[1]3 1 2 5 5 , 0 0 7 United States Patetit Office 3,255,007 DIAZOTYPE REPRODUCTION MATERIALS Jaromir Kosar, Beechhurst, N.Y., assignor to Keuffel & Esser Company, Hoboken, N.J., a corpoiation of New Jersey 5 Filed Mar. 19, 1963, Ser. No. 266,230 13 Claims. (Cl. 96-49) The present invention relates -to diazotype reproduction materi als and to methods and means for their develop- 10 ment, and refers more particularly to heat-developable diazot ype reproduction materials and to methods and means for their development. Diazot ype reproduction materials are well known and have many advantages over other means of reproduction 15 when considering -the combined bases of quality and cost. Howe ver, they do possess some disadvantages which are inhere nt in the method of development. Tivo methods of development are generally used: the semimoist method and the dry method. In the semi- 20 moist method the exposed diazotype material is passed throug h a bath of coupler and squeezed dry. In the dry metho d, the exposed diazotype material is passed through a chamber of gaseous ammonia to effect development. The semi-moist method of development suffers from the 25 disadv antageous requirements of periodic replenishment of the developer supply, removal of exhausted developer, period ic cleaning of developer -container, and deleterious effects of the liquid developer on the diazotype base which is usually paper. The dry method has the disadvantages 30 of requirin.- equipment to supply, confine, and exhaust the noxious ammonia. Other means for developing diazotype materials have been tried but were less practical than either the semimoist or dry methods. 35 Heat for example has been used to develop images oa repro duction materials but they remained heat-sensitive and ultimately were unsatisfactory as co@ies. In an attempt to eliminate the disadvantages of both the semi-moist and the dry developing systems, hea-t- 40 devel opment of diazotype reproduction materials was tried. This was feasible because exposure of a d ' iazotype reproduction material through a master to a source of actinic radiations decomposes the diazonium compound in the non-image areas. Consequently, these areas 45 cannot devclop and the diazotype reproduction materiol in effect is fixed or stabilized during exposure. The latent image could then be developed by some developing agent in -the sensitized layer, in a separate layer, or in a separate suppo rt. 50 For example, Dieterle in U.S. Patent 2,228,562 relates to a developing sheet treated with a heat-decomposable ammo nia compound. Placed in contact with an exposed diazot ype reproduction material and beated, the developing sheet liberated ammonia vapors which developed the 55 la-tent image. The ammonia compounds, however, had very poor shelf-life and consequently, their practical use was lirnited. Barde in U.S. Patent 2,313,288 incorporated urea into a layer with a diazoic that formed its own coupler as a 60 photol ytic decomposition product. Heat decomposed the urea to libera-te ammonia vapors which then neutr'alized the acid formed during coupling. Morrison in U.S. Patent 2,732,299, on the other hand, incorporated urea into a separate stratum on -the diazotype reproduction 65 materi al to serve as the source of heat-liberated ammonia. Greig in U.S. Patent 2,691,587; Marron in U.S. Patent 2,774,6 69; and Benbrook in U.S. Paten-t 2,789,904 all relate to developing sheets containing either the coupler or the source of heat-liberated alkali. 70 Kenda ll et al. in British Patent 815,005 rela-tes to multilayer diazotype reproduction ma-terial which comprised Patented June 7, 1966 2 a support bearing a coupler layer, a fusible barrier layer, and a diazo layer. Botkin in U.S. Patent 2,727,820 relates to an improvement in the production of photographic prints by the diazotype process wherein carboxamides were included in the photosensitive diazo layer to act as developing aids when the diazotype reproduction material was developed in a conventional ammonia developing machihe. The system of using developin.a sheets containing a source of heat-liberated alkali avoided the disadvantages of liquid developers and of gaseous ammonia, but it introduced the inconveninece of a two-sheet system. The developing sheet had to be placed in uniform contact with the exposed sensitized surface of the diazotype reproduction material to form a two-ply assembly which was then heated to effert development. The developin- sbeet was then separated from the reproduction material and set aside. The major advantage of a developing sheet was the isolation of a critical ingredient until needed. Isolation of the critical ingredient @f the system could also be accomplished by precoatings or multilayer coatings. This would overcome the objection to the twosheet system, but at the expense of increased cost and increased technical difficulty. The simplest system was to coat all ingredients onto one support from one solution in one layer in one opera-tion. One requirement was that both the solution and the coated layer be stabilized to prevent premature coupling of the diazo compound and the coupler. The presen@t invention provides heat-developable twocomponent light-sensitive diazotype reproduction materials,'systems, and methods, which avoid the use of liquid developers -and gaseous ammonia and which are stable a.-ainst further development. The invention is adaptable to the developing sheet system, the precoat or multilayer systeni, and to the single layer coating system. One objer-t of the present invention is to provide a heatdevelopable diazotype reproduction material, system, and method which does not. have the disadvantages of prior art. Another object is to provide a heat-developable diazoI type reproduction material, system, and method which does not require the use of liquid developers or gaseous animonia for development. Another object is to provide a heat-developable diazotype reproduction material which is stable against further color development. Another object is to provide a heat-developable diazotype reproduction material which is inexpensive and which gives good quality diazo reproductions. Another object is to provide a heat-sensitive developin,@ sheet for the thcrmal development of diazotype reproduction materials. Another object is to provide a system which is adaptable to the two-sheet, the precoat, and the single layer systerns of thermal development of diazotype reproduction materials. Other objects of the present invention will become apparent in the course of the following specification. In the present invention, thermally decomposable sources of alkali are used as developing agents for the diazotype reproduction material. These sources of alkali are organic nitrogen compounds which may be classified as amides. Depending upon their cheinical nature, they may be used in the sensitized layer, in a precoated layer, or in a separate developing sheet. Thus these -,Lmides can be used in at least three diazotype reproduction systems. The amides of the present invention are decomposed at elevated temperatures when it is desired to release ammonia. This raises the alkalinity of the sensitized
[2]3,255,007 3 layer and allows coupling to occur and thus renders the latent image visible. Some of the amides found to be suitable for the present invention are those denved from monobasic staturated acids, monobasic unsaturated, acids, aromatic 5 carboxylic acids, aromatic hydroxy acids, saturated dibasic acids, and aromatic dibasic acids. These amides have the general formula: 0 11 10 i-.r-u-N-R2 Where RI is hydrogen, alkyl, substituted alkyl, alkylene, substituted alkylene, amidated alkyl, aryl, substituted aryl, amidated aryl, a heterocyclic ring or a pol- 15 ymeric chain, and Where R2 and R3 may be the same or different and represent hydrogen, alkyl, substituted alkyl, - amidated alkyl, aryl, or substituted aryl. S(>me sub-generic structural formulas are the follow20 ing: (C.H2.+l)-CO-NH where n is 0, 1, 2, 3, 4, 5, 8, or. 17 R,r-cH,-CO-NH, 25 where R4 iS OC6H5, C6H5, or CO-NH2 CH2==C-CO-NH2 I R5 30 where R5 is HI or CH3 Rs-CO-N-C6Hs C oH5 where R6 is H, or CH3 35 R-C,H,,--CO-NH, where R7 is H, CH3, N02, NH2, CO-NH2, or OH c I N 45 where there is at least one amido group per monomer unit for this amidated polymeric chain. n is preferably approximately 560. Arnides are derived from carboxylic acids by replac50 ing the OH group with an NH2 group or NR2 R3 group where R2 and R may be. hydrogen, alkyl, or aryl. The . 3 amides are generally solids at room temperatures; the lower molecular weight amides being readily soluble in water, while the higher molecular weight amides are .55 almost insolubl6 in water. By heating in the presence of acids, the amides are hydrolyzed to carboxylic acids with consequent liberation of alkaline vapors. These alkaline vapors are utilized to develop the exposed diazotype reproduction ma60 terial. The presence -of acid is not required for operation of the invention. Thi@s is demonstrated by Example 17 and others. Combinations of diazonium compounds and couplers that are suitable for the conventional dry developing 65 diazotype reproduction 'materials can be employed in the present invention. Examples of the diazonium compounds are the zinc chloride and the boron - trifluoride stabilized salts of p-dialkylamino benzene - diazonium chlorides. These compounds are used in concen- 70 trations ranging from 1.5 to 10% of the sensitizing solution, and they can be used singly or in combinations. Some suitable couplers are phenols and naphthols, such as phloroglucinol, resorcinol, alpha-naphthol, betanaphthol, and 2,3-dihydroxynaphthalene-6 sulfonic acid 7,5 4 (sodium salt). These couplers may be used singly or inombination to vary the color. The coating solution and the senstized layer can also contain various other chemicals commonly used in the preparation of light-sensit e diazotype repro uction materials. These -include stabilizing acids, anti-oxidants, hygroscopic agents, wetting agents, and image intensifiers. Acids that can be used are tattaric ar-id, citric acid, acetic acid, trichloroacetic acid, and 1,3,6-naphthlenetrisulfonic acid or its sodium salt. Thiourea and allyl isothiocyanate are commonly used anti-oxidants. The sensitizing solution and sensitized layer may further contain hygroscopic agents such as glycerine, ethylene glycol, or the like; wetting agents such as saponin and lauryl sulfonates; and image intensifiers s . uch as zinc chloride and nickel sulfate. The coating solution is applied in a conventional manner to a ;suitable support, the excess removed, and thp coating dried. Suitable supports include not only those types of papers such as ordinaty PUIP paper, rag paper, and document paper, but also starch filled cloth, felt, saponified cellulose acetate film, transparent cellulo.sic material such as cellophane, and the like. In the drawings: FIGURE 1 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 10 of the present invention comprising a support 11 and a heat-develbpable two-component photosensitive diazo-ty-pe layer 12 coated on said su@port; FIGURE 2 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 20 of the present inventian comprising a support 21, a precoat layer 22 'coated on said support, and a two-component photosensitive diazotype layer. 23 coated over said precoat layer on said su port; and @ p FIGURE 3 is a sectional view of a developing.sheet 30 comprising a support 31 and a heat-decomposable with a @two-component photosensitive diazotype reproduction material 33 comprising a support 34 and a two-component photosensitive diazotype layer 35 coated on support 34. One method of -the present invention for the preparation of a heat-developable reproduction material is to first' treat a support material with a solution of an amide. After drying, the same support is treated on the same side or on the opposite side with a sensitizing solution containing as major ingredients: a diazonium con-ipound, a coupler, and where desired, a stabilizing acid. After drying, the sensitized suppo'rt is ready for use. The sensitized support is exposed through a master t,o actinic radiations and is then developed by heat'in the range between the decomposition temperature of the adiide and the scotching temperature of the support material. The heat-activated liberation of alkaline vapors then causes the image to develop. The preparation and'use of a heat-developable twocomponent photosensitive diazotype reprodu--tion material precoated with an amide of the present invention is illustrated in Example 1. In another method of preparation of the present invention, the amide is incorporated with the photosensitive diazonium compound, a coupler, and where desired, a stabilizing acid in a sensitizing solution which is applied to a support and then dried. The sensitized support can then be exposed through a master to actinic radiations. After exposure, heat is applied to the support. The temperature is preferably in the range between the decomposition temperature of the amide and the scorching temperature of the support mate-rial. This method of preparation is illustrated in Example 2. . A @developing sheet war, prepared by impregnating a -support with a solution of an amide in an appropri@ate where R 8 is a heterocyclic five-membered or six-niem40 amide 32 impregnated in support 31, in juxtaposition R,7--CO-NH2 bered ring
[3]solvent. The solvent was then removed by drying. The developing sheet was then used to develop an exposed two-comiponent photosensitive diazotype reproduction material by making face-to-face contact with the exposed sens,itiied supface of the diazotype material and subjectin.- the assembly ta hea@t in the range betnveen the decomposition temperature of the amide and the scorching tom@p--Tature of the diazotype stipport. Alkaline vapor@s were liberated to effect development of the latent ima-ge. The prei)aration and use of a developing sheet utilizing an amide of the present invention is illustrated in Example 3. As an alternative procedure, the alkali-liberating agent may be incorpdrated into the !pulp or raw material used to man,,Lifacture the support in suitable proportions to obtain the desired results. The developing temperature range was determined by two factors: the first was the decomposition temperature of the thermally idecompgsable amid&, and the s--cond was the scorcmng temperature of the support. The deCOmposition temperature of the thermally decomposable arnide is affected by the presence of other chemical-s in the system. Thepresence of a good source of hydrogen ions favors decompos-ition by !hydrolysis. The fohowin.- examples further illustrate the present invention and are not intended to restrict or limit the scope of the invention. EXAMPLES kxaipple l.-30 grams of acrylamide were dissolved in 150 milliliters of water and were coated onto a paper stipport. After drying, the preco ated su@pport was sensitized with t@he following solutibn: Water ---------------------------------- - ml-- 150 Trisodium salt of 1,3,6-naphthalene trisulfonic acid ----------------------------------- 9-- 6 TrichloroacetiG,acid ------------------------ 9-- 5 p-Dimethylamino benzene diazonium ehloride, zinc chloride salt ---------------------------- 4 Sodium salt of 2,3-dihydroxy naphthalene-6-sulfonic acid ---------------------------- ------- 9-- 5 Thi6urea ---------------------------- ----- g-- 7 Zinc chlo@ride ----------------------------- g-- 4 The coating was dried toproduce a precoated and sensitized diazotyp,e reproduction material. This was exposed through a master to actin-ic radiations and developed by subjectin- the reproduction material to 150' C. for a few seconds. The heat liberated alkaline vapors from the amide and allowed the @diazonium compound and the coupler to form a blue dye image corresponding to the master i@mage. No liquid developer or gaseous ammonia was required fordeveloprnent. In addition the deveIGped reproduction material was stable agairst further dye formation under the influence,of heat. This precoating system was particularly suitable for amides w@hich were not waterisoluble or which were not compatible wit the cals in the sensitizing solution. Example 2@A sensitizing solution according to the followinformula was prepared and coated on a conventional silica-sized diazotype paper support: Water --------------------------------- ml-- 4500 Acrylamide ------------------------------ g-- 900 Tartaric acid ---------------------------- 9-- 15 Trichloroacetic acid ----------------------- g-- 150 Sodium salt of 1,3,6-naphthalene trisulfonic acid ---------------------------------- g-- 180 p-Dimethylan,ino benzene diazonium chloride, zinc chlor-ide salt --------------------------- 120 Sodium salt of 2,3-dihy-droxynaphthalene-6- sulfonic acid ---------------------------- ------ g-- 150 T,hiouTea ---------------------------- ---- g-- 210 Zinc chloride ---------------------------- g-- 120 3,255,007 6 The coating was dried to produce a hea@t-developable diazotype reproduction material. TI-iis was exposed through a malster to actinic radiation-s and then subjected to heat in thp- range @of 120' C. to the scorching point of the paper support for a few secotids to li.@berate alkaline vapors and thus develop the blue dye image correspondi@ng to t-he master image. This system and method was preferred whenever the water@solubility and the chenucal -com!patibility of the 10 amide with the Other chemicals permitted incorporation into a siilgle solution. Diazonium compo-unds other than @:-dimethylam-'@no benzene diazonium chloride can be used e.,-., p-diethylamino benzene diazonium chloride, and N-ethylN-(2-hydroxyethyl)-p-amino benzene dia15 zonium, chloride xere alsc> used. Another coupler such @as Dhleroglucinol wa@s also used. Exainple 3.-20 -rams of acrylamide were dissolved in 100 ml. of ethyl alcohol. This solution was used to impregnate a porous pa:per support. After drying, a 2o developing sheet for the heat-development of exposed two-component diazoty@pe reproduction materials was produced. On a separate paper support the sensitizing solution of Example I was applied and dried. This was ex!posed through a master to actinic radiations and devel25 oped by making face-to-face contact withthe developing sheet and subjecting the whole assembly to 150' C. for 5 seconds. A blue dye image. cbrresponding to the master image was produced without benefit of liqii@id developer or .-aseous ammonia. The print was s-table against any 30 further dye forrration diie to the application of heat. This system was id@eal for amides which were not compatible with t-he chemicals of the sensitizing sol-ution since isolation was complete. In principle, this isolation can also be achieved by the multilayer system described 35 in Bribish Patent 815,005 and by microencapsulation of the developing agent or the coupler. T-hes-, first tlime examples demonstrate the fact that an imide can be uscd in three different systems as the source of alkali for theheat-development -o-f diazotype 40 reproduction materials. Example 4.-The following @sensitizing s!olution was prepared and coated on a suppor@t. After the coating was dried, the sensitized support was exposed to actinic radiation through a master and develo-ped by subjecting it to 45 heat, The color of the image was blue. Water ---------------------------------- ml-- 150 Sodium salt of 1,2,6-naphthalene trisulfonic agid ----------------------------------- g-- 6 Trichlofoacetic acid ------------------------ g-- 5 50 p-Dimethylamino, benzene diazonium chloride, zinc chloride salt ---------------------------- 9-- 4 Sodium salt of 2,3-dihydroxynaphthalene6-sulfonic a cid -- --------------------------------- g- 5 Thiourea ------ --------------------------- g-- 7 55 Zinc chloride ------ ----------------------- g-- 4 For mamide ------ ------------------------- 9-- 10 Example 5.-A coating of the following diazo sensitizing solution was applied to a paper support: 60 Water ----------------------------------- ml-- 150 p-Dimethylamino bej3zene diazonium chloride, zinc chlori de salt ---------------------------- g-- 4 . 2,3- dihydroxynaphthalene-6-sulfonic acid, sodium salt --- -------------------------------- g-- 5 65 Thiourea -------------------------------- g-- 7 Zinc chloride ----------------------------- g-- 4 An absorbent sheet. was soaked with the following solution: 70 Ethyl alcohol ---------------------------- ml-- 100 N,N-diphenylformamide -------------------- g-- 10 Trichloroacetic acid ----------------------- g-- 5 After drying, the developing sheet was brought into 75 uniform contact with the sensitized paper which had
[4]7 been exposed through a master to actinic radiations. T'he assembly of developing sheet and the diazo sensitized paper was then heated at 150' C. for 5 seconds to produce a blue image on the diazo sensitized paper corresponding to the master image Exainple 6.-The following sensitizing solution was coated on a support suitable for diazotype reproduction materials: Water ---------------------------------- ml-- 150 Trisodium salt of 1,3i6-naphthalene trisulfonir, acid ------------------------------------ g-- 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt ---------------------------- g-- 4 Sodium salt of 2,3-dihydroxynaphthalene-6- sulfonic acid ----------------------------------- g-- 5 Thiourea--------------------------------- g-- 10 Zinc chloride --------- -------------------- 9-- 4 Acetamide --------- ---------------------- g-- 30 pH adjusted to 3.4 with trichloroacetic acid. The sensitized support was t@en dried and exposed through a master to actinic radiation. Heat was used to deyelop the latent image as a blue dye image. Example 7.-To improve storage life, trichloroacetic acid was added according to the following formula: Water ---------------------------------- ml-- 150 Tartaric acid ----------------------------- g-- -1/2 .Trisodium salt of 1,3,@6-naphthalene trisulfonic acid ----------------------------------- g-- 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt -------------------- -------- 9-- 4 Acetamide ------------------------------- g-- 30 Sodium salt of 2,3-dihydroxynalphthale ne@6-sulfonic acid ----------------------------------- g-- 5 Thiourea---------------------------------- g-- 10 Zinc chloride --------- -------------------- g-- 4 Trichloroacetic acid --------- --------------- g-- 5. The pH of the solution was 1 1.3. Storage life was improved by the addition of trichloroacetic acid. Material stored at 115' F. and 47% relative humidity for three days still produced acceptable and satisfactory prints. Lesser amounts of trichloroactic acid reduced the storage life of the sensitized reproductionmaterial. Examp.le 8.-The following sensitizing solution was prepared and coated on a support suitable for diazotype reproduction materials on a production run basis: Water --------------------------------- ml-- 4500 Tartaric acid --------- ------------------- 9-- 15 Trichloroacetic acid --------- ------------- g-- 150 Trisodium salt of 1,3,6-naphthalene trisulfonic acid ---------------------------------- 9-- 180 p-Dimethylamino benzene diazonium chloride, zinc chl<)ride salt --------------------------- 9-- 120 Acetamide ------------------------------ g-- 900 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid ---------------------------------- g-- 150 Thiourea -------- g-- 210 Zinc chloride --------- ------------------- g-- 120 The coating speed was 16 yards per minute within air-bar pressure of 3112 oz. of water. The drying temperature was 180' F. The sensitized and dried material was then exposed through a master to ' actinic radiation and developed by the application of heat. The developed image was blue in color and satisfactory in density. Example 9.-A support sheet was pre-coated with the f ollowing solution: Water ---------------------------------- ml-- 150 Acetamide ------------------------------- g-- 30 After dryin- the precoated support was sensitized with the following sensitizing solution: 3,255,007 8 Water ---------------------------------- rnl-- 150 Trisodium salt of 1,3,6-naphthalene trisulfonic acid ----------------------------------- g-- 6 Trichloroacetic acid ----------------------- g-- 5 p-Dimethylaniino benzene diazonium chloride, zinc chloride salt ---------------------------- g-- 4 Sodium salt of 2,3-dihydroxynaphthalene-6- sulfonic acid ----------------------------------- g-- 5 Thiourea--------------------------------- g-- 7 10 Zinc chloride ----------------------------- g-- 4 The pH of the sensitizing solution was 1.0 After drying, the sensitized sheet was exposed through a master to actinic radiations and developed by heating at 150o C. for 15 4 seconds. A blue image corresponding to the master ima.-e was obtained. Example IO.-An absorbent base sheet was soaked in a solution containing 10 grams of acetamide in 150 ml. of ethyl alcohol and then dried to remoye the alcohol to 20 produce a developing sheet. A paper supp<)rt was sensitized with the following solution: Water ---------------------------------- ml-'- 150 Trisodium salt of 1,3,6-naphthalene trisulfonic 25 acid ----------------------------------- g-- 6 Trichloroacetic acid ------------------------ g-- 5 p-Dimethylamino benzene diazonium chloride, zinc chlori(te salt ---------------------------- 9-- 4 30 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid ----------------------------------- g-- 5 Thiourea --------------------------------- g-- 7 Zinc chloride ----------------------------- g-- 4 After drying, the developing sheet and the exposed sen35 sitized support were placed in contact and heated at 150' C. for a few seconds to produce a blue image corresponding to the master image. Example II.-The following solution was prepared 40 and coated on an absorbent support to form a deyeloping sheet: Ethyl alcohol -ml-- 25 ---------------- ---------- T-richloroacetic acid ------------------------ g-- Phenoxyacetamide ------------------------- g-- 2.5 45 Heating this sheet in contact at 175' C. for 5 seconds with a printed but undeveloped diazotype paper such as that described in Example 10 produced a brown ima@e. Example 12.-A developing sheet prepared by coat50 ing the following solution on an absorbent support when heated in contact with printed diazotype paper as described in Example 10 caused a blue image to be produced on the diazotype paperEthyl alcohol ---------------------------- cc-- 100 5a Trichloroacetic acid -' --g-- 3 --------------------- N,N-Diphenylacetamide -------------------- g-- 10 Contact tirle was 6 seconds at 170' C. Example 13.-The following solutioii was prepared 60 and coated on an absorbent support: Water ----------------------------------- cc_- 150 Propionamide ----------------------------- g-- 30 1 3 6-naphthalene trisulfonic acid, trisodium salt -g-- 6 65 @r I ichloroacetic acid ------------------------ g-- 5 p-Dimethylamino benzene diazonium chloride, zinc chloride salt ---------------------------- g-- 4 2,3-dihydroxynaphthalene - 6 - sulfonic acid, sodium 70 salt ----------------------------------- 5 Thiourea --------------------------------- g-- 7 Zinc chloride ----------------------------- 9-- 4 After printing through a master, the blue image was 75 developed by heating for 5 seconds at 150' C.
[5]9 Example 14.-Propionamide was used in the following solution to prepare a developing sheet: Water ---------------------------------- cc-- 100 Trichloroacetic acid ------------- ----------- g-- 2 Propionamide ----------------------------- g-- 5 When used to develop a printed diazotype paper such as that described in Example 10, a blue image was obtained. Contact time was 5 seconds at 150' C. Example 15@-The followin.- chemicals were substi tuted individually for the propionamide in Example 13 with the result that the developed images were substantially the same as for propionamide: n-Butyramide n-Valeramide iso-Butyramide iso-Valeramide Exatnple 16.-Hexamide, nonanamide, and stearamicie were used separately in the followin.- solution formula to prepare developing sheets: Ethyl alcohol ---------------------------- cc-- 50 Trichloroacetic acid ----------------------- g-- 1.5 Amide ---------------------------------- g-- 5 When these developing sheets were used to develop printed diazotype sheets prepared as described in Example 10, blue images were obtained. Contact time was 5 seconds at 160' C. Example 17.-The sensitizing solution was prepared with acrylamide according to the following formula: Water ----------------------------------- cc -- loo p-Diethylamino benzene diazonium chloride, zinc chloride salt ---------------------------- 4 2,3-dihydroxynaphthalene - 6 - sulfonic acid, sodium salt ------------------------------------ 5 Acrylamide ------------------------------ g-- 50 This solution was coated on an absorbent support and dried. When heat-developed at 150' C. for 5 seconds a blue color was developed. Exatiiple 18.-Polyacrylamide of low molecular Weight such as PAM 10 was used in the following sensitizing solution: Water ----------------------------------- cc-- 100 Polyacrylamide PAM 10 ------------------- g-- 50 Trichloracetic acid ------------------------- g-- 8 1,3,6-naphthalene trisulfonic acid, trisodium salt -g-- 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt ---------------------------- g-- 4 2, 3-dihydroxynaphthalene - 6 - sulfonic acid, sodium salt ------------------------------------ g-- 5 Thiourea --------------------------------- g-- 7 Zinc chloride ----------------------------- 4 This solution was coated on an absorbent support and was dried. After printin.- with ultraviolet light through a master, the image was developed by heating the coated support at 150' C. for 5 seconds. Example 19-Polyacrylamide such as PAM 10 was used in the following solution to prepare a precoat solution: Water ---------------------------------- cc-- loo Polyacrylamide PAM 10 ------------------- g-- 50 Trichloroacetic acid ------------------------ g-- 10 This solution was coated on a support and dried. The precoated paper was then sensitized with a solution such as described in Example 1. Heat treatment after - xposing the sensitized support through a master produced a blue dye image. Example 20.-The same polyacrylamide solution as in Example 19 was used to coat an absorbent support to make a developing sheet. When used as in Example 3 to develop a diazotype paper by placin.a it in contact with the exposed diazotype paper and heatin.- the assembly for a few seconds at 150' C., a blue image on the diazotype paper was developed. 8,255,007 10 Example 21.-Hexamethylene-bis-acrylamide was used to prepare a solution according to the following formula: Ethyl alcohol ---------------------------- cc-- 100 Hexamethylene-bis-acrylamide --------------- g-- 10 5 Trichloroacetic acid ----------------------- g-- 5 This solution was used to impregnate an absorbent support. After drying, this developing sheet was placed in contact with sensitized and exposed diazotype paper 10 and he,t,d at 150' C. for 8 seconds. A blue image was formed. Example 22.-Methacrylamide was used in place of the acrylamide of examples 2, and 17, with the same results. 15 Example 23.-Malonamid@- was used in the following sensitizing solution to coat a support which was then dried: Water ----------------------------------- cc-- 150 20 Malonamide ------------------------------ g-- 25 1,3,6-naphthalene trisulfonic acid, trisodium salt -g-- 6 Tart aric acid ------ ----------------------- g-- 1/2 Tric hloroacetic acid ----------------------- g-- 5 p-Dimethylamino benzene diazonium chloride, zinc 25 chloride salt ---------------------------- g-- 4 2,3-dihydroxynaphthalene - 6 - sulfonic acid, sodium salt ------------------------------------ g-- 5 Thiourea --------------------------------- g-- 7 Zinc chloride ------------------------------ g-- 4 0 Development of a blue dye image after exposure was accomplished by heating at 180' C. for 4 seconds. Example 24.-Benzamide was used in the following solution to prepare a developing sheet: 35 Ethyl alcohol ----------------------------- cc-- 100 Benzamide ------------------------------- g-- 5 This solution was then used to impregnate an absorbent support. Heat-ing the developing sheet while it was 40 in contact with a diazotype paper prepared as in Example 5 resulted in development of a blue color on the diazotype sheet. Example 25.-The solution of Example 24 was used also as a precoat solution. It was coated on a support, 45 dried, and then sensitized with the following solution on the same side: Water ---------------------------------- cc-- 150 1,3,6-naphthalene trisulfonic acid, trisodium salt g-- 6 50 Tartaric acid ----------------------------- g-- 1/2 p-Dimethylamino benzene diazonium chloride, zinc, chloride salt ---------------------------- g-- 4 2, 3,-dihydroxynaphthalene-6-sulfonic acid, sodium salt ----------------------------------- g-- 5 Thiourea --------------------------------- 9-- 7 '55 Zinc chloride ----------------------------- g-- 4 Af-ter exposure through a master, a bl-ue dye image was developed by heating the exposed sheet for 5 seconds at 150' C. 60 Example 26.-p-Toluamide was used in the following solution to prepare a developing sheet: Ethyl alcoh(>l ---------------------------- cc-- 50 p-Toluamide ----------------------------- g-- 5 65 Trichloroacetic acid ------------------------ g-- 1.5 The developing sheet was used to develop diazotype paper prepared as in Example 5. A blue color was developed by heating the developing sheet in contact with the diazotype paper for a few second at 165' C. 70 Examp-le 27.-p-Nitrobehzamide was used in the following solution to prepare a developing sheet: Ethyl alcohol ---------------------------- cc-- 25 p-Nitrobenzamide ------------------------- g-- 2.5 75 Trichloroacetic acid ----------------------- g-- 1.0
[6]this developing sheet was used to d"elop a ted-brown dye color in ihe same manner as in Example 26. Exa7nple 28.-Anthranilamide was usedin the following solution to prepare a developing sheet:. Ethyl alcohol ---------------------------- cc-- 100 Anthranilamide --------------------------- g-- 10 Trir,hloroacetic acid ------------------------ g-- 5 This solution was coated on a support to make a developing sheet which then was used to develop a diazotype paper as described in Example 5 to produce a blue dye image. Example 29.-Anthranilamide was also used in the follow@ing sensitizing solution: Water ---------------- ---cc-- 150 --------------- Trichloroacetic acid ----------------------- g-- 5 Anthranilamide --------------------------- g--- 10 1,3,6-naphthalene trisulfonic acid, trisodium salt g-- 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt --------------------------- - 9-- 4 2,3-dihydroxynaphthalene-6-sulfonic acid, sodium salt ---------------- ----- g-- 5, -------------- Thiourea -------------------------------- g-- 7 This was coated on a support and dried. Heating the exposed sensitized sheet at 160' C. for 6 seconds produced a blue dye image. Example 30.-Phthalamide was used to make a developing sheet by coating a support with the followin.solution: Ethyl alcohol ----------------------------- cc-- 100 Phthalamide --@ ---------------------------- g-- 5 Trichloroacetic acid ----------------------- g-- 2.5 Placing this developing sheet in contact with a printed diazotype paper and subjecting the assembly to heat at 175' C. for several seconds produced a blue image. Example 31.--Salicylamide was used in a developing sheet prepared by coating a support with the following solution: Ethyl alcohol ---------------------------- cc-- 100 Salicylamide ------------------------------- g-- 5 The developing sheet was used to develop a blue dye image as in Examples 5 and 30. Example 32.--Salicylamide was also used in a precoat layer by coatiilg a support with the following solution: Ethyl alcohol ---------------------------- cc-- 150 Salicylaniide ------------------------------ g-- 10 The precoated support was then sensitized as in Example 9. After exposure through a ma ter to actinic radiations, a blue color was developed by heating the sensitized precoated support for 5 seconds at 150' C. Example 33.-2-furamide was used in the following solution to coat a support to make a developing sheet: Ethyl alcohol ----------------------------- cc-- 50 2-furamide ------------------------------- g-- 5 Trichloroacetic acid ----------------------- g-- 1.5 This developing s@eet was used at 175' C. for 4 seconds to develop printed diazotype paper as described in Example 5. Example 34.-N-Methylacetamide was used to prepare a developing sheet by irnpregnating an absorbent support with the following solution-. Ethyl alcohol ---------------------------- cc-- 25.0 N-methylacetamide ----------------------- g-- 2.5 .Trichloroacetic acid ----------------------- g-- 1.0 After drying, this developing sheet was used to develop exposed diazotype paper prepared as in Example 5 by placing the two sheets in contact and heating them at 165' C. for 7 seconds to obtain a blud color. 3,255,007 12 Example 35.-Example 34 was tepeated with 2-phenylacetamide in place of Nmethylacetamide. After following the same procedure, a blue green image was obtained. Example 36.-Nicotinamide was used in the following solution to impregnate an absorbent support to make adeveloping sheet: -Water ----------------------------------- cc-- 5o Nicotinamide ------------ ------------- g-- 5 10 This sheet was then dried and used to develop an exposed diazotype paper by placing it in contact with the exposed diazotype paper and heating the assembly at 150' C. fo@ 6 seconds to obtain a colored image. 15 10 @Xample 37.-A support was precoated with the folwing solution: Water ------------------------------------ cc-- 50 Nicotinamide ------------------------------ g-- 5 Trichloroacetic acid ------------------------- g-- 2 20 After drying, the precoated support was sensitized with the following solution: Water ------------------------------------ cc-- 150 Tartaric,acid ---------------------- -------- g-- il2, 25 1,3,6-naphthalene trisulfonic acid, trisodium salt -g--6 p-dimethylamino benzene diazonium chloride, zinc chloride salt ---------------------------- g-- 4 2, 3-dihydroxynaphthalene-6-sulfonic acid, sodium salt ----------------------------------- g-- 5 30 Thiourea --------------------------------- 7 Zinc chloride ----------------------------- 4 After drying, the sensitized support was exposed through a master to actinic radiations and then developed by heat3,5 ing at 160- C. for 5 seconds. A blue-black ima.-e was obtained. It is apparent that the described examples are capable of many modifications and variations within the scope of the present invention. All sucli modifications and varia40 tions are to be included within the scope 6f the present invention. What is
