DE1815868B - Radiation-sensitive recording material - Google Patents

Description

The invention relates to a radiation-sensitive recording material consisting of a layer support and a radiation-sensitive layer comprising a radiation-sensitive salt with a cation, optionally a radiation-sensitive diazonium, azoniadiazoketone or onium salt cation contains a spectral sensitizing compound and optionally a binder.

It is well known that printing plates and stencils can be produced by the strahlungs- ι ο sensitive layer of a recording material whose solubility is increased by exposure to radiation can change, imagewise exposed and then with a solvent or solvent system treats which either the exposed or unexposed areas of the radiation-sensitive Removes the layer from the layer. Recording materials from which preferably the exposed Areas of the radiation-sensitive layer that can be detached are usually considered positive working recording materials, whereas recording materials from which preferably the unexposed areas can be extracted, usually as negative working areas Recording materials are designated. It is for example from the British patent specification 844 039 and US Pat. No. 3,050,389 known diazoketones for the production of positive-working To use recording materials. The disadvantage of using the diazoketones is that they do not become spectrally sensitized by adding known photographic sensitizing dyes leave. As a result, the known recording materials containing diazo ketones do not exhibit the sensitivity desired for many purposes.

The production of negative working recording materials of the diazo type is z. B. from the German patent specification 763 388 and USA patents 2,322,982, 2,378,583 and 3,061,429 known. The diazo compounds used for the production of these recording materials can also be used spectrally sensitize themselves satisfactorily with difficulty, if at all.

For example, it is known from German patent specification 763 388 that the for the production Diazo compounds suitable for diazo photocopying materials only when using non-fibrous ones Let the layer carriers sensitize satisfactorily. It follows from this that in the earlier USA patents 2,378,583 and 2,322,982 polynuclear recommended for sensitization of diazo compounds aromatic hydrocarbons, aliphatic ketone compounds, quinoxalines, coumarins, Pseudoazimides, quinones, phenones, acridones and fluorenones were unsatisfactory.

Furthermore, those known from US Pat. No. 3,061,429, for example, cannot be sensitized satisfactorily light-sensitive layers made of a polyacrylic acid and a diazonium chloride or diazonium bromide of a p-aminodiphenylamine, which are used for the production of printing forms.

It is also known e.g. B. from British Patent 1060 561 that certain pyrylium salts and Thiapyrylium salts with fluoborate anions are photosensitive and are used to produce photosensitive Layers are suitable.

The object of the invention is to change the anion of known photosensitive salts To increase photosensitivity and to improve its spectral sensitizability in order to do this to arrive at improved negative and especially positive recording materials, which can be spectrally sensitized with known photographic sensitizing dyes.

It has been found that salts with tetra-substituted borate anions of a certain structure are excellent for the production of negative and especially positive working photographic recording materials, since it is not only the solubilities that are important such salts can be modified by the action of light, but the salts also through let known sensitizing dyes sensitize excellently.

The subject matter of the invention is based on a radiation-sensitive recording material, consisting from a support and a radiation-sensitive layer, which is a radiation-sensitive Salt with a cation, which may contain a radiation-sensitive diazonium, azoniadiazoketone or onium salt cation, contains a sensitizing compound and optionally a binder, and is characterized in that it is a salt or a salt-like salt as the radiation-sensitive salt Contains a compound with at least one central, fourfold substituted boron atom of the following formula:

R ₂

D. R3

X'-

wherein: R ₁ denotes an aryl group, R ₂ , R ₃ and R ₄ each denotes an aryl, short-chain alkyl, aralkyl, cyano or short-chain alkenyl group, or two of each of the groups R ₁ , R ₂ , R ₃ and R ₄ together an arylene radical and X® an organic cation with at least one nitrogen, arsenic, tin, antimony, sulfur, iodine, phosphorus, oxygen, titanium, palladium, chromium or cobalt atom as a carrier of the positive Charge.

In the formula given, R _{1 is} preferably an aryl radical from the phenyl or naphthyl series. If R ₂ , R ₃ and R _{4 have} the meaning of aryl radicals, then these also preferably belong to the phenyl or naphthyl series.

The aryl radicals can optionally be substituted, for example by alkyl radicals having 1 to 10 carbon atoms, Alkoxy radicals with 1 to 10 carbon atoms, thioalkyl radicals with 1 to 10 carbon atoms, Halogen atoms, acetal groups, hemiacetal groups, cyclic acetal groups or acetal groups in which one or both Oxygen atoms are replaced by a sulfur atom.

R ₁ , R ₂ , R ₃ and R ₄ can thus consist, for example, of monocyclic aryl radicals, e.g. B. from phenyl, tolyl, p-dimethylaminophenyl, 4-biphenyl, mesityl, 4-stilbenyl, 4-styryl, cyclopentadienyl or cyclohexadienyl radicals, or from polycyclic aryl radicals, for example l-naphthyl - ^ - naphthyl - Or anthranyl radicals, as well as heterocyclic aryl radicals, e.g. B. 2-thienyl, 2-furyl or 2-pyrrolyl radicals.

If two of the radicals R ₁ , R ₂ , R ₃ and R ₄ together form an arylene radical, this can also be more polycyclic

Be nature, ζ. B. consist of a 2,2'-biphenylene radical.

If R ₂ , R ₃ and R ₄ consist of alkenyl radicals, these preferably consist of short-chain alkenyl radicals with 1 to 6 carbon atoms and an unsaturated bond on at least one of the α or / 3 carbon atoms, for example of vinyl, allyl or butadienyl radicals.

The formula given thus includes, for example, B. also spiro-borates of the following type of form:

where X® has the meaning given.

The invention achieves that the photosensitivity of known photosensitive salts increased by exchanging the anion and their spectral sensitizability is improved. Further is achieved that by exchanging any anions for the organoborate anions described, too with such salts photosensitivity can be caused, which with other anions no photosensitivity exhibit.

As a result of the invention it is also achieved that photographic recording materials with photosensitive systems made of photosensitive salts better than previously possible in terms of modify the extent and direction of the change in solubility produced by the exposure leave. This makes it possible to use recording materials with known light-sensitive Modify basic systems to positive or negative working recording materials.

The invention finally further achieves that the radiation-sensitive salts are contained Recording materials better than hitherto possible with the most varied of customary known Sensitizers can be sensitized, whereby their sensitivity, especially their spectral Sensitivity, can be increased.

The radiation-sensitive recording materials of the invention are suitable for the production of Etching layers (resist images), planographic printing forms, if necessary colored copying and fading images or from other color images.

According to an advantageous embodiment of the invention, the recording material contains as spectral sensitizing compound a sensitizer from the class of acridines, azo dyes, Azomethine dyes, anthrones, diphenylmethane dyes, azines, methine dyes, oxanol dyes, pyrilium dyes. Quinones, quinonimines, sulfur dyes, triphenylmethane dyes or xanthene dyes.

According to a further particularly advantageous embodiment of the invention, the radiation-sensitive Layer of the recording material as a radiation-sensitive salt is a salt of the specified Formula in which the anion is derived from a tetraphenylborate, triphenylcyanoborate, tetratolylborate or bis-2,2'-biphenylene boral anion consists.

Radiation-sensitive, water-insoluble salts with an azoniadiazoketone cation have proven to be particularly advantageous and also radiation-sensitive salts with a diazonium cation. Surprisingly It has been shown that polymeric diazonium organoborate salts are particularly excellent let spectrally sensitize. For example, it has been found that such for production of the radiation-sensitive recording material

ίο Salts which can be used according to the invention, for example Let spectrally sensitize until at least 500 ΐτίμ. The term "salt" used here for the preparation of the radiation-sensitive recording material The connection used is to be interpreted broadly, i. H. the term "salt" includes both tetra-substituted borates as well as their reaction products, which for example consist of complexes be able. Such substances are characterized in that they are water-insoluble and therefore common oleofiler and less soluble in polar solvents such as alcohols, e.g. B. methyl and ethyl alcohol, than the organic compounds from which they are obtained.

In the absence of photosensitive cations in the molecule, the salts used to prepare the recording material of the invention tend to have their To increase solubility in such solvents by exposure to light. Are on the other hand light-sensitive cations are present in the salt molecule or are used according to the invention for production of the recording material used organoborate salts together with other photosensitive Substances or compounds used to produce the radiation-sensitive layers can the process that takes place during the exposure of the radiation-sensitive layer becomes even more complex. Recording materials having photosensitive layers, their solubility characteristics when exposed As is known, can be changed with light can be divided into two categories, and that is:

1. Recording materials with layers in which a large number of photosensitive groups per unit area by exposure to Light must be modified to be 'remarkable To achieve change in the solubility characteristics, and

2. Recording materials in which only a relatively small number of light-sensitive materials are used Groups per unit must be modified by exposure to light in order to produce a remarkable change in solubility characteristics to achieve.

Category 1 recording materials also include recording materials of the invention Organoborate salts which have no additional light-sensitive groups, ζ. Β. Salt some have no o-quinonediazide and simple diazonium salt groups.

Typical representatives of such organoborate salts are z. B.

10-methylacridinium tetraphenylborate;

!, ß-dimethyl-o-nitrobenzothiazolium tetra-

phenylborate;
Phenosafranine tetraphenylborate;

l-methyl-2,6-di- (4-ethoxyphenyl) -4- (4-n-amyl-

oxyphenylj-pyridinium tetraphenylborate;
Tetraphenylarsonium tetraphenylborate and
Tetramine palladium tetraphenylborate.

(See also, for example, Table I below the salts 2, 9, 10 given under D, the salts 2, 3, 5 to 12, 14 to 17, 27 and 28 given under E as well as the particularly listed typical salts 13, 15, 17 to 19, 21 to 23, 28 to 30 and 32.)

Category 1 recording materials also include recording materials of the invention with organoborate salts, which have light-sensitive cations. Typical representatives of such organoborate salts are z. B.

p-Dimethylaminobenzoldiazoniumtetraphenyl-

borate;
8- phenyl-6-diazo-5-oxo-4 a-azoniaanthrazen-

tetraphenylborate;
4'-Azido-1-methyl-2-styryl-pyridinium tetra-

phenylborate;
4'-dimethylamino-2-styrylpyridinium tetra-

phenyl borate and
4- (4-dimethylaminostyryl) -flavilium tetra-

phenyl borate.

(See also the salts 2 to 10 given under A and those given under C in Table I below Salts 2 and 3, the salts 5 to 7 given under D, the salts 13 and given under E 18 to 26 as well as the particularly listed typical salts 1 to 12, 14, 16, 20, 24 to 27, 31 and 33 to 35.)

In the case of the organoborate salts suitable for the production of Category 1 recording materials In order to change the solubility properties, a large number of photosensitive components must be used Groups can be modified per unit.

Category 2 recording materials include photosensitive recording materials Polymers, which by the formation of relatively few cross-linking bonds per unit are made insoluble, as well as polymers that are sensitized by compounds, which on exposure create the necessary cross-linking bonds with light.

Inventive recording materials of this category are z. B. those, the p-diazodiphenylamine formaldehyde resin tetraphenylborate (cf. Table I, SaIzA 11) or organoborate salts of vinyl polymers with stilbazolium salt groups or of poly (1-vinyloxycarbonylmethylenepyridinium) compounds (cf. the particularly listed typical salts 14 and 31).

It is assumed that the quantitative effectiveness of the photosensitive groups in both Categories of recording materials is approximately the same, it follows that the light-sensitive layers significantly higher photographic speeds of Category 2 recording materials than the corresponding layers of the recording materials of category 1. Furthermore it can be seen that when Category 1 and Category 2 materials are used together, the results of the Category 2 material will prevail and the radiation-sensitive layer upon exposure is made insoluble with light, although the category 1 material is also a photo-editing able to enter and thereby tends to affect the solubility of the exposed areas of the layer transferred to. It follows that similar results are obtained using a radiation sensitive Layer with only one material or substance that has both the characteristics of the substances of the Category 1 as well as Category 2.

Those used according to the invention for the production of a radiation-sensitive recording material As already stated, organoborate salts can be both positive and negative-working light-sensitive recording materials are used, which is based on the choice of the organoborate salts, also of substances contained in the photosensitive layer or of the processing conditions, z. B. depends on the choice of developing solvent in which it is used will. The organoborate salts can thus be in the form of defined molecules as positive-working units can be used or else in the form of integral parts of molecules, the other positive-working units or groups, which increases the oleophilicity and the solubility of the unexposed Districts is reduced without being detrimental to the positive working nature of these recording materials to influence. On the other hand, the organoborate salts can also be used as integral components of molecules which have negative working groups, in which case either negative or positive-working recording materials are obtained, depending on whether the negative or positive working ingredients are more effective in modifying the solubility properties and depending on the ratio of positive working groups to negative working groups.

From what has been said it follows that the question of whether

a particular molecule with one or more of the organoborate anions of the invention negative or works positively, depends on the constitution of the entire molecule and its environment. From the Said also shows that certain photosensitive compounds, which are known that they change their solubility when exposed to light, but because of their hydrophilicity or high solubility in polar solvents up to now little or no usability have found for the production of radiation-sensitive recording materials of the invention are nevertheless suitable if they are used in the form of their organoborate salts.

The radiation-sensitive salts used according to the invention can be converted by direct reaction of an alkali metal polyaryl borate with an organic compound with a cation which is a nitrogen, Sulfur, oxygen, iodine, phosphorus, titanium, cobalt, arsenic, tin, palladium, chromium or a Contains antimony atom, prepare in a suitable solvent. The implementation can be done in one Solvent can be carried out in which the reaction product is insoluble, so that the reaction product can be isolated. On the other hand it is also possible to carry out the reaction in a solvent which is a solvent for both Reaktiomomponents and the radiation-sensitive reaction product is, in which case the one obtained Solution used directly for the production of the electrophotographic recording material can be.

The reaction normally takes place at room temperature, but temperatures of, for example, about 50 to 100 ^° C. can also be used. The completion of the reaction can easily be determined by introducing part of the reaction mixture into water, the water-insoluble reaction product separating out.

Primarily all organic ones are suitable for the preparation of the radiation-sensitive organoborate salts Compounds which have an exchangeable anion and a photosensitive cation. Furthermore can the organic starting compounds required for the production of the radiation-sensitive organoborate salts be monomeric or polymeric.

Organic compounds suitable for preparing the organoborate salts are, for example, heterocyclic ones Salts with a photosensitive cation, aliphatic compounds with alkyl and aryl radicals and a photosensitive cation, carbocyclic compounds with positively charged atoms of the already described type attached to the carbocyclic ring by an intermediate atom or group bound by intermediate atoms, and polymeric compounds with a plurality of one or several of the positively charged atoms described above.

Organic compounds such as amines, ethers, hydrazines and the like, which are not positive have charged atoms or no positively charged atoms of the type described can be used in suitable Compounds are converted by treating them with an acid, thereby creating the corresponding Ammonium salts, oxonium salts and the like are formed, whereupon they are treated with a tetra-substituted borate implemented in the manner described.

The organic compound must be soluble in a solvent, for example in one organic solvents, water and the like. Typical solvents of this type are, for example, dimethylformamide, Dimethyl sulfoxide, alcohols and ketones.

Those tetrasubstituted borate anions which are radiation-sensitive are particularly suitable for producing the recording material of the invention Form oleophilic organic salts which are found in common developing solvents, e.g. B. water or isopropyl alcohol, are insoluble, the organic salts generated upon exposure to light disintegrate, with decomposition products soluble in the developer being produced in the exposed areas.

Typical starting compounds for the preparation of the photosensitive salts of the recording materials Tetra-substituted borates suitable for the invention are, for example, triaryl borates and tetraaryl borates and bisarylene borates of the following structural formula:

R ₁ -BR ₃
R ₄

60

wherein R ₁ , R ₂ , R ₃ and R _{4 have} the meaning given and Y * is a cation, for example an alkaline cation, e.g. B. is a sodium, lithium or potassium cation.

Typical examples of such compounds are e.g. B. tetratolyl borate, tetraphenyl borate, triphenyl cyanoborate, Tetra-2-naphthyl borate, phenyl tri-1-naphthyl borate and vinyl tri-1-naphthyl borate.

The recording materials of the invention can be prepared by conventional methods. this means that, for example, a solution of the organoborate salt by active coating, dip coating, Flow coating or coating produced with a conventional coating device can be used, conventional layer supports can be used as the support that are used for the production radiation-sensitive recording materials are common. The support used in the individual case depends largely on the specific use of the recording material to be produced away.

To produce the recording materials, the organoborate salts can be used together with customary Use binders, preferably those which are soluble in polar solvents, although the organoborate salts can also be used alone. Particularly suitable binders are phenol-formaldehyde resins, including those known as novolaks and resole resins Plastics.

The phenol-formaldehyde resins are particularly suitable for the production of recording materials with azoniadiazoketone cations. Such phenol-formaldehyde resins are commercially available.

Novolak resins of particularly advantageous properties are those that have an average molecular weight from about 350 to 40,000.

It has proven advantageous, when using a binder, to have a ratio of radiation-sensitive To apply material to resinous binder from 1: 1.5 to 1:20 parts by weight. As a rule, very particularly advantageous results are obtained with a weight ratio of 1: 5 received up to 1:10.

The radiation-sensitive used according to the invention for the production of the recording material Compounds can also be used together with other radiation-sensitive resins, for example radiation-sensitive polycarbonates are used.

The starting compounds suitable for the preparation of the organoborate salts used according to the invention can themselves be sensitive to radiation and in themselves already used for the production of photographic Recording materials which are usually negative working, i.e. i.e. the exposed ones Districts are less soluble than the unexposed areas. When transferring such radiation-sensitive Compounds in organoborate salts and use thereof with a sensitizer the following usually occurs:

1. The compound generally becomes a positive working compound, at least when it is developed in an aqueous or alcoholic solution;

2. the system becomes less soluble in water and alcohol;

3. the photographic sensitivity is considerably increased, and

009545/396

4. Both the spectral sensitivity and the general sensitivity of the compound can be measured increase, whereas the parent compound of such sensitization usually is not accessible.

The concentration of the organoborate salt, sensitizer and optionally in the coating solution Binder depends on the nature of the radiation-sensitive material, the substrate used and the coating method used in the individual case. In general, good Results obtained when using coating solutions containing 0.5 to 20 parts by weight, preferably 2 to 10 parts by weight, photosensitive compound. However, you can also use concentrations higher than 20 parts by weight give excellent results.

The recording material according to the invention preferably contains radiation-sensitive per part by weight Compounds 0.01 to 1 part by weight of a spectral sensitizing compound.

The recording materials which are particularly advantageous for the production of recording materials according to the invention suitable radiation-sensitive salts with an azoniadiazoketone cation can be prepared, for example, that a tetra-substituted borate, for example an alkali metal tetraphenylborate is reacted with an azoniadiazoketone. The received Salt can then be dissolved in an organic solvent, preferably in the form of 1- to 2% solutions are applied to a layer support, where appropriate customary resinous Binder are present, namely traces thereof up to about 10 parts by weight of binder to 1 part by weight Azonia Salt. When the recording material is exposed to actinic light, e.g. B. ultraviolet Light, a copy-out image is obtained.

The production of azoniadiazoketones is known. The diol catechol derivatives thereof can prepared by the method described by Fields and coworkers in J. Org. Chem., 30, 252 (1965) will. You can also use the method described by M. C a ν a in J. Am. Chem. Soc, 80, 2262 (1968), methods described can be modified.

The use of such azoniadiazoketones for the production of radiation-sensitive recording materials is also known from Belgian patent 711 951, for example.

The preparation of tetraaryl borates and the reaction thereof with amines is also from the Appendix to "The Organic Chemistry of Boron" by W. G e r r a r d, 1961, Verlag Academic Press, known.

The preparation of tetraaryl borates is also known from Annalen, 573 (1951), p. 195. References is also referred to the magazine »Ang. Chemie ", 70. 65 (1958) and the journal" Ang. Chemistry «, Int. Edition, Vol. 5 (1966), No. 4, pp. 351 to 366.

If the radiation-sensitive salts used according to the invention consist of diazonium salts, see above these can be reacted with couplers in the same way as diazonium compounds, the do not have an anion with at least one central fourfold substituted boron atom of the formula given. The reactivity of couplers with the reaction products of tetra-substituted ones Borates with diazonium compounds is practically the same as the reactivity of couplers with diazonium compounds that have not been reacted with the tetrasubstituted borates. Consequently can couplers which are known to react with diazonium compounds, also used for reaction with the radiation-sensitive diazonium organoborate salts of the invention will. The diazonium salts used according to the invention have compared to conventional diazonium salts the advantage that they sensitize themselves to increase their sensitivity to actinic light leave.

For the production of recording materials with resist layers, those for the production of the photosensitive Resist layer components required to be delivered to the consumer in dry form. The coating compositions are then simply dissolved in the dry components a solvent or solvent mixture.

If necessary, alkali-soluble phenol-formaldehyde resins can be used to prepare the coating compositions be used, which form a reaction product with the radiation-sensitive compound, which is insoluble in alkali, but forms decomposition products on exposure to actinic light, which are soluble in dilute alkaline solution. The term reaction product includes complexes and other association products.

The amount of alkali and the strength of the alkali required for developing the exposed resist layer required depend on the ratio of radiation-sensitive salt to binder.

The strength of the alkali solution can optionally be an approximately 5% aqueous sodium hydroxide solution correspond.

The coating compositions used to form resist layers can be applied to any clean surface by spraying, dipping, spin coating and the like, and the applied layer is then air dried. Optionally, the material can then be 10 to 15 minutes to be heated to 6O ⁰ C long to evaporate the solvent completely to remove is exposed and the resulting recording material having a usual for lithographic purposes light source, such as a carbon arc, by a template.
The effectiveness of the recording material obtained depends on the solubility characteristics of both the organoborate salt and the resinous binder. The developer is selected according to whether the exposed areas are to be dissolved, in which case a positive resist image is obtained, or whether the unexposed areas are to be dissolved, in which case a negative resist image is obtained.

A positive resist image is usually obtained, for example, when the organoborate salt and a sensitizer are used in one of the acidic polymers specified above and, furthermore, when the exposed recording material is treated with a dilute alkaline solution, e.g. B. a 5 to 20% aqueous trisodium phosphate solution or a V _{2 to} 5% aqueous sodium hydroxide solution is developed.

The alkalinity of the developer depends on the

used components and the ratio of radiation-sensitive component to binder away.

The developer can optionally also contain dyes and / or hardening compounds.

The developed image can then be rinsed with distilled water, after which it is optionally used heated to 60 to 80 ° C for about 15 to 30 minutes can be. The material obtained can then in the usual way by means of acidic etching solutions, for example Ferric chloride solutions, are etched.

To produce recording materials for lithographic purposes, a solution with at least one of the radiation-sensitive salts applied to a conventional lithographic substrate, for example on a layer support made of a foil or plate made of zinc or anodized aluminum, granulated aluminum, copper or paper or a hydrolyzed cellulose ester, a polyolefin, Polyester or polyamide. For the production of the recording material, i.e. for the application of the radiation-sensitive Salts on the substrate, common organic solvents can be used, which dissolve at least 0.2 percent by weight of the radiation-sensitive compound and face each other the radiation-sensitive compound behave inertly. Suitable solvents are, for example Dimethylformamide, dimethyl sulfoxide, 2-methoxyethynol. Ketones e.g. B. 2-butanone and cyclohexanone and also acetonitrile, benzyl alcohol, benzene, toluene, xylene, 2-ethoxyethanol and mixtures these solvents with one another or with one or more short-chain alcohols or ketones.

Customary additives can optionally be incorporated into the coating compositions or coating solutions which promote film formation, facilitate coating and / or adhesion the applied layer to the substrate or improve the mechanical strength of the recording materials improve. For example, conventional binders can be added to the coating solutions or synthetic resins, stabilizers and surface active compounds are incorporated. Will Plastics or binders are added to the coating solutions, preferably such used in both the coating solvent and the developing solvent are soluble. The amount of binder or resin used in the individual case can vary widely. In general, it has proven to be useful to produce radiation-sensitive layers that 0.1 to 50 parts by weight of resin or binder per part by weight of radiation-sensitive material.

The concentration of the coating solutions depends on the nature of those used in the individual case radiation-sensitive compound, the substrate and the applied coating method. It has proven to be particularly advantageous to use coating solutions that contain 0.05 to 3 parts by weight, in particular 0.5 to 2 parts by weight of one of the radiation-sensitive compounds. If necessary, very advantageous results can also be obtained with higher concentrations.

The recording material obtained can then be passed through a conventional negative with actinic radiation, e.g. B. a conventional standard charcoal arc, a mercury lamp, as it is normally used for the exposure of printing plates , or another light source that emits ultraviolet light, such as a xenon lamp, can be exposed. Advantageously , however, the recording materials of the invention can also be exposed, for example, with tungsten lamps or other light sources emitting daylight , the spectrum of which has little or no ultraviolet light. Exposure can also take place with radiant heaters, which emit very little radiation below 500 ηΐμ.

The exposure time depends on the salt used in the individual case and on the sensitizing agent and also on the thickness of the photosensitive layer, the distance of the photosensitive layer from the light source, the emission spectrum of the light source and, if applicable, the filters used.

By exposing a recording material according to the invention to a borate and a sensitizer , a visible image or an initially invisible image can be generated.
It has proven to be advantageous to produce fading images, in which case a strongly colored recording material is faded in the exposed areas . If necessary , copy images can also be produced which are colored even more strongly or have a color different from the unexposed recording material.

In contrast to the known simple fluoroborate salts , many of the salts with diazonium cations used according to the invention produce strongly colored copy images which are often brown or purple.

The dyes which form the colored images are usually more soluble in aqueous and alcoholic developing solutions than the original salts, which is why the recording materials are positive-working recording materials .

An advantageous process for developing the exposed lithographic recording materials consists in wiping them off with a cotton cloth which has been soaked in a solution of 10% isopropanol in water, after which a greasy lithographic printing ink is applied.

If metallic substrates are used, they can be etched with a desensitizing etchant before being colored. On the other hand, the layer that is receptive to printing ink can be destroyed by the action of an acid if the greasy printing ink is not applied first. The plates can be developable in water and methanol or other alcohols . They can be developed by spraying or in the trough, depending on the particular radiation-sensitive layer, the substrate and the thickness of the radiation-sensitive layer. Optionally, a plate can be made negative working by treatment with an acidic etchant, while it is positive working if it is colored prior to etching. Some of the plates are positive working when developed in water or very dilute solutions of an alcohol in water, but negative working when developed in alcohol or other organic solvents.

In the following Table I some specific salts are listed which are suitable for the preparation of the recording material according to the invention.

13th

Table I A. Diazonium salts

14th

7. CH

HOC ₂ H ₅

OC ₂ H ₅

B (C ₆ H ₅ ) ₄

N ₂ ⁺ B (C ₆ H ₅ ), OC ₂ H ₅

N ₂ ⁺ B (C ₆ H ₅ J ₄

Nf B (C ₆ H ₅ ) I.

Nf B (C ₆ H ₅ ) I.

Nf B (C ₆ H ₅ U

NH

CH

CH,

CH, p-dimethylaminobenzenediazonium tetraphenylborate

p-Diethylaminobenzenediazonium tetraphenylborate

4-diethylamino-2-methylbenzenediazonium tetraphenylborate

4-diethylamino-2-ethoxybenzenediazonium tetraphenylborate

4- (N-hydroxyethyl-N-ethyl) -benzenediazonium tetraphenylborate

4-methoxybenzenediazonium tetraphenylborate

4-p-Tolylmercapto-2,5-diethoxybenzenediazonium tetraphenylborate

4-morpholinobenzene diazonium tetraphenylborate

4-morpholino-2,5-dibutoxybenzenediazonium tetraphenylborate

2 '- (2-styrylpyridine) diazonium tetraphenylborate

p-Diazodiphenylamine-formaldehyde resin-tetraphenylborate

15th

B. Azonia diazoketones

S-phenyl-o-diazo-S-oxo ^ a-azonia anthracentetraphenyl borate

B (QH ₅ )?

C. Quaternary salts with azide groups

CH = CH

■ Ν,

CH,

θ CH ₃

λ / xH O N-

CH = CH

"N ₃ B (C ₆ H ₅ ) I

N ₃ B (QH ₅ ) I 4'-Azido-1-methyl-2-styrylpyridinium tetraphenylborate

4'-Azido-1-methyl-2-styrylquinolinium tetraphenylborate

1- (4-Azidophenyl) morpholinium tetraphenylborate

D. Other nitrogen-containing tetraphenylborates

CH ₃ B (QH ₅ ) I.

B (C ₆ H ₅ ) I.

CH,

CH = CH

O ₇ N

N (CH ₃ ) ₂ B (QH ₅ ) I.

C-CH ₃

B (C ₆ H ₅ ) I.

I CH ₃

/ ^N \ e QH ₅ -C NC ₆ H

NN - C ₆ H ₅

B (C ₆ H ₅ ) I 10-methylacridinium tetraphenylborate

10 a-acridizinium tetraphenylborate

4'-dimethylamino-2-styrylpiridinium tetraphenylborate

2,3-dimethyl-6-nitrobenzothiazolium tetraphenylborate

2,3,5-triphenyl-2H-tetrazolium tetraphenylborate

009 545/396

17th 18th

(CH ₃ ) ₂ NH

CH = CHCH

B (QH ₅ )? 4-dimethylaminocinnamaldehyde tetraphenylborate

CH = CH

B (QH ₅ )?

NH ₂

H ₇ N

NH,

B (C ₆ H ₅ )?

NH ₃ ® B (C ₆ H ₅ ). 2'-amino-2-styrylpyridinium tetraphenylborate

Phenosafranin tetraphenyl borate

NH ₂ · H ₂ O p-rosaniline tetraphenylborate

NH,

10. (CH ₃ ) ₂ N

HB (QH ₅ ) ^

N (CH ₃ ), acridine orange tetraphenylborate

OC ₅ H ₁₁

OCH,

CH ₃ OC ₂ H ₅ B (QH ₅ )?

l-methyl-2,6-di- (4-ethoxyphenyl) -4- (4-n-amyloxyphenyl) -pyridinium tetra- phenyl borate

CH = CH

NO,

B (C ₆ H ₅ ) I ⁵ 4'-nitro-2-styrylpyridinium tetraphenylborate

19th

E. Other "onium" tetraphenylborates

1. (QH ₅ J ₄ As * B (C ₆ H ₅ ) I ⁵

2. [(NH ₃ J ₆ Co] a »®

3. [(QH ₅ ) ₂ Ti] «® [B (C ₆ H ₅ Wf

4. [(NH ₃ ) ₄ Pd] «® [B (C ₆ H ₅ Wf

5. [(C ₄ H ₉ J ₃ P] ₄ Pd ** [B (C ₆ H ₅ WI

Tetraphenylarsonium tetraphenylborate hexamine cobalt tetraphenylborate Dicyclopentadienyl titanium tetraphenyl borate tetramine palladium tetraphenyl borate

Tetra (tributylphosphine) palladium tetraphenylborate

CH = CH

N (CH ₃

CO

QH ₅

B (QH ₅ ) I.

/ NH-CH ₂

S = C

-CH,

₄ [B (C ₆ H ₅ Wf

[Co (NH ₂ CH ₂ CH ₂ NH ₂ ) ₂ · Cl ₂ ] ® [B (C ₆ H ₅ ) je

0 j B (QH ₅ ).

4- (4-dimethylaminostyryl) flavilium tetraphenylborate

Tetra (2-thioimidazolidone) cobalt tetraphenylborate

Cobalt di (ethylenediamine) dichlorotetraphenylborate

Tropylium tetraphenyl borate

11. CH ₃ S

B (QH ₅ J ₄ O Sn © B (C ₆ H ₅ ) J ⁵

Sb

SCH,

[B (QH ₅ ) ₄ ] f 7- (4-Chlorobenzylidene) -3-methylthio-4,5,6,7-tetrahydrobenzo [b] -1,2-dithiolium tetraphenylborate

7,7'-p-Phenylenedimethylidynbis [3-methylthio-4,5,6,7-tetrahydrobenzo [b] phenylborate]

2- (3-aminonaphthalene-1) -4,5-dihydro-1,3-dithiolium tetraphenylborate

Diphenylene iodonium tetraphenyl borate

Triphenyltin tetraphenylborate

Triphenylstibine tetraphenylborate

21

[(NHj) ₆ Cr] * <* ■> [B (C ₆ H ₅ ) Jf 22

Hexamine chromitetraphenyl borate

[CH ₂ NCH ₂ CH ₂ NH ₂ ) ₃ Cr]

[B (QH ₅ ) ₄ ] f> Ethylenediamine chromitetraphenylborate

OCH ₃

Z Z 19th the same 20th the same 21. the same 22nd the same 23 the same 24 the same 25th the same 26th the same CH = CH

B (QH ₅ )?

B (QH ₅ )?

C ₆ H ₅ C ₆ H ₅ B (C ₆ H ₅₎ I * N (CH _{3) 2} 2-methyl-3- (4-methoxyphenyl) -naphtho- [2,1-b] pyrylium

X -CI Y Z (19) -Cl O - H (20) - I. S. - H (21) T O - H (22) - N (CH ₃ ), S. - H (23) -SCH ₃ S. - H (24) -OH O - H (25) - H O -OH (26) S. - H

2,6-diphenyl-4- (4-chlorophenyl) pyrylium tetraphenylborate

2,6-diphenyl-4- (4-chlorophenyl) thiapyrylium tetraphenylborate

2,6-diphenyl-4- (4-iodophenyl) pyrylium tetraphenylborate

2,6-Diphenyl-4- (4-iodophenyl) -thiapyrylium tetraphenylborate

2,6-diphenyl-4- (4-dimethylaminophenyl) -thiapyrylium tetraphenylborate

2,6-diphenyl-4- (4-methylthiophenyl) pyrylium tetraphenylborate

2,4,6-tri- (4-hydroxyphenyl) pyrylium tetraphenylborate

2,4,6-triphenylthiapyrylium tetraphenylborate

Diphenyl-flO-styrylanthryl ^ J-cyclopropylium tetraphenylborate

Diphenyl (4-dimethylaminophenyl) cyclopropylium tetraphenyl borate

- ² ^ C ₆ H ₅ B (C ₆ H ₅ ).

Typical salts

1. 1-Alkyl-2 (4) -styrylpyridinium salts and their vinylogues;

2. 1-alkyl-2 (4) furylvinyl) pyridinium salts and their vinylogues;

3. N-vinyl pyridinium salts;

4. N-styryl pyridinium salts;

5. Polymethine bis [2 (4) pyridinium salts];

6. alkylenebis (styrylpyridinium salts);

7. 2,2'-azobispyridinium salts;

8. 4,4'-azobispyridinium salts;

9. cyclammonium salts having an azido group;

10. Salts of 4-dialkylaminostilbenes;

11. Salts of 4-dialkylaminophenylacrylonitriles;

12. Salts of 4-dialkylaminocinnamaldehydes;

13. Salts of glutaconaldehyde dianil;

14. vinyl polymers with stilbazolium salt groups;

15. Azoniaanthracinium salts;

16. Azoniaanthracinium diazoketone salts;

17. pyridinium salts;

18. quinolinium salts;

19. Benzothiazolium salts;

20. Salts of 4-dimethylaminobenzalanilines;

21. poly (vinyl pyridinium salts);

22. phosphonium salts;

23. dithiolium salts;

24. pyrylium salts;

25. thiapyrylium salts;

26. Metallocene salts, e.g. B. ferrocene salts;

27. Dipyridyl salts;

28. 4,4'-bis (dimethylamino) benzophenone salts;

29. 4-hydrazinoquinaldin salts;

30. p-rosaniline salts;

31. Poly (I-vinyloxycarbonylmethylene pyridinium salts);

32. crotyl triphenylphosphonium chloride;

33. 2,4,6-triphenylpyrylium tetrafluoroborate;

34. diphenylene iodonium bisulfate;

35. 2,6-bis (p-ethoxyphenyl) -4- (p-n-amyloxyphenyl) thiapyrylium perchlorate.

To produce the recording material of the sensitivities listed in Table II below

Sensibilizers suitable for the invention are to be used in the fol- lowers. In this way, to sensitize

in Table II. Some of these ization of the radiation-sensitive recording

Sensitizers are dyes. The selected 55 materials according to the invention, for example

Classification corresponds to the classification of staining- other known sensitizers are used

materials, as they are in the book by G i 1 m a n, "Organic those for the sensitization of common photopolymers

Chemistry ", Vol. Ill, pp. 246 to 391, Verlag John or for photopolymerization or for sensitivity

Wiley and Son, New York, 1953. This sation of common organic photoconductors is used

Classification of dyes will also be described 60.

by Venkataramanin "Synthetic Dyes", Vol. I, The sensitizers can be used in different men-

Chapter 5, pp. 241 to 247. can be used. It has proven to be useful

Many of the suitable sensitizers have been shown to be compatible with the coating solutions or coating

different functional groups and can processing masses 1 to 100 parts by weight of sensitizer

therefore classify in different ways. 65 per 100 parts by weight of organoborate salt to be incorporated

For the production of the radiation-sensitive task. It has proven to be particularly advantageous

Drawing material according to the invention can each have a ratio of sensitizer to organoborate salt

but also other known sensitizers than those of 1:10 to 1:50 parts by weight to be used.

Table II

Particularly suitable sensitizers for the sensitization of organoborate salts

I. Acridines

(a) acridine orange,

(b) N-phenylacridone,

(c) N-phenylthioacridone.

II. Anthrones (a) 9-Diazo-10-phenanthrone.

III. Azines

(a) p-dimethylaminocinnamalazine,

(b) Benzo [a] phenothiazine,

(c) Benzo [b] phenoxazine.

IV. Azo dyes and hydrazo compounds

(a) Orange II,

(b) hydrazobenzene.

V. Azomethine (a) 3,3'-Diethyl-4-methylthiocarbocyanine bromide.

VI. Polycyclic hydrocarbons (a) 5,6,11,12-tetraphenylnaphthacene.

VII. Diphenylmethane dyes

(a) auramine "O",

(b) N- (o-chlorophenyl) -leucauramine.

VIII. Halogen Compounds (a) 2,4,6-Tri- (tribromomethyl) -s-triazine.

IX. Heterocyclic compounds

(a) I-methyl-2-benzoylmethylen- / ⁱ i-naphthothiazoline,

(b) methyl-S-methyl - ^ - benzothiazolidendithioacetic acid,

(c) 4-quinolizone,

(d) 4-thioquinolizone,

(e) 1,2-diazoacanthone,

(f) 2,4,6-tri- (tribromomethyl) -s-triazine.

X. Inorganic Sensitizers

(a) phosphotungstic acid,

(b) phosphomolybdic acid,

(c) chromium acetate,

(d) cerium ammonium nitrate,

(e) chromium chloride.

XI. Ketones

(a) 4,4'-bis (dimethylamino) benzophenone,

(b) 4,4'-bis (dimethylamino) thiobenzophenone,

(c) 2,3-diphenylindenone.

XII. Methine

(a) 4- (Flavan-4-ylmethylene) flavilium perchlorate,

(b) 2,6-bis (4- / 3-hydroxyethoxybenzylidene) -4-methylcyclohexanone,

(c) 1,1 -Dicyano ^ -methyM-phenyl-1,3-butadiene,

(d) 2-styrylbenzo [b] pyrylium perchlorate,

(e) 2,5-difurfurylcyclopentanone.

XIII. Nitro compounds

(a) 5-nitroacenaphthenone,

(b) 2,6-dichloro-4-nitroaniline,

(c) 2,4,6-tri- (4-nitrophenyl) pyrylium perchlorate.

XIV. Organometallic Sensitizers

(a) dicyclopentadienyltitanium dichloride,

(b) dicyclopentadienyl iron,

(c) Cupric (picolin-1-oxide) 6perchlorate2 or hexapicoline-1-oxide cupriperchlorate.

XV. Oxanol dyes

(a) 2,6-diphenyl-4-thionathiapyron,

(b) o-Diethylamino ^ -methylcoumarin.

XVI. Pyrylium dyes

(a) 2,4,6-triphenylpyrylium fluoroborate,

(b) 2,4,6-triphenylthiapyrylium fluoroborate,

(c) 2,6-di- (4-ethylphenyl) -4- (4-n-amyloxyphenyl) thiapyrylium perchlorate,

(d) 2,6-di- (4-ethoxyphenyl) -4- (4-n-amyloxyphenyl) -thiapyrylium perchlorate,

(e) 2,4,6-tri- (4-methylthiophenyl) pyrylium perchlorate.

(a)

(a)

(a)
(b)

(C)

(d)

(e)

(0

XVII. Quinones
2-methylanthraquinone.

XVIII. Quinone imines
p-rosaniline hydrochloride.

XIX. Sulfur dyes
Ν, Ν-dicyclohexyldithiooxamide.

XX. Triphenylmethane dyes
Methyl violet,
basic fuchsin.

XXI. Xanthene dyes
Eosin,
Erythrosine,
Rhodamine B,
4 ', 5'-Diiodofluorescein,
Fluorescein,
Rose Bengal.

The sensitivity given in the following examples was determined by a method as described in J. Appl. Pole. Sci., II, pp. 302 to 311 (1959), is described.

In a series of tests, the known method was used exactly, i. i.e., there were constant exposure times and constant light intensities observed. The determined sensitivities were with the sensitivity of a standard recording material with a polyvinyl cinnamate layer compared.

In a further series of tests, the samples to be tested were placed in a commercially available exposure device exposed. This device had a conveyor belt that could be adjusted to various speeds and a light source with a 1200 watt high pressure mercury vapor lamp, which emitted 75 watts / 2.54 cm over a distance of 16 inches. The exposure time could be changed by changing the speed of the conveyor belt can be varied. At a transport speed of z. B. 0.61 m / min, the exposure time was about 1 minute. For comparison purposes, a non-sensitized comparison sample was also exposed each time. A set of the samples to be tested as well as a set of non-sensitized control samples were made exposed through a series of Wratten filters, each with a different proportion of the light of the visible and near UV spectrum transmitted, so that after development the spectral response of the samples could be determined. Another set of sensitized and non-sensitized Samples were exposed to 0.15 density levels through a silver step wedge.

The following examples are intended to illustrate the invention in more detail.

example 1
p-Dimethylaminobenzenediazonium tetraphenylborate

A solution of 23.5 g (0.10 moles) of p-dimethylaminobenzene diazonium fluoroborate with a melting point of 149 ° C in 200 ml of methanol and 100 ml of water and a solution of 34.2 g of sodium tetraphenylboron in 100 ml of methanol were mixed together. The yellow one immediately separated Tetraphenylborate. After filtering off and washing with water and methanol, the reaction product became dried in a vacuum desiccator at room temperature. The yield of the reaction product was 43.0 g, corresponding to 92% of theory. The melting point of the compound was 113 to 114 ° C. Max. = 377 ΐημ (= 45,000).

Analysis for C ₃₂ H ₃₀ BN ₃ : Calculated ... C 82.2, H 6.5, B 2.3, N 9.0;
Found ... C 82.5, H 6.4, B 2.5, N 9.0.

A solution of the compound in dimethylformamide was made by spin coating on a film support applied with a grained aluminum surface. The coating solution used contained 3% of the photosensitive compound. The recording material obtained was then with exposed to ultraviolet light through an original. Thereafter, the recording material was through Abwabbern developed with methanol, then treated with a desensitizing etching bath and finally colored with a bold lithographic printing ink. The recording material passed from a positive working recording material.

Example 2
p-Dimethylaminobenzenediazonium tetraphenylborate

3% solutions of the applied tetraphenylborate in dimethylformamide after the solutions sensitizers, as listed in Table II were added. The ratio of sensitizer to diazonium salt was either 1:10 or 1:20. The recording materials obtained were then in the im Example 1 described manner exposed, developed and sensitometrically tested.

The results obtained clearly show the effectiveness of the most varied of sensitizers in terms of general sensitivity as well as spectral response.

All recording materials were developed by wiping with methanol, then with treated in a desensitizing etching bath and finally colored with a bold printing ink. Most of the printing plates obtained were found to be positive working printing plates.

Sensitizer ratio of
Sensitizer too
Diazo salt Visible image *) Lithograph **) sensitivity Spectral sensitivity Without 0: 1 Ak P. 50 260 to 440 πΐμ Yes 1:20 away η 350 280 to 540 πΐμ Ib 1:20 Ak P. 350 280 to 500 ηΐμ Ic 1:20 Ak P. 350 280 to 520 η \ μ Ha 1:20 Ak P. 350 280 to 480 ηΐμ III a 1:20 away P. 450 300 to 580 πΐμ IIIb 1:20 Ak P. 450 290 to 550 ηΐμ IHc 1:20 Ak P. 110 290 to 530 ηΐμ IVa 1:20 away P. 180 290 to 480 ΓΠμ IVb 1:20 Ak P. 350 280 to 440 πΐμ Va 1:20 away P. 50 290 to 530 ηΐμ Via 1:20 away P. 110 290 to 500 ηΐμ Vila 1:20 away P. 450 280 to 500 πΐμ VIIb 1:20 away P. 250 280 to 520 πΐμ villa 1:20 Ak P. 450 290 to 500 πΐμ IXa 1: 10 Ak P. 200 290 to 500 πΐμ IXb 1: 10 Ak P. 300 290 to 500 rough IXc 1: 10 Ak P. 100 280 to 460 πΐμ IXd 1: 10 Ak P. 300 280 to 490 ηΐμ IXe 1:20 Ak P. 350 280 to 490 ηΐμ Xa 1:20 Ak η 80 300 to 470 πΐμ Xb 1:20 Ak η 250 280 bi> 540 ηΐμ Xc 1:20 Ak P. 45 280 to 450 ηΐμ Xd 1:20 Ak P. 80 280 to 480 πΐμ

*) Ak = copy image. Ab = fading image.
**) ρ = positive; η = negative.

continuation

ratio of Visible image *) Lithograph **) sensitivity Spectral sensitivity Sensitizer Sensitizer too
Diazo salt away P. 80 280 to 480 m.u. Xe 1:20 Ak P. 300 290 to 460 ηΐμ XIa 1: 10 away P. 110 280 to 540 ηΐμ XIb 1:20 Ak P. 250 280 to 480 ηΐμ XIc 1:20 Ak P. 70 280 to 530 ΐημ XIIa 1:20 Ak P. 30th 280 to 520 ηΐμ XIIb 1:20 Ak P. 100 280 to 450 ηΐμ XIIc 1:20 Ak P. 100 280 to 500 ηΐμ XIId 1:20 Ak P. 70 280 to 530 ηΐμ XIIIa 1:20 Ak P. 120 280 to 450 πΐμ XIIIb 1:20 Ak P. 90 280 to 550 πΐμ XIIIc 1:20 away P. 100 280 to 430 πΐμ XIVa 1: 10 away P. 110 280 to 500 πΐμ XIVb 1:20 away η 180 280 to 440 ηΐμ XIVc 1:20 Ak P. 300 280 to 490 ηΐμ XVa 1:10 Ak P. 350 290 to 480 πΐμ. XVb 1:20 Ak P. 300 290 to 470 ηΐμ XVIa 1:10 away P. 80 280 to 500 ηΐμ XVIb 1:20 away P. 150 290 to 500 ηΐμ XVIc 1: 10 away P. 400 290 to 560 πΐμ XVId 1:10 away P. 150 290 to 600 ηΐμ XVIe 1:10 Ak P. 200 280 to 480 ηΐμ XVIIa 1: 10 Ak P. 30th 280 to 540 ηΐμ XVIII a 1: 10 away P. 350 290 to 440 ηΐμ XIXa 1:20 away P. 80 290 to 440 πΐμ XXa 1:20 away P. 50 290 to 460 πΐμ XXIa 1: 10 away P. 50 290 to 450 πΐμ XXIb 1: 10 away P. 150 290 to 450 ηΐμ XXIc 1: 10 away P. 100 290 to 500 ηΐμ XXId 1: 10

*) Ak = copy image; Ab = fading image.
**) ρ = positive; η = negative.

Example 3

Tetraphenylarsonium tetraphenylborate

(C ₆ H ₅ ) ₄ AsB (C ₆ H ₅ ) ₄

Tetraphenylarsonium tetraphenylborate was prepared by reacting the chloride with an excess of sodium tetraphenylboron in water. The white tetraphenyl borate precipitated and was filtered off and dried. The melting point of the compound was 292 to 296 ° C. By applying 3% Solutions of the borate in dimethylformamide with a content of 0.3 percent by weight sensitizer Grained aluminum disks were used to make recording materials.

The recording materials were then with a quartz resonance lamp (90% emission at 2537 Ä) and using an aluminum step wedge fused silicon dioxide as a test template exposed.

The resulting panels were then buffed with a 10% aqueous trisodium

phosphate solution and with a 10% aqueous Isopropanol solution developed, treated with a desensitizing caustic bath and finally with colored in bold printing ink. The printing forms produced proved to work positively and the Parts or areas of the recording material that were not destroyed by the action of light were taken the ink on. When using the sensitizers IXd and XVId there was a 1.5 to 2.0 fold increase the sensitivity noted.

Example 4

10-methylacridinium tetraphenylborate l _max 340, 347, 348 πΐμ

B (QH ₅ )?

The orange, water-insoluble tetraphenylborate was made from the chloride. It had one Melting point from 194 to 195 ° C.

The tetraphenylborate was then used in the manner described in the previous examples Production of a recording material used, whereupon this through a series of Wratten filters was exposed. Thereafter, the recording material was rubbed off with a 10% aqueous isopropanol solution developed. The material was then etched with a desensitizing solution treated and colored with a bold printing ink. When using the most diverse, in The sensitizers listed in the table below were positive-working printing plates in all cases receive. In all cases, sharp printing forms were obtained when the recording materials passed through positive, transparent line and halftone originals were exposed.

The following table shows the sensitizers used in detail and the relative values achieved Sensitivities and the spectral sensitivities compared to a comparison sample with a specified spectral sensitivity of 180 to 400 mμ.

Sensitizer Sensitivity*) Spectral sensitivity Not sensitive sized ver same sample 1.5 280 to 400 πΐμ IXa 6.0 280 to 530 ηΐμ IXb 6.0 280 to 530 ηΐμ IXc 6.0 280 to 490 ηΐμ IXd 4.0 280 to 530 πΐμ XVIIa 3.0 280 to 460 πΐμ XIIe 4.0 280 to 460 πΐμ XVIb 5.0 280 to 430 πΐμ XVId 4.0 280 to 550 ηΐμ XIb 4.0 280 to 620 ηΐμ

When the sensitizers listed in the following table were used, those in the following Results listed in the table were obtained.

*) Number of 0.15 density levels, made soluble by a 1 minute exposure to a 1200 watt high pressure mercury lamp.

Example 5

Acridizinium tetraphenylborate . _max 352, 370, 399 ηΐμ

B (QH ₅ Ji *

To the effectiveness of the sensitization of the tetraphenylborate with a quaternary bridging nitrogen atom with the effectiveness of raising awareness of an appropriate connection with a To compare quaternary perinitrogen, the tetraphenylborate was obtained from 10a-acridizinium bromide in 96% yield by reaction with sodium tetraphenylboron in a water-methanol solution manufactured. The melting point was 262 to 265 ° C.

The compound was then used as described in Example 4 to prepare a recording material used. The acridizinium salt was found to be somewhat less photosensitive than that Acridinium salt.

number of Spectral sensitivity wedge 6th Sensitizer solubilized stages 280 to 400 πΐμ Comparative sample 0.5 280 to 530 πΐμ IXa 3.0 280 to 530 πΐμ IXb 6.0 280 to 400 ηΐμ IXc 3.0 280 to 420 πΐμ IXd 2.0 280 to 400 ΐημ XVIIa 6.0 280 to 400 πψ XIIe 0.5 280 to 430 ΐτίμ XVIb 3.5 280 to 540 πΐμ XVId 2.0 280 to 550 ηΐμ XIb 2.0 280 to 600 πΐμ XXIb 4.0 example

8-Phenyl-6-diazo-4-oxo-4α-azoniaanthracene tetraphenylborate

35

40

45

or B (QH _S )?

The sensitization of an azoniadiazoketone as both the parent fluoroborate and the was compared as tetraphenylborate by using both of the various sensitizers in Table II applied to aluminum substrates. For the production of the recording materials Coating solutions used the 2 percent by weight azoia compound and 0.2 percent by weight Sensitizer contained in dimethylformamide.

The recording materials produced using the fluoroborate were through a Step wedge with 0.15 density steps and exposed through a series of Wratten filters, the exposure took place in a device through which the test specimens at a speed of 60 cm per Minute were passed through. The specimens were developed with hot water. The photolysis products were found to be alcohol soluble and it was not practical to stain the plates. Some of the sensitizers resulted in colored photolysis products, from which it can be seen in some cases the results consisted of the sum of two independent photoreactions and not just in the Raising awareness of one connection through the other.

The water-insoluble tetraphenylborate was prepared by adding sodium tetraphenylborate to a solution of the fluoroborate in dimethylformamide. The reaction mixture was left without isolation of the photosensitive compound used to produce the recording material.

009 545/396

Without a polymeric binder, the compound can be used to produce an extremely effective, negative working lithographic system can be used when developing in methanol.

The recording materials made using the tetraphenylborate were half as long exposed like the recording materials that were produced using the fluoroborate. The following table shows the levels that have been copied out, i.e. H. the stages that are insoluble could be made, developed and colored.

Fluoroborate Spectral Tetraphenyl borate spectral
Sensation
possibility up at Sensation at 122 cm / minute Sensitizer 60 cm / minute possibility up 470 Πΐμ copied out
stages insoluble
stages 530 ΐη _μ Comparison 530 Ιϊΐμ 530 ΐημ material 3.0 550 πΐμ 8.0 500 ηΐμ IXb 4.0 530 ηΐμ 6.0 600 Πΐμ IXc 3.0 530 m> x 7.0 550 ηΐμ IXd 3.0 530 Πΐμ 7.5 470 Πΐμ XIb 5.0 53Om μ 9.0 550 ΙΠμ XVId 4.0 530 ma 7.5 560 ΙΠμ XVIIa 4.0 600 m ₍ x 8.5 XXIb 5.0 560 ΙΏμ 8.0 XXIc 3.0 6.1

Example 7
Diazonium tetraphenyl borate

The diazonium tetraphenylborates of compounds listed in Table I were made all as described in Example 1, prepared. The starting salts were either fluoroborates or zinc chloride double salts. All recording materials were found to work positively and could, as described in Example 2, be sensitized.

In order to compare the photochemical behavior of a diazonium tetraphenylborate with that of the fluoroborate compare, was both the tetraphenylborate and the fluoroborate (Example 1) in dimethyl sulfoxide solved. Formation took place immediately by adding 2,4-dimethyl-6-methylpyrylium perchlorate of a green dye. When applied to a substrate made of paper or aluminum Both dyes faded on exposure to light. The tetraphenylborate reacted more quickly. The two salts were mixed with 2,3-dihydroxynaphthalene and applied to a paper backing and exposed, in both cases pale violet print-out images were found in the exposed ones Districts received. If the papers were exposed to aqueous ammonia, those not exposed coupled Districts ab with the formation of a deep violet dye, which is characteristic of a diazo system is. In this case the fluoroborate reacted faster because the tetraphenylborate was less soluble in water is. It follows that the tetraphenylborate under both basic and acidic conditions clutch. A recording material made from the same tetraphenyl borate in a polyvinyl butyral binder] resulted in a purple printout image upon exposure to light and becoming insoluble of the polymer in the exposed areas. The tetraphenylborate behaved in this way similar to other diazonium salts.

Example 8

A quaternized nitrogen atom

containing tetraphenylborates
with an azide group

A solution of 3.64 g of 4'-azido-1-methyl-2-styrylpyridinium iodide in 110 ml of methanol, 20 ml of water and 20 ml of acetonitrile became a solution of 3.42 g of sodium tetraphenylboron in 40 ml of methanol and 10 ml of water were added. Immediately afterwards A heavy orange precipitate formed.

The precipitate was washed with water, filtered and dried. The yield was 5.23 g, correspondingly 94% of theory. The melting point of the compound was 165 to 166 ° C.

A solution of 3% of the tetraphenylborate in dimethylformamide was made by the fluidized coating process applied on a substrate with a grained aluminum surface. In further Experiments were further recording materials produced in such a way that instead of tetraphenylborate - Dimethylformamide solution corresponding solutions were used that contain 0.3% of a Contained sensitizer.

The recording materials obtained were then, as described in Example 2, exposed and developed. Methanol was used for development. After that, it was treated with a desensitizing agent Etching agent etched and colored with a bold printing ink. All recording materials proved as negative-working recording materials, since the photolysis products in these cases less were more soluble in the developer solution than the unexposed areas.

From the results obtained, however, it can be seen that the obtained azide radical salts are let sensitize if they are converted into tetraphenylborates. The fact that this and some other tetraphenylborate negative working systems instead of the usual positive working systems deliver, does not prevent their sensitizability.

Sensitizer sensitivity Spectral
Sensitivity up ⁵⁵ Comparative sample 250 450 ΙΉμ IXa 1000 490 m <x IXb 1410 530 ΐη _μ IXc 447 470 Γημ 60 IXd 710 530 Πΐμ XVId 250 500 1Ώμ XVIIa 790 500 Γημ

The tetraphenyl borate of 4'-azido-1-methyl-2-styrylquinolinium iodide was established and found to be particularly effective for producing a negative working lithographic printing plate.

Example 9
Diazonium resin

First, a 3% solution of a resin from p-diazodiphenylamine and formaldehyde was used as the fluoroborate made in dimethyl sulfoxide with 10% water.

A portion of the solution was fluidized onto a conventional aluminum support applied. The recording material obtained served as comparative material (A). An excess of sodium tetraphenylboron was added to the remaining solution, whereupon the Mixture was carefully warmed. When a sample of the resulting solution was poured into water, in this way a precipitate was obtained, from which the conversion of the resin into the tetraphenylborate was evident revealed.

Samples of the solution obtained were in the same way on an aluminum support with and applied without 0.3% of a sensitizer.

All panels were then exposed to a 1200 watt high pressure mercury lamp for 10 seconds exposed through a positive transparent original and a series of Wratten filters.

Plate (A) was found to be negative working plates when exposed to water or a mixture developed from water and methanol in a ratio of 1: 1, etched with an acidic, desensitizing etching bath and colored with bold printing ink would. Plate (B) as well as the other plates comprising tetraphenylborate layers were found all as positive working plates when developed with methanol and negative working plates Plates when developed with acetone. You could do the same with an acidic caustic bath etched and colored with a bold printing ink.

The plates containing the tetraphenylborate all showed a sensitivity that was around the Was 1.5 times greater than the sensitivity of the plate with a fluoroborate layer. All sensitized Tetraphenylborate plates showed spectral sensitization. The extent of the spectral Awareness can be found in the following table:

plate Sensitizer Spectral
Awareness Remarks (A) without 290 to 440 ma Fluoroborate (B) without 290 to 440 ηΐμ Tetraphenyl
borate (C) XVId 290 to 550 ηΐμ Tetraphenyl
borate (D) IXd 290 to 520 ηΐμ Tetraphenyl
borate (E) XXIb 290 to 570 ηΐμ Tetraphenyl
borate

55

60

This example shows that the diazonium resins are effectively sensitized to visible light can if they are converted into a tetraphenylborate.

It has also been found possible to use the tetraphenylborate resins either for the production of positive or for the production of negative working to use lithographic systems.

Example 10

Hexamine cobalt tetraphenyl borate
[(NH ₃ J ₆ Co] ^ ⁺ [B (QH ₅ J] ₄ O

Melting point 116 to 117 ^° C

A solution of 2.0 g (0.0076 mol) of hexamine cobalt dichloride in 100 ml of water became a A solution of 7.7 g of sodium tetraphenylboron in 30 ml of water was added. A bright orange fell Precipitate from which was filtered off and washed with water. The yield of tetraphenylborate was 6.6 g, corresponding to 89% of theory.

The compound was excellently suited for the production of negative-working printing forms, if they are applied to conventional aluminum substrates, developed with a 10% aqueous isopropanol solution, etched with an acidic desensitizing etching bath and finally colored with bold printing ink would.

There were recording materials using coating solutions of 3 percent by weight of the tetraphenylborate and 0.3% sensitizer in dimethylformamide using conventional Aluminum backing made.

The recording materials were exposed to a 1200 watt high pressure mercury lamp for 1 minute exposed, with a step wedge with 0.15 density units and a number of Wratten filters as a template served.

The recording materials were then developed and tested in the manner described. the The results obtained are summarized in the following table:

plate Sensitizer Insoluble
stages (A) without 0.5 (B) IXa 5.0 (C) XIb 4.0 (D) IXb 5.0 (E) IXc 5.0 (F) IXd 3.0 (G) XIIe 6.0 (H) XVIIa 1.0 (D XVIb 9.0

until 430 Πΐμ Spectral until 450 ΙΠμ until 600 ΙΉμ sensitivity until 450 Πΐμ 290 until 440 ΓΠμ 290 until 450 ΙΠμ 290 until 450 Πΐμ 290 until 400 ΙΏμ 290 until 550 ΓΠμ 290 290 290 290

Example 11

In the following table the results are compiled, which when using the in Table I listed tetraphenylborates were obtained. Whether or not these connections produce positive or negative-working printing forms depend on the relative solubilities of the unexposed ones and exposed areas as well as the specific solvent system used for development became, from. Most of the recording materials were found to work positively. Few turned out to be negative working. Others can be developed in such a way that they are positive deliver working printing forms or negative working printing forms.

37

The individual developer solutions used consisted of:

(a) 10% solution of isopropanol in water,

(b) methanol,

(c) desensitizing, rubber-free caustic agent,

(d) water,

(e) acetone,

(f) bold lithographic printing ink,

(g) 10% isopropanol, 10% methanol, 80% water, (h) 10% aqueous trisodium phosphate solution.

Table III
A. Diazonium salts

connection positive negative 1 b, c, f - 2 b, c, f - 3 b, f a, f 4th b, c, f - 5 b, c, f a, c, f 6th b, f - 7th b, f - 8th - a, c, f 9 a, f - 10 Cf d, f 11th b, c, f e, b, c, f

B. Azonia diazoketones

a, c, f

C. Quaternary nitrogen-containing salts with an azide group

b, c, f b, c, f Cf

D. Nitrogen containing tetraphenyl borates

10

11th

12th

a, c, f
b, c, f

b, c, f

a, c, f

a, f, c

b, c, f
b, f

b, c, f

a, c, f a, c, f a, f, c

a, f, c

a, f

b, c, f

E. Other "onium" tetraphenylborates h, a, c f

- a, c f

b, c, f

4th
5
6th

a, c, f
a, f

a, c, f

a, f

connection

positive

negative

E. Other "onium" tetraphenylborates

8th a, f, c - 9 b, cf - 10 d, f - 11th d, f - 12th d, f - 13th a, c, f - 14th a, c, f - 15th a, c, f - 16 - g, f, c 17th - g, f, c 18th a, f, c - 19th a, f - 20th a, f, c - 21 a, f - 22nd a, f, c - 23 d, f - 24 a, f, c - 25th a, f, c - 26th cf. - 27 a, f - 28 a, f - Example 12 p-dimethylaminobenzene diazonium tetratolyl borate

The tetratolyl borate was prepared by reacting equivalent amounts of p-dimethylaminobenzene diazonium fluoroborate with lithium tetratolyl boron in a 20% aqueous methanol solution. The unusual one yellow precipitate of the tetratolyl borate was filtered off, washed and dried. the Melting point was 98 ° C.

To produce recording materials, 3% solutions of diazonium tetratolyl borate in dimethylformamide were applied to conventional, grained aluminum substrates by the fluidized coating process.
Further recording materials were produced in the same way, except that 0.3 % of a sensitizer from Table II was added to the coating solutions.

The recording materials obtained were then exposed in an exposure device which the specimens were passed through at a speed of 91 cm per minute. In all Cases, fading images were obtained in the exposed areas.

Treat by developing by wiping with a 10% isopropanol solution in water with a desensitizing etching solution and coloring with a bold printing ink were positive working printing forms get, whereas when using hot water for wiping off, Application of the printing ink and etching negative-working printing forms were obtained.

The spectral sensitivities of the printing forms obtained were determined using the following

the indicated sensitizers expanded as follows:

Comparative sample up to 440 ηΐμ,
Sensitizer III a to 550 πΐμ,
Sensitizer XI b up to 540 ηΐμ,
Sensitizer XXI b to 630 πΐμ.

The tetratolyl borate was found to be more soluble in alcohol than the corresponding tetraphenyl borate. It can be developed to form either positive or negative working printing forms.

Example 13

p-Dimethylaminobenzoldiazoniumtriphenyl-

cyanoborate

The triphenyl cyanoborate was prepared by reacting equivalent amounts of p-dimethylaminobenzene diazonium fluoroborate with sodium triphenylcyanoboron in a solution of 20% methanol in water. The resulting yellow precipitate was filtered off, washed and dried. The melting point of the compound was 135 ° C.

Using the triphenyl cyanoborate, recording materials were made as described in Example 12 manufactured. The printing forms obtained were found to work positively. Were the recording materials however, overdeveloped, they became negative-working printing forms.

In those cases where the recording materials were exposed through Wratten filters, negative-working images were obtained when the specimens through filters which transmitted light of the regions of the spectrum opposite to which the Test items were very sensitive. In contrast, positive working images were obtained when the specimens were exposed through filters that transmitted light of the regions of the spectrum, opposite to which the test items showed only minimal sensitivity.

The peak sensitivity of the salt is about 370 ηΐμ, so the exposure using a tungsten daylight with little ultraviolet light. This in conjunction with Wratten filters, which allow only one band of the visible spectrum to pass through, clearly shows the effective one spectral sensitization, which is exposures with light sources rich in ultraviolet light, were not showing.

The following table shows the results obtained on exposure of various recording materials with various sensitizers.

The number of (+) signs indicates the relative intensity of the image. If (-) characters were used, so this means that negative working forms were obtained. All recording materials were wiped off with isopropanol. In addition, a desensitizing etching bath was used and a greasy printing ink was used for dyeing.

The fluorescein dyes were found to be generally effective spectral sensitizers for Diazonium triphenyl xyanoborate.

Both the tetratolyl and triphenyl cyanoborate salts were found to be less thermal stable and photographically stable than the tetraphenyl borate. Both salts are more soluble in alcohol and can be more easily hydrolyzed and decomposed in acid than tetraphenylborate.

Table IV
Spectral sensitization of p-dimethylaminobenzene diazonium triphenylcyanoborates

attempt Sensitizer 15th 58 \
47 Vrattenfilter N
32 r.
23 A + Image*) Litho **) A. Without + + + + + + P / N B. HIa + + + + + + + + + + + away P / N C. IXb + + + + + ak P / N D. XIb + + + + + ak P / N E. XVIIIb + + + + + away P / N F. XXIa + + + + + + + + + away P / N G XXIb + + + + + + + + + + + + away P. H XXIc + + + + + + + + + + ak P / N I. XXIe + + _ | " P / N J XXIf + + + + + + + a P.

*) from = can be faded. ak = can be copied out.

P / N = positive working and negative working.

Permeability of the Wratten filter

No. 15> 51θΓη _μ

No. 58 470 to 620 ηΐμ

No. 47 360 to 540 ΐτίμ

No. 32 290 to 510,> 600 πΐμ

No. 23 A> 560ΐημ

B e i s ρ i e 1 14,

° 5

To a solution of 1.42 g / i-ß '-p-phenylenebis (2-vinylpyridine) in 40 ml of dimethylformamide at 100 ^r C an excess of a 5% aqueous hydrochloric acid solution was added to give the dihydrochloride of the base formed. A solution of 3.4 g of sodium tetraphenylborate in 20 ml of water was then added, whereby the corresponding orange-colored tetraphenylborate was precipitated. The latter was filtered off.

A 3% solution of the tetraphenylborate salt in dimethylformamide was then made by spin coating applied to a conventional aluminum support. After drying, the recording material became For 5 minutes using a UV lamp placed at a distance of 10 inches

009545/396

exposed through a halftone negative for 5 minutes. Then the recording material was through Wiping off with a 5% aqueous trisodium phosphate solution, etching with an acidic, desensitizing agent acting etching solution and coloring with a printing ink developed. In this way an extremely effective positive printing form for offset printing was obtained.

Example 15

2,2'-Azopyridine was quaternized with ethylene bis (oxymethylene chloride), whereupon the salt obtained was converted into the corresponding tetraphenylborate in the same way as the dihydrochloride according to Example 14.

The resulting tetraphenylborate was then used as described in Example 14 to prepare a Recording material used. This was then, as described in Example 14, into a printing form processed. In this way, another extremely effective positive printing form was created for the Received offset printing.

Example 16

Initially, 5,6-dihydroxy-4a-azoniaanthracene perchlorate was made according to the method used by Fields and co-workers in »J. Org. Chem. ”, 30 (1965), p. 252. The perchlorate was then oxidized to 5,6-dioxo-4a-azoniaanthracene nitrate by means of an aqueous nitric acid solution, which is then converted into the corresponding tetraphenylborate according to the method described in Example 14 was convicted.

A 3% solution of the resulting tetraphenylborate in dimethylformamide was then after Fluidized coating process applied to a conventional aluminum substrate. After drying of the coating solution, the recording material was for 5 minutes through an in exposed at a distance of 25.4 cm UV lamp through a halftone negative. The recording material was then rubbed off with a 5% aqueous trisodium phosphate solution developed. The recording material was then etched with an acidic desensitizing bath etched, after which it was colored with printing ink. In this way it became an extremely effective one received positive planographic printing form.

When using 5,6-dioxo-4a-azoniaanthrazene perchlorate instead of the described tetraphenylborate a positive printing form was obtained, but this turned out to be considerable less receptive to printing ink.

Example 17

55

Initially, after the approach by Fields and co-workers in »J. Org. Chem. ", 30 (1965), p. 252, described process 5,6 - dihydroxy - 8 - phenyl-4a-azoniaanthrazenbromid manufactured. This was then oxidized to 8-phenyl-4a-azoniaanthracene-5,6-dione nitrate by means of an aqueous nitric acid solution.

A mixture of 34.8 g of 8-phenyl-4a-azoniaanthrazen-5,6-dione nitrate and 25 g of p-toluenesulfonyl hydrazide was dissolved in 100 ml of methanol which was saturated with hydrogen chloride. After standing at room temperature for 15 minutes, the red solution was diluted with 200 ml of water and 50 ml of fluoroboric acid. In this way, the 6-diazo-S-oxo-S-phenyMa-azoniaanthrazentetrafluoroborat was obtained in the form of a yellow crystalline product, which after 2 hours of cooling the reaction mixture - was filtered off 20 ⁰ C.

A 3% solution of 6-diazo-5-oxo-8-phenyl-4-a-azoniaanthracentetrafluoroborate in dimethylformamide was reacted with an equivalent amount of sodium tetraphenylborate for 5 minutes at 50 ° C. The resulting solution was then applied to a conventional granular aluminum support by spin coating.

The recording material obtained was then, as described in Example 16, exposed and developed. In this way, a positive planographic printing form was obtained.

Example 18

A solution of 0.5 g of polyvinyl chloroacetate and 1.0 g of 4'-methoxy-4-stilbazole in 20 g of dimethylformamide was heated ^{to 75 ° C. for 15 minutes.} The resulting solution was then poured into diethyl ether, whereupon a polymeric reaction product precipitated. A sample of the precipitated polymeric reaction product was dissolved in dimethylformamide and reacted with an equivalent amount of sodium tetraphenylborate. The solution obtained in this way was then applied to a conventional aluminum support. The recording material obtained was then exposed and developed in the manner described. In this way, an excellently effective positive planographic printing form was obtained.

Was the quaternized polymer used to produce the planographic printing plate, which was not was reacted with sodium tetraphenylborate, a negative planographic printing form was obtained, however the positive image obtained was found to be considerably less receptive to printing ink.

Example 19

A 3% solution of triphenylphosphonium-2-p-nitrophenylazocyclopentadienylide in dimethylformamide was concentrated with an equivalent amount Hydrochloric acid and an equivalent amount of sodium tetraphenylborate reacted, whereupon the solution obtained by the fluidized coating process on a conventional aluminum support was applied.

The dry recording material was then removed for 10 minutes using a exposed by a UV lamp set up by 2.54 cm through a photographic negative. Subsequently was the recording material developed with the aid of a 5% strength aqueous trisodium phosphate solution. Thereupon the recording material was etched with an acidic, desensitizing etching bath, painted and colored. In this way, a positive planographic printing form was obtained.

Example 20

First, a coating composition was prepared by reaction of a 3% solution of titanocene dichloride in dimethylformamide with an excess of sodium tetraphenyl borate at 5O ⁰ C. The coating composition was then applied to a conventional aluminum substrate. After drying, the recording material obtained was passed through an in

exposed at a distance of 25.4 cm UV lamp through a halftone negative. Subsequently the material was developed, etched with an acidic, desensitizing etching bath and usually colored. In this way, a negative planographic printing form was obtained.

A recording material produced in a corresponding manner, which in place of the titanocentetraphenylborate contained a cobaltocentetraphenylborate, produced in the same way a negative flat

printing form. . .

Example 21

A 3% solution of 4- (4-methylphenyl) -1, 2-dithiolium hydrogen sulfate in dimethylformamide was treated with an excess of sodium tetraphenylborate in the presence of a trace of hydrochloric acid implemented. The resulting solution was then applied to a conventional aluminum support. After the solution had dried, the recording material was used for 10 minutes using a exposed at a distance of 25.4 cm UV lamp through em halftone negative. Subsequently the recording material was developed with water and colored with printing ink. It was receive a positive planographic printing form.

Example 22

A 2% solution of l, 4-Xylylenbis- (4'-methoxy-4-styrylpyridiniumbromid) in dimethylformamide was reacted with an excess of sodium tetraphenylborate by brief heating to 40 ⁰ C with stirring. The tetraphenylborate formed was not isolated. (When a sample of the reaction mixture was poured into water, a yellow precipitate was obtained.) Rather, the reaction mixture was applied to a conventional aluminum support by the fluidized bed process. The dry recording material was then exposed for 4 minutes through a positive negative using a UV lamp set up at a distance of 25.4 cm. The exposed recording material was then developed using a dilute aqueous trisodium phosphate solution and then using water. The recording material was then etched with an acidic, desensitizing etching bath and colored with a conventional printing ink. In this way, a positive planographic printing form was obtained. The spectral sensitivity of the plate was expanded to 300 to 470 ηΐμ.

B e i s ρ i e 1 23

A 2% solution of 2,5-diethoxy-4- (p-tolylmercaptoj-benzenediazonium chloride-zinc chloride in dimethylformamide was applied to a conventional aluminum support by fluidization. The recording material was then for 5 minutes using a at a distance of 25.4 cm placed UV lamp exposed through a positive, transparent original. Subsequently was the recording material is developed with a dilute aqueous trisodium phosphate solution. It was received a good quality negative picture.

To a 2% solution of the diazonium salt in the same dimethylformamide, an excess of sodium tetraphenylborate was added, and the mixture was briefly warmed to 40 ⁰ C. The reaction solution was then applied to a conventional aluminum support. The recording material obtained was then exposed and developed in the manner described. A positive image of excellent quality was obtained. The image obtained accepted printing ink and could be used as a planographic printing plate.

Example 24

A 3% solution of rhodamine B in dimethylformamide was treated with an excess of sodium tetraphenylborate added, whereupon the reaction mixture after the fluidization process on a conventional aluminum support was applied. After the light-sensitive Layer was the recording material in the manner described by a positive, transparent Original exposed. In this way a positive fade image was obtained. By developing the recording material with a dilute aqueous trisodium phosphate solution, etching with a desensitizing agent acting etching solution and coloring with printing ink, a planographic printing form became more excellent Maintain quality.

A 2% solution of rhodamine-B-tetraphenylborate in a mixture of acetone and acetonitrile was applied to a paper carrier equipped with a polyvinyl alcohol-titanium dioxide layer had been. In this way there was obtained a positive working recording material which after exposure and development in the manner described, a planographic printing form was more excellent

Quality delivered. . .

Example 25

A solution of 18.7 g of 5,6-dihydroxy-4a-azoniaanthrazenbromid and 10 g of N-Isobutoxymethylpiperazin in 200 ml of aqueous 50% acetic acid for 5 minutes heated at 8O ⁰ C, then diluted with 150 ml of water and then for 1 hour cooled down to -5 ° C for a long time. A total of 13.8 g of red crystals were filtered off, which were washed with water. The crystals were then oxidized to 8,8'-methylenebis (5,6-dioxo-4a-azoniaanthracene nitrate) using 50% nitric acid. This compound was then reacted first with p-toluenesulfonylhydrazide and then with fluoroboric acid in the manner described in Example 17 in the presence of hydrogen chloride. A total of 9.4 g of 8,8'-methylenebis (6-diazo-5-oxo-4a-azoniaanthrazentetrafiuoroborate) was obtained.

A mixture of 0.04 moles of 8,8'-methylenebis (6 - diazo - 5 - oxo - 4 a - azoniaanthrazentetrafluoroborat) and 20 g of cyclopentadiene in 400 ml of a mixture of nitromethane and acetonitrile in a ratio of 1: 1 was allowed to stand at room temperature for 30 minutes and then diluted with diethyl ether. Included riel 8,8'-methylenebis (6-diazo-5-oxo-5,6,9,10-tetrahydro - 4 a - azonia - 9.10 - cyclopent -14 - enoanthracentetrafluoroborate) the following structural formula:

CH

where X = BF ₄ .

A solution of 2.5 g of sodium tetraphenylborate in 20 ml of acetonitrile was added to a solution of 2.75 g of the compound of the formula given with X = BF ₄ in 30 ml of acetonitrile, whereupon the mixture was briefly heated to about 35.degree. The solution was then poured into diethyl ether, whereupon the resulting yellow precipitate of the tetraphenylborate of the compound of the formula indicated was precipitated. The compound was filtered off and dried.

A 2% solution of the tetraphenylborate in dimethylformamide was made by the fluidized coating process applied to a conventional aluminum support, followed by the applied layer was dried. The recording material obtained was then recorded for 2 minutes by means of a exposed at a distance of 25.4 cm UV lamp through a positive original. Subsequently was the recording material using a 5% aqueous trisodium phosphate solution developed, rinsed with water, treated with an acidic desensitizing etching bath and colored with printing ink. In this way a positive reproduction of the positive original was made obtained that could be used as a printing form.

Example 26

First, a coating solution (A) was prepared from 6.5 ml of a 10% strength solution of the tetrafluoroborate the compound of the formula given in Example 25 in dimethylformamide and 5 ml a 10% solution of sodium tetraphenylborate in dimethylformamide. Starting from this coating solution (A) the following recording materials were produced:

(a) A and 11.5 ml of dimethylformamide on a substrate made of a copper plate;

(b) A and 11.5 ml of a 2% solution of cellulose acetate hydrogen phthalate in cyclohexanone from a substrate made of a copper plate;

(c) A on a substrate made of a copper plate;

(d) A and 11.5 ml of a 2% solution of ethyl cellulose phthalate in cyclohexanone on a substrate made of a copper plate;

(e) A and 11.5 ml of a 2% solution of phthalated Polyvinyl acetal in 2-ethoxyethanol on a copper plate Support;

(0 A on a galvanized aluminum substrate;

(g) A and 11.5 ml of a 2% solution of ethyl cellulose phthalate in cyclohexanone on a galvanized aluminum substrate;

(h) A and 11.5 ml of a 2% solution of cellulose acetate hydrogen phthalate in cyclohexanone on a galvanized aluminum substrate;

(i) A and 6.25 ml of a 2% solution of a copolymer of ethyl acrylate and acrylic acid im Ratio 4: 1 in 2-butanone and 6.25 ml of dimethylformamide on a copper plate existing substrate;

(j) A and 5.8 ml of a 5% solution of a novolac in cyclohexanone and 5.7 ml of dimethylformamide on a copper plate Support;

(k) A and 11.5 ml of a 2% solution of phthalated polyvinyl acetal in 2-ethoxyethanol on a galvanized aluminum substrate;
(1) A and 6.25 ml of a 2% solution of a copolymer of ethyl acrylate and acrylic acid in a ratio of 4: 1 in 2-butanone on a galvanized aluminum support and
(m) A and 5.8 ml of a 5% solution of a novolac in cyclohexanone and 5.7 ml of dimethylformamide on a galvanized aluminum substrate.

The recording materials obtained were each measured for 3 minutes by means of one at a distance exposed from 25.4 cm UV lamp through a transparent, positive template and then with a dilute alkaline solution. In this way, positive images were obtained, which tested for resistance to a 42 "Be remote chloride etch bath.

It was found that the recording material (b) had the best resistance to the etching bath exhibited. After standing in the etching bath for 10 minutes, there was only very little detachment of the resist layer. The resistance of the other recording materials with copper substrates decreased in the following order: (i), (j), (d), (c), (e) and (a).

When using the recording materials with galvanized aluminum supports, in all In some cases, positive resist images were obtained which, however, were not deeply etched by the etching bath.

Example 27

3% solutions of 2,6-diphenyl-4- (4-iodophenyl) -pyrylium perchlorate and 2,6-diphenyl-4- (4-iodophenyl) thiapyrylium perchlorate in dimethyl sulfoxide were fluidized on Aluminum support applied.

Furthermore, in another experiment, the specified perchlorates were converted into the corresponding Tetraphenylborate converted by their 3% solutions in dimethyl sulfoxide in each case an excess of sodium tetraphenylborate were added and the solutions were carefully warmed. The received Solutions were then also applied to aluminum plate supports.

The four recording materials obtained were then each for 20 seconds using a 1200 watt high pressure mercury lamp by a positive original exposed. The recording materials made using the perchlorates did not produce any visible images. After carefully wiping off with a 10% aqueous isopropanol solution and inking with printing ink gave faint negative images.

On the other hand, when using the two recording materials made using the Tetraphenylborates were produced, images that could be bleached were obtained, as well as ink-receptive positives Images, if the recording materials are developed with a 10% aqueous isopropanol solution, were etched with a desensitizing etching bath and colored with the printing ink.

Example 28

3% solutions of diphenyliodonium bisulfate, triphenyltin chloride and triphenylstibine dichloride in An excess of sodium tetraphenylborate was added to each dimethyl sulfoxide, whereupon was slightly heated. In this way the corresponding tetraphenylborate solutions were obtained. The solutions obtained were then applied to conventional aluminum substrates by the fluidized-bed process applied. After the layers had dried, the recording materials were in each case for 10 minutes by means of a quartz resonance lamp with a 90% emission at 2537 Å a positive original is exposed. The recording materials were then rubbed off with a 10% aqueous isopropanol solution developed, whereupon the recording materials are treated with a desensitizing etching bath and were then colored with printing ink. In this way, planographic printing forms became more excellent Maintain quality.

Example 29

To a solution of 0.5 g of butadienyl triphenylphosphonium perchlorate an excess of sodium tetraphenylborate was added in 10 ml of methanol. The precipitated white precipitate of the tetraphenylborate was filtered off and redissolved in dimethylformamide to give a 3% solution.

The resulting solution was then spin coated onto one of a Aluminum plate applied to the existing substrate. The obtained recording material became then for 10 minutes with a UV lamp placed at a distance of 10 inches and below Using a positive transparent line art exposed. No visible image was obtained. However, if the plate was buffed with methanol or an acidic etching bath, it was obtained a positive image that could be colored. In this way a positive printing form could be created can be obtained.

In further experiments, the tetraphenylborates used in the examples given were replaced by other of the borates described. Correspondingly favorable results were obtained in all cases.

Claims (4)

Patent claims: 1. Radiation-sensitive recording material, consisting of a layer support and a radiation-sensitive layer containing a radiation-sensitive salt with a cation that if necessary, a radiation-sensitive diazonium azoniadiazoketone or onium salt cation, contains a sensitizing compound and optionally a binder, thereby characterized in that it is a salt or a salt-like compound as the radiation-sensitive salt with at least one central, fourfold substituted boron atom of the following formula: R ₂ R ₁ -BR ₃
R ₄ χ® wherein R ₁ denotes an aryl group, R ₂ , R ₃ and R ₄ each denotes an aryl, short-chain alkyl, aralkyl, cyano or short-chain alkenyl group, or two of the groups R ₁ , R ₂ , R ₃ and R ₄ together an arylene radical and X® an organic cation with at least one nitrogen, arsenic, tin, antimony, sulfur, iodine, phosphorus, oxygen, titanium, palladium, chromium or cobalt atom as a carrier of the positive charge . 2. Radiation-sensitive recording material according to claim 1, characterized in that that it has a radiation-sensitive salt of the formula given in which the anion from a tetraphenyl borate, triphenyl cyanoborate, tetratolyl borate or bis-2,2'-biphenylene borate anion consists. 3. Radiation-sensitive recording material according to claim 1, characterized in that that there is 0.01 to 1 part by weight of a spectral compound per part by weight of radiation-sensitive compound Contains sensitizing compound. 4. Radiation-sensitive recording material according to claim 1, characterized in that that, as a spectral sensitizing compound, it is a sensitizer from the class of Acridines, azo dyes, azomethine dyes, anthrones, diphenylmethane dyes, azines, methine dyes, Oxanol dyes, pyrylium dyes, quinones, quinone imines, sulfur dyes, triphenylmethane dyes or contains xanthene dyes. 009 545/396