DE1251656B - Diazotype material containing an o-Ammo benzoldiazoverbmdung - Google Patents

Description

TUNDED REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL: G 03 c

.: 57 b-12/05 / f% Q // O

German class

Number: 1 251 656

File number: C 31981IX a / 57 b

Filing date: January 27, 1964

Open date: October 5, 1967

The invention relates to a diazotype material which contains a new diazo compound. This diazotype material can be a one-component diazotype material or two-component diazotype material. At the Two-component di-type material can be developed with ammonia vapor or with heat.

In Fiat Final Report 813, pp. 86, 87 and 1095, there are benzene diazo compounds with an N-acetyl-N-methylamino group described in o-position. In addition, they can carry methyl or methoxy substituents. These diazo compounds have practically no photosensitivity and are very unstable; they couple active, but form bright yellow to red azo dyes. With these diazo compounds no in the Practically suitable diazotype material can be produced.

The German patent specification 881754 describes o-aminobenzene diazo compounds, which in the p-position to the amino group is an alkyl, aryl, aralkyl, alkoxy, Aryloxy, aralkyloxy, alkyl mercapto, aryl mercapto, aralkyl mercapto or acylamino group or a Halogen atom and can have an acylamino group in the p-position to the diazo group. As examples of Diazo compounds with an etherified oxy group in the p-position to the o-amino group and an acylamino group in the p-position to the diazo group are in the patent only 4-diazo-5-piperidino-2-methoxy-N-benzoylaniline, 4-diazo-5-dimethylamino-2-methoxy- N-benzoylaniline and 4-diazo-5-dimethylamino-2-ethoxy-N-benzoylaniline called.

The amino group in o-position to the diazo group is the same as with the others in this patent mentioned diazo compounds have a basic tertiary amino group.

The invention relates to a diazotype material which contains an o-aminobenzene diazo compound which is found in p-position to the amino group an etherified oxy group and in p-position to the diazo group one has further substituents and is characterized in that it is a diazo compound of general formula

N ₂ X

R ₁ O

n;

R ₁

CO-R,

wherein X is an anion, R _{1 is} an alkyl, branched alkyl, cycloalkyl or aralkyl radical, —CO — R _{2 is} an acyl group, R _{n is} a substituent from the group acylamino, diazotype material, the one
Contains o-aminobenzene diazo compound

Applicant:

Chemical Fabriek L. van der Grinten N.V.,

Venlo (Netherlands)

Representative:

Dipl.-Chem. Dr. I. Ruch, patent attorney,

Munich 5, Reichenbachstr. 51

Named as inventor:
Andreas Joseph Johannes Hendrickx,
Adrianus Marie Petrus Hectors,
Venlo (Netherlands)

Claimed priority:

Netherlands of! February 1963 (288 469)

Alkylsulfonamido, aralkylsulfonamido, arylsulfonamido and triazinyl and R _{4 is} an alkyl, branched alkyl, cycloalkyl, aralkyl or aryl radical.

It has been found that the o-aminobenzene diazo compounds contained in the diazotype material of the invention of the above formula have considerably higher coupling activity than those for example diazo compounds known from German patent specification 881754. With polyhydric phenols, like phloroglucinol and resorcinol, they form azo dyes with greater absorption for UV radiation than the corresponding 2,5-di- (alkyl, aralkyl or aryl) -oxy-compounds (these compounds are hereinafter referred to as 2,5-Di-RO compounds).

The diazotype material according to the invention is preferably a one-component diazotype material. By developing with the usual weakly acidic phloroglucinol developers, it gives copies with dark red to brown azo dye images; by developing with the usual weakly alkaline phloroglucinol developers it gives copies with lighter colored ones orange-red to brown azo dye images.

However, it can also be a two component diazotype material. In this case one will be slow coupling azo component such as 7'-hydroxy-1 ', 2', 4,5-naphthimidazole, 2-hydroxynaphthalene-3,6-disulfonic acid or 7-hydroxy-1-biguanidinonaphthalene is used.

709 650/359

The diazotype material according to the invention can also be heat-developing diazotype material.

For example, the following diazo compounds can be used:

^ Diazo-S-N-acetyl-N-methylamino ^ -methoxy-N-acetylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2 (4'-chlorophenoxy) -N-acetylaniline,

^ -Diazo-S-N-octanoyl-N-methylamino ^ -ethoxy-N-acetylaniline,

■ WDiazo-S-N-acetyl-N-ethylamino ^ -methoxy-N-phenacetylaniline,

^ Diazo-S-N-acetyl-N-methylamino ^ -n-propoxy-N-benzoylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2-methoxy-N- (2 ', 4'-dichlorobenzoyl) aniline, 4-Diazo-5-N-acetyl-N-methylamino-2-cyclopentyloxy-N -benzoylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2-methoxy-N-naphthoyl- (l) -aniline,

^ Diazo-S-N-acetyl-N-methylamino ^ -n-butoxy-N-benzoylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2-isobutoxy-N- (2'-chlorobenzoyl) aniline,

4-Diazo-5-N-acetyl-N-methylamino-2- (4'-chlorophenoxy) -N-benzoylaniline,

4-Diazo-5-N-propionyl-N-propylamino-2-benzyloxy-N-butyrylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2-methoxy-N-ethoxycarbonylaniline,

4-Diazo-5-N-propionyl-N-isoamylamino-2-ethoxy-N-propoxycarbonylaniline, 4-Diazo-5-N-butyryl-N-ethylamino-2-methoxy-N-benzyloxycarbonylaniline,

4-Diazo-5-N-acetyl-N-methylamino-2-methoxy-N-phenoxycarbonylaniline,

4-Diazo-5-N-acetyl-N-isopropylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-acetyl-N-n-butylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-acetyl-N-n-hexylamino-2-methoxy-N-benzoylaniline,

4-diazo-5-acetyl-N-cyclohexylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-acetyl-N-benzylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-formyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-chloroacetyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-isobutyryl-N-methylamino-2-isopropoxy-N-benzoylaniline,

i-Diazo-S-N-butyryl-N-methylamino ^ -methoxy-N-benzoylaniline,

4-diazo-5-N-hexanoyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-phenylacetyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-benzoyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-furoyl- (2) -N-methylamino-2-methoxy-N-benzoylaniline,

4-Diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-diazo-5-N-isobutyloxycarbonyl-N-methylamino-2-methoxy-N-benzoylaniline, 4-Diazo-5-N-benzyloxycarbonyl-N-methylamino-2-methoxy-N-benzoylaniline,

4-diazo-5-N-phenoxycarbonyl-N-methylamino-

2-methoxy-N-benzoylaniline,

4-diazo-5-N-cyclohexyloxycarbonyl-N-methyl-

amino-2-methoxy-N-benzoylaniline,
4-Diazo-5-N- (2-phenoxyethoxycarbonyl) -

N-methylamino-2-methoxy-N-benzoylaniline,

4-diazo-5-N-furfuryloxycarbonyl-N-methyl-

amino-2-methoxy-N-benzoylaniline,

N, N'-bis (4-diazo-5-N-acetyl-N-methylamino-2-methoxyphenyl) urea,

N-phenyl-N '- (4-diazo-5-N-acetyl-N-methylamino-2-methoxyphenyl) urea,

Oxalic acid bis (N-methyl-N-2'-diazo-5'-benzoyl-

amino-4'-methoxyphenylamide),
Adipic acid-bis- (N-methyl-N-2'-diazo-5'-benzoylamino-4'-methoxyphenylamide),

Adipic acid-bis- (4'-diazo-5'-N-acetyl-N-methyl-

amino-2'-methoxyphenylamide),

4-Diazo-5-N-acetyl-N-ethylamino-2-methoxy-
»O p-toluene-sulfonamido-benzene,

i-Diazo-S-N-acetyl-N-methylamino ^ -n-propoxymethylsulfonamido-benzene,

l- (4'-Diazo-5'-N-acetyl-N-methylamino-2'-meth-

oxyphenyl) -2-amino-4-imino-6-methyltriazinyl, 3.5).

The diazo compounds are used in the form of their diazonium salts, such as diazonium chlorides, sulfates, nitrates and metal chloride double salts (for example diazonium chlorozincates, chlorostannates), borofluorides. They can be used individually or mixed together in the diazotype material. The diazo compounds which can be used in the diazotype material according to the invention can all be prepared using the 4-chloro-2-aminophenol alkyl, branched alkyl, cycloalkyl, aralkyl or aryl ethers as starting material. The 4-chloro-2-aminophenolalkyl, branched alkyl, cycloalkyl and aralkyl ethers can be obtained from 4-chlorophenol by introducing a nitro group in the o-position to the hydroxyl group, etherifying the hydroxyl group and the nitro group reduced to an amino group.
The 4-chloro-2-aminophenolaryl ethers are obtained by fusing 2,5-dichloronitrobenzene with a hydroxy aryl compound and potassium hydroxide and reducing the nitro group.

The amino group of the 4-chloro-2-aminophenol alkyl, branched alkyl, cycloalkyl, aralkyl or aryl ether will

a) or acylated with, for example, a carbohalide or an ester of chloroformic acid

b) converted into a sulfonamide group with the aid of an organic sulfochloride or

c) reacted with dicyandiamide to form a biguanidino group, after which the Ring closure to a triazinyl ring with a

O ₀ organic carboxylic acid or its anhydride takes place.

In this way the ether of 4-chloro-2- (acylamino, sulfonamido or triazinyl) phenol. This ether is nitrated, after which its chlorine atom by a monoalkyl branched alkyl, cycloalkyl or aralkylamino group, which subsequently is acylated, is replaced.

The 4-acyl, 4-sulfonamido or 4-Triazinyl-2-N-acyl-N- (alkyl, branched alkyl, cycloalkyl or aralkyl) -amino-5- (alkyl, branched alkyl, cycloalkyl, aralkyl or aryl) -oxy-nitrobenzene is reduced to the corresponding amine, from which then a diazo compound is produced in the usual manner.

A diazotype material according to the invention, which is a diazo compound of the general formula according to FIG. 1, in which X is an anion, R ₁ for a non-branched alkyl group with at most 5 carbon atoms, —CO — R ₂ for an acyl group, R _{3 represents} a substituent from the group acylamino and triazinyl groups and R _{4 represents} an alkyl, aralkyl or aryl radical. This diazotype material not only couples faster, but also has a considerably higher photosensitivity than diazotype material which is sensitized with a corresponding 2,5-di-RO compound.

For a one-component diazotype material according to the invention, a diazo compound of the general formula according to FIG. 2 are suitable, in which X is an anion and R _{1 is} a non-branched alkyl group with at most 5 carbon atoms, R _{2 is} a hydrogen atom, an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group, R _{3 is} is an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group and R _{4 is} an alkyl or benzyl radical. Such diazotype material has satisfactory photosensitivity and develops very rapidly when weakly acidic phloroglucinol developers are used. In addition, on development with the above-mentioned developers, copies with azo dyes are produced which often have better absorption for UV radiation than diazotype material which is sensitized with the corresponding Di-RO compounds. Accordingly, the diazo compounds according to the above general formula are extremely suitable for the sensitization of transparent one-component diazotype material for development with weakly acidic phloroglucinol developers.

Among these diazo compounds, those in which R _{2 is} an alkoxy, benzyloxy or phenoxy group stand out. They are more stable than the corresponding diazo compounds in which R _{2 is} an alkyl, benzyl or phenyl radical, and the azo dyes obtained from them are darker and have better waterfastness than those obtained from the corresponding diazo compounds mentioned above, so that with the Diazo compounds in which R _{2 is} an alkoxy, benzyloxy or phenoxy group, a diazotype material of good stability can be prepared from which copies are obtained with a fairly dark brown azo dye image showing no or very little bleeding of the azo dye on development. Since the azo dye also has good absorption for UV radiation, these diazo compounds are extremely suitable for the sensitization of transparent diazotype materials. The copies show a dark, easily legible image with good absorption for UV radiation and are therefore very suitable for use as transparent intermediate originals.

In the diazotype material according to the invention, those commonly used in diazotype materials used tools.

Below are three weakly acidic phloroglucinol developers and one weakly alkaline phloroglucinous developer, which are used in practice and which are used in the following examples for development will be described.

Developer A is a solution of

4 g phloroglucine,

0.1 g acetoacetanilide,
3 ml 2-ethyl hexyl sulfate,
15 g beet sugar,
2.5 g benzoic acid,
14 g sodium benzoate and
g sodium formate
in 1000 ml of water.

The pH of this liquid is around 5.8.

Developer B is a solution from

6.5 g phloroglucine,
ao 4 g resorcinol,

10 g thiourea,

2 g sodium salt of butylnaphthalene

sulfonic acid,
14 g sodium formate,
22 g sodium benzoate,

49 g trisodium citrate (2 aq.) And

1.2 g citric acid
in 1000 ml of water.

The pH of this liquid is 6.5.

Developer C is a solution from

5 g phloroglucine,
1 g resorcinol,

3 g dipotassium phosphate,
3 ml 2-amyl-hexyl sulfate,

52 g maleic anhydride and
75 ml potassium hydroxide solution (13.5 normal)
in 1000 ml of water.

The pH of this liquid is 6.9.

Developer D is a solution from
30 g thiourea,

5.4 g phloroglucine,

6.5 g resorcinol,

Ig of the potassium salt of hydroquinone

monosulfonic acid,
5 g sorbitol,
15 g beet sugar,
50 g potassium tetraborate (5 aq.) And
1.5 g of isopropylnaphthalenesulfonic acid

in 1000 ml of water.

The pH of this liquid is around 9.5.

example 1

White base paper of 80 g / m ² for the diazotype process, which was coated with an aqueous silica dispersion and then dried, is sensitized with a liquid containing 10 g of the double salt of 4- (4'-methylphenyl) -sulfonylamino-S-methoxy ^ -N-methyl-N-acetylaminobenzene-diazonium chloride and zinc chloride, 8 g of tartaric acid, 4 g of boric acid, 600 ml of a polyvinyl acetate dispersion and ml of water, and dried.

An intermediate layer is formed on the photosensitive layer by adding a solution of 100 g of polyvinyl acetate in 1000 ml of trichlorethylene spreads on it and dries.

A top layer is applied to the intermediate layer with the aid of a liquid containing 5 g of 2,3-dihydroxynaphthalene, 20 g of non-colloidal silicon dioxide, 46 g of N-acyl-N'-2-hydroxyethylethylenediamine and contains 1000 ml of ligroin.

The dried photosensitive material is exposed imagewise under a transparent drawing made with Chinese ink until the diazo compound has faded under the non-image parts of the drawing, and is then developed by passing it over a heated roller at a temperature of about 140 ^° C with the back of the sheet in contact with the surface of the roller.

The copy shows a red-brown image on a white background.

In the above-mentioned sensitizing liquid, an equivalent amount of the corresponding 4- (4'-methylphenyl) sulfonylamino-2,5-diethoxybenzenediazo compound is used, the resulting photosensitive compound Material is considerably less sensitive to light and has a slower development rate.

The diazo compound used in the example is prepared as follows: 5-chloro-2-methoxyaniline is reacted with sodium p-toluenesulfonyl chloride and then nitrated. The S-methoxy ^ -p-tosylamino-2-chloro-1-nitrobenzene is reacted with monomethylamine, and the reaction product thus obtained is acetylated. The melting point of the thus obtained 5-methoxy-4-p-tosylamino-2-N-acetyl-N-methylamino-1-nitrobenzene 190 ⁰ C. This nitro compound is reduced catalytically to the corresponding amine, which is then diazotized. The diazonium compound thus formed is obtained in the form of the zinc chloride double salt.

Example 2

White base paper of 50 g / m ² for the diazotype process is made transparent in the usual manner by treating with a resin solution in an organic solvent and drying, and then sensitized with a solution of 50 g of the double salt of 4-benzoylamino-2-N-acetyl -N-methylamino-5-ethoxybenzenediazonium chloride and zinc chloride, 3 g of tartaric acid, 1 g of boric acid, 40 g of the sodium salt of naphthalene-l, 3,6-trisulfonic acid, 2.5 g of gum arabic, 120 g of rice starch and 40 ml of a polyvinyl acetate dispersion in 1000 ml of water.

A sheet of dry photosensitive material is drawn imagewise under a transparent pencil exposed until the diazo compound under the white parts of the original is largely faded and then with the developer B described above by the so-called thin film method developed.

The copy shows a brown image on a veiled light brown background.

The image has good absorption for UV radiation, making the copy well suited for one use as an intermediate original for the production of further copies on diazotype material.

Use an equivalent amount (about 4 g) of the double salt in the mentioned sensitizing liquid of 4-benzoylamino-2,5-diethoxybenzoldiazonium chloride and zinc chloride used, this is what is obtained photosensitive material considerably less photosensitive, has a slower development speed and results in a copy with a dark brown image on a reddish brown background, that has a lower absorption for UV radiation.

The diazo compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide to 2-nitro-4-chloro-l-ethoxybenzene. The nitro group of this product is catalytically reduced, after which the free amino group is benzoylated. The 2-benzoylamino-4-chloro-1-ethoxybenzene thus formed is nitrated, then reacted with monomethylamine and then acetylated, whereby 5-ethoxy-4-benzoylamino-2-N-acetyl-N-methylamino-1-nitrobenzene from mp 194 to 195 ° C is obtained. After the nitro group this compound is catalytically reduced and the amine thus formed is diazotized, becomes the diazonium compound obtained in the form of the zinc chloride double salt.

Example 3

A cellulose acetate film layer of about 20 g / m ² , applied to transparent paper of about 80 g / m ² , is superficially hydrolyzed to a depth of about 4 μ and, after removing the chemicals used for the hydrolysis, sensitized with a solution by washing with water 34 g of double salt of 4-benzoylamino-2-N-hexanoyl-N-methylamino - 5 - methoxybenzene - diazonium chloride and zinc chloride, 4 g of citric acid, 2 g of gelatin and 250 ml of ethanol (96 ° / _o pure) in 750 ml of water and then dried.

A sheet of dry transparent diazotype paper is imagewise under an ink drawing exposed until all of the diazo compound under the non-image parts of the original is bleached, and then developed with developer B according to the thin film method. The obtained transparent copy shows a brown image that has pretty good absorption for UV radiation.

If the transparent diazotype paper produced as described above is made with otherwise the same material, excluding the above-mentioned diazonium compound, instead of the double salt of 4-benzoylamino - 2,5 - dimethoxybenzenediazonium chloride and zinc chloride is used for sensitization, compared, it is found that the latter diazotype material is less light-sensitive and less sensitive Development speed possesses. Copies with violet-brown azo dye images are obtained.

The diazo compound used according to the example is prepared as follows: S-chloro ^ -methoxyaniline is benzoylated and then nitrated. The 5-chloro-4-nitro-2-methoxy-N-benzoylaniline thus formed is reacted with monomethylamine and then acetylated with hexanoyl chloride. The 5-methoxy ^ -benzoylamino ^ -N-hexanoyl-N-methylamino-1-nitrobenzene melts at 117 to 119 ⁰ C. The nitro group of this compound is catalytically reduced, and the amine thus formed is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.

example

A cellulose acetate film layer of about 20 g / m ² , applied to a transparent paper of about 80 g / m ² , is superficially hydrolyzed to a depth of about 4 μ and after removing the for

the hydrolysis chemicals used by washing with water sensitized with a solution of 57 g double salt of 4-benzoylamino-2-N-acetyl-N-η-butylamino-5-methoxybenzene-diazonium chloride and zinc chloride, 5 g of tartaric acid, 2.5 g of gum arabic, 50 g of the sodium salt of naphthalene-1,3,6-trisulfonic acid and 250 ml of ethanol (96%) in 750 ml of water and then dried.

A sheet of the dry, transparent diazotype paper is imagewise exposed and developed as described in example 3. The copy obtained in this way shows a purple-brown image that has good absorption for UV radiation.

If a copy is made in the same way on the same transparent diazotype paper that is obtained, if in the above solution the double salt of 4-benzoylamino-2,5-dimethoxybenzene-diazonium chloride and zinc chloride is used instead of the diazonium compound mentioned, so it is found that the diazotype material produced is less sensitive to light, develops more slowly and copies with azo dye images with less absorption for UV radiation.

The diazo compound used in the example is prepared as follows: 5-chloro-2-methoxyaniline is, as described in Example 3, in 5-chloro-4-nitro-2-methoxy-N-benzoylaniline convicted. This product is then used to react with mono-n-butylamine brought and acetylated to form S-methoxy- ^ benzoylamino ^ -N-acetyl-N-n-butylamino-1-nitrobenzene from 145 to 146 ° C. In the manner described in Example 3, this nitro compound converted into the diazonium compound obtained in the form of the zinc chloride double salt will.

Example 5

By immersion, transparent linen is coated with a layer of about 70 g / m ^{2 of} the following liquid:

100 g polystyrene copolymer,

30 g polyvinyl acetate,

50 ml of ethyl acetate and
900 ml of ethanol (96%).

After drying, a layer of about 80 g / ^{m2 of} a liquid of the following composition is applied to the hydrophobic adhesive layer thus formed:

60 g partially hydrolyzed polyvinyl acetate,
5 g of the sodium salt of isopropylnaphtha-

linsulfonic acid,

500 ml of ethanol (96%) and
500 ml of water.

After drying there is a hydrophilic polyvinyl acetate layer (Thickness about 4.5 μ) on the adhesive layer.

The hydrophilic polyvinyl acetate layer is sensitized with a solution of 42 g of the double salt of 4-acetylamino-5-ethoxy-2-N-octanoyl-N-methylaminobenzene-diazonium chloride and zinc chloride, 5 g tartaric acid, 2 g gelatin, 250 ml ethanol (96%) and 750 ml water and dried.

The hydrophilic photosensitive layer obtained after drying contains about 0.9 millimoles Diazo compound per square meter of sensitized surface.

A sheet of the transparent diazotype linen thus obtained is, as described in Example 2, imagewise exposed and developed. The copy thus obtained shows a dark brown azo dye image on a veiled light brown background. The azo dye image has good absorption for UV radiation. As a result, the copy is extremely suitable for use as an intermediate original Making further copies.

ίο Will be a in the above sensitizing fluid corresponding amount of the double salt of 4-acetylamino-2,5-diethoxybenzene-diazonium chloride and zinc chloride is used, the photosensitive material thus obtained is considerably less photosensitive, has a slower developing speed and results in a copy with a purple-brown image a slightly purple background that has less absorption for UV radiation.

The diazo compound used in the example is prepared as follows: 4-chlorophenol is nitrated and ethylated with ethyl bromide to form 2-nitro-4-chloro-1-ethoxybenzene. The nitro group of this Compound is catalytically reduced, after which the amino group thus obtained is acetylated. That 2-acetylamino-4-chloro-1-ethoxybenzene thus formed is nitrated with monoethylamine for reaction brought and then acylated with octanoyl bromide, wherein 5 - ethoxy - 4 - acetylamino - 2 - N - octanoyl - N - methylamino-1-nitrobenzene from mp 125 to 127 ° C is obtained. After the nitro group of this compound has been reduced and the amine thus formed has been diazotized, the diazo compound is obtained in the form of the zinc chloride double salt.

Example 6

A clear cellulose acetate film of 150 g / m ² with an acetyl content of about 2.5 acetyl groups per glucose unit of the cellulose acetate is hydrolyzed on the surface to a depth of about 4 μ and, after the chemicals used for the hydrolysis have been removed, sensitized with a solution by washing with water of 80 g of 1- (4'-diazo-5'-N-acetyl-N-methylamino-2'-methoxyphenyl) - ^ -amino ^ -imino-o-methyl-1,3,5-triazine, 4 g of tartaric acid , 10 g of the potassium salt of benzene-l, 3-disulfonic acid, 1 g of gum arabic, 250 ml of ethanol (96%) and 750 ml of water and dried.

The diazotype material thus obtained is very light-sensitive and has a high development speed. A sheet of this diazotype material is placed under a transparent one with a Chinese Ink-executed drawing exposed imagewise until the entire diazo compound is among the non-image Parts of the drawing are bleached and then developed with developer B.

The copy shows a brown image on a crystal clear background. The copy thus obtained is extraordinary well suited for use as an intermediate original for the production of further copies.

The azo dye image has good absorption for UV radiation.

The diazo compound used in the example is prepared as follows: 5-chloro-2-methoxyaniline (HCl salt) is made to react with dicyandiamide, S-chloro ^ -methoxy-l-biguanidinobenzene is obtained. With the help of acetic anhydride, this compound is converted into l- (5'-chloro-2'-methoxyphenyl) -2-amino-4-imino-6-methyl-triazine- (l, 3,5)

709 650/359

converted. This compound is nitrated, after which the product thus obtained is reacted with monomethylamine. In this way, 1- (4'-nitro-5'-N-methylamino-2'-methoxy) -2-amino-4-imino-6-methyl-triazine with a melting point of 298 to 300 ^° C. is obtained. This product is acetylated, after which the nitro group is reduced. The amino compound is diazotized and the diazonium compound thus prepared is obtained in the form of the above-mentioned salt.

Example 7

A clear cellulose acetate film of 150 g / m ² with an acetyl content of about 2.5 acetyl groups per glucose unit of the cellulose acetate is hydrolyzed on the surface to a depth of about 4 μ and, after the chemicals used for the hydrolysis have been removed, sensitized with a solution by washing with water of 42.5 g N, N'-bis- (4'-diazo-S'-N-acetyl-N-methylamino-o'-methoxyphenyO-urea-bis- (zinc chloride double salt), 7.5 g citric acid, 40 g of the sodium salt of naphthalene-1,3,6-trisulfonic acid, 500 ml of ethanol (96 ° / _o solution) and 500 ml of water and dried.

The photosensitive layer obtained after drying contains about 0.5 mmol of diazo compound each Square meters of the sensitized surface.

A sheet of the diazotype material thus produced is imagewise exposed and developed, as in the example 3 described. The copy obtained in this way shows a red-brown image on a crystal-clear background. The azo dye image has good absorption for UV radiation.

The diazo compound used in this example is prepared as follows: 4-methoxyaniline is nitrated to give 4-methoxy-3-nitroaniline, and this product is converted with p-tosyl chloride to 4-methoxy-3-nitro-Np-tosylaniline, which is methylated with dimethyl sulfate, after which it is hydrolyzed to 4-methoxy-3-nitro-N-methylaniline. This compound is acetylated and its nitro group is reduced to give 2-methoxy-5-N-acetyl-N-methylaminoaniline. This compound is made to react with phosgene. This forms N, N '- bis - (2 - methoxy - 5 - N - acetyl - N - methylaminophenyl) urea, from which N, N' - bis - (2 - methoxy - 5 - N - acetyl- N-methylamino-4-nitrophenyl) urea with a melting point of 279 to 283 ^° C. is obtained. This nitro compound is converted into the above-mentioned diazonium salt in the usual manner.

Example 8

Transparent linen for diazotype materials is sensitized with a solution of 34 g of the zinc chloride double salt of 4-phenacetylamino-5-methoxy-2-N-acetyl-N-ethylaminobenzene-diazonium chloride, 4 g tartaric acid, 1.5 g boric acid, 60 g of the potassium salt of benzene-1,3-disulfonic acid, 300 ml of ethanol (96%) and 700 ml of water and dried.

A sheet of the diazotype material thus obtained is exposed imagewise as described in Example 3, and developed with developer C.

The copy obtained shows a brown azo dye image.

In the above sensitizing liquid, an equivalent amount of the double salt of 4-phenylacetylamino - 2,5 - dimethoxybenzol - diazonium chloride and zinc chloride are used, this is what is obtained photosensitive material considerably less photosensitive, has a slower development speed and results in a copy with a dark brown image.

The diazo compound used in the example is prepared as follows: 5-chloro-2-methoxyaniline is phenacetylated and then nitrated. The 5-chloro-4-nitro-2-methoxy-N-phenacetylaniline thus formed is reacted with monoethylamine and then acetylated. The 5-methoxy-4-phenacetylamino - 2 - N - acetyl - N - ethylamino -1 - nitrobenzene melts at 158 ⁰ C. The nitro group of this compound is reduced to an amino group, and the amine is diazotized. The diazonium compound is obtained in the form of the zinc chloride double salt.

Example 9

White base paper of 80 g / m ² for the diazotype process is sensitized with a liquid containing 20 g of the zinc chloride double salt of

4 - Benzoylamino - 5 - methoxy - 2 - N - benzyloxycarbonyl - N - methylaminobenzene - diazonium chloride, 6 g aluminum sulfate, 10 g glycerine, 40 g rice starch, 30 ml of a polyvinyl acetate dispersion and 1000 ml Contains water, and dried.

A sheet of the diazotype paper thus obtained is drawn imagewise under a transparent ink drawing exposed until all of the diazo compound under the non-image parts of the drawing is bleached out, and then developed with developer A. The copy obtained shows a brown image on a clear white Underground.

In the above sensitizing liquid, use an equivalent amount of the double salt of 4-benzoylamino-2,5-dimethoxybenzene-diazonium chloride and zinc chloride are used, the resulting diazo type photosensitive paper becomes considerably less sensitive to light and has a slow developing speed.

The diazo compound used in the example is prepared as follows: 5-chloro-2-methoxyaniline is benzoylated and then nitrated. Then the 5 - chloro - 4 - nitro - 2 - methoxy - N - bezoylaniline brought to implementation with monoethylamine. 5 - methylamino - 4 - nitro - 2 - methoxy-N-benzoylaniline are obtained, which is acylated with the benzyl ester of chloroformic acid. The S-methoxy ^ -benzoyl-amino-2 - N - benzyloxycarbonyl - N - methylamino-1-nitrobenzene Melts at 132 to 134 ° C. This nitro compound is converted into the zinc chloride double salt in the usual way the diazo compound produced and obtained.

Example 10

A cellulose acetate film layer of about 20 g / m ² , applied to transparent paper of about 80 g / m ² , is hydrolyzed on the surface to a depth of 4 μ and, after removing the chemicals used for the hydrolysis, sensitized with a solution of 56 g of the zinc chloride double salt of 4-Be / izoylamino-

5 - η - butoxy - 2 - N - acetyl - N - methylaminobenzoldiazoniumchlorid, 8 g alum, 60 g of sodium salt of naphthalene-l, 3,6-trisulfonic acid, 1 g of gum arabic, 300 ml of ethanol (96 ° / _o solution) and 703 ml of water and dried.

13 14

A sheet of dry photosensitive Ma- 2-N-acetyl-N-methylamino-l-nitrobenzene melts when terials is under a transparent pencil drawing 202 to 203 ° C. From this nitro compound is exposed imagewise until the diazo compound of the usual Way, the corresponding diazonium is largely produced under the non-image parts of the original, which is bleached in the form of zinc, and is then obtained with developer B ent- 5 chloride double salt,
wraps. The copy shows a brown image on one. .
veiled light brown background. The picture has B e ι s ρ ι e I 12
good absorption for UV radiation, so that the copy is made transparent. A rag paper made transparent is very suitable for use as an intermediate sensitized with a solution of 38 g of N, N'-Dioriginal. io methyl - N - N '- bis - (2' - diazo - 4 '- methoxy-

If a 5'-benzoylaminophenyl) adipic acid diamide, 6 g of nitro-

equivalent amount of the zinc chloride double salt of nenic acid, 1 g of gelatin, 400 ml of ethanol (96%) and

4 - Benzoylamino - 2,5 - di - η - butoxybenzene - di- 600 ml of water and dried,
A sheet of the diazotype material-sensitive material obtained in this way is considerably less sensitive to light, and is imagewise exposed and developed, as described in Example 10. The copy shows a brownness and results in a copy with a black image Image on a veiled light brown background, on a veiled gray background, which The image has good absorption for UV radiation but less absorption for UV radiation. and is therefore very suitable for use

The diazo compound 20 used in the example as an intermediate master.

is prepared as follows: 4-chlorophenol is nitrated The diazo compound used in the example

and butylated with n-butyl bromide. The nitro group is made as follows: 5-methylamino-4-nitro-

of the product obtained is reduced and the 2-methoxy-N-benzoylaniline (see Example 9) is with

benzoylated amino compound formed in the process. The adipyl chloride reacted, with N, N'-di-

2-benzoylamino-4-chloro-l-butoxybenzene 25 methyl - Ν, Ν '- bis - (2' - nitro - 4 '- methoxy-5'-ben-

is nitrated, with monoethylamine to implement zoylaminophenyl) adipic diamide from F. 229 to

brought and then acetylated. In this way 231 ⁰ C is formed. The nitro groups of this

5 - butoxy - 4 - benzoylamino - 2 - N - acetyl-N-methyl bonds are reduced, the amino groups diazoamino-1-nitrobenzene obtained from the MP of 120 to 122 ° C. benefits, and the bis-diazonium compound is in the The above-mentioned form of the zinc chloride double salt is obtained from this nitro compound.

Diazonium salt formed. _,. . ,. "

Example 13

Example 11 White paper of 150 g / m ² , on one side over-

A cellulose acetate film layer of about 20 g / m ² , traced with a cellulose acetate film layer (approx

applied to transparent paper of about 35 50 percent by weight bound acetic acid) with a

80 g / m ² , is applied superficially to a depth of about 10μ thick, using an adhesive

about 4μ hydrolyzed and after removing the bound to the paper and to a depth of

the hydrolysis chemicals used by about 4μ up to an acetyl content, calculated as

Washing with water sensitizes acetic acid bound with a solution, of an average of about 20

of 53 g of the zinc chloride double salt of 4-ethoxy 40 percent by weight (which corresponds to an average number of acyl

carbonylamino - 5 - methoxy - 2 - N - acetyl-N-methyl groups per glucose unit of the cellulose acetate of

aminobenzene-diazonium chloride, 5 g of alum, 60 g of the 0.7 equivalent) is deacylated, is on the e.itacy-

Sodium salt of naphthalene-1,3,6-trisulfonic acid, lined side of the cellulose acetate layer with the fol-

Ig gum arabic, 300 ml ethanol (96%) and low-grade solution impregnated:

700 ml of water and dried. 45

A sheet of dry photosensitive material 63 g of the zinc chloride double salt of 4-Ben-

is shown under a transparent pencil drawing - zoylamino - 5 - η - propoxy - 2 - N-ethoxy-

wise exposed until the diazo compound among the carbonyl - N - methylaminobenzene - di-

non-image parts of the original largely bleached azonium chloride,

is, and then developed with developer D. The 50 ⁴ S tartaric acid,

Copy shows a brown image on a veiled 60 g of the sodium salt of naphthalene light brown background. The picture has good ab- 1,3,6-trisulfonic acid,
absorption for UV radiation, so that the copy is very 2 g gum arabic,
is suitable for use as an intermediate original. 250 ml ethanol (96%),

In the above sensitizing liquid one 55 750 ml of water

equivalent amount of the zinc chloride double salt of _{un £} j dried 4 - ethoxycarbonylamino - 2,5 - dimethoxybenzene-di-

If azonium chloride is used, the resulting light- The diazotype material obtained in this way is very light-sensitive Material considerably less sensitive to light. A sheet of it is exposed imagewise sensitive and has a lower development 60 and developed, as described in Example 3. the speed. Copy shows a purple black image on top of one

The diazo compound used in the example has a white background.

is prepared as follows: 5-chloro-2-methoxyaniline becomes a in the above sensitizing liquid

is with the ethyl ester of chloroformic acid equivalent amount of the zinc chloride double salt of

acylated and then nitrated. The 5-chloro-65 4 -benzoylamino-2,5-dimethoxyberizol-diazonium-

4-nitro-2-methoxy-N-ethoxycarbonylaniline is then used chloride, the resulting photosensitive

Brought to the reaction with monomethylamine and borrowed material considerably less photosensitive

acetylated. The S-Methoxy ^ -äthoxycarbonylamino- and has a slower development rate.

The diazo compound used in the example is prepared as follows: 4-chlorophenol is nitrated and with n-propyl bromide in 2-NiUO ^ -ChIOr-I-PrOpOXybenzene converted. The nitro group of this compound is reduced and the amino compound thus formed benzoylated and nitrated. 5-chloro-4-nitro-2-propoxy-N-benzoylaniline is made to react with monoethylamine and then with the ethyl ester of chloroformic acid to give 5-propoxy

4 - benzoylamino - 2 - N - ethoxycarbonyl-N-methylamino-1-nitrobenzene from mp 124 to 126 ⁰ C acylated. The zinc chloride double salt of diazonium chloride is obtained from this nitro compound in the usual way.

Example 14

Sized, transparent paper of 80 g / m ² is sensitized with a liquid containing 63 g of the zinc chloride double salt of 4-acetylamino-5- (4'-chloro) -phenoxy-2-N-acetyl-N-methylaminobenzene-diazonium chloride , 5 g of alum, 40 g of rice starch, 2 g of gelatin, 50 ml of a polyvinyl acetate dispersion and 950 ml of water, and dried.

A sheet of the dry photosensitive material is imagewise exposed and developed as in FIG Example 8 described. The copy shows a brown image on a transparent background. The picture has good absorption for UV radiation, making the copy very suitable for use as an intermediate original is.

The diazo compound used in the example is prepared as follows: 5-chloro-2- (4'-chloro) -phenoxyaniline is acetylated and then nitrated. The thus-formed 5 - (A '- chloro) - phenoxy -A- acetylamino-2-chloro-l-nitrobenzene is reacted with monomethylamine to implement, after which the reaction product is acetylated. The melting point of the so produced

5 - (4 '- chloro) - phenoxy -A- acetylamino-2-N-acetyl-N-methylamino-1-nitrobenzene is 210 to 212 ° C. The nitro compound is converted in the usual manner into the diazonium compound, which is obtained in the form of the zinc chloride double salt.

Example 15

Sized transparent paper is first coated with an aqueous dispersion of colloidal silica in which anionic dispersed polyvinyl acetate is present as a binder, provided and dried. The paper coated in this way is sensitized with a liquid containing 35 g of des Zinc chloride double salt of 4-benzoylamino-5-methoxy - 2 - N - acetyl - N - methylaminobenzene - diazonium chloride, 50 g tartaric acid, 20 g boric acid, 15 g 7'-hydroxy-1 ', 2', 4,5-naphthimidazole, 30 ml of a polyvinyl acetate dispersion and contains 970 ml of water, and dried.

A sheet of the transparent diazotype paper thus obtained is placed under a transparent one with Chinese ink drawing exposed image by image until the diazo compound under the non-image parts of the original is bleached. The diazotype photosensitive material is immersed in ammonia vapor developed. The copy shows a red image on a clear background.

In the above sensitizing liquid, becomes a equivalent amount of the zinc chloride double salt of 4 - benzoylamino - 2,5 - dimethoxybenzene diazonium chloride is used, the resulting photosensitive material is considerably less photosensitive and has a slower development speed.

The diazo compound used in the example

is prepared as follows: 5-chloro-2-methoxyaniline is successively benzoylated, nitrated and reacted with monomethylamine. The resulting 5 - methoxy -A- benzoylamino - 2 - methylamino-1-nitrobenzene is acetylated. The nitro compound obtained in this way melts at 206 to 208 ^° C. From

ίο this nitro compound is used in the usual way produced the diazonium compound which is obtained in the form of the zinc chloride double salt.

Example 16

White paper coated with a so-called baryta layer is sensitized with a solution of 18.7 g of the zinc chloride double salt of 4-benzoylamino - 5 - (4 '- chlorophenoxy) - 2 - N - acetyl-N-methylaminobenzene-diazonium chloride, 5 g citric acid, 2 g of saponin, 250 ml of ethanol (96 ° / _o solution) and 750 ml of water and dried.

A sheet of the diazotype paper thus obtained is exposed imagewise, as described in Example 15, and then developed with developer A.

The copy shows a purple-red image on a white background.

The diazo compound used in the example is prepared as follows: 5-chloro-2- (4'-chlorophenoxy) aniline is benzoylated and then nitrated. The 5 - (A '- chloro) - phenoxy -A- benzoylamino - 2 - chloro-1-nitrobenzene is reacted with monomethylamine to implement, after which the reaction product is acetylated. The melting point of the thus produced 5 - (A '- chloro) - phenoxy -A- benzoylamino-2-N-acetyl-N-methylamino-1-nitrobenzene is 182-184 ° C. The diazonium compound is prepared from this nitro compound in the usual way and obtained in the form of the zinc chloride double salt.

Example 17

White base paper of 80 g / m ² for the diazotype process is sensitized with a liquid containing 30 g of the zinc chloride double salt of 4 - benzoylamino - 5 - cyclopentyloxy - 2 - N - acetyl-N-methylaminobenzol-diazonium chloride, 5 g citric acid, 30 ml of a polyvinyl acetate dispersion and 970 ml of water, and dried.

A sheet of the diazotype material thus obtained is exposed imagewise as described in Example 2, and then developed with developer A. The copy shows a dark brown image on a veiled one brown background.

Another sheet is also, as described in Example 2, exposed and then with developer D. developed. The copy shows a brown image on a veiled light brown background.

The diazo compound used in the example is prepared as follows: p-Chlorophenol is mixed with Help of cyclopentyl bromide in 4-chloro-l-cyclopentyloxybenzene converted. This product is nitrated, the nitro group is then reduced and the Amino group benzoylated. The 2-benzoylamino-i-chloro-1-cyclopentyloxybenzene thus formed is nitrated, reacted with monomethylamine and acetylated. In this way, 2-cyclopentyloxy-4 - benzoylamino - 2 - N - acetyl - N - methylamino-1-nitrobenzene obtained from m.p. 138 to 141 ° C. These

Nitro compound is used in the usual way converted above-mentioned diazonium salt.

Example 18

A sheet of white base paper for the diazotype process of 80 g / m ² is sensitized with a liquid containing 17 g of 4-benzoylamino-5-methoxy-2-N-acetyl-N-methylaminobenzene-diazonium chloride-zinc chloride double salt, 2.5 g Gum arabic, 5 g of tartaric acid, 2 g of boric acid, 30 ml of a polyvinyl acetate dispersion and 970 ml of water, and dried. The sheet of diazotype paper thus obtained is marked with an A.

Another sheet of white base paper for the diazotype process of 80 g / m ² is sensitized with a liquid containing 15 g of 4-benzoylamino-5-methoxy -2-dimethylaminobenzene-diazonium chloride-zinc chloride double salt, 2.5 g of gum arabic, 5 g of tartaric acid , Contains 2 g of boric acid, 30 ml of a polyvinyl acetate dispersion and 970 ml of water, and dried ao. The light-sensitive diazo compound of this material is known from German patent specification 881,754. The obtained sheet of diazotype paper is marked with B.

A strip of both sheets is subjected to a standard durability test. It shows that diazotype paper A is much more durable than diazotype paper B.

A second strip of sheet B is exposed under an incandescent lamp until just about all of the diazo connection is faded. Then, under the same conditions for the same time, a strip of sheet A. exposed. The two strips are developed with DeveloperD. After development is strip B white, strip A, on the other hand, has an intense brown color.

A third strip is cut from both leaves. Both strips are made with developer B developed. The strip of sheet A shows an intense dark brown color after development. the The color of the strip from leaf B slowly changes from yellow to pale green-brown.

Claims (4)

Patent claims: 1. Diazotype material, which is an o-aminobenzene diazo compound, which in p-position to the amino group an etherified oxy group and in p-position to the diazo group a further substituent contains, characterized in that it is a diazo compound of general formula N ₉ X R ₁ O CO-R ₂ where X is an anion, R _{1 is} an alkyl, branched alkyl, cycloalkyl or aralkyl radical, - CO - R _{2 is} an acyl group, R _{3 is} a substituent from the group acylamino, alkylsulfonamido, aralkylsulfonamido, arylsulfonamido and triazinyl and R _{4 is} an alkyl, branched alkyl, cycloalkyl, aralkyl or aryl radical contains. 2. Diazotype material according to claim 1, characterized in that R _{1 is} a non-branched alkyl group which contains at most 5 carbon atoms when R _{3 is} an acylamino or triazinyl group and R _{4 is} an alkyl, aralkyl or aryl radical. 3. One-component diazotype material according to claim 2, characterized in that R _{2 is} a hydrogen atom, an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group when R _{3 is} an acylamino group of the formula - NH - CO - R ₆ wherein R _{5 represents} an alkyl, alkoxy, benzyl, benzyloxy, phenyl or phenoxy group, and R _{4 is} an alkyl or benzyl radical. 4. One-component diazotype material according to claim 3, characterized in that R _{2 is} an alkoxy, benzyloxy or phenoxy group. Considered publications:
German patent specification No. 881 754. 1 sheet of drawings 709 690/359 9.67 © Bundesdruckerei Berlin