CA2121865C - Laser imaged printing plate - Google Patents
Laser imaged printing plate Download PDFInfo
- Publication number
- CA2121865C CA2121865C CA002121865A CA2121865A CA2121865C CA 2121865 C CA2121865 C CA 2121865C CA 002121865 A CA002121865 A CA 002121865A CA 2121865 A CA2121865 A CA 2121865A CA 2121865 C CA2121865 C CA 2121865C
- Authority
- CA
- Canada
- Prior art keywords
- layer
- laser
- ablation
- photopolymerizable
- printing element
- 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 - Lifetime
Links
Classifications
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/146—Laser beam
Abstract
Laser-imageable flexographic printing plates and a method of making same are disclosed. A thin polymeric film doped with a UV absorber is laminated to a photopolymer layer. The film is ablated from the photopolymer using a laser operating at a selected wavelength to create an in situ negative. The resulting negative can be subjected to typical UV flood exposure and development.
Description
21218~a
- 2 -Field of the Invention This invention relates to printing plates which can be made without using a negative. More specifically, it relates to a laser-imageable printing plate. Such plates are particularly useful for flexographic printing, but can be used for offset and lithographic printing.
Haokqround of the Invention Flexography is a method of printing that is commonly used for high-volume runs. Flexography is employed for printing on a variety of substrates such as paper, paperboard stock, corrugated board, films, foils and laminates. Newspapers and grocery bags are prominent examples. Coarse surfaces and stretch films can be economically printed only by means of flexography. Flexographic printing plates are relief plates with image elements raised above open areas.
One type of flexographic printing plate resembles a transparent or translucent plastic doormat when it is ready for use. The plate is somewhat soft, and flexible enough to wrap around a printing cylinder, and durable enough to print over a million copies.
Such plates offer a number of advantages to the printer, based chiefly on their durability and the ease with which they can be made. Further ~.mprovements, to the degree of resolution (fineness of detail) which can be obtained as well as reductions in cost, would expand the usefulness of these plates.
The present invention allows both increased resolution by use of laser pracessing, and reductions in cost 21.~186~
Haokqround of the Invention Flexography is a method of printing that is commonly used for high-volume runs. Flexography is employed for printing on a variety of substrates such as paper, paperboard stock, corrugated board, films, foils and laminates. Newspapers and grocery bags are prominent examples. Coarse surfaces and stretch films can be economically printed only by means of flexography. Flexographic printing plates are relief plates with image elements raised above open areas.
One type of flexographic printing plate resembles a transparent or translucent plastic doormat when it is ready for use. The plate is somewhat soft, and flexible enough to wrap around a printing cylinder, and durable enough to print over a million copies.
Such plates offer a number of advantages to the printer, based chiefly on their durability and the ease with which they can be made. Further ~.mprovements, to the degree of resolution (fineness of detail) which can be obtained as well as reductions in cost, would expand the usefulness of these plates.
The present invention allows both increased resolution by use of laser pracessing, and reductions in cost 21.~186~
- 3 through the elimination of the use of a negative to make the printing plate.
A typical flexographic printing plate as delivered by its manufacturer is a multilayered article made of a backing, an unexposed photocurable layer, a protective layer or slip film, and a cover sheet. The backing lends support to the plate. It is typically a plastic sheet about 5 mils or so thick, which may be transparent or opaque. The photocurable layer maybe anywhere from about 25-275 mils thick, and can be formulated from any of a wide variety of known photopolymers, initiators, reactive diluents, fillers, etc. The slip film is a thin (about 0.1 -1.0 mils) sheet which is transparent to W light that protects the photopolymer from dust and increases its ease of handling. The cover sheet is a heavy, protective layer, typically polyester, plastic or paper.
In normal use, the printer will peel the cover sheet off the printing plate, and place a negative on top of the slip film. The plate and negative will then be subjected to flood-exposure by W light through the negative. The areas exposed to the light cure, or harden, and the unexposed areas are removed (developed). Typical methods of development include washing with various solvents or water, often with a brush. Other possibilities for development include use of an air knife or heat plus a blotter.
Exposure of the printing plate is usually carried out by application of a vacuum to ensure good contact between the negative and the plate. Any air gap will cause deterioration of the image. Similarly, any foreign material, such as dirt and dust between the
A typical flexographic printing plate as delivered by its manufacturer is a multilayered article made of a backing, an unexposed photocurable layer, a protective layer or slip film, and a cover sheet. The backing lends support to the plate. It is typically a plastic sheet about 5 mils or so thick, which may be transparent or opaque. The photocurable layer maybe anywhere from about 25-275 mils thick, and can be formulated from any of a wide variety of known photopolymers, initiators, reactive diluents, fillers, etc. The slip film is a thin (about 0.1 -1.0 mils) sheet which is transparent to W light that protects the photopolymer from dust and increases its ease of handling. The cover sheet is a heavy, protective layer, typically polyester, plastic or paper.
In normal use, the printer will peel the cover sheet off the printing plate, and place a negative on top of the slip film. The plate and negative will then be subjected to flood-exposure by W light through the negative. The areas exposed to the light cure, or harden, and the unexposed areas are removed (developed). Typical methods of development include washing with various solvents or water, often with a brush. Other possibilities for development include use of an air knife or heat plus a blotter.
Exposure of the printing plate is usually carried out by application of a vacuum to ensure good contact between the negative and the plate. Any air gap will cause deterioration of the image. Similarly, any foreign material, such as dirt and dust between the
- 4 -negative and the plate results in loss of image quality.
Even though the slip films are thin and made from transparent materials, they still cause some light scattering and do somewhat limit the resolution which can be obtained from a given image. If the slip film were eliminated, finer and more intricate images could be obtained.
Finer resolution would be particularly desirable for the reproduction of elaborate writing as in the case of Japanese characters, and for photographic images.
A negative can be a costly expense item. For one thing, any negative which is used for printing must be perfect. Any minor flaw will be carried through onto each printed item. As a consequence, effort must be expended to ensure that the negative is precisely made. In addition, the negative is usually made with silver halide compounds which are costly and which are also the source of environmental concerns upon disposal.
Given these considerations, it is clear that any process which would eliminate the use of the negative, or reduce the light scattering effects and other exposure limitations of the slip films, would yield significant advantages in terms of cost, environmental impact, convenience, and image quality over the present methods.
The inventors have found a way to obtain these:
advantages by using a laser guided by an image stored in an electronic data file to create an in situ negative on a modified slip film, and then exposing and developing the printing plate in the usual manner.
As a result, the printer need not rely on the use of
Even though the slip films are thin and made from transparent materials, they still cause some light scattering and do somewhat limit the resolution which can be obtained from a given image. If the slip film were eliminated, finer and more intricate images could be obtained.
Finer resolution would be particularly desirable for the reproduction of elaborate writing as in the case of Japanese characters, and for photographic images.
A negative can be a costly expense item. For one thing, any negative which is used for printing must be perfect. Any minor flaw will be carried through onto each printed item. As a consequence, effort must be expended to ensure that the negative is precisely made. In addition, the negative is usually made with silver halide compounds which are costly and which are also the source of environmental concerns upon disposal.
Given these considerations, it is clear that any process which would eliminate the use of the negative, or reduce the light scattering effects and other exposure limitations of the slip films, would yield significant advantages in terms of cost, environmental impact, convenience, and image quality over the present methods.
The inventors have found a way to obtain these:
advantages by using a laser guided by an image stored in an electronic data file to create an in situ negative on a modified slip film, and then exposing and developing the printing plate in the usual manner.
As a result, the printer need not rely on the use of
- 5 -negatives and all their supporting equipment, and can rely instead on a scanned and stored image. Such images can be readily altered for different purposes, thus adding to the printer's convenience and flexibility. In addition, this method is compatible with the current developing and printing equipment, so expensive alterations to the other equipment are not required.
Laser engraving of various materials, such as wood and metal, is well known. Laser engraving of cured hard rubber or lithographic plates is also known. If this procedure were applied to a flexographic printing plate, the plate would first be exposed to UV light without an image. Then the laser would be used to engrave an image on the hardened plate. This has been attempted, but found to be too slow to be commercially competitive. Flexographic printing plates require a high relief (30-40 mil high letters) which take a long time to engrave.
Direct exposure of a photopolymer using a laser is also known. This procedure use a precisely guided laser to replace the UV flood lamps which are normally used to expose the plate. United States Patent 4,248,959, issued to Jeffers et al. February 3, 1981;
relates to the direct exposure of a photosensitive polymer plate using a laser guided by a computer-generated image. The disclosed method is not suitable for the development of flexographic printing plates, again because the thickness of the plate hampers the.
cure. Again, the process is too slow to be commercially competitive.
Other efforts have focussed on generating an image directly in contact with a photocurable layer.
United States Patent 5,015,553 issued to Grandmont et 2~.21~6 _ 6 _ al. May 14, 1991 relates to a method of making a UV
photoresist for a printed circuit board, using a computer-assisted design (CAD) driven photoplotter which selectively exposes a photographic imaging layer without affecting the underlying UV sensitive photoresist. The image layer is then chemically developed on the board and used as an situ mask for the underlying UV resist during exposure to UV light.
After the exposure, the image layer is peeled off to allow conventional processing of the resist. The process requires at least two development steps for the entire plate, and also requires the use of a peelable cover sheet interposed between the image layer and the photocurable layer.
Laser ablation of polymers from relatively insensitive substrates is known. United States Patent 4,020,762 issued to Peterson May 3, 1977 relates to a method of making a sensitized aluminum printing plate for offset lithography. An aluminum sheet was coated with a mixture of finely divided carbon, nitro-cellulose, a non-oxidizing alkyd resin, a diazo sensitizer, cellulose acetate, butylacetate, xylene and ethyl cellosolve. The coating was at least partially etched with a YAG laser. It is not clear whether all the coating was removed from the aluminum substrate although the text alludes to this result.
The patentee discloses that the etched areas became sensitive to UV light, and that the etched areas, after exposure to UV light and development, accepted ink, while the areas which were not etched accepted water. No quantitative results are presented. There is no indication that the liquid coating in the reference would be usable as a flexographic printing plate. There is no indication that the laser ablation was precise enough to allow removal of a polymer layer to uncover a photosensitive polymer layer directly beneath.
Lasers have also been used to physically transfer small amounts of polymer from one layer of a multilayer article to another. United States Patent 5,156,938 issued to Foley et al. October 30, 1992, relates to a method of laser-induced ablative transfer imaging suitable for the production of masks (negatives) for the graphic arts and printed circuit industries. In this process, a laser-sensitive material is physically displaced from a donor layer of a multilayer structure to a receptor layer.
This is described as an ablative transfer because some of the materials from the donor layer are ablated while other materials are deposited on the receptor layer.
The inventors have discovered that if a slip film, of the type already in use with flexographic plates, is modified with a strong UV absorber, a laser can be used to engrave the slip film instead of the photopolymer. The slip film, then, effectively becomes a negative that is created in situ. There is no need to separately manufacture a negative, or to eventually dispose of silver halide. Also, the light scattering effects of the slip film are eliminated, thereby increasing resolution of the image.
Qbiects of the Invention It is therefore an object of the present invention to provide a method of making a printing plate which does not require the use of a photographic negative.
2121$6 _ _ Another object of this invention is to make a laser-imageable printing plate.
Yet another object of this invention is to provide a protective layer for a photocurable article that can be conveniently and accurately removed by laser ablation from the article.
The objects of this invention can be accomplished by providing a protective layer for a photocurable article comprising ~ a polymeric matrix and a dopant having a high extinction coefficient in the range of 300-400 nm, the layer responding to a threshold dosage of radiation at a selected wavelength by photoablation of the polymeric matrix and, preferably, photobleaching of the dopant. The layer is applied to a photosensitive article, and then a laser is employed to selectively remove the protective layer, exposing the photocurable composition underneath to subsequent exposure to UV light and cure. The cured plate then can be developed in the normal fashion.
Other objects and advantages of this invention will become apparent through the disclosure herein.
Detailed Description of the Invention The Ea»osure and Development Process The present invention includes a method of making laser imaged printing plate. First, a solid, uncured printing plate is modified with a UV absorber.
This is most conveniently done by adding a W absorber to the normally UV transparent slip film which is already adapted for use with the printing plate, and applying the same in the usual fashion to the surface 2121~6~
g -of the uncured printing plate. The printing plate with the modified slip~film can be stored for a time, or used immediately, as the printer's needs dictate.
When the printing plate is to be used, a laser is employed to selectively ablate, or remove, the slip film. The uncured plate is then flood-exposed to W
light in the usual fashion. The areas where the slip film was ablated will cure, or harden, upon exposure to the W light. The areas where the slip film was not ablated will remain uncured. The uncured areas can then be washed away in the normal development process.
This application is written in terms of the specific embodiment in which the invention was first applied, that is, flexographic printing plates. One of ordinary skill in the art will readily recognize that this invention is not limited to this embodiment.
For example, in this invention the slip film is used as a carrier for the W absorber. This is a matter of convenience, as the slip film was already available in the existing plates for use. Similarly, a W
transparent film which has been doped with a W
absorber and ablated by a laser operating at a selected wavelength could be used as the printing sleeve for gravure printing, or as an in situ mask for making photoresists.
The W Absorber One important aspect of the present invention is that the slip film, which would normally be transparent to W light in order to facilitate the imaging process, is modified with a W absorber. The presence of the W absorber makes a normally W
transparent slip film into highly W opaque barrier.
2121~~~
It is critical that the UV absorption be nearly complete, at least 97%, preferably more than 99.9%, and even more preferably 99.99%, so that substantially.
all the radiation from the Uv flood-exposure lamps will be blocked. The spectral range of the flood-exposure lamps used in most applications is 300-400 nm. Therefore the UV absorber typically should be active in this range. An alternative way of stating this is to say that the UV absorber must have a high extinction coefficient in the spectral output range of the developer lamps.
Benzophenone derivatives and strongly absorbing dyes are favored. The following materials have high extinction coefficients within the typical spectral range of developer lamps:
Uvinul D 49~" (2,2'-dihydroxy-4,4'-dimethoxy-benzophenone) available from BASF
Corp., Parsipanny, NJ;
Uvinul D 50'" (2,2',4,4'-tetrahydroxybenzophenone) available from BASF Corp., Parsipanny, NJ;
Uvinul N 539 (benzophenone cyanoacrylate) available from BASF Corps, Parsipanny, NJ;
4-(dimethylaminobenzophenone) available from Aldrich Chemical Company, Milwaukee, WI;
Tinuvin P~' (benzotriazole) available from Ciba-Geigy Corp., Hawthorne, NY;
Intrawite OBE" A dye Available from Crompton & Knowles Ltd, Reading, PA;
Intraplast Yellow 2GLN, a dye available from Crompton & Knowles;
4-phenylazophenol t"4-PAP") available from Aldrich.
The UV absorber must also exhibit a specific response to excitation by laser at an appropriate .
- 2~218fi~
wavelength: It must allow the ablation, of the slip film. Finally, the W absorber must be compatible with the slip film, and not exhibit significant migration from the slip film to the photocurable composition.
Preferred W-absorbers which have been found to have these characteristics are Uvinuh" D 49 and D 50 (BASF) and 4-phenylazophenol. These materials cause photoablation of a typical slip film upon exposure to a threshold power level (fluence) at the selected wavelength of 351 nm. Tn addition, they have the added advantage of photobleaching at 351 nm. The W
absorber is typically present in the film in amounts of about 1-20 PHR (parts per hundred, or 1/101-20/1f0 percent); preferably about 4-8 PHR when the slip film is 0.1 to 1.0 mils, preferably 0.3 to 0.5 mils.
The Slip Film As discussed above, the preferred vehicle for the W absorber in some embodiments of the present invention is the slip film, a thin, protective film used with a printing plate which is to be imaged.
These films are made of a wide variety of polymers which are compatible with the underlying photopolymer and easily removed during the development (wash) step.
When a negative is used, the slip film has to be transparent to the light used for curing. Since W
flood lamps normally provide the light for curing, the normal slip film is transparent in the range of 300-400 nm. Such films are well known in the photoprocessing field, and in principle, any such film may be modified by adding the W absorber of the present invention. Examples include polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, 21~1~6~
polycarbonates, polyesters, polyethylenes, cellulosic polymers, polyphenylene ethers, and polyethylene oxides. Cellulosics and polyamides are preferred.
The addition of the UV absorber may change the film's response to the laser used in the present invention.
For example, many films are not normally affected by exposure to laser radiation at 351 nm, but when Uvinul D 50 is added, these films become vulnerable to laser ablation, and useful in the present process.
The Photocurable Composition In principle, any of the known photocurable formulations can be used in the present invention.
However, it is particularly helpful if the type of photopolymer and initiator used are compatible with the laser or the wavelength selected for use in the process.
Photopolymer Of the photopolymers, those which are unaffected by laser radiation at the particular wavelength selected for the practice of the present invention are particularly useful. Of these, polyurethanes, including acrylate golyurethanes, acid-modified acrylate polyurethanes, amine-modified polyurethanes, rubbers, including acrylonitrile rubbers, and di- and triblock copolymers such as those made from styrene-isoprene and styrene-butadiene may be mentioned. The amine-modified acrylate polyurethanes and styrene-isoprene or styrene-butadiene di- and triblock copolymers are preferred. An uncured printing plate made from such a photopolymer can withstand some exposure to the laser energy without incurring thermal damage. Thus the photopolymer and various additives 212.86 except the initiator should have a low absorbance at the laser's operating wavelength.
Initiator The initiator can also have a low absorbance at the wavelength of the laser selected for use in the present invention. However, if the initiator is activated in response to the selected wavelength, cure of the photopolymer will begin during the ablation step, without damage to the photopolymer, before flood-exposure by the UV lamps. Use of the appropriate initiator can, therefore, speed processing of the plate and help insure a faster, more uniform cure.
Photoinitiators for the photocurable composition include the benzoin alkyl ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. Another class of photoinitiators are the dialkoxyacetophenones exemplified by 2,2-dimethoxy-2-phenylacetophenone, i.e., Irgacure~ 651 (available from Ciba-Geigy, Hawthorne, NY); and 2,2-diethoxy-2-phenylacetophenone.
Still another class of photoinitiators are the aldehyde and ketone carbonyl compounds having at least one aromatic nucleus attached directly to the carboxyl group. These photoinitiators include, but are not limited to, benzophenone, acetophenone, o-methoxybenzophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanophenone, alpha-phenyl-butyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone,4'-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, alpha-tetralone, 9-acetylphenanthrene, 212~86~
r"\ -2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindone, 9-fluorenone, 1-indanone, 1,3,5-triacetylbenzene, thioxanthen-9-one, xanthene-9-one, 7-H-bent[de]-anthracene-7-one, 1-naphthaldehyde, 4,4'-bis(dimethylamino)-benzophenone, fluorene-9-one, 1'-acetonaphthone, 2'-acetonaphthone, 2,3-butanedione, acetonaphthene, benz[a]anthracene 7.12 dione, etc. Phosphines such as triphenylphosphine and tri-o-tolylphosphine are also operable herein as photoinitiators.
Benzophenone-based initiators are preferred. An example that is commercially available is Irgacure 651.
The Lsser A laser is employed to precisely remove the slip film exposing the photopolymer underneath to subsequent flood exposure and cure. The wavelength and power of the laser should be such that the laser treatment can ablate the slip film without damage to the photopolymer layer just beneath. Excimer lasers which operate in a pulse mode having a wavelength of 350 ~ 50 nm, preferably about 351 nm are usable. The preferred dosage level is 1-5 Joules per cm2 (J/cm2).
The following examples illustrate the present invention without limiting it, or the claims which follow.
~ple 1 Preparation of Uvinul D 50 Modified Polyamide 8~p Film For 1COR Fiexoaraghia Plates In this example, the slip film which would normally be used with a commercially available flexographic printing plate is modified by the addition of a W absorber so that. zero transmittance 22~~ss~
(as demonstrated by protection from cure upon exposure to UV flood lamps) is achieved.
A stock casting solution was prepared with the following formulation:
Isopropanol 45.6 parts Hexane 23.9 parts VM&P Naphthai 21.6 parts Macromelt 6900m2 8.3 parts Uvinul D 50 0.664 parts Footnote:
Aromatic solveat mixture available from Ashland Chemical Co., Coluabus, OH
Polyaer pellets available from Henkel Corp., Lagrange, IL
Films approximately 5 to 7 mils thick were hand cast on a clear Mylar"' backing sheet using a drawdown bar. Upon drying, the average film thickness was measured using a Ono Sokki micrometer to be around 0.3-0.5 mils.
The films were laminated onto a commercially available photopolymer composition to make a UV
absorber-modified printing plate analagous to the KOR~
printing plate available from W. R. Grace & Co.-Conn., Atlanta, Ga. The plates were exposed through a test negative using commercially available UV flood lamps.
Three different concentrations (4 PHR, 6 PHR and 8 PHR
based on percent solids), three levels of thicknesses (low, medium and high) and two exposure levels were employed for the study which is summarized in Table I.
Presence or absence of an image was an indication of the effectiveness of the UV absorber for blocking the incident UV radiation. For the 4 and 6 PHR loadings, an image was seen when the slip thickness was less than 0.4 mils, indicating a lower threshold concentration of D 50 to effectively block all UV
light. For 8 PHR loadings, 0.3-0.4 mils was seen to 2~.2~.8~
be sufficient to block all UV light as seen by an absence of an image. For all three concentrations, a thickness above 0.5-0.6 mils was effective.
The modified slip film was then laminated.onto a Flex Light KOR~ ("KOR") plate which was approximately 25 to 275 mils thick. The laminated plates were annealed at 75° F, and used for laser ablation trials, as shown in Examples 3-6.
2~~1$~
a .,, 1-i1-Ix N x x x x ~1 O
O a N N ,~,N x x x x D
M
a .~
-ri p~
S
O
m dl N N11f1!~f 1f1O 1~111 . . . . . . . .
0 0 ..to 0 0 0 0 ~1 t 1 1 I 1 1 t 1 d , ~
N .a N ~ N ~ to eno a ~
. . . . . . . .
0 0 .io 0 0 0 0 o m o b ~ ~ .i go E
o ~
. H
.. ~i Ira of E
m o c. o ~ne o ~n e o .
. o a .~r1 .1.~ r1 o p p a . .
v A
a ~
.w ao~
0' b .o a o a p N
wo ~ o caa~
o +
a~x 8 ''' If4.r N
M
ri 2~.2~.865 r...
Euample 2 Preparation of Uvinul D 50 Modified Cellulosia-Based Water-Wash slip Film for l~mine-Modified Palyurethane (AMPUI Aqueous-Developable Flesographia Plates In this Example, another type of slip film, a cellulose film adapted for use with a water-washable flexographic printing plate, is modified with a W
absorber. The concentration and thickness found in the previous Example were utilized to ensure the maximum UV absorption by the film.
A stock solution was prepared using the following formulation:
Isopropanol 50.2 parts Water 39.8 parts Klucel Ll 10.0 parts Uvinul D 50 0.8 parts Footnote:
Hydroxyproppl cellulose polymer pellets available frog llqualon, Inc., wil~iagtoa, D8 As before; films 5 to 7 mils thick were cast on a clear Mylarm backing sheet, dried and laminated onto a developmental amine-modified polyurethane flexo substrate. The plates were between 25 mils and 275 mils thick. Laser ablation and imaging was carried out on the modified plates as shown in Examples 3-6.
Example 3 Laser Ablation and Imaging Osing a solid-state sealed Coz Laser (10.6 nm) The commercially available photopolymer resin of Example 1 was formed into a sheet and laminated with 0.9 mil thick polyamide slip film containing 8 PHIL
212186:1 .- - 19 -Uvinul D 50 to make an experimental printing plate (KOR). The plates for this preliminary study were prepared using a hand cast slip film. Two different laser systems were employed for the ablative studies:
a sealed-COZ absorbing at 10.6 ~,m and a YAG at 1:06~~m.
The YAG laser was found to be essentially ineffective in causing any ablation. The power in the sealed-COZ
laser was varied from 8 watts to a high of 15 watts.
Digital image programming allowed ablation of a rectangular profile (1 cm x 2 cm) and also lettering.
Results from the ablative studies are summari2ed in Table II.
The presence or absence of the polyamide slip film was investigated by ATR-IR analysis. The ablated plate was then flood exposed with hot lamps for 6 minutes and developed in Solvit~, the usual development solvent for commercial purposes available from Polyfibron Division of W. R. Grace & Co.-Conn., Atlanta, GA, for 6 minutes. From Table II it is seen that the etch depth versus fluence (power) was not linear. The difference in etch depth between 8 to 10 Watts is barely more than the experimental error of 0.1 mils. At 12 Watts, the 0.5 mil slip film had been complete ablated, along with some of the underlying photopolymer. There was also a jump in the etch depth from 0.7 mils to 5.0 mils when the power is increased from 12 watts to 15 watts. As expected, only those rectangular profiles which show almost complete ablation of the slip film cured during subsequent flood exposure and development. However, even for those profiles, the surface was highly textured and O ~
0 0 >
.,~..., a ~
N ~ ~o~r a a ,a,~ a~a ar ro m ro O O O N N
d d dl d N
O O O ~ N
r r-- I
x x x a.a.
a ~ u roro ro ~ o ~
ro ~ ro d ~
a ~ ~
a b ~ 3 3 3 3 U
.~
''a N
~
a1 N N
H ~ s~
~ ::
a a ~ ~
a~
a Q' ~ 3 3 3 ~
~ ~
, 00w H ~ t0 i0rt vcvo ~ Q
~
'~f m~ ~. ~ ~ .~ ~ N
' ~ : N N N i.1S.1 fp ' t1~
3 ~ 3 .1 .~
rr ..
O ~ M d' mx w QI,N O
b p:~ o 0 a ~. ~ .-1c~ o ~
N
~
+ co o',~
.~' O.:rtf W
=~.;
'lic N tI1~0 00N
.
..' 2~21~6~
rough. Also, the resolution was poor for the letters.
Thus, it was seen that the basic idea of the laser-imaged printing plate was demonstrated, and that use of the COZ laser resulted in thermal ablation with a consequent loss of resolution.
Bsample 4 Laser ablation and imaging using Krypton Fluoride SlcrF) Euoimer Laser at 248 nm The experimental printing plates made according to Example 1 (KOR) and 2 (AMPU) above were imaged as in Example 3 using a krypton fluoride excimer laser controlled by digital imaging programming. The results are summarized in Table III.
The krypton fluoride excimer laser at 248 nm was found to be extremely effective in causing photoablation. Since most polymers including the polyamide of the slip film and the Kraton~' rubber of the photopolymer of Example 1 have very strong absorption at 248 nm, even small fluences (<0.5 J/cm2) caused ablation of the slip. The mechanism is believed to be mainly photoablation (i.e., chemical bond-breaking of the polyamide) and some thermal ablation~due to heat generation. Unfortunately, since the styrene-isoprene rubber used to make the photopolymer is also very strongly absorbing at this wavelength, some damage to the surface occurred, especially at higher fluences. Where thermal damage occurred, resolution was poor.
,__ , TABLE III
Laser Ablation of ROR and AMPU Using RrF Egcimer Laser (248 am) Tppe Fluence # of Image Comments J/cm2 Pulses ROR 0.4 l0 Yes Thermal Damage.
(Es.i) 40 Yes Poor resolution 70 Yes for all.
1.2 1 No 2 No
Laser engraving of various materials, such as wood and metal, is well known. Laser engraving of cured hard rubber or lithographic plates is also known. If this procedure were applied to a flexographic printing plate, the plate would first be exposed to UV light without an image. Then the laser would be used to engrave an image on the hardened plate. This has been attempted, but found to be too slow to be commercially competitive. Flexographic printing plates require a high relief (30-40 mil high letters) which take a long time to engrave.
Direct exposure of a photopolymer using a laser is also known. This procedure use a precisely guided laser to replace the UV flood lamps which are normally used to expose the plate. United States Patent 4,248,959, issued to Jeffers et al. February 3, 1981;
relates to the direct exposure of a photosensitive polymer plate using a laser guided by a computer-generated image. The disclosed method is not suitable for the development of flexographic printing plates, again because the thickness of the plate hampers the.
cure. Again, the process is too slow to be commercially competitive.
Other efforts have focussed on generating an image directly in contact with a photocurable layer.
United States Patent 5,015,553 issued to Grandmont et 2~.21~6 _ 6 _ al. May 14, 1991 relates to a method of making a UV
photoresist for a printed circuit board, using a computer-assisted design (CAD) driven photoplotter which selectively exposes a photographic imaging layer without affecting the underlying UV sensitive photoresist. The image layer is then chemically developed on the board and used as an situ mask for the underlying UV resist during exposure to UV light.
After the exposure, the image layer is peeled off to allow conventional processing of the resist. The process requires at least two development steps for the entire plate, and also requires the use of a peelable cover sheet interposed between the image layer and the photocurable layer.
Laser ablation of polymers from relatively insensitive substrates is known. United States Patent 4,020,762 issued to Peterson May 3, 1977 relates to a method of making a sensitized aluminum printing plate for offset lithography. An aluminum sheet was coated with a mixture of finely divided carbon, nitro-cellulose, a non-oxidizing alkyd resin, a diazo sensitizer, cellulose acetate, butylacetate, xylene and ethyl cellosolve. The coating was at least partially etched with a YAG laser. It is not clear whether all the coating was removed from the aluminum substrate although the text alludes to this result.
The patentee discloses that the etched areas became sensitive to UV light, and that the etched areas, after exposure to UV light and development, accepted ink, while the areas which were not etched accepted water. No quantitative results are presented. There is no indication that the liquid coating in the reference would be usable as a flexographic printing plate. There is no indication that the laser ablation was precise enough to allow removal of a polymer layer to uncover a photosensitive polymer layer directly beneath.
Lasers have also been used to physically transfer small amounts of polymer from one layer of a multilayer article to another. United States Patent 5,156,938 issued to Foley et al. October 30, 1992, relates to a method of laser-induced ablative transfer imaging suitable for the production of masks (negatives) for the graphic arts and printed circuit industries. In this process, a laser-sensitive material is physically displaced from a donor layer of a multilayer structure to a receptor layer.
This is described as an ablative transfer because some of the materials from the donor layer are ablated while other materials are deposited on the receptor layer.
The inventors have discovered that if a slip film, of the type already in use with flexographic plates, is modified with a strong UV absorber, a laser can be used to engrave the slip film instead of the photopolymer. The slip film, then, effectively becomes a negative that is created in situ. There is no need to separately manufacture a negative, or to eventually dispose of silver halide. Also, the light scattering effects of the slip film are eliminated, thereby increasing resolution of the image.
Qbiects of the Invention It is therefore an object of the present invention to provide a method of making a printing plate which does not require the use of a photographic negative.
2121$6 _ _ Another object of this invention is to make a laser-imageable printing plate.
Yet another object of this invention is to provide a protective layer for a photocurable article that can be conveniently and accurately removed by laser ablation from the article.
The objects of this invention can be accomplished by providing a protective layer for a photocurable article comprising ~ a polymeric matrix and a dopant having a high extinction coefficient in the range of 300-400 nm, the layer responding to a threshold dosage of radiation at a selected wavelength by photoablation of the polymeric matrix and, preferably, photobleaching of the dopant. The layer is applied to a photosensitive article, and then a laser is employed to selectively remove the protective layer, exposing the photocurable composition underneath to subsequent exposure to UV light and cure. The cured plate then can be developed in the normal fashion.
Other objects and advantages of this invention will become apparent through the disclosure herein.
Detailed Description of the Invention The Ea»osure and Development Process The present invention includes a method of making laser imaged printing plate. First, a solid, uncured printing plate is modified with a UV absorber.
This is most conveniently done by adding a W absorber to the normally UV transparent slip film which is already adapted for use with the printing plate, and applying the same in the usual fashion to the surface 2121~6~
g -of the uncured printing plate. The printing plate with the modified slip~film can be stored for a time, or used immediately, as the printer's needs dictate.
When the printing plate is to be used, a laser is employed to selectively ablate, or remove, the slip film. The uncured plate is then flood-exposed to W
light in the usual fashion. The areas where the slip film was ablated will cure, or harden, upon exposure to the W light. The areas where the slip film was not ablated will remain uncured. The uncured areas can then be washed away in the normal development process.
This application is written in terms of the specific embodiment in which the invention was first applied, that is, flexographic printing plates. One of ordinary skill in the art will readily recognize that this invention is not limited to this embodiment.
For example, in this invention the slip film is used as a carrier for the W absorber. This is a matter of convenience, as the slip film was already available in the existing plates for use. Similarly, a W
transparent film which has been doped with a W
absorber and ablated by a laser operating at a selected wavelength could be used as the printing sleeve for gravure printing, or as an in situ mask for making photoresists.
The W Absorber One important aspect of the present invention is that the slip film, which would normally be transparent to W light in order to facilitate the imaging process, is modified with a W absorber. The presence of the W absorber makes a normally W
transparent slip film into highly W opaque barrier.
2121~~~
It is critical that the UV absorption be nearly complete, at least 97%, preferably more than 99.9%, and even more preferably 99.99%, so that substantially.
all the radiation from the Uv flood-exposure lamps will be blocked. The spectral range of the flood-exposure lamps used in most applications is 300-400 nm. Therefore the UV absorber typically should be active in this range. An alternative way of stating this is to say that the UV absorber must have a high extinction coefficient in the spectral output range of the developer lamps.
Benzophenone derivatives and strongly absorbing dyes are favored. The following materials have high extinction coefficients within the typical spectral range of developer lamps:
Uvinul D 49~" (2,2'-dihydroxy-4,4'-dimethoxy-benzophenone) available from BASF
Corp., Parsipanny, NJ;
Uvinul D 50'" (2,2',4,4'-tetrahydroxybenzophenone) available from BASF Corp., Parsipanny, NJ;
Uvinul N 539 (benzophenone cyanoacrylate) available from BASF Corps, Parsipanny, NJ;
4-(dimethylaminobenzophenone) available from Aldrich Chemical Company, Milwaukee, WI;
Tinuvin P~' (benzotriazole) available from Ciba-Geigy Corp., Hawthorne, NY;
Intrawite OBE" A dye Available from Crompton & Knowles Ltd, Reading, PA;
Intraplast Yellow 2GLN, a dye available from Crompton & Knowles;
4-phenylazophenol t"4-PAP") available from Aldrich.
The UV absorber must also exhibit a specific response to excitation by laser at an appropriate .
- 2~218fi~
wavelength: It must allow the ablation, of the slip film. Finally, the W absorber must be compatible with the slip film, and not exhibit significant migration from the slip film to the photocurable composition.
Preferred W-absorbers which have been found to have these characteristics are Uvinuh" D 49 and D 50 (BASF) and 4-phenylazophenol. These materials cause photoablation of a typical slip film upon exposure to a threshold power level (fluence) at the selected wavelength of 351 nm. Tn addition, they have the added advantage of photobleaching at 351 nm. The W
absorber is typically present in the film in amounts of about 1-20 PHR (parts per hundred, or 1/101-20/1f0 percent); preferably about 4-8 PHR when the slip film is 0.1 to 1.0 mils, preferably 0.3 to 0.5 mils.
The Slip Film As discussed above, the preferred vehicle for the W absorber in some embodiments of the present invention is the slip film, a thin, protective film used with a printing plate which is to be imaged.
These films are made of a wide variety of polymers which are compatible with the underlying photopolymer and easily removed during the development (wash) step.
When a negative is used, the slip film has to be transparent to the light used for curing. Since W
flood lamps normally provide the light for curing, the normal slip film is transparent in the range of 300-400 nm. Such films are well known in the photoprocessing field, and in principle, any such film may be modified by adding the W absorber of the present invention. Examples include polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, 21~1~6~
polycarbonates, polyesters, polyethylenes, cellulosic polymers, polyphenylene ethers, and polyethylene oxides. Cellulosics and polyamides are preferred.
The addition of the UV absorber may change the film's response to the laser used in the present invention.
For example, many films are not normally affected by exposure to laser radiation at 351 nm, but when Uvinul D 50 is added, these films become vulnerable to laser ablation, and useful in the present process.
The Photocurable Composition In principle, any of the known photocurable formulations can be used in the present invention.
However, it is particularly helpful if the type of photopolymer and initiator used are compatible with the laser or the wavelength selected for use in the process.
Photopolymer Of the photopolymers, those which are unaffected by laser radiation at the particular wavelength selected for the practice of the present invention are particularly useful. Of these, polyurethanes, including acrylate golyurethanes, acid-modified acrylate polyurethanes, amine-modified polyurethanes, rubbers, including acrylonitrile rubbers, and di- and triblock copolymers such as those made from styrene-isoprene and styrene-butadiene may be mentioned. The amine-modified acrylate polyurethanes and styrene-isoprene or styrene-butadiene di- and triblock copolymers are preferred. An uncured printing plate made from such a photopolymer can withstand some exposure to the laser energy without incurring thermal damage. Thus the photopolymer and various additives 212.86 except the initiator should have a low absorbance at the laser's operating wavelength.
Initiator The initiator can also have a low absorbance at the wavelength of the laser selected for use in the present invention. However, if the initiator is activated in response to the selected wavelength, cure of the photopolymer will begin during the ablation step, without damage to the photopolymer, before flood-exposure by the UV lamps. Use of the appropriate initiator can, therefore, speed processing of the plate and help insure a faster, more uniform cure.
Photoinitiators for the photocurable composition include the benzoin alkyl ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. Another class of photoinitiators are the dialkoxyacetophenones exemplified by 2,2-dimethoxy-2-phenylacetophenone, i.e., Irgacure~ 651 (available from Ciba-Geigy, Hawthorne, NY); and 2,2-diethoxy-2-phenylacetophenone.
Still another class of photoinitiators are the aldehyde and ketone carbonyl compounds having at least one aromatic nucleus attached directly to the carboxyl group. These photoinitiators include, but are not limited to, benzophenone, acetophenone, o-methoxybenzophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanophenone, alpha-phenyl-butyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone,4'-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, alpha-tetralone, 9-acetylphenanthrene, 212~86~
r"\ -2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindone, 9-fluorenone, 1-indanone, 1,3,5-triacetylbenzene, thioxanthen-9-one, xanthene-9-one, 7-H-bent[de]-anthracene-7-one, 1-naphthaldehyde, 4,4'-bis(dimethylamino)-benzophenone, fluorene-9-one, 1'-acetonaphthone, 2'-acetonaphthone, 2,3-butanedione, acetonaphthene, benz[a]anthracene 7.12 dione, etc. Phosphines such as triphenylphosphine and tri-o-tolylphosphine are also operable herein as photoinitiators.
Benzophenone-based initiators are preferred. An example that is commercially available is Irgacure 651.
The Lsser A laser is employed to precisely remove the slip film exposing the photopolymer underneath to subsequent flood exposure and cure. The wavelength and power of the laser should be such that the laser treatment can ablate the slip film without damage to the photopolymer layer just beneath. Excimer lasers which operate in a pulse mode having a wavelength of 350 ~ 50 nm, preferably about 351 nm are usable. The preferred dosage level is 1-5 Joules per cm2 (J/cm2).
The following examples illustrate the present invention without limiting it, or the claims which follow.
~ple 1 Preparation of Uvinul D 50 Modified Polyamide 8~p Film For 1COR Fiexoaraghia Plates In this example, the slip film which would normally be used with a commercially available flexographic printing plate is modified by the addition of a W absorber so that. zero transmittance 22~~ss~
(as demonstrated by protection from cure upon exposure to UV flood lamps) is achieved.
A stock casting solution was prepared with the following formulation:
Isopropanol 45.6 parts Hexane 23.9 parts VM&P Naphthai 21.6 parts Macromelt 6900m2 8.3 parts Uvinul D 50 0.664 parts Footnote:
Aromatic solveat mixture available from Ashland Chemical Co., Coluabus, OH
Polyaer pellets available from Henkel Corp., Lagrange, IL
Films approximately 5 to 7 mils thick were hand cast on a clear Mylar"' backing sheet using a drawdown bar. Upon drying, the average film thickness was measured using a Ono Sokki micrometer to be around 0.3-0.5 mils.
The films were laminated onto a commercially available photopolymer composition to make a UV
absorber-modified printing plate analagous to the KOR~
printing plate available from W. R. Grace & Co.-Conn., Atlanta, Ga. The plates were exposed through a test negative using commercially available UV flood lamps.
Three different concentrations (4 PHR, 6 PHR and 8 PHR
based on percent solids), three levels of thicknesses (low, medium and high) and two exposure levels were employed for the study which is summarized in Table I.
Presence or absence of an image was an indication of the effectiveness of the UV absorber for blocking the incident UV radiation. For the 4 and 6 PHR loadings, an image was seen when the slip thickness was less than 0.4 mils, indicating a lower threshold concentration of D 50 to effectively block all UV
light. For 8 PHR loadings, 0.3-0.4 mils was seen to 2~.2~.8~
be sufficient to block all UV light as seen by an absence of an image. For all three concentrations, a thickness above 0.5-0.6 mils was effective.
The modified slip film was then laminated.onto a Flex Light KOR~ ("KOR") plate which was approximately 25 to 275 mils thick. The laminated plates were annealed at 75° F, and used for laser ablation trials, as shown in Examples 3-6.
2~~1$~
a .,, 1-i1-Ix N x x x x ~1 O
O a N N ,~,N x x x x D
M
a .~
-ri p~
S
O
m dl N N11f1!~f 1f1O 1~111 . . . . . . . .
0 0 ..to 0 0 0 0 ~1 t 1 1 I 1 1 t 1 d , ~
N .a N ~ N ~ to eno a ~
. . . . . . . .
0 0 .io 0 0 0 0 o m o b ~ ~ .i go E
o ~
. H
.. ~i Ira of E
m o c. o ~ne o ~n e o .
. o a .~r1 .1.~ r1 o p p a . .
v A
a ~
.w ao~
0' b .o a o a p N
wo ~ o caa~
o +
a~x 8 ''' If4.r N
M
ri 2~.2~.865 r...
Euample 2 Preparation of Uvinul D 50 Modified Cellulosia-Based Water-Wash slip Film for l~mine-Modified Palyurethane (AMPUI Aqueous-Developable Flesographia Plates In this Example, another type of slip film, a cellulose film adapted for use with a water-washable flexographic printing plate, is modified with a W
absorber. The concentration and thickness found in the previous Example were utilized to ensure the maximum UV absorption by the film.
A stock solution was prepared using the following formulation:
Isopropanol 50.2 parts Water 39.8 parts Klucel Ll 10.0 parts Uvinul D 50 0.8 parts Footnote:
Hydroxyproppl cellulose polymer pellets available frog llqualon, Inc., wil~iagtoa, D8 As before; films 5 to 7 mils thick were cast on a clear Mylarm backing sheet, dried and laminated onto a developmental amine-modified polyurethane flexo substrate. The plates were between 25 mils and 275 mils thick. Laser ablation and imaging was carried out on the modified plates as shown in Examples 3-6.
Example 3 Laser Ablation and Imaging Osing a solid-state sealed Coz Laser (10.6 nm) The commercially available photopolymer resin of Example 1 was formed into a sheet and laminated with 0.9 mil thick polyamide slip film containing 8 PHIL
212186:1 .- - 19 -Uvinul D 50 to make an experimental printing plate (KOR). The plates for this preliminary study were prepared using a hand cast slip film. Two different laser systems were employed for the ablative studies:
a sealed-COZ absorbing at 10.6 ~,m and a YAG at 1:06~~m.
The YAG laser was found to be essentially ineffective in causing any ablation. The power in the sealed-COZ
laser was varied from 8 watts to a high of 15 watts.
Digital image programming allowed ablation of a rectangular profile (1 cm x 2 cm) and also lettering.
Results from the ablative studies are summari2ed in Table II.
The presence or absence of the polyamide slip film was investigated by ATR-IR analysis. The ablated plate was then flood exposed with hot lamps for 6 minutes and developed in Solvit~, the usual development solvent for commercial purposes available from Polyfibron Division of W. R. Grace & Co.-Conn., Atlanta, GA, for 6 minutes. From Table II it is seen that the etch depth versus fluence (power) was not linear. The difference in etch depth between 8 to 10 Watts is barely more than the experimental error of 0.1 mils. At 12 Watts, the 0.5 mil slip film had been complete ablated, along with some of the underlying photopolymer. There was also a jump in the etch depth from 0.7 mils to 5.0 mils when the power is increased from 12 watts to 15 watts. As expected, only those rectangular profiles which show almost complete ablation of the slip film cured during subsequent flood exposure and development. However, even for those profiles, the surface was highly textured and O ~
0 0 >
.,~..., a ~
N ~ ~o~r a a ,a,~ a~a ar ro m ro O O O N N
d d dl d N
O O O ~ N
r r-- I
x x x a.a.
a ~ u roro ro ~ o ~
ro ~ ro d ~
a ~ ~
a b ~ 3 3 3 3 U
.~
''a N
~
a1 N N
H ~ s~
~ ::
a a ~ ~
a~
a Q' ~ 3 3 3 ~
~ ~
, 00w H ~ t0 i0rt vcvo ~ Q
~
'~f m~ ~. ~ ~ .~ ~ N
' ~ : N N N i.1S.1 fp ' t1~
3 ~ 3 .1 .~
rr ..
O ~ M d' mx w QI,N O
b p:~ o 0 a ~. ~ .-1c~ o ~
N
~
+ co o',~
.~' O.:rtf W
=~.;
'lic N tI1~0 00N
.
..' 2~21~6~
rough. Also, the resolution was poor for the letters.
Thus, it was seen that the basic idea of the laser-imaged printing plate was demonstrated, and that use of the COZ laser resulted in thermal ablation with a consequent loss of resolution.
Bsample 4 Laser ablation and imaging using Krypton Fluoride SlcrF) Euoimer Laser at 248 nm The experimental printing plates made according to Example 1 (KOR) and 2 (AMPU) above were imaged as in Example 3 using a krypton fluoride excimer laser controlled by digital imaging programming. The results are summarized in Table III.
The krypton fluoride excimer laser at 248 nm was found to be extremely effective in causing photoablation. Since most polymers including the polyamide of the slip film and the Kraton~' rubber of the photopolymer of Example 1 have very strong absorption at 248 nm, even small fluences (<0.5 J/cm2) caused ablation of the slip. The mechanism is believed to be mainly photoablation (i.e., chemical bond-breaking of the polyamide) and some thermal ablation~due to heat generation. Unfortunately, since the styrene-isoprene rubber used to make the photopolymer is also very strongly absorbing at this wavelength, some damage to the surface occurred, especially at higher fluences. Where thermal damage occurred, resolution was poor.
,__ , TABLE III
Laser Ablation of ROR and AMPU Using RrF Egcimer Laser (248 am) Tppe Fluence # of Image Comments J/cm2 Pulses ROR 0.4 l0 Yes Thermal Damage.
(Es.i) 40 Yes Poor resolution 70 Yes for all.
1.2 1 No 2 No
6 Yes Swell due to 8 Yes incomplete cure.
Poor resolution.
AMPU 0.4 10 Yes Thermal Damage.
(Es.2) 40 Yes Poor resalution 20 Yes 1.2 1 No Incomplete Ablation 2 No Incomplete Ablation 6 Yes 8 Yes Thermal Damage.
Poor resolution -,. = 2 3 -Bxampl~ 5 optimization of Fluenoas for 35i nm genon Fluoride S8eF1 B'scimer Laser Laser ablation and imaging studies and optimization of fluences necessary for ablation was carried out as before on KOR (Ex. 1) and AMPU (Ex. 2). Similar results were seen for both types of plates. The consolidated results are summarized in Table IV.
Most polymers do not absorb at 351 nm. However, the modified slip films (both the solvent-based polyamide and the aqueous-based cellulosic polymers) were very sensitive to the excimer laser at 351 nm due to the high extinction coefficient of D 50 at this wavelength. A combination of photobleaching (destruction of D 50 molecules) and photoablative (transfer of the energy absorbed by D 50 to the polymer causing bond breaking in the polymer) effects were seen.
The modified slip is partially ablated at lower doses (c1 J/cm2) resulting in either no cure (and hence no image) or incomplete cure (and hence poor image and resolution).
A complete ablation was seen at higher doses (>1.5 J/cm2).
There was no damage to the plate surface. Subsequent flood exposure and development gave a very sharp image of the ablated area with good resolution.
21~186~
TABLE ID
Optimization of Flusnoss for Laser Imaging using Benon-Fluoride 8saimer Laser at 351 nm for ROR and AMPU
Fluence # of Image - Comments J/cm2 Pulses 0.14 50 No Fluenae urns below the 100 No threshold and hence 20o No incomplete ablation 0.~ 5 No Below threshold 10 No fluenoe. Did not 15 N0 Cure.
30 No 0.9 i No Not enough ablation.
2 No Not enough ablation.
6 Yes Incomplete cure, l0 Yes image swelled in solvent. Poor reso-lution.
l0 1.6 1 No Not enough ablation.
3 Yas Good resolution, good I
5 Yss image. No damage assn to the surface.
Ex~g'le 6 Imaging studies on IcOR Laminated with D 5o Modified R" p and Print Test pith the Imaced Plate Imaging of D 50 modified slip on KOR was carried out using a xenon fluoride excimer laser lasing at 351 nm.
Imaging of lettering was achieved using a CAD file. The following intensities and number of pulses were utilized:
Fluenae # of Pulses J / om2 1.5 2.0 6 3.1 4 X121.86 The ablated/imaged plates were flood exposed under hot lamps for 5 1/2 minutes and washed in Solvit~ for 6 minutes to give an image with 20-25 mils relief.
Microscopic examination confirmed that the image quality for all fluences was good, giving sharp profiles.
However, the edges were rounded due to insufficient doses in those areas. There was no indication of surface thermal damage and the plate surface was smooth and even in all cases.
Example 7 Laser Ablation and Imaging on a slip Modified with 4PHR D 50 and 4PHR 4-phenyiazo~henol (4-PAPD
In this Example, a mixture of UV absorbers was used with a slip film similar to that of Example 1. A casting solution for the modified slip was prepared using the following formulation:
Isopropanol 45.6 parts Hexane 23.9 parts VM&P Naphtha 21.6 parts Macromelt 6900m* 8.3 parts Uvinul D 50 0.332 parts 4-phenylazophenol 0.332 parts A film 5 to 7 mils thick was cast on a clear mylar backing sheet. Upon drying, the film had.average thickness of 0.3-0.5 mils. The modified slip film was then laminated onto a KOR plate which was about 67 mils thick. Laser ablation and imaging was carried out as in Example 6. Once again, the image quality was excellent for all fluences.
21.21.~~~
Example 8 The printing plates of Examples 6 and '7 were tested for print quality on glossy paper using blue aqueous ink.
The ink laydown was good. The letters printed were sharp and undistorted.
Poor resolution.
AMPU 0.4 10 Yes Thermal Damage.
(Es.2) 40 Yes Poor resalution 20 Yes 1.2 1 No Incomplete Ablation 2 No Incomplete Ablation 6 Yes 8 Yes Thermal Damage.
Poor resolution -,. = 2 3 -Bxampl~ 5 optimization of Fluenoas for 35i nm genon Fluoride S8eF1 B'scimer Laser Laser ablation and imaging studies and optimization of fluences necessary for ablation was carried out as before on KOR (Ex. 1) and AMPU (Ex. 2). Similar results were seen for both types of plates. The consolidated results are summarized in Table IV.
Most polymers do not absorb at 351 nm. However, the modified slip films (both the solvent-based polyamide and the aqueous-based cellulosic polymers) were very sensitive to the excimer laser at 351 nm due to the high extinction coefficient of D 50 at this wavelength. A combination of photobleaching (destruction of D 50 molecules) and photoablative (transfer of the energy absorbed by D 50 to the polymer causing bond breaking in the polymer) effects were seen.
The modified slip is partially ablated at lower doses (c1 J/cm2) resulting in either no cure (and hence no image) or incomplete cure (and hence poor image and resolution).
A complete ablation was seen at higher doses (>1.5 J/cm2).
There was no damage to the plate surface. Subsequent flood exposure and development gave a very sharp image of the ablated area with good resolution.
21~186~
TABLE ID
Optimization of Flusnoss for Laser Imaging using Benon-Fluoride 8saimer Laser at 351 nm for ROR and AMPU
Fluence # of Image - Comments J/cm2 Pulses 0.14 50 No Fluenae urns below the 100 No threshold and hence 20o No incomplete ablation 0.~ 5 No Below threshold 10 No fluenoe. Did not 15 N0 Cure.
30 No 0.9 i No Not enough ablation.
2 No Not enough ablation.
6 Yes Incomplete cure, l0 Yes image swelled in solvent. Poor reso-lution.
l0 1.6 1 No Not enough ablation.
3 Yas Good resolution, good I
5 Yss image. No damage assn to the surface.
Ex~g'le 6 Imaging studies on IcOR Laminated with D 5o Modified R" p and Print Test pith the Imaced Plate Imaging of D 50 modified slip on KOR was carried out using a xenon fluoride excimer laser lasing at 351 nm.
Imaging of lettering was achieved using a CAD file. The following intensities and number of pulses were utilized:
Fluenae # of Pulses J / om2 1.5 2.0 6 3.1 4 X121.86 The ablated/imaged plates were flood exposed under hot lamps for 5 1/2 minutes and washed in Solvit~ for 6 minutes to give an image with 20-25 mils relief.
Microscopic examination confirmed that the image quality for all fluences was good, giving sharp profiles.
However, the edges were rounded due to insufficient doses in those areas. There was no indication of surface thermal damage and the plate surface was smooth and even in all cases.
Example 7 Laser Ablation and Imaging on a slip Modified with 4PHR D 50 and 4PHR 4-phenyiazo~henol (4-PAPD
In this Example, a mixture of UV absorbers was used with a slip film similar to that of Example 1. A casting solution for the modified slip was prepared using the following formulation:
Isopropanol 45.6 parts Hexane 23.9 parts VM&P Naphtha 21.6 parts Macromelt 6900m* 8.3 parts Uvinul D 50 0.332 parts 4-phenylazophenol 0.332 parts A film 5 to 7 mils thick was cast on a clear mylar backing sheet. Upon drying, the film had.average thickness of 0.3-0.5 mils. The modified slip film was then laminated onto a KOR plate which was about 67 mils thick. Laser ablation and imaging was carried out as in Example 6. Once again, the image quality was excellent for all fluences.
21.21.~~~
Example 8 The printing plates of Examples 6 and '7 were tested for print quality on glossy paper using blue aqueous ink.
The ink laydown was good. The letters printed were sharp and undistorted.
Claims (52)
1. ~A photosensitive printing element comprising:
(a) a backing layer;
(b) at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) at least one ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said at least one ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite at least one photopolymerizable layer capable of being exposed to laser ablation, said at least one ablation layer comprising:
(i) at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and (ii) at least one binder, wherein said binder is selected from the group consisting of polyacetals, polyacrylics, polyamides,~
polyimides; polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenyl ethers, polyethylene oxides, and cellulosic polymer, and (d) a removable coversheet;
wherein said at least one ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to laser radiation at the selected wavelength and power of the laser.
(a) a backing layer;
(b) at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) at least one ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said at least one ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite at least one photopolymerizable layer capable of being exposed to laser ablation, said at least one ablation layer comprising:
(i) at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and (ii) at least one binder, wherein said binder is selected from the group consisting of polyacetals, polyacrylics, polyamides,~
polyimides; polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenyl ethers, polyethylene oxides, and cellulosic polymer, and (d) a removable coversheet;
wherein said at least one ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to laser radiation at the selected wavelength and power of the laser.
2. The photosensitive printing element of claim 1 wherein said backing layer is transparent.
3. ~The photosensitive printing element of claim 1 wherein said photopolymer of said at least one photopolymerizable layer is selected from the group consisting of polyurethane, acrylonitrile rubber, and a diblock or triblock copolymer made from styrene-isoprene or styrene-butadiene.
4. ~The photosensitive printing element of claim 3 wherein said photopolymer comprises an acid-modified acrylate polyurethane or an amine-modified acrylate polyurethane.
5. ~The photosensitive printing element of claim 1 wherein the at least one binder is a polyamide.
6. ~The photosensitive printing element of claim 1 wherein the at least one binder is a cellulosic polylmer.
7. ~The photosensitive printing element of claim 6 wherein the at least one binder is a hydroxypropyl cellulose.
8. ~The photosensitive printing element of claim 1 wherein the at least one radiation absorbing material constitutes 1 to 20 weight parts per hundred of said ablation layer.
9. ~The photosensitive printing element of claim 1 wherein the wavelength and power of the laser ablates the at least one ablation layer without damage to at least one photopolymerizable layer beneath said at least one ablation layer.
10. ~The photosensitive printing element of claim 9 wherein the selected wavelength of the laser is 300-400 nanometers.
11. ~The photosensitive printing element of claim 9 wherein the selected wavelength of the laser is 10.6 µm.
12. ~The photosensitive printing element of claim 11 wherein the laser is a laser.
13. ~The photosensitive printing element of claim 1 wherein said at least one layer of photopolymerizable material comprises a first base layer of photopolymerizable material and a second photopolymerizable layer disposed on top of the first base layer of photopolymerizable material.
14. The photosensitive printing element of claim 1 wherein the at least one ultraviolet radiation absorbing material is selected from the group consisting of benzophenone derivatives and absorbing dyes.
15. A photosensitive printing element comprising:
(a) ~a backing layer;
(b) ~a first photocurable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~a second photocurable layer disposed atop the first photocurable layer;
and (d) ~at least one ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said at least one ablation layer is in direct contact with said second photocurable layer and has a~
surface opposite said second photocurable layer capable of being exposed to laser ablation, said at least one ablation layer comprising:
(i) ~at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and (ii) ~at least one binder which is transparent to UV radiation in the range of 300-400 nm;
wherein said at least one ablation layer is ablatable from the surface of the second photocurable layer upon exposure to laser radiation at the selected wavelength and power of the laser.
(a) ~a backing layer;
(b) ~a first photocurable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~a second photocurable layer disposed atop the first photocurable layer;
and (d) ~at least one ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said at least one ablation layer is in direct contact with said second photocurable layer and has a~
surface opposite said second photocurable layer capable of being exposed to laser ablation, said at least one ablation layer comprising:
(i) ~at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and (ii) ~at least one binder which is transparent to UV radiation in the range of 300-400 nm;
wherein said at least one ablation layer is ablatable from the surface of the second photocurable layer upon exposure to laser radiation at the selected wavelength and power of the laser.
16. The photosensitive printing element of claim 15 wherein said backing layer is transparent.
-30-~
-30-~
17. The photosensitive printing element of claim 15 wherein said photopolymer of at least one of said first photocurable layer and said second photocurable layer is selected from the group consisting of polyurethane, acrylonitrile rubber, and a diblock or triblock copolymer made from styrene-isoprene or styrene-butadiene.
18. The photosensitive printing element of claim 17 wherein said photopolymer comprises an acid-modified acrylate polyurethane or an amine-modified acrylate polyurethane.
19. The photosensitive printing element of claim 15 wherein the at least one binder is a polyamide.
20. The photosensitive printing element of claim 15 wherein at least one binder is a cellulosic polymer.
21. The photosensitive printing element of claim 20 wherein at least one binder is hydroxypropyl cellulose.
22. The photosensitive printing element of claim 15 wherein the at least one radiation absorbing material constitutes 1 to 20 weight parts per hundred of said ablation layer.
23. The photosensitive printing element of claim 15 wherein the wavelength and power of the laser ablates the at least one ablation layer without damage to the first and second photocurable layers beneath said at least one ablation layer.
24. The photosensitive printing element of claim 23 wherein the selected wavelength of the laser is 300-400 manometers.
25. The photosensitive printing element of claim 23 wherein the selected wavelength of the laser is 10.6 µm.
26. The photosensitive printing element of claim 25 wherein the laser is a CO2 laser.
27. The photosensitive printing element of claim 15 wherein the at least one radiation absorbing material is selected from the group consisting of benzophenone derivatives and absorbing dyes.
28. The photosensitive printing element of claim 15 wherein the at least one radiation absorbing material comprises a benzophenone derivative and a 4-phenylazophenol.
29. A photosensitive printing plate element comprising:
(a) ~a backing layer;
(b) ~at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~at least one slip film ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite the at least one photopolymerizable layer capable of being exposed to laser radiation, said at least one slip film ablation layer comprising:
i) ~at least one ultraviolet radiation absorbing material which substantially does not migrate from the ablation layer to the photopolymerizable layer; and ii) ~a binder selected from the group consisting of polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenylene ethers, and polyethylene oxide, and (d) a removable coversheet;
wherein the at least one slip film ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to laser radiation at the selected wavelength and power and wherein prior to ablation the at least one slip film ablation layer absorbs at least 97%
of incident ultraviolet radiation at wavelengths of 300-400 nm.
(a) ~a backing layer;
(b) ~at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~at least one slip film ablation layer which is ablatable by a laser at a selected wavelength and a selected power, wherein said ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite the at least one photopolymerizable layer capable of being exposed to laser radiation, said at least one slip film ablation layer comprising:
i) ~at least one ultraviolet radiation absorbing material which substantially does not migrate from the ablation layer to the photopolymerizable layer; and ii) ~a binder selected from the group consisting of polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenylene ethers, and polyethylene oxide, and (d) a removable coversheet;
wherein the at least one slip film ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to laser radiation at the selected wavelength and power and wherein prior to ablation the at least one slip film ablation layer absorbs at least 97%
of incident ultraviolet radiation at wavelengths of 300-400 nm.
30. The photosensitive printing element of claim 29 wherein the removable coversheet is selected from the group consisting of polyester, plastic, and paper.
31. A process for making a photosensitive element comprising the steps for:
.cndot. providing the photosensitive element comprising:
(a) ~a backing layer;
(b) ~at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~at least one ablation layer which is ablatable by infrared radiation, wherein the at least one ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite the at least one photopolymerizable layer capable of being exposed to laser ablation at a selected wavelength and power, the at least one ablation layer comprising:
i) ~at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and ii) ~at least one binder which is selected from the group consisting of polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenylene ethers, and polyethylene oxides;
wherein the at least one ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to infrared laser radiation;
.cndot. ~ablating said at least one ablation layer using a laser, thereby providing ablated and unablated areas forming an image; and .cndot. ~flood exposing said ablated element to UV light in the range of 300-nm without a negative, thereby curing said at least one photopolymerizable layer in areas under ablated areas of said ablation layer; and .cndot. developing said exposed element.
.cndot. providing the photosensitive element comprising:
(a) ~a backing layer;
(b) ~at least one layer of photopolymerizable material on said backing layer, said photopolymerizable material comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
(c) ~at least one ablation layer which is ablatable by infrared radiation, wherein the at least one ablation layer is in direct contact with the at least one photopolymerizable layer and has a surface opposite the at least one photopolymerizable layer capable of being exposed to laser ablation at a selected wavelength and power, the at least one ablation layer comprising:
i) ~at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV radiation at the selected wavelength in the range of 300-400 nm; and ii) ~at least one binder which is selected from the group consisting of polyacetals, polyacrylics, polyamides, polyimides, polybutylenes, polycarbonates, polyesters, polyethylenes, polyphenylene ethers, and polyethylene oxides;
wherein the at least one ablation layer is ablatable from the surface of the at least one photopolymerizable layer upon exposure to infrared laser radiation;
.cndot. ~ablating said at least one ablation layer using a laser, thereby providing ablated and unablated areas forming an image; and .cndot. ~flood exposing said ablated element to UV light in the range of 300-nm without a negative, thereby curing said at least one photopolymerizable layer in areas under ablated areas of said ablation layer; and .cndot. developing said exposed element.
32. ~The process of claim 31 wherein said backing layer is transparent.
33. ~The process of claim 31 wherein said at least one photopolymerizable layer includes a polyurethane, acrylonitrile rubber, or a diblock or triblock copolymer made from styrene-isoprene or styrene-butadiene.
34. ~The process of claim 33 wherein said polyurethane is an acid-modified acrylate polyurethane or an amine-modified acrylate polyurethane.
35. ~The process of claim 31 wherein the at least one binder is a polyamide.
36. ~The process of claim 31 wherein the ultraviolet radiation absorbing material constitutes to 1-20 weight parts per hundred of said at least one ablation layer.
37. ~The process of claim 31 wherein said laser used to ablate said at least one~
ablation layer emits light having a wavelength of 10.6 µm.
ablation layer emits light having a wavelength of 10.6 µm.
38. ~A process comprising the steps of:
.cndot.~ providing a solid, photopolymerizable printing plate comprising:
a backing;
at least one layer of photopolymerizable material on said backing, said at least one photopolymerizable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
at least one ablation layer over said at least one photopolymerizable layer, said at least one ablation layer comprising at least one binder that is transparent to ultraviolet radiation and at least one ultraviolet radiation absorbing material, wherein said at least one ablation layer is capable of being photoablated by a laser operating at a first energy level in the wavelength range of 300-400 nm, and wherein unablated areas of said at least one ablation layer are capable of absorbing at least 97% of irradiated light in the wavelength range of 300-400 nm from an ultraviolet light source operating at a second energy level lower than said first energy level;
.cndot. ablating said at least one ablation layer using a laser, thereby providing ablated and unablated areas forming an image;
.cndot. flood exposing said ablated element to ultraviolet light at a selected wavelength in the range of 300-400 nm without a negative, thereby curing at least one photopolymerizable layer in areas under ablated areas of said at least one ablation layer; and .cndot. developing said exposed element.
.cndot.~ providing a solid, photopolymerizable printing plate comprising:
a backing;
at least one layer of photopolymerizable material on said backing, said at least one photopolymerizable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
at least one ablation layer over said at least one photopolymerizable layer, said at least one ablation layer comprising at least one binder that is transparent to ultraviolet radiation and at least one ultraviolet radiation absorbing material, wherein said at least one ablation layer is capable of being photoablated by a laser operating at a first energy level in the wavelength range of 300-400 nm, and wherein unablated areas of said at least one ablation layer are capable of absorbing at least 97% of irradiated light in the wavelength range of 300-400 nm from an ultraviolet light source operating at a second energy level lower than said first energy level;
.cndot. ablating said at least one ablation layer using a laser, thereby providing ablated and unablated areas forming an image;
.cndot. flood exposing said ablated element to ultraviolet light at a selected wavelength in the range of 300-400 nm without a negative, thereby curing at least one photopolymerizable layer in areas under ablated areas of said at least one ablation layer; and .cndot. developing said exposed element.
39. ~The process of claim 38 wherein said backing layer is transparent.
40. ~The process of claim 38 wherein said photopolymerizable layer includes a polyurethane, acrylonitrile rubber, and a diblock or triblock copolymer made from styrene-isoprene or styrene-butadiene.
41. ~The process of claim 40 wherein said polyurethane is an acid-modified acrylate polyurethane or an amine-modified acrylate polyurethane.
42. ~The process of claim 38 wherein said at least one binder is selected from the group consisting of polyacetals, polyacrylics, polyamides, polymides, polybutylenes, polycarbonates, polyesters, polyethylenes, cellulosic polymers, polyphenylene ethers, and polyethylene oxides.
43. The process of claim 42 wherein said at least one binder comprises a polyamide.
44. The process of claim 42 wherein said at least one binder comprises a cellulosic polymer.
45. The process of claim 44 wherein said at least one binder comprises hydroxypropylcellulose.
46. The process of claim 38 wherein said at least one radiation absorbing material constitutes 1-20 weight parts per hundred of said at least one ablation layer.
47. The process of claim 38 wherein said laser used to ablate said ablation layer emits light having a wavelength of 10.6 µm.
48. The process of claim 38 wherein said laser used to ablate said ablation layer emits light having a wavelength of 300-400 nm.
49. A process for preparing a flexographic printing element comprising the steps of:
.cndot. ~providing a solid; photopolymerizable printing element comprising:
a backing;
at least one layer of photopolymerizable material on said backing, said at least one photopolymerizable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
at least one ablation layer over said at least one photopolymerizable layer, said at least one ablation layer comprising at least one binder that is transparent to ultraviolet radiation and at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV
radiation at the selected wavelength in the range of 300-400 nm, wherein said at least one ablation layer is capable of being photoablated by a laser operating at a selected wavelength and power;
.cndot. ablating said at least one ablation layer using a laser at the selected wavelength and power, thereby providing ablated and unablated areas forming an image;
.cndot.~flood exposing said ablated element to ultraviolet light at a selected~
wavelength in the range of 300-400 nm without a negative, thereby curing at least one photopolymerizable layer in areas under ablated areas of said at least one ablation layer; and .cndot.~developing said exposed element.
.cndot. ~providing a solid; photopolymerizable printing element comprising:
a backing;
at least one layer of photopolymerizable material on said backing, said at least one photopolymerizable layer comprising a photopolymer which is unaffected by radiation at a selected wavelength in the range of 300-400 nm and an initiator activatable at the selected wavelength;
at least one ablation layer over said at least one photopolymerizable layer, said at least one ablation layer comprising at least one binder that is transparent to ultraviolet radiation and at least one ultraviolet radiation absorbing material which absorbs at least 97% of the UV
radiation at the selected wavelength in the range of 300-400 nm, wherein said at least one ablation layer is capable of being photoablated by a laser operating at a selected wavelength and power;
.cndot. ablating said at least one ablation layer using a laser at the selected wavelength and power, thereby providing ablated and unablated areas forming an image;
.cndot.~flood exposing said ablated element to ultraviolet light at a selected~
wavelength in the range of 300-400 nm without a negative, thereby curing at least one photopolymerizable layer in areas under ablated areas of said at least one ablation layer; and .cndot.~developing said exposed element.
50. ~The process of claim 49 wherein said at least one radiation absorbing material constitutes 1-20 weight parts per hundred of said at least one ablation layer.
51. ~The process of claim 49 wherein said laser used to ablate said ablation layer emits light having a wavelength of 10.6 µm.
52. ~The process of claim 49 wherein said laser used to ablate said ablation layer emits light having a wavelength of 300-400 nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8268993A | 1993-06-25 | 1993-06-25 | |
| US08/082,689 | 1993-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2121865A1 CA2121865A1 (en) | 1994-12-26 |
| CA2121865C true CA2121865C (en) | 2006-08-15 |
Family
ID=22172784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002121865A Expired - Lifetime CA2121865C (en) | 1993-06-25 | 1994-04-21 | Laser imaged printing plate |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5925500A (en) |
| EP (1) | EP0634695B1 (en) |
| JP (1) | JP3463953B2 (en) |
| KR (1) | KR950000412A (en) |
| CN (1) | CN1111761A (en) |
| AU (1) | AU665147B2 (en) |
| BR (1) | BR9402431A (en) |
| CA (1) | CA2121865C (en) |
| DE (1) | DE4339010C2 (en) |
| ES (1) | ES2138646T3 (en) |
| NZ (1) | NZ260292A (en) |
| TW (1) | TW247297B (en) |
Families Citing this family (111)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6756181B2 (en) | 1993-06-25 | 2004-06-29 | Polyfibron Technologies, Inc. | Laser imaged printing plates |
| US6916596B2 (en) | 1993-06-25 | 2005-07-12 | Michael Wen-Chein Yang | Laser imaged printing plates |
| DE4339010C2 (en) * | 1993-06-25 | 2000-05-18 | Pt Sub Inc | Photohardenable product for printing plates |
| US6238837B1 (en) | 1995-05-01 | 2001-05-29 | E.I. Du Pont De Nemours And Company | Flexographic element having an infrared ablatable layer |
| DE19536808A1 (en) * | 1995-10-02 | 1997-04-03 | Basf Lacke & Farben | Process for the production of photopolymer high pressure plates |
| DE19536806A1 (en) * | 1995-10-02 | 1997-04-03 | Basf Lacke & Farben | Process for the production of photopolymer gravure plates |
| DE19611262A1 (en) * | 1996-03-22 | 1997-09-25 | Basf Lacke & Farben | Multi-layer recording element suitable for the production of flexographic printing plates by digital information transmission |
| EP0803772A3 (en) * | 1996-04-23 | 1997-11-05 | Agfa-Gevaert N.V. | An imaging element and a method for producing a lithographic plate therewith |
| DE69605646T2 (en) * | 1996-04-23 | 2000-06-21 | Agfa Gevaert Nv | Imaging element for producing a planographic printing plate, wherein the imaging element contains a thermosensitive mask |
| EP0803770B1 (en) * | 1996-04-23 | 1999-12-15 | Agfa-Gevaert N.V. | An imaging element and a method for producing a lithographic plate therewith |
| US5879861A (en) * | 1996-04-23 | 1999-03-09 | Agfa-Gevaert, N.V. | Method for making a lithographic printing plate wherein an imaging element is used that comprises a thermosensitive mask |
| EP0803771A1 (en) * | 1996-04-23 | 1997-10-29 | Agfa-Gevaert N.V. | A method for making a lithopgrapic printing plate wherein an imaging element is used that comprises a thermosensitive mask |
| US5888697A (en) * | 1996-07-03 | 1999-03-30 | E. I. Du Pont De Nemours And Company | Flexographic printing element having a powder layer |
| US5846691A (en) | 1996-07-08 | 1998-12-08 | Polyfibron Technologies, Inc. | Composite relief image printing plates and methods for preparing same |
| US6312872B1 (en) * | 1997-10-24 | 2001-11-06 | Macdermid Graphic Arts | Composite relief image printing plates |
| WO1998016874A1 (en) * | 1996-10-16 | 1998-04-23 | J.G. Systems Inc. | Process for imaging a flexo-graphic printing plate from liquid photopolymers and without using phototools |
| DE59712866D1 (en) | 1997-11-03 | 2007-09-06 | Stork Prints Austria Gmbh | Method for producing a printing form |
| IL122930A (en) * | 1998-01-13 | 2000-12-06 | Scitex Corp Ltd | Printing and printed circuit board members and methods for producing same |
| DE69918205T2 (en) * | 1998-03-18 | 2005-06-30 | Mitsubishi Gas Chemical Co., Inc. | A method of making through-holes by laser, copper-clad laminate suitable for making holes, and filler for making holes |
| FR2779090B1 (en) * | 1998-05-27 | 2000-07-13 | Sagadev | METHOD FOR MANUFACTURING A FLEXOGRAPHIC PRINTING PLATE |
| US20050029689A1 (en) * | 1998-10-05 | 2005-02-10 | Mystix Limited | Lithophane-like article and method of manufacture |
| IL129076A (en) * | 1999-03-21 | 2002-02-10 | Creoscitex Corp Ltd | Gravure short run printing plate and method for using the same |
| EP1216436B2 (en) † | 1999-09-07 | 2020-05-06 | E. I. du Pont de Nemours and Company | Method and apparatus for thermal processing of a photosensitive element |
| US6413699B1 (en) | 1999-10-11 | 2002-07-02 | Macdermid Graphic Arts, Inc. | UV-absorbing support layers and flexographic printing elements comprising same |
| WO2001038096A1 (en) * | 1999-11-19 | 2001-05-31 | Kba-Giori S.A. | Inking plate for rotary printing machine |
| US6367381B1 (en) * | 2000-02-22 | 2002-04-09 | Polyfibron Technologies, Inc. | Laser imaged printing plates comprising a multi-layer slip film |
| NL1015180C2 (en) * | 2000-05-12 | 2001-11-15 | Houtstra Polimero Deutschland | Method for manufacturing a printing plate. |
| DE60000237T2 (en) * | 2000-06-13 | 2003-03-06 | Agfa Gevaert Nv | Directly writable flexographic printing plate precursor |
| US6551759B2 (en) | 2000-06-13 | 2003-04-22 | Agfa-Gevaert | Direct-to-plate flexographic printing plate precursor |
| US6684783B2 (en) * | 2001-08-17 | 2004-02-03 | Creo Inc. | Method for imaging a media sleeve on a computer-to-plate imaging machine |
| AU2002364036A1 (en) | 2001-12-24 | 2003-07-15 | Digimarc Id Systems, Llc | Laser etched security features for identification documents and methods of making same |
| US7694887B2 (en) | 2001-12-24 | 2010-04-13 | L-1 Secure Credentialing, Inc. | Optically variable personalized indicia for identification documents |
| US7728048B2 (en) | 2002-12-20 | 2010-06-01 | L-1 Secure Credentialing, Inc. | Increasing thermal conductivity of host polymer used with laser engraving methods and compositions |
| CA2471457C (en) | 2001-12-24 | 2011-08-02 | Digimarc Id Systems, Llc | Covert variable information on id documents and methods of making same |
| US7793846B2 (en) | 2001-12-24 | 2010-09-14 | L-1 Secure Credentialing, Inc. | Systems, compositions, and methods for full color laser engraving of ID documents |
| US7211656B2 (en) * | 2002-01-30 | 2007-05-01 | Abbott Laboratories | Desaturase genes, enzymes encoded thereby, and uses thereof |
| US7964335B2 (en) * | 2002-01-30 | 2011-06-21 | Ikonics Corporation | Ink receptive photosensitive laminate |
| US6989220B2 (en) | 2002-03-25 | 2006-01-24 | Macdermid Printing Solutions, Llc | Processless digitally imaged photopolymer elements using microspheres |
| US6806018B2 (en) | 2002-03-25 | 2004-10-19 | Macdermid Graphic Arts, Inc. | Processless digitally imaged printing plate using microspheres |
| WO2003088144A2 (en) | 2002-04-09 | 2003-10-23 | Digimarc Id Systems, Llc | Image processing techniques for printing identification cards and documents |
| US7270528B2 (en) * | 2002-05-07 | 2007-09-18 | 3D Systems, Inc. | Flash curing in selective deposition modeling |
| US7824029B2 (en) | 2002-05-10 | 2010-11-02 | L-1 Secure Credentialing, Inc. | Identification card printer-assembler for over the counter card issuing |
| US6893796B2 (en) * | 2002-08-20 | 2005-05-17 | Kodak Polychrome Graphics Llc | Flexographic element having an integral thermally bleachable mask layer |
| US7804982B2 (en) | 2002-11-26 | 2010-09-28 | L-1 Secure Credentialing, Inc. | Systems and methods for managing and detecting fraud in image databases used with identification documents |
| DE602004030434D1 (en) | 2003-04-16 | 2011-01-20 | L 1 Secure Credentialing Inc | THREE-DIMENSIONAL DATA STORAGE |
| US20040241573A1 (en) * | 2003-06-02 | 2004-12-02 | Ray Kevin Barry | Thermally sensitive, white light safe mask for use in flexography |
| DE112004001662B4 (en) * | 2003-09-12 | 2013-08-08 | Eastman Kodak Co. (N.D.Ges.D. Staates New Jersey) | Method of producing a relief printing plate |
| US20050123856A1 (en) * | 2003-12-05 | 2005-06-09 | Roberts David H. | Process for the manufacture of flexographic printing plates |
| US20050170287A1 (en) * | 2004-01-30 | 2005-08-04 | Kanga Rustom S. | Photosensitive printing sleeves and method of forming the same |
| US7402373B2 (en) * | 2004-02-05 | 2008-07-22 | E.I. Du Pont De Nemours And Company | UV radiation blocking protective layers compatible with thick film pastes |
| US7041432B2 (en) * | 2004-03-29 | 2006-05-09 | Markhart Gary T | Apparatus and method for thermally developing flexographic printing elements |
| US6998218B2 (en) | 2004-03-29 | 2006-02-14 | Markhart Gary T | Apparatus and method for thermally developing flexographic printing sleeves |
| US7237482B2 (en) | 2004-03-29 | 2007-07-03 | Ryan Vest | Flexo processor |
| US7055429B2 (en) | 2004-04-23 | 2006-06-06 | Timothy Gotsick | Edge cure prevention process |
| US7044055B2 (en) | 2004-04-30 | 2006-05-16 | Timothy Gotsick | System for thermal development of flexographic printing plates |
| US7125650B2 (en) * | 2004-07-20 | 2006-10-24 | Roberts David H | Method for bump exposing relief image printing plates |
| US7736836B2 (en) | 2004-09-22 | 2010-06-15 | Jonghan Choi | Slip film compositions containing layered silicates |
| US7179583B2 (en) | 2004-10-29 | 2007-02-20 | Albert Roshelli | Edge cure prevention composition and process for using the same |
| US7247344B2 (en) * | 2004-11-16 | 2007-07-24 | Timothy Gotsick | Method and apparatus for applying surface treatments to photosensitive printing elements during thermal development |
| US7060417B2 (en) * | 2004-11-18 | 2006-06-13 | Chris Carlsen | Edge cure prevention process |
| US7202008B2 (en) * | 2005-06-23 | 2007-04-10 | Roshelli Jr Albert | Thermal development system and method of using the same |
| US20110281219A9 (en) * | 2005-10-13 | 2011-11-17 | Vest Ryan W | Apparatus and Method for Thermally Developing Flexographic Printing Elements |
| US20070196770A1 (en) * | 2006-02-22 | 2007-08-23 | David Recchia | Printing sleeve and method of manufacturing the same |
| WO2007123031A1 (en) * | 2006-04-20 | 2007-11-01 | Konica Minolta Medical & Graphic, Inc. | Printing plate material |
| US8501390B2 (en) | 2006-06-27 | 2013-08-06 | Xiper Innovations, Inc. | Laser engravable flexographic printing articles based on millable polyurethanes, and method |
| US7767383B2 (en) * | 2007-08-08 | 2010-08-03 | Roberts David H | Method of pre-exposing relief image printing plate |
| ES2578680T3 (en) | 2007-09-07 | 2016-07-29 | Precision Rubber Plate Co., Inc | System and method to expose a digital polymer plate |
| US8876513B2 (en) * | 2008-04-25 | 2014-11-04 | 3D Systems, Inc. | Selective deposition modeling using CW UV LED curing |
| US8739701B2 (en) * | 2008-07-31 | 2014-06-03 | Ryan Vest | Method and apparatus for thermal processing of photosensitive printing elements |
| US20100173135A1 (en) * | 2009-01-06 | 2010-07-08 | Jonghan Choi | Method of Controlling Surface Roughness of a Flexographic Printing Plate |
| US9720326B2 (en) | 2009-10-01 | 2017-08-01 | David A. Recchia | Method of improving print performance in flexographic printing plates |
| US9069255B2 (en) | 2009-11-18 | 2015-06-30 | Jim Hennessy | Carrier sheet for a photosensitive printing element |
| US8795950B2 (en) | 2010-06-30 | 2014-08-05 | Jonghan Choi | Method of improving print performance in flexographic printing plates |
| JP5174134B2 (en) * | 2010-11-29 | 2013-04-03 | 富士フイルム株式会社 | Resin composition for laser engraving, relief printing plate precursor for laser engraving, plate making method of relief printing plate and relief printing plate |
| US8492074B2 (en) | 2011-01-05 | 2013-07-23 | Laurie A. Bryant | Method of improving print performance in flexographic printing plates |
| US8551688B2 (en) | 2011-04-21 | 2013-10-08 | Ryan W. Vest | Photosensitive resin laminate and thermal processing of the same |
| US8669041B2 (en) | 2011-07-15 | 2014-03-11 | Brian Cook | Method for improving print performance of flexographic printing elements |
| US8871431B2 (en) | 2011-08-08 | 2014-10-28 | Timothy Gotsick | Laminated flexographic printing sleeves and methods of making the same |
| US8697337B2 (en) | 2012-01-23 | 2014-04-15 | Albert G. Roshelli, JR. | Laminating apparatus and method of using the same |
| US20130196144A1 (en) | 2012-01-31 | 2013-08-01 | David H. Roberts | Laser Engraveable Compositions for Relief Image Printing Elements |
| US8524442B1 (en) | 2012-02-13 | 2013-09-03 | David A. Recchia | Integrated membrane lamination and UV exposure system and method of the same |
| US9114601B2 (en) | 2012-03-01 | 2015-08-25 | Kyle P. Baldwin | Clean flexographic printing plate and method of making the same |
| US9134612B2 (en) | 2012-03-27 | 2015-09-15 | E I Du Pont De Nemours And Company | Printing form precursor having elastomeric cap layer and a method of preparing a printing form from the precursor |
| US8808968B2 (en) | 2012-08-22 | 2014-08-19 | Jonghan Choi | Method of improving surface cure in digital flexographic printing plates |
| US8790864B2 (en) | 2012-08-27 | 2014-07-29 | Kyle P. Baldwin | Method of improving print performance in flexographic printing plates |
| EP2738606B1 (en) * | 2012-11-28 | 2024-01-31 | XSYS Prepress N.V. | Method and computer program product for processing a flexographic plate. |
| US9040226B2 (en) | 2013-05-13 | 2015-05-26 | Macdermid Printing Solutions, Llc | Method of improving print performance in flexographic printing plates |
| US9649786B2 (en) | 2013-08-13 | 2017-05-16 | Macdermid Printing Solutions, Llc | Apparatus for thermal processing of flexographic printing elements |
| US9063426B2 (en) * | 2013-09-25 | 2015-06-23 | Uni-Pixel Displays, Inc. | Method of manufacturing a flexographic printing plate with support structures |
| US10025183B2 (en) | 2014-01-22 | 2018-07-17 | Macdermid Graphics Solutions, Llc | Photosensitive resin composition |
| US9256129B2 (en) | 2014-02-19 | 2016-02-09 | Macdermid Printing Solutions, Llc | Method for creating surface texture on flexographic printing elements |
| US9217928B1 (en) | 2014-08-13 | 2015-12-22 | Macdermid Printing Solutions, Llc | Clean flexographic printing plates and method of making the same |
| US9740099B2 (en) | 2014-11-12 | 2017-08-22 | Macdermid Printing Solutions, Llc | Flexographic printing plate with improved cure efficiency |
| US9678429B2 (en) | 2015-08-18 | 2017-06-13 | Macdermid Printing Solutions, Llc | Method of creating hybrid printing dots in a flexographic printing plate |
| US9757919B2 (en) | 2015-08-20 | 2017-09-12 | Macdermid Printing Solutions, Llc | Carrier sheet and method of using the same |
| US20170176856A1 (en) * | 2015-12-21 | 2017-06-22 | Az Electronic Materials (Luxembourg) S.A.R.L. | Negative-working photoresist compositions for laser ablation and use thereof |
| US9925757B2 (en) | 2016-02-10 | 2018-03-27 | Macdermid Graphics Solutions, Llc | Customizable printing plates and method of making the same |
| US10108087B2 (en) | 2016-03-11 | 2018-10-23 | Macdermid Graphics Solutions Llc | Method of improving light stability of flexographic printing plates featuring flat top dots |
| US10036956B2 (en) | 2016-05-03 | 2018-07-31 | Macdermid Graphics Solutions, Llc | Method of making relief image printing elements |
| US10241401B2 (en) | 2016-08-01 | 2019-03-26 | Macdermid Graphics Solutions Llc | Method of making a flexographic printing plate |
| US10599035B2 (en) | 2017-04-12 | 2020-03-24 | Macdermid Graphics Solutions, Llc | Method of improving light stability of flexographic printing plates featuring flat top dots |
| US10429736B2 (en) | 2017-04-27 | 2019-10-01 | Macdermid Graphics Solutions Llc | Method of making a flexographic printing plate |
| US10457082B2 (en) | 2017-05-09 | 2019-10-29 | Macdermid Graphics Solutions, Llc | Flexographic printing plate with improved storage stability |
| ES1192783Y (en) * | 2017-09-15 | 2018-01-04 | Beca Grafic Sa | PHOTOPOLIMERO SOLID SELF-ADHESIVE FOR FLEXOGRAPHIC PRINTING |
| US11719859B2 (en) * | 2018-09-14 | 2023-08-08 | The Regents Of The University Of Colorado | Elastomeric reflection suppressor |
| CN109454973B (en) * | 2018-11-15 | 2021-01-12 | 安徽原上草节能环保科技有限公司 | Method for processing flexographic printing plate |
| US11602947B2 (en) | 2020-07-23 | 2023-03-14 | Macdermid Graphics Solutions Llc | Method of making a flexographic printing plate |
| US11325369B2 (en) | 2020-07-27 | 2022-05-10 | Macdermid Graphics Solutions, Llc | System for thermal development of flexographic printing plates |
| WO2022026847A1 (en) | 2020-07-31 | 2022-02-03 | Digimarc Corporation | Encoding signals on flexographic printing plates to enable tracking and management |
| US11624983B2 (en) | 2021-08-31 | 2023-04-11 | Macdermid Graphics Solutions, Llc | Method and system for thermal processing of flexo printing elements |
| CN114415477A (en) * | 2022-01-26 | 2022-04-29 | 深圳市先地图像科技有限公司 | Method for exposing image by laser imaging equipment and related equipment |
Family Cites Families (62)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4000334A (en) * | 1971-07-15 | 1976-12-28 | Energy Conversion Devices, Inc. | Thermal imaging involving imagewise melting to form spaced apart globules |
| FR2214934B1 (en) * | 1973-01-18 | 1978-03-24 | Thomson Csf | |
| CA1049312A (en) * | 1974-01-17 | 1979-02-27 | John O.H. Peterson | Presensitized printing plate with in-situ, laser imageable mask |
| US4020762A (en) * | 1974-01-17 | 1977-05-03 | Scott Paper Company | Laser imaging a lanographic printing plate |
| US3964389A (en) * | 1974-01-17 | 1976-06-22 | Scott Paper Company | Printing plate by laser transfer |
| US4149798A (en) * | 1977-06-10 | 1979-04-17 | Eocom Corporation | Electrophotographic apparatus and method for producing printing masters |
| EP0001138A1 (en) * | 1977-08-23 | 1979-03-21 | Howard A. Fromson | Method for making lithographic printing plates |
| JPS5497050A (en) * | 1978-01-17 | 1979-07-31 | Fuji Photo Film Co Ltd | Video clock signal generator |
| US4248959A (en) * | 1978-12-07 | 1981-02-03 | American Hoechst Corporation | Preparation of diazo printing plates using laser exposure |
| US4225224A (en) * | 1979-03-13 | 1980-09-30 | The United States Of America As Represented By The Secretary Of The Army | Process and apparatus for laser illumination of printing plates |
| US4422083A (en) * | 1979-05-24 | 1983-12-20 | American Hoechst Corporation | System and method for producing artwork for printed circuit boards |
| JPS5619758A (en) * | 1979-07-27 | 1981-02-24 | Dainippon Printing Co Ltd | Preparation of gravure cylinder made of resin |
| US4396284A (en) * | 1980-04-21 | 1983-08-02 | Howard A. Fromson | Apparatus for making lithographic printing plates |
| EP0039094B1 (en) * | 1980-04-22 | 1985-06-12 | Agfa-Gevaert N.V. | Recording material for storage of digital information and a recording method for storage of digital information |
| JPS5738141A (en) * | 1980-08-20 | 1982-03-02 | Konishiroku Photo Ind Co Ltd | Manufacture of printing plate |
| JPS5756259A (en) * | 1980-09-19 | 1982-04-03 | Dainippon Printing Co Ltd | Manufacture of gravure plate |
| DE3036710A1 (en) * | 1980-09-29 | 1982-05-13 | Siemens AG, 1000 Berlin und 8000 München | Photolacquer structure with photoresist layer - is on deep UV or electron positive resist |
| DE3167878D1 (en) * | 1980-12-04 | 1985-01-31 | Dainippon Printing Co Ltd | Sleeve-type gravure printing cylinder and method and apparatus for its assembly |
| DE3270540D1 (en) * | 1981-02-06 | 1986-05-22 | Crosfield Electronics Ltd | Formation of print surfaces |
| US4429027A (en) * | 1981-05-21 | 1984-01-31 | E. I. Du Pont De Nemours & Co. | Photoimaging process |
| IT1159073B (en) * | 1981-07-22 | 1987-02-25 | Basf Ag | METHOD TO IMPROVE THE PREPARATION, DRYING AND STORAGE OF MULTI-LAYER ELEMENTS SUITABLE FOR THE PREPARATION OF MOLDS FOR RELIEF MOLDING |
| JPS5852646A (en) * | 1981-09-25 | 1983-03-28 | Dainippon Printing Co Ltd | Manufacture of flexographic plate |
| US4420363A (en) * | 1981-12-04 | 1983-12-13 | Dai Nippon Insatsu Kabushiki Kaisha | One-bath etching method for processing gravure plate, and etching condition calculating device |
| US4460675A (en) * | 1982-01-21 | 1984-07-17 | E. I. Du Pont De Nemours And Company | Process for preparing an overcoated photopolymer printing plate |
| US4427759A (en) * | 1982-01-21 | 1984-01-24 | E. I. Du Pont De Nemours And Company | Process for preparing an overcoated photopolymer printing plate |
| DE3380640D1 (en) * | 1982-08-11 | 1989-11-02 | Ici Plc | Assembly for use in making a printing plate |
| US4515877A (en) * | 1982-11-27 | 1985-05-07 | Basf Aktiengesellschaft | Image-recording materials and image-recording carried out using these to produce an optical mask |
| DE3342579A1 (en) * | 1982-11-27 | 1984-05-30 | Basf Ag, 6700 Ludwigshafen | Image-recording materials and image-recording process feasible therewith |
| JPS59111608A (en) * | 1983-12-09 | 1984-06-27 | Hitachi Ltd | Color filter |
| US4521503A (en) * | 1984-05-11 | 1985-06-04 | Minnesota Mining And Manufacturing Company | Highly photosensitive aqueous solvent-developable printing assembly |
| JPS6124451A (en) * | 1984-07-13 | 1986-02-03 | Ricoh Co Ltd | Material for direct plate-making and its use for plate-making |
| JPS6136750A (en) * | 1984-07-30 | 1986-02-21 | Ricoh Co Ltd | Direct photoengraving material |
| JPS61114647A (en) * | 1984-11-09 | 1986-06-02 | Sharp Corp | Picture reader |
| US4705729A (en) * | 1984-11-19 | 1987-11-10 | Hewlett-Packard Company | Method for photochemically enhancing resolution in photolithography processes |
| NL8500992A (en) * | 1985-04-03 | 1986-11-03 | Stork Screens Bv | PROCESS FOR FORMING A PATTERNED PHOTOPOLYMER COATING ON A PRINTING ROLLER AND PRINTING ROLLER WITH PATTERNED PHOTOPOLYMER COATING. |
| US5015553A (en) * | 1985-06-10 | 1991-05-14 | The Foxboro Company | Method of patterning resist |
| DE3521955A1 (en) * | 1985-06-20 | 1987-01-02 | Basf Ag | METHOD FOR PRODUCING ADHESIVE-FREE, SMOOTH SURFACES OF PHOTOPOLYMERIZED RELIEF PRINTING FORMS FOR FLEXO PRINTING |
| US4617085A (en) * | 1985-09-03 | 1986-10-14 | General Electric Company | Process for removing organic material in a patterned manner from an organic film |
| DE3537829A1 (en) * | 1985-10-24 | 1987-04-30 | Antriebs Steuerungstech Ges | Method for producing artwork, particularly for fabricating printed circuits |
| EP0225676B1 (en) * | 1985-12-09 | 1994-07-06 | Nippon Paint Co., Ltd. | Photosensitive resin base printing material |
| US4864324A (en) * | 1986-08-13 | 1989-09-05 | Canon Kabushiki Kaisha | Color image forming method and ink used therefor |
| US5286594A (en) * | 1988-01-29 | 1994-02-15 | International Paper Company | Photographic elements utilizing a single photosensitive layer containing a photopolymerizable compound, photoinitiator, diazonium compound and barrier material encapsulated pigment particles |
| US5139918A (en) * | 1988-03-02 | 1992-08-18 | Hewlett-Packard Company | Photoresist system and photoetching process employing an I-line peak light source |
| GB2224860A (en) * | 1988-11-14 | 1990-05-16 | Esselte Letraset Ltd | Production of coloured images |
| US5171650A (en) * | 1990-10-04 | 1992-12-15 | Graphics Technology International, Inc. | Ablation-transfer imaging/recording |
| US5156938A (en) * | 1989-03-30 | 1992-10-20 | Graphics Technology International, Inc. | Ablation-transfer imaging/recording |
| ES2097758T5 (en) * | 1989-03-30 | 2000-06-01 | Polaroid Corp | A PROXIMATE INFRARED LASER ABSORBING COATING AND METHOD FOR USE IN IMAGE FORMATION AND COLOR PROOF SHOOTING. |
| JP2518404B2 (en) * | 1989-06-20 | 1996-07-24 | 日本電気株式会社 | Equalizer amplifier circuit |
| AT394634B (en) * | 1989-12-20 | 1992-05-25 | Raganitsch Gmbh | PRINTING PROCESS |
| US5169678A (en) * | 1989-12-26 | 1992-12-08 | General Electric Company | Laser ablatable polymer dielectrics and methods |
| JP2516087B2 (en) * | 1990-05-17 | 1996-07-10 | 日本ビクター株式会社 | Plate making equipment |
| TR24835A (en) * | 1990-07-07 | 1992-05-01 | Thomson Brandt Gmbh | TELEVISION TRANSFER SYSTEM |
| JPH04168167A (en) * | 1990-10-31 | 1992-06-16 | Nippon Paint Co Ltd | Water-base ink composition and method for preparing lithographic plate |
| DE4107378A1 (en) * | 1991-03-08 | 1992-09-10 | Basf Ag | Multiple use copying masks for prodn. of printing plates - comprising transparent support film bearing the image to be copied, covered with protective layer of transparent film-forming polymer contg. transparent matting agent |
| DE4300966A1 (en) * | 1992-01-17 | 1993-07-22 | Siemens Medical Electronics | Signal processing unit for e.g automatic blood pressure instrument - produces at least one pressure measurement value and contains pressure activated sleeve and pressure transducer for producing electric DC signal |
| US5351617A (en) * | 1992-07-20 | 1994-10-04 | Presstek, Inc. | Method for laser-discharge imaging a printing plate |
| US5607814A (en) * | 1992-08-07 | 1997-03-04 | E. I. Du Pont De Nemours And Company | Process and element for making a relief image using an IR sensitive layer |
| US5262275A (en) * | 1992-08-07 | 1993-11-16 | E. I. Du Pont De Nemours And Company | Flexographic printing element having an IR ablatable layer and process for making a flexographic printing plate |
| DE4339010C2 (en) * | 1993-06-25 | 2000-05-18 | Pt Sub Inc | Photohardenable product for printing plates |
| US5387496A (en) * | 1993-07-30 | 1995-02-07 | Eastman Kodak Company | Interlayer for laser ablative imaging |
| US6238837B1 (en) * | 1995-05-01 | 2001-05-29 | E.I. Du Pont De Nemours And Company | Flexographic element having an infrared ablatable layer |
| JP3023705U (en) | 1995-10-12 | 1996-04-30 | チェン・チュン−シュン | Improved umbrella bone wheel and umbrella using the same |
-
1993
- 1993-11-10 DE DE4339010A patent/DE4339010C2/en not_active Expired - Lifetime
-
1994
- 1994-04-12 NZ NZ260292A patent/NZ260292A/en unknown
- 1994-04-12 AU AU59452/94A patent/AU665147B2/en not_active Expired
- 1994-04-21 CA CA002121865A patent/CA2121865C/en not_active Expired - Lifetime
- 1994-04-29 KR KR1019940009633A patent/KR950000412A/en not_active Application Discontinuation
- 1994-05-25 TW TW083104766A patent/TW247297B/zh active
- 1994-06-14 ES ES94250153T patent/ES2138646T3/en not_active Expired - Lifetime
- 1994-06-14 EP EP94250153A patent/EP0634695B1/en not_active Expired - Lifetime
- 1994-06-15 BR BR9402431A patent/BR9402431A/en not_active Application Discontinuation
- 1994-06-22 JP JP16289994A patent/JP3463953B2/en not_active Expired - Lifetime
- 1994-06-24 CN CN94107232A patent/CN1111761A/en active Pending
-
1997
- 1997-08-21 US US08/916,101 patent/US5925500A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU665147B2 (en) | 1995-12-14 |
| AU5945294A (en) | 1995-01-05 |
| EP0634695B1 (en) | 1999-09-08 |
| CA2121865A1 (en) | 1994-12-26 |
| BR9402431A (en) | 1995-01-24 |
| NZ260292A (en) | 1995-12-21 |
| EP0634695A1 (en) | 1995-01-18 |
| KR950000412A (en) | 1995-01-03 |
| DE4339010A1 (en) | 1995-01-05 |
| JP3463953B2 (en) | 2003-11-05 |
| CN1111761A (en) | 1995-11-15 |
| TW247297B (en) | 1995-05-11 |
| DE4339010C2 (en) | 2000-05-18 |
| ES2138646T3 (en) | 2000-01-16 |
| JPH0717151A (en) | 1995-01-20 |
| US5925500A (en) | 1999-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2121865C (en) | Laser imaged printing plate | |
| US6756181B2 (en) | Laser imaged printing plates | |
| CA2387606C (en) | Laser imaged printing plates comprising a multi-layer slip film | |
| EP1488285B1 (en) | Processless digitally imaged printing plate using microspheres | |
| US6037102A (en) | Multilayer recording element suitable for the production of flexographic printing plates by digital information transfer | |
| EP1719017A2 (en) | Processless digitally imaged photopolymer elements using microspheres | |
| JPH08305030A (en) | Element for flexography with infrared ablative layer and creation method of flexographic printing plate | |
| JPH08305007A (en) | Creation method of flexographic printing plate | |
| US7399575B2 (en) | Laminated photosensitive relief printing original plate and method for producing the relief printing plate | |
| EP1737676B1 (en) | Edge cure prevention process | |
| WO2004039601A1 (en) | Thermal generation of a mask for flexography | |
| US6916596B2 (en) | Laser imaged printing plates | |
| US20010053499A1 (en) | Laser imaged printing plates | |
| WO2018222489A1 (en) | Laser imaged printing plates | |
| US7060417B2 (en) | Edge cure prevention process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20140422 |