DE2255118A1 - RADIATIVE MASSES - Google Patents

Description

Patent attorneys

Dr, Ing.Waiter Abitz Dr. Dieter F. M ο rf Dr. Hans-A. ! Brauns 8 iViünelisn ti ο, PicjnzoncaiGrstr. 28.

SUN CHEMICAL CORPORATION

200 Park Avenue, New York, Ν.Ϊ. V.St.A.

Radiation-curable masses

The present invention relates to radiation curable hats, in particular it relates to radiation-curable compounds, thai thai a novel, light-sensitive accelerator.

The use of radiation-curable, ethylenically unsaturated, monomeric substances in coating compounds, printing inks, adhesives and. Like. is known. It is also known that Such monomeric substances are converted into polymers by the action of radiation and that they become more fluid polymerize when irradiated in the presence of a photoinitiator.

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The use of such radiation-curable materials in presensitized, photopolymer printing plates is disclosed, for example, in U.S. Patents 3,551,255, 3,551,246, 3,551,311 and 3,558 described. Although these plates have good health, chemical Durability and abrasion resistance, it has now been found that these properties are accelerated at the same time The curing rate can be improved because the mass is an organic, functional Compound of a metal of Group IV of the Periodic Table I of the elements is incorporated.

The compositions according to the invention generally contain

(1) at least one monomeric, ethylenically unsaturated Ester, (2) at least one photoinitiator and (3) at least one organic, functional compound of a metal Group IVA.

The ester (1) is a monomer or prepolymer; H. a dimer, trimer or other oligomer or a Mixture or a mixed polymer thereof and can generally be described as acrylic acid, methacrylic acid, itaconic acid and the like., Esters of an aliphatic, polyhydric alcohol, for example the di- and polyacrylates, the di- and polymethacrylates and the di- and polyitaconates of ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, Trimethylolethane, trimethylolpropane, butanediol, Pentaerythritol * dipentaerythritol, tripentaerythritol, other polypentaerythrites, sorbitol, d-mannitol, diols of unsaturated fatty acids and the like.

Typical compounds include (but this is not intended to be limiting List): trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, tetraethylene

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glycol methacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetrascrylate, Dipentaerytha pentaacrylate, Dipentaer; ythritol hexacrylate, Tripentaerythritol octoacrylate, pentaerythritol diDethacrylate, pentaerythritol trimethacrylate, dipentaerythrii dimethacrylate, Dipentaerythritol tetramethacrylate, tripentaerythritol dctamethacrylate, pentaerythritol diitaconate, Dipentaery thri t-tri si tacona t, Dip entaerythri-fc-p en tai tacona t, Dipentaerythritol hexaitaconate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1, J-butanediol dimethacrylate, 1,4-butanediol diitaconate, Sorbitol triacrylate, sorbitol tetraacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexacrylate and "the like. Mixtures and prepolymers thereof *

Photoinitiator (2) is any suitable initiator for radiation curing. Examples of suitable photoinitiators include the following: acyloins; Acyloin derivatives such as benzoin methyl ether, benzoin ethyl ether, desyl bromide, desyl chloride, desylamine and the like; Ketones such as benzophenone, acetophenone, ethyl methyl ketone, cyclopentanone, benzil, caproii, benzoylcyclobutanone, dioctylacetone and the like; substituted benzophenones, such as Michler's ¹ ketone and Ν, ΐί-dimethylaminobenzophenone; multi-core quinones such as benzoquinone and. Anthraquinone; substituted polychromatic quinones, halogenated, aliphatic, alicyclic and aromatic hydrocarbons and their mixtures in which the halogen can be chlorine, bromine, fluorine or iodine, and the like; and mixtures thereof. Examples of halogenated photoinitiators include polyhalogenated hydrocarbons such as polychlorinated triphenyls; polyfluorinated phenyls (EI duPont de Nemours & Co.) .; chlorinated rubbers such as Parlone (Hercules Inc.); Mixed polymers of vinyl chloride and vinyl isobutyl ether, such as Vino flex MP-400 (BASF Colors and Chemicals, Inc.); chlorinated aliphatic waxes such as Chlorowax 70 (Diamond Alkali, Inc.); Perchlorpentacyclodecane, such as

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Dechlorane " ¹ '(Hooker Chemical Co-); chlorinated paraffins, such as Chlorafin 40 (Hooker Chemical Co.) and Unichlor-? 0B'(Neville'ChemicalCo.); halogenated ^ polyolefins, such as chlorinated polyethylene and chlorinated polypropylene; Ilono- ur.d \ polychlorobenzenes; mono- and polybroinbenzene; mono- and (polychloroxylenes; mono- and polybromoxylenes; dichloi: maleic anhydride; 1- (chloro-2-methyl) naphthalene ¹ · 2,4-dimethylbenzene sulfonyl chloride; 1- Broni-3- ( ⁱ al ⁾ henoxypherioxy-benzene); 2-bromoethylmethyl ether; chlorendinic anhydride; chloromethylnaphthyl chloride; chlorraethylnaphthalen; betiügt generally about 99 'from 1 to about 10: 90 and vorzugsv; else about 95:. ^ to about 40 60.

The organic accelerator (3) is a compound of the formula

in which:

R., R ₂ and R _{v are} a halogen atom, e.g. B. chlorine, bromine or iodine; -OCH- ,; -OC ₀ H ₁ -; -OC ₀ IL ₁ OCH- ,; or -OOCCIL ,; where R ₀ and R- ,, when R- is a halogen atom, -CIL. and R ₇ , when R- and R _{2 are} halogen atoms, can be _{-CH 7;} R ₄ CH ₀ = CH-, CII ₂ = CHCIl ₀ -, CH ₂ = C (CH ^) COO (CH ₂ L-,

O \

N ^ V (CH ₂ ) ₂ - or OCH ₂ CHCII ₂ U (OH ₂ ) "-; and M Si, Ge, Sn /

or Pb.

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To. Examples of such compounds include (this enumeration should not be limiting): vinyltriacetoxysilane, Vinyl-tris- (2-methoxyethoxy) -silane, γ-methacryloxypropyl- «-

trimefhoxysilane, vinyl trichlorosilane, vinyltr-iethoxysilane, γ-glycidoxypropyltrimethoxysilane, ß- (J, 4-epoxycyclonexyl) -ethyltriinethoxysilane, methylvinyldichlorosilane, vinyltin-trichloride, dimethylchlorovinyltin chi ο rid, ^v inyl-gerir.aniu: trichloride, vinyl-lead triacetoxy and the like, and mixtures thereof.

The amount of accelerator (5) can range from about 0.1 to 50% by weight, based on the total mass, and is preferably about 0.50 to 50 % by weight.

The compositions, when used to make presensitized photopolymeric printing plates, are used as solutions in any of a variety of solvents such as esters, e.g. B. ethyl acetate or n-propyl acetate, aromatic hydrocarbons, e.g. B. benzene, toluene or xylene; Ketones, e.g. B. methyl ethyl ketone or methyl isobutyl ketone, and chlorinated solvents, e.g. B. Tetrachloro |

carbon or o-dichlorobenzene and the like, and mixtures ί

from it, applied. The amount of solvent used is generally up to about 3C %. I.

Also within the scope of the present invention is the addition of Piirbotofi'oii to the Mansoa to increase the pastoral care. ^c is.! rili-eit. Dorarti ^ e Sensibl- '■

lj.sator-i 'dyes, which in an amount of about 0.25%, i

based on the amount of substance in the batch, verv / endct r »

include substances such as dyes from Trip.heiiylmc l'.han- [

-type, e.g. B. Crystal Violet; Aliznringelb; Eo.'jingoIb; Erythrosine; Methyl orange; Mx; cbonsai; Xanthine-9-one; and d [-L.

Don Anfiä biion, bc ί those made by these masses custom v / it'd, can generally bokaniito modes f Iz ierungsiui ttc L ci.nvei. ¹ -

__ 5 _ I.

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become alive, ζ. B. Plasticizers; Wetting agent for the dye, such as dichloromethyl stearate and other chlorinated fatty acid esters; Leveling agents such as lanolin., Paraffin wax *! and natural waxes; and the like. Solohe modifiers are generally used in amounts up to about 5% by weight, preferably about 1%, based on the total weight of the approach.

The approaches can be in any known and appropriate manner. Way to be made. Variables which determine the drying speed of a radiation-curable mass include the nature of the substrate, the special components in the hat, the concentration of the photoinitiator, the thickness of the material, the nature and intensity of the radiation source and its distance from the material, the presence or absence of oxygen, as well as the temperature of the surrounding atmosphere. The irradiation can be carried out by any one or a combination of a variety of methods. For example, the composition can be exposed to nctinic light of any origin and type, provided the light source provides an effective amount of ultraviolet radiation, since actinic light activatable compositions generally have their maximum sensitivity in the range of about 1800 Å to 4000 #, and preferably from show about 2000 Å to 5000 α; it can be exposed to electron beams, Garnraa beams, and the like, and combinations of these sources. Suitable sources include (this list is not limiting) charcoal arcs, mercury vapor arcs, pulsating ionon lamps, fluorescent lamps: lamps with special ultraviolet light emitting phosphors, argon glow lamps, photographic and common use. Van dor Graaff accelerator and so wcibor.

The irradiation zones L mn, ·;. ·; be sufficient to be effective Dosage; to surrender .. The Bo ;; Ii rah lung can with any

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appropriate temperature take place; becomes most appropriate for practical reasons irradiate at room temperature. the Distances of the radiation source from the workpiece can be from about 2.54 cm (1 inch) to 1.829 m (6 feet) and preferential rates range from about seven inches to four feet.

The compositions according to the invention, when they have been cured by radiation, are dry, flexible, and abrasion-resistant and resistant to chemicals; they also have excellent color receptivity, balance between hydrophilic and hydrophobic properties, point resolution and initial curl based on what they are particularly suited to Areas of application, such as presensitized stone printing plates and photoelectric resistors (photoresists) power. The masses are also used as binders for magnetic tape; Printing ink ^ Adhesives-for pollen, films, papers, (textile fabric e and the like; as coatings for metals, plastics, paper, wood, foils, textiles, glass * cardboard, cardboard and the like; as markings for streets, parking lots, airfields and similar areas; etc useful.

When used as a carrier for inks, e.g. B. ' Printing inks, the masses can be any of a variety of conventional organic or inorganic pigments, z. B. molybclator orange, titanium white, chrome yellow, phthalocyanine blue and carbon black, pigmented, as well as being hardened with dyes in conventional amounts. For example, the Carrier in an amount from about 20 to 99> 9 weight% and the "dye In an amount of about 0.1 to 80% by weight, based on the entire mass, can be used.

Materials that can be printed on include paper, clay coated paper and cardboard. The compositions according to the invention are also suitable for the treatment of textiles, both natural and synthetic, for example in carriers for textile printing inks or for

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Special treatments for fabrics to make them water repellent Properties, oil and stain resistance, crease resistance, etc., useful

Are the radiation-curable substances according to the invention used as adhesives, at least one of the substrates must be.i. Use of ultraviolet light translucent or be permeable. If the radiation source is an electron beam or gamma radiation, must at least one of the substrates be able to let through electrons of high energy or Ganima radiation, and none the substrate is necessarily translucent. to typical layers include polymer-coated cellophane-on-polymer-coated cellophane films Polymer-coated cellophane-on-polypropylene, MyIar-on-one metallic material such as aluminum or copper, polypropylene-on-aluminum and the like.

The radiation curable haters of the present invention can for metal coatings and especially for metals that are to be subsequently printed / grounded. Glass and Plastics can also be printed or coated, and the coatings are conveniently made by rolling or spray applied. Pigmented coating systems can for various polyester and vinyl films; Glass; polymer covered cellophane; treated and untreated Polyethylene, for example in the form of disposable cups or bottles; treated and untreated polypropylene; and the like., can be used. Examples of metals that can be plated include press finish ("Sized") and non-press-smoothed tin plate.

Ph.otopo.iymerisiorbaren parts ,, which from the erfind.ungs'fjernäsBon fabrics include a carrier, e.g. B. a foil or a sheet, and a layer placed over it

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the radiation curable material described above. To suitable Substrates or substrates include metals, such as steel and aluminum plates; Sheets; and foils; and films or sheets made from various film-forming synthetic resins or Ilochpolymers, such as Addition polymers, and especially vinyl polymers, e.g. B. Vinyl chloride polymers; Vinylidene chloride polymers; Vinylidene chloride copolymers with vinyl chloride, vinyl acetate or acrylonitrile; and vinyl chloride copolymers with vinyl acetate or acrylonitrile; linear condensation polymers such as a polyester, e.g. B. polyethylene terephthalate; Polyamides, etc. put together. You can use fillers or reinforcing agents present in synthetic resin or polymer bases be. In addition, highly reflective substrates can be treated in such a way that they are exposed to ultraviolet light absorb, or it can be a light-absorbing layer be inserted between the base and the photopolymerizable layer.

Photopolymerizable parts can be made by selected proportions of the photopolymerizable layer of the photopolymerizable parts <* ^. be irradiated for a long time until addition polymerization to the desired depth the irradiated portions has ended. The non-irradiatedi " Portions of the layer are then removed, for example by means of solvents, which the monomer or prepolymer, but does not dissolve the polymer.

When used in photopolymerizable parts, the optimum dry coating thickness is the radiation-curable Mass about 5.08 to 10.16 u (0.2 to 0.4 mil). The flexibility decreases with increasing thickness of the film and so does the abrasion resistance with the thinness of the foils.

The use of these compounds has led to extremely rapid plate development, which only takes about J to ^L V minutes.

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When used as printing inks, coating compounds and Adhesive αϊ are the masses described here without volatile Solvents are used, and they have many advantages over conventional oleoresin and solvent type Associated colors and cover materials. The substrate does not need to be pretreated or prepared in any way. The use of volatile solvents and those associated with them The associated dangers and unpleasant smells are eliminated. The inks and coatings adhere excellently to the substrate after irradiation. They have a good shine and friction resistance and hold temperatures of about 1 ^ 0 C and from only about 20 G. The printed or coated Foils can be processed and rotated immediately after being exposed to the energy source.

The invention and its advantages are illustrated by the following Examples which illustrate the invention, but are not intended to limit it, can be better understood. In the examples Unless otherwise stated, the parts are parts by weight. If the component is solid at room temperature, it can Mixture, unless otherwise indicated, are heated to melt the solid constituent, but generally not above 100 ° C, or it can be mixed with others liquid components are used. The Atuosphere and temperature conditions were, unless otherwise noted, the environmental conditions.

Stone printing plates were produced in the following manner:

1. A grained with a brush ( "brucch-grained ¹¹⁾ aluminum plate (610 mm 686 mm χ χ 0.2286 mm; 24" χ 27 "χ 0.GÜ9") was horizontally for 1 minute in a 3% ίβοε Natrin. 'Sphofjphatbad immersed, lightly brushed to remove surface dust or a protective coating, taken out of the bath and dried in the air'.

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2. A solution of the radiation-curable compositions was applied as a coating on the aluminum plate to a thickness of 7.62 ja + 1.27 Ai (O.3 + O.O5 mil) according to any suitable

■ massive method, for example by casting, roller coating or spin applied. ·

3. The external aluminum plate was then dried.

4-. A Filra slide (or negative) was placed directly over the Cover placed on the plate.

5. The plate and the slide became a radiation source exposed so that the light fries through the light areas of the film but not the dark areas.

6. The plate is designed to remove the legible, non-image portion of the photosensitive coating, for example by dipping and rubbing it in 100% butyl carbitol for 3 minutes and then with 0.1% H ₇ PO for 30 seconds. was etched.

7 · A gum solution, e.g. B. water soluble gum arabicum, used so that those that do not have an image Areas of the plate have been protected from oxidation or other damage during handling.

8. The plate was then dried and placed on a commercial Press placed.

Examples 1 to J?

A. Each of the following masses were made, one at a time Printing plate processed and on a Taber abrasion bar Model 503 tested. The light source was on in either case Carbon arc and the plate was exposed 1,22 π (4 feet) apart for 4 minutes.

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Tabel

composition 1 example 5 4th 5 in pieces 10.0 2 10.0 10.0 10.0 Udder* 12.0 10.0 12.0 12.0 12.0 Pari on I'- ¹ } * 0.5 9.0 0.25 0.5 0.5 Miclilers' ketone * ^r - _ 1.25 - - Benzoin methyl ether 0.5 1.0 1.25 - Accelerator A * - 1.0 - 1.0 - Accelerator B * _ - _ - 0.5 Accelerator C * -

Crystal violet - 0.05

Ethyl acetate 92.0 84.0 98.0 94.0 92.0

Taber abrasive sewing machine; 575 300 550 525 575 Cycles to the Zer
disturbance 5.8 5.9 5.8 4th 4th Curing speed
time in minutes

* Ester - phenyl isocyanate modified penteerythritol triacrylate

Parlon P-5 - chlorinated polypropylene containing 65% chlorine from Hercules.

liichlers ¹ ketone - 4,4'-bis- (dimethylaraino) -benzcphenone.

Accelerator A - vinyl triacetoxysilane

Accelerator B - vinyl-tris- (2-methoxyethoxysilane)

Accelerator 0 - γ-Hethacryloxypropyltrimethoxysilane

In each case, the surface of the plate was dry, flexible, abrasion-resistant and chemical-resistant with excellent I'm water balance and excellent Point resolution and initial winding.

B. Under douse] bon abrasion conditions held a commercial Printing plate (Lydel company duPont) 30 cycles off until it was destroyed.

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C. For comparison purposes, the procedure of Examples 1 through 5 (A) was repeated except that in each Case the accelerator was omitted. The products were on the Taber abrasive machine in 175> I25i 135> 115 or 150 cycles destroyed. Slide products hardened in 4.1, 4.2, 4.1, 4.3 and 4.3 minutes, respectively. In addition, the adhesion of these products to the substrate and their chemical resistance were important less than the products of Examples 1 to

Be ISPI el 6

The procedure of Examples 1 to 5 was repeated with the modification that the compositions under the following conditions were exposed: for 30 seconds at a distance of 12.7 cm from a 100 watts / 2.54 cm (100 watts / inch) mercury vapor lamp; For 3 3/4 minutes at an interval of 1.83 m (6 feet) from a Triarc lamp; and for 2 1/2 minutes at a distance of 1.22 m from a pulse xenon light. The results were comparable.

Example 7

The procedure of Examples 1 and 2 was repeated with the modification that that instead of isocyanate-modified pentaerythritol triacrylate each of the following monomers was used: ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diitaconate, trimethylolethane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, Dipentaerythritol hexacrylate, tripentaerythritol octomethacrylate, Sorbitol · triacrylate and sorbitol tetraniethacrylate. The results were comparable.

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Example 8

The procedure of Example 1 was repeated with the modification that instead of Ilichler's ¹ ketone, each of the following photoinitiators was used: benzoin methyl ether, benzoin ethyl ether, desyl chloride, 2-bromo thy line ethyl ether, chlorenediric acid anhydride, hexachlorobenzene, benzil and benzophenone. The results were comparable.

Example 9

The procedure of Example 2 was followed with each of the following Accelerator instead of vinyltriacetoxysilane repeated: vinyltrichlorosilane, vinyltriäthoxysilan, y-meth ~ acryloxypropyltrimethoxysilane, ß- (3,4 ~ -epoxycyclohexyl) ~ ethyltrimethoxysilane, Vinyl zinii trichloride, vinyl germanium trichloride and vinyl lead triacetoxy. The results were comparable.

Beis piel 10

The procedure of Examples 1 through 5 was followed by each of the Subsequent solvents instead of ethyl acetate repeated: n-propyl acetate, toluene, xylene, methyl isobutyl ketone, Carbon tetrachloride and o-dichlorobenzene. The results were comparable.

At s ρ ie 1 11

The procedure of Example 2 was followed with each of the following I dye sensitizers instead of crystal violet repeats: malachite green, Victoria blue, rosebush ^ al, Eosin yellow and erythrosine. The results are comparable.

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Example 1 2

The method of operation of example 1 continues with the modification repeats that Vinoflex MP-400 (a mixed polymer made from Vinyl chloride and vinyl isobutyl ether) instead of Parlon P-5 was used. The results were comparable.

B ice PJ e l

A. The procedure of Example 1 was repeated except that 12.5 parts of Vinoflex HP-400 were used in place of the Parlon P-5 plus Michler's ¹ ketone. The results were comparable.

B. For comparison purposes, the operation of the section (A) repeated with the modification that the accelerator has been omitted. The product was that of the section (A) inferior in chemical resistance and adhesion to the substrate and was in 130 cycles on the Taber abrasive machine destroyed.

example

The procedure of Examples 1 to 5 was repeated with the modification that the carrier instead of aluminum in each case one of the following supports was: polyethylene plate, tinplate and Iiylai 'polyester film. The results are comparable.

I n s p e

The procedure of Examples 1 through 5 was modified with the modification repeats that the element was exposed in any of the following ways rather than through a negative: (a) through a Template and (b) by projecting an image. The results were comparable.

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B ice ρ i e 1 16

A laminate was produced from a polymer-coated cellophane film and an oriented polypropylene film with an intermediate mixture of the following components: 65 parts of pentaerythritol triacrylate, 35 parts of a polychlorinated triphenyl containing 60% by weight of chlorine (polychlorinated carbon fiber y \ & 3 from the company Jionsanto Chemical Co) and 0.5 part vinyl triacetoxysilane.

The laminate was removed. a distance of 12.7 c exposed with a 100 watt mercury vapor flask. A firm bond was achieved in 1.5 seconds.

B e i s ρ i el 17,

A red ink was made from 80 ° / Ό der Hasse of the example ^L \ without the Athylocetat and from 20 % Litbol-Iiubinrot-Pignent. A glass bottle printed with this ink was with a 100 watt ultraviolet lamp from a distance of 5 »08 cm exposed. The ink dried in 2 seconds. It exhibited excellent adhesion to glass and good l''ett and ~ jveib resistance.

B ο is ρ ie 1 18

E ¹ S was an ink · manufactured by, on a three-Valzenmühle 85% of Iiasse of Example 3 without the ethylacetate and 15 '/ o Benaidingolb were ground. The ink was run through an I-Liehlc press and printed on paper coated with it. The printed paper was from a distance of * \, h ^l \ cm with three 53.3 cm 2100 watt ultraviolet Latnpen belieh let. ]) The ink dried in 2 seconds and showed.; on (Υ \ {\\\ 'λ and Y / assea ^ best'-iridigkoit.

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Example 1 9

The procedure of Example 16 was followed with each of the following Repeated dyes instead of benzidine yellow: lithol ruby red, phthalocyanine blue, liuss, milori blue and Phthalocyanine green. The results were comparable.

Example 20

The procedures of Examples 16-19 were followed with the modification repeated that the samples, instead of being exposed to ultraviolet light, were on a conveyor belt under the beam of a Dynacote 200,000 volt electron enl ine ar-accelerator rs with a speed and in the case of a beam of rays that have been regulated so that a dose level of 0.5 megarads entered.

These systems provided resinous substances of varying degrees of hardness in 12.7 to 508u thick films with sticky surfaces.

Example 21

The procedures of Examples 16-19 were followed with the modification repeats that the samples, instead of being irradiated with ultraviolet light, are a combination of Ultraviolet light and electron radiation in a variety of arrays exposed to: ultraviolet light, then electron beams; Electron beam, then ultraviolet light; Ultraviolet light before and after the electron beam; Electron beams before and after ultraviolet irradiation; and simultaneous irradiation with electron beams and ultraviolet light. The results were comparable.

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Claims (12)

9678-AGS ^ November 10, 1972 patent claims e 1. Radiation-curable composition containing (a) at least an ester of an ethylenically unsaturated acid and a polyhydric alcohol, (b) at least one Photoinitiator and (c) at least one organic functional component Connection of a lie tails of group IV A. 2. Composition according to claim 1, characterized in that the ratio of the amount of ester to the amount of pliotoinitiator about 10 to 99: 1 to 90 and the amount of the compound (c) about 0.1 to 50% based on the weight of the total mass. J. Hasse according to claim 1 or 2, characterized in that the ratio of the ester amount to the amount of photoinitiator is about 40 to 95 · '5 to 60 and the amount of compound (c) is about 0.5 to 5 ^ι /' ° ·> to the weight of the entire mass. 4. Mass according to one of claims 1 to 3 »characterized in that that the ester is an acrylate, a methacrylate or an itaconate. 5. Composition according to one of claims 1 to 4, characterized in that that the organic functional compound (c) has the formula R ₁ . -MR ₀
4, 2 in which: M is Si, Ge, Sn or Pb, H .; Ro and R ₇ a halogen torn, -OCH-., -OGpH ₅ , -OC ₂ II ₄ OCH-, or 308821 / 1V46 «7255118 9678-ACS 43 -0OCCH ₇ , where R ₉ and R, can stand for -GH-, if. R. express. Signifies halogen atom, and where E, _{can stand for -CH 5} , when R. and Rp signify halogen atoms, and R ^, 7 \ (^ 2 ~ ^or 6. Composition according to claim 5 * characterized in that the Compound (c) is vinyl triacetoxysilane. 7 · mass according to claim 5? characterized in that the Compound (c) is vinyl tris (2-methoxyethoxy) silane. 8. Composition according to claim 5> characterized in that the Compound (c) is γ-methacryloxypropyltrimethoxysilane. 9 · Printing ink containing the mass according to one of the claims 1 to 8 and a dye. 10. Coating compositions containing the composition according to one of the Claims 1 to 8. 11. An adhesive containing the composition according to any one of claims 1 to 8. 12. Presensitized printing plate containing a carrier and a "cover out of hatred according to one of the Claims 1 to 8. 13 · Printing plate according to claim 12, characterized in that Dan.'; the coating mass etvja. 5.08 to 10.2 11 thick. 14 ·. "Ancestors for producing a printing plate, characterized in that that one (1) figuratively 'OJ se an element that - 19 - 309821 / i'uss BATH ORIGINAL 9673-ACS ? 255118 exposing a carrier and containing thereon the mass according to any one of claims 1 to 8 to a radiation source, whereby the mass hardens in the irradiated areas, and (2) the uncured register in the non-irradiated areas removed. - 20 - 309871