US3157503A

US3157503A - Diazotype reproduction materials

Info

Publication number: US3157503A
Application number: US266231A
Authority: US
Inventors: Kosar Jaromir
Original assignee: Keuffel and Esser Co
Current assignee: Keuffel and Esser Co
Priority date: 1963-03-19
Filing date: 1963-03-19
Publication date: 1964-11-17
Anticipated expiration: 1981-11-17
Also published as: FR1386060A; NL6402882A; DE1447738A1; AT253928B; AT265016B; BE645320A; GB1060744A

Description

Nov. 17, 1964 J. KOSAR 3, 3

DIAZOTYPE REPRODUCTION MATERIALS Filed March 19, 1965 FIG.|

HEAT-DEVELOPABLE TWO-COMPONENT PHOTO- SENSITIVE DIAZOTYPE LAYER I2 suPPoRT HEAT-DEVELOPED TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTION MATERIAL IO FIG.2

L E 22 DIAZOTYPE LAYER 23 SUPPORT 2| HEAT-DEVELOPABLE TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTION MATERIAL 2O NG SHEET 3O BASE-RELEASING SUPPORT 3 I AGENT 32 BASE-RELEASING AGENT 32 TWO-COMPONENT PHOTOSENSITIVE DIAZO- TYPE LAYER 42 SUPPORT 4| TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE REPROQUCTION MATERIAL 4O INVENTOR. JAROMI R KOSAR 8 AT ORNEY United States Patent 3,157,593 BIAZGTYPE REPRGDUCTIGN MATEREALS .laromir Kosar, Eeechhurst, N.Y., assigns: to gsser Company, Hoholren, N.J., a corporation of New ersey Filed Mar. 19, 1953, Ser. No. 266,231 9 (Cl. %4)

This invention relates to diazotype reproduction mat rials and to methods for their preparation and use, and refers more particularly to heat-developable two-compo nent photosensitive diazotype reproduction materials and methods for their preparation and use.

Diazotype reproduction materials are Widely used commercially because of their combined advantages of quality and low cost. Two types are generally used: the semiwet developing type and the dry developing type. Each has its own inherent disadvantage. In the case of the semi-wet developing type, the handling of a liquid developer is a negative factor. For the dry developing type, the machine requirements for confining and exhausting noxious ammonia fumes are negative factors. In addition, the loading of concentrated ammonia water and the removal of spent ammonia water from the machine are disagreeable tasks in the daily use of dry developing machines.

Thermographic reproduction processes have been used to avoid or eliminate some of the disadvantages of the diazotype processes, but they possess other objectionable properties such as the retention of sensitivity to heat even after the desired reproduction has been made. In addition these materials are not necessarily photosensitive.

The present invention combines the advantages of the diazotype process with that of the thermographic process While avoiding some of the disadvantages of both. The quality and low-cost of the diazotype process is combined with the simplicity of development of the thermographic process. The use of liquid developers and gaseous ammonia is avoided, and the final reproduction is insensitivejo further application of heat.

Therefore one object is to provide a heat-developable photosensitive diazotype reproduction material which does not have the disadvantages of the prior art.

Another object of the present invention is to provide a heat-developable two-component photosensitive diazotype reproduction material.

Another object is to provide a diazotype reproduction material which is developable without the use of liquid developers or gaseous ammonia.

Another object is to provide a heat-developable reproduction material which, after development is stable to further undesirable development due to the application of heat.

Another object is to provide a method for the preparation of heat-developable two-component photosensitive diazotype reproduction material.

Another object is to provide a method for the use of heat-developable two-component photosensitive diazotype reproduction material.

Another object is to provide a developing sheet for the heat-development of a two-component photosensitive diazotype reproduction material.

Another object is to provide a method for the use of a developing sheet in the heat-development of a two-component photosensitive diazotype reproduction material.

Another object of the present invention is to provide a reproduction material which has good quality and low cost.

Other objects will become evident during the course of the specification.

In the drawings:

FIGURE 1 is a sectional view of a heat-developable ice two-component photosensitive diazotype reproduction material 16 comprising a support 11 and a heat-developable two-component photosensitive diazotype layerlZ coated on said support. FIGURE 2 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 29 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 support.

FIGURE 3 is a sectional view of a developing sheet 36 comprising a support 31 and a base-releasing agent 32 impregnated in said support in contact With a two-component photosensitive diazotype reproduction material 40 comprising a support 41 and a two-component photosensitive diazotype layer 42 coated on said support.

The tollowin is a group of chemical structural formulas of the thermosensitive base-releasing agents of the present invention:

Hexamethylenetetrarrine N Thiosemicarbazide NI-l -CSNHNH Semicarbazide hydrochloride NH NHC O-NH HCl Carboxymethyl trimethyl ammonium chloride hydrazide NH NHCOCH N( CH C1 Carbohydrazide NH NHCONHNH Succinhydrazide I Ii-I NHCO-CH CH -COOH Acetone semicarbazone (CH C' 1 INHC O-NH Briefly, it has been found that base-releasing agents can be used to develop the latent image on a two-cornponent or dry developing type of diazotype reproduction material. The base-releasing agent can be incorporated into the sensitized layer, into a separate precoat layer between the support and the sensitized layer, or it can be impregnated into a separate support to make a developing sheet. Compatibility with the other chemicals in the sensitizing solution determines Whether or not it can be incorporated into the various systems. Generally where it is incorporated with the sensi izing solution adjustments are required to prevent precoupling of the diazonium compound and the coupler. Base is released under the influence of heat.

be included with the chemicals in the sensitizing'solution if his compatible with the chemicals. In cases where minor adjustments cannot be made to accommodate the base-releasing agent in the sensitizing solution,

' the agentcan either be coated on the same support in a precoat layer between the support and the sensitizing layer or it can ,be coated or impregnated into a separate support to form a developing sheet.

The base-releasing agents found to be suitable for the present invention are organic nitrogen compounds such 'as hexamethylenetetramine, thiosemicarbazide, and combinations of these with other organic nitrogen com,- pounds. Combinations of hexamethylenetetramine with semicarbazide hydrochloride for example were found to be satisfactory for purposes of the present invention.

' The use of heat-developable two-component photosensitive diazotype reproduction materials with the base releasing agent in either the sensitizing layer or a precoat layer is the same. Both are exposed conventionally through a master to actinic radiations to form latent images in the reproduction material. the master, both can be heated in the temperature range between the heat activation temperature of the thermosensitive base-releasing agent and the scorchingtemperature of the reproduction material support. Temperatures of about 140 to 160 C. have been found to be adequate for development purposes.

In the case of a developing sheet, the developing sheet is placed in face-to-face contact with van exposed twocomponent photosensitive diazotype reproduction material and. the assembly heated preferably from the developing sheet side. The heat releases the base from the base-releasing agent and the base migrates to the exposed diazotype reproduction material and thus permits coupling to take place. Reproduction of the original image is thus effected.

The invention is further illustrated by the following examples which are not intended to limit the scope of the invention.

' EXAMPLES Example 1 A support was coated with a sensitizing solution prepared according. to the following formula:

After drying, the sensitized support was exposed to actinic radiations through a master and then heated at 160 C. for a few seconds. A red-violet image corresponding to the master image was produced on a yellow background.

Example 2 Hexamethylenetetramine was used in the following formula to make a precoat solution:

Water ml 150 Hexamethylenetetramine g .Trichloroacetic acid g 5 Water ml 150 1,3,6-naphthalene trisulfonic acid, sodium salt g 3 Tartaric acid g /z p-Dimethylarnino benzene diazonium chloride, zinc I chloride salt a g 4 .2,3 dihydroxynaphthalene dsulfonic acid, sodium salt g 5 Thiourea g r 6 Zinc chloride -Q. g 1

After removal of This was coated on a support and dried. The precoated After drying, the sensitized precoated support'was exposedand developed as "in Example 1 to produce a dye' image corres onding to the master image.

Example 3 Hexamethylenetetramine was used in the following solution to prepare a developing sheet:

Water m1 150 Hexaznethylenetetramine g 1 This solution was used to impregnate an absorbent support. After drying, the impregnated developing sheet was used redevelop an exposed diazotype material by placing the developing sheet in uniform contact with the exposed sensitized surface of the diazotype material, and heating for 4 seconds at C. 'An; image corresponding to the master image was produced on the diazotype material. Greater amounts of hexamethylenetetramine in the impregnating solution improved the Example 4 Asensitizing solution was prepared according to the following formula: V

Water v Hexamethylenetetramine gu V l Trichloroacetic acid Q; g 5 1,3;6-napl1thalene trisulfonic acid, sodium salt g 6- Semicarbazide hydrochloride g 4 p-ethyl-hydroxyethyl-amino benzene diazonium chloride, zinc chloride salt g 4 2,3-dihydroxynaphthalene G-sulfonic acid, sodium salt L; g 5 Thiourea g 7 Zinc chloride g 4 This solution was coated onto a support and dried. It was then exposed under a master to actinic radiations, and developed by heating at C. for 6 seconds. A violet image with a white background was produced.

Example 5 V A 'precoat solution was prepared according to the following formula:

Water ml 150 Hexamethylenetetramine g 1 Semicarbazide hydrochloride g 4 This was used to precoat a support. After drying, the precoated support was then sensitized with a solution pre pared according to the following formula:

salt

Thiourea g 7 Zinc chloride 5 4 Thiosemicarbazide e 10 This solution was coated onto a support and dried. It

A stock solution was prepared according to the following formula:

Water ml 1,050 Hexamethylenetetramine g 7 Trichloroacetic acid g 1,3,6-naphthalene tn'sulfonic acid, sodium salt g 21 p-Dimethylamino benzene diazonium chloride, zinc chloride salt g 28 2,3-dihydroxynaphthalene-6-sulfonic acid, sodium salt g 3 Thiourea g 49 Zinc chloride g 28 To separate 165 ml. aliquots of the above stock solution were added: 7.5 grams of (carboxymethyl) trimethyl ammonium chloride hydrazide, 6.0 grams of succinhydrazide, 4.0 grams of carbohydrazide, and 5.0 grams of acetone semicarbazone. The remainder was used as a control solution. After the separate solutions had been coated, dried, exposed, and developed as in Example 5, the following color images were obtained on relatively white backgrounds (Carboxymethyl) trimethyl ammonium chloride hydrazide-purple Succinhydrazide-red violet Carbohydrazide-violet Acetone semicarbazone-violet t is apparent that the described examples are capable of many variations and modifications Within the scope the present invention. All such variations and modifications are to be included within the scope of the resent in vention.

What is claimed is:

1. A sheet for the thermal development of a photosensitive diazo layer comprising a photosensitive diazonium compound and a coupler therefor, which comprises:

a support resistant to the scorching effects of heat at the conditions of thermal development, said support having said diazo layer coated thereon; and

a thermosensitive base-releasing agent selected from the group consisting of: hexamethylene tetramine, thiosemicarbazide, and mixtures of hexamethylene tetramine with one of the following: semicarbazide hydrochloride, carboxymethyl trimethyl ammonium chloride hydrazide, carbohydrazide, succinhydrazide, and acetone semicarbazone coated on said support,

whereby heating said coated support to release base in the presence of said layer causes said layer to form a dye.

2. A sheet in accordance with claim 1 in which said agent is intimately admixed with said layer on said support.

3. A sheet in accordance with claim 1 in which said agent is between said support and said layer.

4. A sheet for the thermal development of a photosensitive diazo layer comprising a photosensitive diazonium compound and a coupler therefor, which comprises:

thermosensitive base-releasing hexamethylene tetramine coated on said support in intimate admixture with the diazo layer on said support,

5. A sheet for the thermal development of a photosensitive diazo layer comprising a photosensitive diazonium compound and a coupler therefor, which comprises:

thermosensitive base-releasing hexamethylene tetramine coated on said support between said support and said diazo layer.

6. A method for thermally developing a photosensitive diazo layer comprising a photosensitive diazonium compound and a coupler therefor, which comprises the steps of:

exposing said layer to image wise actinic radiation; and

heatingsaid layer in intimate contact with a support at C. to C. for a few seconds to form a dye image in said layer, said support being resistant to the scorching effects of heat at the conditions of thermal development and coated with a thermosensitive base-releasing agent and said agent being a member selected from the group consisting of: hexamethylene tetramine, thiosemicarbazide, and mixtures of hexamethylene tetramine with one of the following: sernicarbazide hydrochloride, carboxymethyl trimethyl ammonium chloride hydrazine, carbohydrazide, succinhyclrazide, and acetone semicarbazone.

7. A method in accordance with claim 6 in which said agent and the layer are intimately admixed and are coated on the same support.

8. A method in accordance with claim 6 in which said agent is coated on said support between said support and said layer.

9. A method in accordance with claim 6 in which said agent and said layer are coated on separate supports resistant to the scorching effects of heat at the conditions of thermal development.

References Cited in the file of this patent UNITED STATES PATENTS 2,653,091 Greig Sept. 22, 1953 2,732,299 Morrison Ian. 24, 1956 2,774,669 Marron et al. Dec. 18, 1956 2,982,675 Kapral May 2, 1961 FOREIGN PATENTS 816,601 Great Britain July 15, 1961 215,526 Australia Feb. 9, 1961 1,249,913 France Nov. 28, 1960 OTHER REFERENCES Kosar: Photographic Science and Engineering, vol. 5, No.4, July-August 1961, pages 239243.

Claims

6. A METHOD FOR THERMALLY DEVELOPING A PHOTOSENSITIVE DIAZO LAYER COMPRISING A PHOTOSENSITIVE DIAZONIUM COMPOUND AND A COUPLER THEREFOR, WHICH COMPRISES THE STEPS OF: EXPOSING SAID LAYER TO IMAGE WISE ACTNIC RADIATION; AND HEATING SAID LAYER IN INTIMATE CONTACT WITH A SUPPORT AT 140*C. TO 160*C. FOR A FEW SECONDS TO FORM A DYE IMAGE IN SAID LAYER, SAID SUPPORT BEING RESISTANT TO SCORCHING EFFECTS OF HEAT AT THE CONDITIONS OF THERMAL DEVELOPMENT AND COATED WITH A THERMOSENSITIVE BASE-RELEASING AGENT AND SAID AGENT BEING A MEMBER SELECTED FROM THE GROUP CONSITING OF: HEXAMETHYLENE TETRAMINE, THIOSEMICARBAZIDE, AND MIXTURES OF HEXAMETHYLENE TETRAMINE WITH ONE OF THE FOLLOWING: SEMICARBAZIDE HYDROCHLORIDE, CARBOXYMETHLY TRIMETHOL AMMONIUM CHLORIDE HYDRAZINE, CARBOHYDROAZIDE, SUCCINHYDRAZIDE, AND ACETONE SEMICARBAZONE.