CA1037311A - Image transfer element - Google Patents
Image transfer elementInfo
- Publication number
- CA1037311A CA1037311A CA238,453A CA238453A CA1037311A CA 1037311 A CA1037311 A CA 1037311A CA 238453 A CA238453 A CA 238453A CA 1037311 A CA1037311 A CA 1037311A
- Authority
- CA
- Canada
- Prior art keywords
- grams
- layer
- transparent substrate
- indicia
- release coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/12—Transfer pictures or the like, e.g. decalcomanias
-
- 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
-
- 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
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Duplication Or Marking (AREA)
- Materials For Photolithography (AREA)
Abstract
ABSTRACT
A presensitized light-sensitive sheet structure suitable for producing a dry transfer element, comprising a transparent substrate having a release coating thereon and overlying the release coating a photosensitive layer comprising a conventional photopolymerizable compound, an initiator therefor and a binder. After light exposure to an original through the transparent substrate and de-velopment to remove unexposed portions, the remaining image portions have a greater adhesion for a receptor surface when applied thereto under pressure than the adhesion of the indicia to the transparent substrate under like pressure.
A presensitized light-sensitive sheet structure suitable for producing a dry transfer element, comprising a transparent substrate having a release coating thereon and overlying the release coating a photosensitive layer comprising a conventional photopolymerizable compound, an initiator therefor and a binder. After light exposure to an original through the transparent substrate and de-velopment to remove unexposed portions, the remaining image portions have a greater adhesion for a receptor surface when applied thereto under pressure than the adhesion of the indicia to the transparent substrate under like pressure.
Description
~N 9~ l t ~! 5 . _._ IMAE _ AN~s~ER F,LEMENT
This invention relates to a light-sensitive ; element which, after ima~ewise exposure and removal of unexposed areas, can be utilized as a transfer element whereby individual image areas can be transferred to a receptor sur~ace.
Dry transfer sheets consist of a transparent support carrying thereon indicia such as letters, numerals or other symbols which can be individually transferred to a receiving surface, such as a sheet of paper. Transfer ld occurs by application of rubbing pressure to the rear surface of the support while the image contained on the support is in contact with the receptor followed by peeling away the support whereupon the ima~e adheres to the receptor surface.
A conventional technique for manufacturing dry transfer sheets at the present time is to screen print lndicia on a transparent support. Such manufacture ~' is costly and complex, generally being undertaken only '~ by experts in the field. For each of the numerous indicia -' 20 which might be required in practice, a separate screen stencil is necessary thereby economically limiting the manufacture to larger quantities of indicia having the greatest utility in the field. The cost of providing 3 small numbers of special-purpose indicia for individual 1 25 uses is therefore prohibitive.
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i ' .,,;. .' '' ';' ' ~ ' ~(313~73~ IL
Recently~ transfer elements utlllzing light~
sensitive systems have been disclosed. In U. S. patent No. 3~671,236 a method for photo mechanically producin~
multicolored images on a single substrate is disclosed.
In that disclosure, the entire light-sensitive diazo resln-based layer is transferred from a carrier sheet to a receptor prior to imagewise exposure thereof.
Imaging and development is undertaken subsequent to transfer. There is no disclosure of transferrin~
individual indicia comprising only the light exposed areas of the transfer element. Additionally, the llght-sensltive system therein is based on a diazo resin as opposed ~o free radlcal photopolymerizable materlals.
Free radlcal photopolymerizable materials have been utilized in image transfer, generally based on the fact that a differential degree of surface tack exists between unexposed and exposed areas of a photo-polymer system. Unexposed areas of the photopolymer layer generally have a greater degree o~ tack than exposed areas, thereby a~fording ability to selectively transfer unexposed areas to a receptor. In U. S. patent No. 3,342,593 this tack differential occurs upon heating an imagewise exposed transfer element while in U. S.
patent No. 3,202,508 tack differential occurs in sltu upon light exposure.
In U. S. patent No. 3,525,615 a thixotropic gel is interspersed in the photopolymerizable layer.
After imagewise exposure~ unexposed areas are capable
This invention relates to a light-sensitive ; element which, after ima~ewise exposure and removal of unexposed areas, can be utilized as a transfer element whereby individual image areas can be transferred to a receptor sur~ace.
Dry transfer sheets consist of a transparent support carrying thereon indicia such as letters, numerals or other symbols which can be individually transferred to a receiving surface, such as a sheet of paper. Transfer ld occurs by application of rubbing pressure to the rear surface of the support while the image contained on the support is in contact with the receptor followed by peeling away the support whereupon the ima~e adheres to the receptor surface.
A conventional technique for manufacturing dry transfer sheets at the present time is to screen print lndicia on a transparent support. Such manufacture ~' is costly and complex, generally being undertaken only '~ by experts in the field. For each of the numerous indicia -' 20 which might be required in practice, a separate screen stencil is necessary thereby economically limiting the manufacture to larger quantities of indicia having the greatest utility in the field. The cost of providing 3 small numbers of special-purpose indicia for individual 1 25 uses is therefore prohibitive.
,~;
i ' .,,;. .' '' ';' ' ~ ' ~(313~73~ IL
Recently~ transfer elements utlllzing light~
sensitive systems have been disclosed. In U. S. patent No. 3~671,236 a method for photo mechanically producin~
multicolored images on a single substrate is disclosed.
In that disclosure, the entire light-sensitive diazo resln-based layer is transferred from a carrier sheet to a receptor prior to imagewise exposure thereof.
Imaging and development is undertaken subsequent to transfer. There is no disclosure of transferrin~
individual indicia comprising only the light exposed areas of the transfer element. Additionally, the llght-sensltive system therein is based on a diazo resin as opposed ~o free radlcal photopolymerizable materlals.
Free radlcal photopolymerizable materials have been utilized in image transfer, generally based on the fact that a differential degree of surface tack exists between unexposed and exposed areas of a photo-polymer system. Unexposed areas of the photopolymer layer generally have a greater degree o~ tack than exposed areas, thereby a~fording ability to selectively transfer unexposed areas to a receptor. In U. S. patent No. 3,342,593 this tack differential occurs upon heating an imagewise exposed transfer element while in U. S.
patent No. 3,202,508 tack differential occurs in sltu upon light exposure.
In U. S. patent No. 3,525,615 a thixotropic gel is interspersed in the photopolymerizable layer.
After imagewise exposure~ unexposed areas are capable
-2-. ., . ~ . . . . . .
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of liquifyin~ and trans~errlng when contacted with a receptor sur~ace under hi~h pressure.
In all of these transfer processes utilizing photopol~merizable materials, visual inspection of the transferrable image areas is ~enerally unavailable because the exposed and unexposed areas of the light-sensitive layer are indistinguishable and remain as an integral layer until the moment of transfer. Additionally, selective transfer of individual indicia is generally unavailable. ~urthermore, after light exposure, the transferrable image portions remain light sensitive, thereby necessitating storage and transfer under sub-dued light.
It is of course known that a light exposed photopolymerizable stratum can be imagewise developed with a developing medium to thereby remove unexposed areas of the stratum. See Light Sensitive Systems:
Chemistry and Application of Nonsilver Halide Photo-graphic Processes, J. Kosar~ J. Wile~ and Sons tNew York, 1965). To our knowled~e, however, it has never been disclosed that the exposed pol~merized image areas remaining after development can be transferred to a receptor.
British patent No. 1,336,065 discloses a li~ht-sensitive transfer element which can be vi~ually inspected prior to transfer. A component capable of forming a gas upon light exposure is utilized in con-~unction with a gas imperv~ous binder resin in the transfer layer. The ~as causes the bond between the .
,. ~ . .
~L~373~1 transfer layer and the support ~o be weakened, thereby allowing removal of the exposed portions ~rom the support with a developing medium, the unexpose~ por-tions remaining. These remaining unexposed portions are then light exposed a seco~d time to again weaken the bond between the support and image areas and thereby provide indicia which are transferable to a receptor element by pres- ?
sure. ~lowever, this transfer system provides images with limited resolution since the binder in the transfer layer must be able to retain the gas formed upon exposure thereby limiting the sharpness of image boundaries. Similarly, control of the release of the transfer layer from the support is difficult 10 to maintain. Additionally, this transfer element must be light exposed twice before transfer can be effected.
According to one aspect of the present invention, there is provided a presensiti7ed light-sensitive sheet structure suitable for producing a dry transfer element comprising a thin, flexible~ transparent substrate having a release coating thereon and overlying said release coating and releasably bond-ed thereby to said transparent substrate a photosensitive layer comprising an addition polymerisable, non-gaseous ethylenically-unsaturated compound con-taining at least one terminal ethylenic group, a free-radical liberating pho~o-initiator therefor and a binder, said photosensitive layer, after imagewise ex- `
20 posure thereof to actinic radiation and removal of unexposed portion of said layer, having greater adhesion to a receptor surface when applied thereto under pressure than ~he adhesion of said photosensitive layer to said transparent sub-strate under like pressure.
Another aspect of the inventlon provides a dry transfer element com- ;
prising a thin, flexible transparent substrate having a release coating thereon and overlying said release coating and releasably bonded to said transparent substrate, transferable indicia, said indicia comprising an actinic radiation-exposed photopolymerisable compound which is an addition polymerisable, non-gaseous ethylenically-unsaturated compound containing at least one terminal 30 e~hylenic group, an initiator therefor and a binder, and wherein said indiciahave greater adhesion to a receptor surface when applied thereto under pres-sure than the adhesion of said indicia to said transparent substrate under like ~ -4-.Bi :~ . . : . . , :
~ `
73~
pressure.
Thus, in contrast to the aforementioned transfer systems, the inven-tion provides a light-sensitive transfer element ~hich, upon a single image-wise exposure and development, provides pressure transferable indicia having excellent resolution which can be visually inspected prior ~o transfer. Since the light exposed portions are transferable, indicia transfer can be undertaken at normal room temperature and light conditions utilizing a simple stylus.
As mentioned, the basic components of the light-sensitive transfer element of the invention include a thin, flexible, transparent substrate or film support, a release coating on ~he support and a photopolymerizable over-layer.
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~ .
~373~
The ril~ sup~)ort should be transparent slnce exposure ls typicall~ undertaken through the backside of the transfer element, i.e. through the support itself.
Also~ a transparent support is necessary to allow visual positionin~ o~ individual indicia for transfer to a re-ceptor. The support should also be surficiently thin and flexible to allow transfer by stylus pressure.
Typical thin, flexible, transparent film supports in-clude polyesters~ polypropylene~ polyethylene, polystyrene, triacetate and transparent paper, e.g. ~lassine base, ~ -coated with a non-porous material such as cellulose acetate or polycarbonate.
The release layer acts essentially as a barrier to prevent the light-sensitive overlayer from firmly bonding to the transparent film support. Additionally, the release layer must be capable of retaining the exposed areas of the light-sensitive overlayer during ~mage development, yet allow release of these same areas from the film support durin~ image transfer. The release ~.
layer is preferably substantially impenetrable to solvent developers utilized during image development so as to prevent undercutting of the exposed image areas desired to be retained on the transfer element.
For image transfer to occur by proper- functioning of the release layer~ the bond between the image layer and the ~ilm support must fail during transfer by one of the following mechanisms: (1) adhesive failure at the release layer-film support interface; (2) adhesive failure at the image layer-release layer interface; or (3) cohesive iO373~
failure within the r-elease la~er.
~ echanism (1) results rrom release material.s which have lower adhesion ~or the film support than ~or the photopolymeri~ed image layer and have good lnternal strength, i.e. they are ~ood film formers. An exe~plary material is eth~1 cellulose. A filler such as colloidal silica can typically be contained in the ethyl cellulose to control adhesion thereof to the film support. In this instance, the release material should be soluble in or removable by the developing medium utilized during image development.
Mechanism (2)~ adhesive railure at the ima~e layer_release layer interface, results when the release layer has greater adhesion for the film support than -I5 for the ima~e layer. This result is generally attained by utilizing release materials having low surface energies thereby resulting in poorer wetting by the image layer, and/or which are insoluble in the solvents utilized in coating the image layer. An exemplary material exhibiting such characteristics is a silicone resin.
Cohesive failure of the release layer, mechanism ~3), results when the release material has a low internal strength, i.e. lower than either the photosensitive layer/
release layer bond or the release layer/substrate bond.
Commercially available mold release agents such as Vydax AR, tradename for a telomer of tetrafluoroethylene and ~
Mold Wiz PS-9, tradename for a commercial mold release ~ ;
agent, believed to comprlse a silicone, hydrocarbon and carboxylate s~lt blend, are exemplary.
~Lal3~3~
The preferre~ release mec~lanism is b~ cohe.~ive failure o~ the release laver because variabl.e associated with the ima~eable overlayer, such as solvent selection, drying rates, etc. do not af~ect the release mechanlsm.
Release is dependent onl~ on the physical character:Lstics or the release material which can be altered as desired by inclusion of plasticizers, resins, flllers, etc.
The photosensitive material contained in the imageable la~er of my transfer element comprises an addition polymerizable, non-gaseous, i.e. having a boiling point above about 100C at normal atmospheric pressure, ethylenically-unsaturated compound containing at least one terminal ethylenic group and bein~ capable of forming a high polymer by free radical initiated~
chain propagating addition polymerization and a free radical-liberating initiator therefor.
Typical polymerizable monomers include the acrylates, e.g. methacrylate, methylmethacrylate, etc.
and the corresponding ethyl esters; polyhydric alcohol esters of acrylates, e.g. tris-hydroxyethylisocyanurate-trimethylacrylate~ pentaerythritoltetraacrylate and the corresponding esters; vinyl aromatics, e.~. styrene, 1,4-divinylbenzene, naphthalene; unsaturated amides, e.g. acrylamide, methacrylamide; vinyl esters, e.g.
vinyl acetate and vinyl butyrate; and the like.
Free-radical liberating photoinitiators include any compound which liberates free radicals on stimulation by actinic radiation. Exemplary photoinitiators include the vicinal poly ketaldonyl compounds described in U.S.
:- : -: . ,., , . . - .......................................... .
: .- , . ,: . . - . :
, ~373~
patcnt No. 2, 367, 660; t~le alpha-carbonyls described in U. S. patent Nos. 2,~7,661 and 2,367,670; the acyloin ethers described in U. S. patent No. 2,ll48,828; the alpha-hydrocarbon-substituted aromatic acyloins described in U. S. patent No. 2,722,512; the polynuclear quinones described in U. S. patent Nos. 3"0l~6,127 and 2,951,758;
the triarylimidazolyl dimer/p-amino-phenyl ketone com-bination described in U. S. patent No. 3,549,367; dye-sensitized photolyzable organic halogen compounds described in U. S. patent Nos. 3,6llo,718 and 3,617,228~ and the vinyl-substituted halomethyl-s-triazines described in U. S. patent No. 3,987,o37.
For the exposed photopolymerized image areas of the transfer element to trans~er to a receptor, the image area must be either tacky~ i.e. the image will adhere to the receptor surface by adhesive foreces, or soft, such that the image will conform to the receptor ~ -surface and adhere thereto. Suitable receptor sur~aces include paper, cardboard, metal sheets and foils, wood, glass, nylon~ rubber, polyethylene polyesters, etc.
A tacky image can be attained by a variety of methods including addition of plasticizers or plasticizing ;
. , .
resins, monomers, pressure-sensitive adhesives,~ree- ~ `
radical scavengers, soft binders, etc. to the photo-polymerizable layer.
Soft image elements can be characterized as those wherein the polymer will flow when sub~ected to the pressure created by a stylus during transfer. This pressure is ~ .
9~3'7~
believed to be on the order of about 50 to about 1500 pounds per square inch. ~or example, ~ 0.030 inch diameter pencil point~ llnder a 1 pound load creates a pressure of about 1400 pounds per square lnch. The same methods utilized to impart tack to a polymer can be used to make a polymer soft.
Fillers are typically lncluded in the photo-sensitive layer to provide color to the image areas and/
or to improve the characteristics thereof, e.g. by de-creasing the tack, increasing the release, improving theimage development rate~ etc. Exemplary fillers include carbon black, titanium dioxide, zinc o~ide and other organic and lnorganic pigments. Dispersion of pigments or other fillers in the coating composition can be enhanced by utilizing conventional dispersants, sur-factants, etc.
Fillers can generally be present in the light-sensitive layer in an amount up to about 30 percent by welght of the total solids. Decreasing concentrations f pigment would correspondingly reduce the image color density. At increasing filler concentrations, image film strength decreases, correspondingly increasing image loss during development. The preferred range of filler concentration is from about 1 percent to about 20 percent f the total sollds depending on the desired end properties of the light-sensitive layer.
Image coloration is generally desirable ~or registratlon o~ indicia prior to transfer. While this can be undertaken by utilizing a pigment-filled light~
sensitive composition, it can also be accomplished ~0373~
subsequent to exposure and development by utilizinK con-ventional dyes. For example, an aqueous solution o~ a water soluble dye can be rubbed onto photopolymerized ima~e areas after development until d,ye penetratlon and corresponding coloration o~ the image areas occur. By utilizing dyes, a variety of colors can be provided on a single transfer sheet.
The light-sensitive layer can be considered to contain three components--the photopolymerizable monomer~
an initiator therefor and a binder ~wherein the binder is in actuallty a blend of the remaining materials such as plasticizers, fillers~ etc.). The ratio of these three components is important in determining the final propertles of the transfer layer. For example, if` too little photopolymerizable monomer or too much binder is present~ image resolution and dif~erential solubility o~ the image layer will be less than optimum. At the -other extreme, the llght-sensitive layer may be too soft and ~luid before exposure or the exposed image areas may be too hard for e~icient trans~er. While the optimum range will generally depend on the particular photopoly-merizable monomer and binders, typically the llght-sensitive layer contains ~rom about 25 percent to about 90 percent monomer by weight based on total solids.
Initiator concentration is important in that at very low concentrations the polymerizatlon process may -be too slow or poor conversion o~ monomer to polymer can occur (although this poor conversion can e~ectively add to the tack of the exposed transfer areas). Too great a concentration can cause extensive crosslinking -10- ' .... . .... . . . . . . . .
3731~
thereby resultinF~ in loss of tack~ halation, etc., and the added posslbility of po.st-development llght sensitivity.
Initiator concentration ~rom about 0.5 to about 5.0 percent by weight based on the total sol:Lds ls generally satlsfactory, depending on the particular init:lator and monomers chosen.
A protective layer can be applied over the light-sensitive layer to prevent oxygen inhibition and provide ease o~ handling the sheet structure if the photo-polymer ls tacky.
Typical protectlve layers include polyvinyl alcohol, gelatin, gum arabic, methyl vinyl ether/maleic anhydride copolymers, polyvinyl pyrrolldones, etc. The protective layer must be soluble in developer solutions utilized in development of the imagewise exposed transfer element.
Alternatively, a protective cover sheet having a release coating, e.g. silicone, can be laminated to the light~sensitive layer to provide protection thereto.
This cover sheet can be stripped from the photosensitive layer after imagewise exposure. Imagewise exposure can be undertaken by conventional exposure units such as carbon arc, mercury vapor, pulsed xenon~ etc.
Developer solutions utilized should contaln a solvent for the unexposed areas of the light-sensitive ~-layer. Development action can occur by dissolving one or more components comprising the light~sensitive layer.
For example, lf a water soluble component~ such as the binder resin or the monomer ls utilized, the developer can be an aqueous system.
.
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When the preferred binder resin, namel~ a car-boxylated vin~l resin~ is utilized, a dilute base is the pre~erred developer, s~nce the binder resin is soluble therein. Organic solvents such as ethyl alcohol, iso-propanols, etc. can also be utilized in con~unction withwater if deslred.
The developer solution can be used as a bath or in the f~orm of a spray. Removal of the unexposed areas of the photopolymer layer can be generally improved by brushing, rubbing with a wet sponge or other conventional procedures.
My invention will be further illustrated by the ~ollowing nonlimiting examples wherein all parts are by welght unless otherwise indicated.
A release composition was prepared by mixing:
75 grams Mold Wiz PS-259 (a tradename for a 10% dispersion believed to be a blend of silicone, a hydrocarbon and a carboxylate salt) 10 grams Vydax AR (tradename for a 20%
solids solution of a short chain telomer ~of tetrafluoroethylene in Freon TF) .5 gram Polyethylene oxide 50 grams Trichloroethylene The resulting disperslon was cascade coated onto a 3 mil ~ ~;
transparent polyester base and dried at 140F ~or 2 minutes to provide a dry coatin~ weight of 120 milllgrams per square ~oot.
A photosensitive composition was prepared by first milling on a sand or ball mill:
'~ tr~
, , : : - ~
~373~
.7 grams Telva C V 6 (tradename for carboxy~a~ed polyvinyl acetate copolymer) 1.62 grams Cabot Sterling R (tradename for carbon black) 9.8 grams ethyl alcohol 17.4 grams methyl ethyl ketone The milled material was added to a mlxture of the following components followed by thorough agitation-
~3~3~ .
of liquifyin~ and trans~errlng when contacted with a receptor sur~ace under hi~h pressure.
In all of these transfer processes utilizing photopol~merizable materials, visual inspection of the transferrable image areas is ~enerally unavailable because the exposed and unexposed areas of the light-sensitive layer are indistinguishable and remain as an integral layer until the moment of transfer. Additionally, selective transfer of individual indicia is generally unavailable. ~urthermore, after light exposure, the transferrable image portions remain light sensitive, thereby necessitating storage and transfer under sub-dued light.
It is of course known that a light exposed photopolymerizable stratum can be imagewise developed with a developing medium to thereby remove unexposed areas of the stratum. See Light Sensitive Systems:
Chemistry and Application of Nonsilver Halide Photo-graphic Processes, J. Kosar~ J. Wile~ and Sons tNew York, 1965). To our knowled~e, however, it has never been disclosed that the exposed pol~merized image areas remaining after development can be transferred to a receptor.
British patent No. 1,336,065 discloses a li~ht-sensitive transfer element which can be vi~ually inspected prior to transfer. A component capable of forming a gas upon light exposure is utilized in con-~unction with a gas imperv~ous binder resin in the transfer layer. The ~as causes the bond between the .
,. ~ . .
~L~373~1 transfer layer and the support ~o be weakened, thereby allowing removal of the exposed portions ~rom the support with a developing medium, the unexpose~ por-tions remaining. These remaining unexposed portions are then light exposed a seco~d time to again weaken the bond between the support and image areas and thereby provide indicia which are transferable to a receptor element by pres- ?
sure. ~lowever, this transfer system provides images with limited resolution since the binder in the transfer layer must be able to retain the gas formed upon exposure thereby limiting the sharpness of image boundaries. Similarly, control of the release of the transfer layer from the support is difficult 10 to maintain. Additionally, this transfer element must be light exposed twice before transfer can be effected.
According to one aspect of the present invention, there is provided a presensiti7ed light-sensitive sheet structure suitable for producing a dry transfer element comprising a thin, flexible~ transparent substrate having a release coating thereon and overlying said release coating and releasably bond-ed thereby to said transparent substrate a photosensitive layer comprising an addition polymerisable, non-gaseous ethylenically-unsaturated compound con-taining at least one terminal ethylenic group, a free-radical liberating pho~o-initiator therefor and a binder, said photosensitive layer, after imagewise ex- `
20 posure thereof to actinic radiation and removal of unexposed portion of said layer, having greater adhesion to a receptor surface when applied thereto under pressure than ~he adhesion of said photosensitive layer to said transparent sub-strate under like pressure.
Another aspect of the inventlon provides a dry transfer element com- ;
prising a thin, flexible transparent substrate having a release coating thereon and overlying said release coating and releasably bonded to said transparent substrate, transferable indicia, said indicia comprising an actinic radiation-exposed photopolymerisable compound which is an addition polymerisable, non-gaseous ethylenically-unsaturated compound containing at least one terminal 30 e~hylenic group, an initiator therefor and a binder, and wherein said indiciahave greater adhesion to a receptor surface when applied thereto under pres-sure than the adhesion of said indicia to said transparent substrate under like ~ -4-.Bi :~ . . : . . , :
~ `
73~
pressure.
Thus, in contrast to the aforementioned transfer systems, the inven-tion provides a light-sensitive transfer element ~hich, upon a single image-wise exposure and development, provides pressure transferable indicia having excellent resolution which can be visually inspected prior ~o transfer. Since the light exposed portions are transferable, indicia transfer can be undertaken at normal room temperature and light conditions utilizing a simple stylus.
As mentioned, the basic components of the light-sensitive transfer element of the invention include a thin, flexible, transparent substrate or film support, a release coating on ~he support and a photopolymerizable over-layer.
-4a-I
~ .
~373~
The ril~ sup~)ort should be transparent slnce exposure ls typicall~ undertaken through the backside of the transfer element, i.e. through the support itself.
Also~ a transparent support is necessary to allow visual positionin~ o~ individual indicia for transfer to a re-ceptor. The support should also be surficiently thin and flexible to allow transfer by stylus pressure.
Typical thin, flexible, transparent film supports in-clude polyesters~ polypropylene~ polyethylene, polystyrene, triacetate and transparent paper, e.g. ~lassine base, ~ -coated with a non-porous material such as cellulose acetate or polycarbonate.
The release layer acts essentially as a barrier to prevent the light-sensitive overlayer from firmly bonding to the transparent film support. Additionally, the release layer must be capable of retaining the exposed areas of the light-sensitive overlayer during ~mage development, yet allow release of these same areas from the film support durin~ image transfer. The release ~.
layer is preferably substantially impenetrable to solvent developers utilized during image development so as to prevent undercutting of the exposed image areas desired to be retained on the transfer element.
For image transfer to occur by proper- functioning of the release layer~ the bond between the image layer and the ~ilm support must fail during transfer by one of the following mechanisms: (1) adhesive failure at the release layer-film support interface; (2) adhesive failure at the image layer-release layer interface; or (3) cohesive iO373~
failure within the r-elease la~er.
~ echanism (1) results rrom release material.s which have lower adhesion ~or the film support than ~or the photopolymeri~ed image layer and have good lnternal strength, i.e. they are ~ood film formers. An exe~plary material is eth~1 cellulose. A filler such as colloidal silica can typically be contained in the ethyl cellulose to control adhesion thereof to the film support. In this instance, the release material should be soluble in or removable by the developing medium utilized during image development.
Mechanism (2)~ adhesive railure at the ima~e layer_release layer interface, results when the release layer has greater adhesion for the film support than -I5 for the ima~e layer. This result is generally attained by utilizing release materials having low surface energies thereby resulting in poorer wetting by the image layer, and/or which are insoluble in the solvents utilized in coating the image layer. An exemplary material exhibiting such characteristics is a silicone resin.
Cohesive failure of the release layer, mechanism ~3), results when the release material has a low internal strength, i.e. lower than either the photosensitive layer/
release layer bond or the release layer/substrate bond.
Commercially available mold release agents such as Vydax AR, tradename for a telomer of tetrafluoroethylene and ~
Mold Wiz PS-9, tradename for a commercial mold release ~ ;
agent, believed to comprlse a silicone, hydrocarbon and carboxylate s~lt blend, are exemplary.
~Lal3~3~
The preferre~ release mec~lanism is b~ cohe.~ive failure o~ the release laver because variabl.e associated with the ima~eable overlayer, such as solvent selection, drying rates, etc. do not af~ect the release mechanlsm.
Release is dependent onl~ on the physical character:Lstics or the release material which can be altered as desired by inclusion of plasticizers, resins, flllers, etc.
The photosensitive material contained in the imageable la~er of my transfer element comprises an addition polymerizable, non-gaseous, i.e. having a boiling point above about 100C at normal atmospheric pressure, ethylenically-unsaturated compound containing at least one terminal ethylenic group and bein~ capable of forming a high polymer by free radical initiated~
chain propagating addition polymerization and a free radical-liberating initiator therefor.
Typical polymerizable monomers include the acrylates, e.g. methacrylate, methylmethacrylate, etc.
and the corresponding ethyl esters; polyhydric alcohol esters of acrylates, e.g. tris-hydroxyethylisocyanurate-trimethylacrylate~ pentaerythritoltetraacrylate and the corresponding esters; vinyl aromatics, e.~. styrene, 1,4-divinylbenzene, naphthalene; unsaturated amides, e.g. acrylamide, methacrylamide; vinyl esters, e.g.
vinyl acetate and vinyl butyrate; and the like.
Free-radical liberating photoinitiators include any compound which liberates free radicals on stimulation by actinic radiation. Exemplary photoinitiators include the vicinal poly ketaldonyl compounds described in U.S.
:- : -: . ,., , . . - .......................................... .
: .- , . ,: . . - . :
, ~373~
patcnt No. 2, 367, 660; t~le alpha-carbonyls described in U. S. patent Nos. 2,~7,661 and 2,367,670; the acyloin ethers described in U. S. patent No. 2,ll48,828; the alpha-hydrocarbon-substituted aromatic acyloins described in U. S. patent No. 2,722,512; the polynuclear quinones described in U. S. patent Nos. 3"0l~6,127 and 2,951,758;
the triarylimidazolyl dimer/p-amino-phenyl ketone com-bination described in U. S. patent No. 3,549,367; dye-sensitized photolyzable organic halogen compounds described in U. S. patent Nos. 3,6llo,718 and 3,617,228~ and the vinyl-substituted halomethyl-s-triazines described in U. S. patent No. 3,987,o37.
For the exposed photopolymerized image areas of the transfer element to trans~er to a receptor, the image area must be either tacky~ i.e. the image will adhere to the receptor surface by adhesive foreces, or soft, such that the image will conform to the receptor ~ -surface and adhere thereto. Suitable receptor sur~aces include paper, cardboard, metal sheets and foils, wood, glass, nylon~ rubber, polyethylene polyesters, etc.
A tacky image can be attained by a variety of methods including addition of plasticizers or plasticizing ;
. , .
resins, monomers, pressure-sensitive adhesives,~ree- ~ `
radical scavengers, soft binders, etc. to the photo-polymerizable layer.
Soft image elements can be characterized as those wherein the polymer will flow when sub~ected to the pressure created by a stylus during transfer. This pressure is ~ .
9~3'7~
believed to be on the order of about 50 to about 1500 pounds per square inch. ~or example, ~ 0.030 inch diameter pencil point~ llnder a 1 pound load creates a pressure of about 1400 pounds per square lnch. The same methods utilized to impart tack to a polymer can be used to make a polymer soft.
Fillers are typically lncluded in the photo-sensitive layer to provide color to the image areas and/
or to improve the characteristics thereof, e.g. by de-creasing the tack, increasing the release, improving theimage development rate~ etc. Exemplary fillers include carbon black, titanium dioxide, zinc o~ide and other organic and lnorganic pigments. Dispersion of pigments or other fillers in the coating composition can be enhanced by utilizing conventional dispersants, sur-factants, etc.
Fillers can generally be present in the light-sensitive layer in an amount up to about 30 percent by welght of the total solids. Decreasing concentrations f pigment would correspondingly reduce the image color density. At increasing filler concentrations, image film strength decreases, correspondingly increasing image loss during development. The preferred range of filler concentration is from about 1 percent to about 20 percent f the total sollds depending on the desired end properties of the light-sensitive layer.
Image coloration is generally desirable ~or registratlon o~ indicia prior to transfer. While this can be undertaken by utilizing a pigment-filled light~
sensitive composition, it can also be accomplished ~0373~
subsequent to exposure and development by utilizinK con-ventional dyes. For example, an aqueous solution o~ a water soluble dye can be rubbed onto photopolymerized ima~e areas after development until d,ye penetratlon and corresponding coloration o~ the image areas occur. By utilizing dyes, a variety of colors can be provided on a single transfer sheet.
The light-sensitive layer can be considered to contain three components--the photopolymerizable monomer~
an initiator therefor and a binder ~wherein the binder is in actuallty a blend of the remaining materials such as plasticizers, fillers~ etc.). The ratio of these three components is important in determining the final propertles of the transfer layer. For example, if` too little photopolymerizable monomer or too much binder is present~ image resolution and dif~erential solubility o~ the image layer will be less than optimum. At the -other extreme, the llght-sensitive layer may be too soft and ~luid before exposure or the exposed image areas may be too hard for e~icient trans~er. While the optimum range will generally depend on the particular photopoly-merizable monomer and binders, typically the llght-sensitive layer contains ~rom about 25 percent to about 90 percent monomer by weight based on total solids.
Initiator concentration is important in that at very low concentrations the polymerizatlon process may -be too slow or poor conversion o~ monomer to polymer can occur (although this poor conversion can e~ectively add to the tack of the exposed transfer areas). Too great a concentration can cause extensive crosslinking -10- ' .... . .... . . . . . . . .
3731~
thereby resultinF~ in loss of tack~ halation, etc., and the added posslbility of po.st-development llght sensitivity.
Initiator concentration ~rom about 0.5 to about 5.0 percent by weight based on the total sol:Lds ls generally satlsfactory, depending on the particular init:lator and monomers chosen.
A protective layer can be applied over the light-sensitive layer to prevent oxygen inhibition and provide ease o~ handling the sheet structure if the photo-polymer ls tacky.
Typical protectlve layers include polyvinyl alcohol, gelatin, gum arabic, methyl vinyl ether/maleic anhydride copolymers, polyvinyl pyrrolldones, etc. The protective layer must be soluble in developer solutions utilized in development of the imagewise exposed transfer element.
Alternatively, a protective cover sheet having a release coating, e.g. silicone, can be laminated to the light~sensitive layer to provide protection thereto.
This cover sheet can be stripped from the photosensitive layer after imagewise exposure. Imagewise exposure can be undertaken by conventional exposure units such as carbon arc, mercury vapor, pulsed xenon~ etc.
Developer solutions utilized should contaln a solvent for the unexposed areas of the light-sensitive ~-layer. Development action can occur by dissolving one or more components comprising the light~sensitive layer.
For example, lf a water soluble component~ such as the binder resin or the monomer ls utilized, the developer can be an aqueous system.
.
~L03~
When the preferred binder resin, namel~ a car-boxylated vin~l resin~ is utilized, a dilute base is the pre~erred developer, s~nce the binder resin is soluble therein. Organic solvents such as ethyl alcohol, iso-propanols, etc. can also be utilized in con~unction withwater if deslred.
The developer solution can be used as a bath or in the f~orm of a spray. Removal of the unexposed areas of the photopolymer layer can be generally improved by brushing, rubbing with a wet sponge or other conventional procedures.
My invention will be further illustrated by the ~ollowing nonlimiting examples wherein all parts are by welght unless otherwise indicated.
A release composition was prepared by mixing:
75 grams Mold Wiz PS-259 (a tradename for a 10% dispersion believed to be a blend of silicone, a hydrocarbon and a carboxylate salt) 10 grams Vydax AR (tradename for a 20%
solids solution of a short chain telomer ~of tetrafluoroethylene in Freon TF) .5 gram Polyethylene oxide 50 grams Trichloroethylene The resulting disperslon was cascade coated onto a 3 mil ~ ~;
transparent polyester base and dried at 140F ~or 2 minutes to provide a dry coatin~ weight of 120 milllgrams per square ~oot.
A photosensitive composition was prepared by first milling on a sand or ball mill:
'~ tr~
, , : : - ~
~373~
.7 grams Telva C V 6 (tradename for carboxy~a~ed polyvinyl acetate copolymer) 1.62 grams Cabot Sterling R (tradename for carbon black) 9.8 grams ethyl alcohol 17.4 grams methyl ethyl ketone The milled material was added to a mlxture of the following components followed by thorough agitation-
3.5 grams pentaerythritol tetraacrylate 11.9 gramæ triacrylate o~ (tris-2~hydroxyehtyl) isocyanurate 2.g grams Daratak 74L (tradename for a 55 percent solids in water acrylate copolymer adhesive emulsion) 1.9 gram Pycal 94 (tradename for a poly-oxyethylene aryl ether flexi-bilizer) ,~
- 0.24 gram FC-430 (tradename for a fluoro-chemical surfactant) 1.4 gram Polyox N-10 (tradename for a polyethylene oxide) 0.42 gram 2(p-methoxy styryl)-4~6-bis (trichlormethyl)-s-triazine 31.0 grams methyl ethyl ketone The photosensitive composition was knife coated on the dry release layer and dried at 180F for 4 minutes to provide a dry coating weight of 2.5 grams per square foot.
A top coat solution was prepared by mixing:
7 grams ~elvatol 20-30 (tradename for polyvinyl alcohol) 70 grams water 23 grams methyl alcohol The resulting solution was knife coated over the photosensi- , tive layer and dried at 180F for 2 minutes to provide a dry -13~
.,.- -~ . , .
731~
coatlng weight Or ]50 milli~rams per square foot.
The sheet construction was exposed through the polyester baclcing to a right-readlng negative for 2 minutes in a NuArc pulsed Xenon exposure unit.
The exposed sheet was then placed in a development sink wlth the coated side up. A developer solution of 1 percent sodium silicate in water was llberally poured on the sheet. Development was accomplished by gently rubbing the wet sheet with a so~t cotton pad whereupon the unexposed areas were removed. After development, the sheet was rin~ed with clear tap water and carefully blotted dry.
~ransfer occurred by placing the indicia, i.e.
the image areas on the sheet, in contact with the receptor paper and rubbing the polyester backing with a dull pencil.
The polyester carrier sheet was then peeled away whereupon the indicia adhered to the receptor paper.
In this instance, transfer occured due to cohesive failure within the release layer.
A release composition was prepared by mixing the following components:
68.1 grams rrE Sillcone No. 4191 (tradename for a 30 percent solids silicone resln solution in xylene) 2.7 grams GE Catalyst No. 4192 (tradename ~or a 50% solids silicone resin curative solution in xylene) 27 grams ~E Accelerator No. 4193 (tradename for a cure accelerator~
635 grams toluene 635 grams methyl ethyl ketone 1~7;~
1'he mixture was cascade coated on a 3 mll trans-parent polyester base, dried and cured for 4 minu~es at 190~ to provide a dry coatlng weight Or 25 milligram~
per square foot.
The photosensitive la!ler Or Example 1 was applied over the dry release coating and dried as per Example 1.
A top coat solutlon was prepared by mlxln~: -2 grams hydroxyethyl cellulose .1 gram Triton X-100 (tradename for alkylarylpolyether alcohol) 80 grams water 20 grams methyl alcohol The resulting solution was knife coated over the photosen-sitive layer and dried at 180F to provide a final coating -weight of 200 milligrams per square foot.
The coated sheet was exposed~ developed and the . ~-resulting indicia transferred as per Example 1.`
This sheet construction has properties very similar to Example 1 except that upon trans~er, image :
release occurred at the interface of the photosensitive and release layers.
A release compositlon was prepared by mixing the following components:
2~ 100 grams Mold Wiz PS-259 (tradename for a 10~ solids in toluene blend of silicone, hydrocarbon and a carboxylate salt) 100 grams Toluene ~ he composition was cascade coated onto a 3 mil transparent polyester base and dried at 140F for 3 minutes providing a dry coating weight of 100 milligrams ~0;31~3~1 per square foot.
The p~otosensitive laver of Example 1 ~as applied over the dry release coating and dried as per Example 1.
A plece of the 3 mil polyester coated ~rith the release layer o~ Example 2 was u~ed as a liner and lami-nated to the photosensitive laver. The resulting sandwich was exposed as per Example 1, the liner peeled away and the sheet developed as per Example 1. The resultin~ indicia were transferred by placing the transfer e'ement on a paper receptor and passing the sheets between heated nip rolls operating at 210~. The polyester backing was separated as it emerged from the rolls whereupon the indicia were effectively transferred to the receptor. -E Ar_PLE 4 A release composîtion was prepared by mixing the following components:
7.5 grams Methocel 15 (tradename for methyl cellulose) 22.5 grams normal propyl alcohol 120 grams water 20 grams Nalcoag 1050 (tradename ~or a 35 percent sollds aqueous col-loidal silica dispersion) 1 gram Triton X-100 (tradename for alkylaryl polyether alcohol) The composition was knife coated onto a 3 mil transparent polyester base and dried at 180F for 3 minutes resulting in a dry coating weight of o.6 grams per square foot.
The photosensitive layer and top coat of Example 1 was applied over the dry release layer. Exposure, de-velopment and transfer were ~he same as in Example 1.
-., , , . - ,.- ,, .................. . . :
-. : , . . . .
~Excellent visible image release was noted.
EXA~P1E 5 The release layer of Exam~le 1 was overcoated with a photoqensitive compositlon prepared by mixing:
3 grams trlmethylol propane trimethacr,ylate 2 grams trimethacrylate o~ (tris hydroxy-ethyl) isocyanurate 2.5 grams ~elva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 2.2 grams Daratak 74L (tradename for a 55 percent solids in water acrylate copolymer adhesive emulsion) 0.5 gram Polyox N-10 (tradename for poly-ethylene oxide) 0.12 gram 2(p-methoxy styryl)-4,6-bis (trlchloromethyl)-s-triazine 0.5 gram P~cal 94 ~tradename for a flexibilizer) po~lyoxyethylene aryl ether 1.1 gram Sudan Red 0 (tradename for a red dye) 15 grams meth~l ethyl ketone 5 grams ethyl alcohol The photopolymerizable coating was dried at 180F
for 3 minutes providing a dry coating weight of 1.5 grams per square foot.
The top coat of Example 1 was applled over the photosensitive layer.
The sheet was imaged through the transparent polyester backing to a right reading negatlve for 1 minute on a NuArc pulsed xenon exposure unit and developed with a solution of 3.7 percent sodium acetate, 1.2 percent Triton X-100 (tradename ~or alkylaryl polyether alcohol)~ 46.3 percent ., , . : ~
~l~373~
water and 48.8 percent eth,vl alcohol.
Transfer was arfected by placlng the red lndicia in contact with a trans~arent po:L~ester receptor and rubbing the polyester backing with a dull pencil.
.
The release layer of Example 1 was overcoated with a photosensitive compositiorl prepared by mlxing:
3 grams trimeth,ylol propane trimethacry-late 2 grams trimethacrylate of (tris h,ydrox,y-ethyl) isocyanurate ~ -2 grams VERR (tradename ror vinyl acetate/
vinyl chloride resin) 2 grams ~elva RA 788 (tradename for an acrylate copolymer) 0.5 grams dibutyl phthalate ,;,~
0.2 grams Sudan ~reen (tradename for a green dye) 0.15 gram 2-(p-methoxy styryl)-4,6-bis (trichloromethyl)-s-trlazine 18.8 grams methyl ethyl ketone 11.3 grams ethyl alcohol 1.0 grams water ~-The photopolymerizable coating was dried at 180F
for 4 minutes providing a dry coating weight of 1.8 grams per square foot.
After overcoatlng as per Example ls the sheet was exposed through the transparent polyester backing ~or 1 mlnute with a pulsed xenon light source at a distance of 18 inches.
Image development was undertaken utilizing a solution of 40 percent by volume n-propyl alcohol and 60 percent by volume water.
: -,, . : ~ .... .. , - .
: . ~ . . - . , , ,, , .~ .
31~L
Indlcia were transrerred to a receptor utlllæing a simple st~ylus.
The release layer o~ Example 1 was overcoated with a photosensitlve composition prepared by mixlng: ~
1.5 grams pentaerythritol tetraacrylate
- 0.24 gram FC-430 (tradename for a fluoro-chemical surfactant) 1.4 gram Polyox N-10 (tradename for a polyethylene oxide) 0.42 gram 2(p-methoxy styryl)-4~6-bis (trichlormethyl)-s-triazine 31.0 grams methyl ethyl ketone The photosensitive composition was knife coated on the dry release layer and dried at 180F for 4 minutes to provide a dry coating weight of 2.5 grams per square foot.
A top coat solution was prepared by mixing:
7 grams ~elvatol 20-30 (tradename for polyvinyl alcohol) 70 grams water 23 grams methyl alcohol The resulting solution was knife coated over the photosensi- , tive layer and dried at 180F for 2 minutes to provide a dry -13~
.,.- -~ . , .
731~
coatlng weight Or ]50 milli~rams per square foot.
The sheet construction was exposed through the polyester baclcing to a right-readlng negative for 2 minutes in a NuArc pulsed Xenon exposure unit.
The exposed sheet was then placed in a development sink wlth the coated side up. A developer solution of 1 percent sodium silicate in water was llberally poured on the sheet. Development was accomplished by gently rubbing the wet sheet with a so~t cotton pad whereupon the unexposed areas were removed. After development, the sheet was rin~ed with clear tap water and carefully blotted dry.
~ransfer occurred by placing the indicia, i.e.
the image areas on the sheet, in contact with the receptor paper and rubbing the polyester backing with a dull pencil.
The polyester carrier sheet was then peeled away whereupon the indicia adhered to the receptor paper.
In this instance, transfer occured due to cohesive failure within the release layer.
A release composition was prepared by mixing the following components:
68.1 grams rrE Sillcone No. 4191 (tradename for a 30 percent solids silicone resln solution in xylene) 2.7 grams GE Catalyst No. 4192 (tradename ~or a 50% solids silicone resin curative solution in xylene) 27 grams ~E Accelerator No. 4193 (tradename for a cure accelerator~
635 grams toluene 635 grams methyl ethyl ketone 1~7;~
1'he mixture was cascade coated on a 3 mll trans-parent polyester base, dried and cured for 4 minu~es at 190~ to provide a dry coatlng weight Or 25 milligram~
per square foot.
The photosensitive la!ler Or Example 1 was applied over the dry release coating and dried as per Example 1.
A top coat solutlon was prepared by mlxln~: -2 grams hydroxyethyl cellulose .1 gram Triton X-100 (tradename for alkylarylpolyether alcohol) 80 grams water 20 grams methyl alcohol The resulting solution was knife coated over the photosen-sitive layer and dried at 180F to provide a final coating -weight of 200 milligrams per square foot.
The coated sheet was exposed~ developed and the . ~-resulting indicia transferred as per Example 1.`
This sheet construction has properties very similar to Example 1 except that upon trans~er, image :
release occurred at the interface of the photosensitive and release layers.
A release compositlon was prepared by mixing the following components:
2~ 100 grams Mold Wiz PS-259 (tradename for a 10~ solids in toluene blend of silicone, hydrocarbon and a carboxylate salt) 100 grams Toluene ~ he composition was cascade coated onto a 3 mil transparent polyester base and dried at 140F for 3 minutes providing a dry coating weight of 100 milligrams ~0;31~3~1 per square foot.
The p~otosensitive laver of Example 1 ~as applied over the dry release coating and dried as per Example 1.
A plece of the 3 mil polyester coated ~rith the release layer o~ Example 2 was u~ed as a liner and lami-nated to the photosensitive laver. The resulting sandwich was exposed as per Example 1, the liner peeled away and the sheet developed as per Example 1. The resultin~ indicia were transferred by placing the transfer e'ement on a paper receptor and passing the sheets between heated nip rolls operating at 210~. The polyester backing was separated as it emerged from the rolls whereupon the indicia were effectively transferred to the receptor. -E Ar_PLE 4 A release composîtion was prepared by mixing the following components:
7.5 grams Methocel 15 (tradename for methyl cellulose) 22.5 grams normal propyl alcohol 120 grams water 20 grams Nalcoag 1050 (tradename ~or a 35 percent sollds aqueous col-loidal silica dispersion) 1 gram Triton X-100 (tradename for alkylaryl polyether alcohol) The composition was knife coated onto a 3 mil transparent polyester base and dried at 180F for 3 minutes resulting in a dry coating weight of o.6 grams per square foot.
The photosensitive layer and top coat of Example 1 was applied over the dry release layer. Exposure, de-velopment and transfer were ~he same as in Example 1.
-., , , . - ,.- ,, .................. . . :
-. : , . . . .
~Excellent visible image release was noted.
EXA~P1E 5 The release layer of Exam~le 1 was overcoated with a photoqensitive compositlon prepared by mixing:
3 grams trlmethylol propane trimethacr,ylate 2 grams trimethacrylate o~ (tris hydroxy-ethyl) isocyanurate 2.5 grams ~elva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 2.2 grams Daratak 74L (tradename for a 55 percent solids in water acrylate copolymer adhesive emulsion) 0.5 gram Polyox N-10 (tradename for poly-ethylene oxide) 0.12 gram 2(p-methoxy styryl)-4,6-bis (trlchloromethyl)-s-triazine 0.5 gram P~cal 94 ~tradename for a flexibilizer) po~lyoxyethylene aryl ether 1.1 gram Sudan Red 0 (tradename for a red dye) 15 grams meth~l ethyl ketone 5 grams ethyl alcohol The photopolymerizable coating was dried at 180F
for 3 minutes providing a dry coating weight of 1.5 grams per square foot.
The top coat of Example 1 was applled over the photosensitive layer.
The sheet was imaged through the transparent polyester backing to a right reading negatlve for 1 minute on a NuArc pulsed xenon exposure unit and developed with a solution of 3.7 percent sodium acetate, 1.2 percent Triton X-100 (tradename ~or alkylaryl polyether alcohol)~ 46.3 percent ., , . : ~
~l~373~
water and 48.8 percent eth,vl alcohol.
Transfer was arfected by placlng the red lndicia in contact with a trans~arent po:L~ester receptor and rubbing the polyester backing with a dull pencil.
.
The release layer of Example 1 was overcoated with a photosensitive compositiorl prepared by mlxing:
3 grams trimeth,ylol propane trimethacry-late 2 grams trimethacrylate of (tris h,ydrox,y-ethyl) isocyanurate ~ -2 grams VERR (tradename ror vinyl acetate/
vinyl chloride resin) 2 grams ~elva RA 788 (tradename for an acrylate copolymer) 0.5 grams dibutyl phthalate ,;,~
0.2 grams Sudan ~reen (tradename for a green dye) 0.15 gram 2-(p-methoxy styryl)-4,6-bis (trichloromethyl)-s-trlazine 18.8 grams methyl ethyl ketone 11.3 grams ethyl alcohol 1.0 grams water ~-The photopolymerizable coating was dried at 180F
for 4 minutes providing a dry coating weight of 1.8 grams per square foot.
After overcoatlng as per Example ls the sheet was exposed through the transparent polyester backing ~or 1 mlnute with a pulsed xenon light source at a distance of 18 inches.
Image development was undertaken utilizing a solution of 40 percent by volume n-propyl alcohol and 60 percent by volume water.
: -,, . : ~ .... .. , - .
: . ~ . . - . , , ,, , .~ .
31~L
Indlcia were transrerred to a receptor utlllæing a simple st~ylus.
The release layer o~ Example 1 was overcoated with a photosensitlve composition prepared by mixlng: ~
1.5 grams pentaerythritol tetraacrylate
4.5 grams triacry:Late of ~trls 2-hydroxyethyl) isocyanurate 3.0 grams Butvar 76 (tradename for a polyvlnyl butyral resin)
5.0 grams Gelva RA 788 ~tradename for an acrylate copolymer) 0.15 gram 2-(p-methoxy styryl)-4~6-bis - (trlchloromethyl)-s-triazine 0.5 gram dlbut,yl phthalate 0.1 gram Sudan Red 0 (tradename ~or a red dye) 27,0 grams methyl ethyl ketone The photopolymerizable coating was dried at 180F
for 4 minutes to provide a dry coating weight of 1.5 grams per square foot.
A silicone coated polyester sheet was laminated ~ -to the photosensitive layer as per Example 3. Exposure was undertaken through the transparent backing for 1.5 minutes to a pulsed xenon light source at a distance of 18 inches after which the sllicone-coated liner was peeled away.
Development of the imaged photosensitive layer was undertaken utilizing a solution comprising 75 percent isopropanol and 25 percent water by volume. -Transfer of the red indicia was undertaken utilizing a stylus. -~)~31~
F,X MPLE 8 The release layer o~ Example l was overcoated wlth a photosensitlve composition prepared by mixing:
3.0 grams trimethylol propane trimethacrylate 2,0 grams tris methacrylate of (tris hydroxy ethyl)isocyanurate 2.0 grams EAB500-1 (tradename for a cellulose acetate butyrate resin) 5.0 grams ~Telva RA-788 (tradename for an acrylate copolymer) .:!:
0.5 gram Pycal 94 (tradename for a poly-oxyethylene aryl ether flexi- -~
bilizer) 0.2 gram 2(p-methoxy styryl)-4,6-bis ~ .
trichloromethyl)-s-triazine ; : :
0.1 gram Sudan Red O (tradename for a red dye) 18.0 grams methyl ethyl ketone The photopolymerizable coating was dried at 180F
for 3 minutes providing a dry coating weight of 1.8 grams per square foot.
After providing a top coat as per Example 1, the element was exposed and developed as per Example 7 whereupon indicia transferable by stylus pressure were obtained.
A release composition was prepared by mixing the following:
75 grams Mold Wiz PS-259 ~tradename for a lO percent solids in toluene blend of silicone, wax and a carboxylate salt) lO grams Vydax AR (tradename for a 20%
solids solution of a short chain telomer of tetrafluoroethylene in Freon TF 3 a fluorocarbon sol-vent) ,:, , .. - :: .: : , .~ . .
~al37~
25 ~rams Polvox N10 ttradename ~or poly ethylene oxide) in trichloroethylene The mixture was knife coated onto a transparent polyester base and dried at 140:F ~or 2 minutes providing a dr~ coating weight of 150 milligrams per square ~oot.
Over thls layer was coate~ a photopolymerlzable composltlon prepared by mixing: :
1.0 gram pentraerythrito]. tetraacrylate 3.4 grams triacr~late o~ (tris 2-hydroxyethyl) isocyanurate 1.9 grams Thiokol LP-31 (tradename for a liquid polysulfide polymer) 4.0 grams 20 percent solids solution o~
dimethylaminoethyl methacrylate homopolymer in methyl ethyl ketone 1.0 gram Santicizer 8 (tradename for N-ethyl,O,p-toluenesulfonamide) 0.2 gram 2-methyl-4,6 bis(trichloromethyl) s-triazine 0.1 gram 9,10-dimethoxyanthracene 0.7 gram 10% solids dispersion of FC-430 (tradename for a fluorocarbon surfactant) in methyl ethyl ketone 0.15 gram Uvinul 400 (tradename ~or 2,4-dihydroxy-benzophenone) : :
8.3 grams millbase from Example 9 8.o grams methyl ethyl ketone 3.0 grams methyl alcohol The coating was drled at 180F for 4 minutes providing a dry coating weight of 1. 8 grams per square ~oot.
A solution was prepared by mixing:
7 ~rams Gelvatol 20-30 (tradename for a polyvinyl alcohol resin) 0.46 gram Triton X-100 (tradename ~or alkylaryl polyether alcohol) 75 grams water 25 grams methyl alcohol This solution was coated on a second polyester base and dried at 190F for 2.5 minutes to a dry coatin~ weight of 100 milllgrams per square ~oot. This la~er was lami-nated to the tacky photopolymerlzable layer of the first sheet and the polyester base pee:Led away from the polyvinyl alcohol layer.
The transfer element was exposed through a negative mask to ultra~iolet light through the polyester backing.
The imaged light-sensitive layer was developed utilizing a l percent by weight aqueous ammonia developer and slight rubbing action whereupon the unexposed portions of the light-sensitive layer were removed.
The remaining indicia can be transferred to a receptor by utilizing a simple stylus.
A millbase was prepared by ball milling a mixture of: .
11.4 grams Gelva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 2.2 grams carbon black 3.48 grams water 13.5 grams 95/5 parts by weight ethanol/
isopropanol 26.8 grams methyl ethyl ketone This millbase was added to a mixture of:
2.7 grams polyethylene glycol diacrylate 8.9 grams pentaerythritol tetraacrylate 7.7 grams trlacrylate of (tris 2-hydroxyethyl) isocyanurate ~22-:~L03 ~31~
21.2 grams 10% solicls solution of poly-ethylene oxlde in water o.96 Pycal 9ll (tradename ~or a poly-oxyethyLene aryl ether f'lexibilizer) o.66 gram phenanthrenequinone This light-sensitive composition was knife coated onto a release layer prepared as per Example 1 on a 3 mil transparent polyester base and dried at 180F for 3 minutes providing a dry coating weight of 1.5 grams per square foot.
A second millbase was prepared by ball milling a mixture of:
5.7 grams Gelva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 1.0 gram carbon black 13.4 grams methyl ethyl ketone
for 4 minutes to provide a dry coating weight of 1.5 grams per square foot.
A silicone coated polyester sheet was laminated ~ -to the photosensitive layer as per Example 3. Exposure was undertaken through the transparent backing for 1.5 minutes to a pulsed xenon light source at a distance of 18 inches after which the sllicone-coated liner was peeled away.
Development of the imaged photosensitive layer was undertaken utilizing a solution comprising 75 percent isopropanol and 25 percent water by volume. -Transfer of the red indicia was undertaken utilizing a stylus. -~)~31~
F,X MPLE 8 The release layer o~ Example l was overcoated wlth a photosensitlve composition prepared by mixing:
3.0 grams trimethylol propane trimethacrylate 2,0 grams tris methacrylate of (tris hydroxy ethyl)isocyanurate 2.0 grams EAB500-1 (tradename for a cellulose acetate butyrate resin) 5.0 grams ~Telva RA-788 (tradename for an acrylate copolymer) .:!:
0.5 gram Pycal 94 (tradename for a poly-oxyethylene aryl ether flexi- -~
bilizer) 0.2 gram 2(p-methoxy styryl)-4,6-bis ~ .
trichloromethyl)-s-triazine ; : :
0.1 gram Sudan Red O (tradename for a red dye) 18.0 grams methyl ethyl ketone The photopolymerizable coating was dried at 180F
for 3 minutes providing a dry coating weight of 1.8 grams per square foot.
After providing a top coat as per Example 1, the element was exposed and developed as per Example 7 whereupon indicia transferable by stylus pressure were obtained.
A release composition was prepared by mixing the following:
75 grams Mold Wiz PS-259 ~tradename for a lO percent solids in toluene blend of silicone, wax and a carboxylate salt) lO grams Vydax AR (tradename for a 20%
solids solution of a short chain telomer of tetrafluoroethylene in Freon TF 3 a fluorocarbon sol-vent) ,:, , .. - :: .: : , .~ . .
~al37~
25 ~rams Polvox N10 ttradename ~or poly ethylene oxide) in trichloroethylene The mixture was knife coated onto a transparent polyester base and dried at 140:F ~or 2 minutes providing a dr~ coating weight of 150 milligrams per square ~oot.
Over thls layer was coate~ a photopolymerlzable composltlon prepared by mixing: :
1.0 gram pentraerythrito]. tetraacrylate 3.4 grams triacr~late o~ (tris 2-hydroxyethyl) isocyanurate 1.9 grams Thiokol LP-31 (tradename for a liquid polysulfide polymer) 4.0 grams 20 percent solids solution o~
dimethylaminoethyl methacrylate homopolymer in methyl ethyl ketone 1.0 gram Santicizer 8 (tradename for N-ethyl,O,p-toluenesulfonamide) 0.2 gram 2-methyl-4,6 bis(trichloromethyl) s-triazine 0.1 gram 9,10-dimethoxyanthracene 0.7 gram 10% solids dispersion of FC-430 (tradename for a fluorocarbon surfactant) in methyl ethyl ketone 0.15 gram Uvinul 400 (tradename ~or 2,4-dihydroxy-benzophenone) : :
8.3 grams millbase from Example 9 8.o grams methyl ethyl ketone 3.0 grams methyl alcohol The coating was drled at 180F for 4 minutes providing a dry coating weight of 1. 8 grams per square ~oot.
A solution was prepared by mixing:
7 ~rams Gelvatol 20-30 (tradename for a polyvinyl alcohol resin) 0.46 gram Triton X-100 (tradename ~or alkylaryl polyether alcohol) 75 grams water 25 grams methyl alcohol This solution was coated on a second polyester base and dried at 190F for 2.5 minutes to a dry coatin~ weight of 100 milllgrams per square ~oot. This la~er was lami-nated to the tacky photopolymerlzable layer of the first sheet and the polyester base pee:Led away from the polyvinyl alcohol layer.
The transfer element was exposed through a negative mask to ultra~iolet light through the polyester backing.
The imaged light-sensitive layer was developed utilizing a l percent by weight aqueous ammonia developer and slight rubbing action whereupon the unexposed portions of the light-sensitive layer were removed.
The remaining indicia can be transferred to a receptor by utilizing a simple stylus.
A millbase was prepared by ball milling a mixture of: .
11.4 grams Gelva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 2.2 grams carbon black 3.48 grams water 13.5 grams 95/5 parts by weight ethanol/
isopropanol 26.8 grams methyl ethyl ketone This millbase was added to a mixture of:
2.7 grams polyethylene glycol diacrylate 8.9 grams pentaerythritol tetraacrylate 7.7 grams trlacrylate of (tris 2-hydroxyethyl) isocyanurate ~22-:~L03 ~31~
21.2 grams 10% solicls solution of poly-ethylene oxlde in water o.96 Pycal 9ll (tradename ~or a poly-oxyethyLene aryl ether f'lexibilizer) o.66 gram phenanthrenequinone This light-sensitive composition was knife coated onto a release layer prepared as per Example 1 on a 3 mil transparent polyester base and dried at 180F for 3 minutes providing a dry coating weight of 1.5 grams per square foot.
A second millbase was prepared by ball milling a mixture of:
5.7 grams Gelva C5V16 (tradename for a carboxylated polyvinyl acetate copolymer) 1.0 gram carbon black 13.4 grams methyl ethyl ketone
6.7 grams ethanol 1.0 gram water This was added to a mixture of:
2.9 grams polyethylene glycol diacrylate 9.4 grams pentaerythritol tetraacrylate 8.2 grams triacrylate of ~tris 2-hydroxyehtyl isocyanurate 13.0 grams Daratak 74L (tradename for a 55 percent solids in water acrYlate copolymer adhesive emulsion) 10.6 grams 10 percent solids solution of polyethylene oxide in water 0.5 gram Pycal 94 (tradename ~or a poly-oxyethylenje aryl ether ~lexibilizer) o.66 gram phenanthrenequinone 25.9 grams methyl ethyl ketone Thls composition was knife coated over the first light-sensi-tive composition and dried at 180F for 4 minutes to provide - -.; . . .
:, . : . . . . . .
~9373~
a dry coatin~ weight of 1.0 grams per square foot.
After ~op coating, exposin~ and developlng as per Example 1~ a transfer element having black lndicia capable of easy transfer to receptor sur~aces was obtained.
, . ,~
-21~ - .
'' ' " ' '; ' ' ' ~ ` ' ' ' ~ ,. ! ~ .
2.9 grams polyethylene glycol diacrylate 9.4 grams pentaerythritol tetraacrylate 8.2 grams triacrylate of ~tris 2-hydroxyehtyl isocyanurate 13.0 grams Daratak 74L (tradename for a 55 percent solids in water acrYlate copolymer adhesive emulsion) 10.6 grams 10 percent solids solution of polyethylene oxide in water 0.5 gram Pycal 94 (tradename ~or a poly-oxyethylenje aryl ether ~lexibilizer) o.66 gram phenanthrenequinone 25.9 grams methyl ethyl ketone Thls composition was knife coated over the first light-sensi-tive composition and dried at 180F for 4 minutes to provide - -.; . . .
:, . : . . . . . .
~9373~
a dry coatin~ weight of 1.0 grams per square foot.
After ~op coating, exposin~ and developlng as per Example 1~ a transfer element having black lndicia capable of easy transfer to receptor sur~aces was obtained.
, . ,~
-21~ - .
'' ' " ' '; ' ' ' ~ ` ' ' ' ~ ,. ! ~ .
Claims (9)
1. A presensitized light-sensitive sheet structure suitable for producing a dry transfer element comprising a thin, flexible, transparent substrate having a release coating thereon and overlying said release coating and releasably bonded thereby to said transparent substrate a photosensitive layer comprising an addition polymerizable, non-gaseous ethylenically-unsaturated compound containing at least one terminal ethylenic group, a free-radical liberating photoinitiator therefor and a binder, said photosensitive layer, after imagewise exposure thereof to actinic radiation and removal of unexposed portion of said layer, having greater adhesion to a receptor surface when applied thereto under pressure than the adhesion of said photo-sensitive layer to said transparent substrate under like pressure.
2. The light-sensitive sheet structure of claim 1 further comprising a protective layer over said photosensitive layer.
3. The sheet structure of claim 2 wherein said protective layer comprises polyvinyl alcohol.
4. The sheet structure of claim 1 wherein said release coating comprises a silicone resin.
5. The sheet structure of claim 1 wherein said release coating comprises a telomer of tetrafluoroethylene.
6. The sheet structure of claim 1 wherein said binder comprises a pig-mented carboxylated polyvinyl acetate copolymer.
7. The sheet structure of claim 1 wherein said transparent substrate is a polyester.
8. A method for preparing a dry transfer element comprising: a) image-wise exposing the presensitized sheet of claim 1 through the transparent sub-strate to actinic radiation whereby the exposed areas of the photosensitive layer are rendered insoluble to a solvent developing medium and thereby create a latent image; b) developing said image with said solvent developing medium whereby unexposed portions of said photosensitive layer are removed.
9. A dry transfer element comprising a thin, flexible transparent sub-strate having a release coating thereon and overlying said release coating and releasably bonded to said transparent substrate, transferable indicia, said indicia comprising an actinic radiation-exposed photopolymerisable compound which is an addition polymerisable, non-gaseous ethylenically-unsaturated com-pound containing at least one terminal ethylenic group, an initiator therefor and a binder, and wherein said indicia have greater adhesion to a receptor sur-face when applied thereto under pressure than the adhesion of said indicia to said transparent substrate under like pressure.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52343074A | 1974-11-13 | 1974-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037311A true CA1037311A (en) | 1978-08-29 |
Family
ID=24084966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,453A Expired CA1037311A (en) | 1974-11-13 | 1975-10-28 | Image transfer element |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS609247B2 (en) |
| CA (1) | CA1037311A (en) |
| CH (1) | CH613055A5 (en) |
| DE (1) | DE2551216C2 (en) |
| FR (1) | FR2291527A1 (en) |
| GB (1) | GB1521766A (en) |
| IT (1) | IT1049068B (en) |
| SE (1) | SE447426B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2653428C3 (en) * | 1976-11-24 | 1979-05-17 | Claus Koenig Kg, 8520 Erlangen | Color film for making a template for advertising purposes |
| GB1580076A (en) | 1977-07-20 | 1980-11-26 | Marler E T Ltd | Pressure sensitive adhesive transfer |
| GB1604250A (en) * | 1977-11-02 | 1981-12-02 | Reed K J | Water-release transfers |
| GB1603972A (en) * | 1978-02-15 | 1981-12-02 | Reed K J | Transfer sheets with releasable layers |
| US4226927A (en) * | 1978-05-10 | 1980-10-07 | Minnesota Mining And Manufacturing Company | Photographic speed transfer element with oxidized polyethylene stripping layer |
| WO1980001321A1 (en) * | 1978-12-25 | 1980-06-26 | N Smirnova | Dry film photoresist |
| JPH06103391B2 (en) * | 1985-09-20 | 1994-12-14 | 富士写真フイルム株式会社 | Photosensitive recording material |
| GB2182888A (en) * | 1985-11-13 | 1987-05-28 | Colin George Thompson | Method of making transfers |
| DE3706528A1 (en) * | 1987-02-28 | 1988-09-08 | Du Pont Deutschland | LAYER TRANSFER MATERIAL |
| US7273530B2 (en) * | 2004-04-05 | 2007-09-25 | E.I. Du Pont De Nemours & Company | Process for the production of decorative coatings on substrates |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3380831A (en) * | 1964-05-26 | 1968-04-30 | Du Pont | Photopolymerizable compositions and elements |
| DE1522515C2 (en) * | 1965-08-03 | 1980-10-09 | Du Pont | Process for the production of printed circuits |
| US3607264A (en) * | 1967-11-22 | 1971-09-21 | Du Pont | Image reproduction process involving photohardening and delamination |
| GB1254475A (en) * | 1968-03-15 | 1971-11-24 | Process Shizai Kabushiki Kaish | A method for transferring colored image and light-sensitive transfer sheets therefor |
| BE757386A (en) * | 1969-10-13 | 1971-04-13 | Du Pont | DOUBLE TRANSFER PROCESS FOR PHOTOSETTING IMAGES |
| GB1291960A (en) * | 1971-01-07 | 1972-10-04 | Oxalid Company Ltd | Light-sensitive material for use in the preparation of dry transfer sheets |
| DE2204244C3 (en) * | 1971-02-02 | 1981-02-19 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Photopolymerizable recording material |
| US3770438A (en) * | 1971-12-09 | 1973-11-06 | J Celeste | Photopolymerizable transfer elements |
| US3775113A (en) * | 1972-02-09 | 1973-11-27 | Minnesota Mining & Mfg | Positive image transfer |
| US3782939A (en) * | 1972-02-09 | 1974-01-01 | Mining And Mfg Co | Dry positive-acting photoresist |
| JPS4939415A (en) * | 1972-08-14 | 1974-04-12 | ||
| GB1441982A (en) * | 1973-01-18 | 1976-07-07 | Autotype Co Ltd | Dry transfer sheets |
| JPS49111619A (en) * | 1973-02-22 | 1974-10-24 |
-
1975
- 1975-10-28 GB GB4443975A patent/GB1521766A/en not_active Expired
- 1975-10-28 CA CA238,453A patent/CA1037311A/en not_active Expired
- 1975-11-03 SE SE7512264A patent/SE447426B/en not_active IP Right Cessation
- 1975-11-12 FR FR7534407A patent/FR2291527A1/en active Granted
- 1975-11-12 IT IT2920975A patent/IT1049068B/en active
- 1975-11-12 DE DE19752551216 patent/DE2551216C2/en not_active Expired
- 1975-11-12 JP JP50136146A patent/JPS609247B2/en not_active Expired
- 1975-11-12 CH CH1466775A patent/CH613055A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB1521766A (en) | 1978-08-16 |
| DE2551216C2 (en) | 1989-07-20 |
| FR2291527A1 (en) | 1976-06-11 |
| IT1049068B (en) | 1981-01-20 |
| SE7512264L (en) | 1976-05-14 |
| JPS5171124A (en) | 1976-06-19 |
| CH613055A5 (en) | 1979-08-31 |
| DE2551216A1 (en) | 1976-05-26 |
| FR2291527B1 (en) | 1983-04-01 |
| JPS609247B2 (en) | 1985-03-08 |
| SE447426B (en) | 1986-11-10 |
| AU8653175A (en) | 1977-05-19 |
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