DE1720875B2 - METHOD FOR PRODUCING POLYMERIZED IMAGES - Google Patents

Description

2. Processor according to claim 1, characterized in that auxiliary means always leads to the formation of polymers is characterized by the fact that only low molecular weight is considered to be radiation-sensitive.
Precatalyst the chlorocitiate salt of a diazo- 30 Another difficulty lies in the fact that the primary aromatic amine is used for the purpose. Available photopolymerizable mono-

3. The method according to claim ~, characterized in that an optimal spectral sensitivity is characterized in that the chlorozincate salt does not have that. Usually therefore have to-earth diazotized p-Morpholinoanilins, 4-diethyl cessful performing a photopolymerization aminoanilins, 4-CyclohexylaminoaniIins, 35 which Polymerisatbilder should provide sufficient toughness and dino aniline, 4-Thiomorpholinoanilins, N -SS- hybrid layer thickness of 4-piperidone , Unusually long Bedroxyäthyl-N-ethyl-p-phenylenediamines, 6-Amino- light times used and / or very strong 3-benzoylamino-1,4'-diethoxybenzene or the di-light sources are used.

azotized benzidine-2,2'-disulfonic acid is used. The polymer formation depends primarily on this

4. The method according to claim 1, characterized in 40 from the amount of catalyst, d. H. of free radius drawing, that one kaien as ethylenically unsaturated, which occurs during the photolytic decomposition of the Monomeric acrylamide used. the catalyst-releasing material is produced,

which in turn depends on the thickness of the coating to which the layer part in question is exposed. There-

45 through there are several disadvantages. First can

the actual photographic speed of a given radiation sensitive catalyst

The invention relates to a process for the production of monomers and existing system only by Ervon Polymerizatbilder, in which the intensity of the radiation source is increased

a) a photopolymerizable layer with a ⁵ ° supplied exposure or by lengthening the ethylenically unsaturated monomers imagewise increased exposure time. The decisive factor here is the fact that the

........,, ·., · Application of high-intensity radiant energy

b) a Aufze.chnungsmatenal is used _dner at _"en f _{m erroneous} picture reproduction and the d, e photopolymerizable Schicht_zw, J rule _{leads nachteilj other effects. s} * _are an electrically conductive layer carrier and _{p by using} S _{ng of radiation sources with a higher photo-T} connected to it in an electrically conductive manner. - _t -,. _A. · · E- u 1. nu. 1
Eligible layer of high dark resistance ^Ιη ? " ^Sltat f" ^Α "· ^?"'"'" Ϋ " ¹ " ¹ ? f "° '» [>°' ynl = n-

L, and £

f .... cu-u * 1 * ι w · u τ- υ ^o f due to the thermal effect po ymerisieren,

capable layer of applied electric field, · _u , _{A f} » _ut j ni · 11 τ> 1 ·«.-u · il

j-ni · <■■ · ·? · j r> Ji 1 j which easily leads to the fact that no clear deer image is obtained

radicals initiating the polymerization or ·.

onen ie er. Attempts to eliminate or reduce the

It is known that the polymerization of certain 65 mentioned and other related disadvantages

Ethylenically unsaturated organic compounds are already used in technology on a larger scale

namely, of vinyl monomers, carried out by irradiation and by research

high intensity can be achieved, with products and development of new, effective catalyst

I 3 .4

systems, d. H. of photoinitiators, of catalyst, which enables the photoelectric layer

promoters, sensitizers and the like, an electric current is generated in the exposed area

In addition, a large number of people have already been directed. Here is the photoelectric layer

Monomer systems created, which apparently in electrically conductive contact with a vinyl

considerable improvement in the spectral sensitivity 5 monomer layer, which is on an electrically conductive

have, whereby more satisfactory polymerization support is applied. The Monomerscb ^; cht

just en Wbar. consists of a) a normally liquid to solid

With regard to the photographic sensitivity of vinyl monomers, whose group CH ₂ = C <un- and the image quality, however, the improvements that could be determined up to now were bound to an electronegative group were still unsatisfactory, which is important, and b) a precatalyst, the one Compound particularly conspicuous in photopolymerization processes, the polymerization of which occurred during electrolysis, which forms catalysts which initiate energy vinyl monomers, are carried out using poor radiation sources. So the catalyst releasing material is a z. B. proposed to expand and inten- radiation-sensitive, diazotized primary aromasivterung the spectral sensitivity in the known 15 tables amine or its salt. Incorporate one or more trically conductive layers and the conductive layer sensitizers over the photoelectronic catalyst monomer system. Since these, as dyes, are only partially absorptive in the visible spectrum during the entire exposure time, the photopolymerizable layers are retained, and the photopolymerizable layers are essentially evenly colored by them. The resulting consequences of the photoelectric layer and the conductive layer are obvious. In addition, affect the distributed with carrier, whereby during exposure, current flows through the application of these working methods connected to the monomer layer, which in this case the polymerihehe cost greatly the economic application sation of the vinyl monomer layer in the area of the process. photoelectric layer caused indirectly.

The object of the invention is to provide a method for producing a. The invention makes an extraordinary Specify the production of polymer images, in the case of rapid, image-wise polymerization also in the case of others the required exposure times to a known when using only minimal exposure intensities Method previously unattainable level is sufficient, since the exposure in the invention be reduced, and in which the polymer-forming process only the photoelectric layer C is conductive Implementation of the effects of infrared and 30 must do. Once the photoelectrically conductive Heat radiation component of the light source practically un- material according to the exposure impinging on it is dependent. has become conductive, can simply be switched on

The object of the invention is based on adjusting a suitable current density of the polymer

proceed to the production of polymerizate images, which are generated by suitable catalysts

35 Adjustment of the anode and cathode ends

a) ei.ie photopolymerizable layer is easy to reach with an applied voltage. Since the ethylenically unsaturated monomers image-wise the catalyst-releasing electrolytic reaction is exposed and subsequently developed, a direct function of the ^{in the monomer layer}

b) a recording material is used, when the amount of electricity is: in this way the photodem the photopolymerizable layer between ⁴ ° graphic sensitivity and at the same time the degree of an electrically conductive layer support and ^the polymer formation regardless of the strength of an electrically conductive connected photo- ^{the for the} Exposure used radiation set conductive layer of high dark resistance ^we "j. , _nu 1 · · <· ._
is arranged and contains a precatalyst, " _u ^Be !. ^{d! n} known photopolymer ymerisationsverfahren the exposure at the action of a be- "the irradiation exerts a dual function, ie the substrate and the photoconductive see ^{them. causes dl} f, b.ldmass.ge control of the polymer layer applied electric field the ^polysatl ° ⁿ " ^{nd st} ? ^Ut also the immediate energy generation initiating radicals or ions supplies 1 ^ue » ^{e through} ^ J * ^the catalyst .ldungs- and is characterized in that ^react i ' ^{on e} : "^ ^le ' ^tet ^.

... ,. . ,, 50 according to the method irradiation exclusively the

c) a recording material is used _{to effect the funkli the} image-wise control of the polymer as a _{precatalyst in the polymerizable blW> while the} energy source, layer a radiation-sensitive diazotized _{which releases the catalyst, the} electrical current contains primary amine or a salt thereof. _{is> de} _ _{through the part of the} photoclectriceii

It is essential to the invention that the image-wise delamination is guided, soft by the irradiation position of the catalyst, d. H. des are activated in the polymerisation. Using Monomer layer initiate the polymerisation- electrical energy for the formation of the polymerides Factor, not photolytically, but electrolytically sation-initiating catalysts an amplification takes place by thinking of an electric current as causing, d. i.e., the image to be reproduced onto which the Effective force served, the photoelectrically conductive layer 60 initially optically through the pictorial Beiich If a photoelectrically conductive layer reacts to the polymerizable monomers the master copy is generated. layer in the form of an amplified electric current

Forwarded in the manufacture of poly- according to the invention. This enables the polymer

In merizate images there is an image-wise polymerization reaction influencing determinants

formation by adding a photoelectrically conductive layer, 65 largely to control.

which has a high specific dark resistance, The arrangement indicated in the drawings

with electromagnetic rays of one wavelength of the parts is only intended to illustrate the

from ultraviolet to the visible range exposed fahirns serve without one. To represent restriction.

J2C

20th

F i g. 1 of the drawing shows a layer arrangement which can be used in the method of the invention, while

F i g. Figure 2 shows a basic arrangement by which the electrolytically induced polymerization is feasible according to the present invention.

In Fig. 1, E represents an electrically conductive layer support and D represents the polymerizable vinyl monomer layer, ie the layer which contains the diazo precatalyst. In Fig. 2, A is one with a conductive coating B, e.g. B. of tin oxide provided glass layer, while C represents a photoelectrically conductive layer with high dark resistance, the z. B. of ZnO, ZnS or the like.

When the method is carried out, a direct voltage is applied to layers B (cathode) and E (anode), creating a substantially uniformly distributed electrical potential difference running through the anode and cathode layers. In the absence of lighting, due to the high dark resistance of the photoelectrically conductive layer, current of only a few microamps flows through the system, which in no case is sufficient to initiate the polymerization. When exposed through a master copy, however, a conductivity image corresponding to the master copy forms in the photoelectric layer, causing a correspondingly increased current flow between the cathode and anode to such an extent that an electrolytic reaction is initiated in the monomer layer D , whereby the diazotized primary aromatic Amine is converted into a polymerization initiating catalyst.

Aromatic amines, the diazotization of which results in diazo compounds which lead to Suitable for use as precatalysts, comprise a relatively broad group of substances. Out of line of the compounds belonging to this group should be mentioned, for example, the following, where the Specification should not print any restriction:

p-4-morpholinyl aniline,

4-aminocaprylanilide (or 4-caprylamido-

aniline),

5-stearamidoorthanilic acid,

5-lauramidoanthranilic acid,

S-amino - ^ - methoxydodecanesulfonanilide,

4-diethyiaminoaniline,

2-ethoxy-4-diethylaminoaniline,

5-dimethylaminoorthanilic acid,

4-cyclohexylaminoaniline,

4- (di - /? - hydroxyethylamino) aniline,

4-piperidinoaniin,

4-triomorpholinoaniline,

4-hydroxypniline,

S-methyl - ^ - ethylaminoaniline,

4-aminodiphenylamine,

3-methyl-4- (0-hydroxyälhylamino) aniline,

5-aminosalicylic acid,

O-pentadecoxyaniline,

N-0-hydroxyethyl-N-ethyl-p-phenylenediamine,

Benzidine-2.2'-disulfonic acid,

2,5-Dichlcr-l -amino-benzene,

^ Chlorine ^ -amino-l-methylbenzene,

^ Chlorine ^ -amino-l-mefhoxybenzene,

2,5-dichloro-1-methy! -4-aminobenzene,

2-amino-4-methoxy-5-benzoylammo-l-chloro

benzene.

10

2,5-dichloro-4-amino-1-methylbenzene,

4,6-dichloro-2-amino-1-methylbenzene,

4-amino-1,3-dimethylbenzene,

4,5-dichloro-2-amino-1-methylbenzene,

5-nitro-2-amino-l-methylbenzene,

5-nitro-2-amino-1-methoxybenzene,

3-Amino-4-methoxy-6-ni ^f .ro-i-methylbenzene,

S-amino- ^ methoxy-o-benzoylamino-l-methyl-

benzene,

o-Amino- ^ benzoylamino-l.S-dimethoxybenzene,

6-Amino-3-benzoylamino-1,4-diethoxybenzene,

o-Amino-S-benzoylamino ^ -ethoxy-l-methoxy-

benzene,

6-Amino-3-benzoylamino-1,4-dimethoxybenzene,

p-amino-diphenylamine,

p-phenylenediamine monosulfonic acid,

p-ethylamino-m-toluidine,

N-benzyl-N-ethyl-p-phenylenediamine,

p-dimethylamino-o-toluidine,

p-diethylamino-o-phenetidine,

4-benzoylamino-2,5-diethoxyaniline,

2-amino-5-dimethylamino-benzoic acid,

N, N-di- (0-hydroxyethyl) -p-phenylenediamine,

p- (N-ethyl-N- / S-hydroxyäthylamino) -o-toluidine,

p-di- / 5-hydroxyethylamino-l-chloroaniline,

p-phenylenediamine,

2,5-diethoxy-4- (4'-ethoxyphenylamino) aniline,

p-1-piperidylaniline,

α- and / f-naphthylamines.

Diazonium compounds prepared from the amines mentioned can be stable in the form of them Diazonium sulfates, chlorobenzenesulfonates or in the form of the double salts of diazo chloride with zinc chloride,

d. H. the chlorozincate, with cadmium chloride, iron chloride or tin chloride or the like. Can be used. The diazotized primary aromatic amines used according to the invention are uniform characterized in that, during their electrolysis, they form, among other things, substances that are capable are to initiate the polymerization of ethylenically unsaturated vinyl monomers.

Although the polymerization of the vinyl monomer by different, from the diazonium compounds Generatable radical types or ions can be introduced, d. H. both by free phenyl, hydroxyl and diazoxy radicals, as well as by the diazotate ion, Experiments have shown that the polymer-forming reaction is primarily due to free radicals is induced. However, it is also quite possible that the polymerization by superimposition of the Radical mechanism and the ion mechanism takes place. The amount of diazotized used in each case Amine is not essential if it is present in such an amount as to be desired Degree of polymerization is achieved. Most favorable to achieve the advantages of the invention it is when the diazotized amine in amounts of at least about 2 to 10 parts per 100 parts of monomer is used, with a range of 4 parts to parts being particularly preferred.

The vinyl monomers suitable for carrying out the process according to the invention generally all normally liquid up

6s normally solid ethylenically unsaturated organic monomeric compounds commonly used for photopolymerization processes. Such connections should preferably be at least

Il 720 875

At least one non-aromatic double bond is mandatory if, as a result of washout development, see adjacent carbon atoms. whereby non-polymerized monomer removed Particularly suitable compounds are being photo-, a relief image is to be obtained, polymerizable vinyl or vinylidene compounds, C <group Deten In the preparation of CH inventively used ₂ = by direct interlocking that 5 it is film-forming Vinylmonomermassen Fung with an electronegative group such as B. usually required to maintain a - C = O-, -C = N-, acidic pH value, ie a pH value below 7, - C = C- or - O - group is activated. To incorporate a sufficiently gelite amount of an acidic stabilizer series of such photopolymerizable unsators. Unsaturated organic compounds are suitable for this purpose, for example, any of the acidic substances known in the blueprint technique: acrylamide, acrylonitrile, N-ethanol, namely organic carbonacrylamide, methacrylic acid, acrylic acid, calcium acrylic acids, such as. B. citric acid, tartaric acid, oxalic acid lat, methacrylamide, vinyl acetate, methyl methacrylate, or succinic acid. The amount of added methyl acrylate, ethyl acrylate, vinyl benzoate, vinyl stabilizer influences the overall sensitivity of the pyrrolidone, vinyl methyl ether, vinyl butyl ether, vinyl system, ie, an excess of acid promotes the neutral isopropyl ether, vinyl isobutyl ether, vinyl butyrate, ie, butylation of the electrolytically generated base tadiene, or mixtures of ethyl acrylate with vinyl hydroxyl ions, while delaying the acetate, acrylonitrile with styrene, butadiene with acrylonitrile. Dissociation reaction of the diazonium compound. To the

The ethylenically unsaturated organic compound To achieve the best results, it is recommended to adjust the pH

compounds or monomers can either alone 20 value of the photopolymerizable layer at 3 to 4,

or used in a mixture to keep the physi- preferably at about 3.5, with the other

calic properties, such as B. Molecular weight given range the sensitivity of the system

or to vary the hardness of the finished polymer. proven not to be adversely affected

A widely accepted method of achieving it is.

of a vinyl polymer of the desired physical 25 To achieve optimum viscosity values for the Properties is that in the presence of a coating, the monomer mixtures can be mixed small amount of an unsaturated compound, if necessary, other additives, such as. B. one or more polymerized, the at least two terminal vinyl humectants, preferably the organic groups contains, each of which has straight-chain or ring-niche polyhydroxy compounds, such as ethylene is shaped like bonded to a carbon atom. Funk- 30 glycol, propylene glycol, dipropylene glycol and the like this connection is to be given to the polyvinyl chains. The nature of all of these interconnected. This polymerization technique is used by substitutes is not critical K r ο ρ a and B r e d 1 e y in Vol. 31, No. 12, In- however, care must be taken that they are the monomer industry and Engineering Chemistry, 1939. do not harm the mixture. 35 The described electropolymerization of vinyldene Crosslinking agents include, among other things, monomer mixtures can be easily recognized by their color, N.N-methylene-bis-acrylamide, triacryl formal, triallyl- d. H. the polymerized parts of the layer become darker Cyanurat, Divinylbenzol, the Divinylketone and Di- or brownish colored, whereby the exposed BiIdglycoldiacrylat. In general, increasing parts of the background, the unexposed and the the amount of crosslinking agent and the hardness of the unpolymerized parts of the image. The people in the picture Polymer increases and indeed within a coloration can optionally by incorporating a Range in which the weight ratio of the mono- suitable coupler in the polymerizable layer mers to the crosslinking agent from 10: 1 to 50: 1 are reinforced in such a way that by the electrolytic varies. Base formation not only the polymerisation of the vinyl

In some cases it may be necessary for the 45 monomer initiated, but also for the

Mixture of monomers! and catalyst an organic color-forming coupling reaction required alkali

Nice, hydrophilic, colloid binder that is created in the medium. Such a color-

The type of coupler to be conjugated normally used in photography are known in the art

turn around. Colloid binders that are suitable for this and can generally be selected from those

Suitable for this purpose are, for example, polyvinyl alcohol, which is used for the production of two components

Gelatine, casein, glue, saponified cellulose acetate, components of existing light-sensitive diazotype

Carboxymethyl cellulose or starch. Mixtures, i.e. so-called dry process diazo

The location of the initial polymer formation, typically mixtures, used. Of course, the Ausd. H. either at the interface between layer-choice of certain couplers primarily from that for carrier and monomer layer or the boundary surface 55 from the finished Polymerisatbüd desired color. between the monomer layer and photoelectrically conductive The method according to the invention can be advantageous capable layer depends on the relative polarity of the substrate used for a large number of commercial purposes and come from the conductive surface of the turn. So it can be B. for production Nesa glass. Since the free radical forming of letterpress printing plates, negative offset printing, which the electrolytically induced dissociation plates and the like are used. If you leave that »Ation of the diazo compound indicates, in the we- coupling component from the vinyl monomer layer is essentially cathodic in nature, one of the following can be omitted, the density of the image can be determined by the poly-photopolymerization process applied additive formation by coloring the relief image with tang through the layer support, in which of the polyblack or colored printing inks, dyes build-up of merizate on the substrate-monomer-layer 65 etc. are increased. Also, a better one can Interface takes place, equivalent exposure simply contrast by dispersing colloidal carbon thereby achieve that the support to the cathode material can be achieved in the monomer mixture. The surrounding area is made. This particular embodiment can be a white pigment, such as B. titanium dioxide,

9 10

are incorporated into the monomer layer, as is well known art. For use as a photodiese on a black, conductive surface, such as B. electrically conductive insulating layer are suitable, for. B. a carbon-coated film carrier vacuum-evaporated vitreous selenium and mixtures will be carried. In this way, insulating resins with photoelectric conductors are immediately made up recognizable negatives or positives simply 5 made of inorganic phosphorescent or lumines, that the unpolymerized, unexposed compounds such. B. Zinc oxide, Zinkteten Layer parts are removed. sulfide, zinc cadmium sulfide, cadmium sulfide and the like. Except for the purposes mentioned, these compounds can be used in a known manner with the method according to the invention can still be used manganese, silver, copper. Cadmium, cobalt, etc. those for the production of printing materials, are activated by io. These connections include Image transfer materials, pressure masking panels, e.g. B. Mixtures of cadmium sulfide-zinc sulfide-Phosphotolithographic Printing plates of all kinds, from phores, also zinc sulfide phosphors, as well as copper lithographic Cylinders, printing matrices and activated and silver-activated cadmium sulfide, furthermore printed circuits. Zinc oxide. As is well known, the greatest sensitivity is usually to photoconductive The polymerizable vinyl monomer mixtures 15 for such photoelectrically conductive Zinc oxide used in the ultraz through suitable coating processes, capable layers. B. by flow coating easily on the conductive violet area of the spectrum, while usable Apply the substrate. borrowed light sources in this area a ratio that Vinyl monomer mixture will exhibit weak radiation on the conductive basis. However it is Capable layer support preferably up to a thickness of 20 possible, the sensitivity of the zinc oxide also on in the range from about 5 to about 100 microns in the visible region of the spectrum. It is true that the thickness of the layer applied must be expanded to make the layer suitable for the sensitizing layer not of critical importance, however, dyes capable of the same are incorporated the stated range should be used to achieve optimal responsiveness or sensitivity to the Results are adhered to. In general, there are 25 longer waves to bestow. Particularly cheap Higher luminous fluxes through thinner spreads are obtained through application achieve a higher production speed photoelectrically conductive layers that double diness of the polymer image is achieved. activated photoelectrically conductive substances contain:

As the support for the photopolymerizable, these are described below Any conductive support can be used 30 Such a doubly activated photoelectrically conductive layer can be used, it is only necessary that while the capable substance contains z. B. a luminescent, with Exposure of the electrical contact with the conductive copper activated and with chloride co-activated Surface is produced. So z. B. one on cadmium sulfide or one activated with copper and Common plastic substrates applied carbon with chloride co-activated cadmium sulfoselenide. fuel coating can be used. Metal, e.g. B. 35 The aforementioned photoelectrically conductive substances Aluminum can also be used as a conductive medium, preferably for use in the field The electropolymerizable process according to the invention, since it has a spectral Emp layer is applied. In addition, paper can have a sensitivity distribution that is essentially are made electrically conductive by having the same strength as that of the human eye, Carbon particles is impregnated, or that during 40 d. i.e., they are highly sensitive to visible ones rend the manufacture of the same suitable electrolytes to electromagnetic rays, being sensitive to them be incorporated. As a layer support for the speed decreases towards ultraviolet and infrared, The light-conducting layer can be made of cast iron or plastic. Such photoelectrically conductive substances are suitable are applied, whereupon by vacuum evaporation also very well for use as an anode or or any other method using a very thin 45 cathode in practicing the Metal or Mctalloxydfilm is applied, z. B. method according to the invention, electrically conductive glass, which is commercially available as an insulating binder, which is extraordinarily Designation N ESA glass is available. In the latter, good for the production of the photoelectric layer If the metal layer should suitably be so thin, z. B. to mention: silicone resins or be that they are at least 70 to 75 percent light- 5 »epoxy ester resins.

is permeable. The incident light is photoelectric through the. The thickness of the conductive layer carrier is also the conductive layer to charge carriers (current) not of decisive importance as long as only the converts. The measure for the conversion of an energy quantum (photon) in contact with the monomer layer is the yield (G), and the surface is sufficiently conductive. In general, this value is defined as the number of photons of light energy that can be achieved, i.e. in the chemical carriers that are deposited per second between the electrodes, the material of which the conductive layer carrier is made, and per photon of light energy, which are deposited in one second Resistance of less than 130 ohms / cm is sorted out. Those with the invention _we j _s t. According to electrophotopolymerizable systems, the nature of the photoelectrically conductive targetable yield values were also greater than one. In the insulating layer (layer C in FIG. 2), the application of light energy according to the invention is not a decisive factor for the production of electrical current, which in turn is a factor as long as the layer has a high degree of darkness Kataly- • resistor in the order of magnitude of at least satormaterial polymerisation initiators, has a 10 ¹⁰ ohm / cm and becomes conductive when exposed to 65 amplification level. The yield value shows the degree of amplification with electromagnetic radiation of a wave. According to this, length that extends ultraviolet over the visible range has a yield value of 100 in a given electrode spectrum. Such substances are the formation of in the photopolymerizable system

12th

about 100 polymerization-initiating effects from After exposure, a dark brown, po-

a photon of light energy. get a positive halftone image that stood out from the lighter

. -I ₁ brown colored background of the unpolymerized

^{B e l s} P ^{! e ll} layer parts.

The following monomer mixture was prepared: 5 Example 3

Acrylamide (recrystallized) 180.0 g _, .. ,,. . ,,,., _TT , ..

N N'-Methvlenbisacrvlamid 7 0b Example 1 was repeated with the difference

Water 120 0 ε diazonium compound the chlorozincate salt of

diazotized 4-diethylaminoaniline was used. To 3 ecm of the above mixture the following io
Substances added in the following amounts: B eis ρ ie 1 4

Aqueous polyvinyl alcohol 20% 25 ecm _,. . , _Λ , ..... , _{TI t} ...

Triethylene glycol 0.5 ecm. 5 ^e «P« \ 1 was repeated with the. Difference,

p-Morpholinobenzoldiazonium- ^ ^{ß al} ? Diazonium compound the chlorozincate salt of

cHorzincat 100.0 mg ¹⁵ diazotized 4-Cyclohexylaminoanilin used

r'itronic acid ''.'.'.'.'.'.'..'.'.'..'..'...'.lOo'o mg ^became -

A thin aluminum sheet was flow-coated with the mixture, after which it was repeated in the dark. Example 1 was repeated with the difference that let dry. This coating made the 20 that, as the diazonium compound, the chlorozincate salt of electropolymerizable layer formed. diazotized 4-piperidinoaniline was used.

A color-sensitized, photoelectrically conductive one

Zinc oxide layer approximately 60 microns thick. Example 6
was then applied to a NESA glass plate,

whereupon they were allowed to air dry for about 15 minutes. Example 1 was repeated with the difference. Then it was hardened in an oven at 100 ^° C. for 1 hour that the chlorozincate salt was the diazonium compound. A silicone resin and diazotized 4-thiomorpholinoaniline was used as a binder. as a solvent to set the correct viscosity of the mixture for the coating a B ice ρ ie 1 7
Mixture of toluene and methanol used. The 30th

photoconductive surface was then intimate in Example 1 was repeated with the difference,

Contact with the electropolymerizable layer that the chlorozincate salt of the diazonium compound

brought. A 375 watt photo floodlight lamp diazotized N-ß-hydroxyethyl-N-ethyl-p-phenylenedi-

was then used about 16 inches from the glass portion of the amine.

Recording material set up and this then 35. . . _R.

through a photographic line negative 15 seconds example ö

exposed while at the same time a current of 50 mul- Example 1 was repeated with the difference

ampere at 200 volts passed through the device that the chlorozincate salt as the diazonium compound

became. The aluminum support was used as the anode of diazotized benzene-2,2'-disulphonic acid

and the conductive NESA glass surface as the cathode. Turned 40.

Example 9 became dark after exposure was complete
obtained brown positive polymer image, whose

exposed parts of the image from the very light brown background, Example 1 was repeated with the difference

i.e., the unpolymerized parts of the image stood out. that as the diazonium compound, the chlorozincate salt of

_R ... 45 diazotized 6-amino-4-benzoylamino-l, 3-methoxy-

Example 2 benzene was used.

The same arrangement as in Example 1 was used in all of the preceding examples according to with the difference that the end of the exposure is a dark brown polymer

1. Instead of a line negative, get a photographic positive image that was used in contrast to the very light halftone negative, ⁵ ° brown background of the non-polymerized layer

2 that the lamp _search order in a distance of 28 cm ^tel G _{corpse Result} e wi _e in the described Ver from the glass portion of the recording material _{m [to obtain> when} wurüe the method stone, examples repeated, but in place of acrylamido (

3. That the exposure time was 2 seconds and _{S5 used the} following substances: methacrylic acid, acrylic

4. that current with a strength of 150 milliamps for acid, calcium acrylate, methacrylamide, vinyl acetal 200VoIt was applied. Acrylyl pyrrolidone, vinyl pyrrolidone.

1 sheet of drawings

Claims (1)

172G875 / \ 1 ^ 2 high molecular weight can be obtained. For the patent claims: Areas of photographic and related photolithography, the use of this er- 1. Process for the production of polymer appearance proved to be particularly suitable, wherein in which 5 through the use of radiant energy vinyl monomer a) a photopolymerizable layer can be polymerized with a layer. In the process that results in the formation of anethylenically unsaturated monomers, a suitable, moderate moistening is carried out and the substrate is subsequently developed with a polymerizable layer. Verbm-Wi _n J dung, e.g. B. a monomer or monomer b) a recording material is used, ¹⁰ f T ^ ff ^ ™ Τΐ ^ i ^ hto ^ hSS in which the photopolymerizable layer is exposed through just a quill of light ^{ntens' erf} _H ° f · ^tat between an electrically conductive shift ^{to the B} - _t f ^ ^Ü "xfolmerT to be supported thereby and a comparable electrically conductive * ^after Behchtungsintensitat monomers to-bound photoconductive layer of high ^{one, he m} ? ^hr «the less hard imloshchen mass dark resistance is arranged and a ¹ S polymerizes while the not bdhchtetta, places, Precatalyst contains the at exposure ^ ^{che a} f, ^the I fl ™ a I _n Π under the action of one between the changed monomers exist, in most cases The substrate and the photoconductive layer Jurch e.nfach washing le.ch can be removed Applied electric field, the polymer ^co " ⁿ ™. ^On _p ^d . ^en exposed areas persists sation initiating radicals or ions provides, ²⁰ insoluble ^Po 'y ^mermalerial existing resistant characterized in that VlacSig is because the Polymerisat.ons- c) a recording material is used, _React i _O NEN required for an economic Verfahrensdas as precatalyst in the polymerizable passage Photographical Empfindbaren layer a radiation-sensitive, _{25 friendliness} can _{not liefein} why the use diazotized primary Amm or a salt DES toinitiatoren _{of Pho} and promoters and / or of the same. Sensitizers is necessary. The absence of this