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WO1996040528A1 - Compositions de mousse polymeres photosensibles contenant du thiol - Google Patents

Compositions de mousse polymeres photosensibles contenant du thiol Download PDF

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Publication number
WO1996040528A1
WO1996040528A1 PCT/US1996/000963 US9600963W WO9640528A1 WO 1996040528 A1 WO1996040528 A1 WO 1996040528A1 US 9600963 W US9600963 W US 9600963W WO 9640528 A1 WO9640528 A1 WO 9640528A1
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WO
WIPO (PCT)
Prior art keywords
parts
foam
composition
weight
mils
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.)
Ceased
Application number
PCT/US1996/000963
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English (en)
Inventor
Jung Hsien Tsao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
P T Sub Inc
Original Assignee
P T Sub Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by P T Sub Inc filed Critical P T Sub Inc
Priority to AU47055/96A priority Critical patent/AU4705596A/en
Publication of WO1996040528A1 publication Critical patent/WO1996040528A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • 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
    • B41N10/00—Blankets or like coverings; Coverings for wipers for intaglio printing
    • B41N10/02—Blanket structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/834—Chemically modified polymers by compounds containing a thiol group
    • C08G18/835—Unsaturated polymers modified by compounds containing a thiol group
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/38—Meshes, lattices or nets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • B41N2210/00—Location or type of the layers in multi-layer blankets or like coverings
    • B41N2210/02—Top 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
    • B41N2210/00—Location or type of the layers in multi-layer blankets or like coverings
    • B41N2210/04—Intermediate 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
    • B41N2210/00—Location or type of the layers in multi-layer blankets or like coverings
    • B41N2210/14—Location or type of the layers in multi-layer blankets or like coverings characterised by macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • This invention relates to thiol-containing photosensitive polymeric compositions and thiol-containing foam compositions that are formed by mechanically frothing a polymeric composition and curing the resulting froth with radiation to yield a foam composition.
  • the invention also relates, inter alia, to laminates such as printing blankets and foam sheets comprising the thiol-containing polymeric foam compositions of the invention, and graphic art devices such as compressible printing plates comprising the same.
  • Compressible printing blankets offer printers an advantage over noncompressible printing blankets by eliminating the need for precise underpacking to achieve an acceptable amount of pressure between printing plate, printing blanket, and the paper or other material to be printed.
  • These compressible printing blankets often use foam, normally a very thin layer, to keep the pressure relatively constant over a wide range of squeeze.
  • the foam should have good compression set resistance, uniform compressibility, uniform gauge (so as to print uniformly) , should be capable of being applied during the manufacture of the blanket, and should be capable of being cured to a uniform gauge.
  • Foaming agents and blowing agents i.e., compounds capable of releasing gases such as carbon dioxide by decomposition, normally at high temperatures
  • foams have been cured at high temperatures, over an extended period of time, using sulfur as a curative.
  • foams prepared using these systems often did not possess the important properties of uniform compressibility, uniform gauge, and good compression set resistance. These deficiencies were likely caused by the high temperature operations of foaming, curing, and water or solvent removal all of which can result in nonuniform foam formation. Problems associated with foam formation are particularly acute when the operations are time consuming and result in a partial collapse of the foam before sufficient curing has occurred to maintain the foam structure and gauge.
  • Nonuniform foams are poor candidates for use in graphic art devices as printing blankets or printing plates due, in part, to their nonuniform compressibility.
  • foams available in the art made from photosensitive polymeric materials that have the properties of uniform compressibility, uniform gauge, and good compression set resistance. Examples of such foam compositions are disclosed in U.S. Patent No. 4,771,078 entitled, "Method of Producing a Foam From a Radiation- Curable Composition" assigned to a common assignee hereof, the disclosure of which is herein incorporated by reference in its entirety. Foams such as those disclosed in U.S. Patent No. 4,771,078 can result in a relatively hard foam sheet, and thus, a composite printing plate or a printing blanket incorporating the foam can have limited compressibility.
  • This invention presents, inter alia, thiol- containing photosensitive polymeric foam compositions.
  • the novel photosensitive polymeric foam compositions of the invention provide the basis for improved graphic art devices such as printing blankets, foam sheets, and compressible printing plates.
  • the photosensitive polymeric foam compositions of the invention possess unique properties that make them good materials for use in laminates and graphic art devices such as printing blankets and printing plates.
  • the polymeric foam compositions of the invention are softer than those currently used in the art, which, inter alia , provides better compressibility. Yet, the softness of the polymeric foam compositions of the invention does not compromise their property of toughness.
  • the thiol component present in the composition imparts a unique balance of softness and toughness that makes the compositions of the invention excellent materials for incorporation into graphic art devices.
  • the polymeric foam compositions of the invention also have the further quality of being highly transparent to ultraviolet light, even when used in graphic art devices at thicknesses greater than those currently -used in the art. This property enables one to prepare a compressible printing plate that can be back exposed.
  • the use of a thicker foam in such plates also has the added benefit of increased compressibility which, inter alia, prevents distortion of the print.
  • thiol-containing photosensitive resin compositions comprising (a) 100 parts by weight of a urethane prepolymer comprising a plurality of diol segments linked through a urethane linkage and having an addition- polymerizable ethylenically unsaturated group at both terminal ends thereof, the plurality of diol segments being selected from the group consisting of polyester diols, polyether diols, and combinations thereof; (b) about 1 to 50 parts by weight, relative to the 100 parts by weight of the urethane prepolymer (a), of a thiol component; (c) about 5 to 80 parts by weight, relative to the 100 parts by weight of the urethane prepolymer (a) , of a reactive diluent; and (d) about 0.1 to about 5 parts by weight, relative to the 100 parts by weight of the urethane prepolymer (a) , of a photoinitiator and/or photos
  • the thiol-containing photosensitive resin compositions may further comprise a plasticizer and/or surfactant, such resin compositions comprise about 1 to 15 parts by weight, relative to the 100 parts by weight of the urethane prepolymer (a) of a plasticizer and about 0.1 to 5 parts by weight, relative to the 100 parts by weight of the urethane prepolymer (a) of a surfactant.
  • the invention is further directed to thiol- containing polymeric foam compositions made from the photosensitive resin compositions of the invention.
  • articles incorporating the thiol-containing polymeric foam compositions of the invention are disclosed.
  • laminates including, but not limited to, foam sheets and printing blankets are disclosed.
  • the laminates incorporating the novel foam compositions of the invention have various uses including, but not limited to, being used on business forms and envelope printing presses to transfer ink from a printing plate to the paper, printing cushions, as packing blankets on newspaper offset presses, compressible printing blankets when the topcoat selected is ink receptive and solvent resistant, compressible packing blankets for flexographic printing plates, printing blankets for letterpress drawsheets, as a part of rubber stamps, and compressible offset printing blankets. See also U.S. Patent No. 4,771,078.
  • graphic art devices including, but not limited to, compressible printing plates comprising the novel foam compositions of the invention.
  • Uses of foam compositions in printing plates are disclosed, for example, in U.S. Patent No. 4,582,777, the disclosure of which is herein incorporated by reference in its entirety.
  • Figure 1 depicts an embodiment of a compressible printing plate comprising a layer of a foam composition of the invention.
  • the photopolymer layer 1 is used to form a relief image on the facing of the plate.
  • the foam layer 3 which is attached to a film backing 7, in part, by a tie coat 5.
  • Figure 2 depicts another embodiment of a compressible printing plate comprising a layer of a foam composition of the invention.
  • the photopolymer layer 2 is used to form a relief image on the facing of the plate.
  • the foam layer 4 which is reinforced with a mesh reinforcing element 6, such as a fiber-glass coarse screen, rather than the combination of a tie coat and the film backing as shown in Figure 1.
  • graphics art devices is used generally and is meant to include, without limitation, laminates, printing plates, and the like.
  • oligomer As used in this invention, the term "prepolymer” is meant to include adducts or reaction intermediates and includes oligomers.
  • oligomer as used herein includes, but is not limited to, low molecular weight polymers having only a few monomeric units. Typical oligomers normally have molecular weights below 30,000, but such weights may range from 500 to 10,000; 5,000 to 20,000; or 1,000 to 15,000. The molecular weight may be determined using gel permeation chromatography using a styrene standard, which usually gives both the number average and the weight average of the composition of interest.
  • diol is used synonymously with the term oligomer and refers to, without limitation, polyols including, without limitation, polyethers, polyesters, or combinations thereof.
  • polymer and "resin” are used interchangeably and refer to the liquid-like composition that is the precursor to the foam compositions of the invention. In other words, it is the resin composition that is frothed and then cured to yield a foam composition of the invention.
  • reactive diluent refers to a low viscosity monomer which is compatible with the prepolymers used herein and is used to lower the viscosity of the prepolymer to a manageable liquid state and also to take part in the radiation initiated polymerization or crosslinking.
  • reactive functional group or “functional”
  • aliphatic refers to any carbon-hydrogen containing compounds having either saturated or unsaturated bonds
  • alkanes, alkenes, alkynes such compounds may be cyclic or acyclic, straight or branched chains, and may further be substituted with hetero atoms.
  • aromatic refers to any compounds that contains at least one benzene ring.
  • photoinitiator refers to compounds that are effective in promoting free radical addition polymerization by generating reactive species, such as free radicals, by way of unimolecular scission resulting from photoexcitation.
  • photosensitizers refers to compounds that are effective in promoting free radical addition polymerization through bimolecular photochemical reactions of the energy donor or transfer type or hydrogen abstraction type or by formation of a donor-acceptor complex with monomers or additives leading to ionic or radical species.
  • a "plasticizer” is a compound added to a polymeric, prepolymeric, or oligomeric composition both to facilitate processing and to increase the flexibility and toughness of the final product.
  • surfactant is a compound which reduces the surface tension of a liquid or which reduces the interfacial tension between two liquids or between a liquid and a solid and promotes the stability of froths.
  • surfactant is a compound which reduces the surface tension of a liquid or which reduces the interfacial tension between two liquids or between a liquid and a solid and promotes the stability of froths.
  • radiation curable means capable of being crosslinked and/or polymerized and/or copolymerized by exposure to radiation either inherently, ( i . e . , in the absence of photoinitators and/or photo ⁇ sensitizers) , or through the use of photoinitiators and/or photosensitizers.
  • radiation as used herein, is meant to exclude thermal radiation and low energy electromagnetic radiation in the microwave and radiowave regions but to include ionizing radiation such as gamma rays, x-rays, and subatomic charged particles when accelerated in a cyclotron or betatron.
  • radiation curing is intended to include photopolymerization, photocuring, and all forms of polymeric matrix (network) formation resulting from radiation including, but not limited to, covalent carbon to carbon crosslinkings, homopolymerization, copolymerization, branching, and grafting.
  • photocurable denotes the capability of being cured by actinic type radiation (i.e., radiation in the visible and ultraviolet spectral regions) .
  • a "photopolymerizable composition, " as that language is used herein, is one capable of being cured by actinic radiation and generally contains a photoinitiator and/or photosensitizer.
  • compositions to produce cured polymeric materials are well known in the art.
  • the prior art discloses the various forms of radiation which can be used, when photoinitiators and/or photosensitizers should be used, and what compositions may be cured and/or polymerized by the radiation (i . e . , for example, reactive diluent/oligomer compositions) .
  • the radiation i . e .
  • the mechanical frothing of liquid compositions to produce polymeric foams is also well known in the art . See, e . g. , U.S. Patent Nos. 4,582,777; 4,771,078; 4,767,793; and 4,415,615, the disclosures of which are herein incorporated by reference in their entirety.
  • the present invention involves the discovery that by using well .known mechanical frothing techniques with well known radiation techniques, foams having a highly uniform compressibility across their entire surfaces and good resistance to compression set can be prepared from the thiol-containing resin compositions disclosed herein. Both of these properties are extremely important in foam layers used in graphic arts devices.
  • the thiol-containing polymeric foam compositions of the invention are an improvement over the currently available foams used in graphic art devices because they are softer, thus providing better compressibility, but retaining the required property of toughness. It is believed that the thiol component imparts a unique balance of softness and toughness to the compositions that make them excellent materials for incorporation into graphic art devices such as printing blankets.
  • the thiol-containing polymeric foam compositions of the invention also exhibit a high level of ultraviolet transmittance, even at thicknesses greater than those presently used in graphic art devices. This enables one to generate foams with high compressibility which can be back- exposed, making these foams ideal candidates for use in graphic art devices such as composite printing plates.
  • the foam compositions of the present invention generally have the following characteristics.
  • the voids (bubbles) resulting from the frothing technique are essentially spherical in shape and are empty (i.e., do not contain foreign matter such as hollow microspheres, microballoons, frangible bubbles, the byproducts of chemical blowing agents, remnants thereof) .
  • Some prior art foams are prepared by compounding a thin layer of polymer with salt and then extracting the salt with water to form voids.
  • This salt extraction process forms voids with an irregular nonspherical, non-elliptical shape which have a greater tendency to merge into one another, thereby creating void networks.
  • the foam of the present invention does not have irregularly shaped voids and such networks. Rather the voids in the foam of the present invention, as previously mentioned herein, are generally essentially spherical.
  • Some foams require the presence of microballoons, cork, ground sponge rubber, microspheres, or frangible bubbles which either remain intact during the use of the foam or collapse or fracture during the use of the foam, the remnants thereof remaining within the voids.
  • the voids in the foam of the present invention are empty (i.e., contain no such structures or remnants thereof) .
  • the foam compositions of the present invention are generally closed cell foams ( i . e . , normally at least 80% of the void volume does not interact to form networks or pores) .
  • the foam layer is generally essentially skin-free. This differs from some prior art foams where either or both of the upper and lower portions of the foam layer have a much lower concentration of voids (i.e., a lower void to solid ratio than the middle portion of the foam layer) , either intentionally or unintentionally, in essence forming a relatively nonfoamed, skin layer. Where the foam layer can very thin, for example in printing blankets, the formation of a dense layer, essentially free of voids, within the foam layer, can seriously reduce the lower density portion of the foam.
  • a foam layer is 60 mils thick and possesses top and bottom "skins" that are essentially non-foamed, and each 20 mils thick
  • the foamed portion in the center of the layer would only be 20 mils thick.
  • essentially the entire 60 mils of thickness would be foamed. This not only provides increased compressibility, but provides the advantages that, should a variation in the gauge of the foam portion occur (for example by applying the foam layer by spreading, prior to curing or during curing) , the variation in compressibility over the foam would be less than that for "skinned" foams.
  • radiation-curable compositions such as those disclosed herein, can be obtained by mixing a polymer with a reactive diluent that is sufficiently miscible with the polymer to create a composition with a viscosity suitable for applying to a substrate and/or for foaming.
  • a solid composition can be heated to a molten liquid state to prove a suitable viscosity.
  • the radiation-curable compositions of the present invention should have a liquid consistency to permit mechanical frothing. If the liquid consistency can be obtained by heating a composition, such heating is permissible.
  • the resin and foam compositions of the invention generally comprise polyurethanes.
  • polyurethanes are synthesized by reacting a diol with a diisocyanate.
  • Diisocyantes suitable for practicing the invention include, but are not limited to, aliphatic or aromatic diisocyantes, with aliphatic isocyante compounds being preferred.
  • Diols or oligomers suitable for synthesizing the polyurethane prepolymers of the invention include, but are not limited to, polyethers, polyesters, or combinations thereof, with polyethers being preferred.
  • a preferred polyurethane prepolymer of the invention may be synthesized by reacting a diol, with a compound having at least two isocyanate groups, and a compound containing at least one functional hydrogen atom and at least one ethylenically unsaturated double bond.
  • a preferred prepolymer may be synthesized by mixing polytetramethyleneglycol and ethylene-oxide-propyleneoxide block polyetherdiol having about 30% by weight of ethylene oxide terminal units with dicyclohexylmethane diisocyanate to form a polyether urethane terminated with isocyanate groups.
  • At least one compound selected from the group consisting of hydroxy ethylacrylate and hydroxy ethylmethacrylate is added to yield a prepolymer.
  • the molecular weight of the prepolymer may be between about 700 to 30,000, more preferably it may be between about 5000 to 20,000, and most preferably it may be between about 1,000 to 15,000.
  • a preferred resin composition of the invention may then be synthesized, for example, by adding hydroxy ethyl ⁇ methacrylate and polypropylene glycol monomethacrylate, a photoinitiator, such as hydroxy-2-methyl-1-phenylpropan-l- one, and a thiol-containing compound such as trimethylol propane tris- (3-mercaptopropionate) to the above prepolymer.
  • the Brookfield viscosity of the polymeric composition measured at room temperature, generally may be between about 10,000 cps to 50,000.
  • the levels of the components which can be incorporated into the resin compositions of this invention, based on parts by weight per 100 parts by weight of the prepolymer are: preferably between about 5 to about 80 parts, more preferably between about 15 to about 55 parts of the reactive diluent; preferably between about 1 to about 50 parts, more preferably between about 3 to about 15 parts of the thiol component; preferably between about 0.1 to about 5 parts, more preferably about 0.3 to about 2 parts of photosensitizer and/or photoinitiator; between about 1 to about 15 parts, preferably between about 5 to about 10 parts, and more preferably between about 1 to about 8 parts of a plasticizer; and between about 0.1 to about 5 parts, preferably between about 0.5 to about 2, and more preferably between about 0.5 to about 1.5 parts of the surfactant .
  • compositions can be included in the composition, without detracting from the spirit of the invention, such as antioxidants, inhibitors, flame-retardant agents, tackifiers, and the like, the criteria being that the materials do not significantly impede the polymerization of the composition, nor prevent the transmission of radiation.
  • the prepolymers of the present invention may be reactive or non-reactive.
  • Reactive oligomers or prepolymers include those that are capable of forming a free radical by exposure to radiation in the presence, if necessary, of a photoinitiator and/or photosensitizer, and normally contain unsaturation. It is to be understood that oligomers can include those materials which can be cured by exposure to radiation by other than a free radical mechanism ( i . e . , epoxides, which are radiation cured by means of photolytically generated cationic catalysts) .
  • the oligomers used in the foam compositions of the invention be reactive because such oligomers take part in the polymerization or crosslinking reaction which is initiated by radiation as opposed to the non-reactive oligomers which are incorporated within the network of the polymerized reactive diluent.
  • the radiation-curable composition is prepared from an oligomer and the viscosity of the oligomer is sufficiently low to be a liquid at room temperature or with some heating, it may be used with or without a reactive diluent as part of the radiation-curable composition. If no reactive diluent is used, then the oligomer must itself be reactive so as to form a polymer matrix during the radiation step. That is, the oligomer must contain reactive sites such as unsaturation in the form of carbon to carbon double bonds and/or epoxide groups which are activated by radiation, and if necessary, in the presence of a photoinitiator and/or a photosensitizer, to result in free radical and/or cationic cures.
  • the oligomer can be reactive or nonreactive. If the oligomer is nonreactive, then the reactive diluent is preferably multifunctional so as to form a polymer network.
  • Typical reactive prepolymers suitable for practicing the invention include, but are not limited to, those having acrylic or methacrylic acid ester groups in their backbone conforming to the following structural formula wherein R is selected from the group consisting of hydrogen and methyl.
  • Polyurethane prepolymers within the scope of this invention include, but are not limited to, aliphatic or aromatic urethane acrylate oligomers; acrylated epoxy urethanes; acrylated polyether urethanes; and acrylated polyester- polyether urethanes. It is preferred that the polyurethane oligomer be a polyether; more preferably, the oligomer is an aliphatic polyether urethane acrylate oligomer. Urethane prepolymers comprising the above functionality will be known to those skilled in the art and may be used without departing from the spirit of the invention.
  • the prepolymer will comprise two polyol monomeric units and three isocyanate moieties, with the two polyol units internally interrupted by an isocyanate group.
  • a reactive diluent is a low viscosity monomer which is compatible with the prepolymer and is used to lower the viscosity of the oligomer to a manageable liquid state and also to take part in the radiation initiated polymerization or crosslinking.
  • Reactive diluents can be multifunctional monomers or monofunctional monomers. Typical multifunctional monomers are the di- and triacrylates and methacrylates, and combinations thereof.
  • Typical monofunctional monomers are the alkyl-acrylates, aryl-acrylates, alkoxyalkyl-acrylates and methacrylates, and combinations thereof. It is preferred that the reactive diluent comprise at least one multifunctional monomer, preferably the reactive functional group is hydroxyl.
  • Reactive diluents are homopolymerizable, compatible, and polymerizable with the oligomer when the oligomer is reactive.
  • the reactive diluents not only function to adjust (reduce) the viscosity of the composition, but also affect the cure rate as well as the properties of the cured foam compositions of the invention.
  • Reactive diluents suitable for use in the present invention include, but are not limited to, styrene; vinyl toluene; cv-methyl styrene; methyl acrylate; methyl methacrylate; propyl acrylate; butyl acrylate; 2-ethylhexyl acrylate; cyclohexyl acrylate; isodecyl acrylate; vinyl acetate; 2-phenoxy acrylate; glycidyl methacrylate,- tetrahydrofuryl methacrylate; caprolactone acrylate; 1,6- hexanediol diacrylate; pentaerythritol triacrylate; trimethylol propane triacrylate; aryloxyalkyl acrylates and methacrylates; alkoxyalkyl acrylates and methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; N-vinyl pyrrol
  • Particularly preferred reactive diluents are hydroxy ethyl acrylate, hydroxy ethyl methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, tetra hydrofuryl methacrylate, isocyanate methacrylate, tetra ethyleneglycol dimethacrylate, 1,6-hexane diol dimethacrylate, pentaerythritol-tetramethacrylate, and combinations thereof.
  • Particularly preferred reactive diluents include hydroxyethyl methacrylate, diethylene glycol dimethacrylate, and polypropylene glycol monomethacrylate.
  • Other reactive diluents known to those skilled in the art may be used without departing from the spirit of the invention.
  • Thiol-containing compounds suitable for practicing this invention should have more than one reactive SH functional group, and may be aliphatic or aromatic compounds.
  • the thiol compound has at least two, three, or four functional groups.
  • Preferred thiol- containing compounds include, but are not limited to, trimethylolpropane tris- (/3-mercaptopropionate) and pentaerythritol tetrakis (j ⁇ -mercaptopropionate) , with trimethylolpropane tris- ( -mercaptopropionate) being a preferred one.
  • Other thiol-containing compounds known to those skilled in the art may be used without departing from the spirit of the invention.
  • Photoinitiators and/or photosensitizers suitable for use in the present invention include, but are not limited to, 2, 2-dimethoxy-2-phenylacetophenone; 1- hydroxycyclohexyl phenyl ketone; 2-hydroxy-2-methyl-1- phenylpropan-1-one; benzophenone; benzoin; acetophenone; benzoin methyl ether; Michler's ketone; xanthone; propiophenone; fluorenone; carbazole; 2-, 3-, or 4- methylacetophenones; chlorothioxanthones; 2-acetyl-4- methylphenyl acetate; and 2,2-dimethoxy-2-phenyl- acetophenone.
  • a preferred photoinitaitor is 2, 2-dimethoxy- 2-phenylacetophenone, a more preferred photoinitiator is 1- hydroxycyclohexyl phenyl ketone, and an even more preferred photoinitiator is 2-hydroxy-2-methyl-1-phenylpropan-l-one.
  • Other photoinitiators/photosensitizers known to those skilled in the art may be used without departing from the spirit of the invention.
  • the thiol-containing photosensitive polymeric resin compositions of the invention may further comprise a plasticizer and/or surfactant.
  • Plasticizers are used to retain compression and permanent set resistance properties and/or to make a softer foam.
  • Plasticizers suitable for use in the present invention include, but are not limited to, halogenated organics, tri-aryl phosphates, carboxylic acid esters of organic alcohols, phosphate esters of organic alcohols.
  • a preferred plasticizer is dioctylphthalate, a more preferred plasticizer is dipropylene glycol dibenzoate, and an even more preferred one is tri-aryl phosphate.
  • Other plasticizers known to those skilled in the art may be used without departing from the spirit of the invention.
  • Surfactants are used to enhance the frothing as well as to stabilize the froth prior to and during radiation curing.
  • Surfactants suitable for use in the present invention include, but are not limited to, alkylaryl polyether alcohols, dioctyl sodium sulfosuccinate, silicone fluids, and amide derivatives of aliphatic alcohols.
  • Preferred surfactants are ethoxylated-propoxylated block copolymers, a more preferred surfactant is lauryl monoethanolamide, and an even more preferred surfactants are fatty diethanolamides.
  • Other surfactants known to those skilled in the art may be used without departing from the spirit of the invention.
  • the photosensitive polymeric resin compositions disclosed herein may be frothed and treated with radiation to yield the novel thiol-containing foam -compositions of the invention.
  • the methods of making polymeric radiation curable compositions are known in the art.
  • the conventional, well known techniques of mechanical frothing and radiation curing may be used to prepare the foams of the present invention.
  • the resin i . e . , comprising, for example, a prepolymer, reactive diluent, photoinitiator and/or photosensitizer
  • the resin is then frothed by using any one of a number of commercially available high-shear mixers into which is metered the radiation-curable composition and the air or inert gas such as nitrogen.
  • the ratio of gas to liquid is adjusted to produce a foam having the desired void volume and compressibility as well as physical properties.
  • the gas will represent from 10% to 90% by volume of the cured foam, preferably 15% to 65%, and more preferably between about 20% to 45%.
  • Representative equipment and techniques used in mechanical frothing are blenders; homogenizers such as colloid mills; mechanical frothing machines such as those sold by the Oakes Machine Corporation and Ease, Inc., which continuously inject a gas into a liquid and provide high agitation and dispersion, wire whips, such as Hobart mixers with planetary gears. Any other frothing equipment known to those skilled in the art may be used without detracting from the spirit of the invention.
  • the froth is normally distributed on a releasable sheet, on a substrate, or between two substrates (one or both of which will allow the passage of radiation) , and the froth is then exposed to radiation until cured.
  • a process for making a foam composition is set forth in the Examples and is further illustrated in U.S. Patent No. 4,771,078, the disclosure of which is incorporated herein by reference in its entirety.
  • the radiation-curable composition should contain reactive carbon to carbon double bonds (i . e . , unsaturation, and photoinitiators and/or photosensitizers should be used) .
  • unsaturation and photoinitiators and/or photosensitizers should be used
  • a higher energy radiation such as electron beam
  • the unsaturation and photoinitiators/photosensitizer requirements are diminished.
  • the radiation-curable polymer composition Due to the short time required to completely cure the radiation-curable polymer composition, usually from about 0.5 seconds to about 60 seconds, preferably 1 to 15 seconds, if commercially available high intensity actinic radiation or high energy electron beam radiation sources are used, additional stages can be constructed to add further layers to the laminates.
  • the state of cure can be varied by controlling the exposure time, the quantity of radiation, the distance from the source of radiation to the composition and the rate at which the composition is passed by the radiation source.
  • Various states of cure can be utilized to provide any properties to the polymer which would make it more conducive to downstream processing. Any of these variations may be done without detracting from the spirit of the invention.
  • the frothed material need not be completely cured by radiation to benefit by the practice of the present invention. Rather it is sufficient that it be cured to a degree sufficient to cause the foam to maintain its structure indefinitely ( i . e . , to avoid the collapse of a significant portion of the frothed material and to maintain the gauge) .
  • the resulting cured thiol-containing polymeric foam compositions of the invention are a matrix ( i . e . , polymer network) .
  • the network is comprised of the polyurethane prepolymer, the reactive diluent, photoinitiator/photosensitizer, and the thiol component.
  • the cured polymeric foam composition of the invention may .be laid out in sheets and may have a thickness of between about 10 to about 150 mils, more preferably between about 20 to about 120 mils, and more preferably between about 40 to about 100 mils.
  • the particular thickness of the foam used can depend on the application (i.e., whether the foam is used in a printing blanket or a printing plate) .
  • the cured polymeric foam composition should preferably have a density between about 0.3 to about 1.0 g/cm 3 , more preferably between about 0.4 to about 0.9 g/cm 3 , and most preferably between about 0.6 to about 0.9 g/cm 3 .
  • the density of the foamed composition may be determined using ASTM techniques, but other methods known to those skilled in the art can be used without departing from the spirit of the invention.
  • the cured polymeric foam composition should preferably have a resilience between about 25 to about 75%, more preferably between about 30 to about 50%, and most preferably between about 25 to about 45%.
  • the resilience of the cured foam composition is generally determined using ASTM techniques, but other methods may be used without departing from the spirit of the invention.
  • the ultraviolet transmittance of the cured polymeric foam composition should preferably be between about 10% to about 30%, more preferably between about 30% to about 40%, and most preferably between about 40% to about 50%.
  • Ultraviolet transmittance is generally determined by measuring the intensity of a light beam and then measuring the intensity of the same light beam with a piece of the cured foam placed in its path; the percent transmittance is then calculated based on the measured values. Other methods known to those skilled in the art may be used without departing from the spirit of the invention.
  • a preferred cured foam composition of the invention will have a thickness between about 40 to about 100 mils, a resilience between about 25 to about 50%, and an ultraviolet transmittance between about 10 to about 40%.
  • articles incorporating the thiol-containing photosensitive polymeric foam compositions of the invention are disclosed.
  • laminates including, but not limited to, foam sheets and printing blankets are disclosed.
  • a laminate can be formed using the foam of the invention sandwiched between two layers of fabric, without the use of additionally adhesives (i . e . , tie coat) to adhere the foam to the fabric.
  • the foam is its own fabric adhesive.
  • Fabrics useful for practicing the invention include, but are not limited to, cotton, nylon, polyester, aramid, rayon, acrylics, and the like.
  • These fabrics are also suitable for use as backings for printing plates as disclosed herein.
  • type of fabric i.e., its weave, type of material, dip composition, etc.
  • greater or lesser amounts (intensities) of actinic radiation will be necessary for a proper degree of cure.
  • the substrate should have a light color (i.e., not so dark as to absorb large amounts of the actinic radiation and thereby inhibit the curing of the composition) .
  • the laminates incorporating the novel foam compositions of the invention have various uses including, but not limited to, being used on business forms and envelope printing presses to transfer ink from a printing plate to the paper, as packing blankets on newspaper offset presses, compressible printing blankets when the topcoat selected is ink receptive and solvent resistant, compressible packing blankets for flexographic printing plates, printing blankets for letterpress drawsheets, rubber stamps, and compressible offset printing blankets. See, e . g. , U.S. Patent No. 4,771,078.
  • a printing plate comprising a foam composition of the invention may comprise a photopolymer layer having a thickness between about 150 to about 215 mils; a layer of a foam composition of the invention having a thickness of between about 35 to about 100 mils; a very thin layer of a tie coat (adhesive) having a thickness between about 0.1 to about 0.7 mils, preferably about 0.6 mils, and more preferably about 0.5 mils; and a film layer such as polyester having a thickness of between about 4 to about 10 mils.
  • FIG. 1 An example of such a compressible printing plate is depicted in Figure 1.
  • An alternative printing plate within the scope of this invention comprises a mesh reinforcement such as a fiber glass screen in place of the film; this mesh coat has a thickness of between about 1 to about 20 mils, preferably between about 4 to about 20 mils, and most preferably about 10 to about 18 mils. Any mesh reinforcement elements known to those skilled in the art may be used without departing from the spirit of the invention.
  • FIG. 2 An example of such a printing plate is depicted in Figure 2.
  • the foam composition when used in a printing plate it will preferably have a thickness of between about 40 to 100 mils, a density between about 0.6 to about 0.9 g/cm 3 , a resilience of between about 25 to about 50%, and an ultraviolet transmittance of between about 10% to about 40%.
  • the photosensitive polymeric composition of Example 1 was frothed on an OakesTM mixer using nitrogen as the frothing gas at such a level as to give about 20 to 30% volume percent of gas based on the composition.
  • the froth which had the consistency of shaving cream, was then fed into the nip of a doctor over a roll coater between two pieces of transparent, biaxially-orientated polyethylene tetraphthalate films through a spreading means at a speed of 3 yards/minute to set the gauge, then exposed to ultraviolet radiation using a combination of bank of fluorescent black light bulbs (90% emission at 300-400 nm) and medium pressure mercury vapor lamps to cure the foam sheet.
  • Example 2 The same foaming procedure as used in Example 2 was used except that a reinforcing fiber-glass coarse screen was fed with the froth into the coating head and between two polyester sheets. The resulting foam sheet produced had the embedded reinforcing screen instead of the polyester backing.
  • two gauges (40 mils and 63 mils) of foam sheet were produced.
  • the 40 mils thus obtained had a resilience of about 31%, a density of about 0.88 g/cm 3 , an ultraviolet transmittance of about 30%.
  • the 63 mils thus obtained had a resilience of about 35%, density of about 0.88 g/cm 3 , and an ultraviolet transmittance of about 20%.
  • Example 1 was frothed in air by vigorous stirring with a kitchen blender to a creamy mass of about 0.55 g/cm 3 density. It was then coated between two plastic films and then cured under ultraviolet lights. After peeling off the two plastic films, a soft and tough foam sheet resulted having a thickness of about 35 mils, a resilience of about 34%, a density of about 0.62 g/cm 3 , and an ultraviolet transmittance of about 23%.
  • Example 5 Example 5
  • the photosensitive polymeric composition of Example 5 was frothed in air by vigorous stirring with a kitchen blender to a creamy mass with a density of 0.58 g/cm 3 , coated between plastic films, and then cured by ultraviolet radiation to provide a very flexible, and tough foam sheet after peeling off the plastic film.
  • the foam sheet was about 39 mils (1 mm) thick, had a density of about 0.67 g/cm 3 , a resilience of about 29%, and a capability of transmitting about 33% of ultraviolet light.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)

Abstract

L'invention concerne des compositions polymères photosensibles contenant du thiol et des compositions de mousse qui sont formées par moussage mécanique par battage de la composition polymère et par polymérisation de la mousse obtenue par rayonnements pour donner une composition de mousse. L'invention concerne également, entre autres, des stratifiés tels que des blanchets d'impressions et des feuilles de mousse comprenant les compositions de mousse polymère contenant du thiol, et des dispositifs graphiques tels que des planches d'impression comprenant ces dernières.
PCT/US1996/000963 1995-06-07 1996-01-24 Compositions de mousse polymeres photosensibles contenant du thiol Ceased WO1996040528A1 (fr)

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AU47055/96A AU4705596A (en) 1995-06-07 1996-01-24 Thiol-containing photosensitive polymeric foam compositions

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US47344495A 1995-06-07 1995-06-07
US08/473,444 1995-06-07

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FR2770451A1 (fr) * 1997-11-06 1999-05-07 Rollin Sa Couche lithographique perfectionnee pour blanchet d'impression et blanchet equipe de cette couche
EP0919869A1 (fr) * 1997-12-01 1999-06-02 Nichigo-Morton Co Ltd Compositions photopolymérisables contenant des oligomères d'uréthane et des plastifiants du type dibenzoate
FR2803246A1 (fr) * 1999-12-31 2001-07-06 Rollin Sa Plaque d'impression presentee en rouleau et procede d'obtention
FR2803245A1 (fr) * 1999-12-31 2001-07-06 Rollin Sa Plaque compressible pour impression flexographique et procede d'obtention
US6353037B1 (en) 2000-07-12 2002-03-05 3M Innovative Properties Company Foams containing functionalized metal oxide nanoparticles and methods of making same
US6573305B1 (en) 1999-09-17 2003-06-03 3M Innovative Properties Company Foams made by photopolymerization of emulsions
US7138436B2 (en) 2001-06-13 2006-11-21 3M Innovative Properties Company Uncrosslinked foams made from emulsions
WO2007129704A1 (fr) 2006-05-08 2007-11-15 Asahi Kasei Chemicals Corporation Matériau d'amortissement pour une impression
EP2128181A1 (fr) * 2008-05-29 2009-12-02 Heinrich Sommer Système prépolymère
JP2013182174A (ja) * 2012-03-02 2013-09-12 Toyo Ink Sc Holdings Co Ltd 感光性樹脂組成物
EP2993200A1 (fr) 2014-09-02 2016-03-09 Greenseal Chemicals NV Composition de précurseur de mousse à base de thiol-acrylate
WO2017036525A1 (fr) 2015-09-02 2017-03-09 Greenseal Chemicals Nv Composition précurseur de mousse à base de thiol-acrylate
EP2484731A4 (fr) * 2009-09-29 2017-12-27 DIC Corporation Composition de primaire, structure de dalle de plancher imperméable l'utilisant et procédé pour réaliser l'imperméabilisation d'une dalle de plancher
CN111742261A (zh) * 2018-03-29 2020-10-02 富士胶片株式会社 感光性转印材料、电极保护膜、层叠体、静电电容型输入装置及触摸面板的制造方法

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0914966A1 (fr) * 1997-11-06 1999-05-12 Rollin S.A. Couche lithographique perfectionnée pour blanchet d'impression et blanchet équipé de cette couche
US6146748A (en) * 1997-11-06 2000-11-14 Rollin Sa Lithographic layer for a printing blanket and a printing blanket fitted with this layer
FR2770451A1 (fr) * 1997-11-06 1999-05-07 Rollin Sa Couche lithographique perfectionnee pour blanchet d'impression et blanchet equipe de cette couche
EP0919869A1 (fr) * 1997-12-01 1999-06-02 Nichigo-Morton Co Ltd Compositions photopolymérisables contenant des oligomères d'uréthane et des plastifiants du type dibenzoate
US6573305B1 (en) 1999-09-17 2003-06-03 3M Innovative Properties Company Foams made by photopolymerization of emulsions
US6759080B2 (en) 1999-09-17 2004-07-06 3M Innovative Properties Company Process for making foams by photopolymerization of emulsions
WO2001049509A1 (fr) * 1999-12-31 2001-07-12 Macdermid Graphic Arts S.A. Plaque d"impression presentee en rouleau et procede d"obtention
WO2001049510A1 (fr) * 1999-12-31 2001-07-12 Macdermid Graphic Arts S.A. Plaque compressible pour impression flexographique et procede d'obtention
US7384685B2 (en) 1999-12-31 2008-06-10 Macdermid Graphic Arts S.A. Compressible plate for flexographic printing and method for obtaining same
FR2803245A1 (fr) * 1999-12-31 2001-07-06 Rollin Sa Plaque compressible pour impression flexographique et procede d'obtention
FR2803246A1 (fr) * 1999-12-31 2001-07-06 Rollin Sa Plaque d'impression presentee en rouleau et procede d'obtention
US7183041B2 (en) 1999-12-31 2007-02-27 Macdermid Graphic Arts S.A. Printing plate in the form of a roller and method for obtaining same
US7785431B2 (en) 1999-12-31 2010-08-31 Macdermid Printing Solutions Europe Sas Compressible plate for flexographic printing, and process for obtaining
US6353037B1 (en) 2000-07-12 2002-03-05 3M Innovative Properties Company Foams containing functionalized metal oxide nanoparticles and methods of making same
US6462100B1 (en) 2000-07-12 2002-10-08 3M Innovative Properties Company Foams containing functionalized metal oxide nanoparticles and methods of making same
US7138436B2 (en) 2001-06-13 2006-11-21 3M Innovative Properties Company Uncrosslinked foams made from emulsions
WO2007129704A1 (fr) 2006-05-08 2007-11-15 Asahi Kasei Chemicals Corporation Matériau d'amortissement pour une impression
EP2128181A1 (fr) * 2008-05-29 2009-12-02 Heinrich Sommer Système prépolymère
EP2484731A4 (fr) * 2009-09-29 2017-12-27 DIC Corporation Composition de primaire, structure de dalle de plancher imperméable l'utilisant et procédé pour réaliser l'imperméabilisation d'une dalle de plancher
JP2013182174A (ja) * 2012-03-02 2013-09-12 Toyo Ink Sc Holdings Co Ltd 感光性樹脂組成物
EP2993200A1 (fr) 2014-09-02 2016-03-09 Greenseal Chemicals NV Composition de précurseur de mousse à base de thiol-acrylate
WO2017036525A1 (fr) 2015-09-02 2017-03-09 Greenseal Chemicals Nv Composition précurseur de mousse à base de thiol-acrylate
US10875942B2 (en) 2015-09-02 2020-12-29 Greenseal Nv Thiol-acrylate based foam precursor composition
CN111742261A (zh) * 2018-03-29 2020-10-02 富士胶片株式会社 感光性转印材料、电极保护膜、层叠体、静电电容型输入装置及触摸面板的制造方法

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