US2688543A - Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material - Google Patents

Description

Patented Sept. 7, I954 POLY-ACETOACETYL DEREVATIVES 0F POLYAMINES AS AZO COMPONENTS IN DIAZOTYPE PHOTOPRINTING MA- TERIAL William von Glahn,;Loudonville, and Lester N. Stanley, Delmar, N; Y., assignors to General Aniline & Film Corporation, New York, N. 'Y., a corporation of Delaware No Drawing. Application December 20, 1950,

Serial N 0. 201,872

6 Claims.

This invention relates to a diazotype process and more particularly to the use of certain azo components in the light-sensitive layer of a diazotype reproduction medium or in a developing solution for the exposed diazotype image. This application is a continuation-in-part of our copending application Serial No. 704,302, filed October 18, 1946, now Patent No. 2,537,106.

In the reproduction of mechanical drawings, printed material, pictures, or other originals to be copied, it is of particular advantage in many cases to make first an intermediate print or transition print on a transparent diazotypecopying material by exposing the transparent sensitized diazotype material to actinic rays such as ultraviolet light by either the printing through or reflex process and then developing the diazotype material. The development of such diazotype prints may be carried out by any of the developing methods known to the art for development of exposed diazotype materials. Thus, where a two-component system is employed containing the axe component in the light-sensitive layer with the diazo compound, development is effected by passing the exposed diazotype through ammonia vapors, and

where a one-component system is employed which contains the diazo compound. as the only dye component in the light-sensitive layer, the image is developed by treating the exposed diazotype with an alkaline solution containing the azo component by a dipping or fog spraying method. The image thus produced on the transparent intermediate or transition diazotype print can be used for reproduction of further diazotype prints of high contrast. for the reproduction of the image on any suitable photopr-inting material such as silver halide photographic paper and Van Dyke prints and blueprints.

This method of producing transition diazotype prints is particularly useful when it is desired to make a number of reproductions from a frail or valuable original which would be adversely affected if not destroyed in the repeated exposures necessary to make the desired number of copies. 4

It is essential in the so-called reflex process where the diazotype copy material is superimposed on the opaque original to be copied and the light for exposure of the diazotype material-passes through it and is reflected by the surface of the original.

The efliciency of the process involving the production of a transition or intermediate print depends upon the opacity of the azo dye image produced upon such intermediate or transition print to ultraviolet'light and upon the transparency of If desired, they can also be used the background to such light. It depends also upon the visual density of the image produced on the intermediate or transition print, since images of poor visual density such as light yellows on a white ,or transparent background, though they may have the desired degree of opacity to ultraviolet light, nevertheless have the disadvantage of rendering difiicult the detection of flaws in the intermediate image. With such prints, it is necessary to make a contrast print of good visual density from the intermediate before such flaws can be detected, thereby introducing an addi tional and unnecessary step.

Print of a' deep color having good visual density can be obtained from .diazotypes using azo components common .to the art for the production of ordinary diazotypes such as phloroglucin, 2,3- dihydroxynaphthalene and B-naphthol-ZtLG-disulionic acid. However, despite the good visual density of the .color reproducing the image, its actinic opacity or photographic density is not sufilcient to reproduce the image satisfactorily in subsequent copies. The azo ,dye component used for the production of transition print images must be such as to produce upon coupling with the diazo compound employed a color which will sufficiently absorb the ultraviolet light incident upon it during exposure to prevent light decomposition of the diazo compound in the areas to be reproduced from the transition copies. Colors of good visual density do not necessarily have this property. It is well known, for instance, that blues such as are produced from azo .components like phloroglucin are very poor in their ultraviolet absorption characteristics.

Azo components such as resorcinol have heretofore been employed in the production of diazotype prints in order to obtain color images having the necessary light absorption characteristics for transition printing. Resorcinol will reproduce the image on the transition print in a sepia or orange-brown color which has good opacity to ultraviolet light and has sufficient depth of color or visual density to assure detection of printing flaws and the like in the developed intermediate print. Other azo components have been suggested which will produce images of good opacity or covering power when used in combination with polyhydroxy azo components such as phloroglucinol and resorcinol. These azo components are aoetoacetyl derivatives of mono-amines and are disclosed in Patent No. 1,989,065. However, although these acetoacetyl derivatives of monoamines may produce satisfactory results as shaders for other colors which may lack the necessary covering power, particularly in copying half tones or too light lines, they do not produce satisfactory images when used as self colors, that is, when the acetoacetyl derivatives of monoamines, such as the cyclohexyl acetoacetic acid amide and the like disclosed in Patent No. 1,989,065, are used as the only azo components for the development of a diazotype print, the image produced does not have a satisfactory shade or tone value.

It has now been found that the polyacetoacetyl derivatives of aliphatic aromatic, or heterocyclic polyamines are especially effective as azo components for diazotype reproductions. This class of azo components can be used satisfactorily either alone in the production of self shades or in combination with other azo components for shading purposes. In either case the resulting images have excellent opacity characteristics. The opacity to ultraviolet light and covering power of the self shades markedly surpass those properties of colors produced from the monoacetoacetyl derivatives, and when used for shading purposes in combination with such azo components as phlaroglucinol, 2,3-dihydroxynaphthalene, or 2,3- dihydroxynaphthalene sulfonic acid, excellent neutral blacks having good opacity to ultraviolet light are obtained. In general, these polyacetoacetyl derivatives are prepared from the corresponding polyamine by reaction with acetoacetic esters or with diketenes. The acetoacetic esters or diketent condenses with the amino groups of the polyamine, thus forming amide linkages. The amine may be any aliphatic, aromatic, or heterocyclic polyamine wherein the aliphatic chain or aromatic or heterocyclic nuclei may be substituted by any of the uuual substituents such as alkyl, halogen alkoxy, carboxy, sulfo, hydroxy, or other groups which do not discolor the paper or impair the solubility characteristics of the azo component. (For example, nitro groups discolor the paper.) This class of azo components may be represented by the following general formula: R(COCH2COCH3)n wherein R is an aromatic, or heterocyclic polyamino radical and n is a whole number greater than one and each acetoacetyl group is attached to an amino nitrogen atom of R. Examples of polyacetoacetyl derivatives of this class are:

(1) 2,4-diacetoacetamino-benzene sulfonic acid SOzH NHCO CHzC CH:

NHCOCHaC O CH:

NHO OCHaGO OH:

(3) Bis-acetoacet-o-or m-dianisidide CHaCOCHzCONH NHCOCHzCOGHa (4) Diacetoacetyl-piperazine CH2-CH2 N o o 0 mo 0 c H;

CHr-C 2 (5) N,N-diacetoacetyl-4-amino piperidine CHz-CH:

NC 0 CHzC 0 CH:

C Hr C i (6) Diacetoacetyl-melamine CHaC O CHzC ON CHaC 0 CHzC ONHHC CHaCOOHzCOHN? fi-NHCOCHaCOCH;

('7) Diacetoacetyl-benzidine ornooomooHN-OONnooomoooH.

(8) l ,4-diacetoacetamino-naphthalene CHaCOCH2COHN NHCOCHzCOCHs In the preparation of diazotype materials intended for use as intermediate or transition print media in accordance with this invention, a suitable transparent base such as transparentized paper, cellulose acetate film, or other transparent material is coated by means known to the art with a light-sensitive composition containing suitable diazo compounds. Where it is desired to make a two-component diazotype layer on the support or base material for development by the dry developing method, the azo component is also incorporated into the coating composition. Where one-component diazotype layers are desired the azo component is added to an alkaline developing solution and after exposure of the diazotype the exposed image is developed by contacting with the alkaline developing solution by means known to the art. In the preparation of coating compositions for two-component diazotype layers, the coating solution may also contain such other materials as are ordinarily used in the preparation of diazotype two-component light-sensitive coating compositions. These include stabilizing materials such as citric acid, phosphoric acid, and thiourea; swelling agents for cellulose acetate and other cellulosic ester bases such as isopropanol; and shade intensifying agents such as nickel sulfate. In the preparation of light-sensitive layers on paper :for the production of neutral black images or dark tone images which may or may not be intended for reproduction of further copies, it is preferable to employ a two-component coating composition which will contain one or more dark tone producing azo components, preferably such as will produce blue shades with the diazo compounds employed in combination with the polyacetoacetyl amino azo components of this invention. The diazo compound or compounds and other adjuvants are added to the coating composition and the paper used as a carrier for the light-sensitive layer is coated in the same manner as the transparentized paper or cellulosic film base material in the case of the transition print media. As diazo compounds any suitable light-sensitive diazo compound which will couple with the azo components to reproduce a colored image may be employed.

acsasca We prefer, however, to use diazo compounds derived from p-diamines of the benzene series, par ticularly when two-component coating composttions are employed. As is well known in the art, this class of diazo compounds is especially suit able for the 1." oduction of two-component diazo" type photo-sensitized papers. Other diazo compounds have been found suitable for use such as diazo anhydrides of aminohydroxynaphthalene compounds are less extensively employed. The p-diamines most generally used for production of the diazo compounds are those wherein one of the amino groups is unsubstituted for diazotiz-ation and the other is substituted by such groups a" allzyl, allzoxy-alkyl, aryl, aralkyl, alkylol, cycloaliphatic and heterocyclic groups. Examples of these amines from which the diazo compounds are derived include N-hydroxythyl-N-methylamino p aininobenzene; p-amino diphenylamine; l-mono-methyla:nino-2.(or 3) -methyl-- aminobenzene; l"l-hydroxyethyl-N-ethylamino- 3-methyl aminobenzene; ,1-diethylamino-3- nohenzene; s-amino-l-benzoylamip-amino-N-diethylanithoxy'cenzene;

p-amino-N-ethyl -N benzylaniline; l-ethy -azzninobenzene; l-N-hydroxyethyl-N-ethyla ol-arninobenzene; p-phenylene diamine; amino -l l,N- dihydroxyethylaniline;

aminooenzene:

p-- l -ethoxy henyl) amino-2,5-diethoxyaniline;

l-N-ethylarr -2methyl4-arninobenzene; l-diinethylam .o-3-methoxy-4l-aminobenzene; N,N- -paminobenzene; l-dimethylamihyl aminobenzene; p-aminophenyl morpholine and 2-amino-l-naphthol-5-sulfonic acid. The diazo derivatives of these amines are used in the form of their stabilized salts, such as the 211212, CdCla or 811012 double salts, fluoroborates, aryl or alkyl sulfonates, and acid sulfates of the diazoniuin chloride.

fol? specific examples will serve to illustrate in 1 r the invention, it being understood, hortcwr, that they are not intended to limit its scope. Unless otherwise stated, the parts are by weight.

Example 1 Transparentized paper is coated'with a coating solution containing the following ingredients per 100 co. in a 5% aqueous solution of alcohol:

5.0 g. 2,4-diacetoacetarnino-benzene sulfonic acid 3.8 g. N-methyl, N-hydroxyethylamino-p-benzene diazonium chloride-ZnCh double salt 4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride Ordinary paper stock for diazotropes is coated l-l l,l l dihydroxyethylamino -3-chloro-4- with a coating solution containing the following ingredients per cc. .of a 3% aqueous solution of isopropanol:

1.0 g. 2,4-diacetoacetamino-toluene 3.0 g. 2,3-dihydroxynaphthalene-6-sulionic acid 0.12 g. 2,8-dihydroxynaphthalene 3.0 g. N;N-diethylamino-p-benzene .diazonium chloride-211012 double salt 5.0 .g. 'ZnClz 10.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. thiourea The coated paper is first dried in the usual manner and is then exposed under a pattern and gleveloped by contacting with ammonia fumes. The prints thus developed are a neutral black shade having ood gradation and showing little tendenc y for color shift upon standing. These prints also have good opacity to ultraviolet light and good light-fastness and wash-fastness properties.

Upon substituting the following mixtures of oz! components for the three azo components in the formula of this example, diazotype prints havmg similar characteristics and properties are obtained 1.0 g. bis-acetoacet-o-dianisididc 2.8 g. 2,3adihydroxynaphthalene-6esulionio acid 0.1 g. 2,3-dihydroxynaphthalene The coating, formula and procedure are otherwise the same as in thi sexample. The compositions of this example illustrate the utility of the polyacetoacetyl polyamines of this invention for shading to neutral blacks when they are used in mixture with azo components which normally develop to a blue shade. Other azo components which will develop blue shades, such as phloroglucinol, may be substituted for or combined with the 2,3-dihydroxynaphthalene couplers of this example with similar results and azo components which will produce tones other than blue may also be used in combination with the polyacetoacetyl polyamines to produce modified tones which will have good covering power and opacity 0t ultraviolet light.

Example 3 Transparentized paper is coated with a coating solution containing the following ingredients per 100 co. in a 5% aqueous solution of alcohol:

5.0 g. diacetoacetyl piperazine 3.5 g. N,N-diethylamino-p-benzene diazonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride The coated transparency is first dried in the usual manner andis then exposed to light under a pattern and developed by contacting with ammonia fumes. The image of the pattern is developed in a sepia shade which possesses excellent opacity to ultraviolet light. It is, therefore, well suited for further reproduction work as a transition print. Its light-fastness and wash-fastness properties are similar to the prints obtained in accordance with Example 1.

Example 4 Transparentized paper is coated with a coating solution containing the following ingredients per 100 cc. in a 5% aqueous solution of alcohol:

5.2 g. diacetoacetyl-4-amino piperidine 3.6 g. 1-N-ethylamino-2-methyl-4-benzene diazonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chloride The coated transparency is first dried in the usual manner and is then exposed to light under a pattern and developed by contacting with ammonia fumes. The image of the pattern is reproduced in a sepia shade having excellent opacity to ultraviolet light. The light-fastness and wash-fastness properties of this print are also good and it is particularly suited for use as a transition print in the reproduction of further copies.

We claim:

1. The process of producing azo dye images in a light sensitive diazotype material comprising a base carrying a light sensitive diazonium compound which comprises exposing said light sensitive material through a pattern to actinic light to destroy the diazonium compound which is struck by light and treating said material with an alkali in the presence of an azo coupling component of a polyacetyl derivative selected from the class consisting of aryl polyamines of the benzene and naphthalene series and B-membered nitrogenous heterocyclic polyamines in which the acetoacetyl groups are attached to amino nitrogen atoms of the polyamines to effect coupling of said azo coupling component with residual diazonium compound.

2. The process as defined in claim 1 wherein the azo coupling component is present in the light sensitive diazotype material. 1

3. A light-sensitive ,material for the production of diazotype prints comprising a flat carrier base having coated thereon a light-sensitive diazo compound and as azo component the compound 2,4 diacetoacetamino benzene sulfonic acid, having the structural formula:

lOaH NHCOCHICOCHS NHCOCHaCOOHs 4. A light-sensitive material for the production of diazotype prints comprising a fiat carrier base having coated thereon a light-sensitive diazo compound and as azo component the compound diacetoacetyl piperazine having the str tural formula:

5. A light-sensitive material for the production of diazotype prints comprising a fiat carrier base having coated thereon a light-sensitive diazo compound, and as an azo component the compound bis-acetoacet-o-dianisidide having the structural formula moo c1120 0 OHNOONHC o CHaC 0 on;

(gcHa $CH:

and another azo component.

6. A light-sensitive material for the production of diazotype prints comprising a flat carrier base having coated thereon a light-sensitive diazo compound, and as an azo component the compound 2,4diacetoacetamino-toluene having the formula H30 0 CHzC O C-N NHOOCHzCOCHa NBC 0 cmc 0 CH3 and another azo component.

References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. THE PROCESS OF PRODUCING AZO DYE IMAGES IN A LIGHT SENSITIVE DIAZOTYPE MATERIAL COMPRISING A BASE CARRYING A LIGHT SENSITIVE DIAZONIUM COMPOUND WHICH COMPRISING EXPOSING SAID LIGHT SENSITIVE MATERIAL THROUGH A PATTERN TO ACTINIC IS STRUCK BY LIGHT AND TREATING SAID MATERIAL WITH AN ALKALI IN THE PRESENCE OF AN AZO COUPLING COMPONENT OF A POLYACETYL DERIVATIVE SELECTED FROM THE CLASS CONSISTING OF ARYL POLYAMINES OF THE BENZENE AND NAPHTHALENE SERIES AND 6-MEMBERED NITROGENOUS HETEROCYCLIC POLYAMINES IN WHICH THE ACETOACETYL GROUPS ARE ATTACHED TO AMINO NITROGEN ATOMS OF THE POLYAMINES TO EFFECT COUPLING OF SAID AZO COUPLING COMPONENT WITH RESIDUAL DIAZONIUM COMPOUND.