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    • 专利摘要:
    way to improve the surface cure on digital flexographic printing plates the present invention relates to a photocurable embossed image printing element. the photocurable embossed image printing element comprises (a) a backing layer; (b) one or more photocurable layers arranged on the support layer, wherein the one or more photocurable layers comprise: (i) a binder; (ii) one or more monomers; (iii) a photoinitiator; and (iv) an additive selected from the group consisting of phosphites, phosphines, amine compounds, thioether and combinations of one or more of these; (c) a laser ablation mask layer disposed on one or more photocurable layers, the laser ablation mask layer comprising a radiation-opaque material; and (d) optionally, a removable cover sheet. the photocurable embossed image printing element provides improved surface curing in digital embossed image printing elements.
    公开号:BR112015003858B1
    申请号:R112015003858-1
    申请日:2013-08-06
    公开日:2021-04-13
    发明作者:Jonghan Choi；Kerry O'Brate
    申请人:Macdermid Graphics Solutions, Llc；
    IPC主号:
    专利说明:

    Field of the Invention
    [001] This invention relates, in general, to a method for improving the surface cure on digital flexographic printing plates. Fundamentals of the Invention
    [002] Flexography is a printing method that is commonly used for high volume runs. Flexography is used to print on a variety of substrates such as paper, cardboard, corrugated cardboard, films, sheets and laminates. Newspapers and grocery bags are prominent examples. Coarse surfaces and stretched films can be economically printed using flexography only.
    [003] Flexographic printing plates are embossed plates with image elements elevated above open areas. In general, the plate is somewhat soft and flexible enough to wrap around a printing cylinder, and durable enough to print more than a million copies. Such cards offer numerous advantages for the printer, based mainly on their durability and the ease with which they can be produced. A typical flexographic printing plate as released by its manufacturer is a multilayered article produced from, in order, a backing layer; one or more unexposed photocurable layers; optionally, a protective layer or sliding film; and often a protective cover sheet.
    [004] The support layer (or support) supports the plate. The support layer can be formed from a transparent or opaque material, such as paper, cellulose films, plastic, or metal. Preferred materials include sheets made from synthetic polymeric materials, such as polyesters, polystyrene, polyolefins, polyamides and the like. A backing layer used is a flexible polyethylene terephthalate film.
    [005] The photocurable layer (s) can include any of the known polymers, monomers, initiators, reactive and / or non-reactive diluents, fillers and pigments. As used herein, the term "photocurable" refers to a composition that undergoes polymerization, crosslinking, or any other curing or curing reaction, in response to actinic radiation with the result that the unexposed parts of the material may be separated and removed selectively (the exposed cured parts) to form a three-dimensional relief pattern of the cured material. Examples of photocurable materials are disclosed in European Patent Application No. 0,456,336 A2 and 0,640,878 A1 to Goss, et al., British Patent No. 1,366,769, Patent No. 5,223,375 to Berrier, et al. , patent No. 3867153 to MacLahan, US patent No. 4,264,705 to Allen, US patent No. 4,323,636, 4,323,637, 4,369,246, and 4,423,135 all to Chen, et al., US patent No. 3,265,765 to Holden et al, patent No. 4,320,188 to Heinz et al., US patent No. 4,427,759 to Gruetzmacher, et al., US patent No. 4,622,088 to Min, and US patent No. 5,135 .827 de Bohm, et al., The purpose of each of which is incorporated herein by reference in its entirety. More than one photocurable layer can also be used.
    [006] Photocurable materials, in general, undergo cross-linking (cure) and harden by means of radical polymerization in at least some region of actinic wavelength. As used herein, "actinic radiation" is radiation that is capable of polymerizing, crosslinking or curing the photocurable layer. Actinic radiation includes, for example, amplified light (for example, laser) and non-amplified light, particularly in the regions of UV and violet wavelengths.
    [007] The sliding film is a thin layer that protects the photopolymer from dust and increases its ease of handling. In a conventional ("analogue") plate making process, the sliding film is transparent to ultraviolet light, and the printer peels the blank cover sheet from the printing plate and places a negative on top of the film layer slider. The plate and negative are then subjected to flood exposure by UV light through the negative. Areas exposed to light heal or harden, and unexposed areas are removed (developed) to create the embossed image on the printing plate.
    [008] In a "digital" or "plane-oriented" process, a laser is guided by an image stored in an electronic data file and is used to create a negative in situ on a digital mask layer (ie with laser ablation) which is, in general, a sliding film that has been modified to include radiation-opaque material. The parts of the laser ablated layer are then subjected to ablation by exposing the mask layer to laser radiation at the selected wavelength and the laser power. Examples of laser ablation layers are presented, for example, in Patent No. 5,925,500 to Yang, et al., And US Patent No. 5,262,275 and 6,238,837 to Fan, the purpose of each of which is hereby incorporated by reference in its entirety for reference.
    [009] The processing steps for forming the embossed image printing elements typically include the following: 1) image generation, which can be mask ablation for printing “computer to plate” plates or producing negative for conventional analog cards; 2) return exposure to create a floor layer in the photocurable layer and establish the depth of the relief; 3) expose the face through the mask (or negative) to selectively crosslink and cure the parts of the photocurable layer not covered by the mask, thus creating the image in relief; 4) development to remove the photopolymer not exposed by the solvent (including water) or thermal development; and 5) if necessary, post-exposure and elimination of stickiness.
    [010] Removable cover sheets are also provided, preferably, to protect the photocurable print element from damage during transport and handling. Before processing the printing elements, the cover sheet is removed and the photosensitive surface is exposed to actinic radiation in a manner that extends the image. After exposure to actinic radiation in the image extension, polymerization and, therefore, the insolubilization of the photopolymerizable layer occurs in the exposed areas. Treatment with a suitable developer solvent (or, alternatively, thermal development) removes the unexposed areas of the light-curing layer, leaving behind a print relief that can be used for flexographic printing.
    [011] As used here, "return exposure" refers to a covered exposure to actinic radiation from the photopolymerizable layer on the opposite side that, or ultimately, will support the relief. This step is typically achieved through a transparent support layer and is used to create a surface layer of the photocured material, that is, the "floor", on the support side of the photocurable layer. The purpose of the floor is, in general, to sensitize the photocurable layer and establish the depth of the relief.
    [012] After the brief step of return exposure (that is, brief when compared to the step of exposure in the extension of the image below), an exposure in the extension of the image is carried out with the use of a mask with image formed in digital or a photographic negative mask, which is in contact with the photocurable layer and through which the actinic radiation is directed.
    [013] The type of radiation used depends on the type of photoinitiator in the light-curing layer. The mask with digitally formed image or the photographic negative prevents the material below from being exposed to actinic radiation and, therefore, to the areas covered by the unpolymerized mask, while the areas not covered by the mask are exposed to actinic radiation and polymerization. Any conventional sources of actinic radiation can be used for this exposure step. Examples of suitable visible and UV sources include carbon arcs, mercury vapor arcs, fluorescent lamps, instant electron units, electron beam units, LEDs, and photographic flood lamps.
    [014] After image formation, the photosensitive printing element is developed to remove the unpolymerized parts of the layer of photocurable material and reveal the cross-linked relief image on the cured photosensitive printing element. Typical development methods include washing with water or various solvents, often with a brush. Other development possibilities include the use of an air blade or thermal development, which normally uses heat in addition to a blotting material. The resulting surface has an embossed pattern, which typically comprises a plurality of dots that reproduce the image to be printed. After the relief image is developed, the resulting relief image printing element can be mounted on a printing press and started. In addition, if necessary, after the development stage, the embossed image printing element can be post-exposed and / or have reduced viscosity as is, in general, well known in the art.
    [015] The shape of the dots and the depth of the relief, among other factors, affect the quality of the printed image. In addition, it is very difficult to print small graphic elements, such as dots, thin lines and even text using flexographic printing plates, while keeping the reverse text open and the shadows. In the lightest areas of the image (commonly referred to as highlights), the image density is represented by the total area of halftone dots of an on-screen representation of an image in continuous tones. For modulated amplitude (AM) screening, this involves the contraction of a plurality of halftone dots located in a fixed periodic network to a very small size, the density of the highlighted part being represented by the area of the dots. For frequency modulated (FM) tracking, the size of the halftone dots is, in general, kept at some fixed value, and the number of dots positioned randomly or pseudo-randomly represents the density of the image. In both cases, it is necessary to print dots of very small sizes to adequately represent the highlighted areas.
    [016] Maintaining small dots on flexo plates can be very difficult, due to the nature of the plate making process. In the production processes of digital plates that use an opaque UV mask layer, the combination of the mask and the UV exposure produces raised points that have, in general, a conical shape. The smallest of these points are likely to be removed during processing, which means that no ink is transferred to these areas during printing (that is, the point is not "kept" on the plate and / or the press). Alternatively, if the stitches survive processing, they are susceptible to damage to the press. For example, small dots often fold over and / or partially break during printing, causing either an excess of ink or no ink transfer.
    [017] As described in Patent No. 8158331 to Recchia and in US Patent Publication No. 2011/0079158 to Recchia et al., The purpose of each of which is incorporated herein by reference in its entirety, has been verified. it is known that a particular set of geometric characteristics defines a dot shape that produces superior printing performance, including but not limited to, (1) flatness of the dot surface; (2) point bounce angle; (3) raised depth between the points; and (4) edge sharpness at the point where the top point undergoes transition to the point shoulder.
    [018] In addition, in order to improve surface healing, in general, it has been found that it can be beneficial for performing additional procedures and / or using additional equipment. These additional procedures and / or equipment may include: (1) laminating a membrane over the surface of the photopolymer; (2) purging the oxygen from the photopolymer using an inert gas; or (3) image the photopolymer with a high intensity UV source.
    [019] The act of purging the oxygen from the photopolymer using an inert gas typically involves positioning the plate in a photocurable resin in an inert gas atmosphere, such as gaseous carbon dioxide or nitrogen gas, prior to exposure. to displace oxygen from the environment. A notable disadvantage to this method is that it is inconvenient and uncomfortable, and requires a large space for the device.
    [020] Another approach is to subject the plates to a preliminary exposure (ie "roughness exposure") of actinic radiation. During roughness exposure, a dose of "pre-exposure" low-intensity actinic radiation is used to sensitize the resin before the plate is subjected to the main high-intensity exposure dose of actinic radiation. The roughness exposure is typically applied to the entire area of the plate and a short short exposure, the dose of plate that reduces the concentration of oxygen, which inhibits the photopolymerization of the plate (or other printing element) and assists in the preservation of traces. thin (that is, highlights points, thin lines, isolated points, etc.) on the end plate. However, the pre-sensitization step can also cause shadow tones to be filled, thus reducing the range of tones in the halftones in the image. Alternatively, a preliminary selective presentation, as discussed, for example, in US patent publication No. 2009/0042138 by Roberts et al., The purpose of which is incorporated herein by reference in its entirety, has also been proposed. Other efforts to reduce the effects of oxygen on the photopolymerization process involved special plate formulations alone or in combination with roughness exposure.
    [021] As it is easily perceived, all of these techniques involve unavoidable costs, such as capital expenditure on equipment, space, consumer goods, inert gases, license fees, etc. Thus, it would be desirable to provide an embossed image printing element that has improved surface curing without the need to subject the printing element to all further processing steps. In addition, it would be desirable to provide an embossed digital printing element comprising the printing points having a convenient and desirable form of embossed depth without the need to subject the embossed printing element to additional procedures.
    [022] The inventors of the present invention have found that the inclusion of certain additives in the photocurable layer of the embossed printing element, as described herein, produces an embossed printing element comprising points with desirable shapes and depth in relief. Summary of the Invention
    [023] It is an object of the present invention to provide an embossed image printing element that has improved surface cure.
    [024] It is another object of the present invention to provide a method of adapting or modifying the shape of the embossed printing points on an embossed image printing element for better printing on various substrates and / or under various conditions.
    [025] It is another objective of the present invention to provide an improved method for the production of embossed image printing elements that comprise points that have desirable geometric characteristics.
    [026] It is yet another objective of the present invention to greatly simplify the workflow of the digital plate production process.
    [027] It is another objective of the present invention to provide an improved method for creating an embossed image printing element that has embossed points adapted in terms of edge definition, bounce angle and / or the printing surface.
    [028] For that purpose, in one embodiment, the present invention relates, in general, to a photocurable embossed image printing element comprising: a) a backing layer; b) one or more photocurable layers arranged on the support layer, wherein one or more photocurable layers comprise: i) a binder; ii) one or more monomers; iii) a photoinitiator; and iv) an additive selected from the group consisting of phosphites, phosphines, amine compounds, thioether and combinations of one or more of these materials; c) a mask layer with laser ablation arranged on one or more photocurable layers, the mask layer with laser ablation comprising a material opaque to radiation; and d) optionally, a removable cover sheet.
    [029] In another embodiment, the present invention relates, in general, to a method for producing a printing element of a photocurable embossed printing blank, the method comprising the steps of: a) providing a blank photocurable printing, the photocurable printing blank that comprises: i) a support layer; ii) one or more photocurable layers arranged on the support or support layer, wherein one or more photocurable layers comprise: 1) a binder; 2) one or more monomers; 3) a photoinitiator; and 4) an additive selected from the group consisting of phosphites, phosphines, amine compounds, thioether and combinations of one or more of these materials; iii) a laser ablation mask layer disposed over at least one photocurable layer, the laser ablation mask layer comprising a radiation-opaque material; b) perform laser ablation selectively on the mask with laser ablation to create a negative in situ on a desired image on the mask layer with laser ablation; c) exposing at least one photocurable layer to actinic radiation through the in situ negative to selectively crosslink and cure the parts of at least one photocurable layer; and d) developing at least one exposed photocurable layer of the photocurable printing white to reveal the embossed image, said embossed image comprising a plurality of embossed printing points. Brief description of the figures
    [030] Figures 1A and 1B show SEM images of SPF778, SPF779 and SPF771 processed in solvent.
    [031] Figures 2A and 2B show SEM images of SPF778, SPF779 and SPF771 thermally processed.
    [032] Figure 3 shows the average point shoulder angles of SPF778 and SPF779 with respect to the point in the file.
    [033] Figure 4 represents Shore A hardness of several 67 thousand plates investigated.
    [034] Figure 5 shows point gain curves thermally processed SPF778 and SPF779.
    [035] Figure 6 shows real point sizes of SPF778, SPF779, SPF771, SPF802 and SPF803 transformed in solvent in relation to the point in the file.
    [036] Figures 7A and 7B show SEM images (150X) of processed solvent SPF802 and SPF803, as a function of several points in file% at 150 lpi.
    [037] Figure 8 shows the surface roughness (SR) of SPF771 and SPF778 through thermal processing in relation to hot rolling temperatures.
    [038] Figure 9 shows SEM images (150X) of SPF814 processed A) in the solvent and B) thermally.
    [039] Figure 10 shows a means to characterize the flatness of the printing surface of a point, where p is the distance between the top of the point, and r is the radius of curvature along the surface of the point.
    [040] Figure 11 illustrates a flexion point and its edge, where p is the distance from the top of the point. This is used to characterize the sharpness of the contours re: p, where re is the radius of curvature at the intersection of the boss and the top of the point. Detailed Description of Preferred Modalities
    [041] After UV curing in the presence of oxygen, the surface properties of a given photopolymer can be quite different from its volumetric properties. This is mainly due to the fact that oxygen inhibition strongly affects the surface layer on exposure to UV radiation, thus disproportionately suppressing the curing reaction of the surface layer in relation to the volume. As a result, the most desirable properties for the performance of the end-use product are not achieved. In addition, curing the poor surface can significantly alter the size and shape of the embossed features formed in the photopolymer by UV curing.
    [042] An example of this is found in digital flexo printing plates. Due to problems with curing the photopolymer layer, the following effects are typically observed: (1) Spot sizes smaller than intended. Digital boards require "roughness" that uses artificially larger dot sizes in an electronic file to result in the desired board sizes, thus truncating the overall tonality. (2) Poorly defined image edges, particularly in the form of dots, that is, round top dots (IDT), instead of flat top dots (FTD), which contribute to high dot gains through printing during printing. pressing. (3) High roughness of the solids surface on thermal processing, which adversely influences the density of the solid paint (SID).
    [043] These deficiencies negatively affect print quality, and often even limit digital card applications.
    [044] To overcome these disadvantages, the inventors of the present invention have found that the introduction of certain additives in the photocurable composition of flexographic printing plates significantly improves the curing reaction in the surface layer. The significance of the present invention lies in the fact that the curing of the surface can be greatly improved, without resorting to additional technology (including high intensity UV sources, inert gas chambers, membrane lamination, etc.). In addition, the conventional practice of applying roughness to electronic files, to obtain the desired point sizes, can also be reduced or eliminated. Finally, the present invention can greatly speed up the slab production process and reduce the costs necessary to support the conventional procedure, equipment and techniques, without compromising the desirable characteristics resulting from good surface cure.
    [045] Based on this, in one embodiment, the present invention relates, in general, to a photocurable embossed image printing element comprising: a) a backing layer; b) one or more photocurable layers arranged on the support layer, wherein one or more photocurable layers comprise: i) a binder; ii) one or more monomers; iii) a photoinitiator; and iv) an additive selected from the group consisting of phosphites, phosphines, amine compounds, thioether and combinations of one or more of these materials; c) a mask layer with laser ablation arranged on one or more photocurable layers, the mask layer with laser ablation comprising a material opaque to radiation; and d) optionally, a removable cover sheet.
    [046] As described herein, additives can comprise phosphites having the general structure P (OR) 3 or P (OAr) 3, phosphines, which have the general structure PR3 or PAr3, amine thioether compounds, or combinations of one or more more than the previous ones. The additive (s) can be used in the photopolymer composition in an amount of about 0.1 to about 10% by weight, preferably in an amount of about 0.05 to about 2% by weight.
    [047] Suitable phosphites include, but are not limited to, tris (nonylphenyl) phosphite (TNPP) CAS No. 265-78-4, triphenyl phosphite, diphenyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris (tridecyl) phosphite, trilauryl phosphite, disteraryl pentaerythriol diphosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, diphenyl octyl phosphite, diphenyl iso-octyl phosphite, dipropylene glycol monohydrylene diphenyl, alkyl bisphenol A phosphite, tetrafenyl dipropylene glycol diphosphite, phenyl poly (dipropylene glycol) phosphite, tris phosphite (dipropylene glycol), dioleyl phosphite and hydrogen. In one embodiment, the phosphite comprises TNPP.
    [048] Suitable phosphines include, but are not limited to, triphenylphosphine, tri-p-tolylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, dimethylphenylphosphine, diethylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphenylphinephylphine p-tolylphosphine, diallylphenylphosphine, divinyl-p-bromophenylphosphine and diallyl-p-tolylphosphine.
    [049] Suitable thioether amine compounds include, but are not limited to, 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2-ylamino ) phenol (CAS No. 991-84-4), 4 - [[4,6-bis (nonylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol , 4- [[4,6-bis (octadecylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-octylsulfanyl) - 1,3,5-triazin-2-yl] amino] -2,6-bis (2-methylnonan-2-yl) phenol, 4 - [[4,6-bis (- hexylsulfanyl) -1,3,5 -triazin-2-yl] amino] - 2,6-di-tert-butylphenol, 4 - [[4,6-bis (heptylsulfanyl) - 1,3,5-triazin-2-yl] amino] -2, 6-di-tert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2-tert-butyl-6-methylphenol, 4 - [[ 4,6-bis (ethylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (2,4,4- trimethylpentan-2-ylsulfanyl) -1,3,5-triazin-2-yl] amino] - 2,6-ditherc-butylphenol, 4 - [[4,6-bis (2-octylsulfanylethylsulfanyl) -1,3,5 -triazin-2-yl] amino] -2,6- ditert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6- dibutylphenol, 4- [[4,6-b is (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-dimethylphenol, 2,6-di-tert-butyl-4 - [[4- (3,5-di-tert -butyl-4-hydroxyanilino) -6- octylsulfanyl-1,3,5-triazin-2-yl] amino] phenol, 4 - [[4,6-bis (pentylsulfanyl) -1,3,5-triazin-2 -yl] amino-2,6-dimethylphenol, 4 - [[4,6-bis (hexylsulfanyl) - 1,3,5-triazin-2-yl] amino] -2-tert-butylphenol, 2,6-di -tert-butyl-4 - [(4-octylsulfanyl-1,3,5-triazin-2-yl) amino] phenol, 4 - [[4,6-bis (ethylsulfanyl) -1,3,5-triazin- 2-yl] amino] -2,6-dimethylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] -butylamino] - 2,6-ditherc-butylphenol, 4 - [[4,6- bis (octylsulfanyl) -1,3,5-triazin-2-yl] -cyclohexylamino] - 2,6-di-tert-butyl-phenol, 2 - [[4.6 - bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -6-tert-butylphenol, 2-tert-butyl-6-methyl-4 - [[4- octylsulfanyl-6 - [(2 , 2,6,6-tetramethylpiperidin-4-yl) amino] -1,3,5-triazin-2-yl] amino] phenol, 4- [[4,6-bis (octylsulfanylmethyl) -1,3,5 -triazin-2-yl) amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl) methylamino] -2, 6-di-tert-butylphenol, 4 - [(4-am ino-6-chloro-1,3,5-triazin-2-yl) amino] - 2,6-di-tert-butylphenol and 4 - [(4-cyclohexyl-6-cyclohexylsulfanyl-1,3 , 5-triazin-2-yl) amino] -2,6-di (propan-2-yl) phenol. In one embodiment, the thioether amine compound comprises 2,6-di-terr-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2-ylamino) phenol (also referred to as phenol , 4 - [[4,6-bis (octyl) -1,3,5-triazin-2-yl] amino] -2,6-bis (1,1-dimethylethyl).
    [050] In addition, one or more antioxidants, such as 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, butylated hydroxytoluene (BHT ), alkylated phenols, for example 2-6-di-tert-butyl-4-methylphenol; alkylated bis-phenols, for example, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol); 2- (4-hydroxy-3,5-di-tert-butylanilino) -4,6-bis- (n-octyl-thio) -1,3,5-triazine; polymerized trimethyldihydroquinone; and dilauryl thiopropionate can also be used in the compositions of the invention in combination with the aforementioned additives to promote dot shapes in terms of dot angle, dot tops, etc. In a preferred embodiment, the antioxidant is 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, available from Albemarle under the trade name Ethanox 330.
    [051] The photopolymerizable composition of the present invention comprises one or more binders, monomers and plasticizers, in combination with one or more photoinitiators and the additives described above.
    [052] The type of binder is not critical to the photopolymer composition and most, if not all, styrene copolymer rubbers are usable in the compositions of the invention. Suitable binders can include natural or synthetic polymers of conjugated diolefin hydrocarbons, including 1,2-polybutadiene, 1,4-polybutadiene, butadiene / acrylonitrile, butadiene / styrene, thermoplastic elastomeric block copolymers, for example, styrene block copolymer -butadiene-styrene, styrene-isoprene-styrene block copolymer, etc., and copolymers of the binders. It is, in general, preferred that the binder is present in at least an amount of 60% by weight of the photosensitive layer. The term binder, as used herein, also encompasses number carcass microgels or mixtures of preformed macromolecular microgels and polymers.
    [053] Non-limiting examples of binders that can be used in the compositions of the present invention include styrene isoprene styrene (SIS), a commercial product that is available from Kraton Polymers LLC, under the trade name Kraton D1161; and styrene isoprene butadiene styrene (SIBS), a commercial product that is available from Kraton Polymers, LLC under the trade name Kraton Dl 171; and styrene butadiene styrene (SBS), a commercial product that is available from Kraton Polymers LLC under the trade name Kraton DX405.
    [054] Monomers suitable for use in the present invention are ethylenically unsaturated compounds with polymerizable addition. The photocurable composition may contain a single monomer or a mixture of monomers that form mixtures compatible with the binder (s) to produce clear (i.e., not turbid) photosensitive layers. Monomers are usually reactive monomers, especially acrylates and methacrylates. Such reactive monomers include, but are not limited to, trimethylolpropane triacrylate, hexanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol-200 diacrylate , tetraethylene glycol diacrylate, ethylene glycol diacrylate diacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, bisphenol-A ethoxylated diacrylate, trimethylolpropane tetraacrylate, dihydrochloride (3-methylpropylate) acrylate; dipentaerythritol hydroxypenta acrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol-200 dimethacrylate, 1,6-hexanediol, neopentyl glycol dimethacrylate, polyethylene glycol-600 dimethacrylate, 1,3-butylene glycol, bisphenol-A ethoxylated dimethacrylate The dimethacrylate, trimethylolpropane trimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, diethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol diacrylate, or oligomers uretanometacrilati of acrylate and the like, which can be added to the light-curing composition to modify the cured product. Monoacrylates which include, for example, cyclohexyl acrylate, isobornyl acrylate, lauryl acrylate and tetrahydrofurfuryl acrylate and the corresponding methacrylates can also be used in the practice of the present invention. Especially preferred acrylate monomers include hexanediol diacrylate (HDD A) and trimethylolpropane triacrylate (TMPTA). Especially preferred methacrylate monomers include hexanediol dimethacrylate (HDDMA) and triemethylolpropane trimethacrylate (TMPTA). In general, it is preferred that the one or more monomers are present in at least an amount of 5% by weight of the photosensitive layer.
    [055] The photopolymer layer preferably contains a compatible plasticizer, which serves to lower the glass transition temperature of the binding agent and facilitate selective development. Suitable plasticizers include, but are not limited to, dialkyl phthalates, alkyl phosphate, polyethylene glycol, polyethylene glycol esters, polyethylene glycol ethers, polybutadiene, styrene copolymers, hydrogenated polybutadiene, heavy oils, hydrogenated heavy naphthenics and heavy oils, hydrogenated paraffenic oils and heavy oils. polyisoprene. Other useful plasticizers include oleic acid, lauric acid, etc. The plasticizer is generally present in an amount of at least 10% by weight based on the weight of the total solids of the photopolymer composition. Commercially available plasticizers for use in compositions of the invention include 1,2-polybutadiene, available from Nippon Soda Co. under the trade name Nisso PB B-1000; Ricon 183, which is a polybutadiene styrene copolymer, available from Cray Valley; Nyflex 222B, which is a heavy hydrogenated naphthenic oil, available from Nynas AB; Paralux 2401, which is a heavy hydrogenated paraffinic oil, available from Chevron USA, Inc .; and Isolene 40-S, which is a polyisoprene available from Royal Elastomers.
    [056] Photoinitiators for the photocurable composition include benzoin alkyl ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and isobutyl benzoin ether. Another class of photoinitiators are dialcoxyacetophenones such as 2,2-dimethoxy-2-phenylacetophenone and 2,2-dietoxy-2-phenylacetophenone. Yet another class of photoinitiators are the compounds of aldehyde and carbonyl ketone with at least one aromatic nucleus connected directly to the carboxyl group. These photoinitiators include, but are not limited to, benzophenone, acetophenone, o-methoxybenzophenone, acenaphthenoquinone, methyl ethyl ketone, valerophenone, hexanophenone, alpha-phenylbutyrophenone, p-morpholinopropylphenone, dibenzosuberone, 4-morpholinbenzene-4-pyridine-4-benzophenone-4 - aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, alpha-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindone, 9-fluorenone, 1-indanone, 1,3,5-triacetylb thioxanthen-9-one, xanthene-9-one, 7-H-benz [de] anthracene-7-one, 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, fluorene-9-one, 1'- acetonephton, 2'-acetonephton, 2,3-butanedione, acetonephene, benz [a] anthracene 7.12 dione, etc. Phosphines such as triphenylphosphine and tri-o-tolylphosphine are also operable here as photoinitiators.
    [057] Preferred photoinitiators for use in the photopolymer compositions of the invention include benzyl dimethyl ketal, a commercial product which is available from BASF under the trade name Irgacure 651; α-hydroxyketone, a commercial product of which it is available from BASF under the trade name Irgacure 184; phosphine and acyl, a commercial product that is available from Ciba Specialty Chemicals under the trademark of Darocur TPO. In one embodiment, it was determined that Irgacure 651 was the most effective photoinitiator for UV light with a wavelength of ~ 365 nm, to obtain the benefits described here, but other photoinitiators can also be used, alone or in combination with Irgacure 651.
    [058] Various dyes and / or dyes can also optionally be used in the practice of the present invention, although the inclusion of a dye and / or dye is not necessary to achieve the benefits of the present invention. Suitable dyes are referred to as "window dyes" that do not absorb actinic radiation in the region of the spectrum where the initiator present in the composition can be activated. Dyes include, for example, dye red CI 109, Methylene violet (basic violet CI 5), fast blue "Luxol" MBSN (solvent blue CI 38), blue "Pontacyl" Wool BL (acid blue CI 59 or CI 50315), blue "Pontacyl" Wool GL (acid blue CI 102 or CI 50320), pure blue Victoria BO (basic blue CI 7 or CI 42595), Rhodamine 3 GO (basic red CI 4), Rhodamine 6 GDN (basic red CI 1 or CI 45160), l, l'-diethyl-2,2'-cyanine iodide, Fuchsine dye (CI 42510), Calcocid S green (CI 44090) and Anthraquinone 2 GA (basic acid CI 58), etc. Dyes and / or dyes must not interfere with exposure to the extent of the image.
    [059] Other additives, including antiozonants, fillers or reinforcing agents, thermal polymerization inhibitors, UV absorbers, etc., can also be included in the photopolymerizable composition, depending on the desired final properties. Such additives are, in general, well known in the art.
    [060] Suitable fillers and / or reinforcing agents include fillers or immiscible, polymeric or non-polymeric organic agents or which are essentially transparent to the wavelengths used for the exposure of the photopolymer material and which do not disperse radiation inorganic reinforcing actinic, eg polystyrene, organophilic silicas, bentonites, silica, powdered glass, colloidal carbon, as well as various types of dyes and pigments. Such materials are used in amounts that vary with the desired properties of the elastomeric compositions. Filling agents are useful for improving the strength of the elastomer layer, reducing adhesion and, moreover, as coloring agents.
    [061] Thermal polymerization inhibitors include, for example, p-methoxyphenol, hydroquinone, and alkyl and hydroquinones and quinones substituted with aryl, tert-butyl catechol, pyrogallol, copper resinate, naphthalamines, beta-naphthol, cuprous chloride, 2,6-di-tert butyl-p-cresol, butylated hydroxytoluene (BHT), oxalic acid, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. Other similar polymerization inhibitors would also be applicable in the practice of the invention.
    [062] In another embodiment, the present invention relates, in general, to a method of producing an embossed image printing element of a photocurable printing white, the method comprising the steps of: a) providing a photocurable print white, a photocurable print white that comprises: i) a support layer; ii) one or more photocurable layers arranged on the support or support layer, wherein one or more photocurable layers comprise: 1) a binder; 2) one or more monomers; 3) a photoinitiator; and 4) an additive selected from the group consisting of phosphites, phosphines, amine compounds, thioether and combinations of one or more of these materials; iii) a laser ablation mask layer disposed over at least one photocurable layer, the laser ablation mask layer comprising a radiation-opaque material; b) selective ablation of the mask with laser ablation to create a negative in situ of a desired image in the mask with laser ablation; c) exposing at least one photocurable layer to actinic radiation through negative in situ to selectively crosslink and cure parts of at least one photocurable layer; and d) developing at least one exposed photocurable layer of the photocurable printing white to reveal the embossed image thereon, said embossed image comprising a plurality of embossed printing points.
    [063] Table 1 summarizes several examples of various formulas of photocurable compositions prepared in accordance with the present invention. SPF778 and SPF779 contain both TNPP and 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2-ylamino) phenol in combination with Ethanox® 330. SPF802 incorporates 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2-ylamino) phenol and SPF803 and SPF814 use TNPP, respectively.
    [064] Table 1. Various formulas prepared according to the present invention (% by weight).

    [065] These different photocurable compositions in the extent of the image were exposed to actinic radiation and developed to reveal the embossed image on it comprises a plurality of embossed print points. The resulting photoactivated compositions that comprise the plurality of embossed print points were then examined. As described herein, the photocurable compositions were developed with the use of a solvent to dissolve the uncured and uncrosslinked parts of the photocurable composition or were developed with the use of thermal development, in which the uncured and uncrosslinked parts were attenuated and / or fused and then transferred. Other means of developing photocurable compositions are also known to those skilled in the art.
    [066] The photocurable embossed image printing element preferably has a Shore A hardness of between about 45 and about 70, more preferably between about 50 and about 65.
    [067] The improved surface cure on digital flexo printing plates can be more explicitly revealed by the dot shapes.
    [068] Figures 1A, 1B, 2A, and 2B represent SEM images of SPF778, SPF779, and SPF771 thermally processed in the solvent and, respectively, with respect to the point sizes in the linear electronic file used or in the formation image at 150 lpi. It is clearly demonstrated that, unlike the conventional RTD of SPF771, FTD are created on both SPF778 and SPF779.
    [069] For SPF778 and SPF779, the average point shoulder angles are very small, as shown in figures 1A, 1B, 2a and 2B. In one embodiment, an average boss angle, measured as the angle between a boss shoulder along the width of the top or point printing surface is less than about 30 °, preferably less than about 20 °.
    [070] In summary, the single point shapes of SPF778 and SPF779 are considered ideal for printing, because: (i) the tops of the points are flat and therefore require less printing than conventional RTD, which in turn increases the longevity of the plate due to less susceptibility to wear; (ii) the pillars of the points that are at the bases are practically vertical (without rebounds), which minimizes the potential point gains upon the impression. (iii) the dot bases are wide, as clearly illustrated in figures 1A, 1B, 2A and 2B, and thus provide the necessary mechanical stability to withstand the impact of the unidirectional dynamic printing applied during printing.
    [071] In addition to FTD and bounce, without the elimination of roughness, the surface roughness (SR) of solids through thermal processing is also positively influenced by the improved surface cure, so that the greater the surface cure , the smaller will be SR. Figure 8 shows the SR of SPF778 and SPF771 through thermal processing in relation to the hot rolling temperature. Over the entire temperature range examined, the SR is lower for SPF778 than for SPF771. This is directly translated into a more careful heat treatment. In addition, the lower SR contributes to increasing the density of the solid ink (SID) on top of the print. Thus, it can be seen that the present invention benefits both the thermal processing and the end-use performance of the board in the following manner, as a result of the reduced SR: (A) wider thermal processing windows; and (B) high SID.
    [072] Finally, the flatness of the top of a point can be measured as the radius of curvature along the top surface of the point, r, as shown in figure 10. It is observed that a rounded point surface is not ideal from the printing point of view, because the size of the contact area between the printing surface and the point varies exponentially with the printing force. Therefore, the top of the dot preferably has a planarity where the radius of curvature of the top of the dot is greater than the thickness of the photopolymer layer, more preferably twice the thickness of the photopolymer layer, and more preferably, more than three times the total thickness of the photopolymer layer.
    [073] The sharpness of the contours refers to the presence of a well-defined boundary between the flat top of the point and the shoulder and it is, in general, preferred that the point edges are sharp and defined, as shown in figure 11. These well-defined stitch edges better separate the "print" part from the "support" part of the stitch, allowing for a more consistent contact area between the stitch and the substrate during printing.
    [074] The sharpness of the contours can be defined as the ratio of re, the radius of curvature (at the intersection of the boss and the top of the stitch) to p, the width of the top or printing surface of the stitch, as shown in figure 3 For a point with a truly rounded tip, it is difficult to define the exact printing surface, because there is not really an advantage in the commonly understood sense, and the re: p ratio can approach 50%. In contrast, a point with a sharp edge would have a very small value of re, and re: p would approach zero. In practice, a re: p of less than 5% is preferred, with a re: p of less than 2% more preferred. Figure 11 represents a flexion point and its edge, where p is the distance from the top of the point and demonstrates the characterization of the sharpness of the contours, re: p, where re is the radius of curvature at the intersection of the boss and the top from the point.
    权利要求:
    Claims (29)
    [0001]
    1. Embossed image printing element produced from a photocurable printing white, CHARACTERIZED by the fact that the photocurable printing white comprises: a) a support layer; b) one or more photocurable layers arranged on the support layer, wherein the one or more photocurable layers comprise: i) a binder; ii) one or more monomers; iii) a photoinitiator; and iv) an additive selected from the group consisting of phosphites, phosphines, thioether amine compounds and combinations of one or more of these; c) a mask layer with laser ablation arranged over one or more photocurable layers, the mask layer with laser ablation comprising a material opaque to radiation; and d) optionally, a removable cover sheet in which the embossed printing element comprises a plurality of embossed printing points whose embossed printing points comprise at least one of the following characteristics; i)) sharpness of the contours of the embossed printing points, defined as the ratio of the radius of curvature re at the intersection of a shoulder and the upper part of the embossed printing point with the width of the upper printing surface of the point p, is less than 5%; or j) i) the average angle of the boss, measured as the angle between the boss of the stitch and the width of the upper printing surface of the stitch, is less than 30 °.
    [0002]
    2. Photocurable embossed image printing element, according to claim 1, CHARACTERIZED by the fact that the additive is a phosphite selected from the group consisting of tris (nonylphenyl) phosphite, triphenyl phosphite, diphenyl phosphite, phosphite tridecyl, triisodecyl phosphite, tris (tridecyl) phosphite, trilauryl phosphite, disteraryl pentaerythriol diphosphite, phenyl diisodecyl phosphite, isodecyl diphenyl phosphite, diphenyl octyl phosphite, diphenyl octyl phosphite , diphenyl tri-isodecyl monophenyl dipropylene glycol diphosphite, alkyl bisphenol A phosphite, tetrafenyl dipropylene glycol diphosphite, phenyl poly (dipropylene glycol) phosphite, tris phosphite (dipropylene glycol and a combination of phosphite and hydrogen) more of these.
    [0003]
    3. Photocurable relief image printing element, according to claim 2, CHARACTERIZED by the fact that the additive comprises tris (nonylphenyl) phosphite.
    [0004]
    4. Photocurable embossed image printing element according to claim 1, CHARACTERIZED by the fact that the additive is a phosphine selected from the group consisting of triphenylphosphine, tri-p-tolylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, dimethylpropylphosphine, dimethyl , diethylphenylphosphine, dipropylphenylphosphine, divinylphenylphosphine, divinyl-p-methoxyphenylphosphine, divinyl-p-bromophenylphosphine, divinyl-p-tolylphosphine, diarylphenylphosphine, divinyl-p-bromine-pylamine and more.
    [0005]
    5. Photocurable embossed image printing element, according to claim 1, CHARACTERIZED by the fact that the additive is a thioether amine compound selected from the group consisting of 2,6-di-tert-butyl-4- (4,6-bis (octyllium) -1,3,5-triazin-2-ylamino) phenol, 4 - [[4,6-bis (nonylsulfanyl) -1,3,5-triazin-2-yl] amino ] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (octadecylsulfanyl) -1,3,5-triazin-2-yl] amino] - 2,6-di-tert-butylphenol, 4 - [[4,6-octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-bis (2-methylnonan-2-yl) phenol, 4 - [[4,6- bis (-hexylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (heptylsulfanyl) -1,3,5- triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4- [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2-tert -butyl-6-methylphenol, 4 - [[4,6-bis (ethylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4 , 6-bis (2,4,4-trimethylpentan-2-ylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-ditherc-butylphenol, 4 - [[4,6-bis (2-octylsulfanylethylsulfanyl) -1,3,5-triazin-2-yl] amino] - 2,6-di-tert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-dibutylphenol, 4 - [[4, 6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-dimethylphenol, 2,6-di-tert-butyl-4 - [[4- (3,5-di -tert-butyl-4-hydroxyanilino) -6-octylsulfanyl-1,3,5-triazin-2-yl] amino] phenol, 4 - [[4,6-bis (pentylsulfanyl) - 1,3,5-triazin -2-yl] amino-2,6-dimethylphenol, 4 - [[4,6-bis (hexylsulfanyl) -1,3,5-triazin-2-yl] amino] -2-tert-butylphenol, 2,6 -di-tert-butyl-4 - [(4-octylsulfanyl-1,3,5-triazin-2-yl) amino] phenol, 4 - [[4,6-bis (ethylsulfanyl) -1,3,5- triazin-2-yl] amino] -2,6-dimethylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] butylamino] -2,6-di-tert -butylphenol, 4 - [[4,6- bis (octylsulfanyl) -1,3,5-triazin-2-yl] -cyclohexylamino] -2,6-di-tert-butyl-phenol, 2 - [[4, 6- bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -6-tert-butylphenol, 2-tert-butyl-6-methyl-4 - [[4- octylsulfanyl-6 - [( 2,2,6,6, -tetramethylpiperidin-4-yl) amino] -1,3,5-triazin-2-yl] amino] phenol, 4- [[4,6-bis (octylsulfanylmethyl) -1,3 , 5-triazin-2-yl) amino] -2,6-diterc-b utilphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl) methylamino] -2,6-ditherc-butylphenol, 4 - [(4-amino-6-chloro- 1,3,5-triazin-2-yl) amino] -2,6-di-tert-butylphenol and 4 - [(4-cyclohexyl-6-cyclohexylsulfanyl-1,3,5-triazin-2 - yl) amino] -2,6-di (propan-2-yl) phenol, and in one embodiment, the amino thioether compound comprises 2,6-di-tert-butyl-4- (4,6-bis (octyl ) -1,3,5-triazin-2-ylamino) phenol (also referred to as phenol, 4 - [[4,6-bis (octyllium) -1,3,5-triazin-2-yl] amino] -2 , 6-bis (1,1-dimethylethyl)) and combinations of one or more of these.
    [0006]
    6. Photocurable embossed image printing element according to claim 5, CHARACTERIZED by the fact that the additive comprises 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1, 3,5-triazin-2-ylamino) phenol.
    [0007]
    7. Photocurable embossed image printing element, according to claim 1, CHARACTERIZED by the fact that it comprises an antioxidant selected from the group consisting of 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, butylated hydroxytoluene, alkylated phenols, alkylated bis-phenols, polymerized trimethyl dihydroquinone, dilauryl thiopropionate and combinations of one or more of these.
    [0008]
    8. Photocurable embossed image printing element according to claim 7, CHARACTERIZED by the fact that the antioxidant comprises 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- butyl-4-hydroxybenzyl) benzene.
    [0009]
    9. Photocurable embossed image printing element, according to claim 1, CHARACTERIZED by the fact that the photocurable composition further comprises one or more materials selected from the group consisting of plasticizers, antiozonants, fillers, reinforcing agents , thermal polymerization inhibitors, UV absorbers and combinations of one or more of these.
    [0010]
    10. Photocurable embossed image printing element according to claim 9, CHARACTERIZED by the fact that one or more materials comprise a plasticizing agent.
    [0011]
    11. Photocurable embossed image printing element according to claim 1, CHARACTERIZED by the fact that the photocurable embossed image printing element has a Shore A hardness between 45 and 70.
    [0012]
    12. Photocurable embossed image printing element according to claim 11, CHARACTERIZED by the fact that the photocurable embossed image printing element has a Shore A hardness between 50 and 65.
    [0013]
    13. Method for producing an embossed image printing element produced from a photocurable printing white, as defined in claim 1, CHARACTERIZED by the fact that the method comprises the steps of: a) providing a photocurable printing white, the photocurable print blank comprising: i) a support layer; ii) at least one photocurable layer disposed on the support or support layer, wherein the one or more photocurable layers comprise: 1) a binder; 2) one or more monomers; 3) a photoinitiator; and 4) an additive selected from the group consisting of (i) a phosphite selected from the group consisting of tris (nonylphenyl) phosphite, diphenyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris (tridecyl) phosphite, trilauryl phosphite, disteraryl pentaerythriol diphosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, octyl diphenyl phosphite, diphenyl iso-octyl phosphite, tri-isodine diphenylphenyl dipropylene glycol diphenyl, tri-isodecylphenyl diphenyl diphenyl alkyl, tetrafenyl dipropylene glycol diphosphite, phenyl poly (dipropylene glycol) phosphite, tris phosphite (dipropylene glycol) and dioleyl and hydrogen phosphite and combinations of one or more of these, (ii) thioether amine compounds, and (iii) combinations of one or more of these; iii) a laser ablation mask layer disposed over at least one photocurable layer, the laser ablation mask layer comprising a radiation-opaque material; b) perform laser ablation selectively on the mask layer capable of laser ablation to create a negative in situ of a desired image on the mask layer capable of laser ablation; c) exposing at least one photocurable layer to actinic radiation by the negative in situ to selectively crosslink and cure the parts of at least one photocurable layer; and d) developing at least one exposed photocurable layer of the photocurable printing white to reveal the embossed image there, said embossed image comprising a plurality of embossed printing points, wherein the presence of the additive in at least one photocurable layer improves the cure of the surface of at least one photocurable layer without requiring a high intensity UV light source, an inert gas chamber or a laminated membrane.
    [0014]
    14. Method according to claim 13, CHARACTERIZED by the fact that the additive comprises tris (nonylphenyl) phosphite.
    [0015]
    15. Method, according to claim 13, CHARACTERIZED by the fact that the additive is a thioether amine compound selected from the group consisting of 2,6-di-tert-butyl-4- (4,6-bis ( octyllium) -1,3,5-triazin-2-ylamino) phenol, 4 - [[4,6-bis (nonylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di -tert-butylphenol, 4 - [[4,6-bis (octadecylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-ditherc-butylphenol, 4 - [[4,6-octylsulfanyl ) - 1,3,5-triazin-2-yl] amino] -2,6-bis (2-methylnonan-2-yl) phenol, 4 - [[4,6-bis (hexylsulfanyl) -1,3, 5- triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (heptylsulfanyl) -1,3,5-triazin-2-yl] amino] -2 , 6-di-tert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino] -2-tert-butyl-6-methylphenol, 4- [ [4,6-bis (ethylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (2,4,4 -trimethylpentan-2-ylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (2-octylsulfanylethylsulfanyl) -1, 3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (octyl sulfate nil) -1,3,5-triazin-2-yl] amino] -2,6-dibutylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino ] -2,6-dimethylphenol, 2,6-di-tert-butyl-4 - [[4- (3,5-di-tert-butyl-4-hydroxyanilino) -6-octylsulfanyl-1,3,5- triazin-2-yl] amino] phenol, 4 - [[4,6-bis (pentylsulfanyl) -1,3,5-triazin-2-yl] amino-2,6-dimethylphenol, 4 - [[4.6 -bis (hexylsulfanyl) - 1,3,5-triazin-2-yl] amino] -2-tert-butylphenol, 2,6-di-tert-butyl-4 - [(4-octylsulfanyl-1,3,5 - triazin-2-yl) amino] phenol, 4 - [[4,6-bis (ethylsulfanyl) -1,3,5-triazin-2-yl] amino] -2,6-dimethylphenol, 4 - [[4 , 6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] butylamino] -2,6-di-tert-butylphenol, 4 - [[4,6-bis (octylsulfanyl) -1,3, 5-triazin-2-yl] -cyclohexylamino] -2,6-di-tert-butylphenol, 2 - [[4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl] amino ] -6-tert-butylphenol, 2-tert-butyl-6-methyl-4 - [[4-octylsulfanyl-6 - [(2,2,6,6, -tetramethylpiperidin-4-yl) amino] -1, 3,5-triazin-2-yl] amino] phenol, 4- [[4,6-bis (octylsulfanylmethyl) -1,3,5-triazin-2-yl) amino] -2,6-ditherc-butylphenol, 4 - [[4,6- bis (octylsulfanyl) -1,3,5-tr iazin-2-yl) methylamino] -2,6-di-tert-butylphenol, 4 - [(4-amino-6-chloro-1,3,5-triazin-2-yl) amino] -2,6- di-tert-butylphenol and 4 - [(4-cyclohexyl-6-cyclohexylsulfanyl-1,3,5-triazin-2-yl) amino] -2,6-di (propan-2-yl) phenol , in one embodiment, the amino thioether compound comprises 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2-ylamino) phenol (also referred to as phenol , 4 - [[4,6-bis (octyl) -1,3,5-triazin-2-yl] amino] -2,6-bis (1,1-dimethylethyl)) and combinations of one or more of these.
    [0016]
    16. Method according to claim 15, CHARACTERIZED by the fact that the additive comprises 2,6-di-tert-butyl-4- (4,6-bis (octyl) -1,3,5-triazin-2 - ylamino) phenol.
    [0017]
    17. Method, according to claim 13, CHARACTERIZED by the fact that at least one photocurable layer comprises an antioxidant selected from the group consisting of 1,3,5-trimethyl-2,4,6-tris (3,5 -di-tert-butyl-4-hydroxybenzyl) benzene, butylated hydroxytoluene, alkylated phenols, alkylated bis-phenols, polymerized trimethyl dihydroquinone, dilauryl thiopropionate and combinations of one or more of these.
    [0018]
    18. Method according to claim 17, CHARACTERIZED by the fact that the antioxidant comprises 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene .
    [0019]
    19. Method, according to claim 13, CHARACTERIZED by the fact that at least one photocurable layer further comprises one or more materials selected from the group consisting of plasticizers, anti-zonants, fillers, reinforcing agents, thermal polymerization inhibitors , UV absorbers and combinations of one or more of these.
    [0020]
    20. Method according to claim 19, CHARACTERIZED by the fact that one or more materials comprise a plasticizing agent.
    [0021]
    21. Method, according to claim 13, CHARACTERIZED by the fact that the photocurable embossed image printing element has a Shore A hardness between 45 and 70.
    [0022]
    22. Method according to claim 21, CHARACTERIZED by the fact that the photocurable embossed image printing element has a Shore A hardness between 50 and 65.
    [0023]
    23. Method, according to claim 13, CHARACTERIZED by the fact that the sharpness of the contours of the embossed printing points, defined as the ratio of the radius of curvature re at the intersection of a shoulder and the upper part of the printing point in relief with the width of the upper printing surface of point p, is less than 5%.
    [0024]
    24. Method, according to claim 23, CHARACTERIZED by the fact that the proportion of re: p is less than 2%.
    [0025]
    25. Method according to claim 13, CHARACTERIZED by the fact that the flatness of the top surface of the embossed printing points, measured as the radius of curvature by the top surface of the embossed printing points and the radius of curvature by the top surface of the embossed printing points, it is greater than the thickness of at least one photocurable layer.
    [0026]
    26. Method, according to claim 13, CHARACTERIZED by the fact that an average shoulder angle, measured as the angle between a point shoulder along the width of the top or point print surface, is less than 30 °.
    [0027]
    27. Method, according to claim 26, CHARACTERIZED by the fact that an average shoulder angle, measured as the angle between a point shoulder along the width of the top or dot print surface, is less than 20 ° .
    [0028]
    28. Method according to claim 13, CHARACTERIZED by the fact that at least one exposed photocurable layer is developed using solvent development.
    [0029]
    29. Method, according to claim 13, CHARACTERIZED by the fact that at least one exposed photocurable layer is developed with the use of thermal development.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2018-08-28| B25D| Requested change of name of applicant approved|Owner name: MACDERMID GRAPHICS SOLUTIONS, LLC (US) |
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-22| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-13| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/591,375|2012-08-22|
    US13/591,375|US8808968B2|2012-08-22|2012-08-22|Method of improving surface cure in digital flexographic printing plates|
    PCT/US2013/053746|WO2014031329A1|2012-08-22|2013-08-06|Method of improving surface cure in digital flexographic printing plates|
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