DK143621B - PROCEDURE FOR THE PREPARATION OF A PHYSICAL SENSITIVE CONDENSATION PRODUCT OF AN AROMATIC DIAZONIUM COMPOUND - Google Patents

Description

(19) DENMARK (¾)

| p oz) PUBLICATION <n> 143621 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 2535/70 (51) | nt.CI. * 8 03 F 7/08 (22) Submission day 19 · ®β · ί 1970 C 08 Θ 16/00 (24) Race day 1 9 · ma j 1 970 (41) Aim. available Nov. 21; 1970 (44) Presented 1 ^ · 6ep. 1 981 (86) International Application No. ~ (86) International Filing Day ~ (85) Continuation Day - (62) Master Application No. "(30) Priority 20 May 1969 * 826296 * U5 (71) Applicant H0ECHST AKTIENGESELLSCHAFT, 6230 Frankfurt am Main 80, DE.

(72) Inventor Hartmut Dfceppan, DE.

(74) Associate Engineer Hofman-Bang & Boutard.

(54) Methods for preparing a photosensitive condensation product of an aromatic diazonium compound.

The invention relates to a process for preparing a condensation product of an aromatic diazonium compound and a condensable compound thereof. The condensation product produced by the process of the invention is a photosensitive compound. The present description also describes a photosensitive reproduction material comprising a substrate having a reproduction layer der-DQ

on, which contains at least one of the new, photosensitive con-

Two densification products prepared by the process of the invention.

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It is known to use photosensitive aromatic diazonium compounds to sensitize reproductive materials useful

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2 143621 for the production of individual copies or printing plates.

Advantageously, high molecular weight diazonium salts with several diazonium groups in the molecule have been used, especially in the preparation of yellow-brown images or pianographic printing forms, the reproduction layer of which must be made insoluble or oleophilic under the influence of light. These diazonium compounds are usually of a resinous nature and appear e.g. by introducing diazonium groups into phenol-formaldehyde condensation resins either by nitration, reduction and diazotization or by other known reactions. However, the diazo compounds thus obtained have certain disadvantages, e.g. a very limited shelf life, and therefore they have not gained much in practice.

Polyfunctional diazonium salts have been prepared by other means, since certain aromatic diazonium salts have been condensed in an acidic condensation medium with active carbonyl compounds, especially formaldehyde. This type of high molecular weight diazonium compounds is used on a large-scale industrial scale for the production of reproduction materials, especially for the production of printing molds. Among these compounds, e.g. is described in TJ.S.A. Patents Nos. 2,063,631 and 2,667,415, in particular, the condensation products of diphenylamine diazonium salts with formaldehyde have received great technical service.

The preparation of such and similar diazo resins is further described in TJ.S.A. patents Nos. 2,679,498, 3,050,502, 3,311 .605, 3,163,633, 3,406,159 and 3,277,074.

The preparation of yellow-brown images by combining such diazo resins with hydrophilic colloids and, if desired, dyes or pigments in reproduction layers is e.g. described in TJ.S.A. patents Nos. 2,100,063, 2,687,958 and 3,010,389.

These diazo resins, however, find their most widespread application as reproduction materials for photomechanical reproduction of pianographic and open-print forms. The diazo resins can be used in the reproduction layers of these materials without additional additives or e.g. in combination with water-soluble 3 U3621 colloids or with water-insoluble polymers that are not photosensitive. Examples of suitable carriers for such reproduction layers are water resistant paper types with suitable lithographic surfaces, i.e. superficially hydrolyzed cellulose acetate, metal carriers such as aluminum, zinc, copper, brass, chromium, nlob and tantalum; multi-metallic carriers, lithographic stones and the like. Metal carriers are preferred for large printing presses, and aluminum is usually used. The use of metal as a support material for reproduction layers containing the indicated diazo resins has the disadvantage, among other things, that the adhesion of the products obtained on exposure to the diazo resins is usually not very good and that metals can further have a decomposing agent. effect on the diazo resins.

A greater number of options have been proposed to avoid these difficulties, e.g. to pretreat the metal surface with silicates (U.S. Patent No. 2,714,066), with organic polysacids (U.S. Patent No. 3,136,636), with phosphonic acids and their derivatives (U.S. Patent No. 3,220,832), with potassium hexafluorosironate (U.S. Patent No. 2,946,683), further employing diazo resins prepared in phosphoric acid (U.S. Patent No. 3,235,384), adding phosphoric acid to the diazo resins and using them in a metal salt-free state (U.S. Patent No. 3,236,646) and using anodized aluminum surfaces.

Although the known diazo resins have found wide technical spread, they have other drawbacks. With the low molecular weight condensates used advantageously, in terms of the storage durability, only unsatisfactory ink absorption capacity of the exposed products is obtained on non-metallic supports into which the mass can easily penetrate, e.g. on superficially hydrolyzed cellulose acetate film.

Another disadvantage of the known diazo resins is that their commonly used double salt with zinc chloride, and in particular the metal salt-free products containing phosphoric acid or similar acids, gives rise to the formation of repdoduction layers having a high sensitivity to moisture and thus to moisture. fingerprint.

In case of careless treatment, the reproductive layer can be easily damaged.

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To overcome this difficulty it has been suggested, e.g. in USA. U.S. Patent No. 5,300,309 "to reacting the diazo resins with certain phenolic coupling components to obtain water-soluble addition products which gave rise to the formation of moisture-less reproductive layers. These addition products, which contain relatively loose bonds having the character of a salt or complex, can be readily decomposed, e.g. with organic solvents, and thus their stability is not sufficient under all conditions.

Furthermore, the light sensitivity is not satisfactory, especially in the case of the known diazo resins which have excellent thermostability, e.g. condensation products of 3-alkoxy-4-diazo-diphenylamine and formaldehyde.

Furthermore, a common disadvantage associated with the diazo resins used so far has been that they can only be readily separated into a metal salt-free form, for example, as chlorides or sulfates, or as salts of simple organic compounds. sulfonic acids, and their salts are often only insoluble in organic solvents.

The disadvantages of the prior art can be eliminated, or at least significantly reduced, when new diazocondensation products are used in place of the diazonium salts used heretofore for the above applications.

Danish Patent Application No. 2533/70 discloses new photosensitive compounds and a photosensitive reproduction material comprising a substrate having a reproduction layer thereon, the latter containing at least one of the novel compounds which are photosensitive condensation products of aromatic diazonium compounds, which condensation products consist of units of the general types: A - N2X and B, which are linked to a divalent intermediate group which is derived from a carbonyl compound capable of condensing, the unit AN1 being derived from at least one compound of the general formula (¾ - R 1 -) p Ra - n 2x where X is the anion of the diazonium compound, p means 1, 2 or 3, R 1 is an isocyclic or heterocyclic aromatic group having at least one condensable position, R 2 is an arylene group of the benzene or naphthalene series,

Rj is a single bond or one of the groups - (CH2) q-NR4- - (CH2) q-NR4- (CH2) r -NR5- -0- (CH2) r-NR4- -S- (CH2) r-NR4 - -s-ch2-conr4- -o-r6-o-O- - s -CO-NR4- or -so2-no4-, where q means 0, 1, 2, 3, 4 or 5, r means 2 3, 4 or 5> R 4 is hydrogen, an alkyl of 1 to 5 carbon atoms, an aralkyl of 7 to 12 carbon atoms or an aryl of 6 to 12 carbon atoms,

Shrimp is hydrogen or an alkyl of 1-5 carbon atoms and Rg is an arylene group of 6-12 carbon atoms and the unit B is 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 capable of condensing at least one position with an active carbonyl compound in an acidic medium, the average of which is about 0.01 to 50 in the condensation product. B units per unit. unit A- ^ X.

This application further describes a process for the preparation of the new photosensitive condensation products, comprising the process of reacting at least one compound of formula (R -.- R, -) R0-NOX with at least one compound B in the presence of a compound. 1 3 P 2 2 densifiable carbonyl compound in a highly acidic medium.

This process can often be used advantageously when the components A - X and B are sufficiently soluble in the condensation medium. While many diazo compounds exhibit this solubility, only a portion of the components of the present invention are sufficiently soluble in condensation among none.

Unfortunately, however, such compounds B, which give rise to the formation of mixed condensates leading to reproductive materials with particularly advantageous properties, have a very low solubility in the high concentration strong acids preferred as condensation media. This applies for example. for the aromatic hydrocarbons, phenol ethers and certain non-basic, heterocyclic compounds.

A number of such compounds are sufficiently soluble in 96 to 98 µl of sulfuric acid, which is very effective as a condensation medium, but there is slight sulfonation of the constituents B as a reaction in this medium and the desired mixed condensates are not obtained in these cases. The mesitylene, anisole and diphenyl ether are dissolved e.g. in 96 to 98 in * sulfuric acid at 30 to 40 ° C during sulphonation. This difficulty does not occur almost in 80 in. sulfuric acid, but on the other hand, the solubility of the preferred secondary constituents listed is relatively low.

Furthermore, highly concentrated sulfuric acid is not preferred as the reaction medium because a number of diazo compounds, e.g.

The 3-alkoxy-diphenylamine-4-diazonium salts, which give rise to the formation of particularly valuable condensates, are very sensitive to this acid. 80 to 100 $ phosphoric acid is a significantly milder condensation medium, but the solubility of many preferred constituents B is particularly low in this acid.

It is possible to achieve some improvement in the homogeneity during the condensation by adding organic solvents, e.g. glacial acetic acid or methanol, but it must be borne in mind that the efficiency of the condensation medium is often greatly reduced, in comparison with the pure acid, and that there is a danger of side reactions when using the components A-NgX and B at very different reaction rates. relative to the active carbonyl bitterness, it is not easy to prevent the formation of homocondensates of the faster reacting component and to conduct the condensation in such a way as to obtain condensation products of a relatively uniform structure. Due to the extraordinary, numerous reaction possibilities of the three reaction partners, it is difficult always to obtain the same condensation products on the basis of the same starting products. If condensation products with exactly reproducible properties are to be prepared, it is usually necessary to maintain the same reaction conditions carefully.

It is an object of the invention to provide a process for the preparation of a condensation product of an aromatic diazonium compound and a condensable compound which also gives rise, under varying conditions, to the formation of condensation products with accurately reproducible and satisfactory properties.

The method according to the invention is characterized by the method of claim 1.

In the above formula, R 1 is preferably hydrogen and R 2 is preferably hydrogen, methyl, ethyl or acetyl.

Although lower alkyl chains or acyl groups can be used, they usually undesirably reduce the solubility of constituents B1 in the condensation mixture, thus making the condensation process more difficult and making it more expensive.

Depending on the size of the molecule, the value of m can be between 1 and approx. 10. Preferably, it does not exceed 4.

It can be assumed that the component during the condensation reacts completely or partially with the component A-X or with itself (especially when there is an excess of the component B ^ present), during intermolecular decomposition of R 2 OH, the condensation products thereby is formed. The course and composition of the reaction products can be explained by such a condensation process.

The condensation according to the invention goes surprisingly smoothly, i.e. in many cases already under very moderate conditions, e.g. practically quantitatively at 10 to 40 ° C in 80 to 100 in ° phosphoric acid to form mixed condensates.

The process according to the invention for preparing mixed condensates from diazo compounds A-X and B1 has, inter alia, the following advantages over the reaction between A-X and B with carbonyl compound: 1) In cases where the component B, which has a lot of at different reaction rates relative to the diazo compound requirement, the transition to Compound B usually favors the mixed condensation as compared to the homo condensation of the faster condensing partner.

2) In many cases, the condensation of A- ^ X with B ^ is possible under more moderate conditions than the corresponding condensation of A- ^ X B and active carbonyl compound. This is an advantage when A-N2X or B are sensitive to highly active condensation media, e.g. concentrated sulfuric acid.

3) In the case of condensation of A-N ^ X with B ^, it is usually possible to obtain more uniform and better defined condensation products of better quality and in higher yields.

9 U3 & 21 4) The components are usually more easily soluble in the usual highly acidic condensation media than the compound B. An addition of organic solvents during the condensation can thus be avoided in most cases. Particularly suitable is the use of low-melting, especially liquid constituents.

The low alkyl ethers (R 1 = alkyl) are therefore a preferred group of constituents.

5) The process is less sensitive to interference and significantly better reproducible because in many cases it can be implemented in a homogeneous phase.

A group of mixed condensates prepared according to the process according to the invention is also distinctly different in terms of essential properties of the mixed condensates produced according to the process according to the co-pending application from the corresponding components A-N 2, B and formaldehyde. This group is derived from constituents B 2, which are preferably under moderate condensation conditions, e.g. in 80 to 100 $> phosphoric acid at temperatures from 10 to 40 ° C - does not undergo any significant decomposition of formaldehyde.

This group includes, in particular, such constituents B 1, which are derived from constituents belonging to the categories aromatic hydrocarbons, phenol ethers, aromatic thioethers, and non-basic heterocycles, e.g. diphenylene sulfide, diphenylene oxide, phenoxathiine and the like.

As a common feature, these components have the property that they can undergo a condensation reaction with formaldehyde, not in an alkaline medium, but only in an acidic medium.

However, it should also be noted that phenolic alcohols prepared in an alkaline medium from phenols or esters and their derivatives with a free phenolic OH group undergo a surprisingly low degree of decomposition of formaldehyde under the above-mentioned moderate conditions.

However, N-methylol compounds, as well as ethers and esters thereof, have a greater tendency for decomposition of formaldehyde under condensation conditions.

10 U3S21

The specified group of condensation products prepared according to the process according to the invention differs in terms of the arrangement of the units from the condensates prepared on the basis of Α-3ϋΓ2Χ, B and formaldehyde. In the condensates of the invention, the units A-N2X are essentially only linked via bonding groups derived from one or more molecules of B1. This means that the distance from diazo group to diazo group in the mixed condensate usually has at least a minimum value derived from the structure of E, whereas condensates prepared according to the process described in the co-pending application contain the units AN ^ X and B, linked to methylene bridges, which are substantially statistically distributed or arranged in a mixed manner, which are influenced by the reactivity of A-N2X and B and by the way in which A-N2X, B and formaldehyde are introduced into the acid. Of course, such products also comprise multi-unit A-N2X condensates bonded only to methylene bridges, a type practically absent in the condensates produced in accordance with the invention because the components B1 disclosed cannot be considered as agents which decompose formaldehyde under moderate condensation conditions, e.g. 10 to 40 C and 80 to 100 phosphoric acid as a condensation medium.

Within the scope of the invention, the most important process products are those under whose manufacture B 1 is used in such an amount that at least one -CHRgOR 2 group is present in each molecule of N-N 2 X. Particularly preferred are such mixed condensates which contain approx. 0.5 to 2 moles of B unit A-N2X.

Within this large group, another preferred group of condensation products prepared under moderate condensation conditions should be indicated from the components listed above, which practically do not decompose formaldehyde during the condensation, and from easily condensable diazonium salts. is a phenyl group that is either unsubstituted or substituted by one or more alkyl or alkoxy groups, R'2 is a benzene ring which is in addition to the diazonium group may carry one or two identical or different substituents which may be halogen atoms, alkyl groups of 1 to 4 carbon atoms, or alkoxy groups of 1 to 5 carbon atoms, and R 1 is a homopolar bond comprising one of the groups - 0 - - S - - NH -.

Preferably, in the last preferred group of condensation products prepared according to the invention, such as are prepared with chemically similar compounds B.j, i.e. not with isomeric mixtures.

Such particularly preferred compounds are: di-methoxymethyl-diphenyl ether, especially the 4,4'-isomer, di-methoxymethyl-diphenyl sulfide, especially the 4,4'-isomer, di-methoxymethyl-diphenyl, especially the 4,4'-isomer. , 4,4'-bis-methoxymethyl-diphenylmethane.

By using these uniform compounds, in addition to the previously stated, preferably alternating structure of the condensates, a degree of uniformity of the products is not obtained, which usually cannot be obtained by the condensation of Δ-Ν2Χ, B and formaldehyde. The mixed condensates prepared according to the invention usually have a more uniform chemical structure than those prepared according to the last process. It is also possible according to the process of the invention to obtain higher condensate mixed condensates even using more moderate conditions.

12 143621

This, as well as the more uniform structure of the products prepared by the process of the invention, may be the reason for the particularly easy separability thereof from aqueous solutions in the form of heavily soluble salts (see Examples 97 and 98), the high yields during production and the better application properties thereof. photosensitive reproduction layers.

This is particularly true of the condensation products derived from 3-alkoxy-diphenylamine-4-diazonium salts and 0.75 to 2 moles, thereby derived from diphenyl ether, diphenylsulfide, diphenyl, and diphenylmethane, where m is 2 and using similar compounds Bj , especially those whose CHUgOR ^ groups are ip, p 'position.

Although the particular advantages of the condensation process of the invention are obtained in the absence of the active carbonyl compound, it is also possible in certain cases to add a certain amount of active carbonyl compound, especially formaldehyde during the reaction between A-NgX and B This is e.g. the case if condensates with higher molecular weights are to be produced, even in the case of a significant deficit of B1. But this approach is not preferred.

In the case of particularly reactive basic compounds B (= EHm), compounds B 2 can be prepared by adding active carbonyl compounds in an alkaline or neutral medium to the basic compounds (such as phenols, sulfonamides or carbonamides). The primarily formed alcohol-type additives can easily be converted to the corresponding ethers or esters that are usually more stable.

In the case of the basic compounds B, which do not form addition products with active carbonyl compounds in an alkaline medium, but which react in an acidic medium (such as aromatic hydrocarbons and phenol ethers), an indirect production of the compounds B It is impossible to separate the intermediate B-type products in a satisfactory yield when reacting a compound B with an active carbonyl compound in an acidic medium because they further react too quickly under the prevailing reaction conditions.

13 143621

The indirect preparation of the compounds of the type can be carried out, for example, by the following methods: 1. By halo-methylation of the compounds B and subsequent conversion of the resulting halo-methyl compounds to the corresponding alcohols, esters or ethers.

2. By side chain halogenation of the compounds B bearing methyl groups in the aromatic core, i.e. converting these methyl groups to mono-halo methyl groups, which are then reacted as indicated under 1).

3. By cleavage of reaction products from a Mannich reaction with acetic anhydride.

4. By reducing compounds B which carry aldehyde, ketone or carboxylic acid ester groups in their aromatic rings to the alcohol stage and, if desired, further etherification or esterification.

* 5. By reaction between aromatic, metal-organic compounds and formaldehyde or other aldehydes, or reaction between aromatic aldehydes whose CHO group is attached to the aromatic core and metal-organic compounds.

The preparation of compounds similar to the general formula is known and described in detail in the literature. Some B1 type compounds are commercially available.

The compounds of general formula B 1 can be used in the form of mixtures of isomers and / or as mixtures of compounds having different values for the parameter m. However, as stated above, it is advantageous to use uniform compounds of type B 1 or well-balanced mixtures. of such compounds for condensation, because in this way the number of chemical variations in the structure of the condensation products is greatly reduced, so that reproducible condensation products can be produced particularly easily. Preferred are compounds of type B 1 in which the aromatic nuclear positions are capable of condensing with carbonyl compounds or with groups -CHRa-OR 2, or at least some of these positions are taken up by such groups or other groups.

the process according to the invention can be varied in a number of ways, for example with regard to condensation conditions and the quantitative conditions used.

The condensation according to the invention is carried out in the presence of a strongly acidic condensation medium. Preferably concentrated, moderately strong to strong acids are used where the acid content is greater than the diluent content. The condensation medium should be further selected to be liquid under the condensing conditions.

The lower limit of the amount of acidic condensation medium used for the mixed condensations, taking into account all the described variations in the process, is determined by the viscosity of the mixture and the upper limit is determined by the economics of the process. The creaming process is preferably such that one uses as little acid quantity as possible and, on the other hand, obtains a condensation mixture which can be easily stirred and easily mixed. When choosing the type and amount of the acid to be used, consideration should be given to the condensability and solubility of the constituents in the acid.

The most favorable conditions for each combination A-X and are voted on by preliminary trials. Particular attention should be paid to the exothermic condensation reaction so that it does not proceed too violently, as this would impair the control of the reaction and may further lead to decomposition of the diazo compounds.

Examples of acids suitable as condensation media are listed in TT.S.A. Patent No. 3,235,382, column 1, line 71 to column 2, line 5.

Condensation media useful for the present invention are phosphoric acid, methanesulfonic acid and sulfuric acid, which acids are used at a concentration of at least 40 wt.%, Preferably 11 * 3β31 between 70 and 100 wt. $. The remainder is usually water, but it may also consist wholly or partially of solvents, e.g. methanol, acetic acid and N-methyl-pyrrolidone. Eg. 85% of phosphoric acid, 80% sulfuric acid and 90 methanesulfonic acid or mixtures of these acids have been successfully used.

80 - 100 ¢, especially 85 - 90 # phosphoric acid, is a fairly mild condensation medium in which condensations can be carried out very mildly. It is therefore the most preferred condensation medium for all combinations of compounds that will react sufficiently quickly under these rather mild conditions.

$ 80 - $ 100, especially $ 90 methanesulfonic acid is a stronger medium.

This acid is advantageous because it dissolves a number of constituents even more easily than phosphoric acid.

Hydrogen halide acids, such as at least 15 preferably concentrated aqueous hydrochloric acid or hydrogen bromide, are only suitable as limited condensation media. The use of these acids is less convenient because under such conditions, haloalkyl compounds having low reactivity are formed which do not react further under relatively moderate condensation conditions.

For the same reason, diazonium salts, such as diazonium phosphates or sulfates, are in many cases superior in comparison to the halides as starting materials for the condensation.

When diazonium salts are to be used for mixed condensation which are in the form of the commonly used metal halide double salts, it is usually advisable to dissolve them in the condensation medium, then pass dry nitrogen or dry air through the mixture until all the chloride ions have escaped in the form of gaseous hydrogen chloride, and then using the halide-free solution for the condensations.

The amount of the acid serving as a condensation medium can vary between wide limits. It is e.g. possible to use 1 to 16 143 $ 21 100 parts by weight of acid per by weight of the mixture A- ^ X + B- ^, as shown in the Examples. However, the amount of acid can also be higher without generally obtaining additional benefits. It is important to use a condensation medium in an amount sufficient to ensure a readily miscible reaction medium. Usually, the use of very small amounts of condensation medium will result in a reduction in the molecular weight of the condensation product.

Depending on the condensation medium, condensation partners, and their concentration in the condensation medium, it may be necessary to accelerate the condensation reaction upon heating or to decelerate it upon cooling. It is advisable to use a condensation temperature not exceeding 70 ° C because the stability of the diazo compounds A-N2X is usually limited at a higher temperature. However, it is also possible to produce diazo condensation products in the process of the invention above 70 ° C. The preferred temperature range for the preparation of the condensates is between 10 and 40 ° C. When highly active condensation media are used, it may be advantageous to conduct the condensation at temperatures of approx. 0 ° C or above.

It is advantageous to carry out all variations of the mixed condensations in homogeneous reaction media because reproducible results are most readily obtained in such media. Therefore, non-liquid components B.j can be used in the form of solutions, whereby the solvent used e.g. is methanol or acetic acid. However, if some of the constituents are only slightly soluble in the condensation medium, they can also be used in the form of very fine suspensions or as emulsions in the condensation medium. In each case care should be taken to ensure that the condensation mixture is thoroughly mechanically mixed.

If the condensation process is hampered by insufficient solubility of the starting materials or final products, a homogeneous condensation medium can be obtained by the addition of an organic solvent. Of course, in each case, tests must be performed to determine which organic solvents are suitable. It has e.g. in many cases it has been found that glacial acetic acid is suitable. Other suitable 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 efficiency of the condensation medium in comparison with the concentrated concentrated acid and that the use of a solvent can also cause side reactions.

In the preparation of the mixed condensates, the ratios of reactants A-NgX and B- ^ and the condensation conditions may vary within wide limits.

In principle, it is possible to produce mixed condensates of any desired composition, e.g. mixed condensates containing only traces of a diazo compound A-NgX condensed therein. Mixed condensates containing, on average, between 0.1 and 50 'condensed units of the secondary constituent Bj for each diazonium salt group are useful for the production of valuable, photosensitive reproduction materials. Except in special cases, the main mixed condensates are those containing between 0.1 and 20 moles of the secondary ingredient per liter. moles of A-N2X. Within this range, the mixed condensates usually exhibit properties distinctly different from those of the corresponding homocondensates.

In the simplest and also most preferred case, the mixed condensation is carried out by dissolving the A-NgX compound in an acid suitable as a condensation medium, and by stirring with the addition of the component B 2, either in the form of the substance itself or as a solution. . Various modifications can be made to this process, however, it must be considered that in many cases it is disadvantageous to dissolve B 2 in the condensation medium in the absence of A-NgX, because homocondensates of B ^, depending on the reactivity of B can more or less quickly separate from such solutions, which can no longer easily undergo mixed condensation.

However, in many cases it is possible to mix the components A-N2X and B- | and introducing the mixture or individual constituents into the acid, either in the form of a solution or as the substances themselves.

In a few cases, the condensation reaction can be initiated with the B 2 component and the A-NgX component can be added later. It is even possible to condense diazo resins using one of these methods, e.g. those prepared by acidic condensation of diphenylamine-4-diazonium salts with carbonyl compounds, and having lower condensation rates, with one or several constituents B 1 in an acidic medium. In some cases, a mixed condensation of a low molecular weight homocondensate of a secondary component B 2 and A 2 X in an acidic medium is possible, and even a mixed condensation of formaldehyde condensates of a compound A-N 2 X ° g homocondensates of a compound B1 or mixed. condensates of several compounds B 1 in an acidic medium can be successfully carried out.

In the preparation of soluble condensates, such constituents B1 in which m is 2 or slightly greater than 2, are usually preferred. ca. 3 or 4. Within this category, constituents with m = 2 are especially preferred because they give rise to the formation of condensation products with a syrupy structure, and also in some of the cases where several moles of B mole A-X, the tendency to form cross-linked and sometimes insoluble condensation products is reduced. This is especially true when using extreme condensation conditions.

Ingredients B 1, wherein m is greater than 2, are preferably used in smaller amounts, the amount of such compounds usually not exceeding 1 mole per minute. mole of diazo compound.

The upper limit must be determined experimentally in each individual case. An important use of these components in which m is greater than 2 is their combined use with compounds wherein m = 2.

Ingredients B ^ wherein m = 1 can also be used for condensation, but in this case condensates are obtained which carry only one diazo group per unit. molecule when the compound A-N2X contains only one diazo group. The use of such condensation products in the reproduction layers is generally not preferred. However, it is advantageous to combine components of type B ^, where m is 1, with those in which m = 2 or a greater number than 2. In these cases, the first component Bj as a "modifier" for the size of the molecules formed during the condensation.

When m is 2 or a number greater than 2 in the component and B1 is used in an amount per moles of A-N2X corresponding to less than 1 equivalent of -CHRa-OR ^ groups (1 mole of component B ^ with m = 2 contains, for example, 2 group equivalents), an active carbonyl compound, preferably formaldehyde, can be added to the reaction mixture, whereby the amount added at least is such that the sum of the group equivalents -CKE ^ -OR ^ and the molar amount of the added formaldehyde, multiplied by 2 (ie, its condensation equivalent) is at least 1 equivalent per mole of diazo compound. An additional amount of formaldehyde may be added, but usually the sum of the above condensation equivalents should not exceed 4.

As a further possibility of preparing higher condensates from constituents in which m = 1, active carbonyl compounds, preferably formaldehyde, may be added during or after the preparation of the condensate, even in cases where 1 or more moles of component B are used. ^ pr. mole of diazo compound.

In these cases, a minimal amount of formaldehyde in 0.5 moles per ml should be calculated. and per mole of component B mole of diazo compound A-N ^ which exceeds the molar amount of B ^.

The average molecular weights of the condensation products may vary within wide limits, depending on the selection of the condensation partners and conditions. It has been found that for the preparation of good reproductive materials, generally mixed condensates with molecular weights of between about 10% are preferred. 500 and 10 000. It should be considered that these values are average values and that the molecular weights of the individual constituents of each of the condensates obtained are statistically distributed around this average value. The distribution type is shown in some of the following examples by fractionation of the condensates obtained.

The mixtures resulting from condensation can be used directly or further treated. The mixture can also be worked up and the condensates can be separated in solid form.

The work-up of the condensation mixtures can be carried out in various 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 second component can often be separated by stirring the condensation mixture into water. In these cases, it may occur that a more soluble fraction of the mixed condensate can be separated from the aqueous mother liquor in the form of any heavily soluble salt. As the mixed condensate is water-soluble but heavily soluble in organic solvents, it is often possible to separate the product by diluting the reaction mixture with an organic solvent, e.g. a lower alcohol or a lower heton. . .

An advantage of many of the condensates prepared according to the invention is that they can be easily separated in the form of salts that do not contain complex-forming metal salts. Many condensates form e.g. sulphates, chlorides and bromides which are heavily soluble in water and which can be precipitated from aqueous solutions of the condensation mixtures by the addition of the corresponding acids or salts thereof which are soluble in water.

In the following examples, some separation processes are described.

The photosensitive condensation products are preferably used in the form of diazonium salts. They can also be converted from this form into photosensitive azides, diazoamino compounds, diazosulfonates and the like in a known manner, and can be used in this form as constituents of reproduction materials.

Suitable constituents A-NgX and B- for preparing the condensation products of the process of the invention are in principle all compounds capable of condensing in an acidic medium and whose basic structure is not decomposed under the condensing conditions.

As a rule, all components are capable of condensing in an acidic medium by the process of the invention, and the basic structure thereof is capable of reacting with formaldehyde in such a condensation medium.

Groups affecting the condensability of the compounds A-NgX and EH ^ (which is the basic structure from which it is derived) are as follows: (1) Aryl radicals and heterocyclic radicals having nuclear positions capable of condensation. Radicals in which these nuclear positions are activated are preferred. This activation can e.g. is carried out by annealing with additional aromatic rings or by substitution with groups such as -OH, -O-alkyl, -O-aryl, -SH, -S-alkyl, -S-aryl, -alkyl, -aiyl, -amino, - alkylamino, - dialkylamino, -arylamino and -diarylamino.

In addition to these activating substituents, the condensable aromatic or heterocyclic radicals may also contain the condensation Bation inhibiting groups, e.g. nitro or sulfonic acid groups if the activation resulting from other groups is only reduced but not eliminated.

(2) Radicals which are themselves capable of condensation and which can be directly bonded to iso- or heterocyclic radicals or to aliphatic radicals or which, if desired, can be directly bonded to each other. Such radicals are groups such as carboxylic acid amide, sulfonic acid amide, U-alkylsulfonic acid amide, N-arylsulfonic acid amide, nitrile, urea, thiourea, urethane, ureido, thioureido, glyoxal diureine, imidazolone, guanidine, dicyanodiamide, dicyanodiamide, dicyanodiamide, for aromatic rings.

The following compound types or individual compounds illustrate the compounds of general formula A-X and B-2 used to prepare the diazocondensation products of the process of the invention.

Diazonium Compounds A-NgX

The underlying idea is that a benzene core carrying the diazo group is deactivated to such an extent that condensation at nuclear positions in this ring is no longer possible under less extreme conditions, with just a few exceptions (e.g., 4-diazophenol ) not listed here.

Thus, the diazonium compounds to be used in the process of the invention contain in radical A, in addition to the aromatic iso- or heterocyclic nucleus bearing the diazo group, at least one aromatic iso- and / or heterocyclic ring having at least one condensable , nuclear position and / or substituents of the above type 2 which are capable of condensing themselves.

An important group of diazonium compounds particularly suitable for conversion to the condensation products prepared by the process of the invention has a structure similar to the general formula (R1 - R3 -) pR2 - N2X, where p is an integer from 1 to 3, preferably 1, wherein X is the anion of the diazonium salt; However, X may also be an acidic substituent in the molecule, and wherein R 1 is an aromatic iso or aromatic heterocyclic group which may be substituted, if desired, having at least a condensable position and preferably a phenyl group which is substituted if desired.

Preferred substituents are those which increase the reactivity of the core in terms of condensation, e.g. alkyl, alkoxy, alkylmercapto, aryloxy, arylmercapto, hydroxy, raercapto, amino and anilino groups.

23 US $ 21 R2 is an aromatic ring of the benzene series which, in addition to the diazo group, can carry other substituents.

R ^ is a link between the rings R ^ and Rg * e.g. of the following types, whereby the radical R1 should always be considered as lying on the left and the group Rg on the right, if not symmetrical:

Simple homopolar bonds - (CH 2) + - NR 2 - (q is a number from 0 to 5 »R 4 is H, or alkyl of 1 to 5 carbon atoms, or aralkyl of 7 to 12 carbon atoms or aryl of 6 to 12 carbon atoms) - (CH 2) q-NR 2 - (CH 2) r-NR 2 - (r is a number from 2 to 5, is H or alkyl of 1 to 5 carbon atoms) -0- (σΗ2) Γ-ΗΕφ- -S- ( CH2) r-NR4- -O-Rg-O- (Rg is the aryl of 6 to 12 carbon atoms) -O- -S- -CO-NR, - 4 -so2-nr4-

Examples of compounds of formula (R 1 - R 2 -) p B2-H2 X are 2,3 ', 5-trimethoxy-diphenyl-4-diazonium chloride 2,4', 5-triethoxy-diphenyl-4-diazonium chloride 4- [3- (3-methoxy-phenyl) -propylamino] -benzenediazonium sulfate 4- [N-ethyl-N- (4-methoxy-benzyl) -amino] -benzenediazonium chloride 4- [N-naphthyl- (2) -methyl) -Nn-propyl -amino] -benzenediazonium sulfate 4- [H- (3-phenoxy-propyl) -N-methylamino] -2,5-dimethoxybenzenediazonimetetrafluoroborate 4_ [Ν_ (3-phenylmercapto-propyl) ~ N-ethylamino ] -2-chloro-5-methoxy-benzenediazonium chloride 4_ [4_ (3-methyl-phenoxy) -phenoxy] -2,5-dimethoxy-benzenediazonium-ehloride 4_ (4-methoxy-phenylmercapto) -2,5-diethoxy-benzenediazonium chloride 4 - (3,5-Dimethoxy-benzoylamino) -2,5-diethoxy-benzenediazonium hexafluorophosphate earbazole-3-diazonium chloride 3 -'-methoxy-diphenylene oxide-2-diazonium chloride diphenylamine-4-diazonium sulfate 2,5-diethoxy-4 phenoxy-benzene diazonium chloride.

Mixed condensates particularly suitable for use in reproduction layers are obtained by the use of diazo compounds of the general formula (R * i - r 5 -) r »2 - n 2x, where p is an integer from 1 to 3, preferably 1 wherein is a phenyl group which is either unsubstituted or substituted by one or more alkyl or alkoxy groups, wherein R 2 is a benzene ring which, in addition to the diazonium group, can carry one or two identical or different substituents which may be halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 5 carbon atoms and wherein R 1 is a homopolar bond or one of the groups - 0 - - S - - H 1 -.

A particularly important group of diazo compounds of the general formula R 1 - R 1 - R 2 2 n 2 x> 2 g preferably used in the invention for the preparation of the diazocondensation products are the salts of the diphenylamine-4-diazonium ion and its substitution products. these are in many cases particularly easily condensable and because the condensation products produce particularly valuable layers of reproduction.

Particularly preferred substituents which can be bonded to the phenyl cores of the diphenylamine-4-diazonium compounds are alkyl and alkoxy groups having 1 to 6, preferably 1 to 2 carbon atoms. In addition, the halogens and the following groups can be used: -COOfi (R is H, alkyl or aryl) -conh2

-On

-COR (R is alkyl or aryl) -SO20R (R is H, alkyl or aryl) -FHCOR (R is alkyl or aryl) -NHR and URR '(R and E1 are alkyl, aryl or aralkyl).

Examples of such substituents which can be bonded to the phenyl cores of the diphenyldiazonium group are methyl, propyl, isobutyl, trifluoromethyl, methoxy, difluoromethoxy, ethoxy, hydroxyethoxy, ethoxyethoxy, fluoro, chloro, bromo, iodo, ethoxycarbonyl, phenoxy carbonyl, acetyl, methoxysulfonyl, ethoxysulfonyl, acetylamino, methylamino, ethylamino, dimethylamino, diethylamino, methylethylamino, phenylamino, benzylamino, methylbenzylamino and ethylbenzylamino.

Suitable diphenylamine-4-diazonium salts are e.g. the diazonium salts derived from the following amines: 4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 41-amino-2-methoxydiphenylamine, 4'-amino -4-methoxy-diphenylamine, 4-amino-3-methyl-diphenylamine, 4-amino-3-ethyl-diphenylamine, 4'-amino-3-methyl-diphenylamine, 4'-amino-4-methyldiphenylamine, 4-amino 3-ethoxy-diphenylamine, 4-amino-3-hexoxyloxy-diphenylamine, 4-amino-3-hydroxy-ethoxydiphenylamine, 4'-amino-2-methoxy-5-methyl-diphenylamine, 4-amino-3-methoxy -6-methyl-diphenylamine, 4'-amino-3,3,3-dimethyl-diphenylamine, 3'-chloro-4-amino-diphenylamine, 4 '- amino-4-n-butoxy-diphenylamine, 4'- amino-3 *, 4-dimethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-21-carboxylic acid and 4'-bromo-4-amino-diphenylamine.

26 143621

Ian preferably uses 4-amino-diphenylamine and 3-methyl-4-amino-diphenylamine, and in particular, 3-alkoxy-4-amino-diphenylamines with 1 to 3 carbon atoms are used in the alkoxy group, especially 3-methoxy-4-aminodiphenylamine. .

Diazonium compounds A-N2X which can be used in the condensation reaction according to the invention can also be homocondensation products of the desired diazo compounds with active carbonyl compounds, i.e. eg. relatively low molecular types of the known diazo resins which can be considered as larger molecules capable of further condensation and having several. diazo groups.

The diazonium compounds A-N 2 X can be reacted in the form of any soluble salt of a moderately strong to strong acid, e.g. in the form of a salt of sulfuric acid, orthophosphoric acid, hydrochloric acid, trifluoroacetic acid, methanesulfonic acid and benzenesulfonic acid. Preferably, the sulfates and phosphates are used.

Ingredients B1 Similarly, a large number of compounds are suitable as component B1 in the preparation of the mixed condensates. An important category comprises such compounds derived from substituted or unsubstituted aromatic hydrocarbons and aromatic heterocyclic compounds, provided that the basic compounds have nuclear positions which can be condensed in an acidic medium with carbonyl compounds and which can accordingly record the CHRa0Rfe groups.

Thus, a large number of unsubstituted, aromatic, iso-cyclic and heterocyclic compounds are well suited as basic compounds EHm to the constituents e.g. benzene, naphthalene, anthracene, phenanthrene, pyrene, within, fluorine, acenaphthene, thiophene, furan, benzofuran, diphenylene oxide, benzothiophene, acridine, carbazole and pheriothiazine. These aromatic compounds may contain one or more identical or different substituents. Examples of such substituents are: 27 143 621 -NRyRg -n (r8) 2 -0R? -or8 -R8 -sr7 -sr8 wherein 7R may be H, -CO- ¥, -CO-aryl, CO-heterocyclic group, -CO-aralkyl, -SO2-, -SO2-aryl, -SOg-aralkyl, -SO8 heterocyclic group, -CONH2, -CSNH2, -CONH-W, -CONH-aryl, -CO-O-, -CO-O-aryl, -CS-O-aryl, and -CS-OW, and wherein R q may be H, an ω -, aryl or aralkyl group.

The meaning of certain terms is as follows: ¥: a branched or unbranched alkyl group having 1 to 10 carbon atoms which may be substituted, e.g. with halogen, -alkoxy, -OH, -COH, -CONH2, -CN, -CO-CH2, -SO2H, or -PO2Hg.

Aryl: a mono- or polynuclear aromatic ring containing between 6 and 20 carbon atoms, including γ, alkoxy or aralkyl groups, which may be attached thereto. The aryl core can carry additional substituents.

Aralkyl: a group containing between 7 and 20 carbon atoms comprising ¥ and aryl radicals (similar to the above definition).

Alkoxy: an O-alkyl group in which alkyl is a branched or unbranched alkyl group having 1-10 carbon atoms which may be substituted as above under ¥.

The ¥, aryl, aralkyl and alkoxy groups may occur one or more times, either alone or together. W for convenience is hereinafter referred to as alkyl. In order that the portion constituted by these substituents should not exceed the molecular weight of B 1, the proportion of the four substituents listed above is limited in the compound EHm with respect to the structure of the molecule, the primary aromatic iso- or heterocyclic ring 28 present or the condensed ring system germs must be substituted to such an extent that, in the case of substitution, the molecule of this compound only grows by a maximum of 10 carbon atoms when substituted by alkyl groups maximum of 20 carbon atoms when substituted by aryl groups a maximum of 20 carbon atoms * when is substituted by arylkyl groups and a maximum of 10 carbon atoms * when substituted by alkoxy groups.

The total increase of carbon atoms using these four types of substituents together should not exceed 30 carbon atoms relative to the original aromatic nucleus.

It follows that substituents with longer chains, i.e. those having a relatively large number of carbon atoms occur less frequently than those having few carbon atoms. In general, the short-chain alkyl and alkoxy groups and the less aromatic radicals in aryl and aralkyl groups (up to 12 carbon atoms) are preferred because the corresponding compounds are more easily soluble in the condensation media, so that the condensation can be accomplished more easily. Limiting the substitution, as described above, has the same reason.

The condensable iso- or heterocyclic aromatic rings may also have substituents which exert a deactivating effect on the nuclei, e.g. OgN, H00C, DC, HO ^ S and ELjO ^ P-, provided that the condensability is not thereby eliminated. This will be especially the case when the ring as such is readily condensable or when it carries substituents having a significant activating action. Another possibility of introducing deactivating substituents without reducing the condensability of the ring is to place the substituents in side chains, e.g. aliphatic side chains.

Substituents that deactivate the nuclear condensation may also be present in such cases where the reactivity of the condensable core is not necessary because the core has substituents at which condensation can take place. Such substituents have been listed above, e.g. the groups -CO-] ro2, -SO2liH2 and -SOgNH-alkyl.

According to the foregoing, the basic compounds EHm or the constituents derived therefrom, e.g. to the following substance groups: aromatic compounds (iso- and heterocyclic), unsubstituted or substituted aromatic amines phenols and thiophenols phenol ethers and thiophenol ethers urea, thiourea, carboxylic acid amides (aliphatic and aromatic), and sulfonic acid aromatic (aliphatic and aliphatic)

Examples of individual representatives are given below.

Soluble types of the novel diazocondensation products are preferably used. In addition to a corresponding selection of constituents A-NgX and B 2, depending on their properties and ratios, preference is further used to promote the formation of soluble condensation products constituents B 2, whose basic structures EH 2 have molecular weights (amines are considered free amines, not in the form of salts; acid groups are considered in the H-form) below 500, preferably below 250. In the case of aromatic compounds, those compounds which do not contain more than 4, preferably 1 to 2, especially 2, aromatic, single, are preferred. rings (annealed and / or bound via homopolymeric bonds and / or via intermediate groups).

30 143621

The use of the compounds B 2 in the more low molecular region is also advantageous because they are often more easily soluble in the condensation medium and thus can react more readily.

Of the indicated categories of compounds from which the compounds B 1 are derived, those which are unhydrolysable or difficult to hydrolyzable under acidic condensation conditions are usually preferred. The same applies to the diazo compounds A-NgX.

For this reason, the basic compounds of the constituents belonging to the category of the aromatic iso and heterocyclic compounds are advantageous which are unsubstituted or which as substituents carry the groups alkyl, aralkyl, aryl, alkoxy, alkylmercapto, aryloxy, arylmercapto, OH, SH and amino, if desired, in addition to unhydrolyzable, deactivating substituents, e.g. COOH. Among these compounds, the aromatic iso and heterocyclic compounds are particularly preferred which are unsubstituted and / or which. black substituents contain one or more of the radicals alkyl, aralkyl, aryl, alkoxy, alkylmercapto, arylmercapto and aryloxy, especially when condensates which do not contain salt-forming groups other than the diazo group are desired.

Examples of particularly suitable types of compounds B 1 are those derived from diphenyl ether, diphenyl sulfide, diphenyl methane and biphenyl which may contain one or two substituents selected from the group comprising halogen atoms, alkyl groups and alkoxy groups. but which is, however, preferably unsubstituted.

If these compounds are condensed with diphenylamine-4-diazonium salts which are unsubstituted or substituted by a lower alkyl group or a lower alkoxy group containing up to 3 carbon atoms, mixed condensates appear during the course of a very smooth reaction which can easily are precipitated and obtained in good yield in the form of salts of hydrochloric acid, hydrochloric acid or suitable sulfonic acids listed below, especially when constituents B1 are used in an amount of between 0.5 and 2 moles per liter. mole of diazo compound.

31 143621

The new condensation products prepared by the process of the invention contain, on average, between 0.1 and 50 moles, preferably between 0.1 and 20 moles, units of the component mole units of component A-N2X. A particularly preferred range is between 0.2 and 2 moles per day. mol A-N2X. The use of the condensates can be carried out in various ways. In some cases, the new condensation products may be used in the form of raw condensates, i.e. without separating the condensation medium. This is especially possible when the amount of condensation medium moles of diazo compound can be kept at a small value.

The new condensation products are usually separated in the form of any salt, and they are used in this form - after the addition of any desired additional additive to the layer - to prepare the reproduction material.

The diazo condensation products can be separated as salts by the following acids and can then be used: hydrohalogenic acids such as hydrogen fluoride, hydrochloric acid and hydrogen bromide; sulfuric acid; nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid; inorganic iso and heteropoly acids, e.g. phosphorus tungsten acid, phosphorus molybdic acid; aliphatic or aromatic phosphonic acids or their semisters; arsonsyrer; phosphinic acids; trifluoroed-acetic acid; sulfamic acid; selenic acid; fluoroboric acid, hexafluoro-phosphoric acid and perchloric acid; additional aliphatic and aromatic sulfonic acids, e.g. methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylene sulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 2,6-di-tert-butyl-naphthalic acid di-tert.-butyl-naphthalene disulfonic acid, 1,8-dinitronaphthalen-3,6-disulfonic acid, 4,4f-diazidostilben-3,3'-disulfonic acid, 2-diazo-1-naphtho1-4-sialphonic acid, 2- diazo-1-naphthol-5-sulfonic acid and 1-diazo-2-naphtho-4-sulfonic acid. Other organic sulfonic acids suitable for separating the condensates are listed in columns 2 to 5 of U.S.A. Patent No. 3,219,447.

The new diazocondensation products can also be separated in the form of the double salts with metal halides or pseudohalides, e.g. of the metals zinc, cadmium, cobalt, tin and iron, or as the reaction products with sodium tetraphenylborate or with 2-nitroindanedione- (1,3) and then used in known manner.

Under the influence of sodium sulfite, sodium azide or amines, they can also be converted to the corresponding diazosulfonates, azides or diazoamino compounds and used in this form, as known in the context of diazo resins.

The following advantages of the new diazocondensation products have been stated before: (a) Less penetration of the diazo compound in substrates favoring this phenomenon, e.g. superficially hydrolyzed cellulose acetate film. The result is that the image areas have excellent oleophilic properties after exposure to light.

(b) Less sensitivity of the reproductive layers to fingerprints.

Both advantages generally become more and more noticeable with increasing amount of the incorporated ingredient. While the advantage becomes generally apparent in case (a) with condensates containing as little as 0.1 mole of B mole of A-N2X, the desired effect in case (b) is obtained first from ca. 0.5 mol, and in some cases only when these components are incorporated to a greater extent.

The use of the new condensation products has other advantages in addition to those stated above. Compared to the known diazo resins, an improved efficiency of the photosensitivity of the reproductive layers produced with the new condensation products, i.e. that you can cope with shorter exposure times when using the same light source.

This effect generally increases with increasing content of B. | and varies depending on the type of component B.j. The effect is usually more apparent the higher the molecular weight of the component B Usually, the addition of the constituents comprising a second aromatic ring will have a greater effect than the same increase in the molecular weight obtained by introducing other groups.

With a growing content of a suitable secondary component B ^ 33, the resin character of the mixed condensates becomes more and more pronounced while the salt character is weakened with decreasing content of the diazonium salt groups in the condensate molecule. As a result, such mixed condensates are more compatible with polymerizers that do not contain ionizable groups.

For the same reason, the mixed condensates often possess good film-forming properties and, in the fully exposed state, the films exhibit improved flexibility and in many cases good resistance to various etchants. Thus, it is possible with a number of mixed condensates to produce reproductive layers with satisfactory etching resistance without the usual addition of resins. can be used for the photomechanical production of halftone engraving plates and printed circuits.

Mixed condensates containing constituents which are unable to form salt with acidic or alkaline etchants and which have no tendency to hydrolytic cleavage, i.e. secondary constituents selected from the category of substances comprising aromatic hydrocarbons which are either unsubstituted or substituted by alkyl, alkoxy, alkylmercapto, aryloxy or arylmercapto groups are particularly well suited for this purpose.

A particularly favorable group of condensation products is derived from the constituents B 2 containing 2 benzene rings which are joined via a bridging group.

Particularly preferred in this series are the mixed condensates derived from the constituents derived from diphenyl ether, diphenyl sulfide, diphenylmethane or biphenyl with diphenylamine-4-diazonium salts, especially 3-alkoxydiphenylamine-4-diazonium salts.

These condensates have high light sensitivity and those prepared from 3-alkoxy-diphenylamine-4-diazonium salts also have surprisingly high storage stability. The corresponding condensation products can be prepared particularly easily and under moderate conditions. Diphenyl ether derivatives of type B, which are suitable for the preparation of the condensation products, are commercially available.

In contrast to the known diazo resins, the new condensation products can in many cases be very readily separated from an aqueous solution by the addition of hydrochloric acid or a solution of common salts in the form of the chlorides or analogously as bromides.

For this reason, a number of the new condensation products can advantageously be used in cases where the halides of the known diazoresins which can only be separated in a cumbersome manner have preferably been used, e.g. for making screen printing molds. The chlorides can further be readily converted to the salts of low volatile acids, for example, to the orthophosphates, which can of course also be prepared directly, e.g. by condensation of the diazonium phosphates in phosphoric acid.

A particular group of the new condensation products has particular advantages in terms of the acid resistance of the exposed products and their adhesion to metallic supports used for pianographic printing plates. These are the condensation products that carry phosphonic acid groups. The exposed products of these condensates have good adhesive properties on aluminum foils which are roughened exclusively with metal brushes, e.g. without the films being provided with one of the known chemical adhesive layers, and even in the case where the products are used in the form of double zinc chloride salts.

Another special group of mixed condensates has special advantages, especially in the curing of hydrophilic colloids. Mixed condensates include mixed condensates of diphenylamine-4-diazonium salts and urea or similar compounds. Colloid layers cured with these condensates under the influence of light have better hydrophilic properties after curing than those sensitized with the known diazo resins. This effect is important for producing printing molds, as described e.g. in TJ.S.A. Patent No. 3,085,008.

It should also be noted that mixed condensates prepared from diazonium salts and an excess of phenols are capable of producing positive copies by developing with an aqueous alkaline liquid (if desired by adding a small amount of solvent).

35 143621

The new condensation products can be combined with water-soluble and water-insoluble polymers in the reproduction materials. In particular, the preparation of reproduction layers containing water-insoluble polymers is simplified when using the new condensation products, because the latter can be made particularly easily in the form of salts compatible with these polymers which are readily soluble in a number of organic solvents.

The reproduction layer is prepared in a manner analogous to that done in the case of the known diazo resins, i.e., the diazo condensates are dissolved as such or, if desired, with additional components of the layer, in a suitable solvent, and a substrate. is coated with the solution thus obtained. Suitable substrates are, for example, those listed on page 3 of the present description.

In some cases it is also possible to apply the mixed condensate in the form of a very fine suspension. The coating may e.g. is carried out by immersion or casting and drainage, by casting and centrifuging it - excess solution, by brushing, brushing or by applying rollers, and by using other coating methods. The coating is then dried at room temperature or at elevated temperature.

The following list of constituents B1 represents a classification. The characteristic feature in each case is the substituent-inactivating condensation. Of course, when two or more different activating substituents occur, the attribution of a particular property to a certain group is arbitrary.

In some cases, it is also possible to use aromatic compounds substituted only by deactivating substituents as the basic compounds of constituents B 2.

However, compounds of type B1 which carry activating substituents or no additional substituents with the exception of the -CHRα-OR ^ groups are preferred.

36 1A3 & 21

Well-defined derivatives of type B1 of aromatic amines cannot be prepared as readily as in the case of other compound types, partly because they have a clear tendency to decompose water and because a number of side reactions are possible. Examples of such products resulting from the decomposition of water are N, N'-methylene-bis-diphenylamine and anhydro-formaldehyde-aniline.

These compounds are also capable of condensing in an acidic medium according to the invention.

Compounds B- ^ derived from phenols. i.e. wherein the OH group is bonded directly to an iso- or heterocyclic aromatic ring system and may comprise one or more aromatic rings. These rings may also carry additional substituents on the condition that there is at least one position in the molecule capable of carrying a group -CHR 2 OR 2.

The "phenol alcohols" prepared from the above phenols by formaldehyde addition, as well as the ethers and esters thereof of the aliphatic OH group, can be used in the process of the invention. Numerous phenolic alcohols have been described in the literature. One can, for example. find a summary in the monograph by Martin, "The Chemistry of Phenolic Resins", John Wiley & Sons, F.Y., 1956. The journal "Die Macromolecular Chemie", 44, pages 44 to 45 (1961) should also be noted. Phenolic alcohols and the esters and ethers thereof, which can be prepared in a different way, e.g. halogen methylation or reduction of phenol aldehydes or phenol carboxylic acids or the esters thereof is also suitable.

In addition to the phenolic alcohols and their derivatives listed above, it is also possible to use the derivatives obtained by esterification of the phenolic OH group of these compounds by carboxylic and sulfonic acids.

Compounds B ^ derived from thiophenols Instead of phenol derivatives, it is possible to use the corresponding thiophenol derivatives. But the phenols are far superior to thiophenolemes, partly because the latter are considerably more expensive and tend to side reactions, in addition, many of which have an unpleasant odor.

37 143621

Compounds B ^ derived from ethers of phenols and thiophenols.

Alkyl, aralkyl and aryl ethers of the above phenols and thiophenols are e.g. suitable.

Compounds B1 derived from aromatic, iso-cyclic and heterocyclic compounds

Compounds of the type in this group of compounds are prepared e.g. by halo methylation of the basic structures and then by converting the halo methyl groups to the groups -CHgOH, -O₂ alkyl or CE₂O acyl.

Numerous halo methyl compounds (which carry this group directly in the aromatic core) are known, which are suitable as intermediates for the preparation of compounds of the type described above.

Compounds of type B1f derived from phenol ethers can also be prepared by alkylation or aralkylation of the phenolic OH groups in phenol alcohols.

The compounds listed above contain at least one aromatic ring. The following compounds B ^ are also capable of condensing if they do not contain any aromatic rings.

This group of compounds B1 is derived from compounds B containing at least one substituent capable of reacting with an active carbonyl compound during condensation.

In the foregoing, the most important groups of compounds used as constituents B-p are listed. However, the possibilities are not limited to that; it is also possible e.g. using the corresponding derivatives of cyanuric acid hydrazides, guanidine derivatives and aminopyrimidines.

For further possibilities, reference should be made to the literature on condensation resins, e.g. Houben-Weyl, "Methods of Organic Chemistry", 4 'edition, vol. 14/2, pages 193 to 402, "Poly-addition and condensation products of carbonyl and thiocarbonyl compounds, respectively."

38 1438? 1

The following examples describe the preparation of the new mixed condensates and the preparation of copier materials using them.

For better identification of the mixed condensates, in many examples, in which the diazo compound and component are part of the product structure, besides the result of the elemental analysis, the molecular ratio calculated from the values obtained by the analysis is given. This ratio is calculated under somewhat simplified assumptions. While these cannot determine and do not determine the exact structure of the mixed condensates produced by the process of the invention, they are sufficient to identify condensation products whose properties are reproducible.

As stated above, condensation conditions, especially the quantities used, are in many cases important for further identification. The Examples contain all the information necessary for the preparation of the mixed condensates.

In the examples, weight parts and volume parts correspond to each other as g to ml. The percentages are by weight unless otherwise indicated. The temperature is measured in ° C. For the purposes of analysis, N means the total nitrogen content and ND means diazonitrogen.

Normally, no greater emphasis was placed on complete drying of the condensation products, so that the resulting products may contain small amounts of water or condensing agent. In addition, varying amounts of metal salts can sometimes be contained during the precipitation. However, the active substance content of the products can easily be determined by the value of the assay.

The term "raw condensate" used in the Examples generally means the crude condensation mixture produced during the condensation, which usually also contains the condensation medium.

For better orientation, the diazo compounds A-N2X and the components used to prepare the mixed condenser present in the reproduction materials obtained from the condensation products produced by the process of the invention are listed in the the following Table 1, specifying numbers. The examples refer to these numbers.

TABLE · 1;

Mazoforbindelser.

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-dimethoxy-benzenediazonium salt

Diazo 7: 2,5-dimethoxy-4-phenoxy-benzene-diazonium salt

Diazo 8: 4- (2,5-diethoxy-benzoylamino) ~ 2,5-diethoxy-benzenediazonium salt

Diazo 9: 3-methoxy-diphenylene oxide ~ 2-diazonium salt

Diazo 10: 4- [N-methyl-N-naphthyl- (1) methylamino] - benzene diazonium salt

Diazo 11: 4-diazo-diphenylamine-3-carboxylic acid (inner salt)

Diazo 12: 2,5-dimethoxy-4- (N-methyl-N-phenylmercaptoacetylamino) benzene diazonium salt

Diazo 13: 4- [N-methyl-N- (β-phenyl-mercaptoethyl) -amino] -benzene-diazonium salt 40

Ingredients B ^

Ro. 1: R, R'-dimethylol succinic diamide

Row 2: Hexa-methoxymethyl-melamine

Ro. 3: R, R'-dimethylol urea

Ro. 4: R, R'-dimethylol-terephthalic acid diamide

Ro. 5: 2,6-dimethylol-4-methyl-phenol

Ro. 6: 2,6-dimethylol-4-methyl-anisole

Ro. 7i Di-hydroxy-methyl duration

Ro. 8: Di-Acetoxymethyl Duration

Ro. 9: 1,3-dimethyl-4,6-dimethylolbenzene

Ro. 10: 1,3-diisopropyl-4,6-dimethylethyl benzene

Ro. 11: 1,5-di-acetoxymethyl-naphthalene

Ro. 12: 1,4-dimethylol-benzene

Ro. 13: Commercial bis-methoxymethyl diphenyl ether (Composition given in Example 8)

Ro. 14: 4,4'-di-diethoxymethyl-diphenyl ether

Ro »15: 4,4'-di-methoxy-methyl-diphenyleth

Ro. 16: 2,5-diethoxymethylthiophene

Ro ·. 17: 9,10-di-methoxymethyl-anthracene

Ro. 18: Benzhydrol

Ro. 19: 1,4-bis- (a-hydroxybenzyl) -benzene 41

No. 20: 1,3-diisopropyl-4,6-dimethoxymethylbenzene

No. 21: 4,4'-dimethoxymethyl diphenylsulfide

No. 22: Methoxymethyl diphenyl ether, prepared by reaction between technical chloromethylated diphenyl ether and sodium methylate (Composition see Example 53)

No. 23: 2,2-bis (4-hydroxymethylplienoxy) diethyl ether

No. 24: 1,3-bis- (4-hydroxymethyl-phenoxy) -propane

No. 25: Bis-methoxymethyl diphenyloxide

No. 26: 4,4'-bis-methoxymethyl-diphenylmethane

No. 27: Methoxymethylated bipbenyl

No. 28: Methoxymethylated 4,4'-dimethyl diphenyl ether

No. 29: Methoxymethylated 2-isopropyl-5-methyl-diphenyl ether

No. 30: Methoxymethylated 3-bromo-4-methoxy-diphenyl ether

No. 31: Methoxymethylated dibenzo-thiophene

No. 32: Methoxymethylated 1,4-diphenoxybenzene

No. 33: 2,6-bis- (methoxymethyl) -4-methyl-phenol

No. 34: 4,4'-bis (ethoxymethyl) diphenyl ether

No. 35: 4,4'-bis (hydroxymethyl) diphenyl ether

No. 36: Ν, Ν'-dimethylol oxamide

No. 37: Ν, Ν'-dimethylol adipic acid diamide

No. 38: trimethylol citramide.

EXAMPLES 1-21 In the following examples, the good to excellent oleophilic properties of the exposed products of 20 of the new condensation products when applied to superficially hydrolyzed cellulose acetate films, in combination with an improved photosensitivity, are shown in comparison to pure formaldehyde. The composition of the condensation products used and coating solutions are listed in the following Table 2.

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In the case of pure aqueous coating solutions, the coating can be carried out by brushing, whereas solutions which preferably contain organic solvents are applied by means of a rotating plate. Hot air is used for drying. After image exposure, a negative original thins the material, e.g. by over-drying with water or one of the known buffered solutions of water-soluble coupling constituents, for example, of the pyrazoion series. The material is then hardened with greasy ink, whereby the exposure products absorb the ink. In a number of cases, it is also possible to enhance the image by means of lacquers, e.g. the usual emulsion paints. In all cases, the oleophilic properties of the exposure products of the new diazocondensates are superior to the previously known formaldehyde condensates of the corresponding diazo compounds.

This is actually illustrated by the following comparisons:

Pormaldehyde condensates of diazo compounds 1 and 2 prepared in phosphoric acid as described in Example 1 of U.S.A., respectively. U.S. Patent No. 3,311,605 and Example 1 of U.S.A. Patent No. 3-4-06,159, represents exposure products which have little ink absorption ability or do not absorb any ink at all when coated and treated as described above.

By adding phosphoric acid to the coating solution, even poorer results are obtained.

In contrast, the new condensation products produced in phosphoric acid, e.g. the condensation products indicated in Examples 2 to 4, 6, 8, 10, 14, 19 and 21, good for excellent ink absorption in the image areas. The good oleophilic properties are not lost by the addition of phosphoric acid to the coating solutions. The coating solutions used in Examples 3 to 15 can e.g. contain 2 molecules of phosphoric acid per diazo group, without any significant reduction in the black-up ability of the exposed products. In Example 21, 10 molecules of phosphoric acid are present. diazo group. There is also a similar effect in Example 11 in which a crude condensate product in phosphoric acid is used for coating without separation of the condensing agent.

It is also apparent from these examples that the incorporation of small amounts of component B 1 is sufficient to produce a significant effect. The effect occurs even in the case of incorporation of only 0.15 moles of ingredient per day. mole of diazo compound, although optimum results are not obtained in this case.

Examples 12, 13, 16 and 19 show the superiority of the new condensation products as compared to the formaldehyde condensates prepared in sulfuric acid and precipitated in the form of the zinc chloride double salt, which is currently preferred as diazo resins. Even with 0.1% by weight solutions of the new mixed condensates (Example 12) and the addition of 2 molecules of phosphoric acid per ml. diazo group obtains printing forms with good ink-absorbing ability from which pressure can be produced on conventional offset presses. When using a 0.1 wt. # Solution of the corresponding formaldehyde condensate (Example 13) and further processing in the same way, no significant ink absorption ability is obtained. Only a moderately satisfactory ink absorption ability is obtained when increasing the concentration of this diazo compound to a value many times greater than this value.

The preparation and composition of the mixed condensates used in Examples 1 to 21 are described in detail below. EXAMPLE 1 17.75 parts by weight of 4-methoxy-diphenylamine-4'-diazonium sulfate (91 #) (Diazo 3, sulfate, Table 1) dissolves in 150 parts by volume 86 # phosphoric acid. 11.2 parts by weight of dimethylol terephthalic acid diamide (component, # 4, Table 1) is introduced into the solution in the form of a fine powder and with vigorous stirring, and the condensation is carried out for 21 hours at room temperature. The crude condensate is dissolved in 1000 parts by volume of water at 40 ° 0, and the condensation product is then precipitated from the solution by the addition of 2000 volumes by volume of 50 µg of zinc chloride solution. The double salt is precipitated, dissolved in 500 volumes of water at 50 ° 0, and precipitated by the addition of zinc chloride. Yield: 26.8 parts by weight (C 46.6%, N 11.5%). According to the analysis, the product contains elements N and C in a ratio of 5: 23.6.

EXAMPLE 2 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 ° F phosphoric acid at 40 ° C. The solution is cooled to room temperature and allowed to cool to room temperature. rapidly and with stirring, add a solution of 3.4 parts by weight of 2,6-dimethylol-4-methylphenol (component, # 5, Table 1) in 7 parts by volume of N-methylpyrrolidone. The mixture is cooled to such an extent that the temperature of the mixture does not exceed 50 ° C. The mixture is then condensed for 2 hours at 40 ° C.

A crude condensate is obtained which is soluble in water without residue. To precipitate the condensation product, the crude condensation mixture is stirred into 1000 parts by volume of isopropanol and dried. Yield: 7.5 parts by weight. This gives the acidic phosphate of a condensate which, according to analysis, has an excess content of approx. 9 carbon atoms per diazo group, as compared to the uncondensed diazo compound. Thus, approx. 1 mole of the second component per mole of diazo compound (C 47.3 f, Έ7.6 f>, m (diazo-N) 5.1% P 9.4%; atomic ratio: 21.7: 3: 2: 1.67).

Example 3 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% phosphoric acid.

19.4 parts by weight of the bis (hydroxymethyl) duration (component B ^, No. 7, 49 U3B-21 Table 1) is added with stirring in small portions at room temperature and the condensation is carried out for 25 hours at room temperature.

The crude condensate dissolves in 1000 parts by volume of water; a somewhat cloudy solution is obtained which is clarified by pressure filtration. The chloride of the condensation product is precipitated by heating the filtrate to 70 ° C and by adding 220 parts by volume of hydrochloric acid (36 hydrochloric acid diluted with the same volume of water). For purification, the precipitate is repeated in the same way. Yield: 33.8 parts by weight. According to analysis, the condensation product has an excess content of 13 carbon atoms per minute. diazo group, compared to the non-condensed diazo compound. This corresponds to a ratio of approx. 1.1 moles of the second component per mole of diazo compound (C 65.0 #, N 8.7 Cl 1.2 $> atomic ratio: 26.1: 3; 1.25).

Example 4 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 # phosphoric acid.

Ten parts by weight of finely powdered 4-methyl-2,6-bis (hydroxymethyl) anisole (component B1f # 6, Table 1) is then added slowly and with stirring. Stirring is continued for 5 hours at room temperature and for 8.5 hours at 40 ° C, and then the mass is allowed to stand for 30 hours at room temperature. The condensation mixture is dissolved in 300 parts by volume of water (clear solution) and the condensate is precipitated with stirring at 5 ° C with 150 parts by volume of saturated solution of sodium chloride. The precipitate is separated and precipitated in the same way. 18.7 parts by weight of a sticky condensation product is obtained which, according to analysis, has an excess content of 11.2 carbon atoms per minute. diazo group, as compared to the uncondensed diazo compound. This corresponds to a ratio of approx. 1.1 moles of the second component per mole of diazo compound (C 60.3 #, N 8.7 #, Cl 10.2 atomic ratio: 24.2: 3: 1: 1.38).

EXAMPLE 5 15.42 parts by weight of diphenylamine-4-diazonium sulfate (95 #) (Diazo 1, sulfate, Table 1) are dissolved in 100 parts by volume of methanesulfonic acid ($ 90).

6.8 parts by weight of finely powdered 1,5-bis (acetoxymethyl) naphthalene (Component B1, No. 11, Table 1) is then added with stirring. After condensing for 1.5 hours at room temperature, the crude condensate is capable of forming a clear solution in water, 4.15 parts by weight of 1,3-dimethyl-4,6-dimethylolbenzene (component, No. 9, Table 1 ) is then introduced with stirring into the mixture and the condensation is continued for an additional 45 minutes at room temperature. The crude condensate is dissolved in 500 parts by volume of water (clear solution). The condensation product is precipitated at 10 ° C by the addition of 200 parts by volume of hydrochloric acid (36.5% acid diluted with the same volume of water). For purification, the product is dissolved in water and precipitated again as the chloride by the addition of hydrochloric acid. Yield: 14.5 parts by weight.

According to analysis, the condensation product has an excess content of 10.7 carbon atoms per minute. diazo group, compared to the non-condensed diazo compound (C 67> 2 B 10.4 atomic ratio: 22.6: 3).

Example 6 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 $ phosphoric acid. At a starting internal temperature of 25 ° C, 44.5 parts by weight of 1,3-diisopropyl-4,6-dimethylol-benzene (component B ^, No. 10, Table 1) is added in a very finely powdered form. Stirring is continued for 1 hour with heating, and then the condensation is carried out for 20 hours at 40 ° C. A condensate is obtained which forms a clear solution in water.

The condensation product is precipitated from the aqueous solution of the crude condensate by hydrochloric acid, dissolved again in water with purification, and precipitated with hydrochloric acid. Yield: 64 parts by weight (G 68.2 #, N 5.1 atomic ratio: 46.8: 3). On the basis of the analysis results, it can be assumed that per mole of diazo compound is incorporated ca. 2.4 moles of the second stock portion.

EXAMPLE 7

At room temperature and with stirring, 2.8 parts by weight of bis (acetoxymethyl) duration (component Bj, No. 8, Table 1) is gently added 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 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 filtered off by suction, washed with 250 parts by volume of water, dissolved again at 50 ° C in 250 parts by volume of water and precipitated by the addition of 50 parts by volume of 18 # hydrochloric acid. Filtration of the precipitate is improved by briefly heating the suspension to 80 ° C and subsequent repeated cooling. The product is filtered off by suction, washed with 1N 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 assay, the mixed condensate contains approx. 1.1 moles of the second component per mole of diazo compound.

EXAMPLE 8 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. Within 15 minutes, 25.9 parts by weight of methoxymethyl diphenyloxide (with the composition thereof is given below) (Component B1, No. 13, Table 1) is added dropwise and with stirring. A clear, raw condensate is obtained which is kept under stirring for an additional 1.5 hours at room temperature and then for 6 52 143621

The condensate is dissolved in 500 parts by volume of water and the solution containing a slight haze is clarified by filtration. The condensation product is dog precipitated by hydrochloric acid. It is also possible to use sodium chloride for the precipitate. If a product which is essentially free of phosphoric acid is to be obtained, it is advisable to re-precipitate the product in the same way. Yield: 37.6 parts by weight. According to the analysis, the condensation product has a content of 16 more carbon atoms per diazomolecule than the uncondensed diazo compound (C

61.7 #, N 7.4 #, 01 9.3%; atomic ratio: 29.2: 3: 1.5).

The methoxymethyl diphenyloxide used (component B 2) has the following composition: diphenyl ether 1,3 # mono-o- (methoxymethyl) diphenyl ether 2,2 # mono-p- (methoxymethyl) diphenyl ether 11.8 # unknown similar monomethoxymethyl component 3 , 9 # o, p'-di- (methoxymethyl) diphenyl ether 21.9 # p, p'-di- (methoxymethyl) diphenyl ether 47,3 # tri- (methoxymethyl) diphenyl ether 1,3 # tetra- (methoxymethyl) ) -diphenyl ether 9.5 # When introducing the methoxymethyl diphenyloxide into the acid in the absence of a diazo compound, it initially dissolves when vigorously stirred. After a few seconds to a few minutes, a condensate which is insoluble in the acid and in boiling water precipitates.

A mixed condensate is obtained which gives rise to the formation of exposure products having the same oleophilic properties when replacing the sulphate of Diazo 2 with an equimolar amount of the sulphate of Diazo 1, and otherwise using an otherwise identical process. Moreover, the mixed condensates containing Diazo 2 give rise to the formation of reproductive layers with better storage capacity.

Example 9 4.64 parts by weight of diphenylamine-4-diazonium sulfate (Dlazo 1, sulfate, Table 1) (95%) are dissolved in 600 parts by volume of 86% phosphoric acid.

Then 4.65 parts by weight of 1,4-bis- (a-hydroxybenzyl) -benzene (Component B-, No. 19, Table 1) is dissolved in 30 parts by volume of glacial acetic acid, which is so hot that a solution takes place. The hot glacial acetic acid solution is then poured into the diazop solution while vigorously stirring. Condensation is carried out at room temperature over a period of 21 hours. The condensation mixture is then dissolved in 2000 parts by volume of water, filtered for clarity and precipitated by the addition of 300 parts by volume of concentrated hydrochloric acid. The precipitate is separated, dissolved at 60 ° C in 500 volumes of water, filtered and precipitated by the addition of 50 volumes of 6 F hydrochloric acid solution in water. The product that settles is again precipitated in the same way. Thereby, 4.8 parts by weight of the chloride of the condensation product is obtained. According to the analysis, the ratio C: N: C1 equals 26.6: 3: 3.05. This corresponds to a ratio of approx. 0.73 moles of the second component per mole of diazo compound (C 69.2%, K 9.1%, Cl 8.2%).

EXAMPLE 10 30.84 parts by weight of diphenylamine-4-diazonium sulfate (95%) (Diazo 1, sulfate, Table 1) are dissolved in 1000 parts by volume of 86% phosphoric acid.

Over 1 hour, a solution of 18.4 parts by weight of benzhydrol (Component B ^, No. 18, Table 1) is added dropwise in 200 parts by volume of glacial acetic acid. The condensation is carried out for 24 hours at room temperature. A clear, raw condensate is obtained which dissolves in water without residue. Half of the raw condensate is introduced into 2500 parts by volume of water heated to 40 ° C. The condensation product initially forms a clear solution and crystallizes upon cooling in the form of small flakes. Yield: 21.9 parts by weight (C 65.6 fi, U 8.1%, P 8.9 atomic ratio: 24.5: 3: 1.5).

According to the analysis, the condensation product has a content of 12.5 more carbon atoms per diazo group than the non-condensed compound. This corresponds to a ratio of oa. 1 mole of the second compound per mole of diazo compound.

The other half of the crude condensate is mixed with 1.5 parts by weight of paraformaldehyde and condensed for 20 hours at room temperature.

The crude condensate is dissolved in 2000 parts by volume of water and filtered to remove a slight cloudiness so that the solution becomes completely clear. It can be separated in the known manner in the form of the zihchloride double salt. Yield! 22.9 parts by weight (0 59.9 fit U 8.5 atomic ratio: 24.6: 3).

EXAMPLE 11

For the preparation of the crude condensate, 11 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table 1) is introduced into 39.9 parts by weight 86 of phosphoric acid and the mixture is cooled to room temperature. Then, 5.17 parts by weight of a mixture of methoxymethylated diphenyl ethers of the composition of Example 8 is introduced (Component, No. 13, Table 1) and the mixture is kept under stirring for 1 hour.

Then the mixture is heated to 40 ° C, a mixture of 22.1 parts by weight of the same diazo compound with 2.4 parts by weight of paraformaldehyde is added and the condensation is carried out for 24 hours at 40 ° C.

The raw condensate is used directly to prepare the coating mixture.

EXAMPLE 12

To prepare the diazocondensation product, 81% by weight of Diazo 2 sulfate (Table 1) is dissolved in 500 parts by volume of 85 # phosphoric acid, 61 parts by weight of 1,3-diisopropyl-4,6-dimethylol-benzene (Component,

No. 10, Table 1) Introduce 1 over 15 minutes and the mass is condensed for 39 hours at 40 ° C. The condensation mixture, which forms a clear solution in water, is then dissolved in 2500 parts by volume and precipitated again by adding 500 parts by volume 18 aqueous. hydrochloric acid solution. After filtration by suction and washing with 0.5 S hydrochloric acid, the product is dried with air. Yield: 113 parts by weight of chloride of the condensation product (C

66.2 K 8.8 atomic ratio: 26.3: 3). The analysis result shows that the condensate contains approx. 1 mole of the second component per mole of diazo compound.

EXAMPLE 13

A diazo resin in the form of the zinc chloride double salt is prepared by the condensation of equimolecular amounts of diazo 1, sulfate (Table 1) and formaldehyde in 80 µ sulfuric acid, analogous to the process described in U.S.A. Patent No. 2,063,631.

EXAMPLE 14 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 volume parts 86 in> phosphoric acid. 6 parts by weight of 2,5-bis (ethoxy-methyl) -thiophene (Component B1, No. 16, Table 1) are then added dropwise and with vigorous stirring. The mixture becomes reddish but remains clear. The condensation is carried out for 2.5 hours at room temperature.

The crude condensate forms a clear solution in water.

To precipitate the reaction product, the mixture is introduced into isopropanol maintained at a temperature of ca. 65 ° C and kept under thorough stirring and cooled to room temperature. The precipitate is filtered off by suction and washed thoroughly with isopropanol and dried. Yield: 10.9 parts by weight. According to Assay 56 143621, the condensation product, in the form of an acid phosphate, contains the constituents 3-methoxy-4-diazo-diphenylamine, 4-diazo-diphenylamine, and thiophene in a ratio of 0.7 to 0.3 2 (0 46.9 f °, N 6.7 f>, S 10.1 f>, 0CH3 3.1 1 * \ atomic ratio: 24.6: 3: 1.98: 0.73).

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

EXAMPLE 15 3.6 parts by weight of 2,5-dimethoxy-4-phenoxy-benzene-diazonium chloride (Mazo 7, Table 1) in the form of the double salt with 0.5 mole of zinc chloride (containing HaCl, iT = 7.7%) are dissolved in 60 parts by volume 93 % phosphoric acid. Dry air is passed through the solution until no additional hydrogen chloride escapes. 2.7 parts by weight of 1,3-diisopropyl-4,6-di- (methoxymethyl) benzene (Component B 2, No. 20, Table 1) are then added and the mass is condensed for 1 hour at room temperature and for 2 hours at 40 ° C. The condensation mixture is dissolved in water to form a clear solution, the condensate is precipitated with zinc chloride, separated and dried. Yield; 2.9 parts by weight (C 57.6 fo, H 4.4 f>; atomic ratio: 30.6: 2). The analysis shows that the mixed condensate contains approx. 1.2 moles of the second component per mole of diazonium compound.

EXAMPLE 16 3.6 parts by weight of the diazonium salt used as the starting material of Example 15 (Liazo 7, zinc chloride double salt, Table 1) are dissolved in 60 parts by volume of 90 µm of methanesulfonic acid and dry air is passed through the solution until no further hydrogen chloride escapes.

Then 2.7 parts by weight of 1,3-diisopropyl-4,6-bis (methoxymethyl-57-methyl) -benzene (Component B ^, No. 20, Table 1) are introduced and the mass is condensed for 1 hour at room temperature and at room temperature. 2 hours at 40 ° C.

The mixture is introduced into water and freed of undissolved constituents by the addition of charcoal, followed by filtration by suction.

The condensed product is precipitated from the filtrate in the form of the zinc chloride double salt. Yield: 5.8 parts by weight (C 41.0 N 2.7 in atomic ratio: 35.3: 2). This corresponds to a content of approx. 1.5 moles of the second component per mole of diazo compound.

EXAMPLE 17 1.75 parts by weight of 4- (2,5-diethoxy-benzoylamino) -2,5-diethoxy-benzene-diazonium chloride (Diazo 8, Table 1), in the form of the zinc chloride double salt (N = 4.8 10 volumes 90 parts of methanesulfonic acid, and dry air is passed through the mixture until no more hydrogen chloride escapes. Then 0.14 parts by weight of 1,4-bis-hydroxymethylbenzene are added (Component B1, No. 12, Table 1). After condensing for 4 hours at room temperature, the mixture is diluted with water and filtered, and the condensate is precipitated from the filtrate using a zinc chloride solution. Yield: 2.2 parts by weight (C 25.2 N 3.6 $} atomic ratio: 24.5: 3).

EXAMPLE 18 0.78 parts by weight of 3-methoxy-> diphenylene oxide-2-diazonium chloride, in the form of the double salt with 0.5 mole of zinc chloride (N = 7.2 90 (Diazo 9, Table 1)) dissolves ± 10 volumes by 90 methane sulfonic acid and dry air is passed through the mixture until no more hydrogen chloride is released, then 0.14 parts by weight of 1,4-dimethylol-benzene (Component B1, no. 12, tabeil) is added and the condensation is carried out for 4 hours at room temperature. The condensation product is precipitated by zinc chloride Yield: 1.4 parts by weight (C 22.4 $, N 2.9; atomic ratio: 18: 2) .. On the basis of the analysis 58 143521, it can be assumed that per mole diazo compound is incorporated about 0.6 mole of the second component.

EXAMPLE 19

A condensation product is prepared from 3-methoxy-diphenyl-amine-4-diazonium chloride and formaldehyde as described in Example 1) of U.S.A. Patent No. 3,406,159 »and it is separated into an acid phosphate which still contains some phosphoric acid (IT 9.3 f> ·, atomic ratio 0: N: P = 14: 3: 2.3).

The product has an average degree of condensation of approx. 3 units of methoxydiphenylamine diazonium salt per molecule, determined for the diazo-amino compound with diisobutylamine in benzene using the cryoscopic method for determining molecular weight.

10 parts by weight of the diazo condensation product are dissolved in 85 parts by weight 85 f> phosphoric acid. 5.7 parts by weight of 4,4'-bis-methoxymethyl diphenyl ether (Component B ^, No. 15, Table 1) is added dropwise over 10 minutes and the mixture is then condensed for 20 hours without further heating. The clear condensation mixture forming a clear solution in water is diluted with 100 parts by volume of water and then 330 parts by volume of a saturated aqueous solution of sodium chloride is added. The precipitate thus formed is purified by re-dissolving it in water and by precipitating it with a solution of sodium chloride, and the precipitated product is then dried. Yield: 8.1 parts by weight (C 48.3 ΪΓ 4.3 atomic ratio: 39.4: 3).

According to the assay, the diazo homocondensate and the second component are present in the mixed condensate in a molar ratio of about 1: 5.4.

EXAMPLE 20 5 parts by weight of 4-p-tolylmercapto-2,5-dimethoxy-benzene diazonium chloride, in the form of the zinc chloride double salt (N 6.9%) (Diazo 6, Table 1), dissolve in 40 parts by volume of 80 $ sulfuric acid and dry air is passed through the solution, until no additional hydrogen chloride escapes.

0.88 parts by weight of 1,4-bis (hydroxymethyl) benzene (Component B ^, No. 12, Table 1) is added to the solution in portions, the solution is stirred for 1 hour at room temperature and then allowed to stand overnight. Then it is poured into 300 parts by volume of water, 2 parts by weight of charcoal is added to remove a slight haze, and the solution is then filtered under suction.

In the clear filtrate, the condensation product is precipitated by the addition of zinc chloride and sodium chloride. 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 of the second component per mole of diazo compound.

EXAMPLE 21 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, tabeil) are dissolved in 265 parts by weight of 93 $ phosphoric acid. 25.8 parts by weight of 4,4'-bis (methoxymethyl) diphenyl ether (Component B1, No. 15, Table 1) is added dropwise to the solution and the condensation is carried out for 2 hours at 40 ° C. 16 parts by weight of paraformaldehyde are added to the mixture. whereby a clear solution is obtained in water, the condensation is continued for 6 hours at 40 ° C and the mixture is left to stand overnight. The mixture, which is dissolved in water without leaving any residue, is then dissolved in water and a saturated solution of sodium chloride is added. The bulky precipitate formed is kept at 40 ° C for 1 hour, then filtered off by suction as far as possible, and the contents of the suction filter, namely a green paste, are then dried over phosphorus pentoxide, whereupon the product is converted to 60 tough, green pulp that smells strongly of formaldehyde. Yield: 175 parts by weight (C $ 16.4, H $ 1.9, S 0.45%> p ^ .7% f atomic ratio: C: N: P = 30.2: 3: 9> 7). Compared to the uncondensed diazo compound, the condensate has a content of about «17 more carbon atoms.

EXAMPLES 22 - 28

Examples 22-28 show that using the new condensation products, in the presence of phosphoric acid, reproduction layers which are significantly less sensitive to fingerprints during treatment than reproduction layers prepared in the same manner, but using the known formaldehyde condensates of the diazo compounds alone (same anion and same phosphoric acid addition).

Coatings shown in Table 3 are applied to an aluminum substrate which has been roughened with metal wire brushes and pre-treated with polyvinylphosphonic acid according to U.S.A. Patent No. 3,220,832, The coating is then dried with hot air.

The reduction of the material's sensitivity to moisture, which becomes detectable by the sensitivity to fingerprints, naturally involves a reduction of the reproducibility of the reproduction layer with water. However, aqueous solutions of salts, which preferably further contain wetting agents or small concentrations of organic solvents, are generally suitable for development.

Le developers used in the individual examples are listed in the last column of Table 3 which contains the details of the examples.

Developer I means: 100 parts by volume of water, 5 parts by weight of sodium lauryl sulfate ($ 50) (sodium sulfate of the residue), and 3 parts by weight of tartaric acid.

61 143821

Developer II means: Developer I to which 2 parts by weight of benzyl alcohol is added.

The preparation of the copy shows that the reproduction layers obtained using the new condensation products are up to four times as light sensitive as the reproduction layers obtained using the known formaldehyde condensates of the same diazo compounds. The image areas take up ink well to the fullest extent.

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EXAMPLE 28 4.4 parts by weight of diphenylamine-4-diazonium phosphate (Diazo 1, phosphate, Table 1) are dissolved in 300 parts by volume of 96.5 tf phosphoric acid.

A boiling solution of 4.0 parts by weight of 9,10-bis-methoxymethyl-anthracene (Component B1, No. 17, Table 1) in 30 parts by volume of glacial acetic acid is poured into the solution with thorough stirring. The condensation is carried out for 1.5 hours without further heating. The raw condensate is soluble in water without residue. To isolate the condensation product, the condensation mixture is diluted with 150 parts by volume of methanol and the solution is poured into 2,000 volumes of isopropanol with stirring at ca. 65 ° C. The precipitate is filtered off with suction, washed with isopropanol and dried. Yield: 5.4 parts by weight. According to the analysis, the condensate has a content of 24.4 more carbon atoms per minute. molecular diazo compound than the uncondensed diazo compound; this corresponds to approx. 1.5 moles of the second component per mole of diazo compound (C 52.9 tf, N 5, 1 tf, P 11.3 tf; atomic ratio: 36.4: 3: 3).

The examples below show the wide applicability of the new condensation products on different support materials and in different reprographic processes.

In addition to the advantages of the improved oleophilic properties of the exposure products and the improved light sensitivity, which is also repeatedly shown in the following examples, these examples show additional advantages associated with individual groups of mixed condensates.

EXAMPLE 29

An aluminum foil roughened aluminum foil is coated by brushing with a 2 wt. Aqueous solution of the chloride of a condensation product prepared from diazo compound 2 and component No, 14, Table 1. After imaging exposure to light through a negative the foil is developed by drying it over with 1.5 µl of aqueous phosphoric acid and hardening with greasy ink. This results in an effective printing form.

An equally effective printing form is prepared in an analogous manner by applying the same solution to an aluminum mechanical roughened aluminum foil which in a known manner has been "pre-treated with an alkali metal silicate.

Instead of using the chloride of the condensation product, it is also possible to use the corresponding zinc chloride double salt or cadmium chloride double salt. Developer II is suitable for developing.

The condensation product is prepared as follows: 30.2 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table 1) is dissolved in 93.5 parts by volume of 86 fo phosphoric acid.

29.3 parts by weight of finely powdered 4,4-bis-aethoxymethyl-diphenyl ether (Component, No. 14, Table 1) is then added with vigorous stirring, the mixture is stirred for an additional 1.5 hours without heating and finally condensed for 3.5 hours. The clear condensation mixture is dissolved in 500 parts by volume of water (clear solution) and the chloride of the condensation product is precipitated at 40 ° C by the dropwise addition of 220 parts by volume of hydrochloric acid (36 fo HCl diluted with the same volume of water). For purification, the precipitate is dissolved in hot water and the chloride is again precipitated by the addition of hydrochloric acid. The drying is carried out at 30 ° 0 by circulating air in a drying chamber. Yield: 38.7 parts by weight (C 65.7 f, B 8.1 fo, 01 8.6 f> atomic ratio 28.5: 3: 1.26).

EXAMPLE 30

An aluminum foil roughened by metal brushes and pre-treated with polyvinylphosphonic acid according to US Patent No. 3,220,832 is coated with the following coating solutions and the layers are dried: 65 U3S21 1 2 3 4 5 6 diazo-formaldehyde condensate 0 4 - - - 0.04 0.13 (parts by weight) of mixed condensate - 0.34 0.34 0.34 0.31 0.23 (parts by weight) ++ ^ phosphoric acid, moles per, 2.8 0 0.5 2.8 0.5 2.8 moles of diazo groups In each case, dissolve in 100 parts by volume ethylene glycol monomethyl ether / butyl acetate (8: 2 parts by volume).

+) formaldehyde condensate from diazo compound 2, chloride, (Table I) in 2.8 moles of phosphoric acid, analogous to Example 1 of U.S.A. patent no. 3.406.159 ++) The mixed condensate (chloride) is the same as in Example 29.

After exposure to a three-phase carbon bulb with 2.4 kW below a negative original and a 21-step gray wedge with density increments of 0.15, the same amount of cured wedge step is obtained for all layers (judged by developing and blackening with grease black) when apply the following exposure times: 1 2 3 4 5 6

Duration of exposure in relative units 70 18 18 35 25 50

The developer in case 1 is water, in case 2 to 6 developer II (see examples 22 to 28). To further increase the printing surface, it is possible to reinforce the printing molds thus obtained with suitable varnishes, e.g. the products described in U.S.A. Patent Nos. 3,313,233, especially Example 1, and 2,754,279 ·

After storage for 8 weeks at 52 ° C, the pre-sensitized materials 1, 4 and 6 can still be lightly processed. The layers containing less phosphoric acid or no phosphoric acid have less storage stability under these conditions.

By increasing the printing layer of the printing forms made from the reproduction material, it is also possible to provide the reproduction layer with a coating of water-insoluble polymers, e.g. as described in U.S.A. Patent No. 3,136,637.

It is also possible to further add dyes, pigments and diazo compounds to such coatings, e.g. the compounds disclosed in U.S.A. Patent Nos. 3,180,732 and 3,175,906. A similar working method is described in U.S.A. Patent No. 3,522,042, corresponding to French Patent No. 1,538,092.

As a mixed condensate, a product prepared from 1 mole of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, tabeil) and 1.5 moles of 4,4'-bis-methoxymethyl can also be used. -diphenyl ether (Component B1, No. 15, Table 1), analogous to Example 29, and separated as the chloride. In this case, even shorter exposure times can be coped with, but the addition of more phosphoric acid is necessary to achieve layers with the same storage stability.

EXAMPLE 31

The aluminum substrate used in Example 30, previously coated with polyvinylphosphonic acid, is coated with the following solution: 1.25 parts by weight of a crude condensate of 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde in phosphoric acid (molar ratio 1: 1: 2, 8), Condensation for 40 hours at 40 ° C, 10.0 parts by weight of the condensation product described in Example 8, 5.1 parts by weight 85 $ phosphoric acid, 2400.0 parts by weight of ethylene glycol monomethyl ether, and 580.0 parts by weight of butyl acetate.

67 143 * 21

The coating is dried for 2 minutes at 100 ° C.

The sensitivity of the reproductive layers to fingerprints during treatment is significantly reduced, as compared to a reproduction layer containing only the first stated, raw condensate, and the light sensitivity of the new reproduction layer is somewhat more than twice the light sensitivity of a layer which only contains the first specified raw condensate. Development of the exposed reproduction material can be carried out with developer II described in Examples 22 to 28. The printing form can then be lacquered with the conventional lacquers, e.g. those described in the preceding example, and the printing thereof may be further increased.

The reproduction material produced according to this example has an excellent shelf life. Plates stored for three years in the absence of light at room temperature (not air-conditioned) can still be processed into printing molds according to the above method.

EXAMPLE 32

A paper printing sheet manufactured according to what is described in U.S.A. Patent No. 2,778,735 is coated with the following solution by brushing and dryingB.

Coating solution: 2 parts by weight of the mixed condensation product described in Example 12 is dissolved in 97 parts by weight of warm water. The solution is reacted with 0.53 parts by weight of sodium sulfite and kept under stirring for 1 hour. The somewhat cloudy solution is used directly for coating the substrate.

After imaging exposure of the reproduction material and evocation with water, a very satisfactory oleophilic image is obtained which has a good uptake ability for the greasy ink. The image areas have better oleophilic properties than those obtained by the same working method, but using a commercial diazo resin (diphenylamine-4-diazonium sulfate condensed in 80% sulfuric acid with formaldehyde and precipitated as the zinc chloride double salt). .

EXAMPLE 33

An aluminum foil roughened aluminum foil is coated with a solution of the following ingredients: 2.0 parts by weight of the diazocondensate described in Example 12, 80.0 parts by volume of water, 0.284 parts by weight of zinc chloride, 0.527 parts by weight of sodium sulfite, and 20.0 parts by volume of dimethylformamide.

After imaging exposure under a line negative, the film is developed with developer II described in Examples 22 to 28, purified with water, treated with 1 µg of phosphoric acid and inked with greasy ink. An effective printing form is obtained whose image areas have better oleophilic properties than the image areas of a printing mold made in the same way using the same derivative of a commercial diazo resin (see Example 32).

When using the above coating solution, it is also possible to obtain offset printing molds of mechanically roughened aluminum treated in known manner with aqueous solution of alkali metal silicate, whereby the development is carried out in the same way.

EXAMPLE 34

A polyethylene terephthalate film roughened by sand blasting is coated with the following finely divided coating mixture and dried: 1.25 parts by weight of poly-N-vinyl-N-methylacetamide (K value 91), 0.5 parts by weight of Heliogen Blue B powder ( Cl 74,160), 0.1 parts by weight of finely divided silica ("Aerosir MOX 170), 0.375 parts by weight of the diazocondensate described below, 18.0 parts by weight of water, and 1.6 parts by weight of ethanol.

After image exposure under a negative, a blue-colored positive brown-yellow image is obtained by purifying with water. The diazocondensate is prepared as follows: 32.4 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table I) is 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. 9, Table 1) is added with vigorous stirring over 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 crude condensate is soluble in water without residue.

To separate the condensation product, the condensation mixture is dissolved in 1000 parts by volume of water, the product is precipitated by the addition of 60 parts by volume 45 in aqueous hydrogen bromide and the precipitate is filtered off by suction.

70 143621

For purification, the product is redissolved in 1000 parts by volume of water, the temperature of which is 50 ° C, and the product is again precipitated by the addition of hydrogen bromide, washed with 1 in aqueous hydrogen bromide and the filtered product air dried. Yield: 42 parts by weight (C $ 53.1, U $ 7.8, Br 18.6%; atomic ratio 23.8: 3: 1.25)

Ca. 1.1 moles of the second component are present per mole of diazo compound.

EXAMPLE 35

The same substrate as in Example 34 is coated with the following mixture: 4.0 parts by weight of polyvinylpyrrolidone (K value 90), 1.0 parts by weight of the diazocondensate described in Example 29, 0.1 parts by weight of crystal violet (Cl 42.555), 12.0 parts by weight of ethanol, and 88.0 parts by weight of water.

After image exposure during a negative, a blue-colored, positive, brown-yellow image is obtained by rinsing with water.

EXAMPLE 36

An aluminum foil roughened aluminum foil is coated with the coating solution described in Example 35.

After image exposure during a positive, the layers which are not cured by the action of light are removed by dissolution by water. After drying, the substrate surface exposed in the image areas upon development is lightly etched in conventional manner and finally coated with the lacquer described in TJ.S.A, Patent No. 3,374,734. A positive printing form is obtained by blackening and removing the cured reproductive layer by rinsing with warm, dilute phosphoric acid.

EXAMPLE 37

A polyethylene terephthalate film provided with a hydrophilic matt layer of finely divided silica, titanium dioxide and cured polyvinyl alcohol, over series s with a 0.4% solution of the naphthalene-1-sulfonate of the condensation product described in Example 34. solvent used is a mixture of 80 parts by weight of ethylene glycol monomethyl ether and 20 parts by weight of butyl acetate.

After visual exposure during a negative, the development is carried out by over-drying with developer I or II (Examples 22 to 28) and the plate moistened with the developer is hardened with greasy ink. A positive form of printing appears.

As a substrate, a sufficiently water-resistant paper film can also be used with a hydrophilic, matte layer of barite, kaolin and finely divided silica in hardened polyvinyl alcohol. However, the coating solution used in this case is a 2% solution of the condensation product in alcohol. After imaging exposure through a negative, a positive printing form is obtained by means of developer I.

EXAMPLE 38

A nylon fabric conventionally used in screen printing and which has been fixed in a frame is coated by a sharp knife with the mixture specified below. The coating is dried with a cold air stream.

90.0 parts by weight of a polyvinyl alcohol, hydrolyzed to 98%, of which a 4% solution in water at 20 ° C has a viscosity of 8 to 11 cp., 72 US621 423.0 parts by weight of water, 15.0 'parts by weight of finely divided silica (' kerosil 'MOX) 170), 30.0 parts by weight of dibutyl phthalate, 7.5 parts by weight of the condensate described in Example 29, and 0.5 parts by weight of crystal violet (01 42,555).

The screen is exposed for 6 minutes with a 5 kW xenon pulse lamp at a distance of 1 m. A screen printing form is obtained by cleaning with cold water.

EXAMPLE 39

A zinc plate (2 mm thick) which was poorly etched superficially by treatment with dilute nitric acid is coated on a rotating plate (80 rpm) with the coating solution given below. The coating is provisionally dried and then dried for 2 minutes at 100 ° C.

Coating solution: 3.0 parts by weight of the condensate described in Example 29, 10.0 parts by weight of a phenol-formaldehyde resin of the novolak type, melting range 75 to 83 ° C (* η1ηονοϊ1 320 K), 60.0 parts by weight of ethylene glycol monomethyl ether, and 40.0 parts by weight of dimethylformamide.

After storage for 3 days at room temperature, the reproduction material is exposed for 6 minutes under a line positive with a tube-exposing device CPrintaphot1) containing 6 superactinic luminis c end tubes (Philips-type TLA 20 W / 05) mounted 73 148 * * 1 at a distance of 7 cm from the reproduction material. The development is carried out with a 2 wt.

The copied plate is heated to 180 ° C for 15 minutes and then etched with 5% by weight nitric acid. This results in a positive relief printing form.

EXAMPLE 40

A resin film laminated to a thin copper foil is cleaned on the copper surface with an abrasive, purified with acetone and then coated with the solution described in Example 39, and then the coating is dried. The plate is exposed under a positive representing a circuit diagram and developed in the manner described in Example 39. A copied circuit (positive) is obtained by etching the copper into the exposed areas using 40 # aqueous ferric chloride solution.

EXAMPLE 41

An aluminum foil roughened with metal brushes and coated with polyvinylphosphonic acid 1 according to U.S.A. Patent No. 3,220,832 is coated with the following coating solution, and the coating is dried: 0.4 parts by weight of the condensation product described below, 80.0 parts by weight of ethylene glycol monomethyl ether, and 20.0 parts by weight of butyl acetate.

Evolution of the material and image exposure during a negative to obtain a positive printing form are carried out as indicated in Example 30.

74 143 * 21

To prepare the condensation product, 12.9 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (Component B1 '# 15, Table 1) is added 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 is carried out at 40 ° C for 24 hours. . After decanting the aqueous mother liquor, this mass is kneaded with other 100 parts by volume of 2N hydrochloric acid and the aqueous phase is decanted again.

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

EXAMPLE 42

Aluminum substrates which have been roughened electrolytically and then anodized and pre-treated with polyvinylphosphonic acid according to U.S.A. No. 3,220,832, all are coated with one of the following coating solutions and the coating is dried.

(a) (b) (c) (d) parts by weight parts by weight parts by weight

Mixed condensate (see below) 1.1 1.1 1.1 1.1

Diazocondensate according to 0.6 0.6 0.6 0.6 U.S.A. Patent No. 3,406,159 Example 1, adjusted to 2.8 molecules of phosphoric acid per

diazo group p-toluenesulfonic acid, HgO 0.2 0.2 0.2 0.2

Resin 1 0.3 75 143821 (a) (b) (c) (4) parts by weight parts by weight parts by weight

Resin 2 - 5.0

Resin 3 --- 0.1

Resin 4 - - 0.1

Resin 5 - - - 3.0

Ethylene glycol mono-100 100 100 100 methyl ether / butyl-volume-volume-volume-acetate 8: 2 parts parts parts parts (parts by volume)

The mixed condensate is prepared as follows: 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table 1) is dissolved in 170 parts by weight of $ 85 phosphoric acid, 25.8 parts by weight of 4.4, bis-methoxymethyl -diphenyl ether (Component B

15, Table 1) is added dropwise and the condensation is carried out for 5 hours at 40 ° C. After dilution with 250 parts by volume of water, the chloride of the condensation product is precipitated by the addition of 220 parts by volume of semi-concentrated hydrochloric acid. The chloride of the condensate is dissolved again in water and the mesitylene sulfonate of the diazo compound is prepared using the sodium salt of mesitylene sulfonic acid, which mesitylene sulfonate is a water-soluble precipitate. Yield: 53 parts by weight (C 76.2 #, N 6.3 $>, S 4.6 atomic ratio 37.3: 3: 0.96).

The condensation product has a homologous polymeric structure. A mixed condensate prepared in substantially the same way (condensation and work-up conditions are described below) is converted by the 1-phenyl-3-methyl-5-pyrazolone to the azo dye whose molecular weight is determined. The dye is further fractionated and the average molecular weight of the individual fractions determined.

Preparation of the mixed condensate: 3-methoxy-diphenylamine ~ 4-diazonium sulfate 32.3 parts by weight 86io phosphoric acid 170.0 parts by weight 4,4'-bis-methoxymethyl diphenyl ether (98 to 99 $>) 25.8 parts by weight 76 U3321

"Duration of condensation 4.5 hours at 40 ° C

Separation as the chloride twice with hydrochloric acid

Final form of separation salt of mesitylene sulfonic acid

Yield 55.0 parts by weight (0 67.2 in, N 6.4 S 4.5 1 », P 0.2 #, Cl 0.23 00H3 4.9 ί / atomic ratio C * N: S: OCH 5 = 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 this product in ethylene glycol monomethyl ether, with the addition of NH 2 and phenylmethylpyrazolone.

The average molecular weight of the dye is determined by osmometric determination of the vapor pressure of a solution in chloroform and is 3180.

For fractionation, chloroform solutions of the dye are applied to aluminum foils and dried. These thin dye layers are then extracted with solvent (chloroform) and non-solvent (methanol) mixtures, starting with low solvent solvent mixtures and continuing with growing solubility mixtures. Details of the test results and the average molecular weights of the individual fractions are given in the following table:

Fraction Chloroform Methanol Fraction N Average molecular weight

No. (ml) (ml) Amount # (mg) 1 - 150.0 3.2 2 60.0 90.0 13.9 3 67.5 82.5 65.8 11.8 1 115 4 75.0 75, 0 89.6 11.8 1 451 5 82.5 67.5 91.2 11.5 1 828 6 90.0 60.0 152.6 11.3 2.530 7 97.5 52.5 247.3 10 , 8 4 012 8 105.0 45.0 429.4 10.6 6 165 9 112.5 37.5 156.6 10.3 6 674 77 U3621

The following resins are used:

Resin 1: Epoxy resin on hasis of bis-phenol-A-epichlorohydrin.

mp 64 to 76 ° C, average molecular weight 900.

Resin 2: Polyvinyl butyral containing 69 to 71 $ polyvinyl butyral, 1% polyvinyl acetate and 24 to 27% polyvinyl alcohol units; the viscosity of a 6 $ solution at 20 ° C is 4 to 6 cp. (DIN 53015) ·

Resin 3: Non-softened urea, resin with approximate acid number 2 fResamine "106 P),

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

Resin 5: Average molecular weight polyvinyl acetate 10000O.

The plates are imaged for 2 minutes under a negative with a 5 kW xenon pulse lamp at a distance of 1 m and then transformed into printing molds by drying them with a developer of the composition below, whereby the printing molds give rise to large print runs, especially in the case of samples (a), (b) and (d).

The developer used is a mixture of 50.0 parts by weight of water, 15.0 parts by weight of isopropanol, 20.0 parts by weight of n-propanol, 12.5 parts by weight of n-propyl acetate, 1.5 parts by weight of polyacrylic acid and 1.5 parts by weight of acetic acid.

It is also possible to reinforce the printing shapes in known manner by varnishing and in this way to increase the size of the printing bed.

78 tsp

Appropriate layers can also be obtained by avoiding the diazocondensate in the coating solutions (a) to (d) of U.S.A. patent No. 3,406,159 'Example 1, and by replacing the toluene sulfonic acid with approx. 0.5 to 2 moles of phosphoric acid per mole of diazo group.

Instead of the "mixed condensate" used, it is also possible to use "mixed condensates with the same" constituents but with other structural conditions, for example the following: (1) (2) 3 * -methoxy-diphenylamine-4 - 100 parts by weight 64.6 parts by weight of diazonium sulfate (Diazo 2, sulfate, Table 1) 85 in phosphoric acid 527 parts by weight 340 parts by weight 4,4'-bis-methozymethyl- 60 parts by weight 77,4 parts by weight of diphenyl ether (Component Bj, no. 15) Table l)

Condensation duration 6 hours at 4.5 hours at 40 ° C, 40 ° 0 overnight

The precipitate twice as the chloride and finally separated as the salt by mesitylene sulmsitylensulphonic acid phonic acid

Yield 140.0 parts by weight 126.0 parts by weight

Analysis C: 66.5 C: 69.2 # N: 6.8 f N: 4.9 # S: 5.2% S: 4.0 # 0CH3: - 0CH3: 4.9 1 °

Atomic ratio 34.2: 3: 1 49.5: 3: 1.07: 1.35

The average molecular weight of the azo dye of (2) with methylphenylpyrazolone, determined as described above, is' 2390.

EXAMPLE 43

The process is analogous to that of Example 42, but the following solution is employed: 1.0 parts by weight of the mixed condensate described in Example 14 1.6 parts by volume of 1 N hydrochloric acid, 1.0 parts by weight of Resin 2 of Example 42, 0.4 parts by weight of diazocondensate according to the United States Patent No. 3,406,159, Example 1, adjusted to 2.8 molecules of phosphoric acids per slide group, 4.0 parts by volume of water, and: - 96.0 parts by volume of a mixture of ethylene glycol monomethyl ether and volume ratio of 8 s 2.

A highly photosensitive reproduction material is obtained which, by analogy to Example 42, can be further processed into printing forms which give rise to the appearance of high printing stocks.

EXAMPLE 44

An aluminum support pre-coated with polyphenylphosphonic acid according to U.S.A. U.S. Patent No. 3,220,832 and roughened by means of metal brushes are coated with the following coating solution: 0.4 parts by weight of the mixed condensates described below, 0.0505 parts by weight of p-toluenesulfonic acid, 0.080 parts by weight of 4-methoxy ~ 4'- dimethylamino-azobenzene, and 100.0 parts by volume of a mixture of ethylene glycol monomethyl ether and butyl acetate in a volume ratio of 8 {2.

A highly photosensitive reproduction material appears.

80 143621

By pictorial exposure through a negative, a clearly visible positive contrast image is obtained. Evolution to obtain a printing form can be performed with developer I (Examples 22 to 28).

The mixed condensates are prepared analogously to Example 42 as follows: (a) (b) 86 ia phosphoric acid 120 parts by weight 170 parts by weight 4-methoxy-diphenylamine 32.3 parts by weight 32.3 parts by weight. "4'Diazonium Sulfate (Diazo 3" Table 1) 4,4'-Bis-methoxymethyl 12.9 parts by weight 25.8 parts by weight of diphenyloxide (Component B- No. 15, Table 1)

Duration of condensation (40 ° C) 20 hours 3.5 hours.

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

(a) (b)

Yield: 22.1 parts by weight 44.5 parts by weight

To include obtain 0: IT in the condensation product: 29.5: 3 34.2: 3

Analysis: C 64.2% 56.6 # - F 7.6 fo 6.7 *.

According to the analysis, it can be assumed that the mixed condensate in case (a) contains ca. 1.2, and in case (b) approx. 1.5 moles of the second component per mole of diazo compound.

EXAMPLE 45 According to the method described in Example 39, a zinc plate with the following coating solution is coated: ormaldehyde resin used in Example 39, 6.0 parts by weight of ethylene glycol monomethyl ether, and 4.0 parts by weight of dimethylformamide.

A positive relief printing form is obtained by further processing as set forth in Example 39.

Examples 46 to 48

Examples 46 to 48 show the suitability of a number of other mixed condensates as constituents of photosensitive reproduction layers of reproduction materials useful for photomechanical production of offset printing forms. The supports used are aluminum foils roughened using metal brushes and pre-treated according to U.S.A. Patent No. 3,220,832 with polyvinyl phosphonic acid.

The coating solutions used as well as the details of the mixed condensates used are given in the following Table 4.

Referring to Example 46, it should be noted that the reproduction layer has an excellent light sensitivity and in addition an excellent storage stability. Thus, it is possible to copy and develop the pre-sensitized printing plate after storage for 8 hours at 100 ° 0, without the non-imaging areas tending to foam.

Referring to Example 48, it should be noted that a printing form can be produced even after a very short exposure to light. Thus, it is sufficient to expose the copy for 10 to 20 seconds with a 5 kW xenon pulse lamp at a distance of 1 m. The printing form can be enhanced with the usual varnishes.

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83 143621

The preparation of the diazocondensates used in Examples 46 to 48 is described below, EXAMPLE 46

The process is similar to that of Example 42, but the following substances are used: 16.2 parts by weight of 3-methoxy-diphenylamine ~ 4-diazonium sulfate (Diazo 2, sulfate, Table 1), 36 parts by volume 86% phosphoric acid, 6.86 parts by weight of 4,4'-bis-methoxy-methyl-diphenylsulfide (Component B ^ No. 21, Table 1). The condensation is carried out for 1.5 hours at room temperature and 20 hours at 40 ° C.

The crude condensate is dissolved in water and the condensation product is precipitated from this solution by the addition of hydrochloric acid. The viscous precipitate is redissolved in water and is precipitated by addition of hydrochloric acid. The precipitate is redissolved in water and from this solution the corresponding sulfonate of the condensation product is precipitated by the sodium salt of naphthalene-2-sulfonic acid.

After drying at 40 ° C, the yield is 12.9 parts by weight (C 64.7 N 6.4 $, S 9.1 in ° / atomic ratio 35.4: 3 in 1.86).

Approximately 0.86 moles of the second component is then present per day. mole of diazo compound.

A similar good result is obtained under the working conditions set forth in Example 46 when using a condensation product made from the same constituents but in different quantities.

In this case, the condensation takes place as follows: 16.2 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table 1), 50 parts by volume of 86 $ phosphoric acid, and 13.7 parts by weight of 4,4'-bis -Methoxy-methyl-diphenylsulfide (Component B1 no. 21, Table 1) is condensed for 4 hours at 40 ° C. The crude condensate is dissolved in water, clarified by activated carbon, the product is precipitated with a solution of sodium chloride. 84 143621 is separated and Tasked with a solution of sodium chloride. The chloride is dissolved again in Tooth, and the condensate is precipitated as salt of mesitylene sulfonic acid. Yield: 24.8 Cover parts. (0 65.9 $, N 6.5 S 10.2 µS, atomic ratio 55.4: 5: 2.05)

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

EXAMPLE 47 8.3 Cover Parts Diazo Compound 5 (Sulfate, Slight Thread; N 6.2 $>) is dissolved in 60 Tolumene Parts 93 # Phosphoric Acid and 5.2 Cover Parts 4,4'-Bis-Methoxymethyl Diphenyl Ether (Component No. 15, Table 1) add dropTis within 12 minutes. The mixture is kept under stirring for one hour without further heating and for two hours at 40 ° C.

The clear, tooth-soluble, raw condensate is dissolved in Tooth, the condensation product is precipitated by the addition of Dental Hydrochloric Acid, and the precipitate is separated again with hydrochloric acid, after having dissolved it again in Fresh Tooth. After drying, 10 parts of the chloride of the condensation product is obtained (C 62.3 ΪΓ 4.3 in ³ / atom ratio 33.8: 2).

Bette means that there are approx. 1.1 moles of the second component present per mole of diazo compound.

EXAMPLE 48 0.94 Cover parts of diazo compound Ko. 10 (zinc chloride double salt, K 8.9 in °) is dissolved in 10 toluene portions of 92 $ phosphoric acid and dry air is passed through the mixture until no more hydrogen chloride escapes, i.e. until the mixture is essentially free of chloride ions.

85 143921

0.52 parts by weight of 4,4'-bis-methoxymethyl diphenyl ether (Component No. 15, Table 1) is introduced and the condensation is carried out for 15 hours at room temperature. The condensation mixture is dissolved in 100 parts by volume of water and clarified with activated charcoal, and the sulfonate of the diazo compound is precipitated with 0.92 parts by weight of the sodium salt of naphthalene-2-sulfonic acid in 100 parts by volume of water. Yield after drying: 0.9 parts by weight (C 64.4 N 3.8 fo, S 4.8 fa ·, atomic ratio 59.3: 3: 1.66) #

The analysis shows that about 0.66 mole of the sodium salt of the sulfonic acid has been entrained during the precipitation. Given this fact, the result of the analysis is a condensation ratio of diazo compound to the second component of 1: 1.75.

EXAMPLE 49

This example demonstrates that not only the mixed condensates in the form of the diazonium salts, but in principle also the diazoamino compounds which can be prepared from these substances can be used as reaction-sensitive components of reproduction layers and in some cases reproduction layers in reaction with secondary amines. , which is suitable for producing yellow-brown images.

1 part by weight of the mixed condensate described in Example 29 prepared with the equivalent amount of component no. 15, however, is dissolved in 10 parts by volume of water and 0.39 parts by weight of morpholine is added. The gelatinous precipitate is filtered off by suction, washed quickly with water and then introduced into 100 parts by volume of dimethylformamide, in which 2 parts by weight of polyvinylmethylacetamide (K value 91) was previously dissolved. The resulting coating solution is applied with a rotating means on electrolytic aluminum backing, and the coating is then dried. After image exposure, the areas not affected by light are removed with water and after drying, the cross-linked image areas are stained using an aqueous solution of crystal violet.

EXAMPLE 50

A sandblasted polyester film was coated with a rotary member with an aqueous solution containing 0.55 µg of the mixed condensate described below and 5.5 µl polyvinylmethylacetamide (K value 91) * In case of exposure, the areas not affected by the light are removed with water and, after drying, the cross-linked image areas are stained with an aqueous solution of orystal violet.

Lightly mixed condensate is prepared as follows: 6.5 parts by weight of 3-methoxy-diphenylamine-4-diazonium phosphate (Diazo 2, phosphate) is dissolved in 50 parts by volume 86 of phosphoric acid, then 3.9 parts by weight of hexa-methoxymethyl-melamine ( Component B1 # 2, tabil) with vigorous stirring and the mixture is condensed for 20 hours at room temperature.

The condensation product is separated from the crude condensate by precipitation with isopropanol. Yield: 9 »1 parts by weight (C 32.9 f ° in H 11.6 ¢, P 14.9 $) · According to the analysis, the product contains elements C and I in a ratio of approx. 10: 3.

EXAMPLE 51

Len paper support used in Example 32 is coated by brushing with the following coating solution; 2.0 parts by weight of the condensate described below, 0.75 parts by weight 86 fo phosphoric acid, and 100.0 parts by volume of water.

After drying, the reproduction layer is exposed under a negative original and then dried over with water. Thus, clay is obtained in a highly ink-absorbing, positive form.

The mixed condensate is prepared as follows: 87 143621 15.42 parts by weight of diphenylamine-4-diazonium sulfate (Dlazo 1, sulfate, Table 1) is dissolved in 100 parts by volume of 80 $> sulfuric acid. With vigorous stirring, 8.83 parts by weight of finely powdered dimethylol succinic diamide (Component B + # 1, Table 1) is introduced while cooling to maintain a temperature of 25 ° 0. 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 the addition of 80 parts by volume of a 50 zinc chloride solution. The precipitate is separated, dissolved in 500 parts by volume of water at 50 ° 0, precipitated again by the addition of 50 parts by volume of a $ 50 zinc chloride solution, filtered off by suction and dried under reduced pressure. Yield: 18.6 parts by weight. (0 40.8 In 11.6 96, ND 5.35 where ND is the content of diazo nitrogen as opposed to the total nitrogen content, N; atomic ratio: 17.8: 4.3?: 2), the analysis shows that a different component is incorporated, but the carbonic amide groups appear to have been hydrolyzed to some extent.

EXAMPLE 52

This example demonstrates the superiority of certain mixed condensates in comparison to known diazo-diphenylamine-formaldehyde condensates for hydrophilic curing of water-soluble colloids. Hydrophilic cured colloids are important for a speoiel type of positive-working, pre-sensitized printing plates (cf. U.S. Pat. No. 3,085,008). With plates of this type, a mixture of a hydrophilic polymer and a diazo compound is coated on the surface of a substrate which has been made oleophilic. During imaging exposure under a positive master, the colloid becomes cross-linked and anchored to the oleophilic support. The unexposed areas of the layer are then removed, and the oleophilic support is exposed in these areas and will represent the image areas transmitting the ink. Thus, a positive printing form is obtained.

Since the light decomposition products of known formaldehyde condensates have oleophilic properties, the proportion of diazocondensate should not be too high. using a high proportion of diazo compound.

The best example shows a comparison between two printing plates of this type, wherein a) one was prepared with the chloride of the formaldehyde condensate of diphenylamine-4-diazonium chloride prepared in accordance with Example 1 of TT.S.A. Patent No. 3,311,605, b) while the other was prepared with the chloride of a mixed condensate of diphenylamine-4-diazonium salt and dimethylolurine, prepared as set forth below.

A pre-sensitized pianographic printing plate made in accordance with U.S.A. Patent No. 3,396,019 to Example 1 is completely exposed without the use of an original, e.g. under an arc lamp. The plate is then rinsed with water and dried. The plate is cut into two halves, one of which is coated with coating solution 1 and the other with coating solution 2 described below and the coatings are then dried.

1. 0.125 parts by weight of the condensate described under a), 0.38 parts by weight of polyacrylamide (Cyanamer *? 250), and 100.0 parts by volume of water.

2. 0.125 parts by weight of the mixed condensate described under b), 0.38 parts by weight of polyacrylamine (Cyanamer4P 250), and 100.0 parts by volume of water.

After pictorial exposure during a positive original, the plates are developed by drying them with water, and then they are blackened with greasy ink.

89 143621

While in case 1 a positive-print form is exhibited which exhibits extremely high foaming in the non-imaging areas, solution 2 produces a positive pianographic printing plate which, apart from minor overcoating, is fully acceptable and if not imaging areas (hardened hydrophilic colloid) do not accept greasy ink.

The mixed condensate prepared in this example is prepared as follows: 23.2 parts by weight of diphenylamine-4-diazonium chloride (Diazo 1, chloride,

Table 1) is dissolved in 50 parts by volume of a 36.5 tf aqueous hydrochloric acid solution. With vigorous stirring, 12 parts by weight of finely powdered dimethylol urea (Component No. 3, Table 1) is introduced into solution and stirring is continued, first for 3 hours at room temperature, and then for 1 hour at 40 ° C. over in a refrigerator, dilute the mixture with 80 parts by volume of methanol and then introduce it into 1200 parts by volume of isopropanol. The precipitate is filtered off by suction, washed twice, quickly each time, with 400 parts by volume of isopropanol, and dried under reduced pressure at 40 ° C. Yield: 15 parts by weight (chloride). There is thus obtained a yellow, water-soluble powder which according to analysis contains approx. 0.9 molecules of urea per diazo group (E 19.5%, ND (diazo-N) 8.2 tf, Cl 10.8 tf; atomic ratio: 4.8: 2: 1.04).

EXAMPLE 53

A trim metal plate consisting of layers of aluminum, copper and chromium is covered with a coating solution of the composition specified below, to which excess solution is allowed to drain and the plate is dried.

2 parts by weight of the chloride of the mixed condensate described below, 1 part by weight of polyvinyl alcohol (residual acetyl content 12 tf, viscosity of a 4 tf aqueous solution 6.5 to 8.8 cp at 20 ° C), and 50 parts by volume of water .

90 143621

After imaging exposure under a positive original, the plate is developed by developer II described in Examples 22 to 28, and then the clirome is etched away 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 of zinc chloride, and about 1.5 to 3% by weight of ammonium chloride, tartaric acid and concentrated hydrochloric acid, for the chromium layer. The plate is decorated by treatment with a paste consisting of powdered lime and dimethylformamide. Per a multimetal printing form is obtained, by means of which very large prints can be printed.

The mixed diazocondensate is prepared in a similar manner to that described in Example 29, however, using the following reactants and the following reaction conditions: 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate, Table 1); 170.0 parts by weight of 86 # phosphoric acid, and 64.4 parts by weight of methoxymethyl diphenyl ether prepared from CMDPO-32 (Component No. 22; see below).

The pulp is condensed for 4.5 hours at 40 ° C, filtered for clarity, precipitated by hydrochloric acid, dissolved again and precipitated with hydrochloric acid. Yield: 44 parts by weight.

According to the manufacturer's information (cf. US Patent No. 3,316,186, column 3, lines 41 to 64), the chloromethyl-red diphenyl ether CMDPO-32 has a degree of CE ^ Cl of 2.8 and consists of the following components: , 4'-dichloromethyl diphenyl ether 1.9 # 4,4'-dichloro methyl methyl diphenyl ether 8,6 # 2,2 *, 4'-tri-chloromethyl diphenyl ether 17.0 # 2,4,4 ' tri-chloro-ethyl-diphenyl ether 72.0 # 2.2 ', 4,4'-tetra-chloromethyl-diphenyl ether below 2.0 #.

The ether mixture obtained by substituting halogen atoms with methoxy groups had a methoxy content of 28.9 #. It was used to prepare a condensation product whose elemental analysis had the following values: (C 67.5 i, TU 4.4 f, Cl (total) 4.3 f>, Cl (ionogenic) 3.8 f , OCH ^ 12.7 1% atomic ratio: 53.6: 3: 1.16: 1, 03: 3.92).

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

A reproducible material which can also be produced with good results is prepared by coating the same substrate with a coating solution of the following composition and by drying the coating: 1 part by weight of the mixed condensate described in Example 29 2 parts by weight of the polyvinyl alcohol which is as stated above in this example, and 50 parts by volume of water.

After imaging exposure, the plate is evoked by purification with water. Further processing to form a multimetal printing form is carried out as described at the beginning of this example.

Instead of a support consisting of layers of aluminum, copper and chrome, a brass foil coated with a thin chrome layer can be used.

EXAMPLE 54

A copper plate is immersed for a few seconds in a bath of a 1 to 2f ferric chloride solution, purified with water, cleaned with powdered lime, cleaned again and then dried.

Then a solution of 8 parts by weight of the mixed condensate described below is poured into 100 parts by volume of a mixture of 8 parts by volume of ethylene-glycol monomethyl ether and 2 parts by volume of butyl acetate over the plate, and the coating is dried by blowing hot air thereon.

After imaging exposure under a positive screen original, the plate is dried over with a 10 µl aqueous solution of n-propanol for a few seconds and developed with the developer I used in Examples 22 to 28 until the reproduction layer is removed from the unexposed areas.

After drying, the plate is etched in a normal manner with a 40 µl iron III chloride solution. Hereby a halftone engraving form is obtained.

One mixed condensate is prepared as described in Example 53, however, using the following ingredients and conditions: 32.5 parts by weight of diazo 2, sulfate (Table 1), 170.0 parts by weight 86 of phosphoric acid, and 32.3 parts by weight of component Uo. 22 (Table 1).

The reaction mixture is condensed for 4.5 hours at 40 ° C, the condensation product is precipitated by the addition of a solution of sodium chloride, dissolved again and precipitated again with a solution of sodium chloride. A final precipitate is made in the form of the mesitylene sulfonate. Yield: 55.7 parts by weight (0 66.7 f, N 5.8 f, S 4.7 f, OCH 3 7.8 f; atomic ratio: 40.2: 3: 1.06: 1.82).

The result of the analysis shows that this condensate also contains reactive methoxymethyl groups in significant quantities.

By the method described in Example 40, printed circuits can be prepared using the same coating mixture.

Examples 55 to 67

Some examples show the suitability of a series of mixed condensates made from various components and separated into different forms (photosensitive sulfonic acids and polyfunctional sulfonic acids) for photosensitive reproduction layers useful in photomechanical production of pianographic printing plates.

Surprisingly, the precipitated product of the polyfunctional mixed condensate and the bivalent sulfonic acids used in Examples 60 and 61 is readily soluble in organic solvents.

Table 5 contains the data relating to the mixed condensates used, the coating solutions and the development.

In some cases, phosphoric acid was added to the coating solutions. The addition of phosphoric acid, e.g. even in amounts from 0.1 to 0.3 moles per mole diazo group, has a beneficial influence on the shelf life of the coated materials and their developing properties.

After pictorial exposure during a negative, an image becomes clearly visible; this image is usually teal, but more brown in the case of example 60.

The development can be carried out using one of the developers I or II described in Examples 22 to 28.

After hardening with greasy ink, printing plates emerge from which a large number of error-free prints can be produced. The printing pad can be significantly increased by reinforcing the thoroughly developed printing plates with a conventional varnish.

The printing plates coated in accordance with Examples 55 to 62 are more photosensitive than those prepared using the formaldehyde condensate of the diazo compound described in Example 1 of U.S.A. Patent No. 3,406,159 ·

The major increase in light sensitivity is achieved in connection with Examples 59, 64 and 65, the materials of Examples 64 and 65 being particularly advantageous because of their easier synthesis and the increased solubility of the products. The storage durability of the printing plates made with the two last mentioned materials, 94 H3621 is remarkable.

The support used in Examples 55 to 65 was an aluminum foil which had been roughened electrolytically, then anodized and finally treated with pblyvinylphosphonic acid.

Examples 66 and 67 used an aluminum foil which had been roughened by metal brushes and then treated with polyvinylphosphonic acid.

In addition to these substrates, a series of substrates can also be used in combination with the reproduction layers prepared on the basis of the condensation products prepared by the process of the invention, which are recommended for the so-called "diazo resin process" which is commercially available diazo resins .

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The diazo compounds used in Examples 55 to 65 are prepared as follows: EXAMPLES 55 and 56

The condensation is carried out as described in Example 29, however, using the following conditions and substrates: 120.0 parts by weight 86 phosphoric acid, 32.2 parts by weight diazo 2, sulfate, and 8.3 parts by weight 1,3-dimethyl-4,6-dimethylol. benzene (Component Bj, No. 9, Table 1).

The mixture is condensed for 20 hours at 40 ° C. In Example 55, half of the mixture is dissolved in water, the condensate is precipitated by the addition of a solution of sodium chloride, the precipitate is dissolved in water and it is precipitated in the form of naphthalene-1. sulfonic acid salt. Yield: 11.5 parts by weight (C 65.5 $, N 8.0 lo, S 6.1 fa atomic ratio: 28.7: 3: 1).

The average molecular weight of the dye produced with phenylmethyl-pyrazolone is 1256. In Example 56, the other half of the crude condensation mixture is dissolved in water and the corresponding hexafluorophosphate is precipitated by the addition of hexafluorophosphoric acid. Yield: 21.2 parts by weight (C 45.4 N 9.2 $> \ atomic ratio: 17.2: 3). The precipitate contains a small amount of non-condensed diazo compound.

Examples 57 and 58

The procedure used in Examples 55 and 56 is repeated, however, using the following substances and compounds: 98.0 parts by weight 86 f> phosphoric acid, 32.3 parts by weight diazo 2, sulfate (Table 1) and 11.1 parts by weight 4 , 6-diisopropyl-1,3-dimethylolbenzene (Component B1, No. 10, Table 1).

The mixture is condensed for 20 hours at 40 ° 0. In Example 57, half of the mixture is dissolved in water, the condensate is precipitated by adding a solution of sodium chloride, the precipitate is dissolved again in water, and then precipitated in the form of the naphthalene-1-sulfonic acid salt, Yield: 13.3 parts by weight (C 66.3 f>, ,5 7.5 f>, S 5.6 f> in atomic ratio: 31: 3: 0.98). The precipitate contains a small amount of non-condensed diazo compound.

The molecular weight of the pyrazolone dye: 1299 *, as in Example 58, dissolves the other half of the mixture in water and the hexafluorophosphate is precipitated from the solution by the addition of hexafluorophosphoric acid. Yield: 11.1 parts by weight (C 52.9 f, H 10.7% atomic ratio: 17.3: 3).

The product contains a small amount of uncondensed diazo compound.

EXAMPLE · 59

The procedure is similar to that described in Example 28, but the following conditions and substances are used: 200.0 parts by volume of 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. 17, Table 1), in 20.0 parts by volume of glacial acetic acid.

The second component is dissolved in boiling glacial acetic acid and the solution is then poured into the diazo solution. The condensation extends over 20 hours at 40 ° C. The condensation product is separated by the chloride. Yield: 2.8 parts by weight (C 51.1 N 7.8 atomic ratio: 23: 3).

Examples 60 and 61

The condensation product is prepared in a similar manner to Example 12, however, using the following conditions and compounds: 240.0 parts by weight of 86 $ phosphoric acid, 64.6 parts by weight of diazo 2, sulfate (Table 1), and 44.4 parts by weight of component B 10 (see Examples 57 - 58).

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

In the first half (Example 60), the condensate is first precipitated with hydrochloric acid to form the chloride, and finally in the form of the 4,4'-diazido-stilbene disulfonic acid salt. Yield: 41.9 parts by weight (C 63.7 #, N $ 12.9, S 4.8% 5 atomic ratio: 70.6: 12.3: 2).

In the second half (Example 61), the condensate is precipitated directly as the 2,6-di-tert-butyl-naptthalene-isulfonic acid salt. Yield: 38.3 parts by weight. (C 68.1 ¢, N 7.7 S 4.9 atomic ratio: 31: 3: 0.835).

EXAMPLE 62

The condensation is carried out as in Examples 60 and 61. The condensate is first precipitated with hydrochloric acid and then with naphthalene-2-sulfonic acid (0 68.3 ¢, N 6.6 $, S 4.9 atomic ratio: 36.2: 3: 100 143621 0.98).

EXAMPLE 63

A process similar to that described in Example 5 is used, however, using the following compounds and conditions: 4.85 parts by weight of diazo 2, phosphate (Table 1), 15.00 parts by volume of methanesulfonic acid (90 $), and 2, 04 parts by weight of 1,5-di-acetoxymethyl-naphthalene (Component B1, No. 11, Table 1).

The condensation is carried out for 2 hours at room temperature. The condensation product is precipitated in the form of the chloride. Yield: 3.2 parts by weight ($ 64.0, U 9.4 atomic ratio: 23.8: 3).

EXAMPLE 64

The condensate described in Example 42 is precipitated in the form of the 2-diazo-1-naphthol-5-sulfonic acid salt and dried over phosphorus pentoxide to constant weight.

EXAMPLE 65 The 1: 1 condensate corresponds to that used in Example 42 to prepare the azo dye to be fractionated.

The second condensate containing 3-methoxy-diphenylamine-4-diazonium salt and the second component at an approximate ratio of 1: 0.67 is prepared analogously to Example 42 according to the following method: 101 U3S21 120.0 parts by weight 86 phosphoric acid, 32.3 parts by weight of diazo 2, sulfate (Table 1), and 12.9 parts by weight of component, No. 15 (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 aqueous chloride. Finally, the condensate is precipitated in the form of the naphthalene-2-sulfonic acid salt. Yield: 35 parts by weight (C 67.0%, N 7.2 $, S 5.6%, P 0.18%, Cl 0.21 atomic ratio: C: N: S = 32.6: 3: 1) .

The average molecular weight of the azo dye produced with phenylmethyl-pyrazolone is 1455.

A fractionation test whereby a film of the dye on an aluminum foil is fractionally dissolved shows the following results:

Fraction: Chloroform: Methanol: Fraction N Average (ml) (ml) (Quantity) (%) Molecular Weight (mg) 1 ---- 150 1.5 ------- 2 60 90 90.9 13, 5 874 3 67.5 82.5 217.7 13.6 1097 4 75 75 274.1 13.2 1261 5 82.5 67.5 232.0 12.6 1779 6 90 60 204.2 12.2 2475 EXAMPLE 66

The condensate described in Example 59 is used.

EXAMPLE 67

The condensate described in Example 63 is used.

EXAMPLE 68

A screen printing form is prepared as described in Example 38, except that the diazo compound is replaced by the same amount of the mixed condensate described in Example 52 and the coating solution is diluted with 200 parts by volume of water.

EXAMPLE 69

An aluminum foil roughened by metal brushes is treated with polyvinylphosphonic acid as described in U.S.A. Patent No. 3,220,832. This plate is then coated with a 0.5 $ solution of the mixed condensate described in Example 42 (starting material for the preparation of the dye to be fractionated) in a mixture of ethylene glycol monomethyl ether / butyl acetate (8: 2 ratio on a volume basis) and the coating is superficially dried.

The plate is then coated with the following solution: 12.0 parts by weight of a diallylisophthalate prepolymer commercially available under the trade name "Dapon M", 55.0 parts by weight xylene, 33.0 parts by weight 4-methoxy-4-methyl-2-pentanone 0.1 parts by weight Michler's ketone, 0.1 parts by weight of benzil, and 0.4 parts by weight of xanthone.

103 143521

After the plate is dried, it is exposed imagery under a negative master. It is induced by rinsing with a suitable solvent, e.g. 1,1,1-trichloroethane. After drying, the developer is completed with developer II described in Examples 22 to 28 and the plate is then blackened with greasy ink. There is thus obtained a printing plate which provides longer printing layers than a printing plate which was made from a reproduction material without the second coating (of a different reproduction layer). The mixture described in this example exhibits a relatively good light sensitivity because the mixed condensate present in the first layer has a higher light sensitivity.

Instead of the just described coating solution, a similar solution of polyvinylcinnamate can be used for the second coating, which has been made sensitive to longer wavelength light by the addition of 5 in Miehler's ketone.

EXAMPLE 70

The procedure used in Example 54 is repeated, except that the coating solution used is a solution of 6 parts by weight of the mixed condensate described in Example 6 in 12 parts by weight of a mixture comprising ethylene glycol monomethyl ether / butyl acetate (volume ratio: 8 : 2).

After imaging exposure under a positive screen, the material is developed with developer II, set forth in Examples 22 - 28.

Ted treatment with a 40 µl aqueous solution of iron III chloride becomes copper-tight in the unexposed areas.

For removal of the coating, the material is dried over with dimethylformamide. Hereby a halftone engraving plate is obtained, and when the material is exposed to gain a negative and further surface treatment appropriately, a positive relief form can be obtained.

EXAMPLE 71

Easy examples show that mixed condensates containing only very little diazo compound still give rise to the formation of useful reproductive materials.

An aluminum foil roughened aluminum foil is coated with a 2 $ ethylene glycol monomethyl ether solution of a mixed condensate (which, by analysis, contains about 18 p-cre sol units per unit of 3-methoxy-4-diazo-diphenylamine and the coating is dried then.

After pictorial exposure during a negative original, the film is elicited by rinsing with acetone and then dried, dried over with water and bleached with greasy ink.

In this way, clay is obtained in a positive form, which exhibits a slight foaming, but which can be purified by drying with a solution containing 75 parts by volume of water, 35 parts by volume of n-propanol and 2 parts by weight of UaHgPO 2.

One produces a condensate consisting of p-cresol units only under identical conditions and then an amount of 3-methoxydiphenylamine-4-diazonium chloride corresponding to the amount of diazo compound incorporated according to the foregoing is obtained. a mixture from which to produce a reproduction layer which also forms a foaming positive printing form by image exposure and induction with acetone. However, if in an attempt to purify this printing form it is dried with the solution described above, it will be completely destroyed.

Even when you add 10 times the amount of diazo, no better results are obtained.

105 143621

To prepare the mixed condensate, 0.323 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 100% by volume 86% phosphoric acid and this solution is mixed with vigorous stirring with a solution of 3.36 parts by weight of 2,6-dimethylol-4-methyl -phenyl (Component B ^, No. 5, Table 1) in 20 parts by volume of hot methanol.

At the instant of mixing, a clear solution is formed which quickly becomes cloudy while the condensate settles. 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 solution of sodium chloride. The precipitate was filtered off by suction, washed to neutral 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-β-cresol rhomocondensate prepared under identical conditions showed the following values: C 71.6 #, H 7.1 The analysis shows a dibenzyl ether-like bond between the units.

EXAMPLE 72

For the photomechanical preparation of a screen printing stencil, the following procedure is used: 120 parts by weight of a 25 $ aqueous solution of polyvinyl alcohol (residual acetate content: less than 2 viscosity of a 4 ^ aqueous solution at 20 ° C: 17-12 cP) was thoroughly mixed with 100 parts by weight of an aqueous dispersion of a copolymer based on vinyl acetate / maleic ester (protective colloid: polyvinyl alcohol; dry matter content; 55 #, viscosity 5 - 29 F as measured with an HcSppler viscometer).

100 parts by weight of this emulsion are thoroughly mixed with a solution of 1.5 parts by weight of the mixed condensate described in Example 29 in 10 parts by volume of water. Legs thus obtained emulsion are used in known manner for coating screens, from which photomechanical paths are prepared screen printing stone cils. the layers have an exceptionally good light sensitivity.

106 1-43 621 Compared to known screens sensitized by chromates, these screens are characterized by a significantly improved storage capacity at room temperature.

The new diazonium salts can also be used to sensitize commercial, pre-coated but not yet sensitized screens.

For example, the aforementioned non-sensitized emulsion was applied to a screen and dried, and the layer thus formed was then thoroughly wetted with a solution of the mixed condensate described in Example 29 in a 1: 1 mixture of methanol and water. After drying, a screen printing stencil was obtained using the usual method.

Examples 73 to 82 again show the good oleophilic properties of the exposure products of some of the mixed diazocondensates when applied to superficially hydrolyzed cellulose acetate film. The mixtures obtained during the condensation are diluted and then used directly for coating to show that good results are obtained without separation of the large amounts of acid present. Obviously, even better results are obtained when lesser amounts of acid are added. For practical purposes, for this type of support, acid additions of less than 3 moles of acid per day are preferred. mole of diazo group.

Detailed data related to the condensation method and the coating solutions are given in Table 6.

The best results were obtained in Examples 76, 78, 80, 81 and 82. Examples 74 and 75 showed the slightest effects due to the high acid content.

For purposes of comparison, a condensation product is prepared analogous to Example 1 of TJ.S.A. Patent No. 3,406,159 from diazo 3, chloride, (Table 1) and formaldehyde in 2.8 basic moles of phosphoric acid, and the phosphoric acid content is then adjusted to basic moles. Superficially hydrolyzed cellulose acetate film coated with a 1 $ and a 10 $ aqueous solution of this mixture, respectively, exhibits almost no ink absorption ability in the image areas after image exposure and is elicited with water.

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The mixed condensates are prepared as follows: EXAMPLE 73

Preparation of Component 12.4 parts by weight of 4,4'-dimethyldiphenyl ether are dissolved in 27 parts by volume of glacial acetic acid and then 5.7 parts by weight of para-formaldehyde are first added, then 28 parts by weight 63 $ aqueous solution of hydrogen bromide, and finally 16 , 5 parts by weight of 95 sulfuric acid to the solution with stirring. After heating for two hours to 90 - 95 ° C, the mixture is allowed to cool overnight.

The crystals present in the mixture are filtered off by suction, 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 then introduced into a boiling solution of sodium hydroxide in methanol (large excess of NaOH). After heating for two hours at reflux, the solution is mixed with water, the benzene phase is separated, washed, dried and evaporated.

9.2 parts by weight of an oily material is obtained (Component Blf No. 28) (OCH ^ content: 31.7 #) 4.85 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 15 parts by volume of 86 $ phosphoric acid, and 4, 3 parts by weight of the above component B ^, No. 28, are added to the solution with stirring.

A clear, homogeneous reaction mixture is obtained. After condensing 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 the addition of an aqueous solution of sodium chloride.

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

EXAMPLE 74 143621 110

Component B 2, No. 23, is prepared from the potassium salt of p-hydroxy-benzaldehyde and 2,2'-dichlorodiethyl ether (see "Macromolecular Chemistry", Vol. 17, pages 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) is dissolved in 50 parts by volume of 86 $ phosphoric acid and this solution is then mixed with a solution of 1.6 parts by weight of Component B ^, No. 23, in nearly 5 parts by volume. boiling glacial acetic acid. After 5 hours of condensation at 40 ° C and standing overnight, a crude condensate is formed which is used to prepare the coating solution.

EXAMPLE 75

Component B ^, No. 24, is prepared analogously to component B ^, No. 23, from the potassium salt of p-hydroxy-benzaldehyde and 1,3-dibromo-propane, and by subsequent reduction of the resulting dialdehyde to the di-alcohol by sodium borohydride.

To prepare the condensation product, 0.213 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 1.5 parts by volume 93 of * phosphoric acid and mixed with a hot solution of 0.19 parts by weight of component B-no. 24, in 1 volume of glacial acetic acid. After the addition of 3.5 parts by volume of 93 $ phosphoric acid, the mixture is kept for 5 hours at a temperature of 40 ° C. Light clear, crude condensate which forms is used to prepare the coating solution.

Examples 76 and 77

For the manufacture of component. No. 25, bromomethylated 100 parts by weight of diphenylene oxide, analogous to Example 73, in a mixture 111 parts by volume of glacial acetic acid, 54 parts by weight paraformaldehyde, 500 parts by weight 63 # hydrogen bromide, and 294 parts by weight 96 $ sulfuric acid at a temperature of 75 ° C and the reaction product is then recrystallized from acetone, (bis-bromomethyl diphenylene oxide: calculated values - C 47.5 #, Br 45.3 values found: C 47.7 #, Br 46.2 and then reacted with an excess of a solution of sodium hydroxide in methanol.

To prepare the condensation product, 16.2 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 50 parts by volume of 86 $ phosphoric acid, and 12.8 parts by weight of component, No. 51, is heated to 35 ° C and then added dropwise.

The mixture is condensed for 5 hours at 40 ° C. The clear, raw condensate is used directly for the increase. The remaining portion of the mixture (less than 0.2 parts by weight) is dissolved in water and the reaction product is precipitated from the aqueous solution by the addition of a solution of sodium chloride. Yield: 22.6 parts by weight. (C 65.7 N 8.2 P atomic ratio: 28 * 3).

Component B3, No. 31, and the condensation product prepared therefrom, used in Example 77, are prepared analogously to Example 76, except that dibenzothiophene is used as a starting material.

Examples 78 and 79

For the preparation of component B 2, No. 29, bromomethylates thymylphenyl ether prepared according to "Liebig's Annalen der Chemie", vol. 350, page 89 (1906) for 3.5 hours at 90 -95 ° C analogous to Example 73, and the reaction product obtained is reacted with a solution of sodium hydroxide in methanol without further purification. The reaction product thus obtained, which is a viscous oil, has an OCH 2 content of 18.6 ¢.

To prepare the condensate, 4.85 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 20 parts by volume of 86 $ phosphoric acid, 112 143 * 21 6.0 parts by weight of component B., No. 29 is added and the mixture is condensed for 4 hours at 40 ° 0.

The crude condensate thus obtained (1 part by weight) was used to prepare the coating solution. The remaining residue is dissolved in water and the condensation product is precipitated in the form of the chloride by the addition of a solution of sodium chloride. Yield: 9 parts by weight (C 66.9 $, N 6.7 f> in atomic ratio: 35: 3).

The condensate used in Example 79 is prepared analogously to Example 78 except that 3-bromo-4-methoxy-diphenyl ether (prepared according to J.Am.Chem.Soc. 61, 2702, 1959) is used as starting material for the manufacture of component # 30.

EXAMPLE 80

To prepare Component B, No. 26, diphenylmethane is bromomethylated for 5 hours at 90 - 95 ° 0, analogous to Example 73, and the pure 4.4, bis-bromomethyl diphenylmethane (mp 153-154 °) obtained by recrystallization from benzene is then reacted with sodium hydroxide in methanol.

To prepare the condensate, 4.85 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 15 parts by volume of 86 fa phosphoric acid and 3.85 parts by weight of component Bnr. 26, is added dropwise. After adding 15 parts by volume of 93 f> phosphoric acid, the mixture is condensed for 10 hours at 40 ° C.

2 parts by weight of the crude condensate are used to prepare the coating solution. The remaining part is dissolved in water and a solution of sodium chloride is added to precipitate the condensate in the form of the chloride which is separated and dried. (C 68.6 f <>, IT 8.0 f>, atomic ratio: 30: 3).

EXAMPLE 81

For the preparation of component # 27, diphenyl is methylated for 5 hours at 90 - 92 ° C analogous to Example 73, and the component of the reaction product which is heavily soluble in acetone is reacted with sodium hydroxide and methanol ( 0GH3 content: 23.8 ¢).

To prepare the condensate, 6.4 parts by weight of diazo 2, sulfate (Table 1) are dissolved in 50 parts by volume of 86 f of phosphoric acid, and 4.8 parts by weight of component B ^, No. 27, are dissolved in 10 parts by volume of hot methanol and this solution is added to diazo. After heating for 2 hours at 40 ° 0, 50 volumes of 93 f> phosphoric acid are added to the mixture, which is condensed for 12.5 hours at 40 ° 0.

A sample of the raw condensate is used to prepare the coating solution. The remaining part is dissolved in water and hydrochloric acid is added to the aqueous solution to precipitate the chloride of the condensate which is then separated and dried (C 68.2 #, N 8.2 fo, atomic ratio; C: N - 29.1 : 3).

EXAMPLE 82

Por to synthesize component, No. 32, bromomethylated 1,4-diphenoxy-benzene, prepared according to "Liebig's Annalen der Chemie", vol. 350, page 98 (1906) for 3 hours at 90 - 92 ° C analogous to Example 73, and the resulting reaction product is reacted with methanolic solution of sodium chloride (OCH 3 content: 19.2 f).

To prepare the mixed condensate, 2.3 parts by weight of diazo 2, sulfate (Table 1) is dissolved in 20 parts by volume of 86 f of phosphoric acid, and 2.3 parts by weight of components B . After condensing for 6 hours at 40 ° C and standing overnight, a * 114 149 * 21 crude condensate was used which is used to prepare the coating solution.

The mixed condensate can be precipitated from an aqueous solution by the addition of hydrochloric acid, methanesulfonic acid and benzenesulfonic acid.

EXAMPLE 83

The mixed diazocondensate described in Example 42 is dissolved in the form of the chloride in water and the aqueous solution is then added to an aqueous solution of sodium azide. The azide precipitated during nitrogen evolution is dissolved in toluene and a 1 µg toluene solution prepared in this way is used to sensitize an aluminum foil previously coated with polyvinylphosphonic acid.

After imaging exposure during a negative original, a brownish image becomes visible, Yed development with the developer described in Example 1 of U.S.A. Patent No. 2,994,609, an offset printing form having good oleophilic properties is produced.

EXAMPLE 84

An aluminum support that has been roughened with wire brushes and pre-treated with polyvinylphosphonic acid according to U.S.A. Patent No. 3,220,832, is sensitized with a blue-colored, sensitizing solution of the following composition: 0.55 parts by weight of the mixed condensate described in Example 42, 1.65 parts by weight of a polyvinylformal resin (CFormvar) containing 5 , 5 - 7.0 fo hydroxyl groups, 22 - 30 fo acetate groups (OH 2 COO), 115 143821 and 50 $ formal groups and having a viscosity of 18 - 22 op (5 $ solution in ethylene chloride, measured with an Ostwald viscometer) , 0.10 parts by weight of crystal violet, 0.55 parts by volume of 1 M ortho-phosphoric acid, 60.00 parts by volume of ethylene glycol monomethyl ether, 32.00 parts by volume of tetrahydrofuran, and 8.00 parts by volume of ethylene glycol methyl ether acetate.

After drying, the coated aluminum foil is insensitive to moisture and has an excellent shelf life so that it can be stored for many months if kept in the dark.

For preparation of a printing form, the material is exposed for 1 minute under a conventional xenon lamp, developed with the developer II listed in Examples 22-28, to which no 30 $ n-propanol is added, and then blended in the usual manner with the fat. ink. The printing form thus produced can be used for printing about 100 000 prints in an offset machine.

Examples 85 and 86

Aluminum foils roughened by metal brushes and pre-coated with polyvinylphosphonic acid are coated with solutions of the following composition and the coatings are dried.

85 86 MG of Example 80 (chloride) 0.83 parts by weight - MC of Example 81 (chloride) ------ 0.81 parts by weight of p-toluenesulfonic acid * 1 HgO 0.3 parts by weight 0.3 parts by weight

Mixture of 80 parts by volume of ethylene-116 143621 85 86 glycol monomethyl ether and 20 parts by volume of butyl acetate 100 parts by volume 100 parts by volume

After imaging exposure during a screen negative, the development is performed with one of the inducers set forth in Examples 22 to 28 and the foil is blackened with greasy ink. In this way, effective printing forms with good oleophilic properties are obtained.

For the reproduction materials described, approx. a quarter of the exposure time required for a material according to Example 30, Experiment 1, comprising a formaldehyde condensate of the same diazo compound, but without the other component, is sufficient.

It is possible to satisfactorily process the pre-sensitized printing plates prepared according to Examples 85 and 86 into printing molds, even though they have been heated for 6 hours to 100 ° C prior to exposure to light.

The efficiency of the printing forms can be improved in the usual way by varnishing.

The mixed condensate used in Examples 85 and 86 may also first be isolated as salts of organic sulfonic acids and then used, as already described as a particularly advantageous modification in the case of the corresponding condensation products of bis-methoxymethyl diphenyl ether (Example 42 ) and bis-methoxymethyl diphenylsulfide (Example 46).

As sulfonic acids for the separation of the condensation products, aromatic monosulfonic acids, i.e. monosulfonic acids of the benzene and naphthalene series containing up to 12 carbon atoms, e.g. benzenesulfonic acid, toluene sulfonic acid, mesitylene sulfonic acid, p-chlorobenzene sulfonic acid, p-methoxybenzenesulfonic acid, naphthalene-1-sulfonic acid, and naphthalen-2-sulfonic acid; mesitylene sulfonic acid and naphthalene-2-sulfonic acid are particularly advantageous.

The condensates of 3-methoxy-diphenylamine-4-diazonium salts described in Example 46 (1: 1 condensate), 85 and 86, in the form of the salts. of such sulfonic acids, like the corresponding condensation products with bis-methoxymethyl-diphenyl ether, is particularly well suited for combination with water-insoluble resins, as described in Example 42, for the production of storage-stable and particularly efficiently sensitized, pianographic printing plates.

In this case, too, particularly high printing layers are obtained by the addition of polyvinyl formulations, e.g. when the coating solution is prepared analogously to Example 84, except that, instead of the mixed condensates used, the same amount of the mesitylene sulfonates of the diazocondensates according to Examples 46, 85 or 86 is used.

As described in Example 42, the mesitylene sulfonate of the diazocondensates is prepared from the corresponding chlorides.

To develop the image-exposed plates, it is possible to use the developer n listed in Examples 22 to 28, to which approx. 30% n-propanol.

EXAMPLE 87

The aluminum support used in Example 42 is coated with a coating solution of the following composition: 1.0 part by weight of the mixed condensate described in Example 2, 1.8 parts by volume of 1 N hydrochloric acid in ethylene glycol monomethyl ether (to convert the diazo compound to the chloride 2.0, by weight of a bisphenol-based epoxy resin having a melting range of 96 - 104 ° C and an epoxy equivalent weight of 875-975 $ 3picote * (1004), 4.0 parts by volume of water, 75.0 parts by volume of ethylene glycol monomethyl ether and 20.0 parts by volume butyl acetate.

Upon drying the coating, a photosensitive reproduction material is produced. After exposure, it can be converted into a printing mold by the developer solution set forth in Example 42.

Further treatment with the developer II described in Examples 22 to 28 may be advantageous.

The following examples show the suitability of a number of additional compounds for preparing the mixed condensates: EXAMPLE 88

An intimate 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 are introduced with stirring into 11.8 parts by weight of 93 $> phosphoric acid. 1.57 parts by weight of 2,6-bis- (methoxymethyl) -4-methyl-phenpl (Component B ^, No. 33, Table 1) are then added with appropriate stirring. Then, the mixture is condensed under stirring for 24 hours at 40 ° C and a crude condensate is obtained which forms a clear solution in water and does not lose this property even after storage for several months at room temperature.

However, if 2,6-bis- (methoxymethyl) -4-methyl-phenol is introduced into the phosphoric acid in the absence of the diazo compound and formaldehyde, the product dissolves rapidly, but after several seconds, a condensation product which is highly soluble in the 119 U3621 acid is separated. hot water.

EXAMPLE 89 32.3 parts by weight of 3-methoxy-diphenylamine-4-diazonium sulfate (Dlazo 2, sulfate, Table 1) are dissolved in 100 parts by volume of 36 # phosphoric acid, 28.6 parts by weight of 4,4'-bis (ethoxymethyl) diphenyl ether (Component B , No. 34, Table 1) is then added dropwise with vigorous stirring; Stirring is continued for 1 hour without heating and then for an additional 3.5 hours at 40 ° C. After standing overnight (room temperature), the mass is dissolved in water (Clear solution) and the chloride of the Condensation product is precipitated as described in Example 29. Yield : 41.8 parts by weight. Compared to the non-condensed diazo compound, the condensation product has an excess content of 15.8 carbon atoms per diazo group (C 65.9 #, U 8.0 $>, Cl 8.8 ator ratio: 28.8: 3: 1.3).

The 4,4'-bis (ethoxymethyl) diphenyl ether is prepared as a viscous oil from the commercial 4,4, bis (chloromethyl) -dipienyl ether by reaction with sodium ethylate.

EXAMPLE 90

The procedure is the same as described in Example 89 except that instead of 4,4 * bis (ethoxymethyl) di-phenyl ether the equivalent amount (23.0 parts by weight) of 4,4 * bis is used. (hydroxymethyl) diphenyl ether (Component, No. 35, Table 1). The hydroxymethyl compound must be used in very fine powdered form and must be introduced slowly. Careless work can result in the formation of products that are heavily soluble or insoluble in water (predominantly consisting of condensates of the hydroxymethyl compound with themselves). The work-up is carried out in the same way as in Example 89. Yield; 41.2 parts by weight (C

65.6 in, ΓΓ 8.4 Cl 8.7 atomic ratio: 27.4: 3: 1.23).

For example, compound 4,4'-bis (hydroxymethyl) - diphenyl ether by alkaline hydrolysis of the diacetyl compound described in Example 29.

The condensation products prepared according to Examples 89 and 90 can be successfully used for photosensitive layers similar to those in which the condensation product whose preparation is described in Example 29 has been used.

EXAMPLE 91

A mixture of the following ingredients is condensed as described in Example 65: a) b) 4-diazo-diphenylamine-3, 5.5 parts by weight 11.0 parts by weight of carboxylic acid (inner salt) (Liazo 11, inner salt, Table 1) 86 f phosphoric acid 51.0 parts by weight 51.0 parts by weight 4,4'-bis (methoxymethyl) di-phenyl ether (Component B

No. 15, Table 1) 5.2 parts by weight 5.2 parts by weight

Light clear, crude condensate is introduced a) into 290 parts by volume of methanol, and b) into 370 parts by volume of methanol, and the precipitate formed is a) washed with 80 parts by volume of methanol and b) with three times a hundred parts by volume of methanol, and then dried.

Yield: a) 8.0 parts by weight (C 59.1 fo, U 6.1 fo, P 5.6 atomic ratio: 34: 3: 1.25) b) 6.8 parts by weight (C 63.5%, N 7 , 3%, P 5.3 atomic ratio: 30.4: 3: 0.61).

On the basis of the analysis results, it can be assumed that the diazoforb compound and the other component are present in the condensate at a ratio of approx. 1: 1.5 (in case a) and approx. 1: 1.24 (in case b).

Example 92 15.42 parts by weight of diphenylamine-4-diazonium sulfate (Diazo 1, sniffate, Table 1) is dissolved in 100 parts by volume of 96.5 $ phosphoric acid and 7.4 parts by weight of dimethyloloxamide (Component B ^, No. 56, Table 1) is then added with stirring in small portions. The condensation is carried out for 24 hours at room temperature. The condensation mixture is dissolved in 0.5 L of water and 80 parts by volume of 50 F of zinc chloride solution is slowly and dropwise stirred at 40 ° C. After cooling to 10 ° C, the precipitate is filtered off by suction and dissolved again in 0.5 L of water at 50 ° 0, whereupon the product is again precipitated by dropwise addition of a zinc chloride solution (45 parts by volume) and isolated as described above.

Yield: 16.3 parts by weight. According to the analysis, the condensation product contains 3 N atoms per minute. 10.6 C atoms (C 43.0 f>, N 14.2 f). The diazo homocondensate would have a C: N ratio of 13: 3.

EXAMPLE 93 15.42 parts by weight of diphenylamine-4-diazonium sulfate (Diazo 1, sulfate, Table 1) (95 f) are dissolved in 100 parts by volume of methanesulfonic acid (90/6). 10.8 parts by weight of finely powdered dimethylol adipic acid medium (Component B ^, No. 37, Table 1) (94.7%) is added portionwise with appropriate stirring. When the slight heat generation resulting from the reaction is complete, the mass is condensed for 25 hours at room temperature. The crude condensate is dissolved in 500 parts by volume of water. By adding 80 parts by volume of 50 µl of 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 it is again precipitated after cooling to 10 ° C by the addition of 50 parts by volume of 50% zinc chloride solution.

122 1436Æ1

The product is filtered by suction and dried under reduced pressure.

According to the analysis, the condensate contains approx. 0.7 mole of the acidic amide per molecular diazo compound.

Example 94 4.47 parts by weight of diphenylamine-4-diazonium phosphate (Diazo 1, Phosphate, Table 1) (98.4 f>) is dissolved in 60 parts by volume 92 f> phosphoric acid. 4.85 parts by weight of trimethylol citramide (Component B1, No. 38, Table 1) (86, 3 f, residual water) is then added and the mass is condensed for 45 hours at room temperature. The condensation mixture, which forms a clear solution in water, is diluted with 30 parts by volume of methanol and the mixture is kept under stirring in 599 parts by volume of isopropanol. The precipitated reaction product is filtered off by suction and dried under reduced pressure. Body exchange: 10.8 parts by weight. According to the analysis, the ratio ΪΓ: C equals 3: 10.8 (C 28.8 N 9.3 fo).

Examples 95 and 96 In these examples, it is shown how two additional diazo compounds (Nos. 12 and 13, Table 1) can be condensed with a component B 2 in an acid condensation medium to form mixed condensates.

In both examples, the diazo compound is dissolved in the condensation medium in the form of their metal halide double salts. Dry air is passed through the mixture until no more hydrogen chloride escapes. Then the second component is added and the condensation is carried out at room temperature for the specified time. This results in mixed condensates forming clear solutions in water.

If component B ^ is introduced into the condensation medium alone, a homocondensate of component B ^ is formed during a condensation process of the same duration, which homocondensate readily separates from the condensation mixture and does not dissolve upon addition of water.

The following table lists the quantities used and the duration of the condensation:

Example 95 Example 96

Condensation medium: 90 f methanesulfone- 90 f> methanesulfone acid (10 parts by volume) acid (10 parts by volume)

Diazo compound: 2,5-dimethoxy-4- 4- [N-methyl-N- (p- (N-methyl-JT-phenylphenyl-mercaptonyl-mercaptoacetyl) -amino] -ethylamino) -benzenebenzene diazonium - diazonium chloride chloride + 1/2 mol + 1/2 mol of zinc tin tetrachloride chloride (H 8.8 f) (N 6.3 f) (0.95 parts by weight) (1 * 33 parts by weight) Spirit constituent: 1 , 4-Bis-hydroxymethyl-1,4-bis-hydroxybenzene (0.14% by weight methylbenzene) (Component B1, (0.14% by weight) No. 12, Table 1) (Component B1, No. 12, Table 1)

Duration of the condensation process: 4 hours 4 hours.

Examples 97 and 98

The comparison between Examples 97 and 98 shows the advantages of producing the diazopolycondensates according to the process of the invention (Example 98) over the method of Danish Patent Application No. 2533/70 (Example 97) and the various properties of the process - * brought products.

In Example 98, 0.1 mole of 3-methoxy-diphenylamine-4-diazonium sulfate (Diazo 2, sulfate) is dissolved in 100 parts by volume of 86-ortho-phosphoric acid, and after the addition of 0.1 mole 4,4'-Bis-methoxymethyl diphenyl ether (Component B 2, # 15), the solution is condensed for 5 hours at 40 ° C with stirring.

In Example 97, 0.1 mol of diphenyl ether in molten form is added to the same amount of diazo 2, sulfate, 100 parts by volume of phosphoric acid, 0.2 mol of paraformaldehyde is introduced within 10 minutes, and the mixture is also condensed with stirring for 5 hours at 40 °. C.

During condensation, the following properties of the condensation mixture are examined from time to time: (a) Appearance: visually evaluated (b) Solubility: For this purpose 0.5 parts by weight of the condensation mixture is mixed with 3 parts by volume of water and the mixture is visually evaluated.

(c) The precipitate of the resulting condensation product: 1 part by volume of saturated aqueous solution of sodium chloride is added to the mixture obtained under (b) and the resulting resulting precipitate is observed.

When the condensation is complete, the entire amount of the raw condensate in each example is diluted with 300 parts by volume of water and mixed with 100 parts by volume of 20 fo aqueous solution of sodium chloride.

In Example 97, no precipitate separates from the very cloudy mixture of Example 98, there is immediately a very strong precipitation of the chloride of the condensation product. Example 97 finally gives a precipitate in the form of a tough mass after the addition of an additional 200 volume portions 20 in sodium chloride solution.

The precipitates are finally converted to the mesitylene sulfonates.

Further details of Examples 97 and 98 are summarized in the following table:

Example 97 98

Sample on the raw condensate: after 0.5 hours ·

Appearance: cloudy clear

Solubility: cloudy

Precipitation: no sticky precipitate after 2.5 hours:

Appearance: cloudy clear

Solubility cloudy clear

Precipitation: nothing, turbidity, flake density increases precipitously after 5 hours:

Appearance: cloudy clear

Solubility: cloudy

Precipitation: nothing, slightly more vigorous, finely divided than after precipitation 2.5 hours

Treatment: Raw condensate + 300 very cloudy clear solution volume parts water solution 126 143621

Example 97 98

Addition of 100 volume separation very precipitate.

, η no. cf aged at 35 to 37 ° C, male parts, aqueous 20 # filtered off by suction.

KaCl solution at 21 °, washed

with 1000 parts by volume of 4 # NaCl solution = A

Addition of additional sticky precipitate less, subsequent 200 volume portions of 20 # precipitate

NaCl solution

Precipitation dissolved in: 1 000 volumes A in 1 000 volumes water water

The precipitate meds 28 parts by weight of 28 parts by weight of the sodium salt of the tri-salt of mesitymesitylenesulfonic acid sulfonic acid in 500 microns in 500 parts by volume of water

divide water from A

Yield 29 parts by weight 55 parts by weight

Mesitylene sulfonate: green yellow and sticky deep yellow fine powder rich (strong odor of diphenyl ether)

Atomic conditions Atomic conditions

Analysis: G 69.4 $ 44.2 67.4 $ 38.6 H 5.5 # 3 6.1 # 3 S 4.5 $ 1.07 4.8 # 1.035

Yield relative to approx. 38 # approx. 80 # amount of diazo compound used _______________________________________

Yield from B

1.5 parts by weight of yellow powder (C 67.2 #, U 6.4 #, S 5.2 #; atomic ratio 36.7: 3: 1.07).

127 143621

In the condensation experiments carried out as described in Example 97, the condensate present in the crude condensation mixture is precipitated in three fractions with a solution of sodium chloride or zinc chloride. The first fraction contains approx. $ 48 of the diazo compound used and per. diazo group an excess of approx. 16 carbon atoms, the second fraction about, $ 12 of the diazo compound used and per. diazo group an excess of approx. 12 carbon atoms, and the third fraction ca. $ 15 of the diazo compound used and per. diazo group an excess of approx.

6 carbon atoms.

Thus, $ 75 of the diazo compound used is obtained in the form of condensation products.

The mesitylene sulfonates of the condensates isolated in Example 98 from the chloride precipitates A and B contain ca.

$ 82 of the diazo compound used. The analysis of the two fractions differs slightly from each other.

Example 98 thus offers the following advantages over Example 97:

Condensation mixtures are clearly soluble in water.

Significantly easier separability of the condensation products (significantly less amount of precipitant).

Better yields.

Better properties during separation.

Better chemical uniformity of the condensate.

Better quality (no odor, no discoloration, light flowing powder).

The condensation products obtained in Examples 97 and 98 in the form of the mesitylene sulfonates are compared for the yellowing effect. A polyvinyl-pyrrolidone-based reproduction layer and the condensate of Example 98 have a better light sensitivity and thus an improved yellowing effect compared to a similar layer made with the condensate of Example 97 * The experiment is carried out as follows:

Example 97 98

Diazocondensate 1 part by weight 0.9 parts by weight (N 5.5 fo) (V 6.1 fa)

Polyvinylpyrrolidone 4 parts by weight 4 parts by weight (K value 30)

Ethylene glycol monomer 100 parts by weight 100 parts by weight thyle ther / butylac etate 8: 2 (by volume) (The amount of diazocondensate in both layers is adjusted to the same amount of diazo groups per part by weight of binder).

The reproduction materials are prepared by coating with a rotating means electrolytically aluminum-incubated and drying with a cold air stream, then with a hot air stream, and finally for 2 minutes at 100 ° C. The layer weights are: Ex. 97: 39 mg / dm2, ex 98: 42 mg / dm2.

After standing overnight, the exposure is conducted under a Ko-.dald'® step wedge (density increment 0.15) with 5 kW xenon pulse lamp at a distance of 1 m. Both samples are then rubbed vigorously side by side for 1 minute. a flat plush pillow soaked with water.

In Example 97, only step 1 adheres to the support, but not completely. Furthermore, the surface exposed with the 0.05 density already exhibits minor mechanical damage.

129 1 4 3 6 21 In Example 98, step 2 fully adheres and step 3 partially adheres to the substrate. The surface exposed with a density of 0.05 shows no mechanical damage.

EXAMPLE 99

This example shows that the condensation according to the process of the invention can also be initiated with the reactive second component.

25.8 parts by weight of 4,4'-bis-methoxymethyl-diphenyl ether (Component # 15) is added dropwise with stirring to 100 volume 86 l of phosphoric acid. After less than 1 minute, a very milky turbidity arises from a precondensate. The heating is carried out for 20 minutes at 40 ° C, 32.3 parts by weight dia2; o 2, soluble barrel is added and the condensation is carried out for 5 hours at 40 C. Finally, a clear condensation mixture is formed which is clearly soluble in water.

For separation of the condensate, the mixture is dissolved in 300 parts by volume of water, precipitated with 200 parts by volume of 20 NaCl solution, and the precipitate is filtered off with suction, washed with approx. 1 000 volume parts 4 7? solution of sodium chloride and converted to the mesitylene sulfonate as described in Example 98.

Yield: 47.8 parts by volume (G 68.8 $, F 5.8 #, S 4.5 in ° / atom ratio 41.6: 3: 1.02).

The condensation product is suitable for use in various photosensitive reproduction layers.

Claims (11)

130 143621 Patent claims: A process for the preparation of a condensation product of an aromatic diazonium compound and a condensable compound, characterized in that at least one compound A-N2X of the formula (R - ^ - R ^ -) in a highly acidic medium having at least one compound B- of formula E (-CHRa-ORt) m, where X is the anion of the diazonium compound, p means 1, 2 or 3, R substituted aromatic group having at least one condensable position, R 2 is an optionally substituted phenylene group, R 2 is a single bond or one of the groups - (CH 2) q-NR 4 - (CH 2) q-NR 4 - (CH 2) r-NR 5-0 - (CH2) r-NR4 - S- (CH2) r-NR4- -s-ch2-conr4- -o-r6-o- -O- -s-SO2-NR4-, where q is a number from 0 to 5 R is a number from 2 to 5 R 4 is hydrogen, an alkyl group of 1-5 carbon atoms, an aralkyl group of 7-12 G atoms or an aryl group of 6-12 C atoms, R an alkyl group having 1-5 C atoms, and Rg is an arylene group having 6-12 C atoms, E being that group, so m is formed by the decomposition of m hydrogen atoms from a compound without the formation of diazonium groups which can condense at least one position with an active carbonyl compound in an acidic environment and belonging to one of the following groups: aromatic amines, phenols, thiophenols, phenol ethers, aromatic thioethers, aromatic hydrocarbons, aromatic, heterocyelic compounds or organic acid amides, R 2 is hydrogen, an alkyl or an aryl group, R k is hydrogen, an alkyl or an acyl group of 1-4 C atoms or a phenyl group, and m is an integer from 1 to 10, 131 143621 and the reaction takes place in such a ratio of A-NgX to B ^ that a product is obtained containing on average between 0.1 and 50 condensed units for each diazonium salt group. Process according to claim 1, characterized in that the condensation medium used is a concentrated acid. Process according to claim 2, characterized in that the condensation medium is phosphoric acid, methanesulfonic acid or sulfuric acid in a concentration in the range between 70 and 100. Process according to claim 3, characterized in that the condensation medium is orthophosphoric acid at a concentration of approx. 80 to 100%. Process according to claim 1, characterized in that the condensation is carried out at a temperature between 10 and 70 ° C. Process according to claim 4 or 5, characterized in that the condensation is carried out in a temperature range between 10 and 40 ° C. Process according to claim 6, characterized in that the E (-CHR -OR 1 compound is a diphenyl ether, a diphenyl sulfide, a diphenylmethane or a biphenyl). Process according to claim 7, characterized in that a B 1 compound is used wherein m is 2. Process according to claim 1, characterized in that a B-compound in which R 1 is H is used. Process according to claim 1, characterized in that a B1 compound is used in which R 1 is CH 2. Process according to claim 18, characterized in that the A-NgX units are derived from a compound of the general formula