US2537001A - Diazotype layers having cyan acetyl amides as azo components - Google Patents

Description

Patented Jan. 2, 1 951 UNITED STATES DIAZOTYPE LAYERS HAVING CYAN'AGETYIJ AMIDES AS AZO COMPONENTS William H..von Glahn, Loudonville, and Lester N. Stanley, Delmar,.-N. Y., assignors to Generazb Aniline & Film Corporation,.New. York Nr-Y a corporation of Delaware.

No. Drawing. Application Au SerialNo. 766,875

6" Claims.

This invention relates toa diazotype process and more. particularly to the use of organic esters and. nitriles. containing active methylene group as the azo components in the light. sensitive layer of. a diazotypereproduction' medium min a: developing solution for the exposed diazotype image.

Inv 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 transparentdiazotypev copying material by exposingthe. transparent sensitized. diazotype material. to actinicrays, such as. ultra. violet light; by either. the. printing through. 01'. reflex process andithen developing the'diazotype material. The development of. such diazotype prints may be carried out-by any of the develop.-

ing methods known to the artrfor development" ofv exposed diazoty-pe materials. Thus,. where a. two-component: system is employed containing. the azo component in. the. light sensitivelayer.

with the diazo compound; development is effected by passing. the exposed diazotype. through am.- monia vapors, and where. a. one-componentsystem is employed which containsthe diazo come poundv as the only dye component in the light sensitive layer, the image is. developed. by treator'valuable originalwhicl'iz wouldfbeadversely af;- fected, if not destroyed, in the repeatediexposures necessary to make the deslred'number of" copies.

It is essential inthe so-called reflex process; where; i

Q such'as phloroglucinol andaresorcinol... Thesesazo. components are acetoacetyl" derivatives ofmonothe diazotype copy material"v 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 oithe. original.-'- The efii'ciency. ofithe; processinvolving the production of a transition or intermediate.

print depends. upon the opacityof the azo. dye? ing half-tones or too lightlines theydo not proimage produced "upon. such'intermediateor transi.- tion' print to ultraviolet li'ghtta'nd upon .the transparency offthe. background t'oz. such light. It. die.- pen'ds also; upon the visual density of. the. image. produced on the: intermediate-yer transitionv print; since'image's oi.poorivi'sual. ;iinz;.suoh.as li'ghtl. yeilow's; on: a white or: transparent: background',..

though; they may have" the; desired degree: or

opacity-to-ultravioleh light, nevertheless have-thedisadvantages of renderingdifiicult the detection of flaws: in the intermediate image.- Withsuch prints it isr'necessary to-make a contrastprint. i

goodavisualidensity from the intermediate: before suchiflaws canebe detectedthereby introducing: an. additional and unnecessary step;

Prints? of: adeep-cclorhaving good, visual :den.--

l0 sity; can-.b'e obtained vfrom. diazotypes using" azodensity of the colorreproducing the image, its

actinic opacity or photographic density isnotsufe ficient 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 producerupomcouplingawith the:

diazo compound employed a color which will sufficiently absorb the ultraviolet lightinc'ident upon it during exposureto'prevent light-decomposition of the diazo compound in the-areas to-be repro h duced fromthetransition copies. Colors of good visual density do notneeessarilyhave 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 component's, sueh-asresorcinol, 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. Resorcinoliwill" reproduce the:imageron,the:transition print in a sepia or orange-brown color which has good opacity to ultraviolet light and has" sufiicient depth of color orvisualZ-d'ensity to assure detec- 40 tion oi printing flaws and the like in the devel- Other azo components,

oped intermediate print. have. been suggested which will produce images of, good opacity-on covering" power when used in combination witir polyhydroxy azo components,

as shaders for other" colorswhich may lack the necessary-i covering powerr,. particularly inv copy? duce satisfactory images when used as self colors, that is, when the acetoacetyl derivatives of 5 mono-amines, such. assthe cyclohexyl acetoacetic 'acid iamide and. the like disclosed in Patent 7 1,98 9,065,,ares.used as. the" onl'yazo' components for thie'develbpment' of a diazotype printy'the image produced does not have a satisfactory shade or tone value. a

It has now been found that certain cyanacetylamides containing an active methylene groupare especially effective as azo components for di azotype reproduction. These cyanacetylamides containing active methylene groups may be represented by the formula lene or Z S-dihydroXynaphthalene sulfonic acid,

excellent neutral blacks having improved opacity to ultraviolet light are obtained. Examples of cyanacetylamides having active methylene groups of this class are Cyanacetamide f i 2. Cyanacetanilide err-omoo-nnQ 3. p-I-Iydroxy cyanacetanilide 4. Cyanacetbenzylamide 5. l-1nethyl-2w-cyanacetyliminodihydroquinoline.

en meled-um 6. Cyanacetylurea CN-CHzCO-NHCONH:

7. Cyanacetylthiourea oN-omc ONH (ll-NH:

Cyanacetylguanidine I v oN-o Hio o-NH-c-Nm 9. Cyanacetylcyanamide CNCH2CONHCN 10. Cyanacetylethylurethane cn-onzco-mncoocgml 11. 1 w cyanacetylimino 2 methyl-E-ethoxydihydrobenzothiazole Y In the preparation of diazotype materials in tended for useas 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, iscoatedby means known to the art with a light sensitive composition containing suitable diazo compounds. Where it is desired to make a twmcomponent 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 twoeoinponent 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 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 preierable 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 nitrile acetyl, amide azo components of this invention. The diazo compound or compounds and. other ad juvants 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 trans parentized paper or oellulosic 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. We prefer, however, to use diazo compounds derived from p-diamines of the bon zene series, particularly when two-component coating compositions are employed. As is well known in the art, this class of diazo compounds is especiall suitable for the production of twocomponent diazotype photosensitized papers. Other diazo compounds have been found suitable for use, such as diazo anhydrides of aminohyethyl N-ethylaminoA aminobenzene p phe'riyl- 4-ami-no-N,:N-dihydroxyethylaniene :diamine: line; p- (4 -ethoxyphenyl) -.a'm'ino -i2,'5-diethoxyaniline; 1-N-ethylamino-2-methyl-4-aminoben zene; 1-dimethyl-amino-3-methoxy-4-aminobenacne; N;N-dimethyam'ino-p-aminobenzenej 1-'d 'i-" methylamin-o 3 methyl-4-aminobenzene-; -'p-' .aminophenyl morpholine and 2-amino-1-naph- 'thol-S-Sulfon-ic acid. The diazo derivatives 'of Example 1 Transparentized paper is coated with a coating solution containing the following ingredients per 10000. of water containing 5% of alcohol:

4.0grams cyanacetanilide 3.3 grams N-methyl-N-hydroxyethyl-p-benzene diazonium chloride-ZnClz double salt 4.0 grams thiourea 8.0 grams citric acid 2.0 grams phosphoric acid. 5.20 grams ZnCla [The resulting coated paper or diazotype good precoupling stability during prolonged stor-' age. After drying the coating in the usual manner, the diazotyp'e is exposed to light under a positive and the image developed with ammonia fumes. The image of the positive original is thus obtained .in a light brown colored positive print. The dye or color areas reproducing the image have good fade and 'wa'sh-fastness properties and excellent opacity to ultra-violet light. The print can be used as a transition print for the reproduction of further diazotype copies or other photo reproductions.

Example .2

-"-*irans parentized paper is coated with a coating solution containing the following ingredients per 100 cc. of water containing 5% of alcohol:

2.8 grams cyanacetylurea 3.8 grams .N-methyl-N-hydroxyethyl-Pebenzene Example 3 I Transparentized paper is coated with a diazotype coating solution containing the following ingredients per -:cc.-nf water containing 5% of alcohol:

34) grams cyanacetamide 32 grams l-iitil -ethy1amino) -'2-'methyl-&-1benzene diazonium chloride-ZnCh double salt 4.0 grams thiourea 8.0 grams citric acid 2.0 grams phosphoric acid 5.0 grams ZnCla The resulting coated paper-tor .diazot-ype mate-' rial has good precoupling stability during pro- After drying the coating in the' longed storage. usual manner, the diazotype is exposed .to light under a pattern, design or picture to be reproduced and the image .is developed with ammoniafumes... A positive image of the original is thus obtained in a Sepia color. The dye :or color areas reproducing the density sections of;

the original have good fade and wash-fastne's's properties and show excellentopacity to ultraviolet .light. The print, therefore, can be :used as :a transition or intermediate print for the reproduction of further diazotype copies or other photo -reproductions.

Upon substituting 3.5 grams cyanacetbenzyl-- amide,, 3.6 grams .1-iN ethyl-N hydroxyethyleamino) -3-methyl-4-benzene diazonium chloride ZnGlz-double salt or 3.3 grams cyanacetylethylurethane and 3.5 grams N-ethyl-N-hydroxye'thylp-benzene diaaonium chloride-ZnClz' double .salt

for the coupling component and .diazo compound of this example, respectively, diazotype materials having the same properties and reproducing the original in images of the same color as above are obtained.

Example A diazotype---co.ating solution containingthefollowingaingredients per 1-00 cc. of a 5% aqueous solution of alcohol is made up:

.Upon .using this coating solution to produce a diazotype coating on transparentized diazotype paper stock-and upon drying the coating in the usual manner, a-diazotype layer having excellent precouplingstability is obtained. Upon exposing "tne thus sensitized .transpa-rentized paper to light under a pattern, design or picture to .be reproduced and developing with ammonia fumes, a reproduction of the original in a black shade on "a' clear' background is obtained. This'dy'e image has good fade and wash-fastness properties and excellent opacity to ultraviolet light. Therefore, it can be used as a transition or intermediate print in the reproduction of further diazotype copies or other photoprint copies.

If a non-transparentized diazotype paper stock is used in the coating step and the usual diazotype procedure followed of drying and exposing under a pattern followed by ammonia development, an

ground results.

Example 5 Transparentized diazotype paper stock is coated with a coating solution containing the following ingredients per 100 cc. of water containing 5% of alcohol:

3.2 grams of cyanacetylthiourea 3.5 grams N,N-dihydroxyethyl-p-benzene diazonium ChIOIidG-CdClz double salt 4.0 grams thiourea 8.0 grams citric acid 2.0 grams phosphoric acid 5.0 grams ZnClz The resulting coated paper or diazotype material has good precoupling stability during prolonged storage. After drying the coating in the usual manner, the diazotype is exposed to light under a pattern or other original to be reproduced and the image is developed with ammonia fumes. The image of the original is thus obtained in a sepia colored positive print. The dye or color areas reproducing the density areas of the original have good fade and wash-fastness properties and excellent capacity to ultraviolet light. The print, therefore, can be used as a transition or intermediate print for the reproduction of further diazotype copies or other photoreproductions.

Upon substituting for the 3.2 grams cyanacetylthiourea coupling component and the 3.5

grams N,N-dihydroxyethyl-p-benzene diazonium chloride-CdClz double salt diazo compound of this example, th following combinations of coupling components and diazo compounds, diazotype coatings having the same properties as the coatings of this example are obtained:

(1) 3.3 grams cyanacetylguanidine 3.2 grams N-phenylamino-p-benzene diazonium acid sulfate 3.1 grams cyanacetylcyanamide 3.5 grams l- (N-ethyl N hydroxyethylamino) -3-methyl benzene-p a diazonium chloride-ZnClz double salt 3.4 grams cyanacetylethylurethane 3.8 grams N,N-cliethylamino benzene-pdiazonium chloride-ZnClz double salt 3.4 grams 1-w-cyanacetylimino-2-methyl-5- of the benzene series and an azo component selected from the class consisting of cyanacetylamides of the following formula CNCH2COR wherein R is a nitrogen containing radical of the class consisting of amino, arylamino, aralkylamino, a-iminodihydroheterocyclic, carbamido, thiocarbamido, carbamidino, cyanimido, and carboalkoxyimido radicals.

2. A diazotype photoprinting material comprisinga light sensitive diazonium salt of a p-diamine of. the benzene series and as an azo component cyanacetanilide having the structural formula 3. A diazotype photoprinting material comprising a light sensitive diazonium salt of a p-diamine of the benzene series and as an azo component cyanacetylurea having the structural formula 4. A diazotype photoprinting material comprising a light sensitive diazonium salt of a p-diamine of th benzene series and as an azo component cyanacetbenzylamide having the structural formula ON-CHzC ONHCHT 5. A diazotype photoprintlng material compris ing a light sensitive diazonium salt of a p-diamine of the benzene series and as an azo component cyanacetamide having the structural formula 6. A diazotype photoprinting material comprising a light sensitive diazonium salt of a p-diamine of the benzene series and as an azo component cyanacetylthiourea having the structural formula WILLIAM H. VON GLAI-IN. LESTER N. STANLEY.

REFERENCES CITED Thefollowing references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,989,065 Schmidt et a1 Jan. 22, 1935 2;1 08,602 Mannes et a1 Feb. 15, 1938 2,217,189 Sus Oct. 8, 1940 2312,040 Kendall et a1 Feb. 23, 1943 2,436,007 Kendall et al. Feb. 17, 1948: 2,453,661 Glass Nov. 9, 1948

Claims (2)

1. A DIAZOTYPE PHOTPRINTING MATERIAL COMPRIS-

1. A PROCESS FOR RECOVERING THE COMPONENTS OF OF THE BENZENE SERIES AND AN AZO COMPONENT SEA COMPLEX OF HYDROGEN FLUORIDE WITH POLYOLEFINIC LECTED FROM THE CLASS CONSISTING OF CYANACETYLCYCLIC HYDROCARBONS CONTAINING CONJUGATED AND AMIDES OF THE FOLLOWING FORMULA NON-CONJUGATED UNSATURATION, WHICH COMPRISES IN-