DE1814283C3 - Diazotype material - Google Patents

Description

SR ₁

R,

i
Ν, Χ

IO

It is 15 sewing of the invention. To create a slide that has a higher coupling speed and yet delivers dyes with at least slight absorption in the ultraviolet range.

The invention is a diazotype material with a light-sensitive layer which has a Benzene diazonium bond with an acylated secondary amino group in the 2-position. a type of thioether in the 4-position and a further substituent in the 5-position to the diazonium group and contains by the general formula

SR ₁

R,

N y
N, X

is. wherein R _{1 is} a substituted or unsubstituted alkyl radical having 1 to 5 carbon atoms, an aryl radical having 6 to 7 carbon atoms or an aralkyl radical having 7 to 10 carbon atoms. R _{2 is} an alkyl group with 1 to 3 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms or an aralkyl group with 7 to 10 carbon atoms. R _{3 is} an alkylcarbonyl radical having 2 to 3 carbon atoms. the phenylcarbonyl radical. an alkoxycarbonyl radical with 2 to 5 carbon atoms, the phenoxycarbonyl radical or the benzyloxycarbonyl radical. R _{4 is} a halogen atom and X is the anion of the diazonium compound.

2. Diazotype material according to claim!, Characterized in that R _{1 is} an alkyl radical with! to 5 carbon atoms or an aralkyl radical having 7 to 10 carbon atoms.

3. Diazotype material according to claim 1 or 2, 4 "characterized in that c *; it eats a one-component diazotype material is.

45

The invention relates to a diazotype material with a finer light-sensitive layer which contains a benzene diazonium compound with ener acylated secondary amino group in the 2-position, a thioether group in the 4-position> in a further substituent contains in the 5-position to the diazonium group.

From the German patent specification 12 56065 is the use of 2-acylamino-benzenediazonium compounds, which carry a thioether group in the 4-position and an ether group in the 5-position. Door the Production of diazotype materials known. The compounds mentioned there result in copy materials, the rapidly coupling and high contrast azo dyes with good absorption in the ultraviolet range deliver. The compounds are preferred for making one-part diazotype materials used which, because of their high coupling speed, can also develop with weak acidic developer solutions.

is marked. wherein R _{1 is} a substituted or unsubstituted alkyl radical having 1 to 5 carbon atoms, an aralkyl radical having 6 to 7 carbon atoms or an aralkyl radical having 7 to 10 carbon atoms. R, an alkyl radical with 1 to 3 carbon atoms, a cycloalkyl radical with 5 to 6 carbon atoms or an aralkyl radical with 7 to 10 carbon atoms. R _{3 is} an alkylcarbonyl radical with 2 to 3 carbon atoms, the phenycarbonyl radical. an alkoxycarbonyl radical having 2 to 5 carbon atoms, the phenoxycarbonyl radical or the benzyloxycarbonyl radical, R _{4 is} a halogen atom and X is the anion of the diazonium compound.

An aryl radical with 6 to 7 carbon atoms is a phenyl group. which optionally methylated or is roethoxylated. to understand (according to the JUPAC rules).

The diazotype material according to the invention outperforms the known materials in terms of coupling speed. It forms with the usual polyhydric phenols used as coupling components in the one-component process, e.g. B. Phloroglucin and resorcinol, brown dyes with> very good absorption for ultraviolet radiation. The copies obtained are therefore eminently suitable for the production of intermediate originals.

The diazotype material according to the invention preferably does not contain any coupling components. The Material is sensitive to light and can be developed with weakly acidic buffered developer solutions. Of course, the development can also be carried out with alkaline solutions, with which it happens particularly quickly. Naturally, however, the distribution of the high coupling speed falls of the diazotype material according to the invention when developing in neutral or weakly acidic Medium is particularly important, as development generally takes place more slowly at such pH values. The resulting azo dyes are very water-resistant.

However, the material according to the invention can also use coupling components that couple very slowly. e.g. T - Hydroxy - i'.2 ', 4.5 - contain naphthimidazole or 2-hydroxy-8-biguanidino-naphthalene, which is then evolved by ammonia vapor or by heating.

13 14283

Materials with compounds are preferred. in which R ₁ denotes the alkyl radical with 1 to 5 carbon atoms or the Aralkvlrest with 7 to 10 carbon atoms, since they have particularly good photosensitivity.

The radical R ₃ is derived from an aliphatic or aromatic carboxylic acid. It can also be derived from a carbonic acid half-ester, with the amino nitrogen atom forming a urethane group. R 1 can be an alk)! Carbon) resin with 2 to 3 carbon atoms, the pheny! Carbon) group an alkimearbonyl group with 2 to 5 carbon atoms, the phenoxycarbonyl group or the benzyloxycarbonyl group.

Chlorine or bromine is preferably chosen as the halogen atom R ₄ for economic reasons and for ease of access. However, it is also possible to use compounds in which R _{4 is} fluorine or iodine.

X is one of the common anions in the diazotype. ^ o which form stable diazonium salts. The diazonium salt / can thus 1. B. as chloride, sulfate. Telrafluoroborate. Hexafluorophosphate or as a double salt with zinc chloride, tin tetrachloride, cadmium chloride and the like.

Examples of the diazotype material according to the invention Benzoldiazonium compounds used are:

4-diazo-5- (N-acetyl-N-methyl-amino) -2-chloro-

phenyl thioethyl ether,
4-diazo-5- (N-acetyl-N-meth) l-amino) -2-chloro-

phenylthio (4-meth) 1-phenyl) ether. 4-Diazo-5- (N-acet) 1-N-methyl-ammo) -2-bromophenylthioether ether.

4-diazo-5- (N-propionyl-N-methyl-amino) -

2-bromo-phenylthioäthv lather, 4-diazo-5- {N-benzoyl-N-methyl-amino) -

2-chlorophenylthioethyl ether. 4-Diazo-5- (N-acetyl-N-n-propyl-amino) -

2-chlorophenylthioethyl ether, 4-Diazo-5- (N-acetyl-N-cyclohexyl-amino) -

2-chlorophenylthioethyl ether, 4-Diazo-5- (N-acetyl-N-benz) l-amino) -2-chlorophenylthioethyl ether,

4-Diazo-5- (N-ethoxycarbonyl-N-methyl-amino) -

2-bromophenylthioethyl ether. 4-Diazo-5- (N-ethoxycarbonyl-N-methyl-amino) -

2-fluorophenyl thioethyl ether, 4-diazo-5- (N-isopropoxycarbonyl-N-methylamino) -2-iodo-phenylthio- (4-methyl-phenyl) -

ether,
4-diazo-5- (N-benzyloxycarbonyl-N-methyl-

amino) -2-chlorophenylthioethyl ether. 4-Diazo-5- (N-phenyloxycarbonyl-N-methyis <,

amino) -2-bromophenylthioethyl ether. 4-Diazo-5- (N-ethoxycarbonyl-N-n-prop) lamino) -2-chlorophenylthio- (4-methoxy-

phenyl) ether,
4-diazo-5- (N-acetyl-N-methyl-amino) -2-chloro-

phenylthiobenzyl ether,
4-Diazo-5- (N-acetyl-N-eyclohexyl-amino) -

2-chloro-phenylthiobutyl ether. 4-diazo-5- (N-butyloxycarbonyl-N-ethyl-amino | - 2-bromophenylthioethyl ether.

4-Diazo-5- (N-ethoxycarbonyl-N-n-propylamino) -2-bromophenylthio- (4-meih \ l-phen \ ll- 4-diazo-5- (N-benz.oyl-N-meth \ l-amino | -

2-chloro-phenylthiopropy lather.
4-Diazo-5- (N-acetyl-N-benzyl-aniinol-2-chloro-

phenylthio- (2-hydroxy-ath \ l) -ether,
4-diazo-5- (N-ethoxycarbony 1-Nc) clohexyl-

aminü) -2-bromophenylthiogl) colic acid ether,
4-Diazu-5- (N-benzylo \ vcarbon) IN-methyl-

amino-2-chloro-phenylthiobenzy lather,
4-Diazo-5- (N-phenylox) carbonyl-N-meth) l-

amino) -2-chloro-phenylthiobut) lather,
4-Diazo-5- (N-benzoyl-N-methyl-amino) -

2-bromophenylthiobenzyl ether,
4-diazo-5- (N-acetyl-N-meth) l-amino) -2-chloro-

phenylthiobutyl ether.

These diazonium compounds can be prepared using 2-chloro-4-niiro-aniline as a starting material getting produced. 2-Chloro-4-nitro-aniline is obtained by nitrating 2-chloro-acetaniiide and subsequent deacetylation.

via a Sandmeyer or Schiemannsche The reaction becomes the amino group of the 2-chloro-4-nitroaniline replaced by a halogen atom, then reduced the nitro group to the amino group and this acetylated. The 3-chloro-4-haloacetanilide thus obtained is nitrated and then deacetated. In the 4-chloro-5-halogen-2-nitro-aniline thus formed, this is Chlorine atom in p-position to the nitro group with a Mercaptan converted into a thioether of 5-mercapto-4- {halogen l-2-nitro-aniline. The amino group is replaced by a chlorine atom according to Sandmeyer, since the chlorine atom is then replaced by a primary one Amine converted to the secondary amino group and this, for example, with a carboxylic acid chloride or acylated with a chloroformic acid ester. By reducing the nitro group to the amino group and their diazotization gives the corresponding diazonium compound.

The support of the diazotype material according to the invention prepared with the compounds can be opaque be like paper, linen, coated papers and metallic materials or translucent like coated and uncoated tracing papers or transparent such as B. cellulose acetate, polyester or Polycarbonate films. If the surface of the carrier is hydrophobic, as is the case with plastic films, the diazonium compound is preferably used in a hydrophilic film layer that is applied to the surface of the hydrophobic carrier applied, introduced together with the usual additives.

An excellent diazotype material is obtained using a transparent support, e.g. B. natural tracing paper, translucent paper, tracing linen or polyester film that is on the surface a hydrophilic film layer, which is obtained by superficial hydrolysis of a layer of lacquer made of cellulose or polyvinyl ester.

If the carrier is transparent or at least translucent, this is particularly suitable This one-component diazotype material produced very well for the production of intermediate originals, regardless of whether the material is with a weakly acidic or with a weakly alkaline phloroglucinol developer is being developed.

The light-sensitive layer of the diazotized material can, in addition to the diazonium compound and optionally a coupling component, also the contain usual additives, z. B. Acids, such as citric

acid. Tartaric acid, boric acid. Sulphosalicylic acid: stabilizers such as naphthalene-1,3,6-trisulfonic acid and theirs water soluble salts. Antioxidants such as thiourea, Metal salts such as aluminum sulfate. Binders such as gelatin or gum arabic and synthetic resin or silica dispersionci.

B e ι s ρ ι e I I

White blueprint base paper that is mixed with an aqueous ό Dispersion of polyvinyl acetate and finely divided silica coated and then dried ν orden M. becomes i-ih to a solution νon

0.3 g gum arabic.

6.0 g sodium naphthalene-1.3.6-sulfonic acid.

0.5 g citric acid.

1.6g double salt of 4 - benzylthio - 5 - chloro-2 - (N - acetyl - N - methyl - amino) benzene diazonium chloride and zinc chloride * o

coated in JOOmI water and dried.

A sheet of the light-sensitive diazotype material * produced in this way is placed under a transparent Ink drawing exposed until all of the diazonium compound is faded under the non-image parts of the drawing.

According to the so-called thin-film method developed with the following developer solution

(1.5 g phloroglucine.
8.0 g sodium triumin citrate.
2.0 g Natnumben / oat.
0.1 g citric acid.

1.5 g thiourea.

0.2 g of sodium isopropylnaphthalenesulfonate as a network compound

in UX) ml of water.

The pH of this liquid is around 5.9. One receives immediately after applying the developer a copy with strong dark brown images.

With a similarly good result it can be replaced of the above-mentioned diazo compound is 4-p-tolylthio-5-chloro-2- (N-dcetyl-N-methyl-amino) -benzenediazonium tetrafluoroborate use under otherwise identical conditions.

The initially mentioned di-zonium compound is manufactured as follows:

3,4-dichloro-nitrobenzene is reduced and acetylated and nitrided. The 4,5-dichloro-2-nitro-acetanilide obtained is deacetylated and the chlorine atom is in the p-position to the nitro group replaced by the benzyl mercaptan group by reaction with benzyl mercaptan. 2-ChloΓ-4-nitro-5 · amino-phcnylthiobenzyl ether is obtained. according to Sandmeyer in 2,5-dichloro-4-nitro-phenylihiobenzyl ether is convicted. By reacting with monomethylamine, the chlorine atom in o-position to the nitro group is replaced by the Methylamino groups; replaced, and this is then acetylated. The 2-chloro-4-nitro -5- (N-acetyl-N-methyl-amino) -phenylthiobenzyl ether prepared in this way melts at 130 to 131 ° C. The nitro group of this compound is catalytically reduced to the amino group and this is diazotized as usual. The diazoniuro compound is deposited as a zinc chloride double salt.

Example 2

Iransparenlisieries paper comes with a! .Solution from

0.5 g citric acid.

3.5 ΰ naphthalene -). 3.6-sodium irisulfonic acid.

0.1 g saponin.

2.5 ml of triethylene glycol.

3.5 ü 4-Athy! Thio-5-bromo-2- (N-acety! -

N-methyl-arnino) -ben / oldiazoniumieirafluoroborai

coated in 85 ml of water and 10 ml of isopropanol and dried.

A sheet of the photosensitive material prepared in this way is exposed as in Example 1 and then developed with the following solution:

0.33 g phloroglucine,
9.60 g trisodium citrate.
2.40 g of sodium benzoal.
0.201: adipic acid.
2.00 g sodium adipal.
5.70 g table salt.

0.20 g Natnunisal / a dialkylnaphthalmsulfonic acid as a wetting agent

in 100 ml of water

The pH of this Hüssigkeü is around 6.

The copy shows strong purple-tinged brown images, which appear immediately after applying the developer liquid and absorb ultraviolet radiation very well. The copy is therefore extremely suitable only for use as an intermediate original to make further copies.

The diazonium compound used in this example can be made as follows:

2-chloro-4-nitro-aniline is made using a Sandmeyer The reaction is converted into 2-chloro-4-nitro-bromobenz.ol, the nitro group is reduced to the amino group, this acetylated and the product thus obtained nitrated to 5-chloro-4-bromo-2-nitro-acetanilide. After Deacetylation with ethyl mercaptan becomes the 5-ethyl mercapto compound implemented and then after

5 a η d m e y e r the amino group through a chlorine atom ersetzx By reaction with monomethylamine, the one in o-position to the nitro group becomes Chlorine atom is replaced by the methylamino radical and this is then acetylated. One gets in this way

6 - bromo - 4 - nitro - 3 - (N - acetyl - N - methyl - amino) phenylthioethyl ether from melting point 105 to 107 C. The nitro group of this compound is catalytically reduced and the amino group obtained is diazotized. The diazonium compound is isolated as a tetrafluoroborate.

Example 3

A white Giundpapicr commonly used in the diazotype 80 g irr is mixed with a solution of

0.5 g of tartaric acid.

4.0 g sodium naphthalene-1,3,6-trisulfonic acid, 0.02 g saponin.

2.2 g double salt of 4-ethylthio-5-bromo-

2- (N-alhoxycarbonyl-N-methyl-amino) -

ben / oldiazonium chloride and

Cadmium chloride

coated in 100 ml of water and sietrocknel.

Hin sheet of the Diazolypicmatcrials produced in this way is exposed imagewise under a pencil drawing until the diazonium compound under the non-image parts of the drawing are largely bleached is. and then developed with the following developer solution:

0.6 µ phloroglucine.
0.6 g resorcinol.
1.5 g thiourea.

7.2 g of potassium tetraborate.

0.8 μ potassium hydroxide,

0.1 g of sodium isopropylnaphthalenesulfonate
as a wetting agent

in 100 ml of water i) the pH of this liquid is about 9.5.

The copy obtained shows light brown lines on a veiled light brown background.

The diazonium compound used is obtained as follows:

6-Bromo-4 ^: ^ 0-3-methylamino-phcnylthioethyl ether. prepared as described in Example 2, is acylated with ethyl chloroformate. It will 6 - bromine - 4 - nitro - 3 - (N - ethoxycarbonyl - N - melhylamino) phenylthio; ethyl ether obtained, which melts at 122 to 124 C. This nitro compound becomes after reduction and subsequent diazotization, the dia / onium salt is obtained. The diazonium salt is ; i! s cadrnium chloride double salt deposited.

Example 4

Natural tracing paper is coated with acetyl cellulose lacquer and the dried lacquer layer with a solution of

3.0 g citric acid,

1.0 g boric acid.

3.0 g thiourea,

2.0 g of 2,5-dimethyl-4-morpholinomethyl-phenol

as hydrochloride,

3.0 g of 4-ethylthio-5-chloro-2- (N-acetyl-N-cyclohexyl-amino) -benzyldiazonium tetrafluoroborate

65 ml isopropanol.
30 ml of water and
5 ml formic acid

35

40

45

coated and dried again.

A sheet of the diazotype material thus obtained is exposed under an original until the diazonium compound has faded under the non-image parts of the original. Developing with ammonia produces a copy with yellow lines that absorb ultraviolet radiation very well. The copy is therefore very suitable as an intermediate original for making further copies.

The diazonium compound used in this example can be prepared as follows:

^ Dichlor-l-nitro-acctaniüd, prepared as described in Example 1, is deacetylated and the chlorine atom m 5-position replaced by the Äthybnercaptogruppe by reaction with ethyl mercaptan. 2- <Mor ^ nitrc ~ 5-arainc ~ phmylthioethyl ether is obtained, which is converted to Sandmeyerin 2 ^ -dichloro-4-nitrophenylthioethyl ether. By reaction with cyclohexylanine, the chlorofalom ia o * Stefluag to the nitrogroppe is replaced by the cydtohexylanrinorest and this is then acetylated.

The 2-chloro-4-nitro-5- (N-acetyl - N - cyclohexyl - amino) - phenylthioethyl ether melts at 139 to 14 (i "C..

The nitro group of this compound is catalytically reduced to the amino group and this as usual diazoticrt. The diazonium compound S is used as a tetrafluoroborate deposited.

Similar good results are obtained if the double salt is used instead of the diazonium compound mentioned from 4-Ethylihio-5-chloro-2- (N-acetyl-N-benzylamino) -benzoidiazonium chloride and cadmium chloride

used. ". . _c

Example 5

Transparent paper is varnished with acetylcellulose and the varnish layer on the surface to a depth hydrolyzed by about 3.5 μίτι. "After removal of the Chemicals used in hydrolysis by washing with water will make the surface hydrophilic coated with the following solution:

1.0 g citric acid,

4.0g naphthalene-l, 3,6-trisulfonic acid sodium, 3.0 g double salt of 4-ethylthio-5-chloro-2- (N-benzoyl-N-methyl-amino) benzene diazonium chloride and zinc chloride

in 70 ml of isopropanol and
30 ml of water

and dried.

A sheet of the diazotype material produced in this way is exposed imagewise and then with that in the example 3 specified developer developed. The copy obtained shows brown azo dye images transparent ground and is very suitable as an intermediate original for further copying.

The diazonium compound used in this example was obtained in the following way:

The chlorine atom of 2,5-dichloro-4-nitro-phenylthioethyl ether in o-position to the mitro group, prepared as described in Example 4, is exchanged for the methylamino radical by reaction with monomethylamine and this is benzoylated. The 2-chlorine obtained in this way -4-nitro-5- (N-benzoy] -N-methyl-amino) -phenylthioethy] ether melts at 141 to 14.TC. The nitro group of this compound is catalytically reduced to the amino group and this is diazotized in the usual way. The diazonium compound is deposited as a zinc chloride double salt.

Example 6

White base paper commonly used in diazo printing is coated on one side with a dispersion of the following composition:

100 ml water, 9.0 grams of polyvinyl alcohol 20.0 g Ν, Ν-piäthyfbiuret, 5.0 g of partial silica, 1.5 g of polyvinyl acetate dispersion, 0.1 ral B-Octanoi

The precoated paper is at 90 to 100 ⁰ C in flowing air dried and then ,, the same side anif with a solution of _f

1.75 g citrotrene acid, 2.0 g napftthalene-l, 3,6-trisulf <fl! Säaieih sodium, ·

609 (539/79

5.0 ml isopropanol,

4, OmI concentrated hydrochloric acid,

1.0 g of 7'-hydroxy-1 ', 2', 4,5-naphthimidazole,

2.0 g of 4-ethylthio-5-chloro-2- (N-acetyl-

N-n-propyl-amino) -benzene-diazonium-

tetrafluoroborate and
80 ml of water

coated and dried again in a stream of air.

A sheet of the photosensitive material thus prepared is covered with a transparent ink drawing imagewise exposed and then with a roller that was heated to 130 to 140 "C, in Brought in contact. In this case, dye formation occurs in the unexposed areas of the copy. You get a copy with red images.

The diazonium compound used in this example can be prepared as follows:

2,5 - dichloro - 4 - nitro - phenylthioethyl ether, prepared as described in Example 4, is reacted with n-propylamine and acetylated. The thus produced 2-chloro-4-nitro-5- (N -acetyl -Nn-propyl-amino) -phenylthioäthyläther melts at 85 to 87 ^'1 C. The nitro group of this compound is catalytically reduced to the amino group and these diazotized as usual. The diazonium compound is isolated as a tetrafluoroborate.

Example 7
For every 100 ml of a solution that

5 g citric acid,
35 g of naphthalene-1,3,6-trisulfonic acid

Sodium,
1 g saponin,
25 ml triethylene glycol,
100 ml isopropanol,
1000 ml of water

contains 8 millimoles of one of the following diazo compounds:

1.4- ethyl mercapto - 5 - methoxy - 2 - (N - ethoxycarbonyl - N - methyl - amino) - benzene diazonium hydrogen sulfate,

2. 4-Ethylmercapto - 5 - chloro - 2 - (N - acetyl - N - methylamino) benzene diazonium tetrafluoroborate.

Each of the two coating solutions thus produced is used to coat a sheet of transparent paper, which is coated with acetyl cellulose and the surface of which is hydrolyzed to a depth of about 2.5 μm, on the hydrophilic surface. The leaves are marked with the numbers 1 and 2 according to the diazonium compound used.

The sheets are exposed under a transparent ink drawing until the entire diazonium compound under the non-image parts of the drawing is bleached. Then each of the sheets is divided into three equal parts and the parts belonging to a sheet are marked with an "a", "b" or " c «marked. ^ ₀

All samples are treated with the developer described in Example I, including samples "c" twice in a row. To compare the coupling speeds, samples "a" are exposed 15 seconds and samples "b" 30 seconds after the developer has been applied and the dye densities of the full tones compared with the material developed twice on the same sheet (sample "c"). The values in the following table indicate the percentages of the maximum achievable carbon density.

After 15 seconds After 30 seconds I l'rohen »; ι · <| ! Rehearsals "h" l

89.6
99.2

94.5
99.6

35 After winding twice, the full tone of the azo dye images is from

Sheet 1 violet-tinged dark blue,
Sheet 2 brown.

Example 8

White blueprint base paper with a precoat of rice starch and polyvinyl acetate is mixed with a Solution of

0.30 g gum arabic,

0.50 g citric acid,

0.02 g saponin and

1.80 g of the double salt of 4-ethylthio-5-chloro-2- [N-acetyl-N- (4-methoxy-phenyi) -amino] -benzenediazonium chloride and
Zinc chloride

Brushed in 100 ml of water and dried. After exposure under an original, the following one Developer solution

0.6 g phloroglucine,

0.4 g resorcinol,

1.5 g sodium benzoate,

5.0 g tertiary sodium partial

1.0 g sodium formate,

1.0 g thiourea,

0.1 g of 2-ethyl-1-hexanol sulfate

developed in 100 ml of water. The pH of this Solution is about 7.0. Copies are obtained in purple-brown lines on a white background.

55

Example 9

White blueprint base paper is mixed with a solution of

0.5 g tartaric acid,

0.02 g saponin,

3.0 g sodium naphthalene-1,3,6-trisulfonic acid,

14 g of ^ methoxycarbonylmethylthio-S-chloro-2- {N-methyl-N-acetyl-amino) -benzenediazonium tetrafluoroborate and

2.0 ml of a polyvinyl acetate dispersion

Brush in 100 ml of water and dry. It is exposed under an original and obtained by developing with the developer specified in Example 2, a copy with light brown lines on a white background.

Example 10

White blueprint base paper is precoated with polyvinyl acetate and fine silica; provided and then with a solution of

0.5 g tartaric acid,

3.0 g sodium naphthalene-1,3,6-trisulphonic acid, 0.02 g saponin,

1.6 g

• i-Acetyloxyäthylthio-S-chloro-

2- (N-methyl-N-acetyl-amino) -benzof-

diazonium tetrafluoroborate

Brushed in 100 ml of water and dried. Dt exposure under a transparent ink drawing and subsequent development with the developer specified in the example, copies are obtained brown pictures on a white background.

fcerfl

Claims (1)

Patent claims: 1. Diazotype material with a photosensitive layer containing a benzene diazonium compound with an acylated secondary amino group in the 2-position, a thioether group in the 4-position and a further Si substituent in 5-formation to the diazonium group, characterized in that that the benzene diazonium bond is a compound of the formula