US3397058A

US3397058A - Diazotype material

Info

Publication number: US3397058A
Application number: US382670A
Authority: US
Inventors: Arie Van Loon; Ronc Hubertus Wilhelmus Maria
Original assignee: Grinten Chem L V D
Current assignee: Chemische Fabriek L Van Der Grinteen N V; Grinten Chem L V D
Priority date: 1958-11-10
Filing date: 1964-07-14
Publication date: 1968-08-13
Anticipated expiration: 1985-08-13
Also published as: DE1174612B; GB919037A; BE584387A; NL233064A; NL98612C; CH386841A; FR1248122A

Description

United States Patent 20 Claims. (or. 9649) The invention relates to diazotype material of the socalled one-component type, which contains a p-amino benzene diazo compound, derived from a tertiary aromatic amine having only one aryl radical attached directly to the tertiary nitrogen atom, which compound in the para-position carries the diazo group and in one of the ortho-positions an etherified hydroxyl group.

This application is a continuation-impart of our copending US. application Ser. No. 851,968, filed Nov. 10, 1959, now abandoned.

As is known, the light-sensitive diazo compounds used in positive diazotype material are converted by irradiation with actinic light into compounds which are only slightly coloured, if at all, hereinafter called light-decomposition products. The diazo compound left in the diazotype material after the imagewise exposure is converted into an azo-dyestutf during the so-called development following the imagewise exposure, by reaction with an azo-dyestuff component. The light-decomposition products present in the exposed portions do not form an azo-dyestuif with the azo-dyestuff component. The diazo compounds and azodyestutf components or mixtures of diazo compounds and/or mixtures of azo-dyestulf components preferably selected are those which form azo-dyestuffs producinggood contrasts, e.g. dark, such as blue or black, azo-dyestuffs.

In the practice of the diazotype process very many copies, e.g. of transparent pencil drawings and letters are produced with a so-called foggy background.

After the imagewise exposure these copies, even in the most exposed portions, still contain (besides a relatively large quantity of light-decomposition products) a small quantity of diazo compound, which is converted into a corresponding small quantity of dyestuff during development. Except in some cases, in which special effects are aimed at, it is generally desirable for the dyestutf to have the same colour in all the image portions of the developed diazotype copy. It may have an extremely disturbing effect if the dyestuff in the foggy background of the copy shows a colour differing from that of the dyestuff in the image portions that have been only slightly exposed, if at all, especially if that colour, instead of pure blue or pure black, is an impure blue or an impure black owing to the presence of a reddish or violet shade. Such impure colours are called off-shades.

Belgian Patent No. 564,343 describes a process in which diazotype material is used which contains a diazo compound of the type in which R represents an alkyl group with at most 4 carbon atoms and R represents an alkyl group with at most 4 carbon atoms or an aralkyl group with at most 7 carbon atoms, and in which R represents an alkyl group with at most 4 carbon atoms.

The diazo compounds of this type are very sensitive to the light of the mercury-vapour lamps that are frequently 3,397,058 Patented Aug. 13, 1968 employed in the diazotype process, both of the high-pressure lamps and of the low-pressure lamps, and both of the actinically fluorescent and of the non-fluorescent lamps.

Diazotype material sensitized with diazo compounds of this type is extremely suitable for the visual observation of the endpoint of the exposure in the process of copying in the light of actinically fluorescent mercury-vapour lamps.

Many of the diazo compounds mentioned in Belgian Patent No. 564,343 yield dark azo-dyestuffs, producing good contrasts, with the azo components commonly used in the diazotype process, such as phloroglucinol, 2,3-dihydroxynaphthalene and its derivatives, 2,3-hydroxynaphthoic acid amides and 2-naphthal-3,6-disulphonic acid.

In respect to both light-sensitivity and suitability for visual observation of the endpoint of the exposure, diazotype material sensitized with diazo compounds of this type is quite different from the commonly used diazotype material sensitized with p-tert. aminobenzene diazo compounds having no alkoxy group ortho to the tert. amino group. The latter diazotype material is much less lightsensitive and practically is not suited for the visual observation of the endpoint of the exposure.

Copies on diazotype material as described in the said Belgian patent, however, often show off-shades in the image portions, in which after the imagewise exposure both the diazo compound and the light-decomposition products are present, e.g. in the foggy background. The off-shades are especially objectionable when the diazo compound has been converted into a blue or black azodyestuff during development. It has been found that during development both the light-decomposition products and the azo-dyestuff component form dyestutf in the portions in which they are present simultaneously with the diazo compound, so that in those portions mixtures are produced of azo-dyestutf formed by the azo-dyestuff component with dyestuif formed by the light-decomposition products. The latter dyestulf often has a reddish or violet shade, which forms an impurity for the pure colour of the azo-dyestuff formed from the azo-dyestuff component.

Moreover, the azo-dyestuffs of copies on diazotype material according to the said Belgian patent often show an undesirable change of colour in consequence of a decrease of pH occurring in the surface of the diazotype copies. The said surface may turn acid or more acid, either 10- cally, e.g. by spilling of acid liquids, or all over, e.g. when the copies are kept in a humid atmosphere, owing to which the acid from the interior of the paper (as is known, basepaper for the diazotype process often contains comparatively large quantities of acid, e.g. in the form of alum) can diffuse to the surface.

Besides the diazo compounds mentioned in the said Belgian patent, there are corresponding compounds having a chlorine atom, a methyl group or an ethoxy group in the para-position with respect to the alkoxy group. Some of these compounds are disclosed in a copending application Ser. No. 815,781, now US. Patent No. 3,169,869, filed after the priority date of the present application. The compounds 4-diazo-2,5-diethoxy phenyl morpholine and 4-diazo-2,5-diethoxy phenyl piperidine are known. These diazo compounds are also very light-sensitive but when diazotype material is manufactured with these diazo compounds, the azo-dyestuffs of copies on such diazotype material are often found to show an undesirable change of colour owing to a decrease of the pH. Offshades in the incompletely exposed portions of the copies are also frequently obtained, especially when the chloro compounds are used.

Some of the above-mentioned very light-sensitive diazo compounds have such a low coupling activity that they are suited only for the manufacture of two-component diazotype material which is developed by exposure to ammonia vapour. Some of them have a greater coupling activity so that they are suited for the manufacture of one-component diazotype material which is developed by means of an alkaline-reacting developing liquid. None of those compounds, however, is suited for the manufacture of onecomponent diazotype material to be developed by means of an acid-reacting developing liquid. As is well known in the diazotype art, acid-reacting developing liquids are more stable than the alkaline-reacting developing liquids. So the impracticability of using the former involves a very important practical disadvantage.

It is an object of the present invention to provide a material which obviates the above-mentioned disadvantages.

It is a further object of the present invention to provide a very light-sensitive one-component diazotype material which can be developed satisfactorily by means of an acid-reacting developing liquid.

The one-component diazotype material according to the present invention comprises a support sensitized with a light-sensitive composition containing, in the absence of an aZo-coupling component, a light-sensitive diazo compound of the formula in which /Rr N is selected from the class consisting of dialkylamino groups, N-ethyl N-benzylamino groups, N-alkyl-N-cyclohexylamino groups, (alkyl) (acyloxyalkyDamine groups, di(acyloxyalkyl)amino groups (in which groups the alkyl and benzyl radicals may carry further substituents) and the morpholino ring; R is a phenyl group, either substituted or unsubstituted; X is an anion and Y is selected from the class consisting of hydrogen and halogen atoms.

The aforesaid diazo compounds are new chemical compounds per se. Their light-decomposition products which are present, after the imagewise exposure, in the exposed image portions of copies on diazotype material accord ing to the present invention, form, during development, hardly any undesirable dyestuffs with diazo compound still present in those image portions. The azo-dyestuffs of copies on diazotype material according to the present invention are highly resistant to a decrease of the pH.

The diazotype material according to the present invention additionally possesses the above-mentioned good properties possessed by the diazotype material used in the process of Belgian Patent No. 564,343. In using the diazotype material of the Belgian patent it appears that the formation of off-shades is affected by the choice of the azo-dyestuif components and by the choice of the medium in which the formation of azo-dyestulf takes place. The azo-dyestulf component 2,3-hydr0xynaphthoic acid-18- hydroxyethylamide, if used in an alkaline-reacting developing liquid, causes more serious ofi-shades than does phloroglucinol in an alkaline-reacting developer. Phloroglucinol in a developer with an acid reaction causes more serious off-shades than does phloroglucinol in an alkaline-reacting developer.

When diazotype material according to the present invention is used, copies with hardly any off-shades are obtained in all these cases. The diazo compounds and the dyestuff components of course have to be selected in such a way that their coupling activity is sufficient for the medium in which the formation of azo-dyestuff takes place.

Diazotype material according to the present invention which contains a diazo compound in which the amino group carries a benzyl group and an alkyl group is suitable for development with weakly acid, buffered phloroglucinol developers. As is known, these developers in general have better resistance to oxidation than alkaline phloroglucinol developers. Copies on this material developed in such a way do not show off-shades owing to dyestufi formation by the light-decomposition products.

The diazo compounds which are used in the diazotype material according to the present invention also include compounds in which, besides the diazo group, the amino group and the phenoxy or substituted phenoxy group, the benzene nucleus carrying the diazo group carries yet another substituent, such as a halogen atom, in the paraposition with respect to the phenoxy or substituted phenoxy group.

Diazotype material according to the invention which contains a diazo compound in which the amino group carries a benzyl group and an alkyl group, and in which the benzene nucleus carrying the diazo group carries a chlorine atom in the para-position with respect to the phenoxy or substituted phenoxy group, is also very attractive. Owing to the great coupling activity .of the said diazo compound this diazotype material is especially suitable for development with weakly acid, buifered phloroglucinol developers, e.g. according to the so-called semi-wet process, in which a uniform thin layer of the developing liquid of, for example 8 g./m. is applied on the irnagewise exposed material. Copies on this material developed in such a way do not show off-shades owing to dyestufl formation by the light-decomposition products.

In the diazo compounds which are used in the diazotype material according to the present invention the phenoxy group may carry one or more substituents. Such substituents are halogen atoms, alkoxy groups, methyl groups, monoand dialkylamino groups and others. Diazotype material containing a diazo compound in which the phenoxy group carries at least one chlorine atom, shows a greater speed of development than corresponding material containing the corresponding diazo compound with an unsubstituted phenoxy group.

The alkyl groups in the amino group may also carry substituents such as hydroxy, alkoxy, acyloxy, chloro, acylamino etc. Diazotype material containing a diazo compound in which the amino group carries two acyloxyalkyl groups e.g. two acetyloxyethyl groups couples more actively upon development with a weakly acid buffered phloroglucinol developer than does corresponding diazotype material containing a diazo compound having the same structure but for the presence of two ethyl groups in the amino group. Further suitable acyloxy groups are: propionyloxy, butyryloxy, phenacetyloxy, chloroacetyloxy, benzoyloxy, furoyloxy, ethoxycarbonyloxy, phenylamidocarboxyloxy and methylsulphonyloxy groups.

Besides those mentioned in the examples which follow, the following diazo compounds may be especially mentioned as diazo compounds which may serve for the manufacture of diazotype material according to the present invention:

4-diethylamino-3-o-diethylaminophenoxy benzene diazonium borofiuoride double salt,

4 N methyl-N-benzylamino-3-phenoxy-6-fluorobenzene diazonium p-chlorobenzene sulphonate,

4-dimethylamino-3-phenoxy-6 bromobenzene diazonium chloride, zinc chloride double salt,

4-N-hydroxyethyl-N-o, p-dibromobenzylamino 3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, stannic chloride double salt,

4-N-methyl-N-acetoxyethylamino-3-phenoxy benzene diazonium chloride, zinc chloride double salt,

4 di 2'-acetoxyethylamino-3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloride double salt,

4 di-propionyloxyethylamino-3-p-chlorophenoxy-6-chlorobenzene diazoniumchloride, zinc chloride double salt,

4-di-2'-chloroethylamino 3 phenoxybenzene diazonium sulphate,

4 N-methyl-N-p-chlorobenzylaminc-3-p-methyl-phenoxybenzene diazonium chloride, zinc chloride double salt.

4 morpholino-3pchlorophenoxy-6-bromobenzenediazonium chloride, zinc chloride double salt,

4 N methyl-N-cyclohexylamino-3-p-chlorophenoxy-6- chlorobenzencdiazonium sulphate,

4-di(phenylamidocarbonyloxyethyl)amino 3 p-chlorophenoxy 6 chlorobenzene diazonium chloride, zinc chloride double salt,

4-di(ethoxycarbonyloxyethyl)amino-3-p chlorophenoxyfi-chlorobenzene diazonium chloride, zinc chloride double salt,

4-'di(acetyloxyethyl)amino-3-2-,4',5' trichlorophenoxy- '6-cholrobenzene diazonium chloride, zinc chloride double salt,

4-di(phenacetyloxyethyl)amino-3-p chlorophenoxy 6- chlorobenzene diazonium chloride, zinc chloride double salt,

4-di(benzoyloxyethyl)amino-3-p-chlorophenoxy-6 chlorobenzene diazonium chloride, zinc chloride double salt,

4-di(furoyl(2)oxyethyl)amino-3-p chlorophenoxy 6- chlorobenzene diazonium chloride, zinc chloride double salt,

4-di(chloroacetyloxyethyl)amino-3-p-chlorophenoxy 6- chlorobenzene diazonium chloride, zinc chloride double salt,

4-di(methylsulphonyloxyethyl)amino 3 p chlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloride double salt.

The diazotype material according to the invention may of course also contain mixtures of diazo compounds.

However, the use of a mixture containing a diazo compound which upon exposure yields light-decomposition products which form dyestuffs with undesirable shades owing to reaction with a diazo compound present in the mixture, is preferably avoided.

para-position with respect to the tertiary amino group.

The nitroso or nitro compound or the azo-dyestuif thus obtained is reduced to an amino compound, and this amino compound is converted into a diazonium compound by treatment with nitrous acid. The diazonium compound can be obtained as a double salt, e.g. by precipitation with zinc chloride, cadmium chloride, p-chlorobenzene sulphonic acid, sodium borofiuoride and the like.

Forthe preparation of diazo compounds having a substituent such as a chlorine atom in the para-position with respect to the phenoxy or substituted phenoxy group, the

. starting material is p-chloro o-nitro chlorobenzene.

With regard to the alkylation and aralkylation referred to above, it is observed that hydrogen atoms of the alkyl and/or the aralkyl groups may be replaced by substituents such as hydroxy and methyl groups and chlorine atoms.

The following examples will serve to illustrate the invention:

Example I White base-paper of Weight 80 g./m. as used for the diazotype process is sensitized with a solution of:

4-N-methyl-N-benzylamino-3 phenoxybenzene diazonium chloride, zinc chloride double salt g 23 6 Citric acid g 15 Polyvinyl acetate dispersion, Vinnapas H.60 cm. 20

in 1000 cm. of water and dried.

The sensitized surface contains approximately 0.45 millimole of diazo compound per m The light-sensitive side of a sheet of the diazotype paper thus prepared is covered with a sheet of tracing paper, on which a pencil drawing has been made, and exposed in an exposure apparatus equipped with actinically fluorescent low-pressure mercury-vapour lamps. Exposure is continued until in the portions which are in contact with the blank parts of the drawings a small quantity or diazo compound is still left. The amount at which the exposure has to be terminated can be determined very well by visual observation (e.g. from the direction of the light-source) of the change of colour which occurs in the light-sensitive layer during the exposure. This moment is soon reached.

The latent diazotype copy thus obtained is developed by treating it with a developing liquid of the following composition:

Grams Thiourea 25 2,3-hydroxynaphthoic acid fl-hydroxy ethylamide 18 Dibutylnaphthalene sulphonic acid sodium salt, commercially available under the name of Sorbit P 1.5 Mannitol 20 Potassium tetraborate (5 aq.) 74

Potassium hydroxide 12.6 in 1000 cm. of water.

The developed copy shows a violet-coloured image on uniformly foggy background which is also violetcoloured. The violet azo-dyestuff is highly resistant to a decrease of the pH.

If, instead of the above-mentioned diazo compound, a corresponding diazo compound having an alkoxy group instead of the phenoxy group is used, a blue-violet image on a foggy background having a grey-brown violet olfshade is obtained.

The diazo compound used according to this example is prepared as follows:

2-aminodiphenylether is benzylated and then methylated. The o-phenoxy N-benzyl N-methylaniline thus obtained (boiling point mm l94l97 C.) is nitrated, after which the p-nitro-o-phenoxy-N-benzyl-N-methylaniline is reduced and converted into the diazo compound in the usual way.

Example II White base-paper of Weight g./m. as used for the diazotype process is sensitized with a solution of:

4 N methyl N benzylamino-3-p-chlorophenoxy- 6-chlorobenzene diazonium chloride, zinc chloride double salt g 27 Tartaric acid g-.. 4 Boric acid g 1 Polyvinyl acetate dispersion, Vinnapas H.60 cm. 20

Grams Thiourea 15 Phloroglucinol 4 Z-ethylhexyl sulphuric acid mono-ester as sodium salt (commercially available under the name of Tergitol 08) 1.2

Grams Benzoic acid 2.5 Sodium benzoate 15 Sodium formate 150 in 1000 cm. of water. I

The pH of the developing liquid is about 5.9.

Within some tens of seconds after the application of the layer of developing liquid the developed copy shOWS a black image on a uniformly foggy gray-coloured background. The azo-dyestulf in the foggy background has the same colour as that in the black image portions. The black azo-dyestulf is highly resistant to a decrease of the pH.

If, instead of the above-mentioned diazo compound a corresponding diazo compound having an alkoxy group instead of the p-chlorophenoxy group is used, a black image on a foggy background having a red-brown offshade is obtained.

The diazo compound used according to this example is prepared as follows:

2-p-chlorophenoxy-5-chloroaniline (commercially available under the name of Echtrot F.R. base) is benzylated. The product thus obtained has a melting range between 78 and 80 C. It is methylated to 2-p-chlorophenoxy-S-chloro- N-methyl-N-benzyl-aniline, which is nitrated to 2-p-chlorophenoxy-4-nitro-5 chloro N methyl-N-benzylaniline (pale yellow crystals, melting point 102 C.). This compound is reduced and converted into the diazo compound in the usual way.

When, instead of 2 7 g. of 4-N-methyl-N-benzylamino 3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloride double salt, 30 g. of 4-dirnethylamino 3-0, p-dichlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloride double salt, is used in the sensitizing liquid,

a copy with a black image on a grey foggy background is' also obtained, which does not show off-shades and the azo-dyestuif of which is highly resistant to acid.

The latter compound is prepared as follows:

2.5 dichloronitrobenzene is converted into 2-o,pdichlorophenoxy--chloronitrobenzene (melting point 85 C.) by fusion with 2.4-dichlorophenol and potassium hydroxide in the presence of copper powder. This compound is reduced catalytically, after which the amino compound thus obtained is methylated to 2-o,p-dichlorophenoxy-S-chlorodirnethylaniline (boiling point 25 mm, 188-192" C.). This compound is nitrated to 2-o,pdichlorophenoxy-S-chloro-4-nitro dimethylaniline, which compound is reduced and converted into the diazo compound in the usual way.

Example III 4 N methyl N-benzylamine S-p-chlorophenoxybenzene diazoniumchloride, zinc chloride double salt g 28 Citric acid g 5 Ethanol, 96% cm. 250 Water m 750 The excess of liquid is squeezed off and the sensitized layer is dried. It contains approximately 0.9 millimole of diazo compound per 111.

A sheet of the diazotype material thus prepared is imagewise exposed as described in Example I. The endpoint of the exposure can be observed very well; it is reached very soon.

The latent diazotype copy thus obtained is developed by treating its image surface with a developing liquid of the following composition:

N-methyl-4-hydroxyquinolone-2 Isopropylnaphthalene sulphonic acid as sodium salt 2 Sorbitol 25 Potassium tetraborate (5 aq.) 74 Potassium hydroxide 12.6

in 1000 cm. of water.

The developed copy shows a strong red image on a uniformly foggy background having the same red colour. The red azo-dyestuff is highly resistant to a decrease of the pH. Upon. being wetted with a liquid with pH 2, it does not change its colour.

When, instead of the above-mentioned diazo compound, a corresponding diazo compound having an alkoxy group instead of the p-c hlorophenoxy group is used, a red-violet image is obtained, the colour of which changes to yellow upon treatment with the said liquid with pH 2.

The diazo compound used according to this example is prepared as follows:

By reaction of o-nitro chlorobenzene with p-chlorophenol in an alkaline medium at about C., 2-nitro-4- chloro diphenyl ether is prepared, which is reduced to 2- amino-4'-chlorodiphenylether. This product is methylated to 2 p chlorophenoxy-N,N-dimethylaniline (boiling point 13 mm 187 C.) This compound is nitrated and the 4-nitro 2-p-chlorophenoxy-N,N-dimethylaniline thus obtained is reduced and converted into the diazo compound in the usual way.

Example IV White base-paper of weight 80 g./m. as used for the diazotype process is sensitized with a solution of: 4-di(acetoxyethyl) amino-3-p-chlorophenoxy-6-chlorobenzene diazonium chloride zinc chloride double salt g 36 Tartaric acid g 5 1,3,6-naphthalene trisulphonic acid sodium salt g 30 Polyvinylacetate dispersion Vinnapas H.60 cm. 30 in 1000 cm. of water and dried.

The sensitized surface contains approximately 0.5 millimole of diazo compound per m. The diazotype paper has good keeping qualities.

A sheet of the diazotype paper is image-wise exposed as described in Example I. The endpoint of the exposure can be observed very well; it is reached very soon.

The latent diazotype copy thus obtained is developed by applying on its image-surface a layer of approximately 8 g./m. of a developing liquid of the following composition:

Grams Thiourea 10 Phloroglucinol 6.5 Resorcinol 4 Z-ethylhexylsulphuric acid mono-ester as sodium salt 1.2 Sodium formate 14 Sodium benzoate 22 Sodium citrate (2 aq.) 47 Citric acid 1.2

in 1000 cm. of water.

9 When a sheet of the diazotype paper according to this example is image-wise exposed and developed-with a developing liquid of the following composition:

Grams Thiourea 31 Phloroglucinol 6.5 Resorcinol 6.5 Isopropylnaphthalene sulphonic acid sodium salt 2 Sorbitol 5 Saccharose 15 Potassium tetraborate (5 aq.) 53 Potassium hydroxide 9 White base-paper suitable for the diazotype process, of 80 g./m. weight, is sensitized with a solution of:

4-dimethylamino 3-phenoxy 6-chlorobenzene diazonium chloride, zinc chloride double salt g 17 4-(4-methylphenyl) mercapto 2,5-di-n-propoxybenzene diazonium chloride, zinc chloride double salt g 1.8 Tartaric acid g 3.5 Boric acid g 1.5 Polyvinyl acetate dispersion Vinnapas H.60 cm. 30

in 1000 cm. of water and dried.

The sensitized surface contains approximately 0.46 millimole of diazo compound per m. about 92% is formed by the main component of the mixture of diazo compounds.

A sheet of the diazotype paper is image-wise exposed as described in Example I. The endpoint of the exposure can be clearly observed; it is reached very soon.

The latent diazotype copy thus obtained is developed by applying on its image surface a layer of approximately 8 g./m. of a developing liquid of the following composition:

Grams Thiourea 10 Phloroglucinol 4 Sulphonated succinic acid di-isobutylester (commercially available under the trade name of Aerosol IB) 3 Citric acid 1 Sodium benzoate 25 Tertiary sodium citrate (5 aq.) 100 in 1000 cm. of water.

The pH of the developing liquid is about 6.3.

The developed copy shows a black image on a uniformly foggy background. The image becomes visible considerably sooner than when, instead of the above-mentioned mixture of diazo compounds, exclusively 20.6 g. of the main component is used in the sensitizing liquid. The azodyestutf in the foggy background has the same colour as that in the black image portions. The black azo-dyestulf is highly resistant to a decrease of the pH.

If the base-paper has a smooth surface and the developing liquid is applied with the aid of a roller rotating in a direction opposite to that of the movement of the copy, the developed image may show some bleeding owing to the movement, during the development, of molecules of the diazo compound forming the main component of the mixture. In consequence of this bleeding the azo-dyestufi portions show a non-sharp boundary in the form of an edge of clearly visible feathering varying in length between a few tenths of a millimetre and a few millimetres. This edge is completely absent, or much shorter, or much less visible, when the phenoxy group in the diazo compound forming the main component of the mixture carries a chlorine atom as substituent.

What we claim is:

1. A one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive diazo compound of the formula /R: XNg N in which is selected from the class consisting of dialkylamino groups, N-alkyl-N-benzylamino groups, N-alkyl-N-cyclohexylamino groups, (alkyl)(acyloxyalkyl)amino groups, di(acyloxyalkyl)amino groups and the morpholino ring,

R is a phenyl group,

X is an anion, and

Y is selected from the class consisting of hydrogen and halogen atoms.

2. A one-component diazotype material according to claim 1, wherein one of R and R is a benzyl group.

3. A one-component diazotype material according to claim 1, wherein each of R and R is an alkyl group containing at most 2 carbon atoms.

4. A one-component diazotype material according to claim 1, wherein at least one of R and R is an acyloxyalkyl group.

5. A one-component diazotype material according to claim 1, wherein Y is a chlorine atom.

6. A one-component diazotype material according to claim 1, wherein R is a phenyl group.

7. A one-component diazotype material according to claim 1, wherein R is a chloro-phenyl group.

8. A one-component diazotype material according to claim 1, wherein each of R and R is an alkyl group containing at most 2 carbon atoms, R is a chloro-phenyl group, and Y is a chlorine atom.

9. l-diazo 4-(di-alkylamino) 3-phenoxy benzene compounds.

10. l-diazo 4-(di-alkylamino) 3 (4 chlorophenoxy) 6-chloro benzene.

11. l-diazo 4-dimethylamino 3 (4' chlorophenoxy) 6-chlorobenzene.

12. l diazo 4 diethylamino 3 (4' chlorophenoxy) 6-chlorobenzene.

13. l-diazo 4-di(acetyloxyethyl)amino 3 (4' chlorophenoxy) 6-chlorobenzene.

14. A one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dimethylamino 3-phenoxy benzene.

15. A one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-(methyl) (benzyl) amino 3-phenoxy benzene.

16. A one-component diazotype material comprising a support, sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a

1 1 light-sensitive l-diazo 4-di(-acetoxyethyl) amino 3-p-chlorophenoxy 6-chlorobenzene.

17. A one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dialkyl amino 3-p-chlorophenoxy 6-chlorobenzene in which the alkyl groups each contain at most 2 carbon atoms.

18. A one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dimethylamino 3-p-chlorophenoxy 6-chlor0benzene.

19. A process for the production of a diazotype print which comprises imagewise exposing to actinic light a diazotype material as defined in claim 1 and developing the exposed material by applying to it a film of a liquid developer containing phloroglucinol.

20. A process for the production of a diazotype print diazotype material as defined in claim 15 and developing the exposed material by applying to it a film of a weakly acid liquid developer containing phloroglucinol.

References Cited UNITED STATES PATENTS 2,405,523 8/1946 Sease et al 96---91 3,169,869 2/ 1965 Hendrick 96 91 FOREIGN PATENTS 528,606 7/1931 Germany. 865,451 2/ 1953 Germany. 425,235 3/ 1935 Great Britain. 564,343 2/ 1958 Belgium.

OTHER REFERENCES Chemical Abstracts, vol. 46, p. 3510a, April 1952.

NORMAN G. TORCHIN, Primary Examiner.

which comprises imagewise exposing to actinic light a 20 CL BOWERS, JR-,Assismnt Examiner-

Claims

1. A ONE-COMPONENT DIAZOTYPE MATERIAL COMPRISING A SUPPORT SENSITIZED WITH A LIGHT-SENSITIVE COMPOSITION CONTAINING, IN THE ABSENCE OF AN AZO COUPLING COMPONENT, A LIGHT-SENSITIVE DIAZO COMPOUND OF THE FORMULA