US3157499A

US3157499A - Scribe coat on silver halide polyester film

Info

Publication number: US3157499A
Application number: US862340A
Authority: US
Inventors: Frank M Trusheim
Original assignee: Keuffel and Esser Co
Current assignee: Keuffel and Esser Co
Priority date: 1959-12-28
Filing date: 1959-12-28
Publication date: 1964-11-17
Anticipated expiration: 1981-11-17

Description

Nov. 17, 1964 F. M. TRUSHEIM 3,

SCRIBE COAT UN SILVER HALIDE POLYESTER FILM Filed Dec. 28, 1959 TRANS PARE NT 22 POLYE THYLENE IO TERREPHTHALLATE SUBBING 11 MULTI COLOR DIAZO PRINT FIG. 2 V INVENTOR.

FRANK TRUSHEIM Y AT; gRIVEY-I-AGEIVT United States Patent 3,157,499 SCREE CGAT 0N ILVER HALIDE P-SLYESTER FEM Frank M. Trnshehn, Gakhurst, N .11., assignor to Keufiel & Esser Co., Hoboken, Ni, a corporation of New Jersey Filed Dec. 28, 1959, Ser. No. 862,349 11 (Ilaims. (Qi. 96-27) The present invention relates to drafting and more particularly to drafting on a scribe coat or peel coat on a base to obtain accurate lines and more particularly relates to a scribe coat over a developable layer of photographic material adapted to receive selective colorings of selected lines forming a master, for making photographic prints.

Heretofore, maps and the like have been made on a transparent base material coated with a scribable coat or peelable coat in which lines are formed by removing the scribe coat by a stylus, or cutting outlines in a peel coat and removing the peel coat between the cut lines, thereby providing lines for reproduction by photographic processes. The scribing has been found advantageous because of the rapidity with which the drafin can be done and because an operator can become sufiiciently skilled after a short period of training to do satisfactory work. Although the previous processes have been satisfactory for Single color, it has not been practical to obtain multicolored lines or multi-colored areas in a single master or stencil with the previously known methods, and therefore a separate scribed master or stencil was required for each color to be reproduced on a finished map or the like.

There has always been a problem of obtaining correct registration of the masters or stencils when masters or stencils were used in providing the superimposed images in the final product such as a map of several difierent colors and consequently the prior methods of making maps or other graphic colored work have not been entirely satisfactory.

An object of the present invention is to provide a scribable coating on material, a method of using the material, and a process of transferring the information from the material to a final print in color by a direct contact process without requiring accurate registration of separate stencils.

A further object is to provide a scribable or peelable material on a photographic base.

Another object is to provide a stencil material which is useful in making either a positive or negative from the same stock material, and is also useful in providing some portions positive and other portions negative on the same sheet.

A further object is to provide a method of producing selective colored outlines on a single sheet stencil or master.

Another object is to provide a master with selective portions thereof providing filters for controlling the rays of light passing through the selected portions of the master.

Other and further objects will be apparent as the description proceeds and upon reference to the composition described and the drawing, wherein:

FIG. 1 is an isometric view showing the sequence of scribing a line to the colored development of the selected lines and Q50 showing how large transparent or opaque areas are produced in the master.

FIG. 2 is a developed diazo print made from the devel oped portion of the master shown in PEG. 1 showing how two colors the red and green areas of the master print red and the black areas of the master print black while the transparent portions of the stencil print white.

Briefly, the present invention includes a master sheet material having a transparent polyester base with progressively superposed layers of photosubbing, a silver halide emulsion and a pigmented organic scribe coating or a peelable coating in lieu of the scribe coating. With a stylus an operator scribes a line through the scribe coating thereby uncovering the silver halide emulsion and said uncovered halide emulsion is developed with color formers or without color formers to obtain selected colored lines or black lines respectively. After one group of lines has been scribed such one group of lines is developed to produce the selected color, thereafter the same sheet of master material is scribed again for a second group of lines and such second group of lines is developed a different color and still other groups of lines are scribed and developed for as many different colors of lines as desired. If desired, the scribed line may be treated to provide a transparent line such as immersing the scribed line area in a bath of hypo fixing solution to remove the silver halide. After the desired scribed lines have been scribed and developed the pigmented organic scribe coat may be removed from the background area with an organic solvent such as methyl ethyl ketone uncovering the photographic emulsion in the background area. If it is desired to have the background area of the stencil a particular color the stencil is then developed the desired color. If the background is to be transparent the stencil is treated by fixing without developing. If the background is to be black the background area is developed and fixed in the conventional manner. The resulting master or stencil can then be placed in contact with a photosensitive sheet material such as multi-color diazo paper and the diazo paper exposed, the various colored lines will filter out selected Wave lengths of light thereby producing a multi-color diazo print.

Referring more particularly to FIG. 1 of the drawing, a transparent base 16 of orientated polyethylene terephthalate is provided with a photosubbing layer 11 on which a photosensitive layer of silver halide emulsion 12 is formed, and said silver halide emulsion is covered with a pigmented organic scribe coating 13 of suitable materials such as those disclosed in application Serial No. 496,602, filed March 24, 1955, now Patent 2,999,016.

A suitable scribe coating is described in Example IV in the aforementioned application as follows:

2 lbs. of alkyd resin 9 lbs. of titanium dioxide oz. cobalt naphthenate drier 9 lbs. solvent (xylol, toluol and or ethyl acetate) if a colored opaque scribe coating is desired, colored pigments such as chrome yellow, molybdate orange and carbon black may be added or suitable colored dyes may be added.

A transparent coating would be obtained by leaving out all of the pigments and using only a dye opaque to actinic light. However, in this case the cutting properties would not be as good but could be improved by additives without sacrificing much transparency.

Other resins may be added to these coatings. For example, urea and melamine formaldehyde may be added up to about 10% of the resin content. Nitro cellulose may be added up to of the resin content if suitable plasticizers are also added.

Photosensitive coatings may be applied over these scribe coatings. These are useful so that an image can be reproduced on top of the scribing coating and all or part of it cut into the scribing layer with a suitable tool.

The silver halide emulsion is sufficiently hard so that in scribing through the scribe coating 13 with a stylus 15 to uncover the emulsion 12 therebelow as shown at scribe line 14 and the silver halide emulsion will not be removed.

After scribing one group of lines to be made one color thereby uncovering the silver halide emulsion below the said one group of lines the stencil sheet is treated a to produce the desired color of lines in the uncovered silver halide emulsion in said one group by a known developing and fixing procedure. If it is desired to have a line or area be transparent, the silver halide emulsion immediately beneath the scribed line areas to be transparent is treated to produce transparency as by immersion of the scribed master sheet in a photographic hypo fixing bath thereby removing the silver halide from the emulsion.

it is also possible to obtain selective coloring of the silver halide emulsion under any selected uncovered areas of such silver halide emulsion and this is accomplished by development of the uncovered portion of the silver halide emulsion with photographic dye coupling developers and color formers as hereinafter described.

Where a negative master is required, the scribe coating is scribed where the open window areas are required and treated with a hypo fixing bath thereby removing the silver. Thereafter the pigmented organic scribe coating is removed by the organic solvent .by immersion in a bath of the organic solvent and/or by wiping with a cloth soaked in the organic solvent and uncovering the remainder of the silver halide, The emulsion is developed in the usual manner to obtain the desired color thereby making an image in the selected color in the areas in which the scribe coating has just been removed while leaving the open window areas for the transmission of light through the uncolored transparent areas where the silver halide has been removed.

It will be apparent that the method can be used in master material having a peelable coat by removing selected areas of the peelable coat to be colored'a particular color.

Upon reference to FIG. 1, a scribe line 14 is made by means of a scribing tool 15 which removes the scribe coating 13 in the area of the line thereby uncovering the photographic emulsion 12 therebeneath. A scribed line it? may be drawn to outline a closed area 17 and the scribe coating within the area may be removed by further. scribing or other means uncovering "the entire area 17 within the scribe line. The scribe/coating within the line 16 may be removed by wiping with a cloth soakedin methyl ethyl ketone which will soften or dissolve the scribe coat to permit removal. The line 14 and the uncovered area 17 can be developed by photographic processcs to obtain a colored line, a black line, or an open window area. To demonstrate that all of such colored lines, colored areas, transparent lines or open windows or transparent areas may be made in a single master or stencil, FIG. 1 has been drawn to illustrate the various areas and lines on a single master.

Where an area 1% is to be made green for example, the scribe or peel coat is removed inthe desired area and the developing'is accomplished by developing with a dye coupling developer in accordance with pages 16-150 and 151 of Morgan and Lester, Photo Lab Index Quarterly Supplement, replacement pages 70 and 72, respectively, 4th quarter, 1956, and 2nd quarter, 1957, respectively; copyright, 1956, Morgan and Lester, 101 Park Avenue, New York 17, New York. However applicant omits the initial development described in the Photo Lab index.

To illustrate the development of the area 19 to be made green, a stock solution A of dye coupling'developer is made up according to the followingformula:

Water to make one liter.

This is the developing agent. It may be used *with all color formers below, but in the case of phitrophenylacetm nitrile'the magenta tone produced tends toward the red. If a bluer magenta is desired, substitute for the p-aminodietliylaniline hydrochloride an equal amount of 2-amino-5-diethylaminotoluene hydrochloride.

The keeping qualities of this stock solution are poor. If it is to be kept for some time, the developing agent should be omitted, and added just before use.

For use: Add to each cc. of the above developer 10 cc. of one or a mixture of the following color former solutions B. Mix together just before use and discard after the one use. The solution oxidizes rapidly and must be used as soon as mixed. Exposure should be adjusted for at least 3 minutes development at 68 F. (20 C.).

The following stock solutions B of color formers are provided:

Acetone to make 1 liter.

Green To obtain the green developed

area

19, 19A after such area has been uncovered by removal of the scribe coat 13 or peelable coat, the master is developed in the mixture of solution A and solution Bz' 100 cc. of solution Adye coupling developer 10 cc. of solution B (green) consisting of:

6 cc. of yellow color former of o-chloroacetoacetanilide in acetone 4 cc. of cyan color former of 2,4-dichloro-1-naphthol in acetone (1) The uncovered portion of'tne master was developed for 3 minutes in the mixture of solution A (developer) and solution B (green color former) producing the green areas .19, 19A.

(1a) The master was washed to remove surplus developer.

(2) The uncovered portion of the master was bleached in a bleach bath made up of the following:

Grams Potassium ferricyanide 30 Potassium bromide 15 Water to make 1 liter.

The master was kept in the bleach for approximately 2 minutes.

(2a) The master was washed to remove the bleach.

(3) The uncovered portion of the master was fixed in an alkaline fixing bath or the following composition:

Sodium sulfite 40 grams. Hypo (sodium thiosulfate) 240 grams. Water to'make 1 liter. Formaldehyde 100 cc. added to the'l liter 2 mixture.

(3a) The master was washed and dried.

Red

100 cc. of solution A (dye coupling developer) 7 10 cc. of solution B (red) consisting of:

8 cc. of yellow color former 2 cc. of magenta color former (1) The stencil was developed for a period of 3 minutes in the mixture of solution A and solution 3 (red) producing a red image. I V

(1a) The master was washed to remove surplus devel-- oper.

ALL

ais'zaso (2) The uncovered portion of the master was then bleached in a bath described above.

(2a) The master was washed to remove the bleach. (3) The uncovered portion of the master was fixed in an alkaline fixing bath of the composition given above.

(30) The master was washed and dried.

Black A third area to be made black was then scribed in the areas 21, 21A uncovering the silver halide emulsion and the master was developed in a conventional developer used for making a black image in a silver halide emulsion and for this purpose any of the well known developers may be used. The master was fixed in a fixing bath to fix the black image in the usual manner. Thereafter the master was washed and dried leaving the multi-color image areas in green, red and black.

Assuming that the background is to be transparent the remaining area of the scribe coating is then removed by any suitable means such as with a cloth saturated with methylethyl-lietone or other suitable solvent. If a peelable coating is provided the remainder of the peelable coating is removed by peeling. The remaining uncovered area is treated to provide a transparent background and for this purpose the master is immersed in an alkaline fixing bath of the following composition:

Sodium sulfite 40 grams.

Hypo (sodium thiosulfate) 248 grams.

Water to make 1 liter.

Formaldehyde 100 cc. added to the 1 liter mixture.

The resulting stencil includes a green image, a rod image, and a black image with the background made transparent. It will be evident that yellow, magenta or cyan areas may be obtained from the color formers shown, and many other colors may be provided.

It will thus be seen that a master can be made as a negative, a positive, a transparent positive or any combination thereof whereby a single base sheet material may be used for many difierent purposes. It will also be evident that many different colors can be made in the stencil in accordance with the teachings in the Photo Lab Index. The different color areas may abut one another as shown in the red, green and black areas 26A, 19A and 21A.

Where it is desired to have transparent lines in a black background, after the colored lines have been made, the transparent lines are scribed and the stencil immersed in the fixing bath thereby removing the silver halide from the emulsion in the area of the transparent lines. After washing and drying the remaining scribe coat is removed and the stencil developed in conventional developer forming the black background and is then fixed in a fixing bath.

The stencil made according to the above description may be used as a master on a conventional diazo printer using a diazo material which will produce multi-colors such as the diazo material of Leuch US. Patent 2,659,672. Applicant has made a diazo print in which the black lines reproduce substantially black while the red and green lines reproduce substantially red.

In the above process it will be evident that where two scribed lines intersect, the first development of the scribed lines is the color which the intersection takes and subsequent development does not affect the color of the intersection.

It will also be noted that the development for the conventional black image was scribed and developed subsequent to the various color dye forming developments thereby avoiding any deleterious effects from the bleach used in the color forming development.

A suitable developer for the black image is hydroquinone which produces a high density image slowly and monomethyl-p-aminophenol sulfate which produces a lower density image fast and by suitable combinations 6 thereof it is possible to get the desired rate of development and the desired density.

The stencil made according to the present invention provides the equivalent of light filters in the colored areas thereby controlling the wave lengths of light which pass through the colored lines in the stencil thereby controlling the efiect of the light on the diazo material or other material with which the master is used in making prints therefrom.

It will also be evident that the master may be used in a projector for viewing or for making photo copies by any suitable means.

The scribe coat may be marked in pencil or in any suitable way to indicate where the scribing is to be performed and for this purpose a photosensitive material may be applied over the scribe coat as described in the aforementioned application thereby making it possible for an operator to accurately follow the outlines. It will also be apparent that the outlines to be followed can be projected from a conventional projector such as is used in map making or the like.

It will be apparent that various changes may be made within the spirit of the invention as defined by the valid interpretation of the following claims.

What is claimed is:

l. The method of making a light transmitting master from a dimensionally stable light transmitting sheet material having a silver halide emulsion photographic layer thereon and a selectively removable coat superimposed on the photographic layer, comprising removing said coat from a first area of appreciably less than the area of the sheet material uncovering a first area of the photographic layer to permit developing fluids to contact the first area of the photographic layer where the selectively removable coat has been removed, and performing a developing operation on said first area of said photographic layer by a dye coupling developer of sodium sulfate, sodium carbonate, potassium bromide, and a compound selected from the group consisting of p-aminodiethylaniline hydrochloride and 2-amino-5-diethylaminotoluene hydrochloride with at least one color former from the group consisting of l-naphthol, 2,4-dichloro-l-naphthol, o-phenyl phenol, 4-chloro-o-phenyl phenol, 4,6-dibromo-o-cresol, 2,S-dichloroacetoacetanilide, acetoacetanilide, 1-phenyl-3- methyl-S-pyrazolone, p-nitrophenylacetonitrile, o-chloroacetoacetanilide, and ethyl acetoacetate, t ereai'ter bleaching in a solution of potassium ferricyanide and potassium bromide, filing the color in said first area, removing said coat from a second area uncovering a second area of said photographic layer and developing with a dye coupling developer and color former producing a difierent color in the second area from the color in the first area, bleaching the second area, fixing the color image in said second area and repeating the sequence of operations for other areas to obtain a multi-colored master of any desired number of areas.

2. The invention according to claim 1 in which one area is treated only with an alkaline fixing bath of sodium sulfite, hypo and formaldehyde.

3. The method of making a light transmitting master from a dimensionally stable light transmitting sheet material having a silver halide emulsion photographic layer thereon and a selectively removable coat superimposed on the photographic layer, comprising removing said superimposed coat from a first area uncovering a first area of the photographic layer to permit developing fluids to contact the first area of the photographic layer where the coat has been removed, and performing a developing operation on said first area of said photographic layer by a dye coupling developer of sodium sulfite, sodium carbonate, potassium bromide, Z-amino-S-diethyl-aminotoluene, with o-chloroacetanilide 2,4-dichloro-l-naphthol in acetone for 3 minutes then bleaching with potassium ferricyanide and potassium bromide for 2 minutes, fixing the color in said first area with an alkaline fixing bath,

removing said coat from a second area uncovering a second area or" said photographic layer and fixing the second area of said photographic layer to obtain a transparent second area.

4. A method of producing colored lines in sheet material having a silver halide emulsion layer thereon and a selectively removable scribe coat superimposed on the silver halide emulsion layer comprising scribing lines in a first area on the scribe coat to uncover a first area of the silver halide emulsion layer therebeneath,

developing the first area of the silver halide emulison areas of the sheet in additional steps and developing such additional areas in additional colors in respective additional steps thereby providing a stencil having a plurality of difierently colored areas. 1

5. The invention according to claim 4 in which one area oi the silver halide emulsion is made transparent by treating with a fixing bath. 6. A. method of producing distinctly different image reas in a sheet material having a transparent base, a silver halide emulsion on the base and a scribe coat on said silver halide emulsion and which scribe coat is removable by an organic solvent but which scribe coat is impervious to materials used for developing silver halide on said silver halide emulsion comprising scribing the scribe coat with a closed line defining a first image area of the silver halide layer therebeneath, removing the scribe coat in said first image area within the closed line with an organic solvent thereby uncovering the silver halide emulsion in said first area, color developing the first image area to produce a first color image in said first area of the photosensitive layer, fixing said first image thereon, thereafter scribing a second area defining Y a second image area and developing said second image area in a different'manner defining a second image distinctively difierent from said first image, fixing said second image thereby making twodistinctive images in different areas.

7. The method of making a master comprising providing atransparent base, a silver halide emulsion layer on said base, a removable coat on said silver halide emulsion layer, said removable coat preventing materials used for developing and fixing an image from contacting said silver halide emulsion layer, and being accurately removable to accurately outline image areas whereby the removable coat can be precisely removed uncovering the silver halide emulsion layer below said removed portions of the coat, removing the coat in a first image area, developing the first image area in a first definite color and fixing the first definite color in said first image area with first materials to develop and .fix a first image, removing the coat in a second image area, developing said second image area in a second color difierent from the first color of the first image area and fixing the second color in said second image area removable some with second materials to develop and fix a second image thereby providing a master with two distinct difierently colored image areas.

8. The method of making a master comprising providing a transparent-base, a silver halide emulsion on said base, a scribe coat on said silver halide emulsion, said scribe coat being impervious to materials used for developing and fixing an image from contacting said silver halide emulsion, saidscribe coat being accurately removable by a scribing action to accurately outline an image whereby the scribe coat can be removed by a scribing action uncovering the silver halide emulsion which was beneath said removed portions of the scribe coat, accurately removing the scribe coat in a first image area uncovering the silver halide emulsion in a first image area, developing the silver halide emulsion in the first image area in a first definite color, fixing the first definite color in said first image area, thereafter accurately re-' moving the scribe coat in a second image area uncovering the silver halide emulsion in the second image area, developing said silver halide emulsion in said second image area in a second color different from the first color of said first image area, fixing the color in said second image area thereby providing a master with two distinct differently colored image areas.

9. A master material comprising a transparent base, a silver halide emulsion layer on said base, a selectively removable coat superimposed on said silver halide emulsion layer, said removable coat preventing developing.

materials used in developing and fixing an image-from contacting said silver halide emulsion layer, a photographic emulsion layer on said removable coat whereby a photographic image may be formed and developed on said photographic emulsion layer to serve as a guide for removing a first selected area portion of said removable coat to uncover said silver halide emulsion layer in a desired first image area to be developed into a predetermined color and thereafter may serve as a guide vfor removing a second selected area portion of said removable coat to uncover a second image area of said silver halide emulsion layer and such second image area may be developed a second color different from said first color.

10. The invention according to claim 9 in which the coat is distinctively colored from the base and layers.

11. The invention according to claim 10 in which the removable coat is a scribe coat and is essentially an alkyd resin, and titanium dioxide.

References tilted by the Examiner UNITED STATES PATENTS 2,651,603 8/36 Hruska 96-43 2,491,386 12/ 49 Miller et al 96-27 2,537,329 1/51 Campbell 96-27 2,627,088 2/53 Alles et al. 96-87 2,718,476 9/55 Eichorn 96-27 XR 2,810,661 10/57 Newman et al. 1l7138.8 XR 2,943,936 7/ Spechler 96-75 2,999,016 9/61 eeber et al 96-87 XR 3,023,099 2/62 Yaeger et al 96-91 NORMAN G. TORCHIN, Primary Examiner.

HARGLD N. BURSTEIN, Examiner.

Claims

1. THE METHOD OF MAKING A LIGHT TRANSMITTING MASTER FROM A DIMENSIONALLY STABLE LIGHT TRANSMITTING SHEET MATERIAL HAVING A SILVER HALIDE EMULSION PHOTOGRAPHIC LAYER THEREON AND A SELECTIVELY REMOVABLE COAT SUPERIMPOSED ON THE PHOTOGRAPHIC LAYER, COMPRISING REMOVING SAID COAT FROM A FIRST AREA OF APPRECIABLY LESS THAN THE AREA OF THE SHEET MATERIAL UNCOVERING A FIRST AREA OF THE PHOTOGRAPHIC LAYER TO PERMIT DVELOPING FLUIDS TO CONTACT THE FIRST AREA OF THE PHOTGRAPHIC LAYER WHERE THE SELECTIVELY REMOVABLE COAT HAS BEEN REMOVED, AND PERFORMING A DEVELOPING OPERATION ON SAID FIRST AREA OF SAID PHOTOGRAPHIC-LAYER BY A DYE COUPLING DEVELOPER OF SODIUM SULFATE, SODIUM CARBONATE, POTASSIUM BROMIDE, AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF P-AMINODIETHYLANILINE HYDROCHORIDE AND 2-AMINO-5-DIETHYLAMINOTOLUENE HYDROCHLORIDE WITH AT LEAST ONE COLOR FORMER FROM THE GROUP CONSISTING OF 1-NAPHTHOL, 2,4-DICHLORO-1-NAPHTHOL, O-PHENYL PHENOL, 4-CHLORO-O-PHENYL PHENOL, 4,6-DIBROMO-O-CRESOL, 2,5-DICHLOROACETOACETANILIDE,ACETOACETANILIDE, 1-PHENYL-3METHYL-5-PYRAZOLONE, P-NITROPHENYLACETONITRILE, O-CHLOROACETOACETANILIDE,AND ETHYL ACETOACETATE, THEREAFTER BLEACHING IN A SOLUTION OF POTASSIUMFERRICYANIDE AND POTASSIUM BROMIDE, FIXING THE COLOR IN SAID FIRST AREA, REMOVING SAID COAT FROM A SECOND AREA UNCOVERING A SECOND AREA OF SAID PHOTOGRAPHIC LAYER AND DEVELOPING WITH A DYE COUPLING DEVELOPER AND COLOR FORMER PRODUCING A DIFFERENT COLOR IN THE SECOND AREA FROM THE COLOR IN THE FIRST AREA, BLEACHING THE SECOND AREA, FIXING THE COLOR IMAGE IN SAID SECOND AREA AND REPEATING THE SEQUENCE OF OPERATIONS FOR OTHER AREAS TO OBTAIN A MULTI-COLORED MASTER OF ANY DESIRED NUMBER OF AREAS.