DE2125910A1 - Polymers that can be crosslinked by photopolymerization - Google Patents

Description

Crosslinkable polymers through photopolymerization

Polymer systems which cure under the action of light to form insoluble, crosslinked coatings are known in large numbers both in the lacquer sector and for the most varied of copying processes.

3? ÜR copying processes have systems in which vinyl group-containing polymeric compounds that crosslink by a photochemical \ triggered Vinylpolyraerisation, especially on Grimd the achievable high Vernetsungögrades special interest found. As an example known from the literature, the conversion product of a polymer bearing glyoid groups with acrylic acid may be mentioned (DOS 1 643 125). However, this system has the disadvantage that a high level of stabilization is necessary in its production to prevent premature crosslinking and that this severely adversely affects the photosensitivity of the end product. The problem, vinyl group-bearing polyme:. To have e stabilize strongly to barge against premature crosslinking even during the fusing onto the vinyl compounds, disabled generally Λ the application of such products for photocopying processes.

Such systems, as well as practically all other systems which crosslink by photopolymerization, are also one disruptive oxygen sensitivity that requires exposure in a protective gas atmosphere or through a cover film power.

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Surprisingly, it has now been found that the reaction of polymers containing Zei ^ ewitinoff-active water sorbents with T-45ethyol pre-binders or N-Kethyloluthern of acrylic or substituted acrylic amides gives high molecular weight compounds containing vinyl groups no longer have the disadvantages mentioned at the beginning.

The invention accordingly relates to vinyl groups Compounds, preferably those with a molecular weight > 1000, characterized in that they are per molecule at least twice the grouping

included, where

R ₁ = H or C ₁ -C ^ alkyl, ₀
R ₂ = II or Cj-Cg-alkyl and ^ _
-X = -0-j -NH- or -N ⁷

Il

0
mean.

Further object of this invention is a method for preparing such vinyl group-containing compounds, characterized in that one Zerewitinoff-active Wassei ¹ atoms containing dm known to, in particular, hydroxyl and / or carboxylic acid amides and / or Imidgruppenhaltige and / or amino-containing compounds, preferably polymers with a molecular weight> 1000, with vinyl compounds of the general Pormol

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II,

in which It., = hydrogen or C ₁ -C "alkyl"^;

Rp 11 «Ky - hydrogen or Cj-C ^ -alkyl mean,

optionally in a solvent, and homogeneously mixed, for example ,, a Minei in the presence of an acid catalyst: alsäure, organic sulfonic acid or carboxylic acid, wherein lemperaturen between -10 and + 140 °, preferably between +10 and -} - 120 ⁰ uimoetzt. . A.

The invention also relates to the use thereof Yinyl group-containing compounds, possibly in a mixture with further vinyl monomers for the production of coatings that thermally with a whiteness known per se, for example by using the usual thermal radical initiators, and / or radiation-chemically and / or preferably photochemically, optionally with the use of photoinitiators allow to crosslink by polymerization.

Suitable polymers for the purposes of the invention are in principle all those which contain at least two functional groups per molecule which, under acidic catalysis, with F-Methylol- ™ group and / οdc: c IT-Me thy 1 ο 1 ü therη miter Bi nCw, ηgsbi 1 can react. Suitable functional groups are in general all active Zcrewitinoff konracn II Atorae bearing groups, insbesondero hydroxyl groups, but also Carbonamide- and Aminogrwpp ^ J- ^{11 n} ϊ-cage, with both groups funktione.lle only one kind, as well as "various functional Groups can coexist.

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Preferred for the process according to the invention are, above all those polymers that, either from solution or as a melt Applied to a carrier, even in the uncrosslinked state at room temperature, they deliver non-tacky coatings. The falling out however, it is not limited to such connections.

The molecular weight of the polymers depends on the particular}! Purpose and can therefore not be determined independently of this. However, polymers are preferred with a molecular weight of more than alo 1000 is used.

The average molecular weight most suitable for the particular application can be determined in a simple manner a few 3rd test attempts, e.g. by determining the softening point, can be determined. Of course, the optimal one depends The molecular weight range also depends on the type of polymer.

Both natural substances and synthetic high-molecular compounds are suitable. Suitable natural polymers are B, B. Cellulose, 'starch or gelatin or reclaimed Derivatives of these natural substances, such as partially esterified or etherified cellulose.

Suitable synthetic polymers are, for example, polyvinyl alcohols or copolymers of vinyl alcohol with any, not with the K-methylol or N-methylol ether groups of the compounds of the formula II to form solvent products containing vinyl groups reactive, polymerizable monomers, in particular with vinyl monomers, for example with ethylene, propylene, butylene, Butadiene, isoprene, vinyl chloride, vinylidene chloride, with vinyl esters, in particular vinyl acetate or vinyl propionate, with vinyl ethers, e.g. vinyl propyl ether, vinyl sobutyl ether, with Acrylic or methacrylic acid, or with their derivatives such as

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Ebtern j. nit particular aliphatic C. | _r --C ~ alcohols or nitriles, with maleic anhydride or styrene Rait.

Polycondensates also rait'Zorewitinoff-active hydrogens, in particular with alcoholic hydroxyl groups are suitable, for example polyesters from polybasic aliphatic or aromatic carboxylic acids with polyhydric alcohols, hydroxyl-containing polyurethanes or Hydroxyl group-containing epoxy resins, such as those produced by reaction polyvalent carboxylic acids, alcohols or amines obtained with epihalohydrins, in particular epichlorohydrin will.

Preferably polymers find use,-substituted by polymerizing Oxyalkylestern of acrylic acid or (Λ-alkyl-·% acrylic acids or by copolymerization of these compounds with other, for example, those mentioned above, not with the U-Kethy1öl- or N-methylol ether of the compounds of Formula II to give vinyl group-containing reaction products reacting vinyl compounds are available.

In those cases in which, for example, polymers with vinyl alcohol units are used to produce the crosslinkable polymers, the polymers consist of carbon chains which contain recurring units of the formula 3

i. ■ "■": ■ <

III O- CH ₀ - N - C - C = CH ₀ ,

RJ and R _{2 have} the meaning given above, and R is H or Cj-C.-alkyl, preferably methyl.

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In those cases where, for example, polymers are based äer polymeric oxylalkyl acrylates are used the polymers made up of carbon chains, the repeating Units of formula IV included

R

. CJHp - O - -. . R "R"

IT ^ l \ d ι 1 ■

0 = 0- QAO-GH ₉ -NCC = CH ₀ '

² & ²

v / or in

R, R ^ and R _{2 have} the meaning given above - and A is a divalent aliphatic radical which can be interrupted by oxygen atoms, such as ethylene, propylene, isopropylene, butylene, radicals of the formula - (CH ₉ TGH ₂ -O) - CE ₂ -OH ₂ -, where m is an integer of 1 or greater than 1, preferably 1 to 3 ..

From case to case, it may also be expedient to replace the Oxyalkylester of acrylic acid or its derivatives in whole or in part by acrylamide, methacrylamide, maleimide or other amide or imide-containing monomers. Finally, polymers bearing amino groups, such as those obtainable, for example, by copolymerization of aminoethyl acrylate or aminoethyl methacrylate with other vinyl monomers, can also be reacted.

Vinyl compounds containing N-methylol groups or N-methylol ether groups (II) in the sense of the invention can be through the general formula

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II, _f

O ²

R ₁ = H, Cj-C.-alkyl, R ₂ = H _1, Cj-Cg-alkyl and

R = H, C-j-Cq mean _

are preferred, compounds such as N-methylolaerylamide, N-methyl ο! Methacrylamide, N «methoxymethylaerylandd, N-ethoxyinethylacryiamide, N-methoxyrae thyimethacrylamide.

According to the claimed method, a suitable polymer of the aforementioned type is either directly or pre d preferably in a solvent, the selection of which depends on solubility of components to be mixed, blended with the unsaturated N-methylol compound and / or the unsaturated N-Metnyloläther. For example, ethyl acetate, methyl ethyl ketone, butyl acetate, glycol acetate monomethyl ether are used as solvents as a solvent for oxypropyl or oxyethyl acrylate or oxyethyl acrylate or methacrylate-containing copolymers.

The amount of vinyl compound II to be added depends on the number of reactive groups on the polymer; she is usually equimolar or less, since an excess of vinyl monoiaeren (II) in the mixture ate the reactivity resulting S3 stems | not impaired, but through crystallization to inhomogeneity or to undesirable softness of the uncrosslinked Films can lead. However, in some cases, deviations from this rule may be indicated, as well as it It may be useful to add further, non-ethereal-reactive, monomeric vinyl compounds to the system.

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For the mixture of vinyl compounds described above) and Polymercia are 0.01 - 5 according to the invention % By weight, preferably 0.1 - 1% by weight, based on solids, of an acidic catalyst, js.B «an organ. Sulfonic acid like e.g. p-toluenesulfonic acid or a carboxylic acid such as Malonic acid, maleic acid, oxalic acid, tartaric acid, trichloroacetic acid, Diehloroacetic acid, cyclopropane-l, l-dicarbon ~ acid, cyanoacetic acid. However, the process is in no way restricted to these acids, other carboxylic acids as well as mineral acid such as HCl, phosphoteric acid or sulfuric acid can be used. In the event that the starting polymer already contains acidic functional groups such as carboxyl groups or sulfonic acid groups, can optionally be delayed for such an addition.

The condensation of the starting polymer with the added Vinyl compound (II) usually begins with the addition of the acid catalyst. This condensation ujii is an equilibrium reaction: Depending on the choice of Solvent and the number of reactive groups on the polymer, only one part of the vinyl compounds is in solution) condense with the reactive groups of the polymer In any case, this is achieved when the mixture is applied to the desired embossing device and, with the solvent, that too released water and / or released from the IT-MethyIolather Alcohol evaporates.

A complete etherification or Umätherung and thus condensation of the vinyl compounds) on the polymer can can already be achieved in solution if a solvent is chosen that it is due to its rel. high boiling point ice allowed under reduced pressure at temperatures below 40 C the water becoming frozen during the 'condensation' or the

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Free alcohol to be consumed j. to be in a relationship. Suitable Louimgü ··· Medium are liier e.g. Hetliylglykolacetat, Ethylglykolacetat and analogous compounds, but also higher ketones.

In the case of a typed hole application, dot; method according to the invention It is first dissolved in a solvent in a known manner such as ethyl ethyl ketone, isopropanol or ethyl acetate hydroxyl-containing vinyl moieties either alone or in combination with andciL'en Vinyliiionoraeren, their proportion up to can be up to 90% by weight, polymerized.

The polymer solution obtained is cooled to room temperature and a catalytic amount of p-toluenesulfonic acid is added. To this end, the amount of vinyl compound (II) corresponding to the number of hydroxyl groups d is added. The mongrel obtained can depend on. Anwendungsawsck with the usual polymerization inhibitors such as hydroquinone, l'oluhydrochinon, Di - are protected tertiary but3 ^r phenol, di-tert-butyl-p-cresol or copper compounds against premature crosslinking!. The quantities required for this are within the usual range and can be determined for the respective application by simple test experiments, ie by determining the shelf life with increased time limits or determining the reactivity during the subsequent crosslinking process. As a rule, amounts of 0 to 1 wt .- ^ are used.

If the mixture obtained in this way is to be used for the production of copying layers, the usual photoinitiators, for example benzoin derivatives such as benzoin, benzoin ether or hydroxymethylbenzoin, or anthraquinone dex derivatives such as halogen or alkyl-substituted anthraquinones can be added in amounts of 0.1-10 fo will.

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If necessary, it may be necessary to add more solvents, e.g. to influence the ■■ drying behavior, plasticizers, Leveling agents, dyes or andoro fillers.! en, the light that initiates the photopolymerization in the spectral range o not at all or as little as possible absorb clog. Likewise, it can be on a case-by-case basis If appropriate, further internal polymers and / or further mono- or polyfunctional vinyl compounds add to the mixture. .

The solution obtained in this way is applied to the desired layer support by dipping, spraying, pouring, orphaning, spinning or by any other customary application method. After evaporation of the solvent, which can optionally take place at elevated temperature, for example at 8O ⁰ C, a dry, tack-free film is obtained, since usually after this time the unsaturated N-methylol or N-methylol ether group-containing vinyl compound with the functional groups of the Polymer has reacted.

The soluble coating obtained can be crosslinked either directly or after coating onto a further layer support, for example with the aid of light, by polymerization. In contrast to the previously customary systems that can be crosslinked by vinyl polymerization, the coatings according to the invention can dispense with both the use of a cover film and work in an oxygen-free atmosphere. ^v

After the crosslinking polymerization of the exposed parts of the coating, the unexposed parts can with dissolved in an organic solvent and washed off. Suitable solvents for this are above all those which can also be used to apply the layer, moreover those in which the uncrosslinked is preferred

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Lets polymers dissolve; for example kb '/ men chlorinated Hydrocarbons, alcohols, ketones, esters and aromatic hydrocarbons can be used here. 'The networked, insoluble parts of the layer adhere to the substrate and withstand all common detachments vie dilute nitric acid and Eicen III chloride solution as well as metal deposition in common baths,

Suitable substrate binding lietallfolien. Made of copper, Aluminum, zinc, magnesium, steel and the like, furthermore Paper, glass or films made from polymeric products such as cellulose esters, polyvinyl acetate, polystyrene, polycarbonates, in particular based on bisphenylolalkanes, polyesters, in particular based on polyethylene terephthalate, Polyamides such as nylon. As a document "are materials with a reticulated structure such as metal nets are also suitable. With the selection of suitable polymers. it is furthermore possible to make self-supporting layers.

The light-crosslinkable layers according to the invention can be used for Production of relief images or printing forms for portrait, flat or flat printing is used. In particular, be to offset printing, screen printing, lithographic printing plates, or any other printing process that includes one Relief image require, as well as referenced engraving process. Important application of the layers according to the invention is use as a photoresist for the production of printed Schaltimgen, the production of etched molded parts, the production of molded parts using the electroforming process and the manufacture of integrated microcircuits.

There is a particular advantage of the conformal layers in the insensitivity to oxygen. This enables exposure without a protective gas atmosphere. That Application of a cover film that reduces the resolution or top layer is also not required.

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In addition, en succeeds in a particularly simple V / an with a on a tracer applied layer according to dej; bl3cl) v, igen ■■■ exposure and. Creation of finished reliefs on one suitable substrate thermally »u transfer.

The exposure of the layers according to the invention is carried out with the usual in-Reproduktionsteobriik light swollen, as Kohlebo _c ^r., Enlam] .IEN, xenon lamps, QueoJiailberhochdruckÜampen, the visible light rubbed provide a particularly effective for the polymerization proportion of ultraviolet light.

In the foregoing, the Radil'.alpolj-raerisation crosslinkable polymer syotems especially with regard to their Use treated for certain photosensitive copy layers. It is understood that the erfindungsgciiiaßcn Polymers can also be used for other coverings where subsequent crosslinking is important can. So, in general, you can also use it for paints and coatings are used.

The cross-linking reaction cannot be triggered by light alone: other high-energy rays such as electron, x-ray and κ.B. ^ Rays can also be used. It is also possible to initiate the pretreatment reaction by the usual polymerization initiators for vinyl polymerisation on, wio '/,. "<)" Orgai'iocho VcroY.iOö . Thus, the' at 'does not apply to such an extended application either photochemically initiated crosslinking necessary restriction with regard to the fillers: Pr in ζ! χ »ie 11 all common pigments and additives used in unsaturated polyester-styrene lacquers can be οwetted.

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BATH

The various application areas of the invention Some cross-linked polymers are shown in the following examples made clear.

Hcr position the J19J}.

In a 2 l three-necked flask equipped with a stirrer, reflux cooler and dropping funnel, 868 g of ethyl acetate were refluxed under nitrogen. To this end, a mixture of 288 g of oxypropyl methacrylate, 150 g of methyl methacrylate, 150 g of ethyl acrylate and 9 g of azoisobutyric acid dinitrile was added dropwise within 3 hours. After the dripping like vmrde

1 g of azoisobutyric acid dinitrile in 10 g of ethyl acetate was added and the mixture was refluxed for a further 5 hours. The ethyl acetate was partially distilled off and the highly viscous Polymercnlöfjung evaporated in a vacuum drying cabinet at 15 mm / 50 ⁰ for 24 hours to a solid, colorless resin (580 g). 234 g of diene resin, 800 mg of p-toluenesulfonic acid and 60 mg of hydroquinone were dissolved in 300 g of Glylcolacetatiüonomüthyläther ..Tn this solution were 80 g of N-methylol «acrylamide, dissolved in 200 g of methanol, and this mixture for 3 hours at room temperature stirred in a water jet vacuum, methanol and released water of reaction evaporated, ^

The solution of the polymer thus produced is with Glykolacetatiiiionoinethyläther diluted to 30 wt. ~ 5S and mixed with 2 wt. based on the dry film-forming polymer, 2-tert.-butylanthraquinone sensitized. After centrifuging

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on a clean copper sheet at 200 rpm and ans Drying at room temperature for 8 hours results a layer of 25 U thick.

The above layer is 4 rain, long in a Chem-Civt Yafcuum frame illuminated by a 0.15 gray level wedge. .You get When developing with ethyl acetate / i-propanol, a sharp positive relief image of 9 steps of the wedge.

The prepared as described above and sensitized product is due to its good thermoplastic properties after coating and V021 O'rocknen a carrier film (such as Hostaphan PKHH) excellent transferable by means of 120 ⁰ C warm rollers to a suitable substrate. After an imagewise exposure through a line original with continuous development, a sharp positive image of the original is obtained.

In addition, corresponding layers can be applied to a carrier film as a finished etched relief after exposure and development can be transmitted in exactly the same way.

Example 2

Manufacture of the polymer

In a 1 1 three-necked flask with stirrer, reflux condenser and Adding funnels were 150 g of methyl ethyl ketone under nitrogen heated to reflux. For this purpose, a mixture of 108 g of hydroxypropyl methacrylate and 32 g of butyl acrylate was added within 1 1/2 hours and 2.1 g of azoisobutyric acid dinitrile were added dropwise. To

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When the addition had ended, a further 0.2 g of A: oioobi) tertiary dinitrile was added and the flow was allowed to continue for a further 2 hours. The solvent was then partially evaporated off and the highly viscous Polyricrlnrng in the Va]. uinnt rock en cabinet at 15 nrai / 50 ^o for 24 hours zn a solid .far merely cn evaporated resin (135 g). ^ ^as troc); ene Har », 700 mg p-toluene sulfonoacid so; ie 50 mg} i5 ^r drochinon \. ^for dissolved in 180 g of methyl glycocoacetate and mixed with 86 g of N-methoxmethy / acrylamide at skin temperature.

Photosensitive material

The resin solution was 2 Gev; .- $ based on the dry Forming polymers, 2 "tert. butyl-anthraquinone sensitized and colored with 0.5 wt. # VJax.olino rhodamine.

The layering at 0.5 m per minute from an immersion tray onto a 36 micron thick polyester film (Mylar) gave, after drying, films 40 microns thick. This could be on a clean Kupferfolie.bei 12O ⁰ C thermally transferred. Imagewise exposure and development in i-propanol resulted in sharp positive images of the original

lieisp.i el 3

Analogously to Example 2, it became from

65 g of hydroxyethyl methacrylate

75 grams of methyline ethacrylate

40 g of acrylonitrile

in 180 g of ethyl methyl ketone a polymer produced and im YaI: uuio dried.

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150 g of the solid polymer were dissolved in 150 g of methylgly3: olacetate dissolved and after the addition of 480 mg of p-toluenesulfonic acid un'd 190 mg 2,6 ~ di-tert-butyl-p ~ l <resol, with 48 g K-methoxyme tbylacrylamid added and, as described in Example 1, sensitized and. with success for the production of a relief image used.

Example 4

As in Example 2,

144 g of oxpropyl methacrylate

75 g of ethyl acrylate

78 grams of styrene

a polymer produced in 300 g of toluene. 119 g of the solution thus obtained in toluene were mixed with 23 g of N-methoxymethyl-acrylamide, 0.2 g of p-toluenesulfonic acid and 0.074 mg of di-tert-. butyl-p-cresol added and, as described in Example 1, sensitized and successfully used to produce a relief image.

Example 5

60 g of the solid, solvent-free polymer of Example 1 were dissolved in 60 g of methyl ethyl ketone and successively with 0.2 g of p-toluenesulfonic acid, 0.074 g of di-tert-butyl-pcresol and 25.9 g of If-Me thoxyme thy! methacrylamide added. V / ie Described in Example 1, this hybrid can also be after Seiisibilisierung with tert. Butylanthraehinone with success Use to create a relief image.

Example 6

60 g of the solid, solvent-free polymer of Example 1 were dissolved in 60 g of methyl ethyl ketone and successively with 0.25 g of oxalic acid, 0.074 g of di-tert-butyl-p-cresol and 24.5 g of N-methoxymethylacrylamide are added. The solution will be

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BATH

• Rait 2 wt .- ^ i, based on the dry! 'Umbildende Poly ^ exe, 2-tc3. '"T. -Butylanthraquinone sensitized and as in Example 1 spun onto a copper plate,! Laughs 15 minutes igera Drying at 100 ° and exposure through a template received analogous to Example 1, a positive relief image.

Example 7

In a 2-1 three-necked flask equipped with a stirrer, reflux condenser and dropping funnel, 500 g of methyl glycol acetate were heated to 110 ° under nitrogen. A mixture of 142 g of acrylamide, 150 g of methyl methacrylate, 150 g of ethyl acrylate and 15 g of benzoyl peroxide was added dropwise to this over the course of 6 hours, and the mixture was then kept at 110 ° for a further 2 hours. i The slightly turbid polymer solution was allowed to cool and then in a vacuum oven at 6O ° / 12 mm dried (440 g).

110 g of this polymer were dissolved in 150 g of dimethylformamide, one after the other with 250 mg p-toluenesulfonic acid, 23 g N-methoxymethyl-acrylamide, 100 big 2,6-di-tert.-butyl-p-cresol and 6 g of 2-chloromethylanthraquinone are added and homogenized.

The solution obtained was drawn out on a metal plate to form a film 200 η thick. The film was 18 hours at, 50 ° / 12 mm dried and then, as in Example 1 ™ described, exposed through an original. After developing with methyl glycol acetate, a sharp, positive image of the original.

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Example 8.

Analogously to Example 2, it was turned off

67.8 grams of maleimide

70 g methyl methacrylate '

8916 g of butyl acrylate

a polymer prepared in 300 g of methyl ethyl ketone and im Vacuum dried.

The polymer was dissolved in 250 g of methyl glycol acetate "and -after Addition of 800 mg p ~ toluenesulfonic acid and 80 mg hydroquinone, treated with 77 g of NH-methoxymethylacrylamide and, as described in Example 1, sensitized and successfully prepared a positive relief image used.

Example 9

In a 2 l three-necked flask with stirrer, reflux condenser and Adding funnels were 500 g of ethyl acetate under nitrogen Heated to reflux. For this purpose, a mixture of 288 g of oxypropyl methacrylate, 150 g of methyl methacrylate, was added within 1 hour. 150 g of ethyl acrylate, 45 g of acrylic acid and 4.5 g of azoisobutyric acid dinitrile given. After this time, 0.5 g of azoisobutyric acid dinitrile was added over a further hour added dropwise in 40 g of ethyl acetate. After a further 2 hours at reflux, the mixture was cooled to room temperature and the Polymer solution one after the other 1 g 2,6-I) i-tert.-butyl-p ~ cresol, 2 g of p-toluenesulfonic acid and 230 g of N-meth-oxymethylacrylamide admitted. This solution was as described in Example 1, with tert. Butyl anthrachirione sensitized and with success used to produce a relief image. A corresponding one Experiment without using p-toluenesulfonic acid yielded solvent-resistant relief images after a drying time of Days at 40 °. -

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EXAMPLE ₁ 10

100 g of a saturated polyester based on phthalic acid and Triiaethylolpropane with an acid number of 3 and an OH number of 263 (viscosity 50 wt .- ^ ig in ethyl glycol acetate: "850 cp) were dissolved in 100 g of methyl glycol acetate and successively with" 200 mg of p-toliolsulfonic acid, 50 mg Hydroquinone and 54 g'N-methoxymethylacrylamide at room temperature homogenized. This solution was made with 2 g of benzoin isopropyl ether offset and applied in a 200 u. thick layer on a metal plate. After drying for 18 hours at 40 ° / 12 mm a non-tacky coating was obtained, the exposed and developed through a template analogous to Example 1, provided a sharp, positive relief image.

Example 11

The photoinitiator-free polymer solution from Example 1 was 150u thicker on a 0.5 mm thick steel plate. layer applied and after lying for 10 minutes at room temperature under an electron accelerator in Fp-AtmoSphere (type: High Voltage) with 4.4 Mrad electron beams of an energy of 500 kV and a current of 2 mA. After this treatment, a non-tacky, insoluble one was obtained PiIm which did not swell even after 1 minute treatment with ethyl acetate.

Example 12

The photoinitiator-free polymer solution from Example 1 was mixed with 2% by weight benzoyl peroxide (based on pesticide content) 'Relocated. A 200 micron thick coating produced with this

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on a glass plate after 10 minutes of storage at room temperature Man baked at 150 for 10 minutes receives a nail-harder, solvent-resistant coating.

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Claims (2)

Patent claims: j l.j Process for the production of photographic reliefs, in which layers of polymers that can be crosslinked by photopolymerization are selectively cured by image-wise graded exposures and, if necessary, the portions of the polymers that have remained uncrosslinked at the areas of the layer that are not affected by light are removed, characterized in that they are used as by photopolymerization crosslinkable polymers polymers containing vinyl groups, preferably those with a molecular weight> 1000, which contain at least two groups per molecule R ₁ U CH ₂ H c 0 - contain, wherein R ₁ V / an *; · first off or C ₁ -C, -Allyl, R ~ Y / hydrogen or C ₁ -Co-AIkVl χινΛ ~ X -0-, -KH- or "O Ii U mean. . 2. Use of the process products according to claim 1 for the production of printing plates for reproduction technology and of photoresists for the production of printed circuits. AG 834 - 21 - 209861/1128