US 3199982 A
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DIAZOTYPE REPRODUCTION MATERIAL Filed March 19, 1963 HEAT- DEVELOPAB LE TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE FIG. I LAYER I2 SUPPORT I I HEAT- DEVELOPABLE TWO- COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTION MATERIAL IO TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE LAYER 23 PRECOAT LAYER 22 FIG. 2
SUPPORT 2| HEAT-DEVELOPABLE TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTION MATERIAL 20 FIG 3 HEAT-ACTIVATABLE DEVELOPING AGENT 32 SUPPORT 3| DEVELOPING SHEET3O HEAT-ACTIVATABLE DEVELOPING AGENT TWO-COMPONENT TWO- COMPONENT PHOTOSENSITIVE PHOTOSENSITNE DIAZOTYPE LAYER 42 D|AZOTYPE SUPPORT 4| REPRODUCTION MATERIAL 4O INVENTOR. THOMAS KASH I W A BA RA ATTO NEY United States Patent 3,189332 DIAZOTYPE REPRODUCTION MATERTAL Thomas T. Kashiwabara, Fort Lee, N.J., assignor to Keuli'el & Esser Company, Hohoken, N1, a corporation of New Jersey Filed Mar. 19, 1963, Eer. No. 266,332 20 Claims. (Cl. 96--49) This invention relates to diazotype reproduction materials and methods for their production and use, and refers more particularly to two-component photosensitive diazotype reproduction materials which are developable by means of heat,'and to the methods and means for accomplishing the heat development of said materials Photosensitive diazotype materials are well known andhave many advantages over other means of reproduction when consider-ing the combined basis of quality and cost. The photosensitive diazotype materials, however, possess some inherent disadvantages depending upon their type. -,There are two generaltypes of photosensitive diazo systems and materials based 'on the means of development: the two-component diazotype materials using the dry method of diazo development; and the one-component diazotype materials using the semi-wet method of diazo development.
The dry diazo materials utilize gaseous ammonia to raise the pH of the coating after exposure to allow coupling of the diazo compound and coupler which are coated on the same support. The obvious disadvantage of this system is that it requires the use of gaseous ammonia which is obnoxious and dangerous to handle, and
which requires exhaust equipment in order to be utilized in confined spaces;
The semirwet system of diazo development utilizes a photosensitive material which comprises a base sheet and a coating of photosensitive diazo compound coated on the base sheet. After exposure under a master to actinic light, the sheet coated with the diazo compound is passed through a chemical bath which contains an alkali and a coupler to develop the image by dye formation. Among the major disadvantages of this method is that a liquid is required in the development step. The liquid affects the paper base and requires drying.
Among the old attempts at producing a heat-developable reproduction material was one which utilized a base sheet having a dark background on which a layer of a light-colored wax was applied, The master was placed against the wax layer and was exposed to infra-red radiation which was converted in the image areas to heat which then passed by conduction to the wax layer. The wax layer melted under those portions of the master which contained an image and allowed the dark back ground of the base sheet to be seen, which in effect reproduced the master image. The disadvantages of this system of reproduction were cost as compared to the conventional diazo systems, quality inferior to the diazo product, and retained heat sensitivity.
The old systems used melting wax layers and the like inheat sensitive and not necessarily light sensitive materials.
For many years heat development of photosensitive ,clia zo materials had been tried without noteworthy success It had been attempted in order to eliminate. the disadvantages of gaseous ammonia in the dry developing system, and liquid developer in the semi-wet system.
The development of exposed two-component diazotype prints by gases given off by the decomposition of ammonia compounds from a developing sheet under the infiuence of heat had' been tried. The ammonia compounds found to be particularly suitable for development of diazotype prints were the products of ammonia and weak acids. Good results wereobtained from ammonium carbonate,
ammonium bicarbonate, and'the like, which decompose freely at temperatures slightly above room temperature with the release of free gaseous ammonia and water vapor. The solid carbonates were. heated in juxtaposition to the exposed two-component diazotype paper to fully utilize thereleased gaseous ammonia on the exposed surface. This known material had the great disadvantage of very poor shelf life'which severely limited its practical use.
Another known material incorporated urea with a photosensitive diazoic. The ureadecomposed with the heat and liberated ammonia gas which neutralized and acid formed during coupling thereby aiding the'coupling of the diazoic with its photolysis phenol. Urea in a separate stratum was tried in another material. Developing sheets impregnated with a composition containing one compound or a combination of compounds which liberated the vapor of an alkali or a coupler were also tried. Another material incorporated a carboxamide such as formamide,- acetamide, urea, and methyl-urea as a humectant but not as a source of alkali ammonia.
Another material was a multilayer diazotype material comprising a support, a layer containing. a diazo compound, a; fusible barrier layer which melted below the decomposition temperature of the diazo compound, and alayer containing a coupler, all coated on one side of a support. The diazotype material was placed, in contact with a master and subjected to infrared radiation. Imagewise generation and transfer of heat from the master to the multilayer diazotype material melted the fusible barrier. layer and permitted the diazo compound and coupler to form an azo dye.
Another object is to provide a photosensitive heat-.
developable diazotype material and system which requires neither gaseous ammonia nor liquid developer for development. I
Another object is to provide a photosensitive twocomponent heat-developable diazotype'reproduction material whichis heat-developable and which is stable to further application of heat.
Another object of the present invention is to provide a photosensitive heat-developable diazotype material which is inexpensive and which gives'good quality diazo reproduction. i
Other objects. will be apparent fication. In the present'invention, the base necessary for the development is produced on the diazotype material at the time of development by thermally induced chemical or physical conversion of a base-releasing compound. The application of heat causes this compound to release the base necessary for the couplingreaction at the time of development. i
It has been found that many organic nitrogen compounds are suitable sources of base for heat-developable diazo mate-rials. These compounds can be incorporated in a sensitizing layer, in a precoat layer, or in a developing sheetdepending upon solubility and compatibility. The compounds ot the present invention are induced by elevated temperatures to release a base which increases the alkalinity of "the system and permits coupling to take place, thereby developing the latent image.
The organic nitrogen compounds suitable for use in the present invention are those cor-responding to the following general formula and. salts thereof: a i
. RINHR2 wherein R [and R are members selected from the groups from the following speciconsisting of: group A where R is a member selected from the group consisting of alkyl, hydroxyalkyl, ethoxycarbonyl alkyl, carboxyalkyl, carboxy carbamoyl alkyl, guanyl, arylguanyl, aminoguanyl, diallylamino-triazinyl, arylamino triazinyl, thiazoly-l, andpyridyl, and. R is a member selected from the group consisting of hydrogen, alkyl, and guanyl; and group B WHIBH'RL and R are members of the same heterocyclic ring.
One sub-generic group of chemicals is that corresponding to the general formula and salts thereof:
, guanidine (as the bicarbonate salt), phenyi 'guanidine (as the carbonate salt); phenyl biguanide, vN; N-diallylmelamine, 2,4-diamino6 phenyl-s triazine, '2-am'inothiazole, and '2-aminopyridine.
Another sub-generic group is that corresponding to the following general formula:
wherein R and R are members of the same heterocyclic ring. .This group includes imid-azole, benzimidazole, and piperazine (as the hexahydrate).
' In the drawings: a
FIGURE 1 is a sectional v-iewof a heat-developable two-component photosensitive .diazotype reproduction material 10 comprising a support :11 and a heat-developable two-corrip0nent photosensitive diazotype layer 12 coated on said support;
FIGURE 2 is a sectional view of a heat-developable two-component photosensitive diazotype' reproduction material 20 comprising a support 21, aprecoat. layer 22 coated on said support, and a two-component photosensitive diazotype layer 23 coated over said precorat layer on said support; and
FIGURE. 3 is asectional view of a developing sheet 36 comprising a support 31 and "a heat-activatab'le developing agent 3'2 impregnated in said-support. The developing sheet is in contact with a two component'photosensitive diazotypereproduction material 40 comprising a support 41 and atwo-com ponent photosensitvie diazotype layer 42' coated on said support; One method of the present invention for thepreparation of a heatdeveloping reproduction material is to treat a support material with a solution of heat-activatable developing agent. After drying, the same support is coated on the same side or on the opposite side with a sensitizing solution comprising diazonium compound and couple-r. The coating is dried; In this method the heatactivatable developing agent is in the first or precoat layer. The sensitized support is exposed through a master to actinic radiations and is then developed by heat in the range between the activation temperature of the developing agent. and the scorching temperature of the support material. The heat-activated libenation of developing agent then causes the image to develop. The preparationand. .use-ot 'heat-developable tWo-component p'hotosensitive diaz-otype reproduction material precoated with heat-tactivatable developing agent of the present invention is illustrated in Example 5.
In another method of preparation-of the present invention, the heat-activatalble developing agent is incorporated into the sensitizing with the photosensitive solution comprising diazonium compound and coupler. The solution is applied to a supportand then dried. The sensitized support is exposed through a master to actinic radiations and after exposure, heat is applied to the support. The temperature is preferably in range between the activation temperature. .of the developing agent and the scorching temperature of the support material.- This method of preparation is illustrated in Example 3,
A developing sheet is prepared by impregnating a support with a solution of -il1eat-activ.atable developing agent in a suitable solvent. The solvent is then removed by drying. The developingshee-t is used to develop an exposed two-component photosensitive diazotype. reproduction material by placing it in face-to-fiace contact with the exposed sensitized surface of the diazotypc material and subjecting the assembly to heat in the range between the activation temperature of theqdeveloping agent and the scorching temperature of the diazotype support. This activates the developing agentand permits coupling to occur on the sensitized surface of the diazotype material. The preparation and use of a developing sheet utilizing the heat-activatahle developing agentof the present invention is illustnalted in Example 1. 1
The developing temperature range is determined by two factors: first, the activation temperature of'the heatactivatable developing agent; and second, the scorching temperature of the diazotype support material. The activation tempenature is that degree of heat necessary to release or liberate the developing agent in the amount required for development of a two-component photosensitive diazotypereproduction material. The scorching temperature is that degree'of heat which darkens the background of a developed diazotype'print or which causes undesirable physical degradation 'of'the diazotype support material.. V p
The examples herein are given for purposes of illustration, and it .is to be understood that the invention is not limited to these examples.
EXAMPLES G. Ethanol -Q 90 Dodecylamine 10 The prepared developing sheet was used to heat-develop ing sheet was used to heat-develop a diazotype reproduction material by placing it in contact with the sensitized sunface of the reproduction materialthat had been exposed to actinic-radiations through .a master; heating the developing sheet for a few seconds at C. while in contact with thesensitized surfacerof the reproduction material to release the base and thus eifect coupl ing, .and' dinally, sepa-ratingthe developing sheet from the diazo type reproduction material. A colored dye image-was formed on the diazotype reproduction material.
Tetradecylamine, hexladecylamine, ootadecylamine, 2- amino thiazole, Z-aminopy-ridine, and benzim'idazole were used in place of the dodecylamine to produce the same result. 1
Example 2.N-methyl glucamine was :used from a 10% aqueous solution to prepare a developing sheet as in Example, 1. Used in the same manner to heat-develop a diazotype reproduction material, the same results were obtained.
Example 3.-N-methyl 'glucamine was used as a sen- G. Water 150 Tartaric acid A Trichloroacetic acid 7 1,3,6-naphthalenetrisulfonic acid, sodium salt 6 N-methyl glucamine 5 p-Dimethylamino benzene diazonium chloride,
zinc chloride salt 4 2,3-dihydroxy-naphthalene-G-sulfonic acid,
sodium salt 5 Thiourea 7 Zinc chloride 4 This was coated on a support and dried. After exposure to actinic radiations through a master, the sensitized support was heated at atemperature between the melting point of the N-rnethyl glucamine and the scorching temperature of the support. A blue image corresponding to the master image was produced.
Imidazole, n-butylamine hydrochloride, L-glutamine, glycine ethyl ester hydrochloride, phenyl biguanide, aminoguanidine sulfate, guanidine acetate, and phenyl guanidine carbonate were used in place of N-methyl glucamine. Aminoguanidine bicarbonate was used in. half quantities. All produced a blue image with the exception of aminoguanidine sulfate which produced a red-violet image.
Example 4.-N,N-diallyl melamine was used in a precoat layer coated from the following solution:
Dioxane ml 100 N,N-dia1lyl melamine g 20 The precoated support was then coated with the following sensitizing solution:
G. Water 150 Tartaric acid /2 Trichloroacetic acid 5 1,3,6-naphthalenetrisulfonic acid 6 p-Dimethylamino benzene diazonium chloride,
zinc chloride salt 4 2,3-dihydroxynaphthalene-6-sulfonic acid,
sodium salt 5 Thiourea 7 Zinc chloride 4 After the sensitized support was dried, it was exposed to actinic radiations through a master and then heat-developed for a few seconds at 150 C. to produce a blue image corresponding to the master image.
Example 5.-2,4-diamino-6-phenyl-s-triazine was used from a saturated solution in dioxane to prepare a precoat layer on a support. This was then sensitized as in Example 4 to produce substantially the same results when heat-developed.
Example 6.The sensitizing solution of Example 3 was prepared with 3 g. of benzimidazole in place of 5 g. of N-methyl glucamine. After a support was sensitized and heat-developed as in Example 3, a blue image corresponding to the master image was produced.
Example 7.A mixture of the following composition was used to prepare a developing sheet:
Percent Tetradecylamine acetate 5 Hexadecylamine acetate 30 Octadecylamine acetate 65 The solution was prepared according to the following formula:
Percent Ethanol 95 Amine acetate mixture 5 6 A support was impregnated with this solution and .then dried to produce a developing sheet. This was used to heat-develop a diazotype reproduction material as in Example 1 to produce a dye image corresponding to the master image.
Example 8.A sensitizing solution was prepared according to the formula in Example 3 using 15 g. alpha-alanine in placeof the 5 g. N-methyl glucamine. The solution was coatedon a support and heat-developed to produce a blue dye image corresponding to the master image.
It is apparent that the described examples are capable of. many variations and modifications within the scope of the presentinvention. All such variations and modifications are to be included within the scope of the present invention.
What I claim is:
1. A heat-developable diazo-type'material, which comprises:
a support resistant to the scorching effects of heat at the conditions of thermal development; and
a photosensitivediazonium compound, a coupler therefor, and a heat-activatable developing agent coated on said support, said agent having the general formula:
.where R and R are members selected from one of the groups consisting of:
group A in which R is a member selected from the group consisting of: alkyl, thiazolyl, pyridyl, guanyl, and triazinyl, and R is a member selected from the group consisting of hydrogen, methyl, and guanyl; and group B in which R and R are members of the same heterocyclic ring. 2. A method for making a diazo reproduction of an image, which comprises the steps of:
exposing a diazo sheet to imagewise actinic radiation, said sheet comprising a support resistant to the scorching effects of heat at the conditions of thermal development, and a photosensitive diazonium compound, a coupler therefor, and a heat-activatable developing agent coated on said support, said agent having the general formula:
R NHR where R and R are members selected from one of the groups consisting of:
group A in which R is a member selected from the group consisting of alkyl, thiazolyl, pyridyl, guanyl, and triazinyl, and R is selected from the group consisting of hydrogen, methyl, and guanyl; and group B Where R and R are members of the same heterocyclic ring; and
heating said sheet at a temperature between the activation point of said agent and the scorching point of said support to form a dye image on said sheet.
3. A sheet in accordance with claim 1 in which said agent is intimately admixed with said diazo layer.
4. A sheet in accordance with claim 1 in which said agent is coated between said support and said diazo layer.
5. A method in accordance with claim 1 in which said agent is intimately admixed with said diazo layer coated on the same support.
6. A method in accordance with claim 1 in which said agent is coated on said support between said support and said diazo layer.
7. A material in accordance with claim 3 in which said agent is n-butylamine hydrochloride.
8. A material in accordance with claim 3 in which said agent is N-methyl glucamine.
9. A material in accordance with claim 3 in which said agent is phenyl biguanide.
10. A material in accordance with claim 3 in which said 12. A material in accordance with claim 4 in which said agent is N,N-diallyl melamine.
13. A material in accordance with claim 4 in said 'agent is 2,4-diamino-6-phenyl-s-triazine.
14. A method in accordance with claim said agent is n-butylarnine hydrochloride.
15. A method in accordance with calim said agent is N-methyl glucamine.
16. A method in accordance with claim said agent is phenyl biguanide.
17. A method in accordance with claim said agent is guanidine acetate. I
18. A method in accordance with claim said agent is imidazole.
19. A method in accordance with claim said agent is.N,N-diallyl melamine.
20. A method in accordance with claim said agent is 2,4-diamino-6-phenyl-s triazine.
which which which which which which which which Kosar:
UNITED STATES PATENTS Sprongerts 96-91 6/ 31 1/49 Greig 96-91 3/51 Duerr 96-75 4/52 Neumann et a1 96-91 11/52 Reichel 96-49 2/54 Lindquist 117-154 XR 1/ 56 Morrison 96-49 12/56 Marron et al. 96-49 2/58 Barrett et a1; 117-154 XR 7/62 Klimkowski et al 96-75 XR 9 FOREIGN PATENTS 7/59 Great Britain. 11/60 France.
No. 4, July August 1961, pp. 239-243. NORMAN G.-TORCHIN, Primary Examiner.