described in Example 1 remained.

Mixed polyesters in methylene chloride (30% solids), 65 Tests performed as in Example 1 gave a 0.3 g of triethylene glycol diacrylate and 0.033 g of benzoyl good adhesive strength, with the photopoiymeriperoxide being more likely existed as initiator in 5 ecm of methylene chloride, siert material tore than that the connection with which dissolved the adhesive with 0.16 g of 2,2'-dihydroxy-4,4'-dirnethoxy.

Example 7

ok

A steel support treated as in Example 5 was coated with a 0.051 cm thick layer of an adhesive solution coated containing 56% solids dissolved in methylene chloride. The solids passed 100 g of the mixed polyester described in Example 1, 30 g of ethylene glycol dimethacrylate and 0.3 g of benzoyl peroxide as a thermal initiator. After drying as in Example 1, the adhesive formed on the Layer support an anchoring layer 0.0076 cm thick.

As in Example 5, a photopolymerizable film was produced. The cutting, pressing, cooling, exposure and brushing was also carried out as in Example 5, but with the exception that the photopolymerizable material instead of 2 minutes at 140 ° C at 120 ⁰ C was pressed.

One observed after brushing away the unexposed one Part of the layer is a thin polymerized layer over the anchoring layer. Like in Tests carried out in Example 1 showed good adhesive strength, with the photopolymerized material being more likely tore when the bond with the adhesive came loose.

Example 8 Example 9 Example 10

A steel layer support treated as described in Example 5 was treated as in Example 1 with an adhesive solution coated, which consisted of 50% solids dissolved in methyl ethyl ketone. The solids in turn consisted of 30 g of the mixed polyester described in Example 1, 9 g of trietbylene glycol diacrylate

40

A steel substrate treated as described in Example 5 was coated with a 0.051 cm thick layer of an adhesive solution which consisted of 30% solids dissolved in methyl ethyl ketone. The solids in turn consisted of 100 g of the mixed polyester described in Example 1 and 0.5 g of benzoyl peroxide as thermal initiator. As in Example 1, the solution was dried for 2 hours to form a 0.0076 cm thick anchoring layer on the substrate. The cutting, pressing, cooling, exposure and brushing was carried out as in Example 5, except that the photopolymerizable material was pressed for 1.5 minutes at 15O ⁰ C. Tests indicated the presence of a thin polymerized barrier layer over the anchor layer after brushing away the unexposed parts. Adhesion tests carried out as in Example 1 gave good results.

Example 7 was repeated, except that the olefinic, polymerizable material used in the anchoring layer was used Link. consisted of a mixture of 30 g of triethylene glycol diacrylate and 10 g of acrylamide. The solvent was methyl ethyl ketone and the solids concentration was 60%. Tests showed a thin layer of polymerized material over the anchor layer after brushing away the unexposed portion of the photopolymerizable layer. As observed in previous examples good adhesion, with the photopolymerized material tearing rather than the Bond with the adhesive loosened.

and 0.21 g of tert-butyl hydroperoxide as thermal initiator. The adhesive solution was, as in the example 1 described, dried.

A photopolymerizable film was produced as in Example 5 and coated with the steel support in a hydraulic press. The press plates had been preheated to 150 ° C. and pressed for 1.5 minutes under a pressure of 14 kg / cm ^a . The photopolymerizable layer of the plate obtained was exposed to actinic light, and the unexposed polymer was removed by brushing with a solvent as in Example 5. The exposed areas were not attacked by the solvent, while a thin polymerized barrier layer remained in the unexposed areas. The adhesion strength of the photopolymerized material to the support was excellent.

Example 11

As in Example 1, three adhesives were produced, but the concentration of the thermal Initiator according to the following Table 1 was varied. The three plates were produced as in Example 3, exposed and washed out. As can be seen from the table, the thickness of the polymerized changed Barrier layer depending on the concentration of the thermal initiator.

Table 1

Concentration of the thermal initiator

0.3
1.5
3.0

Thickness of the thermally polymerized barrier layer

cm

less than 0.0086
0.0089 to 0.0097
0.0089 to 0.010

As in the previous examples, these three panels exhibited excellent bond strengths.

Example 12

It was as in Example 3 four photopolymerizable plates ago, but the plates were aged for the time indicated in Table 2 (3 minutes at 140 ⁰ C) before the heat treatment of the layer structure. As the table shows, the thickness of the barrier layer made of the thermally polymerized material after washing varied with aging time.

Table 2

Aging time
Minutes Thickness of the thermal polymeri
based barrier layer
cm 5
120
480
10 080 0.0076 to 0.0082
0.0094 to 0.0122
0.0160 to 0.0180
0.0279 to 0.0305

These four plates showed excellent adhesive properties as in the previous examples.

Example 13

A tin-plated steel base about 0.28 mm thick, covered with a thin layer of varnish was coated, which was composed of a mixture of a vinyl acetate-vinyl chloride copolymer and a

Phenolic resin was made with an anchoring layer 0.0076 cm thick when dry an adhesive solution prepared as described in Example 1 coated, only with the exception that the mixed polyester component described in Example 1 was replaced by a polyester, which one obtained by reaction of ethylene glycol with dimethylhexahydroterephthalate (100 mole percent).

A photopolymerizable film produced as described in Example 3 was cut to the size of the Beam cut to size and sandwiched on top of those covered with anchoring layer Layer support laid. This sandwich was pressed and exposed as in Example 3, and the unpolymerized Part of the plate was removed by spraying on 0.08 normal aqueous sodium hydroxide solution. To After washing out the unexposed part of the layer, a thin barrier layer of thermally polymerized remained Material. The exposed areas were not attacked by the solvent washing, ao Tests carried out as in Example 1 gave similar results

Results. . .

Example 14

Example 1 was repeated with the exception that the mixed polyester component was replaced by a mixed polyester was replaced, which is obtained by reacting ethylene glycol with dimethyl terephthalate (50 mol percent) and dimethyl sebacate (50 mole percent). The results were similar.

Example 15

30th

Example 1 was repeated, but using the mixed polyester component has been replaced by a mixture of equal parts of two mixed polyesters, of which the first by reaction of ethylene glycol with dimethyl terephthalate (33 mol percent), dimethyl isophthalate (17 mole percent) and dimethyl sebacate (50 mole percent) and the second by reaction of Ethylene glycol with dimethyl terephthalate (25 mol percent), dimethyl isophthalate (25 mol percent), dimethyl sebacate (25 mole percent) and dimethyl adipate (25 mole percent). The results were alike satisfactory.

It is clear to the person skilled in the art that similar Results are achieved when the substances mentioned in the preceding examples are replaced by equivalent amounts other substances, as described in more detail above.

Of course, the polymeric adhesive can be made from a mixture of two or more mixed polyesters of type (a), (2) with satisfactory results. The mixed polyester can do that too Be the reaction product of glycol with an ester of two or more of the acids mentioned.

Claims (14)

Claims: 55 1. Process for the preparation of a photopolymerizable Plate for the production of printing blocks, which consists of the following parts: I.) from a layer support, II.) From a light-sensitive, photopolymerizable layer, which is composed of a) a polymeric binder, b) an olefinic which forms a high polymer by photoinitiated polymerization Monomers, c) a photo-activatable initiator for addition polymerization, III.) From an anchoring layer, which is located between the support (I) and the light-sensitive Layer (II) is in direct contact with the light-sensitive layer (II), marked by the fact that the Plate under the action of heat and pressure at a temperature not exceeding 185 ° C to one Layered structure is pressed, using an initiator which can be activated by actinic light is, which is thermally inactive at temperatures below the pressing temperature, and wherein in the Anchoring layer an initiator for addition polymerization is used, which is at temperatures is thermally active below 185 ° C, but inactive at temperatures below 60 ° C. 2. The method according to claim 1, characterized in that an adhesive for the anchoring layer is used, the 0.5 to 10 weight percent of the thermally activated initiator contains. 3. The method according to claim 1 or 2, characterized in that an adhesive is used, that also contains up to 33 percent by weight of a polymerization inhibitor contains olefinic, addition polymerizable compound. 4. The method according to any one of claims 1 to 3, characterized in that the adhesive in Form of a solution is applied to the carrier. 5. The method according to any one of claims 1 to 4, characterized in that the used Mixtures are matched to the process conditions used so that on the The bottom of the photopolymerizable, photosensitive layer is no more than 0.051 cm thick layer of a thermally polymerized unsaturated compound. 6. The method according to any one of claims 1 to 5, characterized in that an anchoring layer is used which is at least 66.5 percent by weight from one by esterification of hexahydroterephthalic acid with a glycol with 2 to 10 carbon atoms and zero to four ether bonds linear polyester formed in the molecule. 7. The method according to any one of claims 1 to 5, characterized in that a Veranfcerungsschicht is used that is at least 66.5 percent by weight of one or more linear Polyesters, furthermore from (a) at least one saturated aliphatic dicarboxylic acid of the formula HOOC- (CHs) ₇₁ -COOH, wherein η = 4 to 8 and the total amount of the acid or acids is 50 mole percent of the polyester, (b) terephthalic acid or isophthalic acid or both in a total of 50 mole percent of the polyester and (c) a glycol having 2 to 10 carbon atoms and zero to there are four ether bonds in the molecule. 8. The method according to any one of claims 1 to 5, characterized in that an anchoring layer is used which is a linear polyester of (a) hexahydroterephthalic acid in an amount less than 100 mole percent of the polyester, (b) one saturated aciphatic dicarboxylic acid of the formula HOOC- (CH ₂ ) ^ - COOH, where η = 4 to 8 in an amount up to 50 mole percent of the polyester, (c) terephthalic acid or isophthalic acid or both in an amount up to 50 mole percent of the polyester and (d) a glycol having 2 to 10 carbon atoms and zero to four ether bonds in the Contains molecule. 9. The method according to claim 8, characterized in that hexahydroterephthalic acid in one Amount of 20 to 80 mole percent is used and the other two acid components approximately equal amounts between 10 and 40 mole percent are present. 10. The method according to claim 8, characterized in that the hexahydroterephthalic acid and the other two acid components are present in an ao molar ratio of 8: 1: 1. 11. The method according to claim 8, 9 or 10, characterized in that the three acid components Hexahydroterephthalic acid, sebacic acid and terephthalic acid is used and called glycol Ethylene glycol. 12. The method according to any one of claims 1 to 11, characterized in that the ethylenically unsaturated Monomer in the photopolymerizable, light-sensitive layer triethylene glycol diacrylate is used. 13. The method according to any one of claims 1 to 12, characterized in that as can be activated by light Initiator a substituted or unsubstituted polynuclear quinone is used. 14. The method according to any one of claims 1 to 13, characterized in that as a binder for the photosensitive layer uses a carboxylic acid ester of cellulose. Considered publications:
German patent specification No. 1 031 130. 509 599/248 6.65 © Bundesdruckerei Berlin