NO133035B - - Google Patents

Description

The invention concerns new, light-sensitive connections

see, for use as copying material and method for producing these.

It is known to use light-sensitive aromatic diazonium compounds to sensitize reproduction material intended for the production of single copies or printing plates.

Diazonium salts with several diazonium groups in the molecule and with a high molecular weight have been advantageously used, especially for the production of tinted images or planographic print originals, where the reproduction layer is rendered insoluble or oleophilic by exposure to light. These diazonium compounds usually have a resin character and are produced, e.g. by introducing diazonium groups into phenol-formaldehyde condensation resins,

either by nitration, reduction and diazotization or in other known ways. The diazo resins produced in this way have imide-

lertid some disadvantages, e.g. very low storage stability,

and has therefore not found practical significance.

Polyfunctional diazonium salts have been prepared

in another way, by certain aromatic diazonium salts being condensed in an acidic condensation medium with active carbonyl compounds, especially formaldehyde. This type of high molecular diazonium compounds is used on a large scale for the production of reproduction material, especially for the production of print originals

is. Among these compounds, such as e.g. described in the U.S. pat-

patents Nos. 2,063,631 and 2,667,415, especially condensation products between diphenylamine diazonium salts and formaldehyde have achieved great technical importance.

Production of such and similar diazo resins be-

is further written in the U.S. Patents Nos. 2,679,498, 3,050,502,

3,311,605, 3,163,633, 3,406,159 and 3,277,074.

Production of toned images by combining such diazo resins with hydrophilic colloids and, if desired, dyes or pigments in connection with reproduction layer, is described, e.g. in the U.S. patents Nos. 2,100,063, 2,687,958 and 3,010,389.

However, this class of diazo resins has gained the greatest importance in connection with reproduction material for the photomechanical production of pianographic and offset printing plates or originals. The diazo resins can be used in the reproduction layers in these materials without other additives, or e.g. in combination with water-soluble colloids or with water-insoluble polymers that are not light-sensitive. Examples of suitable substrates or support layers for these reproduction layers are water-resistant paper types with a suitable lithographic surface, e.g. surface saponified cellulose acetate, metal substrates such as aluminium, zinc, copper, brass, chromium, niobium and tantalum, multi-metallic substrates and lithographic stone. Metal substrates are preferred when large layers are to be made, and aluminum is usually used.

The use of metal as a substrate material for a reproduction layer containing the listed diazo resins has, among other things, the disadvantage that the adhesion between the diazo resin exposure products on the metal substrate is usually not very good and furthermore that the metal can have a certain decomposition effect on the diazo resin.

A number of proposals have been made to avoid these disadvantages, e.g. to pretreat the metal surface with silicates (U.S. Patent No. 2,714,066), with organic polyacids (U.S. Patent No. 3,136,636), with phosphonic acids or their derivatives (U.S. Patent No. 3,220,832), with potassium hexafluorozirconate (U.S. Patent No. 2,946,683), further to use diazo resins prepared in phosphoric acid (U.S. patent no. 3,235,384), to add phosphoric acid to the diazo resins and use these in a metal salt-free state (U.S. patent no. 3,236,646), and to use anodized aluminum surfaces.

Despite the fact that they are widely used in technology, the known diazo resins have other disadvantages. With the low molecular weight condensates which offer advantages in terms of storage resistance, only unsatisfactory ink receptivity is achieved on the exposure products on non-metallic substrates into which the mass can easily penetrate, e.g. on surface saponified cellulose acetate film.

Other disadvantages of the known diazo resins lie in

that in the form of the usually used double salts with zinc chloride and especially as metal salt-free products containing phosphate or similar anions, gives a reproduction layer that has great sensitivity to moisture and thus to fingerprints. If the layers are handled carelessly, the layers can be easily destroyed.

To avoid this disadvantage, it has been proposed in the U.S. patent No. 3,300,309 to react the diazo resins with certain phenolic coupling components to obtain addition products that are only slightly soluble in water and provide reproduction layers that are less sensitive to moisture. These addition products,

which contain relatively loose salt-type or complex-type bonds, can be easily decomposed again, e.g. with organic solvents, and their stability is thus not sufficient under all conditions.

Furthermore, the photosensitivity is not satisfactory, particularly for the known diazo resins which have excellent thermal stability, e.g. condensation products between 3-Alkoxy-4-diazo-diphenylamine and formaldehyde.

A common disadvantage of the hitherto most used diazo resins is that they can only be processed in a metal salt-free form with difficulty, e.g. as chlorides, sulfates or salts with simple organic sulfonic acids, and their salts are often insufficiently soluble in organic solvents.

It has now been found that these disadvantages of previous technology can be avoided or at least reduced considerably by using new diazo condensation products instead of the hitherto used diazonium salts, for the above purposes.

The invention relates to the condensation product of an aromatic diazonium compound for use as a light-sensitive substance in copying material, the condensation product being characterized by the fact that it consists of units of the general types A-N2X and B in an average molar ratio between 1:0.01 and 1:50, which is connected by means of divalent intermediates derived from a condensable carbonyl compound, the units A-N2X being derived from at least one compound/ with the general formula

in which

X denotes an anion of the diazonium salt,

p means 1, 2 or 3,

R., means an iso- or heterocyclic aromatic group, which has at least one condensable position,

1*2 means an arylene group of the benzene or naphthalene series,

1*2 means a single bond or one of the groups

-<CH2)q-NR4-

-(CH 2 ) g -NR 4 -(CH 2 ) r -<NR>5<->

-0-(CH2)r-NR4-

-S-(CH2)r-NR4-

-0-R6-0--0-

-s-

-C0-NR4 or

-S0o-NO.-

2 4

where q denotes a number of 0, 1, 2, 3, 4 or 5,

r means 2, 3, 4 or 5,

R4 means hydrogen, an alkyl group with 1-5 carbon atoms, an aralkyl group with 7-12 carbon atoms or an aryl group with 6-12 carbon atoms,

R,, means hydrogen or an alkyl group with 1-5 carbon atoms,

Rg means an arylene group with 6-12 carbon atoms,

and the units B are derived from at least one of the following compounds: aromatic amines, phenols, thiophenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic heterocyclic compounds or organic acid amides, these compounds being free of diazonium groups and in an acidic medium at at least one position in their molecule is able to condense with active carbonyl compound.

The condensation products of the invention have a number of advantages compared to the known materials which have been prepared with the previously known diazo resins. Many of the new diazo mixed condensates do not penetrate certain substrates, e.g. surface saponified cellulose acetate, to the same extent as the known diazo condensates. The result is that the exposure products left after development have better oleophilic properties on the surface. Most of the new reproduction materials also have increased light sensitivity, less sensitivity to moisture, improved compatibility with polymers commonly used as additives in the layers, and other advantages compared to the corresponding known diazonium salts, which is described in more detail in the following.

The light-sensitive condensation products are available in the form of diazonium salts.

The new condensation products can be prepared by condensing in a strongly acidic environment at least one aromatic diazonium compound of general formula AHS^X and at least one compound B, which symbols have the above meanings, with at least one active carbonyl compound in free form, or with substances that produce such carbonyl compounds .

Practically all compounds that can condense

in a known manner in a strong, acidic environment with compounds that have reactive hydrogen atoms, are suitable as active carbonyl compounds for the production of the condensation products of the invention. Suitable compounds are listed in the U.S. patent No. 2,063,631.

Formaldehyde is strongly preferred as a carbonyl compound because this substance is absolutely the most reactive and at the same time the cheapest compound in this class. The other aliphatic, aromatic and heterocyclic aldehydes, and even more so the ketones, are considerably less reactive and, furthermore, they often lead to undesirable side reactions during the condensation process. The term "formaldehyde" in the present description and claims includes: aqueous solutions of formaldehyde, gaseous formaldehyde, formaldehyde oligomers and polymers, such as trioxane and paraformaldehyde, and other substances that give formaldehyde, e.g. urotropin.

From US patent no. 3,277,074, a method is known for the condensation of diphenylamine diazonium salts with formaldehyde in a halogen hydrogen acid. Condensation products are thereby formed in which diphenylamine-diazonium salt units are linked by means of methylene groups. There is no indication that these highly polar water-soluble salts can be reacted together with completely non-polar compounds such as aromatic hydrocarbons or with extremely reactive compounds such as phenols to form a mixed condensation product in which units of both types appear in a statistical arrangement. The feasibility of this procedure could not be predicted.

Another process for the preparation of diazo mixture condensates of the above general type, which has certain advantages, is described below. This method has been patented in Norwegian application no. 1905/70. In principle, mixed condensates of a similar type as described in the present application and according to the procedure below can also be prepared by converting A-^X compounds into B compounds in the presence of an active carbonyl compound, e.g. by the method described in the present application.

In the simplest and also preferred modification of the method described in said ongoing parallel application, no active carbonyl compound is used as such for the mixed condensation and instead of component B, a modified component B.^ with general formula is used:

where

E is a group that results from the removal of m H atoms from a compound B with the above meaning,

R cler equal to H, aryl, alkyl group, preferably hydrogen,

Rfc is equal to H, alkyl or acyl with 1-4 C atoms or phenyl, preferably hydrogen, methyl, ethyl or acetyl, and m is an integer from 1 to about 10.

It is assumed that component B^ during the condensation reacts completely or partially with component A-N2X or with itself (when there is an excess of component B^), during intermolecular cleavage of HOR^, whereby condensation pro-

the ducts are formed.

This method offers a number of variations when it comes to carrying out the condensation, the quantitative ratios used between the compounds or the use of other additives, e.g. active carbonyl compound and components B.

The condensation is carried out in the presence of a strongly acidic condensation medium. Concentrated medium to strong acids are preferably used where the acid content is greater than the diluent content. Furthermore, the condensation medium should be chosen so that it is liquid under the condensation conditions.

The lower limit for the amount of acid condensation medium used for mixed condensations according to all the process variations below is determined by the viscosity of the mixture, and the upper limit by the economics of the process. The method is preferably chosen so that on the one hand as little acid as possible is used and on the other hand a condensation mixture is obtained which can be easily stirred and mixed. When choosing the type and amount of acid to be used, the condensability and solubility conditions of the components of the acid should be taken into account.

The most favorable conditions for each combination A-^X and B^ or B and active carbonyl compound are determined by previous experiments. Particular attention should be paid to ensuring that the exothermic condensation reaction does not take place too violently, since this would make regulation and control of the reaction process difficult and further lead to decomposition of the diazo compound.

Examples of suitable condensing medium acids are listed in U.S. Pat. Patent No. 3,235,382, column 1, line 71, to column 2, line 5.

Particularly advantageous condensation media are phosphoric acid, methanesulphonic acid and sulfuric acid, which acids are used in concentrations of at least 40% and preferably 70 to 100% by weight. The rest is usually water, but can also consist wholly or partly of solvents such as methanol, acetic acid and N-methyl-pyrrolidone. 85% phosphoric acid, 80% sulfuric acid and 90% methanesulfonic acid can e.g. successfully used.

85Sig phosphoric acid is a fairly mild condensation

medium, where the condensations can be made very, nicely. This is therefore the preferred condensation medium due to combina-

tions of compounds that react sufficiently quickly in this rather mild reaction environment. 90% methanesulfonic acid is a stronger environment. This acid has the great advantage that it can dissolve most of the components B and B^.

Hydrogen halide acids that are at least 15% and preferably

show concentrated, aqueous hydrochloric or hydrobromic acid is

■ <. - - ■

only to a limited extent suitable as a condensation environment, e.g. for the production of mixed condensates with highly reactive phenols.

Use of these acids is less favorable with other components B,

e.g. phenol ethers and aromatic hydrocarbons or derivatives B^ of these, since haloalkyl compounds with low reactivity

tet is formed under these conditions" and these do not react further under relatively moderate condensation conditions.

For the same reason, diazonium salts such as diazonium phosphate

fats or sulfates superior in many cases compared to halides, as starting materials for condensation.

When diazonium salts in the form of the commonly used metal halide double salts are used for the mixture condensation, it is usually advantageous to dissolve them in the condensation medium, then pass nitrogen or dry air through the mixture

none until all the chloride ions have been driven off in the form of gaseous

form hydrochloric acid, and then use the halogen-free solvent

ning for the condensation.

The amount of acid that makes up the condensation medium can

vary within wide limits. One can e.g. use 1 to 100

parts by weight acid per weight part mixture A-N2X + B + active carbonyl compound or A-N2X + B^ as shown in the examples. Acid-

the amount can also be higher without, however, leading to

parts in most cases. It is important to use a condensing medium in sufficient quantity to achieve an easily mixable rice jpns mixture.

Depending on the condensing medium, condensing part-

the tags and their concentration in the medium, there may be a need to accelerate the condensation reaction by heating or delay it by cooling. It is beneficial to use one

condensation temperature below 70°C, since the diazo compound's A-N2X is usually limited at higher temperature. Many of the diazo condensation products of the invention can be prepared above 70°C. However, the preferred temperature range is between + 10 and 50°C.

It is an advantage to carry out all modifications of the mixture condensations in homogeneous reaction media, because reproducible results are most easily obtained in such environments. Therefore, components which are not liquid are preferably used in the form of solutions, the solvent used is preferably the condensing acid. If some of the components are only slightly soluble in the condensation medium, they can be introduced in the form of fine suspensions or emulsions in the condensation medium. In all cases, care should be taken to ensure that the condensation mixture is thoroughly mechanically mixed.

If the condensation process is made difficult by insufficient solubility of the starting materials or end products, a homogeneous condensation medium can be obtained by adding an organic solvent. Naturally, tests must be carried out in each case to determine which organic solvents are suitable. Glacial vinegar has proven to be suitable in many cases. Other good solvents are e.g. formic acid, N-methyl-pyrrolidone and methanol. When adding an organic solvent, it should be taken into account that this often reduces the effectiveness of the condensation medium compared to unmixed concentrated acid, and that the use of a solvent can also lead to side reactions.

The amount of active carbonyl compound, preferably formaldehyde, which is used per mol total molar amount of the mixture of diazo compound A-N2X and component B (0.25 mol A-N2X and 0.75 mol B, e.g. is 1 mol, a chain of pre-condensed units A-N2X or pre-condensed units B perceived as a molecule), is usually between 0.5 and 4, preferably between 0.65 and 2 mol.

When the carbonyl compound is used in quantities within the above range, soluble condensation products will usually be obtained from diazo compounds A-N2X and components B which contain one or two reactive positions per molecule. The use of soluble condensation products is preferred for use as light-sensitive material in reproduction materials. If one or both components A-N2X and B have three or more positions that can be condensed, it may in some cases be an advantage, especially under strong condensation conditions, to use less active carbonyl compounds within the above range, if one wishes to obtain soluble products.

For the production of mixed condensates, the quantity ratio between reactants A-N^X and B and the condensation conditions can be varied within wide limits.

It is in principle possible to make mixed condensates

with any desired composition, i.e. all mixed condensates which in composition lie between diazo condensates containing only traces of the second component B which has been condensed in and a condensate of the second component B which contains only traces of the diazo compound A-N2X condensed in. Generally speaking, mixed condensates which on average contain between 0.01 and 50 mol of the second component per mol A-^X be suitable for the production of usable light-sensitive reproduction materials. Apart from special cases, the most important mixed condensates will contain between 0.1 and 20 mol of the second component per moles of A-N2X. Within this range, the mixed condensates usually exhibit properties that clearly distinguish them from the corresponding homocondensates.

If a mixed condensate e.g. contains 0.11 mol of component B per; mol A-N2X, which corresponds to 10 mol-% of the condensate, this would ideally mean that each molecular condensate contains 9 units of A-N2X per unit component B. In this case, a real mixed condensate can only be produced at a degree of condensation of at least 10. Since the degree of condensation is often below 10 and beyond, except in cases with a strong tendency towards co-condensation, since one must assume that the same units are collected in individual molecules of the mixed condensate, it will often happen that during mixed condensation you get mixtures of the same mixed condensates and homocondensates, and these cannot be easily separated in all cases. In the present application, the term "mixed condensate" also includes such mixtures.

If one is to prepare a mixed condensate with a special composition A- U^ X to B = a : b, the starting materials can be carefully mixed in the quantity ratio a: b and the mixture condensed, provided that the reactivity of the two compounds over the active carbonyl compound is the same. However, the reactivity of the individual components towards formaldehyde, e.g. will usually be different, and it will generally be advantageous to determine the ratio of quantities, starting substances and the condensation conditions required to obtain a product having the desired composition, by simple tests in each case. When the reactivity of component A-X towards the carbonyl compound varies considerably from the reactivity of component B, the condensation can be started with a component which condenses last, and the other component can be added later. In the simplest case, the mixed condensation is carried out by dissolving component A-X and component B in an acid suitable as a condensation medium, and the carbonyl compound is added either in the form of the compound itself or as a solution, with vigorous stirring.

However, the performance of the mixed condensation process is not limited to this method. Thus in many cases one can mix the components A-N^X and B with a carbonyl compound, and introduce the mixture or the individual components into the acid either in the form of a solution or as such. Alternatively, the carbonyl compound can be dissolved in the acid and the two compounds introduced one after the other or as a mixture in the form of the substances themselves or as solutions. As another alternative, one component can be present in the acid in solution, and the other component and the carbonyl compound are added either individually or in a mixture, in the form of the compounds as such or in solution.

-The condensation reaction can be started with only one component, and the other component is added later, if desired together with an additional amount of carbonyl compound. One can even, according to one of these methods, condense diazo resins, i.e. resins produced by acid condensation of diphenylamine-4-diazonium salts with carbonyl compounds, which diazo resins have lower condensation

degrees, with one or more components B and an active carbonyl compound in an acidic environment. In some cases, one can carry out a mixed condensation between a low molecular weight homocondensate of the second component with A-^X in the presence of a carbonyl compound in an acidic environment, and even a mixed condensation between homocondensates of a component A-^X with homocondensates of component B, or mixed condensates of different components B in an acidic environment in the presence of a carbonyl compound.

By varying the condensation conditions as indicated above, different end products are obtained (solubility, degree of incorporation of component B,) even if the starting material is used in the same quantity ratio.

You must therefore maintain uniform condensation conditions when you want to reproduce the production of a mixed condensate with constant properties.

When components B^ are used for the production of mixed condensates, either alone or together with other substances, such components B^ are usually preferred for the production of soluble condensates where m = 2 or somewhat greater than 2, i.e. about. 3 or 4. Within this class, components with m = 2 are particularly preferred, since they give condensation products with a simpler structure and, also when using several moles of B^ per mol A-N2X, get condensation products with less tendency to crosslink and form insoluble products. This is off. particularly important if strong condensation conditions are used. Component B, where m is greater than 2, is preferably used in smaller amounts, as the amount of such compounds usually does not exceed 1 mol per moles of diazo compound.

The upper limit must be established in each case by experiment. An important application of such components, where m is greater than 2, consists in using them together with compounds where m = 2.

Components B^ where m = 1 can also be used for condensation, but in this case diazo condensates are obtained which only contain one diazo group per molecule, when n = 1 in A-N^X. The use of such condensation products for reproduction layers is usually not preferred. However, it can be advantageous to combine components of the type B^ where m = 1 with components where m = 2 or greater than 2. In these cases, the first-mentioned component m = 1) can carry out a regulatory function for the molecular size during the reaction .

When m is equal to 2 or a number greater than 2 in component B^ and B^ is used in an amount that per mol A-^X constitutes less than 1 equivalent of -CH^-OR^ groups (1 mol of component B^ with m = 2 contains 2 group equivalents, for example), it is an advantage to add active carbonyl compound, preferably formaldehyde, in an amount so great that the sum of group equivalents -CHR^ORtøAnd the molar amount of formaldehyde added, multiplied by 2 (i.e. its condensation equivalents), amounts to at least one equivalent per moles of diazo compound. Larger amounts of formaldehyde can be used, but usually the above-defined sum of condensation equivalents should not exceed 4. Larger amounts of formaldehyde can, however, be used in special cases. As a further possibility for the production of higher condensates from components B^ where m = 1, one can add an active carbonyl compound, preferably formaldehyde, during the production of the condensate also in cases where one or more moles of component B^ are used per moles of diazo compound. In these cases, a minimum amount of formaldehyde of 0.5 mol per mol component B^ and per moles of diazo compound in excess of the molar amount of B^. The added amount of formaldehyde usually does not exceed 2 mol per moles of diazo compound and component B^.

The average molecular weight of the condensation products can vary greatly, depending on the starting materials and the reaction conditions. It has been found that mixed condensates with molecular weights of between 500 and 10,000 should generally be preferred for the production of good reproduction materials. It must be emphasized that these figures are mean values and that the molar weights for the individual components within each condensate are distributed statistically around this mean value. The type of distribution will appear in some of the later examples after fractionation of the produced condensates.

The mixtures obtained by condensation can be used directly or processed further. The mixtures can also be worked up and the condensates separated in solid form.

The processing of condensation mixtures can be carried out in different ways. The method is adapted to the chemical and physical properties of the particular reaction product. Mixed condensates containing a relatively large amount of

the other component/ can often be worked up by stirring the condensation mixture in water. It often happens in these cases that a water-soluble mixed condensate can be separated from the aqueous mother liquor in the form of some heavily soluble salt.

When the mixed condensate is water-soluble, but poorly soluble in organic solvents, the product can often be separated by diluting the reaction mixture with an organic solvent, e.g. with a lower alcohol or ketone.

An advantage of many condensates produced according to the present method consists in their simple preparation in the form of salts free of complex-forming metal salts. For example, many condensates give sulphates, chlorides and bromides which are sparingly soluble in water and which can be precipitated from aqueous solutions of the condensation mixtures by addition of the corresponding sycers and their salts which are soluble in water.

Certain processing methods are described in the examples below.

Groups that affect the condensability of components A-N2X and B are the following: (1) Aryl radicals and heterocyclic radicals which have condensable positions in the ring. Radicals where these ring or core positions are activated are preferred. This activation can e.g. carried out by linking with several aromatic rings or by substitution with groups such as -OH, -O-alkyl, -O-aryl, -SH, -S-alkyl, -S-aryl, -alkyl, -aryl, -amino, -alkylamino , -dialkylamino, -arylamino, -diarylamino and the like. In addition to these activating substituents, condensable aromatic or heterocyclic radicals may also contain condensation-inhibiting groups, e.g. nitro or sulphonic acid groups, if the activation from other groups is only reduced but not eliminated. (2) Radicals which can themselves be condensed and directly connected with iso- or hetero-cyclic radicals or aliphatic radicals or, if desired, directly connected with each other. Such radicals are groups such as carboxylic acid amides, sulfonic acid amide,

N-alkylsulfonic acid amide, N-arylsulfonic acid amide, nitriles, urea, thiourea, urethane, ureido, thioureido, glyoxaldiurein, imidazolone, guanidine, dicyanodiamide and amino groups directly attached to aromatic rings.

The following compound types or single compounds are examples of components with the general formula A-N2X, B and B^, of types used for the production of diazo condensation products according to the invention.

Diazonium compounds A-N^X

The main idea is that a benzene ring bearing the diazo group, apart from only a few exceptions (e.g. 4-diazophenol) not included here, is deactivated to such a high degree that condensations to this ring are no longer possible under milder condensation conditions .

Diazonium compounds that can be used according to the invention thus contain in the radical A, in addition to the aromatic iso- or heterocyclic nucleus carrying the diazo group, at least one iso- and/or heterocyclic ring with at least one condensable ring position and/or with substituents of the above type 2 which can even condense.

Diazonium compounds for production into condensation products according to the invention have the following general formula:

where

p is an integer from 1 to about 3, preferably 1,

X is an anion of the diazonium salt, it can also be an acid-substituted in the molecule,

is an aromatic iso- or aromatic heterocyclic group, optionally substituted, which has at least one condensable position, and is preferably a phenyl group, optionally substituted.

Preferred substituents will increase the core's reactivity towards condensation, e.g. alkyl, alkoxy, alkylmercapto, aryloxy, arylmercapto, hydroxy, mercapto, amino and anilino. R2 is an aromatic ring in the benzene or naphthalene series, which in addition to the diazo group may contain other substituents,

R^ is a connecting link between the rings R^ and R2, e.g. of the types below, where the radical R should always be thought of as placed on the left side and the group R2 on the right side, if R3 is unsymmetrical:

Single homopolar bond

-(CH2)q - NR4 - (q is a number from 0 to 5, R4 is equal to H or alkyl with 1-5 carbon atoms or aryl with 6-12 C atoms) -(CH2)g-NR4-(CH2) r-NR5- (r is a number from 2 to 5, Rg is H or alkyl with 1-5 C atoms,

-0-(CH2)r-NR4-

-S-(CH2)r-NR4-

-O-Rg-0- (Rg is the aryl with 6 to 12 carbon atoms)

-0-

-S-

-CO-NO.-

4

-S62-NR4-

Examples of compounds with formula

is

2,3',5-trimethoxy-diphenyl-4-disonium chloride

2,4',5-triethoxy-diphenyl-4-diazonium chloride

4-[73-(3-Methoxy-phenyl)-propylamino7-benzenediazonium sulfate 4-£~N-ethyl-N-(4-methoxy-benzyl)-amino7-benzenediazonium chloride 4-£N-(naphthyl-(2)-methyl )-N-n-propyl-amino7-benzenediazonium sulfate 4-^" n-(3-phenoxy-propyl)-N-methyl-amine^-2, 5-dimethoxybenzene-diazonium tetrafluoroborate 4-£" N-(3-phenylmercapto-propyl )-N-ethyl-amino7-2-chloro-5-methoxy-benzenediazonium chloride

4-(3-methyl-phenoxy)-phenoxyY7~2,5-dimethoxy-benzenediazonium chloride

4-(4-Methoxy-phenylmercapto)-2,5-diethoxy-benzenediazonium chloride 2,5-diethoxy-4-phenoxy-benzenediazonium chloride 4-(3,5-dimethoxy-benzoylamino)-2,5-diethoxy-benzenediazonium- hexafluorophosphate

carbazole-3-diazonium chloride

3-Methoxy-diphenylene oxide-2-diazonium chloride

diphenylamine-4-diazonium sulfate.

Mixed condensates that are particularly suitable for use in reproduction layers are produced from diazo compounds with a general formula

where

p is a number from 1 to 3, preferably 1,

is a phenyl group, unsubstituted or substituted with one or more alkyl or ialkoxy groups,

R2 is a benzene ring which, in addition to the diazonium group, may contain one or two identical or different substituents which may be halogen atoms, alkyl groups with 1-4 C atoms or alkoxy groups with 1-5 C atoms, and

R^ is a homopolar bond or one of the groups below -0-

-S-

-NH-.

A particularly important group of diazo compounds with structures according to the general formula R^ - R^ - R2 - N2X' and which are preferably used according to the present invention for the preparation of diazo condensation products, are salts of the diphenylamine-4-diazonium ion and its substitution products, since these are particularly easily condensable in many cases, and the condensation products provide particularly usable reproduction layers.

Particularly favorable substituents which can be connected to the phenyl nucleus in the diphenylamine-4-diazonium compounds are alkyl and alkoxy with 1-6, preferably 1-2 C atoms. Furthermore, halogens and the following groups can be used:

-COOR (R is H, alkyl or aryl)

-CONH2

-CN

-COR (R is alkyl or aryl)

-SO20R (R is H, alkyl or aryl)

-NHCOR (R is alkyl or aryl)

-NHR and NRR' (R and R' are alkyl, aryl or aralkyl).

Examples of such substituents which can be connected to the phenyl nucleus in the diphenyldiazonium group are methyl, propyl, isobutyl, trifluoromethyl, methoxy, difluoromethoxy, ethoxy, hydroxyethoxy, ethoxyethoxy, fluorine, chlorine, bromine, iodoethoxycarbonyl, phenoxycarbonyl, acetyl, methoxysulfonyl, ethoxysulfonyl , acetylamino, methylamino, ethylamino, dimethylamino, diethylamino, methylethylamino, phenylamino, benzylamino, methylbenzylamino and ethylbenzylamino.

Suitable diphenylamine-4-diazonium salts are e.g. diazonium salts derived from the following amines: 4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4*-amino-4- methoxy-diphenylamine,

4-amino-3-methyl-diphenylamine, 4-amino-3-ethyl-diphenylamine, 4'-amino-3-methyl-diphenylamine, 4'-amino-4-methyl-diphenylamine, 4-amino-3-ethoxy- diphenylamine,4-amino-3-hexyloxy-diphenylamine,4-amino-3- 1& hydroxy-ethoxy-diphenylamine,4 *-amino-2-methoxy-5-methyl-diphenylamine, 4-amino-3-methoxy-6- methyl-diphenylamine, 4'-amino-3,3'-dimethyl-diphenylamine, 3'-chloro-4-amino-diphenylamine, 4'-amino-4-n-butoxy-diphenylamine, 4'-amino-3', 4-dimethoxy-diphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-2'-carboxylic acid and

4'-bromo-4-amino-diphenylamine.

Preferred compounds are 4-amino-diphenylamine and 3-methyl-4-amino-diphenylamine, and particularly preferred are 3-alkoxy-4-amino-diphenylamines with 1-3 C atoms in the alkoxy group, and

quite especially 3-methoxy-4-amino-diphenylamine.

Suitable diazonium compounds A-N^X for the condensation reaction according to the invention can also be homo-condensation products of the described diazo compounds with active carbonyl compounds, i.e. relatively low molecular weight types of the known diazo resins, for example, which according to the invention can be regarded as large molecules suitable for further condensation and containing several diazo groups.

Diazonium compounds A-^X can be reacted in the form of any soluble salt of a medium to strong acid, e.g. in the form of salts of sulfuric acid, orthophosphoric acid, hydrochloric acid, trifluoroacetic acid, methanesulfonic acid and benzenesulfonic acid. Sulphates and phosphates are preferably used. Components B.

In the same way, a large amount of compounds are suitable as component B for the production of mixed condensates. An important class are the substituted or unsubstituted aromatic hydrocarbons and aromatic heterocyclic compounds, provided they have ring positions which can be condensed in an acidic environment with carbonyl compounds.

A large number of unsubstituted aromatic, isocyclic and heterocyclic compounds are thus suitable as component B, e.g. benzene (reacts heavily), naphthalene, anthracene, phenanthrene, pyrene, indene, fluorene, acenaphthene, thiophene, furan, benzofuran, diphenylene oxide, benzothiophene, acridine, carbazole and phenothiazine.

Isocyclic and heterocyclic aromatic compounds, especially those that are rather difficult to condense, can advantageously contain one or more identical or different substituents that activate the ring or core, which in this way condenses more easily and increases the solubility of the components as well as the solubility of the products.

Examples of such substituents are

"NR7R8

-<N>(<R>8)2

-0R7

- ORg

"<R>8

- SR7

-SRg

where

R7 can be H, -CO-alkyl, -CO-aryl, -CO-heteroyl, -CO-aralkyl,

-S02-alkyl, -S02~aryl, -S02~aralkyl, -S02~heteroyl, -CONH2, -CSNH2, -CONH-alkyl, -CONH-aryl, -CO-0-alkyl, -CO-0-aryl, -CS-O-aryl and -CS-O-alkyl, and Rg can be H, alkyl, aryl or aralkyl.

Meanings and special expressions are as follows: Alkyl: A branched or unbranched alkyl group with 1 - 10 C atoms, which may be substituted e.g. with halogen, alkoxy, -OH, -COOH, -CONH2, -CN, -CO-CH3, -SO-jH or -PO^, or adjacent hydrogens may be replaced by oxygen (epoxides) or removed (double or triple -bindings). Alkyl radicals can also be interrupted by e.g. -O-, -S-, -N(alkyl)-, -SO 2 - or -SO-.

Aryl: A mono- or polynuclear aromatic ring which, including alkyl, alkoxy or aralkyl which may be attached to the ring system, contains 6 to 20 carbon atoms. The aryl ring may contain other substituents.

Aralkyl: A group containing 7 to 20 C atoms and consisting of alkyl and aryl radicals (according to the above definition).

Alkoxy: 0-alkyl group where alkyl has the indicated meaning.

The alkyl, aryl, aralkyl and alkoxy groups can be present one or more times, either individually or together. In order that this substituent proportion of the molecule in relation to the molecular weight of B does not exceed certain limits, the amount of the four above substituent types is limited in the compound B in relation to the molecular structure, as the primary, aromatic iso- or heterocyclic ring or ring system should only be substituted to such an extent that the compound

The total increase in C atoms due to these four substituent types combined should not exceed 30 C atoms on the original aromatic nucleus present.

It appears from this that substituents with longer chains, i.e. those with a relatively large number of C atoms occur less frequently together with each other than those with few C atoms. In general, short-chain alkyl and alkoxy groups (1-4 C atoms) and the smaller aromatic radicals in aryl and aralkyl groups are preferred

(up to 12 C atoms) since the corresponding compounds are more easily soluble in the condensation media and the condensation in this way can be carried out more easily.

The above-described limitation of the substitution follows for these reasons.

The condensable iso- or heterocyclic aromatic rings can also carry substituents which have a deactivating effect on the core system, e.g. 02N-; H00C-, N=C-, HC^S, H203P-, Cl- and Br- provided that condensability is not thereby eliminated. This will particularly be the case when the ring as such is easily condensable or when it carries substituents which have a considerable activating effect. Other possibilities

/

for the introduction of deactivating substituents without reducing the condensability of the ring is to place the substituents in side chains, e.g. aliphatic side chains.

Substituents which deactivate ring condensation can also be present in such cases where the nucleus does not need to

have condensation reactivity because the nucleus has substituents where the condensation can take place. Such substituents are mentioned above, e.g. the groups -CO-NH2, -SO2NH2 and -SC^NH-alkyl.

According to the above, the compounds that can be used as component B or B^, derived from the former, belong to the following compound groups, e.g.: aromatic compounds (iso- and heterocyclic) unsubstituted,

aromatic amines,

phenols and thiophenols,

phenol ethers and thiophenol ethers,

aromatic compounds substituted with alkyl, aralkyl or aryl,

urea, thiourea, carboxylic acid amides (aliphatic and aromatic), and

sulphonic acid amides, (aliphatic and aromatic). Examples of single connections follow the page.

According to the present invention, soluble types of the new diazo condensation products are preferably used. In addition to a corresponding selection of components A-N2X and B or B.^ according to the properties of these compounds, and with a favorable quantity ratio, preferably used together with these, with the intention of obtaining soluble condensation products, such components B and/or B^ which have molecular weights of less than 500 and preferably less than 250 (amines are considered as free amines, not in the form of salts, acid groups are considered in the H form). As far as aromatic compounds are concerned, those containing no more than 4, preferably 1 - 2 and especially 2, single aromatic rings (fused rings and/or rings connected by homopolar bonds and/or via intermediate groups) are preferred.

The use of compounds B or B^ with a low molecular weight is also an advantage because these are often more easily soluble

in the condensation media and thus reacts more easily.

Among the specified compound classes from which compounds B and B^ can be taken, those which are unsaponifiable or only heavily saponifiable in an acidic condensation environment are preferred. The same applies to diazo compounds A-N2X.

For this reason, preferred compounds B or in the series of aromatic iso- and heterocyclic compounds which are unsubstituted or substituents bear the groups alkyl, aralkyl, aryl, alkoxy, alkylmercapto, aryloxy, arylmercapto, OH, SH and amino, if desired in addition to unsaponifiable deactivators substituents, e.g. COOH. Among these compounds, aromatic iso- and heterocyclic compounds which are unsubstituted and/or contain as substituents one or more of the groups alkyl, aralkyl, aryl, alkoxy, alkylmercapto, arylmercapto, aryloxy and arylthio are particularly preferred, especially when one wants to arrive at condensates which must not contain other salt-forming groups than the diazo group.

Examples of particularly suitable types of these compound classes are compounds B or B^ derived from diphenyl ether and diphenyl sulphide which optionally contain one or two substituents in the group of halogen atoms, alkyl groups and alkoxy groups, but which, however, are preferably unsubstituted.

If these compounds are condensed with diphenylamine-4-diazonium salts which are unsubstituted or substituted with a lower alkyl group or a lower alkoxy group with up to 3 C atoms, mixed condensates are obtained which can be precipitated easily and with good yield in the form of salts of hydrochloric acid, hydrobromic acid or suitable sulphonic acids which are mentioned below, particularly when component B^ is used in quantities of 0.5 to 2 mol per moles of diazo compound.

The new condensation products according to the invention generally contain 0.01 to 50 mol, preferably 0.1 to 20 mol, on average, units of component B and/or per mol units of component A-N2X. Particularly preferred is the range between 0.2 to 2 mol B and/or B^ per moles of A-N2X.

The condensates can be used in different ways. In some cases, the new condensation products can be used in the form of raw condensates, i.e. without separating the condensation medium. This is particularly possible when the amount of condensation/action medium per moles of diazo compound can be kept low.

In general, the new condensation products will be separated in the form of one or another salt, and used in this form, after the addition of other desired layer constituents, for the production of reproduction material.

The diazo condensation products can be worked up or separated as salts of the following acids and used as such: hydrogen halide acids such as hydrofluoric acid, hydrochloric acid and hydrobromic acid, sulfuric acid, nitric acid, phosphoric acids (5-valent phosphorus), especially orthophosphoric acid, inorganic iso- and heteropoly acids, e.g. phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half-esters, arsonic acids, phosphinic acids, trifluoroacetic acid, amidosulphonic acid, selenic acid, fluoboric acid, hexafluorophosphoric acid and perchloric acid, further aliphatic and aromatic sulphonic acids, e.g. methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 2,6-di-tert. butyl-naphthalenesulfonic acid, 2,6-di-t.butyl-naphthalenedisulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid, 4,4'-diazidostilbene-3,3'-disulfonic acid, 2-diazo-l- naphthol-4-sulfonic acid, 2-diazo-1-naphthol-5-sulfonic acid and 1-diazo-2-naphthol-4-sulfonic acid. Other organic sulfonic acids suitable for working up the condensates are listed in columns 2 - 5 of the U.S. patent No. 3,219,447.

The new diazo condensation products can also be separated in the form of double salts with metal halides or -pseudo-halides, e.g. of the metals zinc, cadmium, cobalt, tin and iron, or as reaction products with sodium tetraphenyl borate or with 2-nitro-indanedione-(1,3) and then used in a known manner.

Under the influence of sodium sulphite, sodium azide or amines, they can also be transferred to the corresponding diazosulfonates, -azides or -diazoamino compounds and used in this form, as is known from the use of diazo resins.

The following advantages of the new diazo condensation products have previously been listed: a) Less penetration of the diazo compound into support layers or substrates that are exposed to such penetration, e.g. surface saponified cellulose acetate film. The result is that the image areas acquire outstanding olephilic properties after light exposure. b) Less sensitivity of the reproductive layers to fingerprints and fingerprints.

Both advantages become more and more apparent with increasing

amount of the second component. While the advantage is usually evident in case (a) with condensates containing as little as 0.1 mol B and/or B^^ per mol A-N,,X, the desired effect is achieved in case (b) first with amounts from approx. 0.5 mol and in some cases first. with larger amounts of these components.

The use of the new condensation products has other advantages in addition to the above. Compared to known diazo resins, one can find improved effective photosensitivity for reproduction layers produced with the new condensation products, i.e. with the same light sources, shorter exposure times can be used. This effect also generally increases with an increase in the content of B and/or B^ and varies with the selected component B or B^. This exposure-shortening effect appears more clearly the higher the molar weight of component B or B^. Usually, an enlargement of the component with a new aromatic ring has a greater effect than the same molecular weight increase from other groups.

With increasing content of suitable other component B or B^, the resin character of the mixed condensates becomes increasingly evident, while the salt character decreases with decreasing content of diazonium salt groups in the condensate molecule. Accordingly, such mixed condensates are more compatible with polymers that do not contain ionizable groups.

For the same reason, the mixed condensates often exhibit good film-forming properties, and the films in a fully exposed state exhibit improved flexibility and, in many cases, good resistance to various etching agents. Thus, with a number of the available mixed condensates, reproduction layers with satisfactory etching resistance can be produced without the addition of the usual additive resins, and such layers can e.g. used for photomechanical production of halftone engraving plates and printed circuits.

Mixed condensates particularly suitable for this purpose contain components which cannot form salts with acidic or alkaline etchants and do not tend to hydrolytic cleavage, i.e. secondary components (B or B^) selected from the group of aromatic hydrocarbons, either unsubstituted or substituted with alkyl, alkoxy, alkylmercapto, aryloxy or arylmercapto.

A particularly favorable group of condensation products is obtained from the components B or B^ which contain 2 benzene rings connected by an intermediate group.

Particularly preferred in this series are mixed condensates from components B and especially B^ derived from diphenyl ether or diphenyl sulphide, with diphenylamine-4-diazonium salts and especially 3-alkoxy-diphenylamine-4-diazonium salt. These condensates have a high photosensitivity and condensates produced from 3-alkoxy-diphenylamine-4-diazonium salts at the same time have surprisingly good storage resistance. The corresponding condensation products, especially with components B^, can be produced particularly easily and under mild condensation conditions. Diphenyl ether derivatives of the type B^ suitable for the preparation of condensation products are commercially available.

In contrast to the known diazo resins, the high condensation products can in many cases be worked up and separated from aqueous solutions in a very simple way by adding hydrochloric acid or an ordinary salt solution in the form of chlorides or, analogously, bromides. For this reason, a number of the new condensation products can be advantageously used in such cases where the halides of the known diazo resins, which can be extracted only in a cumbersome way, have preferably been used, e.g. for the production of raster printing plates. Furthermore, the chlorides can easily be transferred to acid salts with low volatility, e.g. to orthophosphates, which of course can also be obtained directly, e.g. by condensation of diazonium phosphates in phosphoric acid.

A special group of the new condensation products has special advantages when it comes to the exposed products' acid resistance to e.g. developer solutions containing phosphoric acid, and when it comes to adhesion to metallic substrates. These are condensation products containing phosphonic acid groups. The exposure products of these condensates have good adhesion properties on aluminum foils roughened only with metal brushes, e.g. without foils provided with the known chemical adhesive layers, and even when the products are used in the form of zinc chloride double salts. j-„

Another special group of mixed condensates has particular advantages when it comes to curing hydrophilic colloids. Mixed condensates belonging to this group are mixed condensates of diphenylamine-4-diazonium salts and urea or similar compounds. Colloid layers that are hardened with these condensates under the influence of light have better hydrophilic properties after hardening than those that are sensitized with the previously known diazo resins. This effect is important for the production of printing plates, such as e.g. described in the U.S. patent No. 3,085,008.

It should further be noted that mixed condensates prepared from diazonium salts and excess phenols are capable of giving

positive copies by aqueous alkaline development (if desired with x addition of a small amount of solvent).

The new condensation products can be combined with water-soluble and water-insoluble polymers in the reproduction materials of the invention. In particular, the manufacture of reproduction layers containing water-insoluble polymers will be simplified when

^~_one uses the\new condensation products, since the latter especially T:tg can be easily obtained<\>^ salt form which is compatible with these polymers,

and easily soluble in a variety of organic solvents. Re-. the production layer is produced in the same way as with the known diazo resins, i.e. the diazo condensates are dissolved as such """"or if desired together with other layer constituents in a suitable solvent and a substrate is coated with the solution. Suitable substrates or support layers are e.g. such as are mentioned on page 2 of the present description.

In some cases, the mixed condensates can also be used in the form of a very finely divided suspension. One can e.g. carry out the coating by dipping or pouring and suction, by pouring and discarding excess solution, by brushing, pad application or roller application, or in other ways. The coating is then dried at room temperature or at an elevated temperature.

A number of substances and compounds can be added in the form of other suitable components to the reproduction layers. Examples can be: Acids: e.g. phosphoric acids (especially acids of 5-valent phosphorus and preferably orthophosphoric acid), phosphonic acids, phosphinic acids and arsonic acids, further the strong acids described in US patent no. 3,235,382, such as sulfuric acid, hydrobromic acid, organic sulphonic acids such as e.g. toluenesulfonic acid, methanesulfonic acid and naphthalene-1,5-disulfonic acid, further arsenic acid and hexafluorophosphoric acid, further the organic polyacids described in

U.S. patent no. 3.17 9.518, e.g. polyacrylic acid, polyvinylphosphonic acid, polyvinylsulphonic acid, mellitic acid and polyvinyl hydrogen phthalate.

Water-soluble polymers: e.g. polyvinyl alcohol, polyethylene oxide, partially saponified polyvinyl acetate with an acetyl content of up to 40%, polyacrylamide, polydimethylacrylamide, polyvinylpyrrolidone, polyvinylmethylformamide, polyvinylmethylacetamide and copolymers of monomers forming these polymers or with monomers forming water-insoluble polymers in such an amount that the water solubility of the copolymers are maintained, further natural substances or modified, natural substances such as gelatin, methylcellulose, carboxymethylhydroxyethylcellulose, alginates and the like.

Polymers that are poorly soluble or insoluble in water, e.g. phenolic resins, epoxy resins, oil-modified alkyl resins, amine-formaldehyde resins such as urea and melamine resins, polyamides, polyurethanes, polyvinyl resins, polyacrylic and polymethacrylic acid esters, polyvinyl acetals, polyvinyl chloride, polyesters and polyethers which e.g. obtained by polymerization of vinyl ethers, of oxiranes, oxetanes or tetrahydrofuran. The polymers can also contain groups that will increase the solubility in alkali, e.g. carboxyl, carboxylic acid anhydride, sulfonic acid, sulfonic acid amide and phosphonic acid groups, further sulfuric acid half-esters, phosphoric acid monoesters and phosphonic acid monoester groups. The polymers can be introduced into the reproduction processes either individually or when they are compatible with each other also in the form of mixtures.

Printing plates with a significantly increased lifespan are obtained with a reproduction layer containing mixed condensates combined with polyvinyl formaldehyde resins, particularly on a grained aluminum substrate.

Colored or uncolored pigment

Dyes

Plasticizers

Moisturizers

Sensitizers

Indicators

Fatty acids

Aldehydes, especially formaldehyde, can also be added to reproduction products.

Naturally, all additives should be chosen so that they are compatible with the diazo condensates and furthermore absorb light as little as possible, in the wavelength range that decomposes the diazo compounds.

The additives can usually be introduced into the reproduction layers in the following amounts: Acids: Acids of 5-valent phosphorus, especially orthophosphoric acid, are added to metal substrates and surface saponified cellulose acetate film, in amounts of e.g. 0.01 to 4 mol, phosphonic acids and arsonic acids in amounts of 0.01 to 3 mol per moles of diazo groups. On paper substrates as described in U.S. patent no. 2,778,735, in addition to phosphoric acid, you can also use strong acids as mentioned earlier, in quantities of 1 to 100 mol per moles of diazo compound. In this connection, 1 mol means the amount containing 1 gram atom of P, As or equivalent COOH.

The organic polyacids are used to the extent that they are easily water-soluble, generally in amounts of only 0.01 to 3 mol per moles of diazo compound.

Water-soluble polymers are usually added in amounts up to 100 parts by weight per part by weight diazo compound, preferably no more than 20 parts by weight.

You generally do not want to add more than 20 parts by weight per weight part diazo compound of polymers which are insoluble in water, the preferred range does not exceed 10 parts by weight.

When the reproduction layers contain water-soluble and/or water-insoluble polymers, colored or uncolored pigments are usually added only in amounts not exceeding 50% by weight based on the polymer weight.

Plasticizers, dyes, wetting agents, sensitizers, indicators and fatty acids are generally added to the reproduction layers in amounts not exceeding 20% by weight and preferably not exceeding 10% by weight based on the weight of the other layer constituents.

Reproduction layers that contain or consist of the new diazo condensates can also be combined with known light-sensitive systems. This applies, for example, to the known diazo resins (formaldehyde condensates of substituted or unsubstituted 4-diazo-diphenylamines), p-quinone diazides, iminoquinone diazides, azido compounds, photo-crosslinking polymers with azido groups, chacon groups, cinnamic acid groups, allyl esters

and allyl ether groups and photopolymer layer.

Depending on the layer components, suitable solvents for producing the coating solutions are e.g. water, alcohols such as methanol, ethanol and ethylene glycol monoethyl ether, dimethylformamide, diethylformamide and the like. Water is preferably used, if desired together with an organic solvent, when it comes to dissolving metal halide double salts, sulfates and phosphates of the new diazo condensates.

Pure organic solvents or those which only contain a small amount of water are preferred in connection with chlorides, bromides and salts of the new diazo condensates which are largely water insoluble, e.g. salts of organic sulphonic acids, fluoboric acid and hexafluorophosphoric acid. In these cases, in addition to alcohols or amides which are usually good solvents for these compounds, solvents can be added which dissolve said substances relatively heavily, e.g. ethers such as dioxane and tetrahydrofuran, esters such as acetic acid ethyl ester, butyl acetate and ethylene glycol monomethyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone and the like, to improve the leveling properties of the coating compositions.

The reproduction materials produced in this way can be used directly after production, but days, weeks or months can also pass between production and development. It is an advantage to store them dry and cool.

The reproduction material is processed by pictorial exposure through an original. For pictorial exposure with light, any light source known for reproduction purposes can be used, provided that it emits light in the long-wave ultraviolet region and in the short-wave visible region, e.g. carbon arc lamps, high pressure mercury vapor lamps, xenon impulse lamps and others.

After light exposure, develop with a suitable developer. Suitable developers are e.g. water, mixtures of water with organic solvents, aqueous salt solutions, aqueous solutions of acids such as phosphoric acid with the possible addition of salts or organic solvents, or alkaline developers, e.g. aqueous solutions of sodium salts of phosphoric acid or silicic acid. Likewise, organic developers can be added to the mentioned developer type. In some cases, you can also develop with undiluted organic solvents. The developers may contain other components, such as e.g. wetting agents and hydrophilizing agents.

The development is carried out in a known manner, e.g. by dipping or brushing or rinsing with developer liquid.

Reproduction layers made with the new condensation products form negative copies of the originals in almost all cases. However, when phenolic resins are added to the reproduction layers, especially phenol in excess of the mixed condensate, positive copies of the original can be obtained with alkaline development.

Depending on the layer composition, the substrate material and the development, one can e.g. with the new diazo condensates make single copies, relief images, toned images, printing plates for raster printing, relief printing, intaglio printing and planographic printing or printed circuits. In many cases, the abrasion resistance and chemical resistance of the image stencil can be improved by burning in.

Reproduction materials according to the present invention can be stored for months, provided that suitable components have been chosen. Alternatively, the reproduction layers can be applied to the substrate immediately before use if this is desired. The mixed condensates according to the invention are suitable for so-called "iron-on" methods, whereby a metal substrate, in particular an aluminum substrate that has been mechanically and/or chemically pre-treated in a favorable way, is coated either manually or with the aid of simple devices with a light-sensitive layer by the printer for photomechanical production of a printing plate. For this purpose, the present diazo compounds' high photosensitivity and outstanding oleophilic properties of the light-decomposed products are a particularly great advantage.

The new diazo mixed condensates can also be used by the printer for sensitizing pre-coated (but not pre-sensitized) print textiles. Alternatively, they can be used for the production of pre-sensitized raster printing stencils which have the advantage compared to the known chromate-sensitized raster printing stencils that they have considerably better storage capacity. The good photosensitivity of the new diazo compounds is also an advantage in raster printing.

In order to achieve better identification of the mixed condensates in addition to elementary analysis results, the molecular ratio - calculated from the values that the analysis gives - is listed in many examples where the diazo compound, component B and/or component B^ enter the product's structure. This molecular ratio was calculated based on somewhat simplified assumptions. Although the results cannot and do not claim to determine the exact structure of mixed condensates according to the invention, the values are sufficient to identify condensation products that have reproducible properties.

As mentioned earlier, the condensation conditions and in particular the amounts used, of starting materials, are important and necessary for identification of the end products. The examples contain all the information necessary for the production of the mixed condensates.

In the examples, parts by weight and parts by volume relate to each other like grams to milliliters. Percentages are listed on a weight basis unless otherwise stated. The temperatures are °C. In the analysis values, N denotes total nitrogen content and ND diazon-itrogen.

Normally, no special efforts have been made to achieve a complete drying of the condensation products, so that the manufactured products possibly contain smaller amounts of water or condensation agent. Furthermore, varying amounts of metal salts may have been introduced in some cases during the precipitation. However, the content of active compound can be easily determined by the analytical values.

The term "raw condensate" used in the examples generally denotes the raw condensation mixture which is obtained after condensation, and which normally contains condensation medium and possibly solvent.

For better orientation, diazo compounds A-^X and components B and B^ used for the production of the mixed condensates according to the invention are listed in the following table 1 with reference numbers. In the examples, reference is then made to these numbers.

Table 1.

Diazo compounds.

diazo 1: diphenylamine-4-diazonium salt diazo 2: 3-methoxy-diphenylamine-4-diazonium salt diazo 3: 4 *-methoxy-diphenylamine-4-diazonium salt diazo 4: 2'-carboxy-diphenylamine-4-diazonium salt diazo 5: 2 ,4',5-triethoxy-diphenyl-4-diazonium salt diazo 6: 4-(4-methyl-phenylmercapto)-2, 5-dimethoxybenzene diazonium salt

diazo 7: 2,5-dimethoxy-4-phenoxy-benzene-diazonium salt diazo 8: 4-(2,5-diethoxy-benzoylamino)-2,5-diethoxybenzene-diazonium salt

diazo 9: 3-methoxy-diphenylene poxyd-2-diazonium salt diazo 10: 2-sulfo-4-diazo-diphenylamine (inner salt)

diazo 11: 4-/R-methyl-N-naphthyl-(1)-methylamino7~benzene-diazonium salt

diazo 12: 4-diazo-diphenylamine-3-carboxylic acid (inner salt) diazo 13: 2,5-dimethoxy-4-(N-methyl-N-phenylmercaptoacetylamino)-benzenediazonium salt

diazo 14: 4-ZTN-methyl-N-(p-phenyl-mercaptoethyl)-aming7-benzene-diazonium salt

Components B and B^

No. 1: 3,5-dimethylaniline

No. 2: diphenylamine

No. 3: 4-chloro-diphenylamine No. 4: 3-methoxy-diphenylamine No. 5: 4-methyl-diphenylamine No. 6: 4-nitro-diphenylamine No. 7: 2-dimethylamino-naphthalene No. 8 : phenol

No. 9: 4-tert-butyl-phenol No. 10: .4-nitro-phenol

No. 11: 4-hydroxycinnamic acid No. 12: 4-hydroxy-benzoic acid No. 13: 2-hydroxy-naphthalene-6-sulfonic acid'

No. 14: benzene

No. 15: phenanthrene

No. 16: mesitylene

No. 17: anisole

No. 18: 2-phenoxy-ethanol

No. 19: phenoxy-acetic acid

No. 20: 3-methyl-phenoxymethyl-phosphonic acid No. 21: 4-chloro-phenoxymethyl-phosphonic acid No. 22: 4-tert-butyl-phenoxymethyl-phosphonic acid No. 23: 2-methoxy-naphthalene-6-sulfonic acid no. 24= diphenylene oxide

No. 25: p-toluene sulfonic acid amide No. 26: N,N'-dimethylol-succinic acid diamide No. 27: sebacic acid diamide

No. 28: hexa-methoxymethyl-melamine No. 29: N,N<T->dimethylol-urea No. 30•* N,N'-dimethylol-terephthalic acid diamide No. 31: 2,6-dimethylol-4- methyl-phenol No. 32: 2,6-dimethylol-4-methyl-anisole No. 33•" dihydroxymethyl-durene No. 34: di-acetoxymethyl-durene No. 35: 1>3~dimethyl-4)6-dimethylol -benzene No. 36: 1,3~diisopropyl-4>6-dimethylol-benzene No. 37: 1,5-di-acetoxymethyl-naphthalene No. 38: 1,4-dimethylol-benzene No. 39: technical bis- methoxymethyl diphenyl ether

(composition given in example 21)

No. 40; 4>4'-di-acetoxymethyl-diphenyl ether

No. 41: 4>4'-di-methoxy-methyl-diphenyl ether No. 42: 2,5-di-ethoxymethyl-thiophene

No. 43: 9,10-dimethoxymethyl-anthracene

No. 44*• benzhydrol

No. 45: 1,4-bis-(a-hydroxybenzyl)-benzene No. 46: 1,3-diisopropyl-4,6-dimethoxymethyl-benzene No. 47: 4-4'-dimethoxymethyl-diphenyl sulfide No. 48: methoxymethyl diphenyl ether, produced by reaction of technical chloromethylated diphenyl ether with sodium methylaV

(composition see example 84)

No. 49: 2,2'-bis-(4-hydroxymethyl-phenoxy)-diethyl ether No. 50: 1,3-bis-(4-hydroxymethyl-phenoxy)-propane No. 51: bis-methoxymethyl-diphenylene oxide

No. 52: 4»4'-bis-methoxymethyl-diphenylmethane No. 53: Methoxymethylated biphenyl

No. 54: methoxymethylated 4>4'-dimethyl-diphenyl ether No. 55: methoxymethylated 2-isopropyl-5-methyl-diphenyl ether No. 56: methoxymethylated 3-chromo-4-methoxy-diphenyl ether

No. 57- methoxymethylated dibenzo-thiophene

No. 58: methoxymethylated 1,4-diphenoxybenzene No. 59: 2,6-bis-(methoxymethyl)-4-methyl-phenol No. 60: diphenyl ether

No. 6l: N,N'-dimethylol oxamide

No. 62: adipic acid diamide

No. 63: N,N'-Dimethylol-adipic acid diamide No. 64: Trimethylolcitramide

No. 65: p-toluenesulfonic acid anilide

No. 66: p-toluenesulfonic acid ethylamide

No. 67: 1,3-benzene-disulfonic acid diamide

No. 68: phenylthiourea

No. 69: phenylurea

No. 70: 2-benzoylamino-1,4-diethoxy-benzene No. 71: 3-amino-pyrene

No. 72: 2-phenyl-amino-pyridine

No. 73<:> thiophene

Examples 1 to 35

In the following examples, it is shown how good to excellent oleophilic properties can be achieved for the exposure products of 35 of the present new condensation products when these are applied to a surface saponified cellulose acetate film, combined with improved light sensitivity, compared to known, pure formaldehyde condensates. The composition of condensation products and coating solutions is listed in table 2 below.

In the case of purely aqueous coating solutions, the coating can be carried out by brushing on with various aids, while solutions that predominantly contain organic solvents are applied with the help of a sling plate. Hot air is used for drying. After pictorial exposure under a negative original, the material is developed, e.g. by sweeping over with water or one of the known buffered solutions of water-soluble coupling component, e.g. component of the pyrazolone series. The material is then blackened with fatty ink as the exposure products absorb the black.

In many cases, you can also enhance the image with the help of lacquers, e.g. the usual emulsion varnishes. In all cases, the oleophilic properties of the exposed products of the new diazo condensates are superior to the previously known formaldehyde condensates containing corresponding diazo compounds.

This is illustrated by the following comparisons: Formaldehyde condensates of diazo compounds 1 and 2, prepared in phosphoric acid as described in U.S. U.S. Patent No. 3-3H-6O5 °g Example 1 patent no. 3.4-06.159", respectively, give exposure products which have only poor ink receptivity or do not absorb any ink at all, when they are coated and processed as described above.

By adding phosphoric acid to the coating solution, even worse results are achieved.

In contrast, they have new condensation products prepared in phosphoric acid, e.g. products according to example 2, 3> H> 15 to 17, 19, 21, 23, 27, 32, 33 and 35, good for excellent ink absorption capabilities in the image areas. These good oleophilic properties are not lost when phosphoric acid is added to the coating solutions. The coating solutions used in examples 8 and 16 to 22 can e.g. contain 2 moles of phosphoric acid per diazo group, without appreciable deterioration of the ink absorption on the exposed products. In example 35, even 10 moles of phosphoric acid are present per diazo group. This is also evident from examples 4" 5 °g 24" where raw condensates prepared in phosphoric acid are used for coating without removing the condensing agent.

In these examples it is also shown that the incorporation of smaller amounts of component B or component B-^ is sufficient to produce a considerable oleophilic effect. This effect appears even when introducing only 0.15 m°l of component B per moles of diazo compound, although optimal results are not obtained i

this case.

Examples 25, 26, 29 and 33 show the superiority of the new condensation products compared to the formaldehyde condensate prepared in sulfuric acid and precipitated in the form of zinc chloride double salt, which at the present stage is preferred as diazo resins. Even with 0.1% ±ge solutions of the new mixed condensates (example 25) and the addition of 2 mol of phosphoric acid per diazo group, you get printing plates with good ink receptivity and which produce good prints in aqueous offset machines. With a 0.1%±g solution of corresponding formaldehyde condensate (Example 26) and treatment in the same way, no significant ink absorption is obtained. Fairly satisfactory ink uptake is only achieved by increasing the concentration of this diazo compound many times the above amount.

The preparation and composition of mixed condensates used in examples 1 to 35 are now described in detail as follows:

Example 1

10.8 parts by weight of 3_methoxy-diphenylamine-4-diazonium chloride (diazo 2, chloride, table 1) (97%) are dissolved in 16 parts by volume of methanesulfonic acid (90%)• 1>8 parts by weight of paraformaldehyde are introduced into the solution and the condensation is carried out in 10 minutes at a temperature below ^ 0°C. A solution prepared from 4.3 parts by weight of 4-nitro-diphenylamine (component B, no. 6, table 1) and 32 parts by volume of 90% methanesulfonic acid is immediately added dropwise at 25°C with stirring, and the stirring is continued for 1 3/4 hour. The raw condensate is stirred in 600 parts by volume of water without a time delay, after which fraction I of mixed condensates is precipitated in the form of a resin mass. For purification, this mass is dissolved in 120 parts by volume of ethylene glycol monomethyl ether and reprecipitated by introducing the solution into 750 parts by volume of isopropanol. The precipitate is filtered and air-dried. Fraction I: 5>3 parts by weight of mixed condensate in the form of methanesulfonate which, according to analysis, contains approx. 1.5 units of 4-nitro-diphenylamine per diazo group (N 11.6 f>, ND 3.8 f>,

S 4.8 fo, atomic ratio: 6.08 : 2 : 1.1).

From the filtrate from the first precipitation (fraction I), a fraction II is obtained by adding zinc chloride and sodium chloride, and this fraction II is reprecipitated by dissolving it in water and adding zinc chloride and sodium chloride. Yield: 8.0 parts by weight.

Fraction II: A mixed condensate containing approx. 0.5. mol 4-nitrodiphenylamine per moles of diazo compound. (N 8.2%, ND 4.1%, Cl 29.2 Zn 5.1%, atomic ratio 4 : 2 : 5.6 :.0.54).

Example 2 1' -; " ;'°: -' '• C <' iso'j kp 14»6 parts by weight 4-met yl'*di:f ényiamin'v- •'( kbrap'6'n'ént"-: B-j rir.- - 57 " table 1) _ dissolve at 80°C in 120 parts by volume*'86; 7 foig 'phosphoric acid. We After cooling to' 40°C add "25V8>'ektdrél'éri:'3^eVok-sy-diphenyl -- - :

amine-4-diazonium phosphate' '('diazo ' 2'' ; foi-fafe,<:-> table'"i-')V hl'anai:ngeh^ stir^c! until all components are bppl<!>est and the mass is then cooled to room temperature. At this temperature, a solution of 48 parts by weight of formatealdehyde in 48 parts by volume is added to 86.7% ± g' phosphoric acid, drop by drop, under "stirring"' which is continued -i-'for 5 hoursv '! Råkondehssftfét. forms, no 'precipitation' 'éirér residuum'when the stream is 'dissolved'' -in- ' vanh."ij;Fb~r precipitation of the condensate1 f diluted •reaks-jbrisbrandihgen: "f •med, 440.-:volume--j..-..r:-. in parts methanol and then added to 6000 volume parts isopropanol....The^,^ formed ,-rf ine , suspension is •heated-, to- ^O0? with stirring .until it"" settles, easily . when the stirring is turned off. The precipitate is suctioned off, ,suspended , twice each time; in 1000 parts by volume of isopropanol, washed and dried under reduced pressure at 40°C. Exchange: -32.5, parts by weight. According to the analysis, the mixed condensate, which exists in the form of acid phosphate, consists of approx. 0^75 mol-4-methyl-rdiphenylamine per mol r diazof orbin-, r deise. (C 48.4%, ND 4.6%, P 10.8%, atomic ratio: 24^5 :' 2 :"'2.12)'.' One can with equally good results coat the surface saponified cellulose acetate support layer with a mixed condensate which is produced in an analogous manner, starting from the fact that 20% of the 4rnietyi-diferiylamide is er.s-t.at.tet- . with diphenylamine. '• '":,v • 1 Example' .............. - ; ■ - . • ■ •„ 'Vie, ,t> • Man repeats the procedure described in example 2, but uses the following starting materials: 7, 3 parts by weight. .amrri -('component 3, no v; .5»; table 1)., 80 parts by volume, 86..„„%ig phosphoric acid, 25»8 parts by weight, ^-meth.oxy-diphenylamine^.- Diazonium phosphate (diazo 2, phosphate, table 1) and 3.6 parts by weight of paraformaldehyde in 32 volumes of 86.7% phosphoric acid. One uses 40 parts by volume of methanol and 5000 parts by volume of isopropanol. precipitation, and the precipitation is washed twice

"• ■'• :- • •'.: '.. ; ;.v X:..v in each'time in-600-vol parts.e.r, isopropanol.. Yield:, 33» 2 parts by weight. Add-. analysis ::intains the mixed condensate, which is in the form of acid phosphate, about 0.42 mol; c4-™ety.l^di.pheny]jami^..>pp>.mol. diazo compound. (C 43.5 ND 5.1 fo, P 12.4 atomic ratio:' I9/9 i \ ~ 2\ z)'.'

Example 4" • -

• . •/ i.-.-V' .iJ.

242 parts by weight of 3-methoxy-diphenylamine-4-diazonium chloride

(diazo 2, chloride, Table 1) is dissolved in a mixture of 265.5, parts by weight

93% phosphoric acid and 8.55 parts by weight of water, after which 29.7 parts by weight of paraformaldehyde are added to the solution. The condensation is carried out for 48 hours at 40°C. The reaction mixture is divided into three equal parts. To each of these three parts, add a phenol solution consisting of 18.8 parts by weight of phenol (component B, no. 8, table 1) and 4.4 parts by weight of water, dropwise, in the following quantities: 1: 5»22 parts by weight = 0 .15 m°l of phenol per mol diazo compound 2 : 6.97 parts by weight = 0.20 mol phenol per mol diazo compound 3: 8.64 parts by weight = 0.25 m°l phenol per moles of diazo compound.

The condensation is continued for 3 hours after the addition of the phenol solutions. The raw condensates form clear solutions in water.

Example 5

6.6 parts by weight of paraformaldehyde are introduced into 63.4 parts by weight of 86.7% phosphoric acid with stirring, and then 46.3 parts by weight of diphenylamine-4-diazonium chloride (diazo 1, chloride, table 1) are added. After two hours of condensation at 40°C, 6.2 parts by weight of phenol-water mixture are introduced (weight ratio 9 - Di °g and the condensation is continued for 17 hours at 40°C. A crude condensate is obtained in this way which forms a clear water solution.

Example 6

4>parts by weight of diphenylamine-4-diazonium chloride (diazo 1, chloride, table 1) and 3>3 parts by weight of 4-hydroxycinnamic acid (component B, no. 11, table 1) are dissolved at room temperature in 30 parts by volume of methanesulfonic acid (90 folg) . The solution is cooled to <+>3°C and 1.2 parts by weight of paraformaldehyde are slowly introduced at this temperature. Condensation is continued for 30 minutes at the same temperature. At this stage, the crude condensate forms a clear solution in water. The reaction mixture is immediately diluted with 10 parts by volume of methanol while cooling, and the reaction product is separated by stirring the mixture in 400 parts by volume of isopropanol. The precipitate is suspended twice, each time in 200 parts by volume of isopropanol, suctioned off and dried under reduced pressure. Yield: 7.4 parts by weight. The mixed condensate (methanesulfonate) contains approx. 1 mol of 4-hydroxycinnamic acid per moles of diazo compound. (C 52.4%, ND 5.1 #rS 6.3%, atomic ratio: 24 : 2 : 1.08).

Example 7

12 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) (97.6% ±g) and 5.6 parts by weight of 4-nitrophenol (component B, no. 10, table 1) are dissolved at room temperature in 25 parts by volume 96 % lg sulfuric acid. The solution is quickly cooled to +5°C, and then 2.4 parts by weight of paraformaldehyde are introduced with stirring, while the temperature is maintained at +5°C to +10°C. The stirring is continued for 3 hours at this temperature and the condensate precipitates out in the form of the sulphate by stirring the mixture in 500 parts by volume of isopropanol. After washing four times with each time 200 parts by volume of isopropanol, the precipitate is suctioned off and dried under reduced pressure. Yield: 17.1 parts by weight. According to analysis, the condensed product contains approx. 0.8 mol 4_nitrophenol per moles of diazo compound. (C 47.0%, ND 5.7%, S 7.7%, atomic ratio: C : ND : S = 19.25 : 2 : 1.18).

Example 8

0.78 parts by weight of benzene (component B, no. 14, table 1) are dissolved in 100 parts by volume of methanesulfonic acid (90%), 6.17 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) (95%) are added, and, as soon as the whole mass is dissolved, 1.2 parts by weight of paraformaldehyde are introduced with stirring. A warm solution (100°C) prepared in advance of 1.78 parts by weight of phenanthrene, (component B, No. 15, Table 1) in 20 parts by volume of glacial acetic acid is immediately poured into the carefully stirred mixture which is condensed for 14 hours at room temperature. A crude condensate is formed which forms a clear solution in water, i.e. a true mixed condensate. In a known manner, e.g. by adding a saturated normal salt solution, the condensation product can be precipitated and isolated as chloride. Yield: 4.5 parts by weight. The product contains a small amount of common salt. (C 60.7 f°, N

9.0%, atomic ratio: 23.6 : 3).

Example 9

11.3 parts by weight of mesitylene (component B, no. 16, table 1) are introduced under vigorous stirring at +5°C in 100 parts by volume of 80% sulfuric acid. With continued vigorous stirring, a careful mixture of 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) and 6 parts by weight of paraformaldehyde is added to the mixture over the course of 20 minutes while the temperature is prevented from rising above + 12°C. After continued stirring for 1 hour at +10 to <+>15°C, the mixture is immediately poured into 40°° volumes of ice water and heated to 60°C to dissolve the entire mixture. The zinc chloride double salt is separated in a known manner from the solution which is clarified over bone charcoal by adding zinc chloride and sodium chloride. To free the zinc chloride double salt from excess common salt, dissolve

the crude product in 260 parts by volume of dimethylformamide (after drying), the salt is filtered off and the condensate is precipitated again by stirring in 2000 parts by volume of isopropanol, washed carefully with isopropanol and dried under reduced pressure, at 40°G. Yield: 23.2 parts by weight. According to analysis, the condensate contains approx. 0.7 mol of the second component per moles of diazo compound. (C 56.4%, N 9.4%, atomic ratio: 21 : 3).

Example 10

30 parts by weight 97 > 6% ±g diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) and 5>4 parts by weight anisole (component B, no. no. 17, table 1), stirred vigorously at room temperature in 100 parts by volume 80% sulfuric acid. 4.5 parts by weight of paraformaldehyde are introduced with vigorous stirring at 20°C for 10 minutes and stirring is continued for a further 1 hour at room temperature and then for 2 hours at 40°C. To precipitate the condensate, the mixture is diluted with 120 parts by volume of methanol, stirred into 2400 parts by volume of isopropanol, the precipitate is filtered off and washed twice by suspension in 1200 parts by volume of isopropanol. The condensate is dried at 40°C under reduced pressure. Yield: 30 parts by weight. According to analysis, the mixed condensate, which is in sulfate form, contains approx. 0.5 mol second component per moles of diazo compound. (C 51.3%, N 10.7%, atomic ratio: 16.8 : 3).

Alternatively, the raw condensate can be treated by dissolving it in 2,000 parts by volume of water and precipitating the mixed condensate using zinc chloride and sodium chloride in a known manner.

Example 11

6.9 parts by weight of 2-phenoxy-ethanol (component B, no. 18, table 1) and 16.2 parts by weight of 3_methoxy-diphenylamine-4-diazonium phosphate (diazo 2, phosphate, table 1) are dissolved at room temperature in 5° parts by volume 86, 7% phosphoric acid. 3 parts by weight of paraformaldehyde are added with stirring at room temperature, and the mixture is condensed for 16 hours at 40°C. The crude condensate is completely soluble in water and is diluted with the same volume of methanol, and the product is precipitated by stirring the mixture into 1,200 parts by volume of isopropanol. The precipitate is quickly filtered off, washed twice by suspension in 5°° parts by volume of isopropanol and dried under reduced pressure at 40°C Yield: 22.7 parts by weight. According to analysis, the mixed condensate contains approx. one mole of the other component per moles of diazo compound. (C 46.4 fo, N 7.0%, P 8.7 ?°, atomic ratio: 23.2 : 3 : 1.68).

You can get. a similar condensation product by condensing the following starting materials for 16 hours at 40°C as indicated above: 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1), 13.8 parts by weight of 2-phenoxyethanol (component B, No. 18, Table 1), 60 parts by volume of 86.7% ± g phosphoric acid and 6

parts by weight paraformaldehyde. The raw condensate is dissolved in 4°0 parts by volume of water, the solution is filtered over activated carbon and after heating to 40°C slowly precipitates out by adding 50 parts by volume of 50% zinc chloride solution. The precipitate is filtered off, washed with 5% sodium chloride solution and dried under reduced pressure. Yield: 54 parts by weight. According to analysis, the mixed condensate contains approx. 1 mol of the second component per moles of diazo compound. C 48.0%, N 7.3%, atomic ratio: 23 : 3).

Example 12

3 parts by weight of phenoxyacetic acid (component B, no. 19, table 1) are dissolved while stirring at 60°C in 20 parts by volume of methanesulfonic acid (90%). The solution is cooled to room temperature, 4>6 parts by weight of diphenylamine-4-diazonium chloride (diazo 1, chloride, table 1) are dissolved in the mixture and 1.2 parts by weight of paraformaldehyde are added slowly while stirring, while avoiding a temperature rise above 40°C at cooling in a cold water bath at intervals. Stirring is continued for a further 3 hours at room temperature. A crude condensate is obtained which is easily soluble in water. To precipitate the mixed condensate, the mixture is diluted with 20 parts by volume of methanol and introduced with stirring into 400 parts by volume of isopropanol. The precipitate is quickly filtered off by suction, washed twice by suspension in 150

.volume parts isopropanol, and immediately dried at /\. 0°C under reduced pressure. Yield: 6.9 parts by weight. According to analysis, the mixed condensate, in the form of methanesulfonate, contains approx. 1.4 mol of the second component per moles of diazo compound. (C 55.2%, N 7.4%, atomic ratio: 26.2 : 3).

Example 13

4.84 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) and 3.0 parts by weight of sebacic acid diamide (component B, No. 27, Table 1) are dissolved in 3° parts by volume 90% ±g methanesulfonic acid. 0.9 parts by weight of paraformaldehyde are then added, and the mixture is condensed for 45 hours at room temperature. The raw condensate is dissolved in 300 parts by volume of water, the solution is filtered over 1

part by weight of activated charcoal, and the condensate is separated from the filtrate by adding 3 parts by volume of 50% zinc chloride solution. For purification, the precipitate is redissolved in 5°0 parts by volume of water and precipitated again in the same way. Yield: 5.9 parts by weight.- Based on the analysis, it is assumed that the second component has been introduced, but it seems as if the carbonamide groups are saponified to a certain extent (C 39.3%, N 8.2 fo, ND 4.0 ? fo, atomic ratio: 23.8 : 4.07 : 2).

Example 14

17>75 parts by weight of 4-methoxy-diphenylamine-4'-diazonium sulfate (91 fo) (diazo 3, sulfate, Table 1) are dissolved in 150 parts by volume of 86% phosphoric acid. 11.2 parts by weight of dimethylol terephthalic acid diamide (component B^, no. 30, table 1) are introduced in the form of a fine powder into the solution with vigorous stirring and the condensation is carried out for 21 hours at room temperature. The raw condensate is dissolved in 1000 parts by volume of water at 40°C, and the condensation product is then separated from the solution by adding 200 parts by volume of 50% ± g zinc chloride solution. The double salt is separated, dissolved in 500 parts by volume of water at 50°C and reprecipitated by adding zinc chloride. Yield: 26.8 parts by weight.

(C 46.6 fo, N 11.5 According to analysis, the product contains the elements N and C in a ratio of 5 : 23.6.

Example 15

6.5 parts by weight of 3-methoxy-diphenylamine-4-diazonium phosphate (diazo;2, phosphate, Table 1) are dissolved in 60 parts by volume of 86.7 $±g phosphoric acid at 40°C. The solution is cooled to room temperature and a solution of 3.4 parts by weight of 2,6-dimethylol-4-methylphenol (component B^, no. 31, table 1) in 7 parts by volume of N-methylpyrrolidone is added rapidly while stirring. The mixture is cooled so much that the temperature does not exceed 50°C, and then condensed for 2 hours at 40°C. A crude condensate is obtained which is soluble in water without any residue. To precipitate the condensation product, the crude condensate is stirred into 1000 parts by volume isopropanol, the precipitate is filtered off, washed twice with 200 parts by volume isopropanol and dried. Yield: 7>5 parts by weight. An acid phosphate is obtained from the condensate which, according to analysis, contains an excess of approx. 9 C atoms per diazo group compared to uncondensed diazo compound. Thus, approx. 1 mol of the second component condensed per moles of diazo compound. (C 47.3 fo, N 7.6 f>, ND 5.1 f, P 9.4 fo, atomic ratio: 21.7 : 3 • 2 : 1.67).

Example 16

32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) are dissolved in 100 parts by volume of 86 flg of phosphoric acid. 19.4 parts by weight of bis-(hydroxymethyl)durene (component B-p no. 33" table 1) are added with stirring in small portions at room temperature and the condensation is carried out for 25 hours at room temperature.

The raw condensate is dissolved in 1,000 parts by volume of water, whereby a somewhat cloudy solution is obtained which is clarified by pressure filtration. The chloride of the condensation product is then precipitated by heating the filtrate to rJ0°G and adding 220 parts by volume of hydrochloric acid (36% lg hydrochloric acid diluted with the same volume of water). For cleaning, the felling is repeated in the same way. Yield: 33>8 parts by weight. According to analysis, the product has a surplus of approx. 13 C atoms per diazo group relative to uncondensed diazo compound. This corresponds to approx. 1.1 mol second component per moles of diazo compound. (C 65.0 f>, N 8.7 f>, Cl 9.2 f, atomic ratio: 26.1 : 3 : 1.25).

Example 17

17.8 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) are dissolved in 55 parts by volume of 86 flg of phosphoric acid. 10 parts by weight of finely powdered 4-methyl-2,6-bis-(hydroxymethyl)-anisole (component B^, no. 32" table 1) are then slowly dissolved while stirring. Stirring is continued for 5 hours at room temperature and for 8.5 hours at 40°c, and the mixture is allowed to cool to room temperature. The condensation mixture is dissolved in 300 parts by volume of water (clear solution) and the condensate precipitate out while stirring at +5°C. With 150 parts by volume of saturated boron salt solution. The precipitate is -filtered off and reprecipitated in the same way. You get 18.7 parts by weight of a sticky condensation product which, according to analysis, has an excess of 11.2 C atoms per diazo group compared to uncondensed diazo compound. This corresponds to a ratio of about 1.1 mol second component per mol diazo compound. (C 60.3 fo, N 8.7 Cl 10.2%, atomic ratio: 24.2 : 3 : 1.38).

Example 18

15.42 parts by weight diphenylamine-4-diazonium sulfate (95 f°)

(diazo 1, sulfate, table 1) is dissolved in 100 parts by volume of methanesulfonic acid (90 f). 6.8 parts by weight of finely powdered 1,5-bis-(acetoxymethyl)-naphthalene (component B-^ no. 37, table'1) becomes. then added while stirring. After condensing for 1.5 hours at room temperature can

the raw condensate form a clear solution in water. 4.15 parts by weight of 1,3-dimethyl-4,6-dimethylol-benzene (component B-^, No. 35, Table 1) are then introduced into the mixture with stirring and the condensation is continued for a further 45 minutes at room temperature. The raw condensate is dissolved in 500 parts by volume of water (clear solution). The condensation product is precipitated at +10°C by adding 200 parts by volume of hydrochloric acid (36.5 parts of acid diluted with the same volume of water). For purification, the product is dissolved in water and re-precipitated as chloride by the addition of hydrochloric acid. Yield: 14j5 parts by weight.

According to analysis, the condensation product has an excess of 10.7 carbon atoms per diazo group compared to uncondensed diazo compound. (C 67.2 fo, N 10.4 fo, atomic ratio: 22.6 : 3).

Example 19

32.4 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) are dissolved in 320 parts by volume of 86 fig phosphoric acid. At an internal starting temperature of 25°C, 4415 parts by weight of 1,3-diisopropyl-4,6-dimethylol-benzene (component B^, no. 36, table' 1) are added in very finely powdered form while stirring. Stirring is continued for 1 hour without heating and condensation is carried out for the next 20 hours at +40°C. You get a crude condensate that forms a clear solution in water.

The condensation product is precipitated from the aqueous solution of the raw condensate using hydrochloric acid, which is again dissolved in water for purification and reprecipitated with hydrochloric acid. Yield: 64 parts by weight.

(C 68.2%, N 5.1 fo, atomic ratio: 46.8 : 3). One can conclude from the analysis results that approx. 2.4 mol of the second component is introduced per moles of diazo compound.

Example 20

At room temperature and with stirring, 2.8 parts by weight of bis-(acetoxymethyl)durene (component B^, no. 34, table 1) are added slowly to a solution of 3.4 parts by weight of 2'-carboxy-diphenylamine"4-diazonium phosphate (diazo 4" phosphate, table 1) in 20 parts by volume of 90% methanesulfonic acid, and the stirring is continued for 24 hours at room temperature. To isolate the reaction product, the clear condensation mixture is stirred in 250 parts by volume of water. The precipitate is suctioned off, washed with 250 parts by volume of water, dissolved again at 50°C and reprecipitated by adding 50 parts by volume of 18% hydrochloric acid. Filtration of the precipitate is facilitated by heating the suspension briefly to 80°C and cooling

(again. The product is filtered off, washed with N hydrochloric acid and dried at 35°C. The yield is 3.7 parts by weight. (C 64.0%, N 8.5%, atomic ratio: 26.3 : 3)" According to the analysis it contains. the mixed condensate approximately 1.1 mol of the second component per mol of diazo compound.

Example 21

33.2 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) (97.5%) are dissolved in 100 parts by volume of 86% phosphoric acid. During 15 minutes, 25.9 parts by weight of methoxymethyl-diphenyl oxide (composition see below) (component B-^, no. 39, table 1) are added dropwise while stirring. A clear crude condensate is obtained which is stirred for a further 1.5 hours at room temperature and then for 6 hours at 40°C. The condensate is dissolved in $ 00 by volume of water and the solution is clarified for slight clouding by filtration. The condensation product is precipitated using hydrochloric acid. You can also use ordinary salt for precipitation. If you are going to have a product that is essentially free of phosphoric acid, it is an advantage to repackage the product in the same way. Yield: 37.6 parts by weight. According to analysis, the condensation product has a content of 16 carbon atoms in excess per diazo molecule relative to uncondensed diazo compound. (C 61.7 N 7.4%, Cl 9.3%, atomic ratio: 29.2 : 3 : 1.5).

The methoxymethyl diphenyl oxide used has the following

composition:

When methoxymethyl diphenyl oxide is introduced into the acid in the absence of a diazo compound, it initially dissolves under vigorous stirring. After a few seconds to a few minutes, a condensate is precipitated which is insoluble in the acid and in boiling water.

A mixed condensate which gives exposure products with the same oleophilic properties is obtained by replacing the sulphate of diazo 2 with an equimolar amount of sulphate of diazo 1, and otherwise following the same procedure. However, this gets mixed condensate with diazo 2

reproduction layer which exhibits better storage resistance.

Example 22

4.65 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, Table 1) (95 fo) are dissolved in 600 parts by volume of 86% phosphoric acid. 4.65 parts by weight of 1,4-bis-(a-hydroxybenzyl)-benzene (component B-^ no. 451 table 1) are then added, which is dissolved in 3 parts by volume of glacial acetic acid and heated sufficiently for the compound to dissolve. The hot acetic acid solution is then poured into the diazo solution with vigorous stirring. The condensation is carried out at room temperature within 21 hours. The condensation mixture is then dissolved in 2,000 parts by volume of water, filtered until clear and precipitated by adding 3 parts by volume of concentrated hydrochloric acid. The precipitate is separated, dissolved at 60°G in 5 parts by volume of water, filtered and precipitated by adding 50 parts by volume of 6 N hydrochloric acid in water. The product that precipitates is reprecipitated once more in the same way. 4.8 parts by weight of chloride of the condensation product are obtained in this way. According to analysis, the ratio C : ■N : Cl equals 26.6 : 3 : 1.05. This corresponds to a ratio of approx. 0.73 mol second component per moles of diazo compound. (C 69.2 fo, N 9»! f°> Cl 8.1 fo).

Example 23

30.84 parts by weight diphenylamine-4-diazonium sulfate (95 f°)

(diazo 1, sulphate, table 1) dissolve in 1000 parts by volume of 86 fo phosphoric acid. In the course of 1 hour, 18.4 parts by weight of benzhydrol (component B^, no. 44, table 1) are added to 200 parts by volume of glacial acetic acid, which is added dropwise while stirring. The condensation reaction is carried out within 24 hours at room temperature. You get a clear condensate which, in its raw state, dissolves in water without residue. Half of the raw condensate is introduced into 25OO parts by volume of water heated to 40 C. The condensation product initially forms a clear solution and crystallizes in the form of small flakes on cooling. Yield: 21.9 parts by weight. (C 56.6 f, N 8.1 f, P 8.9 fo, atomic ratio: 24.5 ■ ' 3 1.5).

According to analysis, the condensation product has a content of 12.5 more carbon atoms per diazo group than uncondensed compound. This corresponds to a ratio of approx. 1 mol of the second compound per moles of diazo compound.

The other half of the raw condensate is mixed with 1.5 parts by weight of paraformaldehyde and condensed for 20 hours at room temperature. The raw condensate is dissolved in 2,000 parts by volume of water and clarified to get rid of a slight cloudiness during filtration. The raw condensate can be worked up in a known manner in the form of zinc chloride double salt, yield equal to 22.9 parts by weight. (C 59.9%, N 8.5%, atomic ratio: 24.6 : 3).

Example 24

For the production of raw condensate, 11 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1) are introduced

in 39 >9 parts by weight 86% phosphoric acid and the mixture is cooled to room temperature. Then 5A7 parts by weight of a mixture containing methoxymethylated diphenyl ether with a composition as stated in example 21 (component B-^, no. 39» table 1) are introduced dropwise and the mixture is stirred in

1 hour.

The mixture is then heated to 40°C, a mixture of 22.1 parts by weight of the same diazo compound is added together with 2.4 parts by weight of paraformaldehyde and the condensation is carried out for 24 hours at 40°C. The raw condensate is used directly for the production of the coating composition.

Example 25

For the production of diazo condensation product, 8l parts by weight of diazo 2, sulfate (table 1) are dissolved in 500 parts by volume of 85% phosphoric acid, 6l parts by weight of 1,3-diisopropyl-4,6-dimethylol-benzene (component B^, no. 36, table 1 ) is introduced over 15 minutes, and the mixture is condensed for 39 hours at 40°C. The condensation mixture forms a clear solution in water and is dissolved in 2500 parts by volume of water and reprecipitated by the addition of $00 parts by volume of 18%±g aqueous hydrochloric acid solution. After filtering off and washing with 0.5 N hydrochloric acid, the product is dried in air. Yield: 113 parts by weight of condensation product chloride. (C 66.2%, N 8.8%, atomic ratio: 26.3 : 3). From the analysis results, it appears that the condensate contains approx. 1 mol of the second component per moles of diazo compound.

Example 26

Diazo resin in the form of zinc chloride double salt is prepared by condensing equimolar amounts of diazo 1, sulfate, (Table 1) and formaldehyde in 80% sulfuric acid, in the same manner as indicated in U.S. Pat. Patent No. 2.O63.63I.

Example 27

4.84 parts by weight of 3-methoxy-diphenylamine-4-diazonium phosphate

(diazo 2, phosphate, table 1) and 4.4 parts by weight of diphenylamine-4-diazonium phosphate (diazo 1, phosphate, table 1) are dissolved in 300 parts by volume of 86% phosphoric acid. 6 parts by weight of 2,5-bis-(ethoxy-methyl)-thiophene (component B^, no. 42, table 1) are added dropwise with vigorous stirring. The mixture will be reddish but still clear. The condensation is carried out for 2.5 hours at room temperature. The raw condensate forms a clear solution in water.

To precipitate the reaction product, the mixture is introduced with vigorous stirring into isopropanol at approx. 65°C, and cool to room temperature. The precipitate is suctioned off, washed carefully with isopropanol and dried. Yield: 10.9 parts by weight. According to analysis, the condensation product, in the form of acid phosphate, contains the component 3-methoxy-4-diazo-diphenylamine, 4-diazo-diphenylamine and thiophene in a mutual ratio of 0.7 to 0.3 to 2. (G 46.9% , N 6.7%, S 10.1%, OCH^

3.1%, atomic ratio: 24.6 : 3 : 1.98 : 0.73).

When 2,5-bis-(ethoxymethyl)-thiophene is introduced into phosphoric acid in the absence of a diazo compound, a homocondensate of this compound is immediately formed, which is practically insoluble in acid and in water.

Example 28

3.6 parts by weight of 2,5-dimethoxy-4-phenoxy-benzene-diazonium chloride (diazo 7, Table 1) in the form of a double salt with 0.5 mol of zinc chloride (containing NaCl, N = 7.7%) are dissolved in 60 parts by volume 93% phosphoric acid. Dry air is passed through the solution until no more hydrogen chloride is emitted. 2.7 parts by weight of 1,3-diisopropyl-4,6-di-(methoxymethyl)-benzene (Component B-p No. 46, Table 1) are then added, and the mixture is condensed for 1 hour at room temperature and for 2 hours at I\ . 0oC. Condensate The ionic mixture-dissolves-in-water- - where it forms a clear solution, the condensate is precipitated with zinc chloride, separated and dried. Yield: 2.9 parts by weight. (C 57.6%,

N 4.4 7°» atomic ratio: 30>6 : 2). Analysis shows that the mixed condensate contains approx. 1.2 mol of the second component per moles of diazo compound.

Example 29

3.6 parts by weight of diazonium salt used as starting material in example 28 (diazo 7, zinc chloride double salt, table 1) are dissolved in 60 parts by volume of 90% methanesulfonic acid and dry air is bubbled through the solution until no more hydrogen chloride comes out.

Then 2.7 parts by weight of 1,3-diisopropyl-4,6-bis-(methoxymethyl)-benzene (component B-^, no. afi, table 1) are introduced, and the mixture is condensed for 1 hour at room temperature and for 2 hours at /\. 0°C.

This is then mixed with water and it is freed from undissolved components by adding activated carbon and filtering.

The condensation product is precipitated from the filtrate in the form of zinc chloride double salt. Yield: 5.8 parts by weight, (C 41.0%, N 2.7 fo, atomic ratio: 35>3 : 2). This corresponds to an eb content of approx. 1.5 mol second component per moles of diazo compound.

Example 30

1.75 parts by weight of 4~(2,5-diethoxy~benzoylamino)-2,5-diethoxybenzene-diazonium chloride (diazo 8, Table 1) in the form of zinc chloride double salt (N - 4)8 f°) are dissolved in 10 parts by volume of 9% methanesulphonic acid, and dry air is bubbled through the mixture until hydrochloric acid gas no longer escapes. 0.14 parts by weight of 1,4-bis-hydroxymethyl-benzene (component Bn, no. 38; table 1) are then added. After condensation for 4 hours at room temperature, the mixture is diluted with water, filtered, and the condensate is precipitated from the filtrate using zinc chloride solution . Yield: 2.2 parts by weight. (C 25.2%, N 3)6 fo, atomic ratio: 24.5 : 3)-

Example 31

0.78 parts by weight of 3-methoxy-diphenylene-oxide-2-diazonium chloride in the form of a double salt with 0.5 mol of zinc chloride (N - 7.2 f)

(diazo 9, table 1), dissolve in 10 parts by volume 90 f of methanesulphonic acid, and dry air is passed through the mixture until no more hydrochloric acid gas escapes. Then 0.14 parts by weight of 1,4-dimethylolbenzene (component B-^, no. 38) table 1) are added and the condensation is carried out for 4 hours at room temperature. The condensation product is precipitated using zinc chloride. Yield: 1.4 parts by weight. (C 22.4 fo, N 2.9%, atomic ratio: 18 : 2). From the analysis it can be concluded that approx. 0.6 mol of the second component is introduced per mol of diazo compound.

Example 32

16.2 parts by weight of 3-methoxy-y-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, Table 1) are dissolved in 100 parts by volume of 93 flg of phosphoric acid. 8.6 parts by weight of p-toluenesulphonic acid amide (component , no. 25, table 1) and 22.5 parts by weight of 40% ± g aqueous formaldehyde solution are mixed separately, and the mixture is boiled briefly. You get a tough condensation product that falls out. After heating for 10 minutes

in a steam bath, the mass is cooled and the solution above the resin is poured off. The resin is washed by grinding it out with 10 parts by volume of water. After removing the wash water, the resin is dissolved in 8 parts by volume of hot methanol and the clear mixture obtained in this way is poured into the diazo solution with vigorous stirring. After condensation for 2.5 hours at 4-0°G °g and subsequent standing for 15 hours at room temperature, a solution containing a moderate amount of undissolved white matter in suspension is obtained. By suctioning this through a plastic filter, you get a clear condensate that forms a clear solution in water. The filtrate is dissolved in 250 parts by volume of water and the condensation product is combined in the form of a tough mass by adding 210 parts by volume of saturated aqueous Bordaal solution. The pulp is purified by refolding in the same way and is then dried over phosphorus pentoxide under reduced pressure and gives a solid product that can be shredded. Yield: 7.6 parts by weight. (C 52.2 fo, N 11.5 f, S 4.5 f, atomic ratio: 21.2 : 4 : 0.685).

From the analysis, it is assumed that there are units of the diazo compound and of the other component in the condensate in a ratio of approx. 1 : 0.7.

Example 33

A condensation product is made from 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde as described in example 1 in the U.S. patent no. 3,406,159»°g processes this in the form of an acid phosphate which still contains some phosphoric acid (N 9.3%, atomic ratio C : N : P = 14 : 3 : 2.3).

The product has an average degree of condensation of approx. 3 units of methoxydiphenylamine diazonium salt per molecule, which is determined for the diazoamino compound with diisobutylamine in benzene by freezing point depression for measuring molar weight. 10 parts by weight of diazo condensation product are dissolved in 85 parts by weight of 85% phosphoric acid. 5.7 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (component B-p No. 41; Table 1) are added dropwise to the mixture over 10 minutes and it is condensed for 20 hours without further heating. The clear condensate mixture, which forms a clear solution in water, is diluted with 100 parts by volume of water and 33 parts by volume of saturated, aqueous common salt solution. The precipitate formed in this way is cleaned by dissolving again in water, reprecipitating with normal salt solution and the precipitated product is dried. Yield: 8.1 parts by weight.

(C 48.3 f, N 4.3 f, atomic ratio: 39.4 <:> 3).

According to the analysis, diazo-homocondensate and the other are found

component in the mixed condensate in a mutual molar ratio of approx.

1: 5.4.

Example 34.

5 parts by weight of 4-p-tolymer capto-2,5-dimethoxy-benzene-diazonium chloride in the form of zinc chloride double salt (N = 6.9%)

(diazo 6, table 1) is dissolved in 40 parts by volume of 80% sulfuric acid, and dry air is bubbled through until it is no longer torn with hydrogen chloride.

0.88 parts by weight of 1,4-bis-(hydroxymethyl)-benzene (component B^, no. 38, table 1) is added in portions to the solution, which is stirred for one hour at room temperature, and then allowed to stand overnight . The mixture is then poured into 300 parts by volume of water, 2 parts by weight of activated charcoal are added to remove a slight turbidity, and the solution is deacidified. From the clear filtrate precipitate the condensation product by adding zinc chloride and common salt. Yield: 5.4 parts by weight, air dried. (C 31.0%, N 3.5%, atomic ratio: 20.6:2). The condensate contains approx. 0.7 mol second component per moles of diazo compound.

Example 35.

32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table ]) are dissolved in 265 parts by weight of 93% phosphoric acid. 25.8 parts by weight of 4,4'-bis-(methoxymethyl)-diphenyl ether (component B^, no. 41, table i) are added dropwise to the solution and the condensation is carried out during 2 hours at 40°C. 16 parts by weight of paraformaldehyde are introduced into the mixture, which forms a clear solution in water, and the condensation is continued for 6 hours at 40°C, after which the mixture is allowed to stand overnight. The mixture is dissolved in water without any re: Iduum and dissolved in water, after which a saturated, ordinary bslt solution is added. The voluminous precipitate that forms is kept in the liquid for 1 hour at 40°C and is then filtered from the liquid as strongly as possible, and the contents of the suction filter root, which is a green paste, are then

dried over phos forpen toxide, whereupon the product passes into a tough, green mass smelling cfcertly of formaldehyde. Yield: 175 parts by weight. (C 16.-4%, N 1-9?>, S 0.45%, P 13.7%, atomic ratio: C : N : F = 30.2 : 3 : 9.7). Compared to uncondensed d-iazophote*, the condensate contains approx. 17 c atoms in excess.

Example 36

4.4 parts by weight of diphenylamine-4-diazonium phosphate (diazo 1, phosphate, Table 1) are dissolved in 300 parts by volume of 9^.5 f° phosphoric acid, A boiling solution of 4.0 parts by weight of 9,10-bis-methoxy.3ethyl-anthracene ( component B^, no. 43» table 1) in 3 parts by volume of glacial acetic acid is poured into the solution, with vigorous stirring. The condensation is carried out within 1.5 hours without further heating, Råk onder, a,ri tet is soluble in water without any residue. For isolation a1/ the condensation product, the mixture is diluted with 150 parts by volume of ethanol and the solution is poured out while stirring into .2000 parts by volume of isopropanol at approx. 65°G, The precipitate is filtered off, washed with isopropanol and dried. Yield: 5.4 parts by weight. According to analysis, the condensate has a content of 24.4 carbon atoms in excess per molecular diasophic compound in relation to the uncondensed diazo compound, and this is approx. 1.5 mol of the second component per mol diazoforbindei.se, (C 52.9 N 5.1 %,

P 11.3%.• atomic ratio: 36.4 : 3 : 3)..

The examples below show^ . Lrakt:-. use of them. new condensation products on different layers and in connection with different reproduction methods.

In addition to the advantage m&cl .CWt> :»&reb ol 6 of il it et hop. the exposure products and improved lysioleumability, which can be seen from the examples below, the examples show other advantages of the individual types of mixed condensates.

Example 37

Electrolytically roughened aluminum foil is coated by coating with a 2% by weight aqueous solution of the chloride of a condensation product prepared from diazo compound 2 and component B-p no. 40, table 1. After pictorial exposure with light through a negative, the foil is developed by coating with 1 .5 µg of aqueous phosphoric acid and blackened with fatty black. You have an effective pressure plate.

A good result is also achieved by coating the same substrate with a 2% solution of acid phosphate of the condensation product described in example 2 in water, with the addition of 4% n-butanol. In this case, the development is carried out with water.

Likewise, a good printing plate is obtained in the same way by applying the former solution to a mechanically grained aluminum foil which has been pre-treated in a known manner with an alkali silicate.

Instead of using the chloride of the condensation product, one can also use the corresponding zinc chloride double salt or cadmium chloride double salt. Developer II is suitable for development.

The condensation product is worked up in the following way: 30.2 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulphate (diazo 2, sulphate, table 1) are dissolved in 93.5 parts by volume of 86% phosphoric acid. 29.3 parts by weight of finely powdered 4,4-bis-acetoxymethyl-diphenyl ether (component B^, no. 40, table 1) are then added with vigorous stirring, the mixture is stirred for a further 1.5 hours without heating and is then condensed for 3.5 hour at 40°C. The clear condensate mixture is dissolved in 500 parts by volume of water (clear solution) and the condensation product chloride is precipitated at 40°C by the dropwise addition of 220 parts by volume of hydrochloric acid

(3 6% HC1 diluted with the same volume of water). For purification, the precipitate is dissolved in warm water and the chloride is reprecipitated by adding hydrochloric acid. It is dried at 30°C by air circulation in drying chambers. Yield: 38.7 parts by weight. (C 65.7%, N 8.1%, Cl 8.6%, atomic ratio: 28.5 : 3 : 1.26.

Example 38

A paper printing foil is produced according to the description in U.S. patent no. 2,778,735, and this is coated with the following solution by rubbing and drying.

Coating solution: 2 parts by weight of mixed condensate described in example 25, dissolved in 97 parts by weight of warm water. The solution is reacted with 0.53 parts by weight of sodium sulphite and stirred for 1 hour. The somewhat cloudy solution is used directly for coating the substrate.

After pictorial exposure of the reproduction material and development with water, one has a very satisfactory oleophilic image szm absorbs fatty blacks well. The image areas have better ol.ophilic properties than areas produced by the same method with ordinary diazo resins (diphenylamine-4-diazonium sulphate condensed in 80% sulfuric acid with formaldehyde and precipitated as zinc chloride double salt).

Example 39

A polyethylene terephthalate film roughened by sandblasting is used which is coated with the following finely divided coating composition, after which it is dried: 1.25 parts by weight poly-N-vinyl-N-methylacetamide (k value 91),

0.5 parts by weight Heliogen Blue B powder (CI 74.160),

0.1 parts by weight finely divided silicon dioxide (Aerosil MOX 170),

0.375 parts by weight of diazo condensate, described below, 17.0 parts by weight of water, and

1.6 parts by weight of ethanol.

After pictorial exposure under a negative, get

a blue-colored positive-toned image when rinsed with water. The diazo condensate is prepared in the following way: 32.4 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulphate (diazo 2, sulphate, table 1) are dissolved in 320 parts by volume of 85% phosphoric acid. 16.6 parts by weight of finely powdered and sieved 1,3-dimethyl-4,6-dimethylol-benzene (component B^ no. 35, table 1) are added with vigorous stirring over the course of 10 minutes, and stirring is continued for 30 minutes at room temperature . The condensation is then carried out with stirring for 42 hours at 40°C. The raw condensate is soluble in water without any residue.

To separate the condensation product, the condensation mixture is dissolved in 1000 parts by volume of water, the product is precipitated by adding 60 parts by volume of 45% aqueous hydrobromic acid and the precipitate is filtered off.

It is purified by redissolving the product in 1000 parts by volume of water at 50°C, and reprecipitation by adding hydrobromic acid, washing with 1% aqueous hydrobromic acid and filtering off the product followed by air drying. Yield: 42 parts by weight. (C 53.1%, N 7.8%, Br 18.6%, atomic ratio: 23.8 : 3,

: 1.25). About. 1.1 mol of the second component is present per moles of diazo compound.

Example 40

An aluminum foil brushed with metal brushes and precoated with polyvinylphosphonic acid according to U.S. patent no. 3,220,832 is coated with the coating solution below and dried.

0.4 parts by weight condensation product described below, 80.0 parts by weight ethylene glycol monomethyl ether, and 20.0 parts by weight butyl acetate.

Development of the material, pictorial exposure under a negative to produce a positive printing plate is carried out as in example 45.

To prepare the condensation product, 12.9 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (component B^, no. 41, table 1) were added, with vigorous stirring, to a solution of 3.23 parts by weight of 3-methoxy -diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1) in 12 parts by weight of 86% phosphoric acid, and the condensation was carried out for 24 hours at 40°C. The clear crude condensate was poured into 100 volumes of 2-N hydrochloric acid, and a viscous, sticky mass separated. After decanting off the aqueous mother liquor, the mass was kneaded with a new 100 volume parts of 2-N hydrochloric acid and the aqueous phase was decanted off again.

After drying under reduced pressure, the somewhat sticky condensate was used for coating. (C 64.6%, N 3.4%, atomic ratio 66.5:3).

Example 4l

Aluminum outer layer electrolytically roughened and anodized and pretreated with polyvinylphosphonic acid according to U.S. Pat. patent no. 3,220,832 is coated with one of the coating solutions below, which is dried.

The mixed condensate is produced as follows:

32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1) are dissolved in 170 parts by weight of 85% phosphoric acid, 25.8 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (component B ^, no. 41, table 1), which is added dropwise, after which the condensation extends over 5 hours at 40°c. After dilution with 250 parts by volume of water, the chloride of the condensation product is precipitated by adding 220 parts by volume of semi-concentrated hydrochloric acid. The condensate chloride is redissolved in water and the mesitylene sulphonate of the diazo compound is prepared by adding the sodium salt of mesitylene sulphonic acid, and is a precipitate which is poorly soluble in water. Yield: 53 parts by weight (C 67.2%,

N 6.3%, S 4.6%, atomic ratio 37.3 : 3 : 0.96).

The condensation product has a homologous polymer structure. A mixed condensate prepared in practically the same way (condensation and work-up conditions are described below) is transferred with l-phenyl-3-methyl-5-pyrazolone to the azo dye for which the average molecular weight has been determined. This dye is fractionated further and the average molar weights for the individual fractions are determined.

Preparation of the mixed condensate:

(C 67.2%, N 6.4%, S 4.5%, P 0.2%, Cl 0.23%, QCH3 4.9%, atomic ratio C : N : S : OCH3 = 36.7 : 3 : 0.95 : 1.04).

The dye is obtained in a yield of 9.23 parts by weight from 10 parts by weight of the product in ethylene glycol monomethyl ether, by adding NH3 and phenylmethylpyrazolone.

The average molar weight of the dye is determined by osmonetic measurements of the vapor pressure in chloroform solution and is equal to 3,180.

For fractionation purposes, chloroform solutions of the dye are applied to aluminum foils and dried. These thin dye layers are then extracted with mixtures of solvent (chloroform) and non-solvent (methanol), starting the extraction with mixtures that have little dissolving power and continuing with mixtures of increasing dissolving power. Details regarding this procedure and the measured average molecular weights for the individual fractions follow in the table below.

The following resins are used:

Resin 1: Epoxy resins based on bis-phenol-A-epichlorohydrin, m.p. 64 - 76°C, average molecular weight 900.

Resin 2: Polyvinyl butyral, containing 69-71% polyvinyl butyral, 1% polyvinyl acetate and 24-27% polyvinyl alcohol units, a viscosity for a 6% solution at 20°C of 4-6 cp.

(DIN 53015)

Resin 3: Unplasticized urea resin with an approximate acid number equal to 2 (Resamin 106 F).

Resin 4: Ricin-modified alkyd resin (phthalic anhydride 38%, oil content 30%, acid number below 10, viscosity 40% in xylene equal to 550 - 700 cp. ("Alphthalate 814 B").

Resin 5: Polyvinyl acetate with an average molecular weight of 100,000. The plates are exposed photographically for 2 minutes under a negative with a xenon impulse lamp of 5 kw at a distance of 1 meter, and transferred to printing plates by rubbing them over with a developer of the composition below, in this way the printing plates give a long life, especially in the cases (a), (b) and (d) .

The developer used is a mixture of:

50.0 parts by weight water,

15.0 parts by weight isopropanol,

20.0 parts by weight n-propanol,

12.5 parts by weight of n-propyl acetate,

1.5 parts by weight polyacrylic acid, and

1.5 parts by weight of acetic acid.

You can also reinforce the pressure plates in a known way by painting and in this way increase their service life even further.

Suitable pressure beds can also be obtained by omitting the diazo condensate in the coating solutions (a) and (d) according to U.S. Pat. patent no. 3,406,159, example 1, and replace the toluene<p>ul-phonic acid with about 0.5 to 2 moles of phosphoric acid per moles of diazo groups.

Instead of the mixed condensate used, one can also use mixed condensates of the same components but with a different structural ratio, e.g. below:

Average molecular weight for the azo dye of (2) with methyl-phenylpyrazolone, determined as previously described, equals 2.390.

Example 42

An aluminum substrate precoated according to U.S. Patent No. 3,220,832 with polyvinylphosphonic acid and roughened with metal brushes, is coated with the following coating solution: 0.4 parts by weight of one of the mixed condensates below, 0.0605 parts by weight of p-toluenesulfonic acid,

0.080 parts by weight of 4-methoxy-4'-dimethylamino-azobenzene, and 100 parts by volume of a mixture of ethylene glycol monomethyl ether and butyl acetate in a volume ratio of 8:2.

With pictorial exposure through a negative, a clearly visible positive contrast image is obtained. Development to a printing plate can be carried out with developer I (examples 36-43).

The mixed condensates are prepared analogously to example 57 as follows:

The condensation mixtures form a clear solution in hot water. The condensation products precipitate as chlorides with hydrochloric acid.

According to analysis, it can be assumed that the mixed condensates in case (a) contain approx. 1,2, and in case (b) approx. 1.5 mol of the second component per moles of diazo compound.

Examples 43-48

Examples 43-48 demonstrate the utility of a variety of other mixed condensates as constituents of photosensitive reproduction layers in reproduction materials used for photomechanical production of offset printing plates. The substrates used are aluminum foil roughened with metal brushes and pre-treated according to U.S. patent No. 3,220,832 with polyvinylphosphonic acid.

The coating solutions and details regarding the mixed condensates are listed in table 4 below.

Also in example 44, the reproduction layer containing this mixed condensate has a higher photosensitivity than a reproduction layer of the same thickness, but only containing corresponding formaldehyde condensate of the diazo compound or a mixture of this formaldehyde condensate with an equivalent amount of formaldehyde condensate of 4-methyl-diphenylamine.

In connection with example 46, it must be emphasized that the reproduction layer has very good light sensitivity and also very good storage resistance. One can thus copy and develop the sensitized printing plate after storage for 8 hours at 100°C without the imageless areas tending to float.

Regarding example 48, it should be mentioned that a printing plate can be laxed even after a very short exposure to light. It is therefore sufficient to expose the copy for 10 - 20 seconds with a 5 kw xenon impulse lamp at a distance of 1 metre. The pressure plate can be reinforced with the usual varnishes.

Preparation of diazo condensates

is described in the following.

Example 43

6.1 parts by weight of 3>5-dimethylaniline (component B, No. 1, Table 1) are dissolved in ^0 parts by weight of 80% sulfuric acid by heating to 70°C. The solution is cooled to room temperature and after the addition of 13.8 parts by weight of diazo compound it is further cooled to 0°C. 3 parts by weight of paraformaldehyde dissolved in 15 parts by weight of 80 mg sulfuric acid are added to the crystal slurry and a clear crude condensate is obtained. After stirring for 5 hours at room temperature and standing overnight, the raw condensate is introduced into 1000 parts by volume of water, the precipitate is filtered off and thoroughly washed with water and dried. Yield: 11 parts by weight.

(C 50.9 fo, N 12.5%, ND 7.4 f, S 10.1 f, atomic ratio: 16.1 : 3.38 :

2 : 1,2). The analysis indicates a content of approx. 0.35 mol of the second component per moles of diazo compound.

Example 44

Production of mixed condensate as in example 2.

Example 45

Production of mixed condensate is carried out as in example 12.

Example 46

One repeats the same procedure as in example 57, a reaction where the following compounds are used: 16.2 parts by weight 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1), 36 parts by volume 86 fig phosphoric acid, 6.86 parts by weight 4 ,4'-bis-methoxy-methyl-diphenyl sulfide (component B^, no. 47» table 1). The condensation is carried out for 1.5 hours at room temperature and 20 hours at /\. 0°C.

The raw condensate is dissolved in water and the condensation product is precipitated from the solution by the addition of hydrochloric acid. The viscous precipitate is redissolved in water and precipitated again by the addition of hydrochloric acid. The precipitate is dissolved again in water and from this solution the corresponding sulphonate of the condensation product with the sodium salt of naphthalene-2-sulphonic acid is precipitated. After drying at 40°C, the yield is 12.9 parts by weight. (C 64.7%, N 6.4f, S 9.1%, atomic ratio: 35.4 : 3 = 1.86).

Around 0.86 mol of the second component is present per moles of diazo compound.

Equally good results are obtained by following the same production method as in example 65, with a condensation product produced from the same components but in different quantities.

In this case, the condensation is carried out as follows: lo.2 parts by weight of 3-methoxy-diphenylamine^-diazonium sulfate (diazo 2, sulfate, Table 1), 50 parts by volume of 86 fo phosphoric acid and 13.7 parts by weight of 4,4'-bis-methoxy- methyl diphenyl sulfide (component B^, No. 47 > Table 1) is condensed for 4 hours at /\. 0°C. The raw condensate is dissolved in water, clarified with activated charcoal to avoid a slight turbidity, and the product is precipitated with common salt solution, worked up and washed with common salt solution. The chloride is dissolved again in water and the condensate is precipitated as a salt of mesitylene sulphonic acid. Yield: 24.8 parts by weight.

(C 65.9%, N 6.5%, S 10.2 f, atomic ratio: 35.4 : 3 : 2.05).

The condensate contains approx. 1 mol of the second component per moles of diazo compound.

Example 47

8.3 parts by weight diazo compound 5 (sulphate, slightly moist,

N 6.2 f) is dissolved in 60 parts by volume of 93 f° phosphoric acid and 5.2 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (component B-^, no. 4. 1, table 1) which is added dropwise during 12 minutes. The mixture is stirred for 1 hour without further heating and for two hours at 40°C.

The clear, water-soluble crude condensate is dissolved in water, the condensation product is precipitated by the addition of aqueous hydrochloric acid and precipitated again with hydrochloric acid after re-dissolving in clean water. After drying, you have 10 parts by weight of chloride from the condensation product.

(C 62.3 f, N 4.3 fo, atomic ratio 33.8 : 2).

This means that approx. 1.1 mol of the second component is present per moles of diazo compound.

Example 48

0.94 parts by weight of diazo compound No. 11 (zinc chloride double salt, N 8.9 f) is dissolved in 10 parts by volume of 92% phosphoric acid and dry air is passed through the mixture until no more hydrochloric acid is emitted, i.e. until the mixture is essentially free of chloride ions.

0.52 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (component B-^, no. 41» Table 1) is introduced into the mixture and the condensation is carried out for 15 hours at room temperature. The condensation mixture is dissolved in 100 parts by volume of water, clarified with activated carbon and the sulphonate of the diazo compound is precipitated with 0.92 parts by weight of sodium

salt of naphthalene-2-sulfonic acid in 100 parts by volume of water. bcchange after drying: 0.9 parts by weight (C 64.4 fo, N 3.8 f, S 4.8 f, auom ratio: 59.3 :; 3 : 1,<66>), ' .... Analysis shows that approx. 0.66 mol sodium salt. of sulphonic acid is introduced during the precipitation. In consideration of this, the analysis result gives a condensation ratio between diazophorbinois and secondary component, second component, of approx. 1 : 1.75. , Examples., 49- 54^ > >..:...•;>?••' a - -;; ; ■,■. ^ r--^. :. ;.,v ht • ■\ ;?L. i- >'\ *p.-Exe.nipples .4.9...^il :54 -..shows.,.^use -of certain.vbl-and-r;-condensates^forv- frejstillinggav planographic iske .. printing plates; .on -aluminium substrate ('which -is only ,roughened^raedrme_ta.ll brushes and not; forb.ehandr; easy,;in-,,other way.. $ide,ret/ppply.s^dngej?;.cf£emgårj a.v Table 5, and the description of the preparation of the diazo-blendkpndensa-^r-,follows -after-the-table. r% It should be noted that according to Examples 49 and .54""get~ma'rf"_' positive printing plates from pbjsdtive .originals.. But the developer-,^ resistance% is not very, high , especially .in efesemp.ei^ 50 . The other examples., (5.I to 5.4) -give again negative reproduction materials, i.e. positive printing plates are obtained by exposure under an original negative. While printing plates made according to Example 5T have only medium acid resistance, printing plates made according to Examples 52 to 54 are very resistant to aqueous phosphoric acid, even when the -sates are used in the form of metal halide doubles. This is clear from the fact that, dilute, aqueous phosphoric acid serves, which induces.......... .. _ lr , . ,

The mixed condensates are produced as follows:

Example 49

A solution is prepared from 25.2 parts by weight of diphenylamine-4-diazonium chloride (diazo 1, chloride, table 1) (92.5 f), 18.8 parts by weight of phenol (component B, no. 8, table 1) and 40 parts by volume acetic acid. The solution is poured with stirring at room temperature into a mixture of 200 parts by volume of 3.5% aqueous hydrochloric acid, 29.6 parts by weight of 30.4% aqueous formaldehyde solution, and 40 parts by volume of glacial acetic acid. After approx. 1 minute fel].es the reaction product out as a viscous mass. Stirring is continued for 10 minutes, the aqueous solution is poured off and the condensate is crushed five times with 200 parts by volume of water each time. For purification, the reaction product is dissolved in 360 parts by volume of ethylene glycol monomethyl ether and precipitated by pouring; -e the solution into 4000 parts by volume of water to which 40 parts by volume of 36.. 5 $Lg aqueous hydrochloric acid have been added. The precipitate is thoroughly washed with water and dried, finally under reduced pressure over phosphorus pentoxide. A dark yellow resin is obtained in an amount of 22 parts by weight which, according to analysis, has a nitrogen content of 2.2 f. The ratio that can be calculated from this is approx. 7 phenol units per diazo group.

Example 50

13.6 parts by weight of 4-methoxy-diphenylamine-4'-diazonium chloride (diazo 3" chloride, Table 1) are dissolved together with 7.5 parts by weight of 4-t.-butylphenol (component B, No. 9, Table 1) in a mixture of 49 .1 parts by weight of methanesulfonic acid (98% ± g) and 49>1 parts by weight of glacial acetic acid, and the solution is cooled to + 10°C. At this temperature, a solution of 3 parts by weight of paraformaldehyde in 20 parts by volume of 98 fig methanesulfonic acid is added dropwise with stirring over the course of 10 minutes. Stirring is continued for 20 minutes at this temperature, the mixture is heated to room temperature, stirred for a further 1 hour and finally heated for 10 minutes at 40°C. The mixture is stirred into 1000 parts by volume of water. It is purified by dissolving the precipitate in 200 parts by volume of ethanol and precipitates out at 70°C by stirring in a mixture of 50 parts by volume of 36.5 fig, aqueous hydrochloric acid, and 1000 parts by volume of water. Clean again in the same way.

A dark yellow resin is obtained in a yield of 10.3 parts by weight. The analysis shows a condensation ratio between diazo compound and phenol of approx. 1 : 2.1. (C 67.6%, N 6.3%, atomic ratio C : N = 37.6 : 3).

Example 5i

A mixed condensate is produced as in example 2.

Example" 52

3.03 parts by weight of 3-methyl-phenoxymethyl-phosphonic acid (component B, No. 20, Table 1) and 9 parts by weight of diphenylamine-4-diazonium sulfate (97.6 f) (diazo 1, sulfate, Table 1) are dissolved in 36 ^ parts by volume 90 f methanesulfonic acid. A solution of 1.4 parts by weight of paraformaldehyde in 14 parts by volume of 90 fig, methanesulfonic acid is then added slowly while cooling, and the mixture is finally heated for 3 hours at 40°C.

The crude condensate is then diluted with water to 1000 parts by volume, and the condensation product is precipitated from the solution with zinc chloride. Yield: 11.6 parts by weight. (C 47.4%, N 9.4 f, P 3.3 f, atomic ratio: 17.7 : 3 : 0.48).

The mixed condensate contains approx. 0.5 mol of the second component per moles of diazo compound.

Example 53

8.2 parts by weight 96.2 fig 4-methoxy-diphenylamine-4'-diazonium chloride (diazo chloride, table 1) are dissolved in 40 parts by volume 80 fig sulfuric acid. To this solution, a solution of 3.3 parts by weight of 4-chloro-phenoxymethyl-phosphonic acid (component B, no. 21, table 1) in 10 parts by volume of N-methyl-pyrrolidone, to which 1.4 parts by weight of paraformaldehyde in suspended form.

After condensation for 1 hour at 40° C, the mixture is stirred into 1000 parts by volume of isopropanol, the precipitate is filtered off, washed and dried.

Yield: 6.4 parts by weight (G 46.1 f, N 10.8 f, P 1.18 fo, atomic ratio: 15.8 : 3 : 0.16).

The condensation product contains approx. 0.2 mol of the second component per moles of diazo compound.

Example 54

The procedure is as in example " Jl, but with the following

starting materials:

15.0 parts by volume 99 f° methanesulfonic acid,

3.0 parts by weight diazo 1, sulfate (97.6 f),

0.6 parts by weight of 4-tert-butyl-phenoxymethylphosphonic acid

(component B, no. 22, table 1), and

0.38 parts by weight of paraformaldehyde in 5 parts by volume of methanesulfonic acid.

The condensation is carried out for 3 hours at 40°C and the product is precipitated as a zinc chloride double salt.

Yield: 3.8 parts by weight (C 44.8%, N 9.3%, P 1.9%, atomic ratio: 16.9 : 3 : 0.28).

The condensate contains approx. 0.3 mol of the second component per moles of diazo compound.

Examples 55-57

These examples show that not only mixed condensates in the form of diazonium salts but, in principle, also azides and diazoamino compounds that can be produced from these by reaction with sodium azide or with secondary amines, can be used as light-sensitive components in a reproduction layer, and in special cases reproduction layers that are suitable for production of toned images. (Monochrome images).

Table 6 contains the most important data from these examples.

In all cases, the coating compositions were sling coated onto the substrates used and the coating then dried. After image exposure, the unilluminated areas were removed with water and after drying, the cured illuminated image areas were stained with an aqueous crystal violet solution.

In table 6 means:

EGMME = ethylene glycol monomethyl ether

BA = butyl acetate.

The mixed condensates are produced as follows:

Example 55

5.68 parts by weight of 2-naphthol-6-sulfonic acid (sodium salt, 87 fo, component B, no. 13) are dissolved in 80 parts by volume of methanesulfonic acid (90 fo) under heating. The solution is cooled to 20°C, after which 6.17 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate) and then 1.2 parts by weight of paraformaldehyde are added while stirring. After the condensation mixture has been stirred for 24 hours at 20°C, it is poured into 1000 parts by volume of water. The mixed condensate is excreted in the form of an internal salt that is poorly water-soluble. It is filtered off, washed by suspending several times in water and dried. Dividend:

7.1 parts by weight. The product contains the diazo compound and the sulphonic acid in a molar ratio of approx. 1 : 1. The poorly water-soluble mixed condensate (inner salt) can be transferred to a completely water-soluble azide by treatment with sodium azide, which shows that the condensate is a true mixed condensate. (C 58.2 f, N 8.5 f, S 6.9 f, atomic ratio: 24 : 3 : 1.06).

Example 56

5>58 parts by weight of 2-methoxy-naphthalene-6-sulfonic acid (93»3 f°> component B, no. 23, table 1) are dissolved in 80 parts by volume of methanesulfonic acid (90 f) heated to 60°C. After cooling, 6.17 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, Table 1) are dissolved in the solution while stirring, and 1.2 parts by weight of paraformaldehyde are introduced while stirring. After condensing the mixture for 20 hours at room temperature, it is poured into 1000 parts by volume of water heated to 40°C, and kept at this temperature for 1.5 hours. The condensation product is suctioned off, washed by suspension in water and dried. Yield: 8.2 parts by weight. According to analysis, the product contains, in the form of inner salt, diazo compound and sulphonic acid in a ratio of approx. 1 : 1.1

(N 7.8 f, S 6.2 f, atomic ratio: 3 : 1.04). By treatment with an aqueous sodium azide solution, the practically water-insoluble condensation product can be transferred to an azide compound which is soluble in water. This shows that it is a true mixed condensate.

For the preparation of coating solutions used in examples 74 and 75, the diazo solutions are dissolved in water, reacted with the amount of sodium azide indicated in Table 6, and the reaction mixture is added to a solution of the polymer in the other solvents.

Example 57

The diazo mixture condensate is prepared as indicated in example 44, but with the use of component 41 instead of component 40.

Example 58

A sandblasted polyester film was spin coated with an aqueous solution containing 0.55% of the mixed condensate described below and 5.5% polyvinyl methyl acetamide (K value 91). After image exposure, the unexposed areas are removed with water, and after drying, the hardened image areas are colored using an aqueous crystal violet solution.

The mixed condensate was prepared as follows:

6.5 parts by weight of 3-methoxy-diphenylamine-4-diazonium phosphate (diazo 2, phosphate) are dissolved in 50 parts by volume of 86$ phosphoric acid, then 8.9 parts by weight of hexa-methoxymethylmelamine (component B-^ no. 28, Table 1) are introduced under vigorous stirring, and the mixture is condensed for 20 hours at room temperature.

The condensation product is separated from the crude condensate as dihydrogen phosphate containing 1 mol of phosphoric acid by precipitation with isopropanol. Yield: 9.1 parts by weight. (C 32.9%, N 11.6$, P 14.9$). According to analysis, the product contains the elements C and N in a ratio of approx. 10 : 3.

Example ' 5 9

A water-resistant paper substrate with a matte, hydrophilic surface layer of barite, kaolin and finely divided silicon oxide in hardened polyvinyl alcohol is coated by coating with the following solution, followed by drying:

2.0 parts by weight of mixed condensate described below,

0.52 parts by volume 10 N hydrochloric acid,

10.0 parts by volume water,

50.0 parts by volume of ethylene glycol monomethyl ether, and 50.0 parts by volume of dimethylformamide.

After pictorial exposure under a negative, the material is developed with an aqueous solution containing 2.2% NajHPOjj. 12 H20 and 2.7$ ammonium chloride. You get a printing plate with good ink receptivity.

The mixed condensate used is prepared as follows: 3.0 parts by weight of 3-methoxy-diphenylamine (component B, No. 4, Table 1) and 3.1 parts by weight of 4-chloro-diphenylamine (component B, No. 3, Table 1) are dissolved rapid in 150 parts by weight 80 flg sulfuric acid heated to 80°C. As soon as all components have dissolved, the mixture is rapidly cooled to +30°C and 14.7 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, Table 1) are dissolved at this temperature. A solution of 2.4 parts by weight of paraformaldehyde in 25 parts by volume of 80 flg of sulfuric acid is then slowly added dropwise, at room temperature, avoiding that the temperature goes above 25°C during cooling. After condensation for 1 hour at 40°G, a water-soluble raw condensate is obtained. It is diluted with 50 parts by volume of methanol, precipitated by adding 2000 parts by volume of isopropanol, the precipitate is suctioned off, washed twice by suspending in 500 parts by volume of isopropanol and finally dried under reduced pressure at 40°C. Yield: 17.5 parts by weight. According to analysis, the mixed condensate (sulphate) contains approx. 0.26 mol of 3-methoxy-diphenylamine and approx. 0.08 mol 4-chloro-diphenylamine per moles of diazo compound.

(C 50 f, N 11 fo, Cl 0.7 f, 0CR"3 1.9 f, S 9.5 f, atomic ratio: 68 : 12.8 : 0.32 : 1 : 4.84).

Example 60

The procedure from example 51 is repeated, but a solution with the following composition is used:

1.0 parts by weight of mixed condensate described below,

4.0 parts by weight polyvinylpyrrolidone (K-value 90),

0.1 part by weight crystal violet (CI. 42555),

88.0 parts by weight water, and 12.0 parts by weight ethanol.

By processing as described in example 51, a positive printing plate is obtained from a positive original by a reversal process.

When the reproduction material is exposed under a negative original and then developed by rinsing with water, a positive blue-toned copy is obtained.

The mixed condensate is produced as follows:

3.42 parts by weight of 2-dimethylamino-naphthalene (component B,

no. 7, table 1) and 6.17 parts by weight 95 flg diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) are dissolved in 40 parts by volume 90 f methanesulfonic acid. At room temperature, 1.2 parts by weight of paraformaldehyde are added slowly while stirring. After condensation for 50 hours at room temperature, the mixture is diluted with 3°0 parts by volume of water and

the condensate is precipitated at 80°C by adding 50 parts by volume of 50 fig aqueous zinc chloride solution. After cooling to 20°C, the condensate is filtered off, dissolved in 30° parts by volume of water at 50°C, reprecipitated by - adding 30 parts by volume of the above zinc chloride solution, suctioned off and dried. Yield: 9>4 parts by weight. According to analysis, the mixed condensate contains approx. 0.6 mol amine per moles of diazo compound. (N 9.2%, ND 5.1 f, atomic ratio: 3.61 : 2).

Example 61

The paper substrate used in example 47 is coated by spreading with the following coating solution:

0.5 parts by weight of mixed condensate described below,

50.0 parts by volume of ethylene glycol monomethyl ether, and 50.0 parts by volume of water.

After drying, the reproduction layer is illuminated pictorially under the negative original and overlaid with water. You get a very black-receptive positive printing plate.

The mixed condensate is produced as follows:

13.8 parts by weight of 4-hydroxy-benzoic acid (component B, no. 12, table 1) are dissolved at 40 C in a mixture consisting of 100 volume parts 90% sulfuric acid and 40 parts by volume 96 fig sulfuric acid. The solution is cooled rapidly to room temperature, then 30 parts by weight of 97.6 mg of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) are introduced, and the solution is cooled to +5°C to 10°C. At this temperature, a solution of 6 parts by weight of paraformaldehyde in 20 parts by volume of 90 mg sulfuric acid is added carefully, drop by drop. Stirring is continued for 30 minutes at the same temperature and the mixture is then poured into 1,000 parts by volume of ice water. The precipitated product is suctioned off, suspended in 500 parts by volume of water, filtered again and dried. Yield: 46.6 parts by weight. The analysis shows that the condensate contains 4-hydroxybenzoic acid and diazo compound in an approximate molar ratio equal to 1:1. (C 49.7 f, N 8.5 f, ND 5.6 f, S 6.9 f, atomic ratio: C : N : ND : S = about 20.7 : 3 : 2 : 1.08).

Example 62

The procedure described in example 80 is repeated except that the following coating solution is used:

2.0 parts by weight of mixed condensate described below,

0.75 parts by weight 86 fig phosphoric acid, and

100.0 parts by volume of water.

You proceed as indicated in example 80 and the result is very similar.

The mixed condensate is produced as follows:

15.42 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) are dissolved in 100 parts by volume of 80% sulfuric acid. With vigorous stirring, 8.83 parts by weight of finely powdered dimethylol succinic acid diamide (component B-^, no. 26, table 1) are added, cooling the mixture so that it remains at +25°C. The mixture is condensed for 15.5 hours at room temperature, the crude condensate is dissolved in 500 parts by volume of water and the condensate is precipitated by adding 80 parts by volume of 50% zinc chloride solution. The precipitate is separated, dissolved in ^ 00 parts by volume of water at ^ 0°C, reprecipitated by adding 50 parts by volume of 50% ± g zinc chloride solution, sucked off and dried under reduced pressure. Yield: 18.6 parts by weight. (C 40.8%, N 11.6%, ND 5.35%, atomic ratio: 17.8 : 4.35 : 2). From the analysis it can be established that the second component has been introduced into the molecule, but the carbonamide groups seem to have been saponified to some extent.

Example 63

This example shows the superiority of certain mixed condensates in relation to known diazodiphenylamine-formaldehyde condensates for hydrophilic curing of water-soluble colloids. Hydrophilically hardened colloids are important in special types of positive-acting, presensitized printing plates (see U.S. Patent No. 3,085,008). With plates of this type, a mixture of a hydrophilic polymer and a diazo compound is coated on the substrate surface, which has been made oleophilic. By pictorial exposure under a positive original, the colloid is cross-linked hardened and bonded to the oleophilic support layer. The unexposed areas of the layer are removed and the oleophilic substrate becomes free in these areas and will form the image areas that transfer the ink. This results in a positive pressure plate.

Since the light-decomposition products of known formaldehyde condensates have oleophilic properties, the content of diazo condensate should not be too high, on the other hand, the cross-link curing of the layer should be as complete as possible to make it more resistant to attack during the printing process, and this is best achieved at a higher content of diazo compound.

The example below shows a comparison between two printing plates of this type where

a) a plate was prepared with the chloride of the formaldehyde condensate of diphenylamine-4-diazonium chloride prepared according to Example 1 in U.S. patent no. 3«3H«605,

b) while the second plate was being prepared" with the mixed condensate chloride of diphenylamine-4-diazonium salt and

dimethylol urea prepared as described below.

A presensitized intaglio printing plate made according to U.S. Pat. patent no. 3*396,019, example 1, is fully exposed without using original, e.g. under an arc lamp. The plate is then rinsed with water and dried. The plate is split in two and one half is coated with coating solution 1, the other with coating solution 2, described below, and the coatings are dried.

1. 0.125 parts by weight of condensate described under a),

0.38 parts by weight polyacrylamide ('Cyanamer P 250'), and 100.0 parts by volume water. 2. 0.125 parts by weight mixed condensate described under b), 0.38 parts by weight polyacrylamide ("Cyanamer P 250"), and 100.0 parts by volume water.

After pictorial exposure under a positive original, the plates are developed by stroking them with water and they are blackened with fatty ink.

While in case 1 a you get a positive pressure plate which

is extensively blackened in the image-free areas, with resolution 2 you get a positive flat printing plate which, apart from insignificant weaknesses in the coating, is fully usable and where the image-free areas (hardened hydrophilic colloid) do not absorb greasy ink.

The mixed condensate used in this case is prepared as follows: 23.2 parts by weight of diphenylamine-4-diazonium chloride (diazo 1, chloride, table 1) are dissolved in 50 parts by volume of a 3^.5% aqueous solution of hydrochloric acid. With vigorous stirring, 12 parts by weight finely powdered dimethylol-urea (component B-^, no. 29, table 1) in the solution and stirring is continued, first for 3 hours at room temperature and then for 1 hour at 40° C. After resting overnight in a refrigerator, the mixture is diluted with 80 parts by volume of methanol and poured into 1200 parts by volume of isopropanol. The precipitate is suctioned off, washed briefly twice each time with 400 parts by volume of isopropanol and dried under reduced pressure at 40°C. Yield: 15 parts by weight (chloride). In this way, a yellow water-soluble powder is obtained which according to analysis contains approx. 0.9 mol of urea per diazo group (N 19.6%, ND 8.2%, Cl 10.8%,

atomic ratio: 4.8 : 2 : 1.04).

Example 64

An aluminum substrate of the same type as in example 57 is coated with a coating solution that has the following composition:

1.0 parts by weight of mixed condensate described below,

2.0 parts by volume 1 N hydrochloric acid,

0.4 parts by weight of diazo condensate prepared according to example 1

in the U.S. patent no. 3,406,159 and adjusted to 2.8 mol phosphoric acid per diazo group,

1.0 part by weight of polyvinyl acetate with an average molecular weight of

110,000 (determined by light diffusion),

* 4»0 parts by weight water,

77.0 parts by weight of ethylene glycol monomer and 19.0 parts by weight of butyl acetate.

After drying the coating, you have a very light-sensitive reproduction material, which can be transferred to printing plates using a developer solution as indicated in example 57•

A further treatment with developer II described in

examples 36 to 43 may be an advantage.

The mixed condensate is produced as follows:

7.33 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, Table 1) are dissolved in 100 parts by volume of 90 flg of methanesulfonic acid. 2.1 parts by weight of diphenylene oxide (component B, no. 24" table 1) are then added, which are dissolved in 35 parts by volume of glacial acetic acid and 3>75 parts by weight of 30 flg aqueous formaldehyde solution in 5 parts by volume of glacial acetic acid, the two glacial acetic solutions are combined and the mixture is then added dropwise under stirring to the first prepared diazo solution. The mixture is further stirred for 4 hours at 40°C. After standing for 36 hours at room temperature, the crude condensate - which dissolves in water without any residue - is stirred in 1250 parts by volume of isopropanol. This suspension is stirred at /\. 0°C until a precipitate is deposited when the stirrer is switched off. The precipitate is suctioned off, washed twice in 250 parts by volume of isopropanol, suspending the precipitate, and dried under reduced pressure. Yield: 5.9 parts by weight. According to analysis, the mixed condensate contains approx. 1 mol of diphenylene oxide per mol' diazo compound. (C 60.8 f, .N 8.1 f, S 6.1 f, atomic ratio: 26 : 3 : 1).

A suitable reproduction material is also obtained. to by coating the same substrate with a solution that has the following composition: 1.0 parts by weight of mixed condensate described in example 15, 1.8 parts by volume of 1 N hydrochloric acid in ethylene glycol monomethyl ether<*> (for transfer of the diazo compound to the chloride), .. f 2.0 parts by weight epoxy resin based on biphenol A and with a melting point range of 96 - 104 C and epoxy equivalent weight' equal to 875 - 975 ("Epikote 1004"), '

««ufe-,

4.0 parts by volume water,

75.0 parts by volume ethylene glycol monomethyl ether, and 20.0 parts by volume butyl acetate.

: ■ >,

Example 65

A trimetallic plate consisting of layers of aluminium, copper and chromium is coated with a solution with a composition as indicated below, the excess solution is dripped off and the plate is dried: 2 parts by weight of chloride of the mixed condensate described below, 1 part by weight of polyvinyl alcohol (residual acetyl content 12%, viscosity for 4% aqueous solution 6.5 to 8.8'cp at 20°G), and

50 parts by volume of water.

After image exposure under a positive original, the plate is developed with developer II described in examples 36 to 43, °g then the chrome is etched away down to the copper layer in the areas not covered by the reproduction layer, using an aqueous etching solution containing 30% by weight of calcium chloride , 20% by weight zinc chloride and approx. 1.5 to 3 f° ammonium chloride, tartaric acid and concentrated hydrochloric acid for the chromium layer." The coating is removed by treatment with a paste consisting of powdered chalk and dimethylformamide. In this way, a positive multi-metal printing plate has been obtained which has a very long life.

The diazo mixture condensate is prepared in a similar way as in example 44, although the following reactants and reaction conditions have been used: 32.3 parts by weight 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1),

170.0 parts by weight 86% phosphoric acid, and

64.4 parts by weight of methoxymethyl-diphenyl ether prepared from GMDPO-32 (component B^, no. 48, see below).

The mass is condensed for 4.5 hours at 40°C, dissolved in water, filtered until clear, precipitated with hydrochloric acid, redissolved and precipitated again with hydrochloric acid.

Yield: 44 parts by weight.

According to information provided by the manufacturer (see U.S. Patent 3,316,186, column 3, lines 41 to 64), chloromethylated diphenyl ether CMDPO-32 from Dow Chemical Co. a CHgCl degree of substitution of 2.8 and consists of the following components:

The ethereal mixture which one obtains by being stubborn; te halogen atoms with methoxy groups had a methoxy content of 28.9 The mixture was used to produce a condensation product which had the following elemental analysis: (C 67.5 ^ 4»4 % > Cl (total) 4.3 %, Cl (ionic form) 3.8%, OCH^ 12.7 f°> atomic ratio: 53.6 ; 3 <:> 1.16 : 1.03 : 3.92).

The analysis results show that considerable amounts of reactive methoxymethyl groups are found in the mixed condensate.

A reproduction material is produced which can also be used with good results by coating the same substrate with a coating solution which has the following composition; and dried:

, 1 part by weight of mixed condensate described in example 44,

2 parts by weight of polyvinyl alcohol of the type used above in this example, and

50 parts by volume of water.

After image exposure, the plate is developed by rinsing with water. Further processing with the aim of arriving at a multi-metal printing plate is described at the beginning of this example.

Instead of a substrate consisting of aluminium, copper and chrome layers, you can use a brass foil that is coated with a thin layer of chrome.

Example 66

A copper plate is immersed for a few seconds in 1 - 2 volumes of ferric chloride solution, rinsed with water, cleaned with chalk powder, rinsed again and dried.

A solution consisting of:

8 parts by weight of mixed condensate described below, and

100 parts by volume mixture of 8 parts by volume ethylene glycol monomethyl ether and 2 parts by volume butyl acetate

over the plate and the coating is dried by blowing hot air over it.

After image exposure under a positive raster original, the plate is brushed for a few seconds with a 10% aqueous solution of n-propanol and developed with developer I as used in examples 36 to 43 until the reproduction layer is removed from the unexposed areas.

After drying, the plate is etched in the usual way with 40 $Lg of iron III chloride solution. You get a halftone raster plate.

The mixed condensate is prepared as described in example 84, but with the following components and conditions:

32.3 parts by weight of diazo 2, sulfate (Table 1),

170.0 parts by weight 86% phosphoric acid, and

32.3 parts by weight component B^, No. 48 (Table 1).

The react ion mixture is condensed for 4.5 hours at /\. Q°G, the condensation product is precipitated from aqueous solution by adding common salt solution, redissolved and reprecipitated with common salt solution. The final precipitation is carried out in the form of the mesitylene sulphonate. Yield: 55.7 parts by weight. (G 66.7%, N 5.8%, S 4.7%, OCH^ 7.8%, atomic ratio: 40.2 : 3 : 1.06 : 1.82).

The analysis results show that this condensate also contains significant amounts of reactive methoxymethyl groups.

Following the method described in example 55, printed circuits can be produced by using the same coating composition.

Examples 67-79

These examples show the usability of a number of mixed condensates prepared from different components and precipitated in different forms (light-sensitive sulfonic acids and polyfunctional sulfonic acids) for briu. as light-sensitive reproduction layers suitable for the photomechanical production of planographic printing plates.

It is surprising that the precipitation product of the polyfunctional mixed condensate and divalent sulphonic acids as used in examples 72 and 73 is easily soluble in organic solvent.

Table 7 contains data relating to the mixed condensates used, coating solutions and developers.

In some cases, phosphoric acid was added to the coating solutions. The addition of phosphoric acid, e.g. down to 0.1 to 0.3 mol per moles of diazo groups, have a beneficial effect on the storage stability of the coated materials and their development properties.

After image exposure under a negative, the image becomes clearly visible and is usually blue-green, but browner in example gi.

After inking with fatty ink, you get printing plates that can be used for a large number of blemish-free prints. The service life can be increased further by reinforcing the finished plate with an aqueous varnish.

Printing plates coated according to Examples 67 to 73 are more light sensitive than plates prepared with formaldehyde condensates of diazo compounds described in Example 1 of U.S. Pat. patent No. 3-4-06. 159* The clearest increase in photosensitivity is achieved in examples 71, 76 and 77, as materials according to examples 76 and 77 are particularly advantageous because they have a simple synthesis and the products are very well storage-resistant. The storage resistance of printing plates made with the latter two materials is remarkably high.

The carrier layer used in examples <&7> to 77 was aluminum foil which was electrolytically roughened, then anodically treated and finally treated with polyvinyl phosphoric acid. In examples 78 and 7.9, aluminum foil was used which had been roughened with metal brushes and treated with polyvinylphosphonic acid.

In addition to these substrates, a number of substrates can also be used in combination with those of the invention's reproduction layer which are recommended for the "whip-on" process with known commercially available diazo resins.

The diazo compounds used in examples 6<7> to 77 are prepared as follows:

Examples 6 7 and 68

The condensation is carried out as described in example 37 and the following conditions and starting materials are used:

120.0 parts by weight 86 fig phosphoric acid,

32.2 parts by weight diazo 2, sulfate, and

8.3 parts by weight of 1,3-dimethyl-4,6-dimethylolbenzene (component B-^, No. 35, Table 1).

The mixture is condensed for 20 hours at /\. 0°G. In example 67, half of the mixture is dissolved in water, the condensate is precipitated by adding aqueous ealt solution, the precipitate is dissolved in water and reprecipitated in the form of naphthalene-1-sulfonic acid salt. yield: 11.5 parts by weight. (C 65.5 f, N 8.0 f, S 6.1 f, atomic ratio: 28.7 : 3 : 1).

Average molecular weight for the dye prepared with phenyl-methyl-pyrazolone is 1256.

In example 68, the other half of the crude condensate is mixed into water and the corresponding hexafluorophosphate is precipitated by adding hexafluorophosphoric acid. Yield: 21.2 parts by weight. (C 45.4 f, N 9.2 fo, atomic ratio: 17.2 : 3). The precipitate contains a small amount of uncondensed diazo compound.

Examples 69 and 70

The procedure from examples 67 and 68 is repeated and the following compounds and reaction ratios are used:

120.0 parts by weight 86 fig phosphoric acid,

32.3 parts by weight of diazo 2, sulfate (Table 1), and 11.1 parts by weight of 4,6-diisopropyl-1,3-dimethylolbenzene (component B-^, No. 36, Table 1).

The mixture is condensed for 20 hours at /\. 0°C. In example 69, half of the mixture is dissolved in water, the condensate is precipitated by adding a common salt solution, the precipitate is dissolved again in water and reprecipitated in the form of naphthalene-1-sulfonic acid salt. Yield: 13.3 parts by weight. (C 66.3 #. N 7.5 f, S 5.6%, atomic ratio: 31 : 3 : 0.98).

Average molecular weight for pyrazolone dye: 1299»

As in example 70, the other half of the mixture is dissolved in water and the hexafluorophosphate is precipitated from the solution by adding hexafluorophosphoric acid. Yield: 11.1 parts by weight. (C 52.9 f, N 10.7 #in atomic ratio: 17.3 : 3).

The product contains some uncondensed diazo compounds.

Example il

"The procedure is as described in example 42, but the following conditions and starting materials are used:

200.0 parts by volume phosphoric acid,

3.23 parts by weight of diazo 2, phosphate (Table 1), and 1.33 parts by weight of 9,10-bis-methoxymethyl-anthracene (component B^, No. 43» Table 1), in

20.0 parts by volume glacial acetic acid.

The second component is dissolved in boiling glacial acetic acid and

the solution is poured into the diazo solution. The condensation extends over 20 hours at 40°C. The condensation product is separated in the form of chloride. Yield: 2.8 parts by weight. (C 51.1 fo, N 7.8 f, atomic ratio: 23 : 3).

Examples 72 and 73

The condensation product is prepared in the same way as in example 25 and the starting materials and reaction conditions below are used:

240.0 parts by weight 86 fig phosphoric acid,

64.6 parts by weight diazo 2, sulfate (Table 1), and 44.4 parts by weight component B-^, No. 36

The mixture is condensed for 20 hours at 40°C. The crude condensation bianding is dissolved in water and the solution is divided into two parts.

From the first half (Example 72), the condensate is decomposed 'first with hydrochloric acid to chloride, and finally in the form of 4,4'-diazido-stilbene-disulfonic acid salt. Yield 41.9 parts by weight. (G 63.7%,

N 12.9 f°> S 4.8 f, atomic ratio: 70.6 : 12.3 = 2).

Out frc. the other half (Example 73) separates the condensate directly as 2,6-di-tert-butyl-naphthalene-disulfonic acid salt. Yield 38.3 parts by weight. (G 68.1 f, N 7.7 f, S 4.9 f, atomic ratio: 31 : 3 : 0.835).

Example 74

The condensation is carried out as indicated in examples 72 and 73. The condensate is first precipitated with hydrochloric acid and then with naphthalene-2-sulfonic acid. (C 68.3 f, N 6.6 f, S 4.9 f, atomic ratio: 36.2 : 3 : 0.98).

Example 75

One repeats a procedure as described in example l8, but however uses the following compounds and reaction environment:

4.85 parts by weight diazo 2, phosphate, (Table 1),

15.00 parts by volume methanesulfonic acid (90 f) and

2.04 parts by weight of 1,5-di-acetoxymethyl-naphthalene (component B-^ no. 37 > table 1)..

The condensation is carried out for 2 hours at room temperature, and the product precipitates out in the form of chloride. Yield: 3.2 parts by weight.

(C 64.0 f, N 9.4 f, atomic ratio: 23.8 : 3).

Example 76

The condensate described in example 57 precipitates out in the form of 2-diazo-1-naphthol-5-sulfonic acid salt and is dried over phosphorus pentoxide to constant weight.

Example 77

The 1:1 condensate corresponds to the condensate used in example 57 for the production of the azo dye which was to be fractionated.

The second condensate, which contains 3_methoxy-diphenylamine-4-diazonium salt and the second component in an approximate ratio of 1:0.67, is prepared analogously to example 4i according to the procedure below:

120.0 parts by weight 96 flg phosphoric acid,

32.3 parts by weight of diazo 2, sulfate (Table 1), and

12.9 parts by weight component, No. 41 (Table 1) (98 - 99 #).

The mixture is condensed for 21 hours at 40°C and the reaction product is precipitated twice with hydrochloric acid to form the chloride. Finally, the condensate precipitates in the form of the naphthalene-2-sulfonic acid salt. Yield: 35 parts by weight. (C 67.0 f, N 7.2 f, S 5.6 f, P 0.18 f, Cl 0.21 f,

atomic ratio: C : N : S = 32.6 : 3 : 1).

Average molecular weight for the azo dye prepared with phenyl-methyl-pyrazolone is 1455*

A fractionation experiment where a film of the dye on aluminum foil is triggered fractionally can be found in the table below:

Example 78

The condensate is used as described in example 90.

Example 79

The condensate is used as described in example 94.

Example 80

The substrate as used in examples 1 to 35 is coated

with 1% aqueous solution of diazo mixed condensate described below, which contains 50% by weight - based on the weight of mixed condensate - 85% phosphoric acid. (The coating resolution is somewhat unclear).

After drying, the material is exposed and then developed as described in Examples 1 to 35, giving a printing plate with good ink receptivity.

The mixed condensate is produced as follows:

4.6 parts by weight of diphenylamine-4-diazonium sulfate and 2.2 parts by weight of 3-aminopyrene are dissolved under gentle heating in 30 parts by volume of 90% methanesulfonic acid. After cooling down to room temperature, 0.75 parts by weight of paraformaldehyde are added under pipetting. After stirring for a further 3.5 minutes, the crude product is immediately introduced into aqueous hydrochloric acid heated to 90°C. (200 parts by volume water and 100 parts by volume 18% aqueous hydrochloric acid). After rapid cooling in an ice bath, filter off the precipitate under suction, wash with 0.5 N hydrochloric acid and dry. Ratio: 4.8 parts by weight. According to the analysis, the product has an atomic ratio of C : N = 31.4 : 4, while the diazo homocondensate will have a ratio of 17.3 : 4, and the amine homocondensate a ratio of 68 : 4 (C 65.1%, N 9.7 %).

Example 81

An electrolytically roughened aluminum foil is coated with the following composition, after which the coating is dried:

5.0 parts by weight polyvinyl alcohol (degree of saponification:

88%, viscosity for a 4% aqueous solution at 20°C =6.5 to 8.8 cP),

0.5 parts by weight of diazo mixed condensate described below, 94.5 parts by weight of water.

After image exposure, develop by rinsing with water. When colored with an aqueous solution of crystal violet (CI. 42555), a blue-tinted image is obtained.

A mechanically roughened polyethylene terephthalate film can also

used as a substrate.

The mixed condensate is produced in the following way:

8.5 parts by weight of 2-phenylamino-pyridine are dissolved in 50 parts by volume of 80% sulfuric acid at a temperature not exceeding 35°C. The solution is cooled to 15 - 20°c and within 10 minutes a mixture of 15 parts by weight of 97.6% diphenylamine-4-diazonium sulfate and 3 parts by weight of paraformaldehyde is added, while stirring. The mass is stirred for a further 3 hours at room temperature and allowed to stand for 14 hours. To recover the mixed condensate, it is diluted with 70 parts by volume of methanol while cooling and stirred into 700 parts by volume of isopropanol. The product is filtered off and suspended and washed twice in 500 parts by volume of isopropanol. Yield: 25.6 parts by weight, as sulfate. The analysis shows that the product contains approx. 0.8 mol of the second component per moles of diazo compound. (N 10.4%, ND 4.6%, atomic ratio: 4.52 : 2).

Example 82

This example shows that the oleophilic properties of exposure products from the new diazo condensates are clearly noticeable even under extreme conditions: Surface saponified cellulose acetate film is coated by brushing with a solution containing 2 parts by weight of crude condensate described below in 98 parts by weight of water, and the coating is dried. Despite the fact that the solution is highly diluted and contains approx. 75 molecules of phosphoric acid per diazo group, the image areas on the exposed foil repel water when the foil is brushed over with water, but absorb fatty ink.

For comparison, a plate is coated in a similar way with a solution containing an amount of diazo group equivalent to the above coating solution, but where a formaldehyde condensate prepared as described in U.S. patent No. 3,406,159, without any other component in the mixture. The ratio between diazo groups and phosphoric acid was adjusted to the same number as in the above mixture containing mixed condensates.

After pictorial exposure, both unexposed and exposed areas are hydrophilic. The exposure products cannot be blackened with fatty ink.

The diazo mixed condensate is prepared as follows:

1.29 parts by weight of 3-methoxy-diphenylamine-4-diazonium phosphate are dissolved in 33.8 parts by weight of 86% phosphoric acid. At room temperature, first add 0.36 parts by weight of paraformaldehyde and immediately afterwards 0.68 parts by weight of thiophene with vigorous stirring. The mixture is stirred for 3 hours at room temperature and allowed to stand overnight. With the exception of a slight deposit of resin on the stirrer, the crude condensate formed will produce a clear solution in water. The raw condensate is used in this form for the production of coating solution.

Example 83

This example shows that mixed condensates containing only very small amounts of diazo compound still provide usable reproduction materials.

An electrolytically roughened aluminum foil is coated with a 2% ethylene glycol monomethyl ether solution of a mixed condensate (which according to analysis contains approx. 18 p-cresol units per unit of 3-methoxy-4-diazo-diphenylamine) and the coating is dried.

After image exposure under the negative original, the foil is developed by rinsing with acetone, dried, brushed over with water and blackened with fatty ink.

In this way, a positive printing plate with an unwanted blind surface blackening has been obtained, but can be cleaned by brushing over with a solution containing 75 parts by volume of water, 35 parts by volume of n-propanol and 2 parts by weight of Nal^PO^. 2 H^O.

When a condensate containing only p-cresol units is prepared under equal conditions and an amount of 3-methoxy-diphenylamine-4-diazonium chloride corresponding to the above introduced amount of diazo compound is then added, a mixture is obtained which gives a reproduction layer which gives blind surface blackening in the positive printing plate after image exposure and development with acetone. If, however, one tries to clean this printing plate by brushing with the previously mentioned solution, this printing plate is completely destroyed.

Even when ten times this amount of diazo compound is added afterwards, no better results are obtained.

For the preparation of the mixed condensate, 0.323 parts by weight of diazo 2, sulfate (table 1) were dissolved in 100 parts by volume of 86% strength

phosphoric acid, and this solution was mixed with vigorous stirring with a solution of 3.36 parts by weight of 2,6-dimethylol-4-methylphenol in 20 parts by volume of hot methanol. At the moment of mixing, a clear solution formed which quickly became cloudy as the condensate precipitated out. After stirring for 1 hour and standing overnight, the mass was diluted with 400 parts by volume of water and mixed with 150 parts by volume of saturated normal saline solution. The precipitate was aspirated, washed to neutrality with water and dried. Yield: 2.8 parts by weight. (C 71.0%, N 1.4%, atomic ratio: 177 : 3).

An analysis of the 2,6-dimethylol-p-cresol homocondensate prepared under identical conditions gave the following figures: C 71.6%,

H 7.1%. This analysis indicates the presence of a dibenzyl ether-like link in the unit.

Examples 841 to 93 again show the good oleophilic properties for exposure products of some of the diazo mixture condensates when applied to surface saponified cellulose acetate film. The mixture obtained after condensation is diluted and used directly for coating to show that the effect according to the invention can be achieved without separating the large amounts of acid. Naturally, even better results are achieved with a smaller amount of permitted acid. For practical purposes, acid additions of less than 3 mol of acid per mol diazo compound to this type of substrate.

Detailed data regarding the condensation method and the coating solution are listed in Table 8.

Examples 87, 89, 91, 92 and 93 gave the best results. Because of their high acid content, Examples 85 and 86 showed the worst ■ results.

For comparison, a condensation product was prepared in the same manner as in Example 1 according to U.S. Pat. patent no. 3,406,159 from diazo 2, chloride (Table 1) and formaldehyde in 2.8 mol of phosphoric acid, and then the phosphoric acid content was regulated to 15 mol. Surface saponified cellulose acetate film coated with 1% and 10% aqueous solutions of this mixture, respectively, showed virtually no ink receptivity in the image areas after exposure and development with water.

The mixed condensates are produced as follows:

Example 84

Preparation of component B^

12.4 parts by weight of 4,4'-dimethyl-diphenyl ether are dissolved in 27 parts by volume of glacial acetic acid and then first 5.7 parts by weight of paraformaldehyde are introduced, then 28 parts by weight of 63% aqueous hydrobromic acid solution and finally 16.5 parts by weight of 95% sulfuric acid , while stirring. After heating for 2 hours at 90 - 95°C, the mixture is set aside for cooling overnight.

The crystals present in the mixture are filtered off, washed with water and recrystallized from acetone without intermediate drying. Yield: 14.75 parts by weight. Melting point: 109 - 110°C.

The compound is dissolved in benzene and the solution is poured into a boiling solution of caustic soda in methanol (large excess of NaOH). After heating for 2 hours under reflux, the solution is mixed with water, the benzene phase is separated, washed, dried and evaporated.

9.2 parts by weight of an oily compound are obtained (component B1} no. 54). (OCH^ content: 21.7 f).

4.85 parts by weight of diazo 2, sulfate (table 1) are dissolved in 15 parts by volume of 86 fig phosphoric acid, and 4.3 parts by weight of the above component B^, No. 54, are added while stirring. A clear, homogeneous reaction mixture is obtained. After condensation for 5 hours at 40°C, the mass is dissolved in water, and the condensation product is precipitated in the form of the chloride by adding an aqueous common salt solution.

Yield: 6.9 parts by weight. ' (C 65.0 f, N-7.4 f, atomic ratio: C : N = 30.8 : 3).

Example 85

Component B^, No. 49" is prepared from the potassium salt of p-hydroxybenzaldehyde and 2,2'-dichlorodiethylether (see "Makromoleku-lare Chemie", vol. 17, page 156, 1955-56) and subsequent reduction with sodium borohydride in a water-methanol mixture.

To prepare the condensate, 1.62 parts by weight of diazo 2, sulfate (Table 1) were dissolved in 50 parts by volume of 86 flg of phosphoric acid, and this solution was mixed with a solution of 1.6 parts by weight of component B-^, No. 49, in 5 parts by volume of almost boiling glacial acetic acid. After 5 hours of condensation at 40°c °g standing overnight, a crude condensate formed which was used for further production of coating solvent

nothing.

Example 86

Component B1, no. 50, was prepared analogously to component B-p no. 49" from the potassium salt of p-hydroxy-benzaldehyde and 1,3-dibromo-propane, with subsequent reduction of the dialdehyde to the dialcohol by sodium borohydride.

To prepare the condensation product, 0.213 parts by weight of diazo 2 sulfate (table 1) was dissolved in 1.5 parts by volume of 93% ± g phosphoric acid and mixed with a warm solution of 0.19 parts by weight of component B-p No. 50, 1 part by volume of glacial acetic acid. After adding 3.5 parts by volume of 93%±g phosphoric acid, the mixture was kept for 5 hours at 40°C. The clear raw condensate that was formed was used to prepare the coating solution.

Example 87. and 88

For the production of component B-^, No. 51» hie 100 parts by weight diphenylene oxide bromomethylated as indicated in example 108, in a mixture of ^ 00 parts by volume glacial acetic acid, 54 parts by weight paraformaldehyde, 500 parts by weight 63% ±g hydrobromic acid and 294 parts by weight 96% ig sulfuric acid at 75°C> and the reaction product recrystallized from acetone. (bis-bromomethyl-diphenylene oxide : calculated values - C

47.5%, Br 45.3%, found: C 47.7%, Br 46.2%) and then reacted with excess caustic soda solution in methanol.

To prepare the condensation product, 16.2 parts by weight of diazo 2 sulfate (table 1) were dissolved in 50 parts by volume of 86% phosphoric acid and 12.8 parts by weight of component B-^, No. $1, heated to 35°C and then added dropwise.

The mixture was condensed for 5 hours at 1/. 0°C. The raw condensate was used for the experiment directly. The remainder of the mixture (less than 0.2 parts by weight) was dissolved in water, and the reaction product precipitated from the aqueous solution by addition of normal saline. Yield: 22.6 parts by weight. (C 65.7%, N 8.2%, atomic ratio: 28 : 3).

Component B^., no. 57 > °S the condensation ion product prepared from this, used as in example 88!, was prepared in an analogous manner according to example 87, except that dibenzothiophene was used as starting material.

Examples 8 9 and 90

For the manufacture of component- B-^, No. 55> hie

/

thymylphenyl ether prepared according to "Liebig's Annalen der Chemie", volume 350, page 89 (I9O6) bromomethylated for 3.5 hours at 90 - 95°C analogously to example 84>, and the reaction product formed reacted with caustic soda solution in methanol, without .further purification.

The reaction product thus formed, which is a viscous oil, has an OCH^ value of 18.6 f.

For the production of the condensate, 4.5 parts by weight were used

diazo 2, sulfate (table 1) dissolved in 20 parts by volume of 86% phosphoric acid, 6.0 parts by weight of component B^, no. 55, was added and the mixture condensed for 4 hours at 40°C..

This crude condensate (1 part by weight) was used to prepare the coating solution. The residue was dissolved in water and the condensation ion product precipitated in the form of the chloride by addition of aqueous salt solution. Yield: 9 parts by weight. (C 66.9 f, N 6.7 f, atomic ratio: 35 <:> 3).

The condensate from example 90 is prepared analogously to example 113, except that 3-hr,om-4-methoxy-diphenyl ether (prepared according to J. Am. Chem. Soc. 6l, 2702, 1939) is used as starting material for the preparation of component B- ^, No. 56.

Example 91

For the preparation of component B^, no. 52, diphenylmethane was bromomethylated for 5 hours at 90 - 95°C analogously to example 84, and the pure 4,4'-bis-bromomethyl-diphenylmethane (m.p. 153 - 154° C) recovered by recrystallization from benzene, after which this was reacted with sodium hydroxide in methanol.

The condensate was prepared by adding 4.85 parts by weight of diazo 2,

.sulphate (table 1) was dissolved in 15 parts by volume of 86% phosphoric acid and 3.85 parts by weight of component B-^, No. 52, added dropwise. After adding 15 parts by volume of 93% phosphoric acid, the mixture was condensed for 10 hours at 40°C. 2 parts raw condensate was used to prepare the coating solution. The residue was dissolved in water and common salt solution added to precipitate the condensate in the form of chloride, which was then separated and dried. (G 68.6 f, N 8.0 f, atomic ratio: 30 : 3).

Example 92

For the production of component B-^, no. 53, diphenyl was bromomethylated for 5 hours at 90 - 92°G analogously to example 84, and the component of the reaction product which is poorly soluble in acetone

reacted with sodium hydroxide and methanol (OCH^ content: 23.8 f).

For the production of the condensate, 6.4 parts by weight were used

diazo 2, sulfate (Table 1) dissolved in 50 parts by volume of 86 fig phosphoric acid and 4>8 parts by weight of component B^, No. 53, dissolved in 10 parts by volume of hot methanol, and this solution added to the diazo solution. After heating for 2 more hours. At 40°C, 50 parts by volume of 93 mg of phosphoric acid were added to the mixture, which was condensed for 12.5 hours at 40°C.

A sample of the raw condensate was used to prepare a coating solution. The residue was soluble in water and hydrochloric acid was added to the aqueous solution to precipitate the condensate chloride which was recovered and dried. (C 68.2%, N 8.2 f, atomic ratio: C : N = 29.1 : 3).

Example 93

For synthesizing component B-^, No. 58, 1,4-diphenoxybenzene was prepared according to "Liebig's Annalen der Chemie", volume 350, page 98 (I9O6) and bromomethylated for 3 hours at 90-92°C as indicated in Example 108, and the reaction product reacted with methanolic caustic soda solution. (OCH^ content: 19.2 f).

To prepare the mixed condensate, 2.3 parts by weight of diazo 2 sulfate (table 1) were dissolved in 20 parts by volume of 86 fig phosphoric acid, and 2.3 parts by weight of component B-^, No. 58, were added as a hot solution in 1 part by volume of glacial acetic acid. After condensing for 6 hours at 40°C and standing overnight, a crude condensate had formed which was used for the preparation of the coating solution.

The mixed condensate can be precipitated from an aqueous solution by adding hydrochloric acid, methanesulfonic acid or benzenesulfonic acid and the like.

Example 94

The diazo mixture condensate described in Example 41, in the form of chloride, is dissolved in water and the aqueous solution is added to an aqueous solution of sodium azide. The azide, which is precipitated during the evolution of nitrogen, is dissolved in toluene, and a 1% toluene solution is prepared for sensitizing aluminum foil, pre-coated with polyvinylphosphonic acid.

After image exposure under a negative original, a brownish image appears. When developing with the developer described in Example 1 of the U.S. patent no. 2,994,609 one has an offset printing plate with good oleophilic properties.

Example 95

A careful mixture of 10.8 parts by weight of 3-methoxy-diphenylamine-4-diazonium chloride (diazo 2, chloride, Table 1) (97.3%) and 0.96 parts by weight of paraformaldehyde is introduced with stirring into 11.8 parts by weight of 93% phosphoric acid. Then 1.57 parts by weight of 2,6-bis-(methoxymethyl)-4-methyl-phenol (component B^, no.

59, table 1), under sufficiently vigorous stirring. The mixture is condensed while stirring for 24 hours at 40°C and you have a raw condensate which forms a clear solution in water and does not lose this property even after several months of storage at room temperature.

If, however, 2,6-bis-(methoxymethyl)-4-methylphenol is added to the phosphoric acid in the absence of diazo compound and formaldehyde, the product will dissolve quickly, but after a few seconds a condensation product is separated which is very poorly soluble in acid and in warm water.

Example 96

32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1) are dissolved in 200 parts by weight of 86% phosphoric acid. With vigorous stirring, 8.5 parts by weight of molten diphenyl ether (component B, no. 60, table 1) are added and then, over the course of 10 minutes, 3.0 parts by weight of paraformaldehyde in portions. After condensation for 1.5 hours at room temperature and 15 hours at 40°c, the mixture is poured into water and the water-insoluble components are removed after adding activated carbon. By adding a saturated common salt solution to this solution, the condensation product is precipitated in the form of the chloride and reprecipitated with the help of common salt solution from water.

Yield after drying under reduced pressure: 18.3 parts by weight (C 54.2%, 10.2a, atomic ratio: 18.55:3). From the analysis, it can be concluded that the diazo compound and the other component are in the condensate in a molar ratio of approx. 1 : 0.4. Average molecular weight for azo dye prepared with 1-phenyl-3-methyl-parazolone-(5), according to the method described in Example 50, is equal to 1611. Example 97

32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (diazo 2, sulfate, table 1) are dissolved in 180 parts by volume of 93% phosphoric acid. Separately, 17 parts by weight of diphenyl ether (component B, no.

60, table 1) dissolved in 34 parts by weight of glacial acetic acid. During reddening, the latter solution is poured together with 45 parts by weight of 40% aqueous formaldehyde solution into the solution of diazo compound. The mixture is stirred for 6.5 hours without further heat input and left overnight. The very cloudy crude condensate is introduced into 1000 parts by volume of water, extracted by shaking with ether and treated with enough activated carbon to obtain a clear filtrate. The condensate is worked up from the filtrate by adding zinc chloride and common salt. Yield: 27 parts by weight (C 47.5%, N 8.1%, atomic ratio: 20.6 : 3). This means that the mixed condensate has an excess of 7.6 gram atoms of carbon per moles of diazo compound.

The condensation product prepared according to examples 123 and 124 gives printing plates with good ink-receiving fluid when used as described in detail in examples 1 to 35.

Example 98

A mixture is made from the following components which are condensed as described in example 58:

The raw condensate is introduced a) in 290 parts by volume of methanol and

b) in 370 parts by volume of methanol, and the precipitates formed are washed a) with 80 parts by volume of methanol and b) with three times 100 parts by volume

methanol, and dried.

Yield: a) 8 parts by weight (C 59.1%, N 6.1%, P 5.6%, atomic ratio: 34 : 3 : 1.25) b) 6.8 parts by weight (C 63.5%, N 7 .3%, P 3.3%, atomic ratio: 30.4 : 3 : 0.61).

The analysis results show that the diazo compound and the other component are present in the condensate in a ratio of approx. 1 : 1.5 (in case a) and approx. 1 : 1.24 (in case b). Example 99

15.42 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table lj dissolve in 100 parts by volume of 96.5% phosphoric acid

and 7.4 parts by weight of dimethyloloxamide (component B^, No. 61,

table 1), which is added while stirring in small portions. The condensation is carried out for 24 hours at room temperature. The condensed ion mixture is dissolved in 0.5 liters of water and 80 parts by volume of 50% zinc chloride solution are added slowly and dropwise while stirring at 40°c. After cooling to +10°C, the precipitate is filtered off under [-: suction, 1-peak dissolved'' again'' in 0.5 liters of water at 50°C, the product is reprecipitated by dropwise addition of zinc chloride solution (45 parts by volume) and isolated as before described. Yield: 16.3 parts by weight.' According to analysis, the condensation product contains; 3 N atoms per 10.6 C atoms. (C 43.0%, N 14.2%). The diazo homocondensate would have a C : N ratio equal to 13 : 3. Example iQO

30.9 parts by weight of cliphenylamine-4-diazonium sulfate (diazo 1, sulfate, Table 1) (95%) bg 14.4 parts by weight of adipic acid diamide (component B, No. '62, Table 1) are mixed, and the mixture is dissolved in 200 parts by volume of 90% methanesulfonic acid. 6 parts by weight of paraformaldehyde are added with stirring over 10 minutes and the mixture is condensed for 24 hours at room temperature. The crude condensate is dissolved in 750 parts by volume of water, 25 parts by weight of zinc chloride (anhydrous) is also dissolved, and the zinc chloride double salt of the condensation product is precipitated by adding 10 parts by volume of ethanol and 100 parts by volume of 3G.5% hydrochloric acid. The product is filtered off, washed with 300 parts by volume of 2 N aqueous hydrochloric acid and dried at +35°C. Yield: 45.2 parts by weight. According to analysis, it contains the condensation product about 0.5 mol acid amide per mol diazo compound Example iQl

15.42 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) (95%) are dissolved in 100 parts by volume of methanesulfonic acid (90%). 10.8 parts by weight of finely powdered dimethyloladipic acid diamide (comp.:. B^, no. 63, table 1) (94.7%) are added in portions with sufficient stirring. When the weak, spontaneous heat generation has subsided, the mass is condensed for 25 hours at room temperature. The raw condensate is dissolved in 500 parts by volume of water. By adding 80 parts by volume of 50% zinc chloride solution, the condensate separates as a sticky precipitate at room temperature. The mother liquor is decanted, the precipitate is dissolved in 500 parts by volume of water at 50°C and re-precipitated after cooling to +10°C at

addition of 50 parts by volume of 50% zinc chloride solution. The product is filtered off and dried under reduced pressure. According to the analysis, the condensate contains approx. 0.7 mol acid amide per moles of diazo compound.

Example 102

4.47 parts by weight of diphenylamine-4-diazonium phosphate (diazo 1, phosphate, table 1) (98.4%) are dissolved in 60 parts by volume of 92% phosphoric acid. 4.8 5 parts by weight trimethylolcitramide (component B^, no. 64,

table 1) (86.3%, the rest water) is then added and mixed

none condensed for 45 hours at room temperature. The condensation mixture forms a clear solution in water and is diluted with 30 parts by volume of methanol, after which the mixture is stirred into 500

parts isopropanol. The precipitated reaction product is filtered off and dried under reduced pressure. Yield: 10.8 parts by weight. According to analysis, the ratio N : C = 3 : 10.8 (C 28.8%, N 9.3%).

Examples 103 and 104

In these examples, it is shown how two other diazo compounds (no. 13 and 14, table 1) can be condensed with compounds

ent B^ in an acidic condensation medium while forming mixed condensates.

In both examples, the diazo compounds are dissolved in the condensation ion medium in the form of their metal halide double salts. Dry air is bubbled through the mixture until hydrogen chloride is no longer expelled. The second component is then added and the condensation is carried out at room temperature for the specified time. Mixed condensates are formed which give clear solutions in water.

If component B^ is introduced alone into the condensation medium, a homocondensate of component B.^ is formed during a condensation which has the same duration, which homocondensate is quickly separated from the condensation mixture and is not dissolved by the addition of water.

In the following table, the specified quantities and the duration of condensation are indicated:

Examples I05-II0

In each of the examples below, 0.74 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) are dissolved

(2.5 millimoles) in so much $ 0% ±g methanesulfonic acid that a 5 volume parts solution is obtained. The respective second component (2.5 millimoles) is mixed with 0.5 parts by volume of JO% ± g aqueous formaldehyde solution, the mixture is heated for a few seconds in a steam bath and then dissolved in as little organic solvent as possible, if necessary under

.warming up.

Half of the solution containing the second component is then introduced, with stirring, into the first prepared diazo solution (trial series a). The second half of the solution containing the second component is added to 5 parts by volume of 90% methanesulfonic acid (test series b - blank test). After a delay of approx.

After 20 hours, the resulting reaction mixtures are first assessed visually and then processed further.

The condensation mixtures in test series b) are diluted with water and freed from precipitation and turbidity by adding some activated carbon and filtering. In this way, clear solutions are obtained which do not form precipitates when saturated NaCl solution or zinc chloride solution is added.

Solutions according to test series a) (examples 1O6 to 110 ) are made clear with activated charcoal if necessary (examples 1O6 , 107, 109 and iiO) and are then mixed with saturated normal salt solution and zinc chloride. The precipitated metal halide double salts of the condensates are worked up, dried and analysed.

The precipitate formed according to example i05 is dissolved in hot water, reprecipitated by the addition of hydrochloric acid, filtered off, dried and analyzed in this form.

Based on the following analysis results combined with the above visual observations, it can be assumed that mixed condensates formed. Furthermore, the analysis result seems to indicate a certain partial saponification of the second component during the condensation, in some cases.

Example III

15.5 parts by weight of diphenylamine-4-diazonium sulfate (diazo 1, sulfate, table 1) are dissolved in 100 parts by volume of 80% sulfuric acid. While stirring, a mixture of 6.9 parts by weight of 2-phenoxy-ethanol (component B, no. 18, table 1), 14.8 parts by weight of 50% aqueous glyoxylic acid solution and 2 parts by volume of glacial acetic acid is added, which is poured over the solution, whereby the temperature rises rapidly to 58°C. During cooling, the temperature is reduced to 40°C within 4 minutes. It is then cooled to room temperature, stirred for 5 hours at room temperature and allowed to stand overnight. A clear condensation mixture is formed. By adding 350 parts by volume of water, a product precipitates out which is suctioned off, washed carefully with water and dried. One has 21.1 parts by weight of a greenish-brown powder which is practically insoluble in aqueous solutions and in organic solvents. (C 56.0%, N 7.0%, atomic ratio: 28 : 3).

Since the condensation of phenoxyethanol with glyoxylic acid under the specified conditions forms a condensate with relatively good water solubility, which in the form of polyacid has a precipitating effect on diazonium salts, it is not impossible that the isolated product also contains such a precipitate.

Claims (10)

1. Condensation product of an aromatic diazonium compound, for use as a light-sensitive substance in copying material, characterized in that it consists of units of the general types A-N2X and B in an average molar ratio between 1 : 0.01 and 1 : 50, which are connected by by means of divalent intermediates derived from a condensable carbonyl compound, the units A-N2X being derived from at least one compound of the general formula in which X denotes an anion of the diazonium salt, p means 1, 2 or 3, R means an iso- or heterocyclic aromatic group, which has at least one condensable position, 1*2 means an arylene group of the benzene or naphthalene series, R3 means a single bond or one of the groups -rCH2)q-NR4- -(CH2)g-NR4-(CH2)r-NR5- - 0-(CH2)r-NR4- -S-(CH2)r-NR4- -0-R,-0- -0- -S- -CO-NR4- or -SO2~NR4-in which q denotes a number of 0, 1/2, 3, 4 or 5, r means 2, 3, 4 or 5, R4 means hydrogen, an alkyl group with 1-5 carbon atoms, an aralkyl group with 7-12 carbon atoms or an aryl group with 6-12 carbon atoms, R,, means hydrogen or an alkyl group of 1-5 carbons atoms, Rg means an arylene group with 6-12 carbon atoms, and the units B are derived from at least one of the following compounds: aromatic amines, phenols, thiophenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic heterocyclic compounds or organic acid amides, these compounds being free of diazonium groups and in an acidic medium at at least one position in their molecule is able to condense with active carbonyl compound • 2. Condensation product according to claim 1, characterized in that it contains on average 0.1 to 20 units of B for each unit of A-N2X. 3. Condensation product according to claim 1, characterized in that the units A-N„X are derived from a compound with the general formula in which <R>10' <R>ll°g R12 means hydrogen, halogen, alkyl groups with 1-3 carbon atoms or alkoxy groups with 1-5 carbon atoms and X means the anions of the diazonium salt. 4. Condensation product according to claim 1, characterized in that the intermediates derived from a condensable carbonyl compound are made up of methylene groups. 5. Condensation product according to claim 1, characterized in that the units B are derived from a diphenyl ether, diphenyl sulphide, diphenyl or diphenylmethane. 6. Process for the production of a condensation product according to claim 1, characterized by reacting at least one compound with the formula where the symbols involved have the previously indicated meaning and at least one compound B in the presence of a condensable carbonyl compound in a strongly acidic medium. 7. Method according to claim 6, characterized in that a concentrated acid is used as condensation medium. 8. Method according to claim 7, characterized in that phosphoric acid, methanesulfonic acid or sulfuric acid is used as condensation medium in a concentration of 70 - 100% by weight. 9. Method according to claim 6t, characterized in that the condensation is carried out in the temperature range from 10 to 50°C. 10. Method according to claim 6, characterized in that formaldehyde is used as the condensable carbonyl compound.