DE2062563A1 - Crosslinkable polymers and processes for their production - Google Patents

Description

DR. MÖLLER-ΒΟΚέ DIPL-PHYi. DR. MANITZ DIPL-CHEM. DR. DEUFEL DIPL-ING. FINSTERWALD DIPL-ING. GRÄMKOW

1I7I

McCaIl Corporation

230 Park Avenue, New Xork, N.Y. 10017,

UNITED STATES.

Crosslinking polymerizates and processes for their preparation

The invention relates to photoinitiated polymer crosslinking reactions and in particular to an improved Hasse and an improved method for crosslinking an elastonic polymer and a halogenated polymer for the production an improved product, e.g. a resilient, abrasion-resistant one Letterpress form or relief printing plate.

The use of photopolymerizable materials for the production of i-hole printing image elements which are suitable for use as printing forms is known. In the typical, previously known method of operation, an ethylene-like non-inactive substance is used with suitable solvents and photo initiators to form a liquid layer on a base plate. The layer then becomes selective for

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• "! I FK 3OB6 'r. MWjIT /, Dr. DEUFa, Dlpl.-Iwj. FINSTERWAID Dipl. Ing (.RAMKOW

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Polymerization of the exposed area is exposed to light, and it is subsequently by selective dissolution of the not exposed, unpolymerized areas of the layer Image developed. To increase the insolubility of the polymerized sheets, some have included photopolymerizable Compositions of the Prior Art Crosslinking agents, usually addition polymerizable materials with a plurality of ethylene-like residues in their Molecule.

Although the procedures and compositions described above enable the production of letterpress images, they are not entirely satisfactory in several important respects. For example, structures of uniform quality are not easily obtained by such methods because of the difficulty in controlling the degree of polymerization. In addition, the starting monomeric materials are often volatile liquids, thereby increasing the difficulty of producing uniform layers and images. Attempts have been made to polish this Froblen by adding polymers or other viscosity-increasing agents to the polymerizable. To loosen layer, however, clic;.: Additives increase the hosting of the product. In addition, the foliarization systems used up to now did not have a high degree of reliability and therefore required longer training sessions, which also contributes to higher hosting. A veLtero Soriwierl ^ keit with the previously used, poly-Li or L s L orb ar en systems for the production of long letterpress images left ^, b hu'in that si.;: The mechanical and chemical properties which are required for printing forms aind, not g-3- Χ) θΙ ~ - ^γ ι have. Iλ tjini'.en! 'All gave the image ex "inadequate üxydafcionnt'fj £ jHiiilLi: ki:""b, while in other cases the Besbänr: ■. Lg keit {jegonäber lcn 'mri' / ention ^ llen Druckff rlnösungsnLtteln not only nuf.L'oiche-iit; was. In addition, the ErCorde fritidigLen ^ -

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nesses for a printing form in terms of toughness, flexibility, Durability, abrasion resistance and impact resistance are not. the The polymers produced are often unyielding and brittle, which results in breakage.

The invention solves the above-mentioned problems of the previously known working methods by a new composition and a new process in which selected, unsaturated Elastopolyraerisate (elastic Polynerisr / be) with a halogenated polymer and a bifunctional crosslinking agent by exposure to light or high-energy radiation in the presence of a Pnotoinitiator implemented. It has been found that by pre-selection of special polymer systems better than in-situ polymerization of a high level control of both aer practice: ¹ can be achieved · the Verarbeitungstecliniken and properties of a reaction product at a photoinitiated crosslinking reaction. In addition, a highly sensitive, rapid crosslinking reaction is obtained through the inclusion of a photofunctional polymer, e.g. a halogenated PolymeriGates, in the reaction system, in which the elastopolymer is crosslinked not only with the bifunctional crosslinking agent, but you with the halogenated polymer, whereby a new, three-dimensional system results which has the necessary physical and chemical properties which are required for the formation of relief images which are suitable for use in printing forms.

Although the reaction described above can be carried out with a wide variety of crosslinking agents, relates the invention also the use of a new class of crosslinking agents, namely / ai- and polyfunctional, monomeric Salts of unsaturated mono- and polycarboxylic acids with unsaturated amines. It has been found that these materials

1 0 9 8: 36/15 3 0 _eA0 original

further increase the sensitivity of the crosslinking reaction and in addition the solubility and speed of the dissolution of the non-crosslinked portion of the polymer system "afterwards to improve the crosslinking reaction.

In the production of printing forms or printing plates, the elastopolymer, the halogenated polymer, the Photoinitiator and the composition containing the crosslinking agent on a support in one layer or in several layers applied depending on the end use of the mold and exposed to UV light through a transparent image. The exposure can also "line by line" by electron beams take place in order to effect the crosslinking of the elastopolymer in the irradiated parts. In those of the light or Areas hit by the electron beam crosslink the elastomer, with the remaining or unexposed parts removed from the mold with a solvent to make a letterpress image form. This form can be used directly on a press, e.g., a printing press, or it can be used as a flexographic form. The letterpress image form can also as an original for the production of an intaglio intermediate

T ^. ,, "" can be used.

image for the production of galvanos or clichés / by suitable Approach and suitable processing, which are familiar to the person skilled in the art, can be made gravure forms by means of the invention and round shapes can be produced directly. The composition is such that it can also be used in the manufacture of etched Molds or can be used as a coating for the production of planographic printing forms of the so-called "deep etching type".

It will be apparent that the compositions, method, and features of the invention can be used in areas other than in the manufacture of printing plates, although for the purpose of illustration the invention is in conjunction with the manufacture of such molds will be described.

1 09836/1 530 öad origi _NAl

The elastopolymers which are crosslinked according to the invention, are those that have a large number of internal ethylene-like residues in a non-aromatic structure. at the photoinitiated crosslinking reaction at least some of the accessible, ethylene-like bonds are opened to to bring about the crosslinking between the polymer chains. It has been found that the use of an Oopolymerisates which is derived from monomeric butadiene or butadiene derivatives and monomeric an acrylonitrile or acrylonitrile derivatives, is essential in order to obtain a reaction product which has the properties required for use in printing forms having.

Typical butadiene monomers, either alone or in Combination can be used for the formation of the copolymer can include butadiene, isoprene, chloroprene, piperylene and 2,3-dimethylbutadiene. Examples of acrylonitrile monomers include acrylonitrile or its methyl and ethyl derivatives; As another alternative, small amounts of additional monomers, e.g. ethylene, propylene, styrene, acrylic acids or esters and the like, can be used to make terpolymers sate, which has the basic structure of the butadiene-acrylonitrile copolymer include, form.

The preferred composition of the Elastppolymerisates is a Copolymeri sat of acrylonitrile and butadiene with an acrylonitrile content from about 15% by weight to 50% by weight of the total copolymer. The copolymer can additionally contain carboxyl residues within its structure in order to improve the adhesion of the polymer layer to raise a foundation.

The new polymer compositions of the invention are distinguished by the inclusion of a saturated, halogenated polymer as an essential component of the reaction mixture.

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BATH ORIGINAL

109,836 / $ 163 "

Particularly preferred polymers include polyvinyl chloride or copolymers thereof which contain smaller amounts, for example 10-20% by weight of vinyl acetate. However, other halogenated polymer systems _? eg vinylidene _s polyvinyl and copolymers of these materials. Although not wishing to be bound by any particular theory, it is currently believed that the absence of a halogenated polymer in the reaction mixture catalyzes the overall crosslinking reaction by the presence of light or high-energy radiation, where hydrogen halides are released and free Eadikale ~ it ^ ^ Bt2rg4L ₉ itfelche quickly in crosslinking reactions with other polyme ^^ St ates and monomers that are present in the system ,, enter "

The amount of halogenated used in the reaction system Polymer is not critical. ! Usually lying equal parts of the elastopolymer and the halogenated Polymerisates in the mixture, although larger or smaller amounts of either material do not adversely affect the reaction.

A wide variety of monomeric substances can be used as crosslinking agents for the polymeric mixtures described above. The crosslinking agents can generally be characterized as polyfunctional monomers, preferably difunctional monomers, which have at least two active, functional groups, in particular monomers in which each functional group has an ethylene-like group and an adjacent activating group, e.g. a cyano, amide , carbonyl, oxygen or imide group includes SuIfonester- _$. Such materials sehließen one

BATH ORIGINAL

Di- or polyfunctional, monomeric ester reaction products he polyfunctional epoxides and unsaturated acids. Eör-such typical material is obtained by a diepoxide, ^ z »JL__31 ^ -Epoxy-6-methylcyclohexylmethy 1— 3 »4-epoxy-G-iaethylcyclohexane carbonic oxylate or dipentene dioxide with acrylic acid in a toluene solvent using of triethylamine as a catalyst and copper (II) chloride is implemented as a polymerization inhibitor.

(2) Di- and polyfunctional, monomeric, ethylenically unsaturated Diesters or diamides, which have at least two terminal, Ethylene-like groups and an adjacent carbonyl, amide or sulfonic ester residue j> the ~ combinations thereof in activating Position to the ethylene-like group, e.g. • dracrylates of alcohols, glycols, glycerines and the like.

(3) Functional, cyclic, monomeric imide compounds, e.g. Diüialeinimide of the general structure

O HC C

HC QS > C CH

where B is an aromatic best, aliphatic best or a Coabination of this can be.

BIfünktionelle _t aonoaere charge transfer complexes (charge transfer complexes), for example Divinyläthermaleinsäure (anhydride) complexes Divinyläthermaleinimidkomplexe and Tinylcarbazol charge complexes.

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In a preferred embodiment, it represents another Characteristic of the invention is to use a new class of crosslinking agents which are non-volatile and inexpensive and improve the solubility of the uncrosslinked polymer after exposure to light. The new crosslinking agents are di- or polyfunctional, monomeric salts of mono-, di- or polycarboxylic acids or their amino esters with unsaturated, tertiary amines. Typical acids include acrylic, methacrylic, fumaric, cinnamon, oil, maleic, mesaconic, Citracon, trans and cis glutacone, itacon, mucon and cis and trans aconitic acids, although acrylic, methacrylic, fumaric and maleic acids are preferred due to their accessibility are. The unsaturated amines include vinyl pyridines such as 2- vinyl or 4-vinyl pyridine, acrylic or methacrylic esters of dimethylaminoethanol, diethylaminoethanol or tributylaminoethanol, e.g., dimethylaminoethyl acrylate (DMAEA), diethylaminoethyl acrylate, tributylaminoethyl acrylate. Examples of the new salts are DMAEA maleate and acrylic acid salt of 4-vinyl pyridine.

The number of crosslinked ethylene-like bonds depends on the degree of internal saturation in the copolymer and on the desired hardness of the product obtained. For resilient (elastic) abrasion-resistant products which have been obtained from a -äcrylnitril-Butadi encopolymeri sat, a crosslinking of about 10 % to 15 % of the accessible, ethylene-like groups is sufficient. Above this amount, the crosslinked polymer becomes increasingly hard, although it can still be used as the uppermost printing surface of a letterpress plate or for other applications where harder polymeric materials are required. Below this amount can not be sufficiently crosslinked, the polymer to be resistant to the employed solvents in printing inks, however, if it is stable in such solvents _s is the crosslinked polymer as

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BATH ORIGINAL

Intermediate coating in a high pressure mold to create an "inner cushion" in the form or as a resilient, outer corner surface, completely satisfactory.

The properties of the systems made of crosslinked polymer can be changed by varying the amount of crosslinking agent used. As a general rule, the crosslinking agent should be used in an amount between 4% by weight and 15% by weight of the total mixture and between 3% and 20%, based on the weight of the crosslinkable elastopolymer, if the coating is to be used to form a letterpress image Lower percentages of crosslinking agents based on the weight of elastopolymer are used for softer products, and higher percentages of crosslinking agents are used for harder products.

The crosslinkable mixture, which the elastomeric copolymer! Sat, including the halogenated polymer and the crosslinking agent also contains a photoinitiator. The photo initiators can be any of the following materials or a combination thereof depending on the type of applied radiation:

(a) Vicinal etaldony! compounds, e.g. diacetyl and benzyl

(b) OC / -Eetaldonyl alcohols, e.g. benzoin, tolyoin, pivaloin, Acyloin ethers, e.g. benzoin methyl or ethyl ether Ot - hydrocarbon-substituted, aromatic acyloins, e.g. 06-methyl-, ßC-allyl- and Ot-phenylbenzoin

(c) benzophenone, acetophenone, benzalacetophenone and p-dimethylaminopheny! ketone} and

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(d) Polynuclear quinones, for example 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methyl anthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthaquinone, 1,2-benzanthraquinone, 2,3 -Benzanthraquinone, 2-methyl-1,4-naphthaquinone, 2,3-dichloronaphthaquinone, 1,4-dimethy 1 anthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 3-chloro-2-methyl anthraquinone, retenquinone, 7 »8> 9» 10- ^T e'fci ^> 8ihydronaphthacenquinone and 1,2,3,4-tetrahydrobenzene- (a) -anthracene-7 »12-dione,

In the case of materials to be crosslinked by electron irradiation, it was found in accordance with the invention that that photoinitiators such as thioketones, e.g. thio analogs of benzil, benzophenone, acetophenone, benzilacetophenone and dimethylaminobenzophenone can be used and that they have the advantage that they are scattered radiation prevent the networking of neighboring image areas.

The photo initiator is present in an amount which ranges from 0.01 to 25%, preferably from 0.01 to 6%, based on the weight of the elastopolymer, and varies with the thickness of the layer. In the higher percentage range, the crosslinkable elastomer composition is more sensitive to radiation and the crosslinking reaction is "triggered" in a shorter time. In the case of multiple coats, the change in the percentage of photoinitiator from one coat to the next offsets the attenuation of radiation by the thickness of the coat.

If necessary, thermal initiators can be used, e.g. the peroxides usually used for free radical addition polymerization, e.g. benzoyl peroxide, tert-butyl peroxide, acetyl benzoyl peroxide, tert-butyl peroxide benzoate, Di-tert-butyl peroxide and the like.

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BATH ORIGINAL

In some cases it may be desirable to use a small amount of the thermal polymerization inhibitor to prevent the crosslinking reaction from occurring due to the heat generated by the process transparency image or as a result of low, external amounts of the "non-image radiation" can be generated. Suitable crosslinking inhibitors include p-methoxyphenol, hydroquinone, alkyl and aryl-substituted hydroquinones, tert-butylcatechol, Pyrogallol, naphthylamine, ß-faplfchol, 2,6-di-tert.-butyl-pcresol, Phenothiazine, 4- (methylthio) -phenol, 4- (methylthio) -m-cresol, Hitrobenzene, Dinitrobenzene, Ohloranil and Thiazine dyes, e.g. methylene blue B, a.

The mixture of crosslinkable polymer can also include a compatible, non-extractable plasticizer, in particular of the glycol type, e.g. a polypropylene glycol with a molecular weight between 1000 and 3000, or polyethylene glycol with a molecular weight between 400 and 4000. Other, compatible plasticizers can be used, as is known per se. In addition, fillers can be added to the elastopolymer mixture, provided that they belong to the clear, transparent types, so that they have the property of transparency of the elastopolymer mixture do not decrease significantly. Typical such transparent fillers or reinforcing agents are powdered glass, Silica, bentonites, organophilic silicas with a particle size of less than about 1.0 mm (18 mesh) mesh size, calcium, magnesium or aluminum te ar at. dyes and Color-forming materials can be used in the crosslinkable mixture, however, they should not be used in appreciable amounts absorb radiation in the wavelengths of exposure or inhibit the crosslinking reaction.

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In the production of fi © € m «eelebiläepn, the mixture of crosslinkable polymer is molded or cast on a suitable carrier, for example a plate made of aluminum, stainless steel, steel or another metal, or a plastic carrier, for example made of polyethylene terephthalate, nylon Polyurethane and the like. Applied. Cellulosic materials such as paper, fibers in a woven or non-woven arrangement and various metals and plastics in addition to the substances mentioned above can be suitable substrates for other applications.

If hochreflektiereo.de carriers, e.g. "polished aluminum, copper or steel, are used, a suitable anti-halo primary layer can be applied between the carrier and the mixture of crosslinkable polymer to form a light-absorbing intermediate layer." Lioht-absorbent layers Kimen are formed, in V μ »lie surface cd &« p enodiecli oxidized aluminum plate ff'-fl *. ' ι ") * Al ^f % ^ ind" tia trap of SfeafelplolfeeB, «,. by under Yerwp ¹ UJ υ / 0 * 1 ä ^f civ ("5 V'i '" ~ Hh I * ¹ "**" f ¹ VbPdcrt »nh © iaisch blackened J Ί j« li "' JTt *> t. ij.it 1 ¹ OH " % i / iröiienachicht can also, • Ι '" τ ί "lebiiAt In'» © /, hear aoohebposptionsbaren Pig _f j, B. "Ei ^ enorial nö ^ x- 01"", ^ hLjUu 3? ArRstoff ₉ distributed sisii, ijAilfle · '* woj.ti OJ * b «1 lytieti resin for use as?' Lr 4n? Given over laughs ^ bboorptionsfänige Zwi ~ • are I ^ rojgrhaTZO» «* 0o lysis products toe. ΏρΙ < hiüThy 'r *? ^ and Bispljiwiol A · Ia oiaigcn cases it can r'iwiiij, c "l" * io Tiiitforsehicht between äev Metalluad iom PolwUi *. »->. ιί> siych zn '» orwtaäea »j;" ijlrt * '/ \ ¹ , ο; * L ^ iT "ν / * ?,'" di.acte33end _s although others

its Ii jnn. 1 ¹ ^

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A solution of the mixture of crosslinkable polymer in organic solvent can be applied to a suitable substrate, as described above, by one of the various methods in order to produce single-layer or multi-layer, flat coatings of the desired thickness, which range from 0.025 to 8.9 mm ( 1 to 350 mils) or more, preferably from 0.64 mm to 2.5 mm (25 to 100 mils). For example, the mixture can be applied by means of a doctor blade of a curtain coater, doctor blade, spray coater, offset or direct coater, roller coater with rolling compound or an extrusion coater, if the mixture has a high viscosity. It can also be compression molded, layered, or applied by hand or by spraying, in cases where controlled thickness of the coating is not essential. Depending on the end product, the mixture can be applied in a pattern or in the form of a controlled, discontinuous pattern, e.g. as a print or in the form of a repeating, varying pattern and the like. non-flammable organic solvent such as the chlorinated solvents such as methylene chloride, 1,1,1- trichloroethane, although other solvents such as methyl ethyl ketone or mixtures of ketones and chlorinated hydrocarbons can be used. The mixture of vulnerable

Elastopolymereate is dissolved in the solvent feel. After the coating, the solvent is removed by evaporation or some other known method in order to leave a virtually uniform coating on the carrier part. The dried coating or dried / pattern can then be exposed to a suitable source of radiation.

The dried coating is transparent to the radiation used, so that even the under- breath layers dee

Coating can be networked, either directly old that

part or ainsr any lower class _% which applied cu-ii fcanr; _} & * h. the Antihaloaciiicht or Liohthofechutachicht

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or an intermediate adhesive layer. The entire coating or the pattern can be crosslinked to form a top layer of cured elastomeric material on a base or selected parts of the coating under Yerwencurr " ¹ -" ν £ Bclia'blone or a FrozeBtraasparenfbildes \ i ^ , cx ^, -. <-fo) become exhausted «. The radiation source should deliver an effective amount of radiation in the over-range, since the reciprocal number of photoinitiators have maximum sensitivity in this range, ie 3000 to 4000 X ₈ with a spite and generally correspond to a narrow band. The radiation source can be a source of energy or a broad spectrum, 2S..B "Jrgoaglillilaiapeiis, coal" b8gen _s Qaecksilberdsapfbog © a _s Gliöilampea with W-omittiarendea pliosphorus and äe.rgl «,» Ia some cases know it wimschenswsrt getroclaaeta Beechiekfeumg mx% islelitfcarem light using an- im visible, Bm: <& ± ie ₂ ^ fOOO bis

ο
7OOO A ans3pa? Eclien.äeii ΡΙ; ο% ο1ΐϋ-ίίΜ; οκί · Β _$ is®asiMlisieenden dyes »Ecaiu / imia zu tQl ± Qhii <m, Ibeafalls can be a line-wise irradiation with eiu ^ a Hein33? Oaenstralil with sensitizers and QhM sBgewamctf; ^ ex-dea «Bd.e shtoi? "bescliriebeaea fliiofeston-iPhotoinitialiOjfem & x-gs ^ ea gate pictures _o

Another feature of the © Ä? fii2inEg "shall look äsrnn ,, regulate the G-Rossa uad DI® form of seiaktiv.vemststen laslcMessproduktas by voft Helirf achsohiöllteii-übepziigen same or ver" Bt ^ xken "u. ¥ © 3? t" mdiib @ This kind of me »χ toil ι to regulate the Γο3Ώί äev-characters of the Seliefbildes or / UwKwiVur & iXa & B , uttö-.eiieterziistic. that the

U'Um . »Feea soliiohten in the same size as the other Schich-Y« 3, Tlf | »t5 ■ ^ ind · lade» «in © Hetessalili voä layers.

where the% m »5scMcitt« was; sensitive list is, 7p tin hijher'ea 4tiiaafi an.TttnMtssutts in the izateren 5th ^! express _$

pyvanldttofSxpiie «Sticbea- eclex · Bxiftte formed.

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iS836 / 1S30 BAD ORIGINAL

For example, a 0.46 mm (18 mil) thick coating consisting of nine layers of 0.05 stroke (2 mil) thick can now be applied so that the three bottom layers have 5 % photoinitiator, 3 % in the middle three coatings and 0.25% contained in the three surface coatings, all percentages being based on the weight of the elastopolymer. The number of film layers, the thickness peeler layer and the amount of photoinitiator in each layer can be varied in order to achieve the desired properties in the crosslinked product.

Following the selective exposure of the crosslinkable mixture to light or a radiation source, the high pressure image is developed by selectively dissolving the non-crosslinked portions of the coating. Any of the aforementioned organic solvents for the non-crosslinked mixture can be used by brushing the entire polymer surface with the selected solvent. Typical solvents include methyl ethyl ketcn, butyrolactone, Ilethylene chloride, xylene _s a Beixsol-Wstoer-Eiaulsion ύ3ΐά mixtures such as ButyrοIacton / Hethanol, Butyrol & £ tu8 / V & 88e? usd 2h $ lol / ethylene chloride. The product obtained is an eefcarfes image, which the template »or the copy template * dl ·, *; bsi the exposure were used.

Another feature of the working techniques used in the present invention is the physical Properties of the hot image due to its high irradiation treatment to regulate. If, for example, a harder relief image is desired the developed image can be exposed to irradiation again in order to bring about further crosslinking. initiators are brushed onto the image surfaces, which

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then exposed to radiation again in order to bring about further surface hardening through increased crosslinking. As a further alternative, a chemical surface hardening reaction can be used by treating the image surfaces with any of a wide variety of compositions prepared with one or more of the functional groups react in the crosslinked product, are induced.

The following examples illustrate the invention without restricting it:

■ EXAMPLE 1

A mixture of crosslinkable polymer was produced which contained the following components:

3 g of a 20% pesticide solution (Ilethylethylketon) of a (.zwl see 1 % and 20 %) carbo: cylated acrylonitrile-butadiene copolyesters,

3 g of a 20% pesticide solution (Ilethylethylketon) of polyvinyl chloride-vinyl acetate copolymer (13 % vinyl acetate),

0.060 g of a crosslinking agent which was the reaction product of 3,4-epoxy-6-methylcyclohe2q7lmethyl-3,4-epoxy-6-methylcyclohexane carboxylate and acrylic acid (10 % based on the acrylonitrile copolymers),

0.065 g polypropylene glycol (molecular weight 2025), 0.0012 g of di-tert-butyl peroxide, and

0.007 g benzophenone (1 % of the combined weight of you acrylonitrile cop ο lymerise.t and crosslinking si suffered).

A 0.05 mn (2 rill) thick was placed on an Iletallmrberlage The coating was bent over and the coating was allowed to dry golasren. »Ur-chs samples were exposed to UV light from a 25Ο V

- ßAD ORIGINAL 109836/1530

Uviarc-lsiipe through a described template for periods of time exposed from 0.5 to 10 min. The exposed plate was treated with Ilethylene chloride, -which applied with a brush - Cen t-mrcle, uia to remove the unexposed parts. the Results were as follows:

Beliclitunr; sda.uer (min)

0.5

image

low ο remote change e tw a s Palt enb λ 1 dung rut cut

, C ₁ 3, 10

EXAMPLE 2

A coating of about 0.4G ϊ-lj. (1C mil;) thickness, which iioui schicTiten, each- of 0.05 ^ - <■ (2 mil ;; which had a polyurethane coating on it, each layer being applied at intervals of 15 minutes. The composite panel was left over night under atmospheric place Dr ^ ok troclaien and it was bed Zi; .u: ierteupere.tLLr Lint or Valaiuj.1 4- h getDclaiot. The following approach with Ilethylü bhylketon as Lüiaingsmituol \ / u: cde applied:

JG g of a 20% solids solution of carboxylated .acrylni tri1-Butadi encopolymoris from;

3G g of a 20% fatty substance solution dos Polyvinylchloridcopolymei'isatos from example 1}

1.00 g of the crosslinking agent from Example 1 (15 % based on acrylonitrile copolyraerisab),

0.77 C plasticizer of Example 1 and

0.144 g of di ~ tert.-butyl peroxide (1 % based on the combined weight of acrylonitrile coxoolymerisate and crosslinking agent),

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Benzophenone was used as a photoinitiator in a concentration of 5 ° / ° of the combined weight of the acrylonitrile copolymer and the crosslinking agent in the three lower coatings, 3 % in the three middle coatings and 0.25 % in the upper three coatings.

-Different samples of the coating were exposed through a paper-dot stencil for 3 »4, 6 and 8 minutes, and the plate was developed with methylene chloride at approximately 5 elin. Sample plates were also exposed to UV light through a black-and-white negative for periods of up to 15 w-Ώ. exposed. Pyramidal images were obtained and tested with inks to give good prints. The color went well to the letterpress image and from the letterpress image to the paper.

In the following examples, the materials from Example 1 applied unless otherwise specified. The amounts are w / 3 parts of the total composition.

EXAMPLE 3 Elastopolynerizat 47.25 % Polyvinyl chloride copolymer 47.25 % Crosslinking agents 5 % No plasticizer Photoinitiator 0.5 %

The samples exposed to UV light for 0.5 to ρ min produced satisfactory images.

Elastopolymer) 85.50

Polyvinyl chloride copolymer) crosslinking agent 7.5

BATH ORIGINAL

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Plasticizer 6 ^c / o

Pliotoin initiator - 1.0 %

Inhibitor (Biantliron) 0.001 %

By exposure to UT light fib? Periods of 1, 2, and 3 millimeters were obtained in fate three times. Good images were also obtained on exposure to electron beam exposure at a C tr aiii current of 40 ml using a perpendicular jiblion time of 200.0 Ω and 1000 nsec. The samples were-don ebe3if? -Lls with Elrl; t3 ^ onenbestrr> .lvjiG with a Gtr-v jsb2>? U of "0 VA and a sen1i ?? realii Xbleni time of 200 imi ° 0 A at 100 r.rec The nit Elc'it belicabeten pictures ir ^ rfieii in one: Iv / j ^ rolrcton- -uaxl Iletlirr. G- eui α ch ent ", n. clzel t.

In clan fol ^ on ^ en examples was eiiio Vielnruil vn Jjis '^^ lier. ^ Ttell'j uii-f bcGtrrlilt, i_.ic! Ie'/ir"!:..η j en ve.vicliiefen ^ r Y ^ nr's ^ .Jii.xix ^^ nl, inhibitors and clo:? ^ l. zu beGtiu.-ru Di Π - TT ^; .. onsOt ^ ViIi ₀ Cn i-iiä results c-ind in tables foru εη _ο .ν

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EXAMPLE

POLYMERIZE

cn ca ο

Elastopolymer from Example 1, 43.5 % i vinyl chloride copolymer from Example 1, 4-3.5 %

Cold-polymerized acrylonitrile-butadiene with slightly more acrylonitrile content and cscrbosyl residues in the polymer chain (28-34 % acrylonitrile), 35.75 % and vinyl chloride copolymer from Example 1, 35.75 %

As in example 6

Elastopolymer and copolymer as in Example 6, present in each case in an amount of 36.2 % and 8.1 % of "brominated, liquid acrylonitrile butadiene rubber with a medium-high acrylonitrile content (28-34 %)

KITS

Ethylene glycol diacrylate (EGDA), 6 jo

Ή , ΪΤ-Hexamethy-1 endiial einimi d, '7.5 %

PHOTOSENSIBILI-SATOE

(and soft

maker)

Polypropylene Glyco 1 tPPG) 6% Benzophenone (BP) 1 % Hydroquinone 0.0001 %

RADIATION AND RESULTS

UV, good picture in 1 min

PPG 6% BP 15%

Reaction product of acrylic acid and the low molecular weight Condensation product of epichlorohydrin and bisphenol A

As in Example 1, 7.5 % and maleic acid salt of dimethylaminoethyl methacrylate (DJIAEM), 5%

PPG
BP

6% 15 %

PPG 6 % BP 15 %

UT, satisfactory picture in 20 see

UT, satisfactory picture in 20 seconds

UY, good picture in 30 see

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109836/1530

U)

ORIGINAL INSPECTED

POLYMERIZE

CROSSLINKING AGENTS

Vie in example

19 20 21

Vie in example

Vie in example

Substances as in example 6 but present in the following amounts:

^% / 40.25 % for the

ink ere half,

42.25% / 42.25 % for the οι) ere half

Vie in example

Substances as in Example 6, but in quantities of 39) 5 ° / ° present PHOTOSENSITIVITY

SATOR

(and plasticizers)

m-Dini trob enz ο1
and vinyl carbazole in the same,
molar quantities,

Z int acid it as
from DEAEA, 5 %

oleic acid as of
DEAEA, 5 %

Acrylic Sal
from DEAEA, 7.5 %

PPG 6
BP 15

PPG 6 '
EP 15

PPG 6
BP 15

PPG
BP

RADIATION AND RESULTS

UV, satisfactory image in 30 seconds

UV, good picture in 20 seconds

UV, good picture in 20 seconds

6 ° / o for lower

_t half 1.5 ^c / ° for upper

Half hydroquinone 0.001 ^c / o for lower

half

0.01 Jj for the upper half

UV, good image with 4 min exposure through a negative

Me tli acryl 0 aur e- as in example 21 As in Bei / / ro sal ζ from DEAEA, game 21, 0 7.5 X however 6 min CD exposure KJ Ac ry 1 acid e s al ζ PPG 6 ^c / o / UV, good cn of .dimethylamino- BP 5 yo / Picture at 1min. CD ethyl methacrylate, Hydroquinone / Exposure 10% 0.01 % /' through a negative

^: "^{ll; i} ": i ""; s "ι ■ ' τ τ '""" - τ ¹ !! » ■ ■■ '■. ■ · ■■■■■ »·>■!>. ■■■■■■. .-. ·. ■, ... ,,,, ~.:. ,, _; ,., ,,,, ,,,,,,, _{l:. "Ilfl:}

The compositions and the method of the invention can be used to produce improved, elastomeric products which can be crosslinked by radiation, e.g. Line or halftone relief forms or combinations of line and halftone forms can be produced. Z sätzlida, the invention offers the advantage that it makes it possible to structure the relief image by using a waste layer plate with different percentages of photoinitiator and / or crosslinking agents is delivered, so that the relief image is generally pyramidal, thereby increasing the strength. Since the relief image is resilient (elastic) and resistant to abrasion, it can be used as intaglio EOrm, the paint is applied by a doctor blade in plural marriage.

The preferred subject matter of the invention is accordingly a photosensitive material which is suitable for the production of printing plates and the like and which contains the coating compositions which together with the substrate form the photosensitive hearing aid, as well as a method for crosslinking the coating compositions of the light, sensitive Hateric.ls and call relief printing plates produced in this way.

- patent claims -

109836/1530

Claims (1)

Claims 1. Molding and casting compounds that can be crosslinked to form crosslinked, three-dimensional polymers, characterized by (1) a multitude of non-terminal, Elastopolymer containing ethylene-like residues, (2) a saturated, halogenated polymer, (3) a polyfunctional, monomeric crosslinking agent, wherein the crosslinking agent is used in one for crosslinking of the molecules of the elastopolymer and of the saturated, halogenated polymer over at least a portion sufficient amount of the non-terminal, ethylene-like radicals is present, and (4) a photoinitiator, wherein the photoinitiator is present in a sufficient amount to cross-link the elastopolymer, the saturated, halogenated polymer and the crosslinking agent on exposure to high-energy radiation initiate. 2. Molding and casting compounds according to claim 1, characterized in that g e k e η η ζ ei chnet that the elastopolymer is a copolymer, this copolymer being the reaction product of Butadiene or butadiene derivatives as the first monomer and acrylonitrile or acrylonitrile derivatives as the second monomer is. 3. Molding and casting compounds according to claim. 2, thereby g e k e η η ζ ei chnet that the elastopolymer is a copolymer of butadiene and acrylonitrile. 4. Molding and casting compounds according to i & nspruch 2, characterized geke η η - we ich η et that the copolymer has an acrylonitrile content of 15 "to 50 wt.%. - 24 - 10 9 8 3 6/1530 bad original 5. molding and casting compositions according to claim 2, characterized in that the copolymer is a is carboxylated acrylonitrile-butadiene copolymer. 6. molding and casting compositions according to claim 1, characterized in that the halogenated polymer a homopolymer of vinyl chloride or a copolymer of vinyl chloride and vinyl acetate is. 7. molding and casting compounds according to claim 1, characterized in that the crosslinking agent is a difunctional monomer, each of the functional groups including an ethylene-like radical. 8. molding and casting compounds according to claim 1, characterized in that the crosslinking agent is a polyfunctional, monomeric salt, which results from the reaction of an unsaturated, tertiary amine with a mono-, di- or polycarboxylic acid, or amino esters of these acids comes from. 9. molding and casting compositions according to claim 1, characterized in that the crosslinking agent in an amount between 5 and 20% by weight of the elastopolymer and the photoinitiator is present in an amount between 0.01 and 25% by weight of the elastopolymer. 10. A process for the production of a crosslinked, three-dimensional polymer product, characterized in that a transparent to radiation, crosslinkable polymer mixture is produced, this mixture (1) being a multitude of not terminal, ethylene-like residues containing elastomer - 25 -109836/1530 polymer, (2) a saturated, halogenated polymer, (3) a polyfunctional, monomeric crosslinking agent and (4) comprises a crosslinking piiotin initiator and the photoinitiator to radiation of a predetermined amount The type is sensitive and is present in sufficient quantity to prevent the crosslinking between the elastopolymer, the halogenated polymer and the crosslinking agent when the mixture is exposed to radiation to effect the predetermined type and that at least part of the mixture of this radiation for a sufficient Amount of time to. the crosslinking of at least some of the non-terminal, ethylene-like bests in that portion of the mixture to cause soft exposure to radiation., exposed will. 11. The method according to claim 10, characterized that the polymer mixture is deposited on a substrate as a film, the film being an essentially has uniform thickness in cross-section in the range of 0.025 to 8.9 mm (1 to 350 mils), and in the exposure stage only selected portions of the film to produce the crosslinking of the entire cross-section exposed to the radiation of this are exposed and the unexposed portion of the film following the irradiation with formation a relief image is removed. 12. The method according to claim 10, characterized that the exposure level is the irradiation of the Film with UV light through a copy master (transparent) bearing an image, the master copy being opaque and has transparent surface areas, 13. The method according to claim 10, characterized that a thioketone is used as the photoinitiator and electron beams are used as the radiation. 14. The method according to claim 10, characterized that a multitude of film layers of the form 109836/1530 and casting compound are deposited on a substrate prior to the exposure step, the photoinitiator in each of the layers and in at least some of the layers is present in different amounts. 15 · Method according to Claim 14, characterized in that the one closest to the base lying layers contain the largest amount of phdtoinitiator. 16. The method according to claim 10, characterized in that the crosslinking agent in an amount between 5% by weight and 20% by weight of the elastopolymer and the photoinitiator is present in an amount between 0.01% by weight and 25% by weight of the elastopolymer is available. 17 · The method according to claim 10, characterized in that the Elastopolymeisat a Oopolymerisat ie t, this copolymer being the reaction product of butadiene or butadiene derivatives as the first lunar mer and acrylonitrile or acrylonitrile derivatives as the second monomer! is. 18. The method according to claim 17, characterized in that the elastopolymer is a Copolymer of butadiene and acrylonitrile is. 19. The method according to claim 17, characterized in that g e k e η η draws that the copolymer! sat is a carboxylated acrylonitrile-butadiene copolymer. 20. The method according to claim 10, characterized in that the halogenated polymer - 27 -109836/1530 a homopolymer of vinyl chloride or an copolymer of vinyl chloride and vinyl acetate. 21. The method according to claim 10, characterized in that the crosslinking agent is a difunctional monomer, each of the functional Groups includes an ethylene-like residue. 22. The method according to claim 10, characterized in that the crosslinking agent is a is polyfunctional, monomeric salt, which is from the Eeaction of an unsaturated, tertiary amine with a mono-, di- or polycarboxylic acid or amino esters of these Acids originates. 2Y. Method according to claim 11, characterized in that the film is treated with a solvent in the step of removing the unexposed parts "is treated, the solvent being the selectively removes unexposed Seil® of the film. 24. The method according to claim 11, characterized in that the exposed parts of the j Film of a hardening treatment following the removal of the unexposed parts of the film be subjected to 25 · The method according to claim 24 ·, characterized in that the exposed parts of the Oil films following the removal step with radiation to be re-exposed » '26 »Strictly sensitive material for the production of Beliefbildung, which one underlay and one on top of it deposited * radiation transparent film - 28 - ' BATH ORIGINAL 109836/1530 a polymer mixture comprises., wherein the polymer mixture is characterized by (1) a multitude of non-terminal, ethylene-like radicals enclosing elastopolymer (27 a saturated, halogenated polymer (3) a polyfunctional, monomeric crosslinking agent and (4) a radiation sensitive Photoinitiator, the photoinitiator in a sufficient amount to crosslink the Elastqpolymerisates, of the halogenated polymer and the crosslinking agent on exposure of the polymer mixture with radiation is present, 2 ?. Radiation-sensitive material according to claim 26, characterized in that the elastopolymer is a co-polymer, this being Oopolymer is the reaction product of butadiene or butadiene derivatives as the first monomer and acrylonitrile or acrylonitrile derivatives as the second monomer. 28. Radiation-sensitive material according to claim 26, characterized in that the Elastopolymer is a copolymer of butadiene and acrylonitrile. 29. Radiation-sensitive material according to claim 26, characterized in that the Oopolymer has an acrylonitrile content of 15 "to 50 wt. # Has. 30. Radiation-sensitive material according to claim 27, characterized in that the copolymer is a carboxylated acrylonitrile-butadiene copolymer 1st. 31 * radiation-sensitive material according to claim 26, characterized in that the halogenated polymer is a homopolymer of vinyl chloride or an Oopolymerlaat of vinyl chloride and 109836/15 Vinyl acetate is. 32. ßrahlungssensliclies material according to claim 26, characterized in that the crosslinking agent is a non-discriminatory honey, where the functional groups are an ethylene like hest includes * 33 · Radiation-sensitive material according to claim 26 _S, characterized in that the crosslinking agent is a polyfunctional, monomeric salt "which results from the reaction of an unsaturated, tertiary amine with a monof-di- or polycarboxylic acid or Αυΐηοβstern, these acids, comes from » A radiation-sensitive KatsriaL to spoke 26, characterized in that _s & aB the crosslinking agent is present in an BsEge between 5 wt · ^ and 20 (lew.fS of Elastoi> oljiieri.sates and OCE photoinitiator in an Heng @ between O ₈ OI wt '% wad 25 weight .S ^ of the Elastopolpier isate is available ", 35. Straialungsempfindliches HateifiaX according M- ^ iaich 26, characterized in that the ₉ tDäßsparente film gesetzer a composite film, which comprises separate film layers, wherein the Ehotoinitiator some d®der in these layers and in different amounts in at least of said layers is present, 36. Strahlungsempfindliohes material according to claim 26, characterized in that _a transparent film is a zusaaiaengesetzter Jfila, wslcher units of getresmtes environmentally FilEscMeliten f ^ Bt '*; where the amount of Kh.otoiiiitia * © 2? s in 3 © äB3? the layers irerseliieiBB i © t and m & b® ± the base closest to », gsls-gpse» SeM © lit © a die . ^,,.,. '.BAD ORIGINAL contain the largest amount of photoinitiators. 37 · Relief image element for use in printing processes, the element comprising raised portions and at least the outer surfaces of the raised portions contain a crosslinked polymer mixture, characterized in that it is the reaction product of (1) an elastomer with a plurality of non-terminal, ethylene-like residues, (2) a saturated, halogenated polymer and (3) a monomeric, polyfunctional crosslinking agent is what radiation has been exposed in the presence of a photoinitiator. 38. Relief image element according to claim 37 »characterized in that the element has a Has base, the raised portions of the relief image being carried by the base and consist entirely of crosslinked polymer mixture. 39 · Relief image element according to claim 37t, characterized in that the raised portions have a pyramidal cross-section ¹ ^; 40. Relief image element according to claim 371, characterized in that the elastopolymer is a copolymer, the copolymer being the reac tion product of butadiene or butadiene derivatives as the first monomer and of acrylonitrile or acrylonitrile derivatives as the second monomer. 41. Relief image element according to claim 40, characterized in that the elastopolymer is a copolymer of butadiene and acrylonitrile. - 31 - ORIGINAL BATHROOM 109836/1530 42. Relief image content according to claim 40, characterized in that g e that the copolymer! sat has an acrylonitrile content of 15 "to 50% by weight» 43 »Relief picture element according to claim 40, characterized in that the copolymer it carboxylates acrylonitr!.! - butadiene copolymer is. 44. Relief image element according to claim 37 »characterized in that the halogenated Polymer is a homopolymer of vinyl chloride or one of the copolymers of vinyl chloride and vinyl acetate is. 45 »Relief picture element according to claim 371, characterized in that a crosslinking agent is a difunctional monomer and each of the functional Groups includes an ethylene-like residue. 46. Relief image element according to claim 37 »thereby g e - indicates that the crosslinking agent is a polyfunctional, monomeric salt, which is the reaction of an unsaturated, tertiary amine with a mono-, di- or polycarboxylic acid or amino esters these acids come from » 47 »RelieBeTemerit according to claim 37» characterized by this that the crosslinking agent in an amount between 5 and 20 wt.% Of the elastopolymer present » 109836/1530 BATH ORIGINAL