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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N1/00—Printing plates or foils; Materials therefor
  • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/115—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having supports or layers with means for obtaining a screen effect or for obtaining better contact in vacuum printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C1/00—Forme preparation
  • B41C1/055—Thermographic processes for producing printing formes, e.g. with a thermal print head

Definitions

• a common technique for bringing a photosensitive element and a photomask into close contact with one another is to juxtapose the elements and draw a vacuum from between them usually by use of a vacuum frame.
• a vacuum frame When smooth-surfaced elements are brought into such vacuum contact, however, the time required to evacuate air from between the elements and obtain a substantially uniform and complete contact between them becomes exceedingly high.
• uniform and complete contact might not be achieved and the photomask may stick so strongly to the photosensitive element that it is damaged when stripped off.
• at least one of the photosensitive element or the photomask has a rough outermost layer to avoid these disadvantages.
• Use of photomasks having rough surfaces are disclosed in US 4,997,735 and US 5,124,227.
• a photosensitive element for use as a flexographic printing plate comprising a) a support, b) at least one elastomeric photopolymerizable layer on the support containing at least one elastomeric binder, at least one ethylenically unsaturated compound photopolymerizable by actinic radiation, and at least one photoinitiator or photoinitiator system, and c) a matted layer disposed above a surface of the photopolymerizable layer opposite the support comprising a polymeric binder and at least one matting agent, the at least one matting agent capable of being anchored in the surface of the photopolymerizable layer, and selected from the group consisting of i) matting agents having a pore volume of > 0.9 ml/g, ii) matting agents having a BET surface of > 150 m 2 /g, iii) matting agents having an oil number of > 150g/100g
• the present invention provides an easy and economical way to prepare a photosensitive element used to make a flexographic printing plate in which the photosensitive element can be used with photomasks having a smooth surface.
• the present invention also provides for a flexographic printing plate prepared from the photosensitive element showing good ink transfer and printing quality and having enhanced print life.
• the present invention can be integrated in usual production processes with no additional, special production steps being necessary. It can be adopted for all sorts of flexographic printing plates and various types of flexographic composition.
• the photosensitive element provides better vacuum contact with the photomask during imagewise exposure than conventional photosensitive elements. Even photomasks having smooth surfaces can be used. Developability of the present photosensitive element is comparable to conventional elements. But the present photosensitive element can have the advantage that no sludge is formed in the processor during development.
• a matting agent with a BET surface of > 200 m 2 /g is used.
• matting agents with a BET surface of > 280 m 2 /g are suitable.
• the oil number is measured according to DIN ISO 787-5 (ASTM D 281). The oil number represents the amount of oil in g necessary to process 100 g of a pigment (here the matting agent) to form an adhering cementlike mass.
• crosslinkable group for matting agents having at least one crosslinkable group of iv) is intended to encompass photopolymerizable and photocrosslinkable groups as well as such groups which are thermally crosslinkable.
• Preferred crosslinkable groups are ethylenically unsaturated groups, such as, e.g., vinyl groups, acryloyl groups or methacryloyl groups, and epoxy groups. Especially preferred are ethylenically unsaturated groups.
• Matting agents comprising such crosslinkable groups are prepared by conventional surface modification of silicic acids or silica matting agents with silanes comprising the crosslinkable group and an alkoxy group or halogen atom.
• the matting agent has a mean particle size of > 3 ⁇ m.
• the mean particle size is the particle size determined according to ASTM- D 4438-85 (Coulter Counter method).
• matting agents having a mean particle size of 3-15 ⁇ m.
• > 60 % by volume of the total particles of the matting agent are between 3 to 15 ⁇ m; especially preferred are > 80 % by volume.
• the matting agent may include ⁇ 20 % by volume of particles with a particle size of > 15 ⁇ m.
• a matting agent having a mean particle size of > 3 ⁇ m, a pore volume of > 0.9 ml/g, and an oil number of > 150 g/100 g is suitable, and further including a BET surface of > 150 m 2 /g is particularly suitable.
• Most suitable are those matting agents having a mean particle size of > 3 ⁇ m, a pore volume of 1.0-2.5 ml/g, an oil number of > 200 g/100 g, and a BET surface of > 200 m 2 /g.
• the matting agent has a refractive index similar to that of the other components of the photosensitive element.
• a matting agent that is filled and/or loaded with at least one ethylenically unsaturated compound photopolymerizable by actinic radiation.
• Suitable monomers are those which are used in the photopolymerizable layer and which are disclosed below.
• polar monomers with good adsorption to the surface of the matting particles, especially such with low viscosity and high diffusion capability in the photopolymerizable layer can be used, for example, hexamethylene glycol diacrylate and/or hexamethylene glycol dimethacrylate.
• the matting agent is present in an amount of > 10 % by weight of the matted layer, preferably > 15 % by weight, and most preferably 15-20 % by weight.
• the matting agent may be used in an amount up to 60 % by weight of the matted layer.
• the matting agent may include ⁇ 20 % by weight of other particulate materials not capable of being anchored in the surface of the photopolymerizable layer, such as, for example, polymer beads, etc.
• the matted layer may comprise colorants, e.g., dyes and/or pigments as well as photochromic additives, i.e., for identification or for better contrast between imaged and non-imaged areas of the photosensitive elements directly after imagewise exposure or after imagewise exposure and development.
• a dye can provide enhanced exposure latitude to the photosensitive element. Exposure latitude means the fill-in of reverse depths due to light scattering. This is especially important for print quality and good reproduction of fine elements. These colorants must not interfere with the imagewise exposure of the photopolymerizable layer.
• Suitable colorants are, e.g., soluble acridine dyes, anthraquinone dyes, phenazine dyes, and phenoxazine dyes, such as, for example, methylene violet (C.I. Basic Violet 5), methylene blue B (C.I. 52015), Solvent Black 3 (C.1.26150), Rhodamin 3 GO (C.I. Basic Red 4), Solvent Blue 11 (C.I. 61525), Victoria Pure Blue BO (C.I. Basic Blue 7 or C.I. 42595), anthraquinone Blue 2 GA (C.I. Acid Blue 58), Safranin T (C.I. 50240), etc.
• the colorant is present in an amount of 0.0001-2 % by weight of the matted layer.
• the matted layer comprises 0.001-1 % by weight of the colorant.
• the matted layer When the matted layer is IR-sensitive, it may include as the polymeric binder, for example, nitrocellulose, homopolymers or copolymers of acrylates, methacrylates and styrenes, polyamides, polyvinyl alcohols, etc. All these compounds are described in detail, for example in WO 94/03838 and WO 94/3839 which disclose IR- sensitive layers as integrated photomasks for flexographic printing plates.
• Other auxiliary agents such as plasticizers, coating aids, waxes, surfactants, etc. can be included in the matted layer.
• waxes with a softening temperature > 70 °C especially polyethylene waxes having a softening temperature > 90 °C, can be used.
• elastomeric binder usually comprises at least one elastomeric binder, at least one photopolymerizable, ethylenically unsaturated monomer, and at least one photoinitiator or photoinitiator system, wherein the photoinitiator is sensitive to actinic radiation, which usually includes ultraviolet radiation and/or visible radiation.
• elastomeric binders are polyalkadienes, alkadiene/acrylonitrile copolymers; ethylene/propylene/alkadiene copolymers; ethylene/(meth)acrylic acid((meth)acrylate copolymers; and thermoplastic, elastomeric block copolymers of styrene, butadiene, and/or isoprene.
• Linear and radial thermoplastic, elastomeric block copolymers of styrene and butadiene and/or isoprene are preferred.
• the binder is present in an amount of > 65 % by weight of the photopolymerizable material.
• the photopolymerizable compositions may comprise conventional additives like, for example, UV absorbers, thermal stabilizers, plasticizers, colorants, antioxidants, fillers, etc.
• the thickness of the photopolymerizable layer can vary over a wide range depending upon the type of flexographic printing plate desired. For so called “thin plates” the photopolymerizable layer can be from about 0.05-0.17 cm in thickness. Thicker plates will have a photopolymerizable layer up to 0.25-0.64 cm in thickness or greater. Support
• the photosensitive element optionally comprises a cover sheet as outermost protective layer on top of the matted layer or if present on top of the IR-sensitive layer.
• cover sheets consist of flexible polymeric films, e.g., polyethylene terephthalate, which preferably is unsubbed but optionally may be subcoated with a thin silicone layer, polystyrene, polyethylene, polypropylene, or other strippable polymeric films.
• polyethylene terephthalate is used. Additional layers Additional layers may be present on top of the photopolymerizable layer. Suitable layers are those disclosed as elastomeric layers in the multilayer cover element described in US 4,427,759 and US 4,460,675.
• Such elastomeric layers comprise layers which are insensitive to actinic radiation themselves but become photosensitive when contacted with the photopolymerizable layer as well as such layers which are photosensitive themselves.
• These photosensitive elastomeric layers comprise preferably an elastomeric binder, a monomer, and a photoinitiator, and optionally fillers or other additives.
• Elastomeric layers which become photosensitive when contacted with the photopolymerizable layer do not comprise any monomer. Binder, monomer, and other compounds can be the same or similar to those compounds comprised in the photopolymerizable layer. These elastomeric layers are disposed between the photopolymerizable layer and the matted layer.
• the photosensitive element can optionally include a wax layer as disclosed in DE-C 199 09 152 between the matted layer and the photopolymerizable layer, or between the matted layer and the elastomeric layer if present.
• Suitable waxes are all natural and synthetic waxes, such as polyolefin waxes, paraffin waxes, camauba waxes, stearin waxes, and steramide waxes.
• Conventional methods like casting, printing, or spray coating are used to prepare the wax layers from dispersions of the waxes in suitable solvents.
• the wax layer is usually 0.02-1.0 ⁇ m thick, preferably 0.05-0.5 ⁇ m.
• the photosensitive element may optionally comprise an IR-sensitive layer on top of the matted layer.
• the IR-sensitive layer can form an integrated masking layer for the photosensitive element.
• the preferred IR-sensitive layer is removable during treating, i.e., soluble or dispersible in a developer solution or removable during thermal development; opaque to actinic radiation, i.e., ultraviolet or visible light, that is, has an optical density > 2.5; and can be imaged with an infrared laser.
• the IR sensitive layer contains material having high infrared absorption in the wavelength range between 750 and 20,000 nm, such as, for example, polysubstituted phthalocyanine compounds, cyanine dyes, merocyanine dyes, etc., inorganic pigments, such as, for example, carbon black, graphite, chromium dioxide, etc., or metals, such as aluminum, copper, etc.
• the quantity of infrared absorbing material is usually 0.1-40 % by weight, relative to the total weight of the layer.
• the infrared-sensitive layer contains a material that prevents the transmission of actinic radiation.
• This actinic radiation blocking material can be the same or different than the infrared absorbing material, and can be, for example, dyes or pigments, and in particular the aforesaid inorganic pigments.
• the quantity of this material is usually 1-70 % by weight relative to the total weight of the layer.
• the infrared-sensitive layer optionally includes a polymeric binder, such as, for example, nitrocellulose, homopolymers or copolymers of acrylates, methacrylates and styrenes, polyamides, polyvinyl alcohols, etc.
• Other auxiliary agents such as plasticizers, coating aids, etc. are possible.
• Such antihalation layer can be made by dispersing a finely divided dye or pigment which substantially absorbs actinic radiation in a solution or aqueous dispersion of a resin or polymer which is adherent to both the support and the photopolymerizable layer and coating it on the support and drying.
• Suitable antihalation pigments and dyes include carbon black, manganese dioxide, Acid Blue Black (Cl 20470), and Acid Magenta O (Cl 42685).
• Suitable polymeric or resin carriers include polyvinyl compounds, e.g., polyvinyl chloride homo- and copolymers, copolymers of acrylic and methacrylic acid, etc.
• the present photosensitive element can be prepared by contacting the matted layer with one surface of a photopolymerizable layer.
• the matted layer is disposed on a cover sheet, and is then laminated onto the outermost surface of the element opposite the support, which is typically the photopolymerizable layer, with a conventional laminator.
• the photopolymerizable layer itself may be prepared in many ways by admixing the binder, monomer, initiator, and other ingredients and forming it into a sheet layer. It is preferred that the application of the matted layer onto the photopolymerizable layer is integrated within the usual production process of photosensitive elements for use as flexographic printing plates.
• the photopolymerizable mixture is formed into a hot melt and then calendered to the desired thickness.
• An extruder can be used to perform the function of melting, mixing, deaerating and filtering the composition.
• the extruded mixture is then calendered between the support and a cover element.
• this cover element comprises a cover sheet, optionally an IR-sensitive layer, the matted layer, and optionally a wax layer and/or an elastomeric layer.
• the photopolymerizable material can be placed between the support and the cover element in a mold. The layers of material are then pressed flat by the application of heat and/or pressure. The combination of extrusion/calendering process is particularly preferred.
• the photosensitive element After the photosensitive element is prepared, it is cooled, e.g., with blown air, and is passed under a bank of fluorescent lamps, e.g., black light tubes, placed traverse to the path of movement. The photosensitive element is continually exposed through the support to partially polymerize a predetermined thickness of the photopolymer layer adjacent the support.
• a long exposure time may improve the anchoring of the matting agent on the surface of the flexographic printing plate and thereby enhance the surface coverage by the matting agent.
• An overall back exposure may be conducted before or after the imagewise exposure to polymerize a predetermined thickness of the photopolymer layer adjacent the support. This polymerized portion of the photopolymer layer is designated a floor. The floor thickness varies with the time of exposure, exposure source, etc. This exposure may be done diffuse or directed. All radiation sources suitable for imagewise exposure may be used. The exposure is generally for 1-30 minutes.
• the photosensitive printing element is treated to remove unpolymerized areas in the photopolymerizable layer and thereby form a relief image.
• the treating step removes at least the photopolymerizable layer in the areas which were not exposed to actinic radiation, i.e., the unexposed areas or uncured areas, of the photopolymerizable layer.
• the matted layer disposed above the non-exposed areas of the photopolymerizable layer and the polymeric binder of the matted layer which are disposed above the exposed areas of the photopolymerizable layer are removed with the treating step.
• the surface opposite the support ultimately is the printing surface of the printing element.
• the printing surface is the raised area/s of the relief which carry ink.
• This printing surface of the photopolymerized printing plate may be covered with particles of the matting agent from the matted layer. Surface coverage, as herein described is measured under a microscope in transmission or by SEM/EDX techniques as described below. In one embodiment of the invention, > 0.5 % of the printing surface of the flexographic printing plate is covered with the matting agent, preferably, 0.5-1 % of the printing surface. In another embodiment of the invention,
• the printing surface > 20 % of the printing surface.
• 20-30 % of the printing surface can be covered with the matting agent.
• Flexographic printing plates showing a high covering of the printing surface with matting agent can advantageously be used in offset lacquering applications.
• the additional layers that may be present on the photopolymerizable layer are removed or substantially removed from the polymerized areas of the photopolymerizable layer.
• the treating step also removes the mask image (which had been exposed to actinic radiation).
• the developers can be organic solvents, aqueous or semi-aqueous solutions, or water.
• Suitable organic solvent developers include aromatic or aliphatic hydrocarbon, and aliphatic or aromatic halohydrocarbon solvents, for example, n-hexane, petrol ether, hydrated petrol oils, limonene or other terpenes or toluene, isopropyl benzene, etc., ketones such as methyl ethyl ketone, halogenated hydrocarbons such as chloroform, trichloroethane, or tetrachloroethylene, esters such as acetic acid or acetoacetic acid esters, or mixtures of such solvents with suitable alcohols.
• the relief printing plates are generally blotted or wiped dry, and then more fully dried in a forced air or infrared oven. Drying times and temperatures may vary, however, typically the plate is dried for 60 to 200 minutes at 60 °C. High temperatures are not recommended because the support can shrink and this can cause registration problems.
• the absorbent material is selected having a melt temperature exceeding the melt temperature of the uncured portions of the photopolymerizable layer and having good tear resistance at the same operating temperatures. Preferably, the selected material withstands the temperatures required to process the photosensitive element during heating.
• the absorbent material is selected from non-woven materials, paper stocks, fibrous woven material, open-celled foam materials, porous materials that contain more or less a substantial fraction of their included volume as void volume.
• the absorbent material can be in web or sheet form.
• the absorbent materials should also possess a high absorbency for the molten elastomeric composition as measured by the grams of elastomer that can be absorbed per square millimeter of the absorbent material. Preferred is a non-woven nylon web.
• the flexographic printing plate may be post exposed and/or chemically or physically after-treated in any sequence to detackify the surface of the flexographic printing plate.
• the matting agent was dispersed with glass beads having a diameter of 2 mm for 5 min on a disperser (BAS-20 from Lau GmbH, D-58675, Germany) with a vibration frequency of 620 min" 1 according to DIN 53238-13 (draft ISO 8780).
• the dispersion was coated with a 30 ⁇ m doctor-box on a polyester cover sheet to form a matted layer. After air drying at ambient room conditions (22 °C, 45% relative humidity) the resulting dry matted layer had a measured total coating weight of 27.50 mg/dm 2 and a corresponding calculated coating weight of the matting agent of 8.25 mg/dm 2 .
• the surface roughness Rmax was 9.2 ⁇ m, Rz was 8.4 ⁇ m and Ra was 1.5 ⁇ m measured on top of the dry matted layer before lamination to the Cyrel ® plate.
• Rmax 3.25 ⁇ m
• Rz 2.63 ⁇ m
• Ra 0.35
• the photosensitive element was back and front exposed, washed-out, dried and finished. After processing the press- ready printing plate was measured again and the following surface roughness data were measured: for Rmax 4.85 ⁇ m, for Rz 4.10 ⁇ m and for Ra 0.40 ⁇ m.
• This matted layer was overcoated with a polyethylene wax layer.
• this cover element according to the present invention was used as cover element instead of the conventional cover element.
• As comparative examples DuPont Cyrel® 45HiQ and 67HiQ photopolymerizable printing plates with standard cover element (polyester cover sheet with release layer comprising Macromelt ® 6900 and an amphoteric interpolymer) were produced, too.
• an extruder was used to perform the function of melting, mixing, deaerating and filtering the conventional photopolymerizable mixture for Cyrel ® HiQ photopolymer printing plates.
• Inventive and conventional printing plates were printed on a Lemo Masterflex® flexographic printing machine using a 500er anilox with a ink volume of 3,5 cm 3 /nr ⁇ 2 at a print speed of 120 meters per minute.
• paper Saappi Algro Finess; 70 g/m 2
• film Tespaphan® SHD 50.0
• solvent based ink for film LM magenta from Siegwerk Druckmaschine/Siegburg
• water based ink for paper Hardtmann Magenta
• a photosensitive element based on Cyrel® 67NOW was prepared according to Example 4, wherein the standard release layer was replaced by a release layer comprising Syloid® ED5 and Macromelt ® 6900 as described in Example 4 and having a matting agent/polymeric binder ratio of 17/83.
• the photosensitive element was processed to a flexographic printing plate as described in Example 4.
• the final printing plate was evaluated with the previously described SEM/EDX techniques.
• Ra 0.60 ⁇ m.
• a commercial Cyrel® 67NOW plate was processed in the same way.
• the surface of the press-ready plate was highly glossy.
• Two sets of printing plates were prepared by standard procedure as described in Example 1 and Example 4. Exposure conditions for backflash were 65 sec and 70 sec, respectively, and for main exposure 18 min and 15 min, respectively.
• the plates were exposed in a Cyrel® Exposure Unit 1000 EC/LF and washed-out in a Cyrel® Processor Smart 1000 P with Cyrel® Flexosol as wash-out solvent.
• the plates were dried in a Cyrel®Dryer 1002 D for 3 h at 60 °C. Light finishing and post exposure was done in a Cyrel® Lightfinisher 1002 LF for 3 min with UV-A and UV-C radiation simultaneously.
• Sample 2 showed a matte surface different from Sample 1 which had a glossy surface.
• HiQ-NS-A was a flexo plate based on a Cyrel® 67HiQ plate wherein the standard release layer was replaced by a matted layer comprising Syloid® ED5 and Macromelt® 6900 and having a matting agent/polymeric binder ratio of 17/83 and a silica coating weight of 5.5 mg/ dm 2 ;
• HiQ-NS-B was a flexo plate based on a Cyrel® 67HiQ plate wherein the standard release layer was replaced by a matted layer comprising 17.25 % of weight of Syloid® ED5, 76.5 % of weight of the Macromelt® 6900, and 6.25 % of weight of a blue dye (Orasol Blue GL from Ciba Specialty Chemicals Inc., CH-4002 Basel, Switzerland), the total coating weight was 32 mg/ dm 2, the silica coating weight was
• HiQ-NS-C was a flexo plate based on a Cyrel® 67H ⁇ Q plate wherein the standard release layer was replaced by a matted layer comprising Syloid® ED5 and Macromelt® 6900, and having a matting agent/polymeric binder ratio of 30/70 and a silica coating weight of

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• 2003
  • 2003-03-14 DE DE60322030T patent/DE60322030D1/de not_active Expired - Lifetime
  • 2003-03-14 WO PCT/US2003/008058 patent/WO2003079114A1/en not_active Ceased
  • 2003-03-14 CA CA002477779A patent/CA2477779A1/en not_active Abandoned
  • 2003-03-14 JP JP2003577056A patent/JP4231791B2/ja not_active Expired - Lifetime
  • 2003-03-14 US US10/507,950 patent/US20050142480A1/en not_active Abandoned
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