DE1815457A1 - Process for the production of polymeric relief printing plates - Google Patents

Description

PATENTANWÄLTE A Λ χ- ι

DR. F. ZUMSTEIN - DR. E. ASSMANN 1815457 DR. R. KOENIQSBERQER - DIPL.-PHYS. R. HOLZBAUER

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. TELEaRAMMEiZUMPAT BRAUHAUeSTRA33E 4 / II1

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EMC CORPORATION, ffew York, 3J.Y., USA

Process for the production of polymeric relief printing plates.

The invention relates to methods for photomechanical manufacture of relief printing plates through the light-triggered polymerization of a light-sensitive allyl ester resin

In the production of relief printing plates, as they are usually used in light printing processes, a thin layer of photosensitive composition through an original, such as a negative, with the one to be reproduced Image exposed · The light used here is usually rich in ultraviolet radiation, which causes hardening of the photosensitive layer. the The plate is then treated with certain solvents that remove the uncured layers in the unexposed areas.

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suffice to dissolve or at least to detach them, but the through the irradiation do not attack hardened, resinified sections · On the coated, usually made of metal The baseplate leaves an belief in the desired image, but it is so thin that it normally is not is suitable for printing, and that only serves as an etching base. After the selective itaen of the metal surface up to a two-kilometer depth in the free or unprotected Areas can then be used for printing purposes,

the ÄtP5vorg ».T> g in a series of as Processing steps designated by partial etchings, in order to reduce undercutting or undercutting of the picture surface to a minimum. Between those ! Bearing etch the plate is treated so that the "flanks of the relief formed in the previous treatment. Apart from what is required In terms of time, this procedure is extremely difficult to control to produce an image with smoothly beveled paragraphs receives. The overall effect of the successive partial etchings is, of course, such that stepped shoulders are formed which are often jagged and uneven. As a result, it also accumulates when such plates are used Printer's ink or color on these paragraphs, which means that the printing press has to be stopped from time to time, so that you can remove the excess printing ink. In addition, these paragraphs can scratch the support rollers and scratch.

Other undesirable properties of the light printing plates produced in this way are the extensive processing by hand and the re-etching operations that are normally required to get a sharp

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Distinction between printing and non-printing areas is preserved. Such plates are generally insufficient for most commercial printing purposes long life and difficult to reproduce by repeating the plate making process, the duplication processes, such as by stereotype or electrodeposition, involve the tedious and difficult are to be controlled. For example, when duplicating by electroplating, the duplicated printing plates are often different in height, and it Very skilful manual work is necessary to correct the printing plates so that they have constant printing heights. All these manipulations and operations naturally go through a considerable amount of the details of the Image irretrievably lost.

Proposals were also made to eliminate the heavy metal printing plates and the time-consuming process associated with them "Eln" Such a much-noticed proposal is to use the relief printing plates made of plastic to produce light-triggered polymerization. With this procedure, one layer is made of one through Light polymerizable composition on a suitable base plate through a translucent template with the The image to be reproduced is exposed in such a way that the composition polymerizes or otherwise on the exposed Areas is hardened, but remains unaffected in the unexposed areas. The exposed plate is then treated with solvents, which the non-polymerized Wash out or remove the layer on the exposed surface of the plate without affecting the irradiated areas. The resulting relief image forms the Printing surface. A typical method of manufacture photographlsoher ReUefbilder in the manner described above

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and whiteness is described in U.S. Patent 2,760,863, in which the polymerisable · sends an äthyleniech unsaturated monomer let. Although relief images are produced according to the method according to this US patent specification can, this is the procedure with regard to the use of liquid, polymerizable substances a bit cumbersome * since you have several auxiliary layers, like about an anchoring schioht and various overlying it Use layers such as a glass plate and protective membranes Must · An improved »presensitized relief plate based on photopolymerizable Layers is available under the trademark DYCRIL · im Trade. However, this plate requires conditioning with carbon dioxide immediately prior to use.

The invention therefore aims, in order to meet existing needs, a completely presensitized » To create a storage-stable relief printing plate »that does not require any further treatment or conditioning.

According to the invention, this is essentially achieved by that a sensitized or light-sensitive coating is made for the layer polymerizable by light a crosslinkable allyl ester resin is used. The polymeric relief images produced with it turn out to be the bicker well-known far superior.

According to the invention, a metal plate or another suitable pad with a photosensitive allyle mineral resin Coated sufficient thickness so that the production of a relief image with the desired thickness is possible. Generally, the thickness of the layer will be from about 1 mm to 6.5 "mm (3 to 250 mils). Layers having a Diokes from da.1 to "3/4 mm (30 mils) and usually those with a thickness of approximately 1 to 1/5 mm (7 mils) aind for

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Halftone plates sufficient, while flattened by about 1 /; are (10 mils Me 60) used to 11/2 min thickness principally lypendruckplatton "The invention relates in particular to Typandrückplatte ^ which is why the polymerisiex'bare by Iiicht allyl ester resin about 1/4 to it. 11/2 ram thick should be applied. This layer can be polymerized by light. Extruding or calendering a film to the desired thickness and applying it to a base with or without an anchor anchor. Other coating methods can also be used, such as roller or bakel application with a viscous liquid and evaporation of any residual solvent into one ? *! Urookenkawjiflr, In any! Case, the resulting product is a dry, light-sensitive layer of homogeneous allyl ester resin, which can be further polymerized or crosslinked by residual allyl ester groups. The calibrating, presensitized plate is exposed to actinic light through a negative or other suitable translucent gate layer. The development of the image consists in removing the uncured resin from the non-printing, non-exposed areas. This can be done by immersion in a solvent so that the unexposed material is dissolved ₉ or by Wasohon with a solution spray. Suitable solvents for this purpose include chlorinated solvents such as irichlorethylene, 1,1,1-irichloroethane and methyleadlechloride; Ketone solvents such as acetone and methyl ethyl ketone as well as higher molecular weight derivatives such as hexanone and 4-methyl-4-methoxypentanone ~ 2; and also esters such as methyl, ethyl, propyl and butyl acetates and glycol ether esters of acetic acid, for example cellosolve acetate and the glycol ether solvents, for example cellosolves and oarbitols.

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Haoh did not remove the for the formation of the picture Resin is used to remove traces of the plate completely washed in residual solvent. In Depending on the particular type of solvent used To facilitate the complete elimination of the solvent, an alcohol wash or a Heating to be applied «After that, the plate is ready Hum printing, for the type printing by attaching on an Irägesrplatte, so that the required thickness results, and for the type set by attaching it to a appropriate Plattenßylinaer,

The allyl used in the manufacture of such plates Resins are preferably prepolymers comprising aryl allyients more than one allyl group, Dieoe prepolymers are in solvents soluble, solid at ambient temperature and contain at most "a very small percentage of the monomers, .from which they are derived so that they shrink very little when exposed to actinic radiation further crosslinked or polymerized by Tiioht v / ground.

The crosslinkable allyl resins used in the manufacture of such panels are obtained by addition polymerization an addition polymerizable allylcarboacyl ester with many aliphatic, ethylenically unsaturated bonds » preferably 2 to 4, of which at least one is in an allyl ester group «As stated in detail later, the polymerization is carried out under such conditions that at least one of the äthylenisoh unsaturated Bonds, preferably in one of the allyl ester groups bonded to a monomer, remains in tact and is not converted. This results in a polymeric system of one Chain of ^ C-O ^ * units, each of which © ine al ip ha tables, ethylenically unsaturated group, preferably one

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Allyl ester. Bieoe Reßtaentren des Unsaturated, Zostandea make it possible for such resins to be polymerized by if they are manufactured and used according to the invention «

The polymerization of allyl ester monomers in the manner described above is a well-known technique, and it is based on the polymerization between allyl monomers, which takes place more rapidly than the crosslinking of the allyl ester groups or other unsaturated groups in the polymer. This difference in reactivity enables ββ to produce the non-crosslinked allyl resin and to isolate it = the latter type of ilaraeu. ± ατ iu Ijb'öuögmaittel lös-iiCH ₉ solid at ambient temperature and contains at most very low Prosentsätse & n output Mono Meron _t so that they very little shrink during the crosslinking or polymerization by actinic radiation "These physical properties are in addition to those desired, the non-crosslinked from Allyl resin is an excellent material for the manufacture of presensitized printing plates.

Allyl esters, which are used in the manufacture of crosslinkable allyl resins Generally those carboxylic esters can be used with two or more carboxylic acid functions which are esterified with an allyl group, and they can be alXiphatically or be aromatic.

To the crosslinkable, aliphatic allyl ester prepolymers belong to the following classes:

a) prepolymers derived from allyl esters of unsaturated monobasic acids either of the general formula C _n H _2n-1 COQR or O _n H _2n ^ ₁ JK “COOR, such as allyl aylate, allyl chloroacrylate, allyl methaorylate,

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Allyl crotonate, alljloinnamt, allyloinnaioalaoetat, IHy-I-furoate and allylfurfuryoaopjlate. Sa 1st also note that in all « stated here. Ponnaln Ä an allyl group let and η an integer from 1 to 17 inclusive be loami, unless the acid is unsaturated, whereby in this »lal le η 2 to 17, y 1 or 2 and X a halogen, hydroxyl, phenyl" - «is substituted phenyl or ffurfuryl group or an alkyl or alkoxy group with 1 to 4 carbon atoms.

b) Sraoopolymers of illyl esters of unsaturated monohydric ethers Acids, such as allyl methaorylate with butadiene, allyl methaorylate with methyl methaorylate, allyl methacrylate with styrene, lllyl methaorylate with vinylidene chloride, allyl crotonate with methyl »Ethaorylate, allylorotonate with styrene, allyl crotonate with Vinyl chloride, allyl crotonate with vinyl acetate, allyl crotonate with vinylidene chloride, allyl crotonate with diethylene glycol maleate, Allyl cinnamate with vinylidene chloride, allyl cinnamate with Styrene, allyl cinnamate with oinnamyloinnamate, allyl furoate with styrene and allyl furoate with vinylidene chloride.

c) prepolymers derived from allyl esters of aliphatic carboxylic acids with two or more allyl groups and one of the following general formulas Bind: CH _2n (000R) ₂ ,

3 AWVS n ^ n1yV3 h * ^C n ^H 2n-2-yV ^000R) 2 ^or ^ ώ (ή ₉ such as allyl oxalate, diallyl salonate, diallyleuccinate, diallyl sebacate, diallyl maleate, diallylfuaarate, diallylitaoonate, diallylallyriallyl tartrate, diallyl allyriallyl tartrate, diallyl carbo-diallyl tartrate, diallyl carbo-diallyl , Diallyl malate and diallylo traconate

d) Preoopolymers of the allyl esters of aliphatic carboxylic acids with two or more allyl groups, such as diallyloscalate with vinylidene chloride, diallylo aalate with styrene, DiaHyl-

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BBlonate with vinylidene chloride, dallylsuocinate with vinyl acetate _? Diallyl succinate with vinylidene chloride, biallyl succinate with polyvinyl acetate, diallyl sebacate with vinylidene chloride, piallyl sebacate with vinylidene chloride, diallyl maleate with methyl methaorylate, diallyl mleate with styrene »diallyl maleate with vinylidene chloride and diallyl carbonate with methyl methacrylate«,

These are the aromatic and heterocyclic series Connectable prepolymer hair derived from an allyl ester, that is to say that the acid is normally composed of benzene, baphthalene and cyanuric acid series, with typical monomers Diallyl isophthalate, diallyl phthalate, piallyl orthophthalate, IrJÄllylmellitat, letraallylpyromellitat and iPriallylcyanurab are *

In the production of cross-linked Allylharae, which also ale Prepolymers are known, the monomeric substances are in conventional manner in order to obtain a solution of a soluble polymer in the honey, to the Point just before the (toleration that occurs, when the network of polymers approaches the point where it becomes insoluble in the monomer · This;> - Polymer solutions or Oußmaesen are then in a solvent soluble prepolymer fraction and a honey fraction separately.This is done by treatment with a solvent, which dissolves the monomer while polymerizing Part is precipitated, or by other means that result in a soluble prepolymer that is essentially free of monomer. Sin typical procedure sun Separation of such irrelinkable prepolymers is In the U «S · - Patent drill 3 030 341 described.

If you get coatings that are sufficiently durable Polymerize light so that it is suitable for industrial

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Advertising is useful «is * e necessary, dot frapoljaer tin sensitizing agent, which absorbs actin-like radiation, so that ββ dissolves into free radicals, which accelerate the complete polymerization of the prepolymer Leso. Beneoin ethers, such as He bhyläther dee Beneoine, can be used as sensitizers »Bensophenon; ρ, ρ'-substituted benzophenones, such as 4t4 ^l -Bie- (Dimethylamiuo) -bensophenane and 4 »4 ^t -bie- (i) iiietbylaiiino) -bensophenone; or ljin- (1-Äntlimohinpnylamiiio) -authi "ehinone such as _1,4-t bending (1 -Authraohinonylamino) -anthracoition and 1.5-bis ~ (1-lnthracliinonylamino) -antbrachiiion and their loabinatlonen. Other useful sensitizers include polynuclear quinones such as xanthone, 1,2-bena-anthraohinoii, and 2-methylanthraohinone; mononuclear quinones such as 2,5-biphenyX-p-ohinone; aromatic QC -pilcetones such as Beneil; substituted ArjlioethylQndiojqr7erbindungen _y as Piperoi | _f Piperoin al, 3 * 4 ~ Methylendioxycüaloon and 5,6-Methylendioxyhydrindon-1; substituted ß-laphthoseldnaitollne, such as 1-methyl-2-acetylmöthYl © n-ß-Baphthosel «naisol in; eubet ituted ß-Benz ülazollnö, such as J-Mp + hyl- E-benaoylaethjlenbenaothiasolia; Substituted a ifepi ^ othiasolin ©, such as I-methyl-2-benzoylmethylene-β-naphthothiazoline; Groups of anthrons, such as anthron itself; Benzanthrones, such as lten £ - ~ 2-etnylbens ~ anthron and 7-H-bena (de) - * nthra «erj 7- ^ott * f, and Aeabensanthrones, such as 2-keto-3Houthyl <~ 1 _f 3-dlassabeniianthron»

You Consentration of the Sensitizer ^ in the by Lioht polymerizable border setting depends on the lightness inherent in the irernettable acrylic ester resin that is present. -Aensitivity from. In a typical pail where the Bora a.u8 consists of the prepolymer of diallyl ophthalate, will use about 1 to 20, preferably 1 * 5 on prepolymer of 1,4-bis »{1-Anthraquinonylaaino) -

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anthraohlnon recommended · Some sensitizers, such as PtP'-substituted beneophenones, such as 4,4'-bis- (Dl »ethTlamino) -beneophonon ₉ cause an amount of less than 1.5 ^ a considerable increase in the sensitivity to actinic Lioht. The sensitizer is excited by the internal radiation, which in turn initiates the polymerization. It has been assumed that the reaction takes place in such a way that the sensitizer breaks down into free radicals through the airborne radiation or the energy it has absorbed, and the resulting free radicals initiate the decomposition of the prepolymer so that it becomes insoluble.

The addition of the sensitizer to the allyl prepolymers increases their reactivity to actinic radiation 100- to 200-fold «Polymerize at the bake the films fast enough that they can be used in conventional plate-making processes

Pie use dee prepolymers that start at around $ 2 to $ 3 Monomer is essentially free of this "guaranteed, dafi the photosensitive coating as soon as it is free of solvent that is used to apply as 711m, is non-sticky and during taring and the transfer to the non-hollow state of the prepolymer does not shrink when exposed to actual radiation, so that one can get a true reproduction from paintings and the like.

Metals such as steel and aluminum in the form of plates, Sheet metal, pollen, films and the like, as well as various, film-forming synthetic resins or high polymers are used, such as the polymers of Vinylohloride, Styren, Isobutylen ·, AJuyl ·

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nitrile «polyethylene», the fexephtlmlJite and 2oljfeaiat · Seefee * fillers or TemstMxiransflsmittel can be erweeted, if you deal with different modifications of the carrier material * Obtain · Examples of such additives are Oelluloßefaeera, such as such as cotton, cellulose acetate, viscose rayon and paper or glass and

The photosensitive coatings or coatings produced according to the invention are remarkably stable in storage for up to one year, and furthermore, because of the Use of a dry »curable resin as a light-sensitive layer easy to handle and transport · In addition, the high degree of solubility of the uncured areas of the image facilitates their removal without damage of the hardened image areas · The flattening is relatively easy to manufacture and there are no misleading legends Protective layers or pads as a carrier for the polymerizable composition are necessary, as is the case with the Sail when the polymerizable θ material is made from liquid monomers consists «The relief images produced with it have a high level of strength and have smooth and continuously sloping sides, which makes them superior to the previous liohtdruokplatten-with those by the sacked and Uncommon seldom the pressure whales are damaged can. In addition, in such relief images with a smooth bevel of the planks, the Xendens that printer swear bsw. Earbe accumulates, off or at least Globally guided to a minimum.

The invention is illustrated below with the aid of examples explained.

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Example 1

10Og dialiyl isophthalate prepolymer (trademark Dapon-H), 150 g pentoxone (4-methoxy-4-methylpentanone-2) _t 0.8 g Miehler's ketone »1.6 g benzil and 3.2 g xanthone are mixed thoroughly *, A homogeneous, viscous syrup is obtained, which is then applied to a flat sheet of aluminum, allowing it to flow apart so that a uniformly thick coating of about 1 ram (35 mils) results, with an edging formed in the edge of the plate which prevents the syrup from flowing over the sand of the plate. The plate is danaoh kept overnight at 40 ⁰ C to allow most of the solvent evaporates, whereafter it is heated in a vacuum furnace at a vacuum of about 740 mm / Hg further to a temperature of 50 ° 0 for complete removal of the solvent. After this treatment the coating is hard and dry and the measured thickness is about 1/4 mm (10 mils).

You plate comes with a charcoal sheet as he goes through a Model KE-40 H Flip-Over-Jump Plate Maker (NuArc Company, Inc., Chicago, St.) exposed a translucent negative. The exposure time is about 10 minutes. The development of the exposed plate consists in that it is sprayed with trichloroethane that dissolves the unexposed coating. The plate is then dried. Remains on the plate a hardened relief image that has been blackened baw. colored and conventionally used for printing can be"

Using the general procedure outlined in Example 1, the following photosensitive compositions are made and made relief plates from them, as described above

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Very praiseworthy, manufactured Example 2

1 »5 S allyl methacrylate prepolymer

2.5 S methyl isobutyl ketone

2.5 g cellosolve acetate 0.05 g benzil 0.01 g 4,4- '~' biö- (I ⁾ tinethylamlno) -t) eTi3ophenon.

DiQBQ fabrics are mixed together, with the nail heating a little H, until all the greats are loosened. The solution is then filtered, whereupon it is ready for use. For this light-sensitive composition, methyl cellosolve acetate is preferably used as the developer, although ketones such as methyl ethyl ketone or chlorinated solvents such as irichlorethylene can also be used.

Example 3

2.4 g prepolymer of a copolymer of a monoallyl disturbance of an unsaturated acid, such as allyl methacrylate with styrene, are dissolved in a mixture of 5.0 g of methyl isobutyl ketoa and 5.0 g of cellosolve acetate with gentle heating and stirring. Then 0.48 g of methyl ether from Beiusoin are added directly to the LöaungemÜtel-HarK- w solution and mixed until it is dissolved "Bach dem! Filter Is the composition ready for use

In the following further examples of coating changes are given «

Example 4

1.5 g diallylouccinate prepolymer 5.0 g methyl isoamyl köton

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0.04 g plperonal

0.02 g 4.4 ^t -bia- (l) lnitthyiJUiiiio) - beti * oph «w» _<

Example 5

1.5 g kiallyl maleate prepolymer 5.0 g of methyliaoaeyllcetoii 0.02 g 4,4'-1) ίΘ- (ΒΙηιβΐ ^ 1οΐι1ιιο) -1) θηΑορ1ι§ηοη.

Example 6 Example 7

1.5 g prepolymer of a copolymer το &

xnaleate with Metbylaethaorylat 5.0 g Celloaolve acetate 0.02 g 4.4 ^f -bis- (diethylamlno) ~ beiiaopaenon.

1.5 € prepolymer of a copolymer T <m ülyl

clrtnBiaat with styrene 2.0 g methyl isodiityl ketone 2.0 g xylene 1.0 g GelloBolveaoetat 0.05 g 2-keto-3-mQtbyl-1,3-diaBabenuanthroii _< ,

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Claims (1)

18154F7 Claims · Terfahren βατ production of an impression printing plate, by fekennaelohnet that a lioatempflndliobe layer Kit a) an edible allyl ether resin, the nan duroh polymer i oat ion a polymer is borne by addition Allyl esters contain many aliphatic, ethylenic unsaturated bonds, of which At least one run in an alkyl ester group, whereby this resin has a residual exposure and Soluble in a solvent, is solid at ambient temperature and shrinks very little when it is is worldly linked by actinic irradiation, and with b) a sensitive agent, the helmet absorbing actinic radiation at room temperature accelerates the polymerization of this polymer, whatever this Layer on the exposed areas is converted to the wrong state, Bunäohflt irradiated with actinic light through a picture template and then to remove the unhardened areas , this layer is developed, leaving a raised image polymerized therefrom, which forms the printing relief. 2 «Method according to claim 1, characterized in that« ekennieiobnet, d * 0 · 1η crosslinkable bars derived from diallyl phthalate are used 3. Method according to claim 1 or 2, characterized in that a mixture of this as a senslbilislerungsmttel Beneil, Wickler'ε ketone and xanthone is used 909830/0973 4. The method according to address 1 tile 3 »daduron characterized in that the liohtempXlndllche sole is aofgelixaent on a Huainiumiinterlage · 909830/0973