GB2035591A - Process for preparing multicolor toned images on a single photosensitive layer - Google Patents
Process for preparing multicolor toned images on a single photosensitive layer Download PDFInfo
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- GB2035591A GB2035591A GB7939134A GB7939134A GB2035591A GB 2035591 A GB2035591 A GB 2035591A GB 7939134 A GB7939134 A GB 7939134A GB 7939134 A GB7939134 A GB 7939134A GB 2035591 A GB2035591 A GB 2035591A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/28—Processing photosensitive materials; Apparatus therefor for obtaining powder images
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- Photosensitive Polymer And Photoresist Processing (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
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Abstract
Process for preparation of multicolor images on a single negative-working photosensitive layer which comprises image-wise exposing the layer through a transparency to form tacky image areas; toning the tacky image areas with a toner which becomes swollen or solubilized upon contact with the tacky areas; buffing or rubbing the toned image areas until glossy; and repeating the exposing, toning and buffing or rubbing using a different image-bearing transparency and appropriate toner. The resulting toned multicolor image can be transferred to a receptor material at elevated temperatures. The process is useful in preparing multicolor proofs, e.g. maps, textile and wall covering design proofs and samples.
Description
SPECIFICATION
Process for preparing multicolor toned images on a single photosensitive layer
This invention relates to a process for preparing
multicolor toned images on a single layer and more
particularly to a process wherein the layer is a
negative-working tonable photosensitive layer.
Image reproduction processes are known wherein photosensitive elements, such as photopolymerizable elements comprising a base support bearing a photopolymerizable layer comprising at least one addition polymerizable monomeric compound and a photopolymerization initiator, are exposed imagewise through an original transparency forming nontacky image areas in the exposed image areas. The image is made visible by dusting with a suitable toner which adheres only to the unexposed tacky areas and excess toner is removed from the exposed, nontacky image areas.
By the aforementioned process, positive colored images of the original are obtained which are equivalent of press proofs. It is also desirable, however, to form negative images with respect to the original.
One system for preparing such negative images is described in German Application P 27 58 209.8 filed
December27, 1977. While the latter system is useful in forming good negative images, it heretofore has been useful only for forming single color toned images in a layer. Multicolor images can be obtained, but this requires the use of two or more layers applied consecutively by coating or laminating, each layer containing a single-colortoned image. No process is presently known whereby good quality multicolor toned negative images can be achieved on a single photosensitive layer.
In accordance with this invention, there is provided a process for the preparation of a multicolor image using a negative-working tonable photosensitive layer which comprises:
(a) exposing said layer image-wise to actinic radiation through an image-bearing transparency, the exposed image areas of the layer becoming tacky;
(b) toning the tacky image areas by applying and adhering thereto a toner material which is swollen or solubilized when in contact with the tacky image areas; characterized by
(c) buffing or rubbing the toned image areas whereby the areas become glossy; and
(d) repeating steps (a), (b) and (c) at least once using a different image-bearing transparency for each exposure (a) and toning with a toner of appropriate color different from the color of the toner of step (b).
The process of the invention is useful with negative-working tonable photosensitive layers. The negative-working layers must be capable of retaining toner in the exposed image areas, generally at normal room temperature conditions. Preferred negative-working tonable photosensitive compositions are compositions which comprise at least one thermoplastic binder and a photosensitive system of at least one dihydropyridine compound of the formula
wherein
R is alkyl, alkylene, aryl and heteroaryl, Rt and R2, which can be the same or different, are
alkyl, and
R3 and R4, which can be the same or different, are
COOR', COR', ON, R' is alkyl, and at least one hexaarvlbiimidazole compound.These compositions are disclosed in Abele and Grossa German
Application P 27 58209.8 filed December 1977.
Suitable dihydropyridine compounds, one component of the photosensitive system, are described in Table 1 of the German Application P 27 58 209.8, including the following compounds: 2,4,6-trimethyl -3,5- bis(carbethoxy) - 1,4- dihydropropyridine; 2,6 - dimethyl - 4 - ethyl - 3,5 - bis(carbethoxy) - 1,4 - dihydropyridine; 2,6 - dimethyl - 4 n - propyl - 3,5 - bis(carbethoxy) - 1,4 - dihydropyridine; 2,6 - dimethyl - 4 - benzyl - 3,5 - bis(car bethoxy) - 1,4 - dihydropyridine; etc.
Suitable hexaarylbiimidazole compounds, the second component of the photosensitive system are described in U.S. Patent 3,630,736, column 7, line 62 to column 10, line 64, including the following compounds: 2,2',4,4',5,5' - hexaphenyibiimidazole; 2,2' - bis(2 chlorophenyl) - 4,4',5,5' - tetraphenylbiimidazole; 2,2' - bis(2 - chlorophenyl) - 4,4',5,5' - tetrakis(3 methoxyphenyl)biimidazole; 2,2' - bis(2 - methox- yphenyl) - 4,4',5,5' - tetraphenylbiimidazole; etc.
Useful compatible thermoplastic binders in the negative-working compositions include: Acrylic acid and/or methacrylic acid ester polymers and/or their copolymers with other suitable monomers, e.g., acrylic or methacrylic acid or other acrylic or vinyl monomeric compounds; copolymers of maleic acid anhydride, or its di or half esters with styrene or other vinyl monomers; chlorine-containing vinyl polymers or copolymers, e.g., polyvinyl chloride including post chlorination products, polyvinylidene chloride, chlorinated polyethylene, etc.; polystyrene and polystyrene copolymers; ethylene and ethylene copolymers, e.g., with maleic acid, etc.; synthetic types of rubber, e.g., butadiene, chloroprene and their copolymers, e.g., with styrene, acrylonitrile, etc.; polyethers, e.g., high molecular weight polyethylene oxide, polyepichlorohydrin, etc.
In addition to the preferred negative-working tonable photosensitive compositions containing at last one dihydropyridine compound described above, other useful negative-working tonable photosensitive compositions include: (1) a composition described in U.S. Patent 3,915,704 comprising
i. at least one acid degradable polymer of the formula
wherein
R is an aliphatic hydrocarbon radical of 1-6 carbon
atoms, a chlorinated aliphatic hydrocarbon rad
ical of 1-6 carbon atoms, or a nitrile substituted
aliphatic hydrocarbon radical of 1-5 carbon
atoms; and
n n is at least 50
ii. at least one acid generating polymer of the formula
wherein
X is selected from among chlorine, bromine or
iodine
Y y and Y' are independently selected from X or
hydrogen; and
Z is selected from among Y, alkyl of about 1 to 8
carbon atoms, phenyl or alkyl substituted
phenyl, said alkyl substituent having from about
1 1 to 8 carbon atoms a and b represent the mole
percent of each of the components within the
acid generating polymer and have an aggregate
value equal to 100% and
iii. an organic electron acceptor; the weight ratio of acid degradable polymer to acid generating polymer ranging from about 99:1 to about 1:99 and the concentration of electronic acceptor ranging from about 0.1 to about 5 weight percent based upon the concentration of acid generating polymer, the acid degradable polymer is present in an amount of about 25 to about 40% by weight based on the weight of composition; and (2) a composition described in U.S. Patent 3,917,483 comprising at least one acid degradable polymer of the formula:
wherein
R is an aliphatic hydrocarbon radical of 1-6 carbon
atoms, a chlorinated aliphatic hydrocarbon rad
ical of 1-6 carbon atoms, or a nitrile substituted
aliphatic hydrocarbon radical of 1-5 carbon
atoms; and n is at least 50; and
a catalytically effective amount of at least one latent
acid, a material generally regarded as nonacidic in
the ground state but, which upon irradiation with
ultraviolet light undergoes an electronic transition
from the ground to the excited state whereupon a pro
tein becomes disassociated from the latent acid and
is released into the presence of the degradable
polymer which is generally present in the composi
tion in an amount of about 25 to about 40 /O by
weight based on the weight of composition.
Representative of acid degradable polymers for
compositions (1) and (2) are poly(acetaldehyde),
poly(propionaldehyde); poly(butaldehyde) and mix
tures or copolymers thereof and other compounds disclosed in U.S. Patent 3,915,704. Acid generating
polymers for composition (1) include: poly(vinylc
hloride), poly(vinylbromide), poly(vinyliodide), po
ly(vinylidene chloride), etc., as disclosed in U.S.
Patent 3,915,704. Also disclosed in this patent are representative organic acceptors present in trace amounts, e.g., tetracyanoethylene, bromanil, chloranil, cyananil, dicyanodichlorobenzoquinone, tetracyanoaquinodimethane and 2,4,7 - trinitio - 9 fluorenone. Latent acids which are present in an amount of 0.1 to about 5.0 parts by weight per 100 parts by weight acid degradable polymer disclosed in U.S. Patent 3,917,483 include: Hydroxylfunctional naphthalene compounds such as beta-naphthol, phenols, and the halogen substituted naphthols and phenols, e.g., p-chlorophenol.
While not desiring to be limited to such an explanation, we believe it is necessary to the functioning of the invention that the toners, when applied to the exposed tacky image areas, become swollen or solubilized. This can be accomplished by having suitable organic plasticizers present in the system, e.g., in the photosensitive composition or formed therein.
It is also possible, in the event that the photosensitive composition does not contain a plasticizer or a sufficient amount of the plasticizer, that the plasti cider can be present with the toner. Plasticizer materials present in the photosensitive composition include a monomeric compound, e.g., a diacrylate ester, or common plasticizer compatible with the binder material, e.g., dialkyl phthalates, polyoxyethylene(4)monolaurylether, polyethylene glycol, triethylene glycol diacetate, alkyl phosphates, etc.
The photosensitive layer can be present on a surface such as a polymer film, plastic, metal or sheet such as paper, wherein it strongly adheres. The photosensitive composition can be either laminated or coated on the surface under conditions known to those skilled in the art. Preferably the layer is laminated on paper such as Kromekotes cast-coated one side cover paper manufactured by Champion Paper and Fiber Company or a baryta-coated phototypesetting paper manufactured by Intermills Company. A known protective film, such as is described in U.S.
Patent 3,060,026, can be present on the photosensitive layer. The protective film, e.g., polyethylene terephthalate, polyethylene, etc., can be present during image-wise exposure but is removed priorto toning.
The photosensitive layers are exposed image-wise through image-bearing transparencies, e.g., line or halftone bearing color separation negative of the image to be reproduced. The image, e.g., block images, may be formed, if desired, by means of a mask of the desirnd shape and size. In order to pre- pare a multicolored toned image, it is necessary that at least one exposure occurforeach color toner used.
Since most of the photosensitive compositions
preferred in this invention generally exhibittheir maximum sensitivity in the ultraviolet range, the
radiation source should furnish an effective amount
of this radiation. Such sources include carbon arcs,
mercury-vapor arcs, fluorescent lamps with special
ultraviolet-emitting phosphors, argon glow lamps, electronicflash units and photographic flood lamps.
Several specific radiation sources are disclosed in
the examples below. The amount of exposure
required for satisfactory reproduction of a given
photosensitive layer is a function of exposure time,
type of radiation source used, and distance between
the radiation source and layer surface. In general,
exposure times range from 1 to 10 minutes or more
using standard commercial radiation sources.
After the image-wise exposure the tacky exposed image areas are toned with an appropriate toner to
reproduce the desired color. Toning is accomplished by dusting, applying toner particles in the form of a mound over the image surface, bringing the image surface in contact with a surface bearing loosely bound colorant, and other means known to those skilled in the art. As indicated above, generallythe toner is applied at normal room temperature conditions. Slight heating of the photosensistive layer, e.g., at a temperature of up to about 70 C is useful when increased toner density is required. The elevated temperature used should not materially affect the photosensitive layer. Suitabletoners include solid organic resin dispersions of pigments as disclosed in U.S. 2,649,382 or of dyes as disclosed in
U.S. Patent 4,124,384.The resultant colorants have particle sizes within the range 0.2 to 30 microns, with less than 50% of the particles having equivalent spherical diameters less than 1 micron. Preferably, more than 50% of the particles will have sizes in the range of 1 micron to 10 microns to limit background staining as disclosed in U.S. Patent 3,620,726. Suitable organic resin matrices for these toners include: polyvinyl chloride; cellulose acetate; cel luiose acetate butyrate; poystyrene; polymethylmethacrylate; etc. A particularly preferred resin is cellulose acetate, about 160 poises viscosity and about 39% by weight acetyl content.Suitable pigments include: Pigment Red 122 (C.l. not assigned),
Pigment Red 123 (0.1.71145), Black No.88 (copper chromite), Dalamars Yellow (Pigment Yellow 74, C.l.
11741), Pigment Blue 15(0.1.74160), Pigment Green 7 (0.1.74260), Pigment Yellow 101(0.1.48052), etc.
Suitable dyes are classified in the Colour Index as "Disperse Dyes". Examples include: Latyl Blue BCN (C.l. Disperse Blue 56); Latyl~Yellow36 (C.l. Disperse Yellow 54, 0.1. 47020); Latyl Cerise N (C.l.
Disperse Red 60,0.1.60756); C.l. Disperse Violet 28 (C.1.61102); Sinclair and Valentine Brown dye 50-1301-06 and disperse blue dye C.I. 14(0.1.61500); Sinclair and Valentine Blue dye 50-0305-06 and dis perse blue dye 0.1. 14(0.1.61500); Magenta 0.1. 17 (C.1.11210); and Disperse Red 60 (C.l. 60756); etc.
After toning, any excess toner is removed by brushing, wiping or blowing techniques known to those skilled in the art. The toned tacky imge areas are then buffed or rubbed until the areas become glossy. This is generally accomplished with a soft material so that the image surface is not damaged. A soft cloth such as cotton or a swab of cotton on a stick, etc. make effective buffing means. It is also possible to rub the toned image areas with resin powders such as ionic copolymer resins described in
U.S. Patent 3,264,272. Glossy image areas have been found to reject additional toner applied to the image areas. Occasionally, it may not be necessary to buff or rub the first tacky image on the photosensitive layer.This is due to the factthat the image consists of fine lines and lettering which covers less than about 3% of the tonble layer, e.g., a black record. The initial toned area, as well as the second toned image areas, are subsequently buffed or rubbed simul taneouslypriorto exposing the photosensitive layer through the third image transparency and buffing of the third toned image.
As indicated above, upon completion of the exposing, toning and buffing or rubbing steps (steps (a), (b) and (c)),these steps are repeated using a different image-bearing transparency whereby different areas of the photosensitive layer become tacky upon exposure, toned with a different color toner and are buffed or rubbed to seal the toned image areas. Each sequence as it is repeated, of course, uses a different image-bearing transparency and toner. As many colors as desired can be present on the same photosensitive layer. In orderto protect the toned surface from damage during handling, a protective layer, e.g., a clear photopolymerizable layer of the type described in U.S. Patent 3,649,248 can be applied, e,g., laminated, thereto.The protective layer is then hardened by exposing non image-wise to actinic radiation from a source such as described above.
Best Mode for Carrying Out the Invention
The best mode is illustrated in Example 6 wherein the photosensitive layer contains a photosensitive system containing several dihydropyridine compounds and hexaarylbiimidazole compounds with a polymethylmethacrylate binder and polyoxyethylene (4) monolauryl ether and dioctyl phthalate as plasticizers. Preparation of a 5-color map is illustrated but other numbers of colors can be present.
Industrial Applicability
The invention is useful for the low cost preparation of map proofs, colored engineering drawings, textile and wall covering design proofs. A large number of different colored images can be put on a single tonable layer resulting in savings in material, labor and cost, compared with multilayer systems. With respect to the textile and other design proofs the final layer toned with sublimable dyes or pigments, with or without the photohardened protective layer, can be brought into contact with a suitable receptor material such as fabric, e.g. polyethylene terephthalate; the tone surface of the receptor material, or both, heated for at least five seconds to a temperature at which the dyes or pigments sublime, and the toned layer removed from the receptor material.
Thermal transfer of sublimable dyes in a photosensitive system is described in U.S. Patent 4,124,384.
Color mixtures can be simulated by exposing the color separation negatives through a fine screen pattern, e.g. alternating opaque and clear lines. The pattern is moved between exposures to provide closely spaced tonable areas which when toned with the respective color for the particular negative used gives an appearance of a mixture of colors.
Examples 1 and 2 are controls and describe the use of positive-working compositions which require physical masking if a multicolor image is to be produced. Examples 3 to 7 illustrate the invention. All percentages in the Examples are by weight.
Example 1
A photopolymerizable element of the type described in Example Ill-H of U.S. Patent 3,854,950, minus the cover sheet, is laminated at 104 C onto the smooth side of 12 point Kromekote cast-coated one
side cover paper manufactured by The Champion
Paper and Fiber Company. The pressure rolls of the
laminator are set to provide a wrinkle- and bubble
free laminate without stalling the laminator. The laminate is placed face-up in a vacuum frame, half
the laminate is masked with opaque paper, and the
vacuum frame is closed and pumped until Newton's
rings appear between the glass cover and the sur
face of the protective cover and then the pumping is
continued for an additional 45 seconds.The masked
film is exposed for 2 units integrated exposure at 1
KW lamp input power on a nuArc N 1000 Instant
Mercury Printer. After removal from the vacuum
frame, the protective cover is removed and the sur
face is toned with a yellow toner of the type man
ufactured by the process of U.S. Patent 2,649,382.
Half of the toned image area is rubbed to make the
areas shiny or glossy using an ionic copolymer resin
powder of the type described in U.S. Patent
3,264,272. The entire image is toned again with addi
tional toner, either cyan or magenta in color, and is
cleaned with a cotton pad. The additional toner
adheres only in the areas not rubbed with the ionic
copolymer powder.
The above procedure is repeated except that only
the image areas toned yellow are buffed until glossy
with a cotton swab on a stick. The cyan toner subse
quently applied does not adhere to the buffed yellow
image areas but adheres in the unbuffed areas.
Example 2
This example describes the preparation of
nonoverlapping multicolor images on a single ton
able surface. All toners used in this example are of
the type manufactured by the process of U.S. Patent
2,649,382, but are given a surface treatment of
Dow-Corning silicone DC 200/100 C.S. in proportions
of 19.8 to 121.1 ml per kilogram of toner powder,
during the manufacturing process.
A photopolymerizable element is laminated to
Kromekote paper as described in Example 1. After
being placed in the vacuum frame, the laminate is
shielded from exposing radiation by means of a
larger rectangle and four small rectangles located
near one long side of the large rectangle and is
exposed as described in Example 1. As shown in the
drawing, the large rectangular area of the element is
marked off vertically from top to bottom reading
from left to right by lines designated, 3,-3, 2-2, 1-1 to
divide the rectangle in four equal parts. The four
areas are then divided in half by a horizontal line A-A
which bisects the large rectangle. Immediately
below the large rectangle are small rectangles (d),
(c), (b), (a) located to the left of line 3-3, left of line
2-2, left of line 1-1 and right of line 1-1, respectively.
The area of the laminate to the left of line 1-1 is
masked, the area to the right is toned with a black
toner, and the excess toner is removed. The area
above line A-A and the small rectangle (a) are
masked, and the portion of the large rectangle below
line A-A and to the right of line 1-1 is buffed until
shiny with a soft cotton cloth. The mask above line
A-A is removed, the mask on the laminate to the left
of line 1-1 is moved to the left of line 2-2, and the
entire areas to the right of line 2-2 is toned with a
cyan (blue-green) toner. The area above line A-A and the small rectangle (b) are masked and the area
below line A-A between lines 2-2 and 1-1 is buffed
with the cotton cloth as described above. The mask
above line A-A is again removed and the mask to the
left of line 2-2 is moved to the left of line 3-3.The entire area to the right of line 3-3 is toned with a
magenta (blue-red) toner and the excess toner is
removed. The area above line A-A and the small
rectangle (c) are masked and the area below line A-A and between lines 3-3 and 2-2 is buffed with the cotton cloth as described below. The mask above line
A-A and to the left of line 3-3 is removed, and the entire laminate is toned with yellow toner and the excess toner is removed. Masks over small rectangles (a), (b) and (c) are then removed. A photopolymerizable element as described above is laminated to the toned surface and is exposed nonimage-wise to harden the layer.The appearance of the toned laminate is as follows:
(a) The outer boundary area is substantially white with a small amount ofstain,
(b) Except for the yellow-toned region which was singly toned, the unbuffed, multitoned areas in the large rectangle above line A-A exhibit contaminated colors due to retention of toner from each toning,
(c) The multitoned areas below line A-A, the buffed areas of the large rectangle, exhibit single toned noncontaminated colors: yellow, magenta, cyan and black from left to right,
(d) The singly-toned small rectangles exhibit no contamination: (d) is yellow, (c) is magenta, (b) is cyan and (a) is black.
Example 3
A photosensitive composition is prepared by mixing the following ingredients:
Component Amount (g) Polymethylmethacrylate, of
very high M.W., inherent
viscosity 0.92' 42,857.00
Polyoxyethylene (4)monolauryl
ether 15.00 ml
Triethylene glycol diacetate 8.57 ml
Benzophenone 6.50 2,2',4,4',5,5',-hexaphenyl
biimidazole 28.10 2,2'-bis(2-chlorophenyl)-4,4',5,5'
tetraphenylbiimidazole 31.38 2,2'-bis(2-methoxyphenyl)-4,4',
5,5'-tetraphenylbiimidazole 30.95 2,4,6-trimethyl-3,5-bis(car bethoxy)-1 4-dihydropyridine 9.54 2,6-di methyl-4-ethyl-3,5-bis (carbethoxy)-1,4-dihydropyridine 10.04 2,6-dimethyl-4-propyl-3,5-bis- (carbethoxy)-1 ,4-dihydropyridine 10.54 2,6-dimethyl 4 propyl-3,5-bis- (carbethoxy)-1 4-dihydropyridine 12.24
Hydroquinone2 1.00 Polyethylene oxide2, MW ~ 4,000,000 1500-3500 cps/1% soln/25 C 1.00
Methylene chloride 2,100.00
1 0.25 g polymer in 50 ml chloroform at200C using a
No. 50 Cannon-Fenske Viscometer.
2 2 Dissolved at40"C in 6C ml methanol
The solution is coated on 0.75 mil (0.019 mm) polypropylene film and is dried to give a dry coating weight of 30 mg/dm2. A cover sheet of siliconetreated 1.0 mil (0.25 mm) thick polyethylene terephthalate film is laminated thereon. This element after removal of the cover sheet, is laminated to Kromekote paper as described in Example 1 exceptthatthe lamination temperature is about 99 C. The laminate is given a 10-unit integrated exposure employing the exposure device described in Example 1 using an opaque template comprising a four-inch (10.16cm) square with a two-inch (5.08 cm) square removed from one corner to provide a symmetrical L shape.
The toners used in this example are described in
U.S. Patent 3,909,282. The exposed two-inch (5.08 cm) square is toned with a high strength yellow toner and is buffed with a cotton cloth as described in Example 2 until all toned image areas are shiny except for a small triangular area near the center which is unbuffed.
The template is rotated 90 , a second exposure is made as described previously above, the tacky area is toned with high strength magenta toner, and the toned area is buffed leaving an unbuffed area as previously described. The same procedure is repeated two more times using cyan and blacktoners, respectively. The image areas toned black are not buffed since this is the last toner applied. The toned film exhibits relatively pure color in each of the four squares except that in the unbuffed area of each color contamination is observed due to some toner retention.
The above procedure is repeated except that the order of toner application is reversed, i.e., black, cyan, magenta and yellow. Identical results are achieved.
Example 4
The photosensitive element prepared as described in Example 3, after removal of the cover sheet, is laminated to Intermillse baryta-coated phototypesetting paper as by the procedure described in Example 3. The laminate is exposed through a black record separation negative using a nuArc FT40LC FlipTop
Platemaker operating a 4KW power input to the pulsed xenon source, and employing two 120-unit integrated exposures as registrated by a Luxometer
Model H exposure integrator, or about 50 seconds at high intensity. The image areas are toned with black toner described in Example 3, and the excess toner is removed. No buffing is used on the black image which consists of fine lines and lettering covering a minimal area (less than 3 percent of the total area) of the element.The exposure, toning and removal of excess toner are repeated three times, each time using a different color separation negative and appropriate toner prepared as described in U.S.
Patent 3,909,282. Each toned image area is buffed as described in Example 2 after the application of each toner. The separation negatives (in sequence of increasing area covered with appropriate toner) are: magenta, cyan and green. A4-color map is achieved.
The procedure of this example is repeated using a 60 second exposure of about 268 units integrated exposure for each record separation negative. A good 4-color map is thus achieved.
Example 5
The laminate described in Example 4 is exposed through a black separation negative of a map for 50 units on the integrator (about 2.5 minutes) of a Berkey Ascorx Vacuum Printer radiation source. The exposed image areas are toned with the black toner described in Example 3, excess toner is removed and the toned areas buffed with a clean-up cloth, LAS
STICK manufactured by LAS-STIK Manufacturing
Co., of Hamilton, Ohio. The same exposure procedure, excess toner removal and buffing is repeated four additional times using brown, magenta, blue and green separation negatives of the map in this order. A photopolymerizable element as described in Example 1 is laminated over the 5-color map image, and the layer is hardened by exposing for 42 units with the radiation source described in Example 1.The support of the element is removed leaving a good quality image of the original map protected by a clear completely photohardened layer.
Example 6
A photosensitive composition is prepared by mixing the following ingredients:
Component Amount (g)
Polymethyl methacrylate described
in Example4 60.00
Polyoxyethylene (4) monolauryl
ether described in Example 3 20.00 ml Dioctylphthalate 6.00 ml 2,2'-bis(2-chlorophenyl)4,4',5,5'
tetraphenylbiimidazole 25.02 2,2'-bis(2-methoxyphenyl)4,4',5,5'
tetraphenylbiimidazole 24.78 2,2'-bis(2-chlorophenyl)-4,4',5,5'
tetrakis (methoxyphenyl)biimidazole 29.64 2,4,6-trimethyl-3,5-bis(carbethoxy)- 1,4-dihydropyridine 7.62 2,6-dimethyl-4-ethyl-3,5-bis (carbethoxy)-1,4-dihydroxypyridine 8.02 2,6-dimethyl-4-propyl-3,5-bis- (carbethoxy)-1 4-dihydropyridine 8.42
2,6-dimethyl-4-benzyl-3,5-bis
(carbethoxy)-1,4-dihydropyridine 9.78 Bis-(2-hydroxy-3-butyl-5-ethyl- phenyl)methane, 4.00
Polyethylene oxide as described in
Example 3 0.80
Methylene chloride 2,800.00
The solution is coated on 0.75 mil (0.019 mm) polypropylene film and the coating is dried to give a dry coating weight of 35 mg/dm2. A cover sheet is laminated thereon as described in Example 3. The ele mentformed is exposed image-wise and after removal of the cover sheet is toned, the excess toner is removed, and the image areas are buffed as described in Example 4. A 5-color map is achieved by using the following separation negatives and appropriate toners in order of increasing area covered, i.e., red, blue, black, brown and magenta.
Similar good results are achieved by using the following separation negatives and appropriate toners, i.e., magenta, red, cyan, black and green. The toners are all of the type used in Examples 3 and 4.
Example 7
This example describes the use of single layer,
multitoned elements in a thermal transfer process
onto textile fabrics.
A Aphotosenstive element as described in Example 3 is used to make a 2-color proof by exposing through each of two separation negatives and toning the respective image areas with cyan Latyle Blue BCN (C.l. Disperse Blue 56) and magenta Latyl Cerise N (C.l. Disperse Red 60) dyes dispersed in a cellulose acetate matrix 0.2 to 30 equivalent particle diameter.
The first toned image is buffed as described in
Example 2 prior to the second exposure and application of toner. The 2-color image is transferred to a 100% Dacron polyethylene terephthalate double knit fabric prepared from fibers manufactured by E. l.
du Pont de Nemours and Company. A 16 inch (40.64 cm) flatbed press made by Precision Screen
Machines, Hawthorne, New Jersey is usedfortrans- fer. The press conditions are: one minute at 1000 psi (7030 kg/m2) and 4000F (204 C). A good quality cyan and magenta image on the fabric is achieved.
The procedure of this example is repeated except that a good quality 3-color image from a single layer is prepared and transfered to the fabric. The 3-color transfer is prepared by exposing the layer in order through cyan, magenta and violet separation negatives. The violet toner used is C.l. Disperse Violet 28 (0.1.61102) dye dispersed in a cellulose acetate matrix 0.2 to 30,a equivalent particle diameter. The press is heated to 4100F (210 C), other conditions remaining the same.
The procedure of this example is again repeated exceptthata good quality 4color image from a single layer is prepared and transferred to the fabric.
The 4-color transfer is prepared by exposing the layer in order through cyan, magenta, violet and yellow separation negatives. The yellow toner used is Latyle Yellow 3G (C.l. Disperse Yellow 54) dye dispersed in a cellulose acetate matrix 0.2 to 30 equivalent particle diameter. The press is heated to 3900F (199 C), other conditions remaining the same.
Claims (19)
1. A process for the preparation of a multicolor image using a negative-working tonable photosensitive layer, which process comprises:
(a) exposing said layer image-wise to actinic radiation through an image-bearing transparency, the exposed image areas of the layer becoming tacky;
(b) toning the tacky image areas by applying and adhering thereto a toner material which is swollen or solubilized when in contact with the tacky image areas;
(c) buffing or rubbing the toned image areas whereby the areas become glossy; and
(d) repeating (a), (b) and (c) at least once using a
different image-bearing transparency for each
exposure (a) and toning with a toner of different
color for each toning step (b).
2. A process according to claim 1 wherein there
is applied completely over the multitoned layer a
photo-hardenable layer which is nonimage-wise
exposed to actinic radiation to form a protective
layer.
3. A process according to claim 1 or 2 wherein prior to step (a) thetonable photosensitive layer is laminated to a surface.
4. A process according to claim 3 wherein the surface is of paper.
5. A process according to claim 1 or 2 wherein prior to step (a) the photosensitive layer is coated onto a surface and dried.
6. A process according to claim 5 wherein the surface is of paper.
7. A process according to any one of the preceding claims wherein each imageobearing transparency used in step (a) is a color separation negative.
8. A process according to any one of the preceding claims wherein the toned tacky image areas are made glossy by buffing with a soft material.
9. A process according to claim 8 wherein the buffing is accomplished with a soft cotton cloth.
10. A process according to any one of claims 1 to 7 wherein the toned tacky image areas are made glossy by rubbing with an ionic copolymer resin.
11. A process according to any one of the preceding claims wherein the photosensitive layer comprises at least one thermoplastic binder and a photosensitive system which consists essentially of at least one dihydropyridine compound of the formula: wherein
R is alkyl, alkylene, aryl or heteroaryl,
R1 and R2, which can be the same or different, are alkyl, and Rs and R4, which can be the same or different, are COOR', COR' or ON and R' is alkyl, and at least one hexaarylbiimidazole compound.
12. A process according to any one of the preceding claims wherein initial toned image areas which consist of fine lines and lettering covering less than 3% of the tonable layer and which have not been buffed or rubbed are provided before steps (a) and (b) are effected.
13. A process according to any one of the preceding claims wherein any excess toner is removed prior to step tc).
14. A process according to any one of the preceding claims wherein step (b) is accomplished at a temperature up to about 7000.
15. A process according to any one of the preceding claims wherein the photosensitive layer contains an organic plasticizer compound which swells or solubilizes the toner when the toner is brought in contact with the tacky image areas.
16. A process according to claim 1 substantially as described with reference to any one of Examples 3to7.
17. A process for preparing a multicolor image on a receptor material, which process comprises contacting a multicolor toner image produced by a process as claimed in any one of the preceding claims with the receptor material, and transferring the multicolortoned image to the receptor material at an elevated temperature.
18. A process according to claim 17, wherein the receptor material is fabric.
19. A process according to claim 18 wherein the fabric is polyethylene terephthalate.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US95962778A | 1978-11-13 | 1978-11-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2035591A true GB2035591A (en) | 1980-06-18 |
GB2035591B GB2035591B (en) | 1982-10-27 |
Family
ID=25502228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7939134A Expired GB2035591B (en) | 1978-11-13 | 1979-11-12 | Process for preparing multicolour toned images on a single photosensitive |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPS5815783B2 (en) |
BE (1) | BE879968A (en) |
DE (1) | DE2945564A1 (en) |
FR (1) | FR2441872B1 (en) |
GB (1) | GB2035591B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5250387A (en) * | 1992-01-29 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Transfer process using ultraviolet curable, non-prolonged tack toning materials |
GB2304201A (en) * | 1995-08-04 | 1997-03-12 | Sony Corp | Photographic method of forming a fluorescent screen on a CRT |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4330613A (en) * | 1980-11-07 | 1982-05-18 | E. I. Du Pont De Nemours And Company | Process for toning tacky image surfaces with dry nonelectroscopic toners |
DE3340210C2 (en) * | 1982-04-07 | 1995-06-22 | Sony Corp | Photosensitive material and process for the production of an image |
FR2536548B1 (en) * | 1982-11-18 | 1985-10-18 | Teyssonneau Yves | SINGLE-COLOR, BICHROME OR QUADRICHROME PHOTOGRAPHY, AS WELL AS TEXTS AND VINTAGES ON VARIOUS MEDIA FOR ORNAMENTS OF TOMB STONES |
DE10326324B4 (en) * | 2003-06-11 | 2007-02-08 | Kodak Polychrome Graphics Gmbh | Lithographic printing plate precursor with coating containing 1,4-dihydropyridine sensitizer, process for imaging and imaged lithographic printing plate |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1572058A1 (en) * | 1964-12-30 | 1970-03-05 | Keuffel & Esser Co | Reprographic process |
US3649268A (en) * | 1969-02-05 | 1972-03-14 | Du Pont | Process for forming images by photohardening and applying a colorant |
IL32890A0 (en) * | 1969-02-05 | 1969-11-12 | Staley Mfg Co A E | Dye imbibition imaging |
FR2030311A1 (en) * | 1969-02-05 | 1970-11-13 | Staley Mfg Co A E | Dispersion of coloured images |
US3676121A (en) * | 1969-08-12 | 1972-07-11 | Staley Mfg Co A E | Multi-color reproductions |
US3636385A (en) * | 1970-02-13 | 1972-01-18 | Ncr Co | Protection circuit |
DE2242106A1 (en) * | 1972-08-26 | 1974-03-21 | Agfa Gevaert Ag | LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL |
US3915704A (en) * | 1973-11-01 | 1975-10-28 | Xerox Corp | Photoinduced, acid catalyzed degradation of degradable polymers |
JPS5646142B2 (en) * | 1974-01-17 | 1981-10-31 | ||
FI71851C (en) * | 1977-04-13 | 1987-02-09 | Hitachi Ltd | Method of forming a powder coating layer according to a pattern on an image surface of a color image tube |
DE2758209C3 (en) * | 1977-12-27 | 1980-07-10 | Du Pont De Nemours (Deutschland) Gmbh, 4000 Duesseldorf | Photosensitive recording material |
-
1979
- 1979-11-10 DE DE19792945564 patent/DE2945564A1/en active Granted
- 1979-11-12 BE BE0/198067A patent/BE879968A/en not_active IP Right Cessation
- 1979-11-12 FR FR7927802A patent/FR2441872B1/en not_active Expired
- 1979-11-12 GB GB7939134A patent/GB2035591B/en not_active Expired
- 1979-11-13 JP JP54147598A patent/JPS5815783B2/en not_active Expired
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5250387A (en) * | 1992-01-29 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Transfer process using ultraviolet curable, non-prolonged tack toning materials |
GB2304201A (en) * | 1995-08-04 | 1997-03-12 | Sony Corp | Photographic method of forming a fluorescent screen on a CRT |
GB2304201B (en) * | 1995-08-04 | 1999-04-07 | Sony Corp | Methods of forming a fluorescent screen on the front panel of a cathode ray tube |
US5942358A (en) * | 1995-08-04 | 1999-08-24 | Sony Corporation | Method of forming a fluorescent screen on a front panel of a cathode ray tube |
Also Published As
Publication number | Publication date |
---|---|
DE2945564C2 (en) | 1987-10-08 |
FR2441872B1 (en) | 1987-02-06 |
JPS5569140A (en) | 1980-05-24 |
FR2441872A1 (en) | 1980-06-13 |
GB2035591B (en) | 1982-10-27 |
JPS5815783B2 (en) | 1983-03-28 |
BE879968A (en) | 1980-05-12 |
DE2945564A1 (en) | 1980-05-22 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19961112 |