DE2204244C3 - Photopolymerizable recording material - Google Patents

Description

to form a) at least one at normal pressure above 100 ⁰ C boiling ethylenically unsaturated monomers which is capable, initiated via a free radical, is a chain-like propagating Additionspolymerisationspolymerisation a high polymer, and

b) a photoinitiator which produces free radicals and can be activated by actinic radiation and in amounts of 0.01 to 20.0% by weight, based on the total solids, in the Dispersion is present,

contains, as well as containing between the support and the photopolymerizable layer an intermediate layer of a hydrophilic, macromolecular organic colloid, characterized in that the intermediate layer contains a surface-active agent and has a layer weight of at least 1.0 mg / dm ² .

2. Use of the photopolymerizable recording material according to claim 1 for production of image-wise modified metal surfaces by diffusion etching.

3. Use of the photopolymerizable recording material according to claim 2 for the production of gravure forms.

The invention relates to a photopolymerizable recording material according to the preamble of the claim 1 and its use for the production of image-wise modified metal surfaces by diffusion etching.

It is known to carry out the photopolymerization in such a way that text and original images are reproduced as described in US Pat. No. 2,760,863. Such a method is used in practice, for example, for the production of relief printing forms by washing out non-polymerized areas. Thermal coating of non-polymerized areas, as described in US Pat. No. 3,060,025. is also possible. Usually, the known photopolymerizable mixtures are homogeneous mixtures in which the polymerizable monomer, the photo-initiator and the binder are all present in a single phase. In such a single-phase system, the polymerization reaction is known to be greatly inhibited by the presence of oxygen. It is therefore difficult to reproduce images with continuously running light values or color values by photopolymerization of homogeneous mixtures, probably due to the inhibiting effect of oxygen. It is also known to produce photographic layers for intaglio printing forms using a stripping film which is coated with a gelatin-silver halide emulsion by the process of US Pat. No. 2,993,792. This method and material have found widespread use in technology. However, the method of use involves several steps which include development and fixation of the exposed silver halide in liquid processing solutions and which must be carried out by a skilled person.

ίο It also does not require washing out exposed areas of the photographic layer with hot water to remove these areas from the surface to remove before the usual ferric chloride caustic solution is used.

In US-PS 3418 118 and in Belgian patent 7 15 520 heterogeneous, photopolymerizable mixtures are described which are subject to the inhibiting influence of oxygen wen, _D 'cr mentioned. These mixtures are applied to a support for the formation of both single-layer and multilayer recording materials which contain part of a color image-forming component and are suitable for the production of color images. It does not appear from these patents that similar mixtures containing no colored image-forming components can be used as high quality photographic layers for gravure forms and for printing forms for printed circuits and circuits, and that the application of these can be used

jo mixtures requires only a minimum of simple steps to carry out the process.

DE-OS 19 50 120J describes a photopolymerizable one Recording material, in particular for the production of gravure printing plates, with a layer carrier

J5 ger and this adjoining layer from one heterogeneous, photopolymerizable mixture with a dispersion medium made of a hydrophilic, macromolecular, organic polymers and a dispersed phase. This dispersed phase consists of:

a) at least one ethylenically unsaturated monomer boiling below 100 ° at normal pressure, that is capable of propagating in a chain-like manner via a chain-initiated, free radical Addition polymerization to a high polymer

^{4 <i} form and

b) a photoinitiator which produces free radicals and which can be activated by actinic radiation and which is in Amounts from 0.01 to 20% by weight, based on the total solids content, are present in the dispersion.

The material is characterized in that the The support can be separated from the heterogeneous, photopolymerizable layer and preferably is transparent to actinic radiation.

y; In Example 22 of DE-OS 19 50 120 is a Gelatin layer with a content of p-tert.-octylphenol described. However, this gel layer does not serve as an intermediate layer in the context of the present invention, because the gelatin layer is on the other side of the support and therefore has a different function fulfilled, which cannot be compared with the intermediate layer provided according to the invention. the Oeiatin layer from example 22 serves in particular as an antihalation layer which also has an un * to prevent the desired build-up of static charge on the substrate.

As a macromolecular, organic polymer Vep Preferably gelatin is used - the unsaturated one

Monomers is preferably pentaerythritol triacrylate and / or trimethylol propane triacrylate. The dispersed phase can also be triethylene glycol dicaprate and triethylene glycol dicaprylate contain. The photoinitiators are 9,10-phenanthrenequinone and 4,4'-bis-dimethylaminobenzophenone or mixtures of these initiators have proven successful. Good results have also been achieved with one Photo initiator, which is a lophine dimer that is made up consists of two lophine residues, which are connected to one another by a single covalent bond, in particular an ortho-chlorophenyW ^ -diphenylimidazolyl dimer.

While these materials have been found to be commercially useful, they have certain disadvantages. Turning antihalation \ s protective compounds to, these must either be incorporated into the photosensitive layer, the sensitometric effects associated occur, or placing them in a lying on the back Schich * under and must exhibit a certain loss of effectiveness accept. In addition, when transferring these materials to the surface to be etched and when stripping the substrate, special solvents, such as alcohol / water mixtures, and critical exposure conditions must often be used in order to achieve the best results. Another disadvantage of the materials described above is that the substrate can be easily peeled off the resist layer before exposure, while after exposure the adhesion of the substrate to the layer in the exposed areas of the material is much greater. As a result, it is difficult to peel the substrate from the resist layer after the material has been adhered to the surface to be etched without damaging the resist layer. This problem is of particular concern when water, the preferred liquid, is used to wet the surface to which the resist layer is being adhered.

The invention is based on the object of providing a photopolymerizable recording material To provide training of a heterogeneous diffusion-etching resource that is simple and damage-free is transferable to the surface to be etched and with which the etching resist in simple and with can be produced in just a few steps.

The object is achieved by the measure according to claim I. The thus obtained photopolymerizable Recording material is particularly suitable for the production of imagewise modified metal surfaces by diffusion. especially for the production of gravure forms.

The invention achieves that the hydrophilic Colloid layer the photopolymerizable layer after exposure to actinic light Effectively prevents polymerization from adhering to the support. Suitable hydrophilic, macromolecular, organic colloids suitable for use in the hydrophilic colloidal layer are Gelatin, polyvinyl alcohol and polyvinylpyrrolidone, the hydrophilic layer can contain auxiliaries that make it make it possible to ensure additional effects. This way you can prevent halation protective dyes or pigments are present, as well as compounds that are capable of forming a through light to form evoked image-providing system for generating a visible image.

The layer of the hydrophilic, macromolecular, organic colloid should essentially contain additional be free of polymerizable ingredients.

For the production of image-wise modified metal surfaces, especially for the production of gravure printing forms using the recording material according to the invention, exposure is first carried out through a gravure screen and then through a template of an image with continuously running tonal values, >. and the formation of a resist image modified by photopolymerization, then transfers the surface of the Material on a water-damp surface to be etched, pulls off the layer support and etches the surface image-wise producing a deep pressure form surface.

A common solvent, for example iron (III) chloride, is used to etch the surface. the The etched surface can then be washed out, for example with the aqueous solution, to remove the residue the etching solution and the transferred, exposed layer to remove. This way of working can be done according to a variant can also be carried out in such a way that one can go through a transparent screen with the gravure screen Layer substrate exposed and then from the opposite side with a template of an image with continuous tone values. The material can also adhere to the surface to be etched and peeled off the top of the support before the imagewise exposure.

The support used for the manufacture of the materials of the invention preferably consists of one Polyäthylenterephthaiatbahn, the biaxially stretched, in the Heat made dimensionally stable and relaxed in the heat. This support is not a surface treatment subjected and not provided with an adhesive layer on which the photopolymerizable Layer is applied. However, layers can be used which have a surface exposed to electrical discharges in the manner described in US Pat. No. 2,113,208 or as in US-PS 3145 242 Deschrieoen with a Air propane flame have been treated. Hydrophobic films have also proven useful as a layer carrier organic polymers, e.g. B. from intralinear polyesters and cellulose esters, such as cellulose acetate smooth, non-porous, water-impermeable paper, as it is used in photography as a layer carrier also possible as a layer carrier.

The hydrophilic organic colloid layer in the materials of the invention is preferably freely permeable to the etching solution used to etch the intaglio images. This permeability can be achieved by forming a suitable thin hydrophilic colloid layer or by incorporating suitable plasticizers, for example nonionic surface-active substances, into the hydrophilic layer. For layers containing these small amounts of a surface-active agent for perfect application, a layer weight range of 1.0 mg / dm * to 26 mg / dm ^{2 has} proven particularly useful. A relatively thick hydrophilic layer can be used in a material of the invention and removed from the photopolymerized resist layer by washing with water after it has been applied to the area to be etched and the substrate has been peeled off. Such a layer, however, corresponds to a non-preferred embodiment of the invention, since it requires a special operation during use. To effectively do that

Clinging the exposed. To prevent resists on the substrate, the hydrophilic layer must be thick enough to treat its structure when it is overlaid with the photoresist layer. The layer preferably has a layer weight of at least 1.0 mg / dm ² .

In the coating solution of the colloid is a suitable surfactant incorporated so that the solution hits the surface of the support uniformly wetted The choice of agent depends somewhat on the particular type of colloid that is on the substrate is applied, but presents no difficulties for the person skilled in the art. If the substrate exists made of polyethylene terephthalate, phosphate esters have proven particularly useful, the long chains of Have ethoxy groups, which carry an alkylphenoxy group at the end, also sodium or Potassium salts of alkyl sulfates containing 8-20 carbon atoms and saponin.

Although the hydrophilic, organic colloid considerably facilitates the removal of the layer support from the resist layer after the latter has been transferred to the surface to be etched, the hydrophilic layer can also perform other functions. One or more finely divided antihalation dyes and / or pigments can be incorporated into the layer in order to ensure both antihalation and protective filter properties in the layer. A layer containing these finely divided substances adsorbs image-providing actinic radiation which passes through the light-sensitive layer of the material so that it is not reflected into the light-sensitive layer to deteriorate the sharpness of the image. After the material has been transferred to the surface to be etched and the support has been removed, such a layer also prevents scattered radiation of the actinic light when it reaches the photosensitive layer. This property makes it possible to keep a surface with adhering resist for some time under normal spatial conditions without damage.

The applied antihalation protective and filtering compounds have been chosen to absorb the radiation causing the polymerization the photopolymerizable layer will initiate. For general photoresist layers used for ultraviolet Sensitive to light, dyes such as C. 1. Solvent Yellow 47 and C. I. Disperse Yellow 5 have proven to be very good proven.

The hydrophilic layer can also contain compounds which, alone or in combination, produce a visible image when they contain actinic light. Such a visible image is useful for identifying exposed samples and for properly fitting the resist onto the area to be etched. Any image-forming system having a photosensitivity comparable to that of the photopolymerizable layer can be employed. A particularly preferred image-providing system consists of a combination of a hexaarylbiimidazolyl compound with a leuco dye; the combinations described in US Pat. No. M 45,234 have proven particularly useful.

To prepare a preferred photopolymerizable dispersion and layer, an aqueous solution or dispersion of a macromolecular organic polymer, e.g. B. an aqueous gelatin solution, untor high Scherwirkur.g stirred during the addition of a non-aqueous phase or oil phase, which consists of a solution of at least one addition polymerizable monomer or polymerizable polymer and a photoinitiator in an organic solvent, e.g. B. Ethyl acetate. In order to obtain good dispersions of photopolymerizable droplets, effective surfactants should be present. The surfactant can be mixed with the aqueous gelatin solution. A single addition polymerizable monomer, e.g. B. pentaerythritol triacrylate is generally sufficient, but a combination of monomers can also be used. Polymerizable polymers containing a linear carbon backbone with extralinear terminal ethylenically unsaturated groups, such as those described in US Pat. Nos. 3,418,295 and 3,448,089, can also be used. Further agents can be added to the layer mixture in order to control the properties during layer formation and / or the mechanism of photopolymerization, e.g. 8. Crosslinking agents such as N, N'-M. ethylene-bis-acrylamide and diacetor.acrylamide; additional binding agent! B. polyacrylamide, plasticizers, e.g. B. glycerin. Furthermore, an inhibitor that prevents thermal polymerization, e.g. B. p-methoxyphenol can be used. Ethyl acetate is suitable as an organic solvent for the preparation of heterogeneous photopolymer systems because it has a low boiling point and can easily be removed before the application of the dispersion without the use of high temperatures which could damage the emulsion. It is also a good solvent for the oil phase. Ethyl acetate of the dispersion to 50 ⁰ C can be removed, for example by heating in a rotary evaporator.

The layers can also be drawn up without the use of a low-boiling solvent. In In these cases, the oil phase is dissolved in a water-miscible, high-boiling solvent such as 2-methoxyethanol. solved. The latter system works just as well as the provisional low boiling point, with Water immiscible solvent system and makes the measure of removing the low-boiling solvent by evaporation before application the dispersion layer superfluous. The size of the dispersed photopolymerizable droplets is between 0.1 and ΙΟμιτι. the greater part being one Has a diameter of about 0.5 μm. The evenness the dispersion is directly related to the length of time and the degree of mixing. Dyes to protect against halation and to color the image can also be added to the system.

The dispersions may be on the substrate films with a small laboratory Beschichtungsapparatu ^r at a temperature of about 35 ° C and about 73 m / min, can be applied. The layers are boiled to solidify by cooling and then dried at room temperature. The gelatin concentration of the layer mass directly determines the viscosity of the emulsion and thus indirectly the layer weight. The thickness of the phot polymerizable layers depends on the Ar ^{f of} the desired resist, it is, for. B. 0.0013 to 0.025 mm and more, preferably. Ö, ÖÖ5 to 0.018 mm. A 0.0003 to 0.0076 mm thick surface protective layer containing a surface active agent can be applied to the photopolymerizable layer.

The process for producing the gelatin relief as a resist image can be carried out in any conventional manner.

However, in contrast to the known methods, it is not necessary to use the unexposed To remove parts of the layer by washing before the support, e.g. B. the copper surface, with aqueous iron (III) chloride solutions is etched. A method in which the copying is expedient is made with the help of a copy frame, for example with a copier in which a Xenon lamp is used as a copy light.

Two exposures can be made on the photosensitive backing for conventional gravure forms will. First, a conventional gravure screen is copied onto the side, whereupon a negative or Positive original is applied with an image with continuously running tonal values. The grid can be applied to the surface of the photosensitive layer or through the transparent support on which the light-sensitive layer is applied, can be copied, VürüüSgcsciZt that no LiC ~ iiuiüi5Chüi25CmCni

has been applied to the back. Surprisingly, it was found that when copying the points are better formed by the layer support. The reason for this is that in this Method a desired improved wall shape is created during the etching.

The ratio of line to point width in the grid can be 1: 1, but this is by no means crucially important and can be varied. Copying in one operation is sufficient if that Image through which the layer is exposed is already a gravure halftone image.

After the exposures, the surface of the exposed layer is transferred to the area that is to be etched imagewise. The surface to be etched is moistened and the exposed layer transferred by placing the photopolymer layer on the base film with the layer side through a Hard rubber roller on the moistened surface, e.g. B. a copper plate is pressed. The one to be corrosive Surface must be cleaned well to remove any contamination how to remove grease and fog. In the case of a copper plate, the surface can be finished with a Solution of the following composition to be cleaned:

Glacial acetic acid
Sodium chloride
distilled water

50 ml
250 g
95OmI

45

After cleaning with this solution, the plate can be polished by rubbing it with damp Viennese lime rubbed off and rubbed off: is then dried. It is important that the surface does not repel water After the transfer, the carrier film is removed from the photopolymer layer by lifting one corner and the foil is peeled from the copper plate.

After removing the carrier film, an etching solution, e.g. B. iron (III) chloride from 41 to 42 Be on the surface of the resist layer for 25 to 35 minutes or until the required etching depth is reached The image is etched in direct proportion to the degree of hardening in the resist layer because that Ferric chloride diffuses through the gelatin at a rate that depends on the degree of hardness of the depends on the photosensitive layer The etching can also be done using several etching solutions, z. B. an etching solution of 44 Be for 44 min. And then an etching solution of 40 Βέ for a duration of 5 minutes.

50

55

60

65 After the end of the etching, the copper plate is rinsed with hot water in order to interrupt the action of the etching solution and to remove the remaining gel layer.

The photopolymerizable layer can be exposed using the following methods:

A. Exposure of the layer through an overlay Gravure raster and danfi through an overlay image with continuous tonal values.

B. Exposure of the layer through a gravure screen which is in contact with the substrate. and then through an image with continuous tone values that is made with the photopolymerizable Layer is in contact.

C. Exposure of the layer through a calf tone image.

D. Exposure of the layer through a halftone image and through an image mn continuously Tonal values.

Instead of gelatin as a binder in the dispersing medium, other natural or synthetic ones can also be used water-permeable, organic colloids are used as binders. Examples of such binders are water-permeable or water-soluble polyvinyl alcohol and its derivatives, e.g. B. partially hydrolyzed Polyvinyl acetates, polyvinyl ethers and acetyls, which contain a large number of extralinear - ChbCHOH groups contain hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable compounds such as maleic anhydride, acrylic and methacrylic acid ethyl esters and styrenes.

Suitable colloids of the latter type are described in U.S. Patents 2,276,322 and 2,276,323.

Suitable polyvinyl acetate are polyvinyl acetaldehyde acetal, Polyvinyl butyraldehyde acetal and polyvinyl sodium o-sulfobenzaldehyde acetal. Further colloids suitable as binders are the poly-N-vinyllactams described in US Pat. No. 2,495,918, which are described in US Pat US-PS 28 33 650 described hydrophilic copolymers of N-acrylamide alkyl betaines and hydrophilic Cellulose ethers and esters.

If a binder is to be added to the disperse phase, water-insoluble binders are suitable Polymers, e.g. B. methyl methacrylate resins, polyvinyl acetate such as polyvinyl butyral and polyvinyl formal, vinylidene chloride copolymers (e.g. vinylidene chloride-acetonitrile, Vinylidene chloride-methacrylate and vinylidene chloride-vinyl acetate copolymers), synthetic Rubbers (e.g. butadiene-acrylonitrile copolymers and chloro-2-butadiene-1,3 polymers); Cellulose ester (e.g. Cellulose acetate, cellulose acetosuccinate and cellulose acetate butyrate); Polyvinyl ester (e.g. polyvinyl acetoacrylate, Polyvinyl acetomethacrylate and polyvinyl acetate-polyvinyl chloride and mixed polymers (e.g. polyvinyl chloride acetates), polyurethanes and polystyrene. If materials of the type mentioned above are added to the disperse phases, they can be used as viscosity-modifying agents Means to be effective. For example, the viscosity of the droplets can be up to a point in the Close to the "threshold value" can be increased, causing an additional increase in viscosity due to polymerization cause a very noticeable change in certain physical or chemical properties.

Other suitable polymeric binders for the dispersed phase are disclosed in US Pat. No. 3,418,295 described. These unsaturated polymers can be crosslinked or grafted on by growing monomer chains become, whereby they have an increased physical

see effect, especially a stronger hardening of the effect dispersed droplets. A non-polymerizable plasticizer in an amount from 1 to 10 % By weight of the total solids, or in an even greater amount, can be in the organic phase of the photopolymerizable Dispersion can be used to improve photographic sensitivity. To the preferred plasticizers include the mixed ester voj? {"riethyleneglycol dicaprylate and dicaprate.

As ethylenically unsaturated compounds, which are initiated by free radicals, form a chain propagating addition polymerizatioa a high polymer able to form, one preferably uses alkylene or polyalkylene glycol diacrylates, which from an ethylene glycol with 1 to 15 carbon atoms or a polyalkylene ether glycol with 1 to 10 ether bonds have been prepared and the ethylenically unsaturated compounds described in US Pat. No. 2,927,022 are described, e.g. B. Connections with multiple

. uu: ι> -: _: ι

auuflluiMpuijltlciiaiui υαιυΐι

1,3-propaflodiol dimethacrylate,
1,2,4-butaniriol trimethacrylate,
l / f-cyclohexanediol diacrylate,
1,4-benzenediol dimethacrylate,
Pentaerythritol tetramethacrylate,
13-propanediol diacrylate,
1,5-pentanediol dimethacrylate,

the bisacrylates and methacrylates of polyethylene glycols from molecular weight 200 to 500, vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate and Divi-ethyl terephthalate, styrene and its derivatives and unsaturated aldehydes, e.g. B. Sorbaldehyde (hexadienal). An outstanding class of these preferred addition polymerizable components are the esters of α-methylenecarboxylic acids and substituted carboxylic acids with polyols and polyamides, in which the molecular chains between the hydroxyl groups and Amino groups made up exclusively of carbon or

C l _n

especially if these are present as terminal bonds, and in particular ethylenically unsaturated Compounds in which at least one, preferably most of these bonds with a double bonded carbon atom including a carbon atom that doubles on carbon and on Heteroatoms, such as nitrogen, oxygen and sulfur, are bonded, are conjugated. Are particularly advantageous Materials in which the ethylenically unsaturated groups, especially the vinylidene groups, with Ester structures are conjugated. The following special. * Compounds further illustrate this class: Unsaturated esters of alcohols, preferably the unsaturated esters of polyols, especially esters the <x-methylenecarboxylic acids, e.g. B.

Ethylene glycol diacrylate, diethylene glycol diacrylate,
Glycerine diacrylate, glycerine triacrylate,
Ethylene glycol dimethacrylate,

Preferred monomeric compounds are difunctional ones Monomers, however, monofunctional monomers can also be used. Also can the polymerizable, ethylenically unsaturated polymers, described in U.S. Patents 3,043,805 and 29 29,710, and similar materials alone or in Mixture with other materials can be used.

In addition to the initiator systems described above, cyanine, carbocyanine or merocyanine dyes can be used can be used as materials capable of absorbing actinic radiation. The different Cyanine dyes and related dyes have been known in photography for many years. These include dyes such as 3-ethyl-5- (2-ethyl-lbenzoxazyIiden-0-methylethylidene) -2-thio-2,4- (3,5) -ox- azoldione (prepared in the manner described in Example 16 of US Pat. No. 2,272,163) and dyes of the following formulas:

1 ^Θ

C ₂ H ₅

CH ₃

C ₂ H ₅

Ι ^θ

Suitable photo-reducible dyes of the foregoing have recently been disclosed in U.S. Patents 28 50 445 and 28 75 047.

Combinations of one or more of the aforementioned dyes are also suitable Quinone compounds, e.g. B. phenanthrenequinone in combination with that according to Example 16 of US-PS 22 72163 produced dye. Other suitable compounds that absorb actinic radiation are the addition polymerization initiators that form free radicals and actinic light can be activated and are thermally inactive at or below 185 ° C. These include the substituted or unsubstituted polynuclear quinones, d. H. Compounds with two intracyclic carbonyl groups attached to intracyclic C atoms are bound in a conjugated carbocyclic Rihgsystem. Examples of suitable initiators are of this type

Q JG -, ^ *> * J * rschinon 1 "Chiorsnthrschinon 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone,

2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone,

1,4-dimethylanthraquinone,

2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,

the sodium salt of anthraquinones sulfonic acid, 3-chloro-2-methylanthraquinone, retenquinone, 7,8,9,10-tetrahydronaphthacenquinone and 1,2,3,4-tetrahydrobenz (a) anthracene-7,12-dione.

More photoinitiators are also suitable, although some of them run at temperatures down to Can be thermally active 85 ° C, are described in US Pat. No. 2,760,863. These include vicinal ketaldonyl compounds, z. B. diacetyl, benzil, "-Ketaldonylalkohole such as benzoin, pivaloin, acyloin ethers, e.g. B. Benzoin methyl and ethyl ether, «-kohlenwasserstoffubstituierte aromatic acyloins including Λ-methylbenzoin, α-allylbenzoin and -phenylbenzoin.

Other suitable initiator systems in the photopolymerizable dispersions and materials can be used according to the invention, the lophine dimers (2,4,5-triphenylimidazolyldimers), which consist of two lophine radicals linked together by a single covalent bond are e.g. B. the 2 (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and others described in GB-PS 9 97 396 and 0 47 569. Suitable electron donors, which form free radicals and can be used in these systems, e.g. B. organic amines, Mercaptans, triphenylmethane dyes, are described in the aforementioned British patents. Suitable amine-substituted leuco dyes, both as color formers and as free radicals forming agent can be used in the recording materials according to the invention will. Particularly advantageous leuco dyes contain at least one dialkylamino group. Furthermore can any amine-substituted leukotriphenylmethane dyes or various salts of the dyes be used. Leuco forms of crystal violetc that form visible upon exposure Images are oxidized are preferred. Other suitable leuco dyes or their salts are in the US Pat. No. 3,549,367.

Since the recording materials according to the invention are used in a photopolymerization process they should of course be resistant to thermally initiated polymerization. As inhibitors thermal polymerization, which can be used in photopolymerizable mixtures, p-methoxyphenol, hydroquinone and alkyl and aryl-substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol, copper resinate, naphthylamines, ^ -Naphthol, copper chloride, 2,6-di-tert.-butylp-cresol, Phenothiazine, pyridine. Nitrobenzene and Dinitrobenzol as well as p-ToIuchinon and Chloranil and Thiazine dyes, C.I. Basic Blue 25, C.I. Basic Blue 9, and C.I. Basic Blue 17. Among the most preferred Embodiments containing certain dyes as photoinitiators or photoinitiators of the quinone type, however, no thermal inhibitor is required because

* t A \ nr-n Initintnpan Airtn / Jrtnrwaltn Ci art L · (U _n K ο War » ttnA irr»

Dark as thermal inhibitors are effective.

There are free radical initiators of addition polymerization that can be activated by actinic radiation The radiation source should generally have its maximum sensitivity in the ultraviolet range usually emit an effective amount of this radiation. Carbon arc lamps are suitable as radiation sources, Mercury vapor lamps, fluorescent lamps with fluorescent materials that emit UV radiation.

Argon incandescent lamps, electronic flash lamps and photo flood lamps.

The generation of the image by exposure of a heterogeneous system according to the invention is based on the different polymerization of the individual droplets in the dispersed phase. Those differences can make the image visible without further treatment, d. H. a visible relief image is often created. Preferably, a surfactant is used in dispersing the droplets, however this is not essential. Suitable surfactants are alkylnaphthalenesulfonic acid, organic Phosphoric acid esters, benzyl alcohol, octyl alcohol, lauryl alcohol. Sodium Laurel Sulphate. sulfonated derivatives of fatty acid amides, the condensation products of octylphenol and sorbitan monolaurate with polyethylene oxide.

Other suitable low-boiling solvents that are immiscible with water are esters (e.g. Ethyl formate, propyl acetate, n-butyl acetate and ethyl butyrate), hydrocarbons (e.g. benzil), chlorinated Hydrocarbons (e.g. chloroform and methylene chloride) and ethers (e.g. diethyl ether).

The invention is illustrated in the following examples

example 1

A gelatin solution was prepared as shown below. 18 g of gelatin in 725 ml given cold water and left to swell. The solution was heated to 35 °, 0.5 g of nonylphenoxypolyethoxyphosphate added as a surfactant and the solution mixed for 3 min. In a mixer that was equipped with a high-speed agitator. The gelatin solution was then cut to a 0.18 mm thick, No adhesive layer having a web of polyalkylene terephthalate applied, which on the back a Antihalation layer, at a temperature of 35 ° C at a rate of

7.62 m / min. Then with warm air to form a gelatin layer about 0.0025 mm thick.

A photopolymerizable dispersion was now prepared as follows:

Solution a

Gelatin 18 g

Water 250 ml

Solution b

Water 75 ml

Nonylphenoxypolyethoxyphosphate 0.5 g

10% solution of saponin in

Alcohol / water 3 ml

Yellow dye

(C.I. Pigment Yellow 74)

(22% aqueous dispersion with 6%

Nonylphenoxypolyethoxyethanol) 1 g

Solution Γ

Mi hylene chloride 25 ml

2- (o-Chlorophenyl) -4,5-diphenylimidazolyl dimer 3 g

Tris- (4-diethyIamino-o-tolyi) methane 1.5 g

Leuco crystal violet 0.3 g

Trimethylolpropane triacrylate 12 g

Mixture of the esters of ocia and
Decacarboxylic acid with triethylene glycol 2 g

Polyvinyl pyrrolidone
(Average molecular weight: 40,000;
25% solution in methylene chloride 0.75 g

Solution in methylene chloride were added to the gelatin solution while it was running at high speed running mixer was carried out. Using this solution, the procedure was analogous to Example 1 instead of the solution used there for the lower layer, a material was produced; this became accordingly Example 1 exposed and, as described there, a copper plate using the material of this Etched for example. A gravure pattern of the gravure screen was etched into the surface of the copper plate been.

Example 3

Example 2 was repeated with the exception that

! 5 a protective layer of the same composition as she had the lower layer, over which the photosensitive layer was applied by skimming off at a temperature of 35 ° C and a speed of 7.62 m / min, coated and with warm air was dried. The material was exposed and further treated as in Example 2. In the A gravure pattern of the gravure screen was etched into the surface of the copper plate.

Solution A was heated to 35 ° C and placed in an intensive mixer, Solutions B and C became added in succession and the mixture mixed for 2 minutes, after which it was heated again to 35 °. The present mixture was wiped at a temperature of 35 ° C and a coating speed of 7.62 m / min, over the gelatin layer _ "_" [.: "!,.; .. sb ~ c! iühlt and with - / srmcr air unisr Formation of a 0.01 mm thick layer dried.

A sample of the material was exposed to an ultraviolet light source (mercury vapor lamp) exposed through a gravure screen at a distance of 66 cm for 2 minutes. The exposed sample was then transferred to a water-moistened copper plate by pushing the laminate through the gap cold rubber rollers, with a pressure of 535.7 kg / m and a speed of 1.83 m / min, was adhered to. The support was then made leaving the resist on the copper surface deducted. The copper with applied resist was mixed with an aqueous ferric chloride solution of 42 ° Be etched for 20 min. And the resist from the copper plate by washing with hot water removed A gravure pattern of the gravure screen had been etched into the surface of the copper plate.

Example 2

A coating solution was prepared as described in Example 1, except that 3 g of one Containing 25% by weight polyvinylpyrrolidone having an average molecular weight of 40,000

Example 4

Solution a

Dye (C.I. Solvent Yellow 47) 2 g

Dye (C. 1.21 230) 2 g

Ethanol 60 ml

Solution b

Gelatin 18 g

Water 300 ml

Solution C

Water 100 ml

Nonylphenoxypolyethoxyphosphate 0.2 g

Solution D

Mixture of triethylene glycol esters of octa and

Decacarboxylic acid 3 g

Polyvinylpyrrnlidnn
(Average molecular weight: 40,000;

25% solution in methylene chloride 3 g

Methylene chloride 25 ml

Solutions A, B, C and D were crushed for 30 minutes in a high-speed grinder? mill mixed. The emulsion obtained was smeared onto a 0.18 mm thick, non-adhesive layer having a sheet of polyethylene terephthalate at a speed of 3.05 m / min, coated, cooled and dried in warm air to form a layer thickness of about 0.004 mm.

A heterogeneous photopolymerizable emulsion similar to that of Example 1 with the following was obtained Composition made:

Aqueous phase

Gelatin 18 g

Sodium salt of technical grade octyl alcohol sulfate 3 ml

10% solution of saponin
in alcohol / water 3 ml

Nonylphenoxypolyethoxyphosphate 0.5 g

Water 325 ml

Organic phase
Methylene chloride
Trimethylol propane triacrylate
Mixture of the triethylene glycol esters of the octa and J the
Decacarboxylic acid
2- (o-chloro-4,5-diphenylimidazolyl dimer
Tris (4-diethylamino-o-toyl) methane

Leuco crystal violet
CI Solvent Yellow 47 dye
Dye CL 1.21 230
Polyvinyl pyrrolidone
(Average molecular weight: 40,000;
25% solution in methylene chloride)

22 u4 244

25 ml
12 g

2g
3g

50 mg
50 mg

3g

The photosensitive layer was produced and used up as described in Example 1. A sample of the material produced in this way was exposed for 1 minute through a conventional gravure screen with the aid of the light source specified in Example 1 and then a 1/2 step wedge with an exposure time of seconds Copied on with the same light source The exposed resist was transferred to a copper plate in accordance with Example 1, the layer carrier peeled off and d ^; The plate was etched for 30 min. at 22 ° C in a ferric chloride solution of .43 ° Βέ The resist was removed by washing with hot water , 6 emerged.

Another sample was treated in the same way except that after the transfer of the Resists on the copper and before the then present material was subjected to the etching, this 9 hours. at a distance of 0.61 m with a desk white light fluorescent lamp was exposed. After the etching, there could be no difference between this sample and that one Sample that had not received any post-exposure to white light.

Example 5
Three solutions were made:

Solution a
gelatin
water

Solution b
water

Nonyiphenoxy polyethoxy phosphate
yellow dye
(CI Pigment Yellow 74)
(22% aqueous dispersion with
6% nonylphenoxypolyethoxyethanol)

Solution C

Mixture of triethylene glycol esters of octane 'and decanoic acid
2- (o'Chlor) -4,5'diphenyl
imidazolyl dimers
LeukökfiställviöIeU

18 g
375 ml

75 ml
0.5 g

3 g

Polyvinyl pyrrolidone 4g P. (average molecular 25 ml Ϊ weight: 40 000; 1 Solution containing 25% by weight in Methylene chloride) I. Methylene chloride

Solutions A, B and C were mixed in a mixer at high speed for 2 minutes and the Dispersion with wiping at a temperature of 35 ° onto a 0.18 mm thick, no adhesive layer comprising polyethylene terephthalate web at a coating speed of 4.57 m / min, coated, chilled and air dried

A photopolymerizable resist layer was made as follows manufactured:

Solution D

Gelatin 18 g

Water 250 ml

Solution E

Water 75 ml

Nonyiphenoxy polyethoxy phosphate 0.5 g

Yellow dye

(C I. Pigment Yellow 74)

(22% aqueous dispersion with 6% NonyIphenoxvpoIyäthoxyäthanol) 1.0 g

Solution F.

2- (o-Chlorophenyl) -4,5-bis- (m-methoxyphenylj-imidazolyldimers
2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer 1.5 g

Tris (4-diethylamino-o-tolyl) methane 1.5 g

Hydroquinone 5 mg

Trimethylolpropane triacrylate 12 g

Mixture of triethylene glycol esters of octanoic and decanoic acids 3 g

Polyvinyl pyrrolidone
(Average molecular weight: 40,000;

25% solution in methylene chloride) 3 g

Methylene chloride 25 ml

The three solutions were mixed in a high-speed mixer for 2 min. And at a temperature of 35 ° C and a coating speed of 4.57 m / min, over the light adhesion control layer applied, cooled and dried with warm air.

A gravure screen with the light source of Example 1 at a distance of 1.5 m and an exposure time of 2 minutes and then a 1/2 step wedge with an exposure time of 1 minute was copied onto a sample of the material. The sample was used to etch a copper plate as in Example 4 / with the exception that it was etched for 26 minutes. A gravure image showing 9 steps from an optical density of 03 to 1.65 was obtained on the surface of the copper plate.

There were three Example 6 18g I. Solution a Solutions made: 3Ö0ml ff * E "Gelatin 130 208/98 1 1.2 g water S. ig M.
■ |

Solution b
water
Nonylphenoxy polyethoxy phosphate

Solution C

2- (o-Chlorophenyl) -4,5-bis- (m-methoxyphenyl) -imidazolyl dimeric leuco crystal violet
Dye CI. Disperse Yellow 5 Mixture of triethylene glycol esters of octa- and deeacarboxylic acid polyvinylpyrrolidone
(Average molecular weight: 40,000;

25% by weight solution in methylene chloride)
Methylene chloride

As in Example 5, the three solutions were mixed with one another and, as indicated there, coated at a coating speed of 7.62 m / min. The solution of Example 5 covering the photosensitive layer was coated over the hydrophilic colloid layer as indicated there. A customary gravure screen was copied onto a sample of the material produced in this way, exposure to the light source indicated in Example 1 for 3 minutes at a distance of 1.5 m became. Then, with an exposure time of 1 minute, a / Z-step key was copied on. Analogously to Example 4, the sample was used to etch a copper plate with the exception that it was etched for 42 minutes with an iron (1H) chloride solution of 43 % Be. On the copper plate 10 levels of \ 2-step wedge were reproduced as gravure picture

Example 7

Solution D

ml gelatin 10 g

0.5 g of water 250 ml

Solution E

Water 75 ml

Nonylphenoxypolyethoxyphosphate 0.5 g

Yellow dye

(C I. Pigment Yellow 74)
ίο (22% aqueous dispersion with

6% nonylphenoxypolyethoxyethanol 1.0 g

Solution F.

2- (o-Chlorophenyl) -4,5-bis (m-methoxyphenylj-imidazolyl dimers 1.5 g

2- (o-chlorophenyl) -4,5-diphenylimide-

azolyl dimers 1.5 g

Tris- (4-diethylamino-o-tolyl) -

methane 1.5 g

Hydroquinone 5 mg

Trimethylolpropane triacrylate 15 g

Methylene chloride 25 ml

Polyvinyl pyrrolidone

(Average molecular weight: 40,000;

25% solution in methylene chloride) 3 g

1.0 g 3 g

5 g

4 g 25 ml

Three solutions were made:

Solution a

Gelatin 18 g

Polyacrylamide (molecular weight: 5,000,000-6,000,000) 0.5 g

Water 375 ml

Solution b

Water 75 ml

Nonylphenoxypolyethoxyphosphate 0.5 g

Yellow dye

(C.I. Pigment Yellow 74)

(22% aqueous dispersion with 6% nonylphenoxypolyethoxyethanol) 1.0 g

Solution C

Mixture of the triethylene glycol esters of octa- and deeacarboxylic acid 5 g 2 (o-chlorophenyl) -4,5-diphenyl

imidazolyl dimer 1.0 g

Leuco crystal violet 0.5 g

Methylene chloride 25 ml

The solutions were mixed with one another for 2 minutes in a high-purity mixer and, at 35 ° and a coating speed of 4.57 m / min., Coated onto a polyethylene terephthalate web with no adhesive layer, with wiping, cooled and dried in warm air

Then the following solutions were made:

Solutions D, E and F were mixed with one another in a high-speed mixer for 2 min

jo and a coating speed of 7.62 m / min with wiping over the previously applied gelatin layer, cooled and dried in warm air
A conventional intaglio screen was copied onto a sample of the material using the light source of Example 1. Exposure was carried out at a distance of 1.5 m for an exposure time of 3 minutes, after which a ½ step number was given for an exposure time of 1.5 minutes was copied. The material was

-to used to make a Kupferplat'.e according to Example 4 to etch with the exception that the etching away 44 min. Using a ferric chloride solution of 43.5 ° Be took place and 16 min. With a corresponding Solution of 38 ° Be. On the surface of the copper plate

4ϊ a gravure image of the step wedge was created.

Example 8 Three solutions were prepared as follows:

Solution a

Gelatin 18 g

Water 30OmI

Solution b

Water 100 ml

Nonylphenoxypolyethoxyphosphate 0.5 g

Sodium salt of technical

Octyl alcohol sulfate 3.0 ml

6ö) 0% solution of Saportiii in

Alcohol / water 3.0 ml

Solution C

2- (O'Chlorophenyl) "4 _i 5-bis (m ⁱ methoxyphenylj-imüdazolyldimeres 1.5g

Leuco crystal violet 1.0 g

Mixture of triethylene glycol esters dor Octa * and Decacarböflsäüf e 5.0 g

Methylene chloride

Dye (C, L Disperse Yellow 5) polyvinylpyrrolidone
(Average molecular weight: 40,000;
25% solution in methylene chloride)

25 ml 3.0 g

3.0 g

The solutions A ₁ B and C were mixed with one another in a high-speed mixer (2 min,), with skimming at 35 ° C and a coating speed of 4.57 m / min, coated on a polyethylene terephthalate sheet without an underlayer, cooled and with warm Air dried Three more solutions were made

Solution a

Gelatin 18 g

Water 300 ml

Solution b

Water 100 ml

Nonylphenoxypolyethoxyphosphate 04 g

Yellow dye

(C I. Pigment Yellow 74)

(22% aqueous dispersion with

6% nonylphenoxypolyethoxyethanol) 1.0 g Sodium salt of technical

Octyl alcohol sulfate 3.0 ml

10% solution of saponin in

Alcohol / water 3.0 ml

Solution C

2- (o-ChlorophenyI) -44-bis- (m-Metnoxyphenylj-imidazolyldimeres 14 g

2- (o-chlorophenyl) -43-diphenyl-imidazolyl dimers 13 g

Tris (4-diethylamino-o-toyl) methane 14 g

Trimethylolpropane triacrylate 12 g

Mixture of triethylene glycol esters of octa- and

Decacarboxylic acid 2.0 g

Methylene chloride 25 ml

Polyvinyl pyrrolidone
(Average molecular weight: 40,000;
25% solution in methylene chloride) 3.0 g

Solutions D, E and F were mixed together in a high speed mixer (2 min.), With wiping at 35 ° and a coating speed of 447 m / min, over the applied and dried lower layer piled up, cooled and dried

A sample of the material was exposed as described in Example 7 with the exception that the The step wedge was copied on with an exposure time of 2 minutes. The sample was as in Example 1 described, transferred to a copper plate, half of the picture with an opaque cover sheet covered and the whole thing at a distance of 0.61 m for 1 hour. exposed with a 40 watt fluorescent desk lamp. then the opaque shielding was removed and the resist-coated copper plate with an iron (III) · chloride solution at 44 ° B6 etched for 40 minutes. There was a Depression image on the surface of the Küpferplatte showing the steps of the foot wedge. Between Parts of the image that were covered with the opaque shield during post-exposure and those that

had not been covered, there was no difference.

Example 9

A 1% solution of high molecular weight polyvinyl alcohol was prepared and scraped off at room temperature and a speed of 9.14 m / min, on one not with an adhesive force equipped, 0.18 mm thick polyethylene terephthalate sheet, which has an antihalation layer on the back, after which it was dried with warm air at about 50 °. Dry density of the polyvinyl alcohol layer: 0.0013 to 0.0018 mm.

A photopolymerizable layer was applied over the polyvinyl alcohol layer Gravure resist emulsion corresponding to that of Example 8, with stroking at 35 "and a speed of 9.14 m / min cooled and dried with hot air at 50 °. The coating was 0.0076 mm thick.

A conventional intaglio printing form was copied onto a sample of the material thus produced using a carbon arc exposure device operating at 220 volts and 15 amps at a distance of 45.7 cm. Exposure time: 60 seconds. The exposed sample was laminated onto a copper plate moistened with water and the whole thing is the gap between a pair of rubber rollers guided. Pressure: 44.64 kg / m, speed: 1.83 m / min. Then the support was peeled off and the copper plate covered with resist in an iron (III) chloride solution of 453 Be at 23 ° C (234 min.) etched An intaglio image of the gravure screen was created on the surface of the copper plate.

Example 10
Two solutions were made:

Solution a

5% aqueous solution of

Polyvinyl alcohol with high

Molecular weight

Yellow dye

(C I. Pigment Yellow 74)

(22% aqueous dispersion with

6% nonylphenoxy polyethoxyethanol)

Solution b

Methylene chloride

2,2'-dihydroxy-4-methoxybenzo-

phenone

Mixture of ethylene glycol

esternderOcta and

Pecacarboxylic acid

400OmI

100 g

100 ml
40 g

70 g

Solutions A and B were ground in a high shear mill for 15 minutes. 9OmI one

10% saponin solution in alcohol / water added.

The dispersion obtained was at room temperature and a coating speed of 18.28 m / Min. On a non-adhesive layer of polyethylene rephthalate layered The coating he followed using an air knife at a pressure of 0.0037 atm., followed by Inflating warm air over the web dried at a temperature of I07 ° C. The thickness of the

dried layer was 0.005 to 0.006 mm.

A photopolymerizable gravure resist disperser * stan the same composition as that of Example 8, as described in Example 9, on the

no f \ A η λ λ

Polyvinyl alcohol layer layered The thickness of the Layer was 0.005 to 0.006 mm.

A sample of the material produced in this way was, as described in Example 9, exposed, laminated and etched An intaglio image of the gravure resist screen was created on the surface of the copper plate.

Example 11

Two solutions were made as follows:
Solution a

Gelatin 72 g

Water 2736 ml

The gelatin was soaked in water for 0.5 hour and then digested at 52 ° C. for 0.5 hour

Solution b

10% solution of nonylphenoxypolyethoxyphosphate 36 ml

10% solution of saponin in
Ethanol / water 36 ml

Solution A was cooled to 34 ° C. and solution B was added by diluting with water

Solutions of different concentrations prepared. The solutions obtained were coated at a coating speed of 9.14 m / min and at 32 ° on a 0.18 mm thick polyethylene terephthalate sheet which had no adhesive layer and which had an antihalation layer and an antistatic layer on its back to produce several coatings with layers of gelatin of different thicknesses in this way. Each of the layers was coated with a heterogeneous, photopolymerizable layer which was suitable for the production of a gravure resist, as described in Example 8. A gravure screen (59 lines / cm, ratio of dots to lines: 2.5 : 1) was copied onto samples of each material produced in this way. ). The exposed samples were then transferred to a water-moistened copper surface, as described in Example 1, and pelted in flowing Fl -.>; N (III) -chloride solution of 52.1 "Be at a temperature" of 23 ° C below in Table I the results.

Panel I.

Coating solution
% Solids

layer thickness weight (mg / dm ² ) (mm) 76 0.006 26th 0.0025 5.1 _ U _ 1.2 _

2.5

1.25

0.625

0.14

0.14

(3.05 m / min.
Coating speed)

Example 12

The coating solution of the hydrophilic, colloidal layer of Example 11 was applied with a solids content of 0.625% by weight under the coating ratios of Example 11 to a non-adhesive layer. 0.14 mm thick photographic film base made of cellulose triacetate applied with a layer weight of 5.7 mg / dm ² . As in Example 11, a photopolymerizable gravure resist layer was applied over the light adhesion control layer. A sample of the material produced in this way was exposed according to Example 11 with the exception that an exposure time of 20 seconds was used. The further treatment took place as in Example 11 with etching of the surface of a copper plate. A gravure image was formed on the surface of the copper plate

Example 13

Example 12 was repeated using an untreated, non-adhesive layer, photographic paper backing practiced with polyethylene wherein the hydrophilic colloid layer

transmission Etched and peeling image satisfactory Yes satisfactory Yes satisfactory Yes satisfactory Yes satisfactory Yes satisfactory Yes

a layer weight of 8.6 mg / dm ^{2 was set} up. A gravure image was obtained on the surface of a copper plate etched using this material.

Example 14

A 1% strength aqueous solution of polyvinylpyrrolidone having a molecular weight of 40,000 and containing 0.1% nonylphenoxypolyethoxyphosphate and 0.1% saponin was prepared. The solution was prepared as described in Example 11 on an uncoated 0.18 mm thick Layer support made of polyethylene terephthalate coated with formation of a layer weight of 37 mg / dm ² . As indicated in Example 11, a gravure resist was applied over the hydrophilic colloid layer. A sample of this material was exposed and tested in accordance with Example 11. A gravure image had been produced on the surface of the copper plate.

Example 15

It was eif.fi: 2.5% / cige aqueous gelatin solution produced, the 0.045% monooleyl ether of decaethylene glycol The solution was prepared according to Example 11 with formation of a coating weight

of 30 mg / dm ² applied. A gravure resist layer was coated over the hydrophilic colloid layer as indicated in Example 11. A sample of the material produced in this way was exposed and tested in accordance with Example 11. A gravure image was obtained on the surface of the copper plate,

Example 16

Example 15 was repeated with the exception that 0.075% saponin was used instead of the monooleyl ether of the

Decaethylene glycol were applied. A sample of this material was made according to example! 11th exposed and tested. An intaglio image was created on the surface of the copper plate.

The metal plates having the intaglio images of each of the above examples were of high quality and suitable for printing using conventional gravure printing applied inks.

Claims (1)

Patent claims: 1. Photopolymerizable recording material for the formation of a heterogeneous diffusion etching resist with essentially constant layer thickness, with a smooth, flexible removable support and a layer of a heterogeneous, photopolymerizable mixture in a hydrophilic, macromolecular, organic polymer a disperse phase from: