US2833649A - Light-sensitive diazotype material - Google Patents

Description

United StatesPateiit LIGHT-SENSITIV E DIAZOTYPE MATERIAL Oskar Siis, Wiesbaden-Biebrich, and Manfred Grundkiitter, Wieshaden, Germany, assignors, by mesne assignments, to Keutfel & Esser Co., Hoboken, N. 1., a corporation of New Jersey No Drawing. Application August 6, 1954 Serial No. 448,393

Claims priority, application Germany August 11, 1953 12 Claims. (CI. 96-91) This invention is concerned with light-sensitive diazotype material. It is particularly advantageous when applied to diazotype materials of the one component or moist developing type.

Diazo compounds derived from para-phenylene diamine in which the non-cliazotized amino group is secondary or tertiary have been used for the production of a lightsensitive layer on base material suitable for diazotype printing. Diazo compounds derived from para-phenylene diamine and having alkyl residues with external atom groups at the nitrogen of the un-diazotized amino group, e. g. substituted amino groups or hydroxyl groups etherified by aliphatic hydrocarbon residues, are described for this purpose in German patent specification No. 831,804 and U. S. Patent No. 2,336,309. On account of their low coupling activity, diazo compounds of this type are used particularly for the production of so-called two-component diazotype layers for dry development.

An object of the present invention is to provide an improved light-sensitive diazotype material particularly for one component .or moist development.

The improved diazotype materials according to the present invention provide light sensitive diazotype material in which the light-sensitive layer includes a diazo compound of para-phenylene diamine of the general formula:

wherein -Ph is a phenylene residue which may be substituted 7 when the diazo compounds. of acylated p-phenylene1diamines were used as the light-sensitivesubstance.

By introducing substitutents into R e. g. halogen atoms, or by enlarging this residue, the coupling process during development can frequently be accelerated.

by the diazo compounds of this invention. The com pounds are preferably applied in the form of water-soluble phloroglucinol and resorcinol are particplarly suitable.

NJ The shade of color can also be affected by introducing substituents into the phenylene residue which carries the diazo group. Positive substituents generally cause a lightening of the tone. Diazo compounds of this nature are suitable for the production of intermediate originals of good opacity for ultraviolet light.

The ligh-sensitive layers may contain the usual stabilizers in the form of inorganic or organic acids, acid salts and salts of aromatic sulphonic acids. Anti-yellowing materials, particularly thiourea and its water-soluble derivatives may also be present in the layers to improve the background of the copies after development. The light-sensitive material may be further improved to produce copies with increased contrast by incorporating suspensions of finely-divided silicon dioxide or of silicates of alkaline earth metals in the sensitizing solutions.

Known methods are used to produce the diazo compounds of this invention. For example, monoalkylated amines are used as starting material and, are caused to react with the toluene-sulphonic acid esters of glycol-- monoaryl-ethers or the aryl ethers of ethylene chlorhydrin or ethylene bromhydrin. The aryloxy alkylated amino benzenes thus obtained are converted to azo dyes by coupling with ,diazotized sulphanilic acid or diazotized aniline, and from these the corresponding phenylene diamines can be obtained by reduction and can be converted in'the usual manner to the diazo compounds. The amino group can also be introduced by nitrosating the tertiary bases and reducing the nitroso compounds.

The sulphur analogues are obtainable in a similar manner. in this case the thioaryl ethers of thiochlorhydrins are used as starting materials for reaction with the secondary bases.

The following is a description by way of example of methods of carrying the invention into efiect. The formulae referred to are tabulated below the examples.

Example I A raw paper base material suitable for the production of photo-copying material is coated with this solution in normal manner and after drying is exposed under a transparent drawing original. The exposed paper is developed with a solution containing 2 gms. of sodium carbonate, 2.5 gms. borax, 3 gms. thiourea, 4 gms. sodium sulphate, 0.4 gm. phloroglucinol, 0.4 gm. resorcinol and 0.03 gm. saponin in cc. water. The copies have dark black lines, slightly tinged with red, on a white background. They do not run and they have high contrast. The coupling speed of the diazonium chloride zinc chloride double salt used is so high that the azo dye can be developed even with a neutral to slightly acid developer (pH 7-6.5) to give sufiiciently thorough development. For example, black copies with a blueish tinge are obtained with a neutral developer containing 10 gms. tertiary sodium citrate, 5 gms. sodium benzoate, 5 gms. anhydrous sodium acetate, 0.7 gm. phloroglucinol, 0.03 gm. acetoacetic anilide and 0.03 gm. saponine dissolved in water to 100 cc.

The diazo compound of Formula 1 is produced either by nitrosating N ethyl N (fi-phenoxy-ethyD-aniline (Clemo and Perkin, Journal of the Chemical Society 121 (1922), 645) reducing the nitroso compound and 0 diazotizing the reduction product or by reducing the azo dyestutf obtained from the above-mentioned N-tertiary aniline by the coupling on diazotized sulphanilic acid and then diazotizing in known manner.

For example, 52 gms. N-ethyl-N-(B-phenoxyethyD- aniline are suspended in 520 cc. of sulphuric acid and nitrosated with 40 cc. of 33% sodium nitrite solution. The nitroso compound is reduced by the introduction of zinc dust at 25-30 C. The resulting sulphuric acid solution is mixed with 150 gms. ice and diazotized with 35 cc. of 33% sodium nitrite solution. The diazo compound first comes out as an oil. 60 gms. sodium chloride are added and the reaction mixture is stirred until the zinc chloride double salt appears in the form of crystals which are filtered off with vacuum. The raw product is purified by dissolving in 1500 cc. water at 50 C., filtering over animal charcoal and separating out the zinc chloride double salt by adding 140 gms. sodium chloride.

Example II 1.7 gms. of the zinc chloride double salt of N-ethyl- N (B phenyl mercapto ethyl) p phenylene diamine-diazonium chloride (Formula 2) is dissolved in water with 0.5 gm. tartaric acid, 0.5 gm. aluminum sulphate and 6.0 gms. 1:3:6-naphthalene trisulphonic acid sodium salt and made up to 100 cc. Paper is coated in known manner with this solution and exposed under an original after drying. Development of the exposed paper is carried out with the alkaline developer described in Example 1. Copies are obtained with very strong deep black images with no tendency to run. The

contrast is even better than with the copies obtained in the manner described in Example I, and the shade is rather more neutral, so that the half-tones showvas pure blacks in the copies.

Equally goodresults are obtained by using for producing the light-sensitive layer the zinc chloride double salts of the diazonium salts of other paraphenylene diamine derivatives of the general formula stated above,

for example the diazonium chlorides of Formulae 3-12;

Boiling point of the correspending paraphenylene dlamlne C.)

1. N-eiihyl-N-lflheno xyethyll-p phehylene diaminediazonlum c lorlde CzH|N.CHzCH:OCtHt NzCl 2. N -ethyl-N-(fi-phenylercapto-ethyl)-p phenylene diamiue diazonlum chloride CS IILCHlGHISCIHI 3. N-ethyl- -[fi-(p-chlor)- henoxyethyl1-p-phenylene 258-260 at 15 diamlne-diazonium eh oride mm,

CSHLNiCHA-O NaGl.

Boiling point of the corresponding paraphenylene dlamine C.)

4. N-ethyl-N-[fl-(2:4-dichlor)-phenoxyethyl]-p-pheuylene diamipediazonium chloride (2-methoxy)- phenoxye thylI-p-phenyleue dlamlne-diazonium chloride 6, N-ethyl-N-[B-naphthoxy (a)-etliyl]-p-phenylcne.

dlamine-diazonium chloride campfire-8 7; N-meth mine l-N-[B-phenoxyethyH-p-phenylene diazonlum chloride NEG] 8. N-propyl-N-Ifl-ghfggxyethyll-p-phenylene dtaminediazonium ch nzene onium cram-0mm ,v The diazo compound is used in the form of the sta'nnicchloride double salt.

Boiling point of the corresponding paraphenylene diamine C.)

10. N-[d-phenoxyethyllpphenylene diamine-diaz o- 208-213" at 16 mum chloride mm.

lELN'LCz tll) NzCl 11. N-ethyl-N-[B-phenyl-snlphonyl-ethyH-p-phenylcannot be disene diamine-diazonium chloride tilled without decomposition. C2 s.N.G:H4.SO2

12. N-ethyl-N-(y-phenoxypropyl)-p-phenylene-dla- 2243-228 at 1 mine-diazonium chloride mm.

CI fi-lf-O mCHI-CHL? To produce N ethyl N(fi phenyl sulphonylethyl) p phenylene diamine, phenyl B chlorethyl sulphone is reacted with ethyl aniline in the presence of copper at 120 C. The reaction product is then treated according to the instructions in Example 1.

Having now particularly described the invention, what we claim is:

1. Light sensitive diazotype material for development by the semi-wet process comprising a base material coated with a light-sensitive layer including a diazo compound of a para-phenylene diamine of the general formula:

Ph is a phenylene radical X is selected from the group consisting of O, S and S0 R is selected from the group consisting of H and alkyl radicals having 1 to 3 carbon atoms R is an aromatic radical directly attached to X by a carbon atom of the aromatic ring n is selected from the group consisting of 2 and 3 2. Lightsensitive diazotype material for development by the semi-wet process comprising a base material coated with a light-sensitive layer including a diazo compound of a para-phenylene diamine of the general formula:

HzN-Ph-N 2),-XRa wherein Ph is a phenylene radical substituted by a substituent selected from the group consisting of alkyl groups and alkoxy groups X is selected from the group consisting of O, S and S0 R is selected from the group consisting of Hand alkyl radicals having 1 to 3 carbon atoms R is an aromatic radical directly attached to X by a carbon atom of the aromatic ring n is selected from the group consisting of 2 and 3 3. Light sensitive diazotype material for development by the semi-Wet process comprising a base material coated with a light sensitive layer including a diazo compound of a para-phenylene diamine of the general formula:

4. Light sensitive diazotype material for development by the semi-wet process comprising a base material coated with a light-sensitive layer including a diazo compound of a para-phenylene diamine of the general formula:

Ph is a phenylene radical X is selected from the group consisting of O, S and S0 R is selected from the group consisting of H and alkyl radicals having 1 to 3 carbon atoms R is an aromatic radical directly attached to X by a carbon atom of the aromatic ring and substituted by a substituent selected from the group consisting of halide atoms, alkyl groups and alkoxy groups n is selected from the group consisting of 2 and 3 5. Light sensitive diazotype material for development by the semi-wet process comprising a base material coated with a light-sensitive layer including a diazo compound of a para-phenylene diamine of the general formula:

HzN-Ph-N 0 H2) n 2 wherein Ph is a phenylene radical X is selected from the group consisting of O, S and 50;;

R is selected from the group consisting of H and alkyl radicals having 1 to 3 carbon atoms R is an aromatic radical directly attached to X by a carbon atom of the aromatic ring and substituted by halogen atoms n is selected from the group consisting of 2 and 3 6. Light sensitive diazotype material for development by the semi-wet process comprising a base material coated with a light-sensitive layer including a stabilizer and a diazo compound of a para-phenylene diamine of the general formula:

Phis :a phenylene radical X is selected from the group CHSlStiI1g' Of 0, S and SO,

R is selected 'from 'the group consisting *of H and alkyl radicals having 1 to 3 carbon atoms R, is an aromatic radical directly attached toX by a carbon atom of the aromatic .ring n is selected from the [group consisting .of 2 and 3 7. .Light. sensitive diazotype material vfor development by thesemi-wet process comprising a base material coated with a light-sensitive layer including an anti-yellowing material and a diazo compoundof a para-phenylene diamine of the general formula:

.Ph isa phenyleneradical.

Xris selected from thergroup consisting-0f O, .S and 80;;

R is selected from the group consisting of H and alkyl radicals having 1 to? carbon iatoms R, istan aromatic radical directly attachedlto X by a carbon atom of the aromatic ring n is selected from the "group consisting of 2'and 3 8. Lightsensitivediazotypematerial comprisinga base material coated with a light-sensitivelayer including N- ethylsNsfp phenoxyethyl) -p-phenylene diamine-diazonium chloride. l

9. Light sensitive diazotype material comprising a base material coated with a light sensitive layer including N- ethyl-N (fl-phenyl-merc ap to-ethyl -p-phenylene diamine- References Cited in the file of this patent UNITED STATES PATENTS 2,542,566 Pedlow et a1 Feb. 20, 1951 2,551,133 Jennings et a1. May 1, 1951' FOREIGN PATENTS 507,153 Great Britain June 9, 1939 831,804 Germany Feb. 18, 1952

Claims (1)

1. LIGHT SENSITIVE DIAZOTYPE MATERIAL FOR DEVELOPMENT BY THE SEMI-WET PROCESS COMPRISING A BASE MATERIAL COATED WITH A LIGHT-SENSITIVE LAYER INCLUDING A DIAZO COMPOUND OF A PARA-PHENYLENE DIAMINE OF THE GENERAL FORMULA: