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    • 专利摘要:
    METHOD TO PRODUCE FLEXOGRAPHIC PRINTING PLATES, AND, APPARATUS FOR ON-LINE PRODUCTION OF FLEXOGRAPHIC PRINTING PLATES BY DIGITAL IMAGE FORMATION. The invention relates to a method for producing flexographic printing plates, in which a photopolymerizable flexographic printing element is used as the starting material, said element comprising at least the following, arranged on top of each other: a dimensionally stable carrier ; and at least one photopolymerizable layer that forms a relief, comprising at least one elastomeric binding agent, an ethylenically unsaturated compound and a photoinitiator; optionally, a rough UV-transparent layer comprising at least one particulate substance; and a layer that can undergo digital imaging. The method according to the invention comprises at least the following steps: (a) generating a mask by imaging the layer that can undergo digital imaging; (b) illuminate the photopolymerizable layer that forms the relief through the mask using actinic light and photopolymerize the image areas of the layer; and (c) develop the photopolymerizable layer by washing away the non-photopolymerized areas of the layer that forms the relief with an organic solvent or (...).
    公开号:BR112013001262B1
    申请号:R112013001262-5
    申请日:2011-07-12
    公开日:2021-01-05
    发明作者:Jens Schadebrodt；Armin Becker；Uwe Stebani；Maximilian Thate
    申请人:Flint Group Germany Gmbh；
    IPC主号:
    专利说明:

    The invention relates to a method for producing flexo printing plates and also to the apparatus suitable for this purpose.
    The most widespread method for producing flexographic printing plates involves exposing image to image of the light-curing relief layer with actinic radiation, especially long-wave UV radiation, through a mask produced digitally or photographically. In an additional step of the method, the exposed layer is treated using a suitable solvent or solvent mixture, with the unexposed and unpolymerized regions of the relief layer being dissolved, while the exposed and polymerized regions are retained and form the relief. the printing plate.
    Digital imaging of photosensitive flexographic printing elements is known in principle. In this context, flexographic printing elements are not conventionally produced, by placing a photographic mask, followed by exposure through the photographic mask. Instead, the mask is produced in situ directly on the flexographic printing element using appropriate technologies. Flexographic printing elements can be provided, for example, with opaque IR-ablative layers (EP-B 654 150, EP-A 1 069 475) that can be removed image by image using IR lasers. Other known technologies include layers that can be engraved using inkjet technology (EP-A 1 072 953), or layers that can be engraved thermographically (EP-A 1 070 989). Following the image-by-image recording of these layers using the appropriate technologies for the purpose, the photopolymerizable layer is exposed through the resulting mask by means of actinic light.
    Image-to-image exposure with actinic radiation occurs on a standard basis using UV radiation sources that have significant emissions in the range of about 315 nm to 420 nm (long-wave UV to violet region of the visible spectrum). The most frequently used radiation sources are UV / A tubes, which have a maximum emission at a wavelength of around 370 nm and generate UV intensities of 10 mW / cm2 - 30 mW / cm2, measured over a distance of 50 mm (typical distance from the radiation source to the surface of the flexographic printing element). UV / A tubes of this type are available, for example, under the designation “R-UVA TL 10R” by Philips.
    In addition, mercury vapor lamps are also used for image-to-image exposure, with preference being given to doped medium pressure mercury vapor lamps, as doping with iron and / or gallium allows an increase in fraction emitted in the UV / A region. Units comprising at least one mercury vapor lamp and also a reflector are referred to below as UV lamps. As well as the declared fractions of UV / A radiation, the emission spectrum of UV lamps also includes fractions of UV / B and UV / C radiation. In the course of image-to-image exposure, these shorter-wave UV radiation fractions can lead to unwanted side effects, such as, for example, the weakening of the irradiated surface or the formation of ozone. Usually, therefore, medium pressure mercury vapor lamps are selected for image-to-image exposure, in which the appropriate selection of the lamp glass greatly reduces the emission of UV / B and UV / C radiation. In addition, filters are also used that substantially absorb the fractions of UV / B and UV / C radiation, while still being substantially transparent to UV / A radiation. Since most available UV lamps convert about 40% of the electrical energy consumed into thermal radiation, the intensity of the UV lamps, which is really high, cannot simply be transferred directly onto the substrate, since an excessive temperature load can damage the flexo printing element. In order to reduce the thermal load on the substrate that is to be irradiated, the distance selected for the UV lamp to the substrate must be relatively large, 500 mm, for example, thereby reducing the UV intensity that strikes the substrate. By means of special reflectors and / or mirrors, which are at least partially transparent to infrared radiation, but substantially reflect UV radiation, it is also possible to reduce the temperature load on the substrate that must be irradiated. However, it is usually not possible to perform UV / A intensities of> 100 mW / cm2 at the level of the flexographic printing element, since the element, due to severe heating, will be otherwise damaged and, additionally, in the case of elements flexographic printing with a PET film substrate, there is a risk of a loss of dimensional stability.
    However, for radiation curing of photopolymerizable compositions, there is also an increasing use of LEDs (light emitting diodes) that emit UV light.
    Common LED systems for UV curing are currently focused, in practice, on the 395 nm and 365 nm wavelengths. Other possible spectral ranges are 350 nm, 375 nm, 385 nm and 405 nm. Scientific publications also mention the wavelengths of 210 nm, 250 nm, 275 nm and 290 nm. LEDs are distinguished by a narrow intensity distribution (typically +/- 10 - 20 nm). They have no significant heating phase and can be adjusted from about 10% to 100% of the maximum intensity.
    Using UV light emitting diodes it is possible to reach energy levels of a few watts / cm2, and the efficiency, depending on the UV LED system, is between 1% and 20%. The rough rule of thumb here is as follows: the shorter the wavelength, the lower the efficiency. And the shorter the desired emission wavelength, the higher the production costs.
    Currently, LED systems for real curing are commercially available with a wavelength of 395 nm and UV energy between 1-4 W / cm2 and a wavelength of 365 nm in the range of 0.5 - 2 W / cm2 from various suppliers.
    In order to allow higher cure speeds, LED unit suppliers are currently increasing UV output energy at the expense of efficiency. Currently most powerful LED units have an efficiency of about 8 - 12% at 395 nm, while a medium pressure mercury lamp is located at 28% efficiency. The efficiency of a 365 nm LED unit is currently below 10%.
    LED arrays are very expensive. The current price for an 8 x 1 cm UV LED array is between 5,000 - 6,000 euros. If the network width is doubled, then, for an LED set, there is also a doubling in the number of LEDs and therefore also in the price. In the case of mercury vapor lamps, the price difference between different lamp lengths is smaller.
    US 6,683,421 discloses a device for the photoreticulation of photoreactive materials comprising (A) a housing, (b) a light-emitting semiconductor arrangement mounted in the housing and capable of emitting light with a wavelength suitable for initiating photoreactions, (c ) a power source to energize the array to emit light, (d) a control unit coupled to the power source to regulate the energy supplied by the power source to the array, where (e) the array consists of a plurality of semiconductors light emitters and (f) the plurality of semiconductors is organized into a plurality of groups. No specific use applications are given for the device described.
    US 6,931,992 discloses a system for exposing a photopolymerizable element with UV light comprising a rotation device for rotating the photopolymer and a radiation source set arranged around the rotation device, the set comprising at least one radiation source which can distribute at least two different light emissions over the photopolymer and which can move at least partially across the direction of rotation and along the photopolymer, the different light emissions being arranged in such a way that their rays overlap each other, in order to allow the exposure of all points on the photopolymer surface continuously with at least one radiation source. Also described is a system for removing a flexographic printing plate and performing exposure with UV light. Specific radiation sources identified are mercury plasma capillary lamps.
    WO 2008/135865 describes a method which comprises the positioning of a printing plate with photoreticulable material in an image forming unit, the image formation of the plate according to image data, the application of UV radiation from a plurality of UV-emitting diodes to cross-link the photoreticulable material on the plate during image formation of the printing plate, where the printing plate can be a photopolymerizable flexographic printing plate, a photopolymerizable typographic composition printing plate or a photopolymerizable shirt. Also described is the removal of the plate from the image forming unit and its subsequent exposure from the reverse or from the front and, optionally, also from the reverse, with UV radiation from a plurality of UV-emitting diodes.
    DE 20 2004 017 044 UI discloses apparatus to exhibit screen printing stencils, offset printing plates, flexographic printing plates or the like, with at least one light (1), with a transparent support plate (8) for an item intended for display and with a device (10, 11) for moving at least one light (1) back and forth, at least one light (1) being arranged in a small distance from the support plate (8), characterized in that the light (1) has at least one UV LED (3).
    During the exposure of the photopolymer plates with UV light through a mask produced by laser ablation, an undesired effect that occurs is the inhibition of polymerization due to oxygen, which diffuses inside the photopolymer layer from the surrounding atmosphere. The same effect occurs if a layer that can undergo digital imaging using other technologies is employed, since these layers are, in general, only a few micrometers thick and therefore are thin enough for the oxygen in the air environment can spread through them.
    During the exposure of the flexographic printing element through a photographic mask, it is necessary to ensure that the negative is uniformly arranged on the surface of the flexographic printing element, without air inclusions, since, in other circumstances, there may be cases of failed exposure ( “Hollow copies”). In the photopolymerizable layer, therefore, there is usually a substrate layer that is less sticky than the surface of the photopolymerizable layer; on the other hand, it is usual to use film negatives with at least one side of rough film. Finally, by applying reduced pressure (with the aid of a vacuum film, for example), intimate contact between the film negative and the surface of the plate is produced, with the air present between them being very widely removed. Consequently, oxygen can no longer inhibit light curing. The most frequently used UV beam sources, namely UV / A tubes, have very diffuse light. Scattered light plays a significant role, promoted with low intensity UV and the associated long exposure time. UV / A light is spread on the vacuum film and on all sides of the contour (for example, between the film negative and the plate surface). As a result, there can easily be an increase in the positive elements that must undergo image formation, while thin structures of the region without image may be reduced in size.
    Inhibition of oxygen polymerization can also lead to severe element reduction, since at least at the edges, the image elements no longer undergo sufficient polymerization and are ultimately removed by solvent, for example, in the course of exposure image by image. The result of this is what is called a reduction in the tonal value - that is, the tonal value measured on the printing plate for a screen of positive elements (halftone dots) is less than the value corresponding to the image data. In certain circumstances, this may be desirable, for example, in order to compensate for the increase in tonal value in the printing operation itself; on the other hand, below a certain tonal value, points of the canvas are no longer steadily anchored and will no longer undergo image formation. As a result, gray gradations are lost and the tonal value range on the printout is lower. The effect of reducing the tonal value during the exposure of digital photo printing plates is known according to the previous technology with UV / A tubes. As a result of this inhibition effect of polymerization by oxygen during the exposure, the polymerization of the halftone dots is interrupted and, then, the halftone dots on the plate will be smaller than those provided in the data.
    It is an object of the invention to provide an economical method for producing flexo printing plates that remedies deficiencies in the prior art. More particularly, the intention is to substantially suppress the oxygen polymerization inhibiting effect during exposure of the photopolymerizable plate and to suppress the associated deleterious consequences for the printing result. The objective is achieved by a method for producing flexographic printing plates using, as a starting material, a photopolymerizable flexographic printing element comprising at least, arranged on top of each other, * a dimensionally stable support, and * at least one layer light-curing relief, which comprises at least one elastomeric binder, an ethylenically unsaturated compound and a photoinitiator, * a layer that can undergo digital image formation that is in direct contact with the light-curing relief layer, * the method it comprises at least the following steps: (a) producing a mask by forming the image of the layer that can undergo digital image formation, (b) exposing the light-curing relief layer through the mask with actinic light and light-curing the regions of image of the layer, and (c) develop the light-cured layer by washing away the non-light-curing regions of the relief layer with an organic solvent or by thermal development, characterized in that stage (b) comprises two stages of exposure (b-1) and (b-2), in which, in a first stage (b -1), exposure with actinic light occurs with an intensity of> 100 mW / cm from a plurality of UV LEDs and, subsequently, in a second stage (b-2), exposure occurs with actinic light with an intensity of <100 mW / cm2 from a source of UV radiation other than UV LEDs.
    According to the invention, using a plurality of UV LEDs for actinic light that are arranged in an arrangement, an "initial exposure" is performed for image formation with precise copy of the elements on the surface of the photopolymerizable plate. The remaining “final exposure” for the adjustment of the elements is carried out with other sources of radiation more favorably economical, such as with UVA tubes or UV lamps, for example.
    The first exposure step is carried out, preferably, with an intensity of> 150 mW / cm, more preferably, with an intensity of> 200 mW / cm2, measured on the surface of the flexographic printing element.
    It emerged that the order of the exposure steps is essential. In this way, satisfactory results are achieved only if exposure occurs first with a UV light source of high radiation intensity, followed by exposure with a UV light source more favorably economical with lower radiation intensity. The opposite order does not lead to satisfactory results, since the inhibition of polymerization by oxygen, once it has already occurred, can no longer be reversed by subsequent exposure to high-energy UV radiation - in this case, therefore, reproduction no longer has an accurate copy .
    If exposure is performed exclusively using UV LEDs, the difficulty arises from the provision of a stable anchorage to the thin isolated image elements, since there is no enlargement of the image elements in the deeper regions of the photopolymerizable layer. Exposure with conventional UV radiation sources, on the contrary, leads to a broader anchoring of the isolated image elements (short or thin lines), since the light coming from the UV tubes or UV lamps is more diffuse and, therefore, less well targeted, leading to an enlargement of the imaging elements in the deeper regions of the photopolymer layer. If the inhibitory effect of oxygen on the surface is minimized through exposure using high intensity UV LEDs, it no longer plays virtually any role in the case of downstream exposure with UV tubes. Then, the lower regions of the photopolymer layer can subsequently be exposed with a conventional UV light source (UV tube or UV lamp) and provided / with good anchoring at the same time.
    Generally speaking, the intensity of the UV LEDs used according to the invention is> 100 mW / cm2, preferably> 150 mW / cm2, more preferably> 200 mW / cm2, measured on the surface of the flexo printing plate. Generally speaking, this intensity is not above 2,000 mW / cm2, preferably not above 1,000 mW / cm2.
    The intensity at the level of the plate surface is measured using a suitable calibrated UV measuring device, the sensor of the measuring device being placed at the same distance from the radiation source as the surface of the plate would be from the radiation source. Suitable UV measuring devices are commercially available from a variety of suppliers. Important factors here are that the measuring device is calibrated and sensitive in the UV wavelength range under test.
    The distance between the surface of the printing plate and the source of UV radiation in the first exposure step is typically 2 to 20 mm, preferably 2 to 10 mm. The radiation from the LEDs has virtually no IR fraction, so a high intensity in combination with a low distance from the substrate is possible without a high thermal load on the substrate that must be irradiated.
    A high intensity UV in the first exposure step (b-1) minimizes the 02 inhibition of light curing and therefore the degree of element reduction - in other words, there is only a very small reduction in the copy size of the image elements . Low reduction in copy size may be desirable, as there may be an increase in tonal value in printing as a result of the printing procedure.
    The radiation dose in the first exposure stage (b-1) is, in general, from 1 to 8 J / cm2, preferably from 1 to 5 J / cm2. A minimal dose of UV LED is required, since if the dose of UV LED is small, only the immediate surface will be reticulated, but the fractions of the layer that connect the element's anchors are very weakly reticulated, which can lead to leakage . This minimum dose of UV LED is approximately 0.5 J / cm2.
    In the second exposure step (b-2), a source of UV radiation other than UV LEDs, with a lower intensity, is used. Suitable radiation sources used in the second exposure stage emit UV / A light, that is, UV light in a range of 315 - 420 nm. Generally speaking, the light emitted has a wide distribution of intensity. Suitable UV radiation sources used in the second exposure step are the above-described UV tubes and UV lamps. UV lamps are used, in general, at a greater distance (typically 500 mm) from the surface of the flexographic printing plate, due to the higher level of heat developed, than are UV tubes (typically, 50 mm).
    Generally speaking, the intensity of the UV tube is> 8 mW / cm2, preferably> 10 mW / cm2, more preferably> 12 mW / cm2. The intensity is, in general, not above 50 mW / cm2, measured, in each case, on the surface of the flexographic printing element.
    For example, the intensity of a UV tube is 10-30 mW / cm2, measured at a distance of 50 mm. The intensity of a UV lamp is, for example, 50 - 60 mW / cm2, measured at a distance of 500 mm.
    The radiation dose in the second exposure step (b-2) is, in general, from 1 to 15 J / cm2, preferably from 2 to 10 J / cm2.
    Generally speaking, 10% to 80% of the total dose will be applied in the first exposure stage (b-1), and 20% to 90% of the total dose in the second exposure stage (b-2). It is preferable to apply 15% to 50% of the total dose in the first exposure stage (b-1) and 50% to 85% of the total dose in the second exposure stage (b-2).
    Suitable LEDs that can be used in the first stage of exposure (b-1) are LEDs that are commercially available and known for UV curing. They have a maximum emission in the wavelength range of 350 - 405 nm, as, for example, at 395 nm or 365 nm. Other possible emission wavelengths are 350 nm, 375 nm, 385 nm and 405 nm. Preferred commercial LED systems used according to the invention are those with wavelengths of 375 and 365 nm.
    According to the invention, the first exposure step (b-1) occurs with a plurality of UV LEDs that are generally arranged in an arrangement. Therefore, such an arrangement can consist of a plurality of square LED modules disposed adjacent to each other, with each module comprising a plurality - for example, 5 x 5 - of individual LEDs.
    The first exposure step (b-1) can also occur with a plurality of such LED arrangements.
    Exposure occurs, in general, with the photopolymerizable flexographic printing element being transported through the bottom of the exposure units (LED arrangement or UV tube or UV lamp). Of course, it is also possible for the display units to move.
    During the production of cylindrical flexo printing plates, it is also possible to use what is called multilateral display systems, which then comprise one or more LED arrays and one or more UV tubes.
    Generally speaking, the flexographic element is subject to preliminary exposure from the reverse. For this purpose, before step (b) is carried out, the layer of photopolymerizable material is pre-exposed with actinic light through the transparent UV support film, from the reverse of the photopolymerizable flexographic printing element. Preliminary reverse exposure is performed, preferably, in the case of flexographic printing elements with a thickness of> 1 mm, this number is related to the total sum of the dimensionally stable support film and the photopolymerizable layer.
    Generally speaking, preliminary reverse exposure occurs with a UV tube or UV lamp, preferably of the same type also used in the exposure step (b-2).
    The photopolymerizable flexographic printing element used as a starting material comprises - arranged on top of each other - at least • a dimensionally stable support, and • at least one photopolymerizable embossing layer, comprising at least one elastomeric binder, a compound ethylenically unsaturated and a photoinitiator, • a layer that can undergo digital imaging by laser ablation.
    Examples of dimensionally stable support suitable for the photopolymerizable flexographic printing elements used as a starting material for the method are sheets, films and also conical and cylindrical liners made of metals, such as steel, aluminum, copper or nickel, or plastics , such as poly (ethylene terephthalate) (PET), poly (ethylene naphthalate) (PEN), poly (butylene terephthalate) (PBT), polyamide, polycarbonate, optionally, also, woven and non-woven cloths, such as cloth of woven glass fiber and also composite materials, comprising glass fibers and plastics, for example. Dimensionally stable support contemplated includes, in particular, dimensionally stable support films, such as, for example, polyester films, more particularly, PET or PEN films, or flexible metallic supports, such as thin sheets or metal sheets made of steel, preferably stainless steel, magnetizable sprung steel, aluminum, zinc, magnesium, nickel, chrome or copper.
    If preliminary reverse exposure of the flexographic printing element needs to be performed, the dimensionally stable support must be transparent to UV light. Preferred supports are plastic films made from PET or other polyesters.
    The flexographic printing element additionally comprises at least one photopolymerizable embossing layer. The light-curing relief layer can be applied directly to the substrate. Between the support and the relief layer, however, there may also be other layers, such as adhesion layers and / or lower resilient layers.
    Between the support film, optionally coated with an adhesion layer, and the light-curing relief layer, there may be an elastomeric support layer. The backing layer can optionally be photochemically crosslinkable.
    The light-curing relief layer comprises at least one elastomeric binder, an ethylenically unsaturated compound, a photoinitiator or a photoinitiator system, and also optionally one or more additional components, examples being plasticizers, processing assistants, paints and UV.
    Elastomeric binders for producing flexographic printing elements are known to those skilled in the art. Both hydrophilic and hydrophobic binders can be used. Examples include styrene - diene block copolymers, ethylene - acrylic acid copolymers, polyethylene oxide graft copolymers - polyvinyl alcohol, natural rubber, polybutadiene, polyisoprene, styrene - butadiene rubber, nitrile - butadiene rubber, butyl rubber, styrene - isoprene rubber, styrene - butadiene - isoprene rubber, polynorbomenal rubber, or ethylene - propylene - diene rubber (EPDM). It is preferred to use hydrophobic binders. Binders of this type are soluble or at least swellable in organic solvents, whereas - in water, they are largely insoluble and are also not swellable, or at least not substantially swellable in water.
    The elastomer is preferably a thermoplastic block copolymer of aromatic alkenes and 1,3-dienes. Block copolymers can be linear, branched or radial block copolymers. Typically, they are type A-B-A triblock copolymers, but they can also be type A-B diblock polymers or copolymers with two or more alternating elastomeric and thermoplastic blocks, for example, A-B-A-B-A. Mixtures of two or more different block copolymers can also be used. Commercial triblock copolymers often include certain fractions of diblock copolymers. The diene units can be 1,2- or 1,4-linked. Not only can block copolymers of the styrene - butadiene type or the styrene - isoprene type, but also those of the styrene - butadiene - isoprene type can be used. They are commercially available under the name Kraton®, for example. In addition, it is also possible to use thermoplastic elastomeric block copolymers with final blocks of styrene and a block of the random medium of styrene - butadiene, these copolymers being available under the name Styroflex®. Block copolymers can also be completely or partially hydrogenated, such as in SEBS rubbers, for example.
    Elastomeric binders present, most preferably, in the photopolymerizable embossing layer are triblock copolymers of type A-B-A or radial block copolymers of type (AB) n, where A is styrene and B is a diene.
    Elastomeric binders present, most preferably, in an elastomeric support layer are ABA type triblock copolymers, radial block copolymers of type (AB) n, where A is styrene and B is a diene and also random copolymers and copolymers statistical results of styrene and diene.
    Of course, it is also possible to use mixtures of two or more binders, subject to the condition that this does not adversely affect the properties of the relief layer.
    The total amount of binders in the case of the embossing layer is typically 40% to 90% by weight, relative to the sum of all the constituents of the embossing layer, preferably 40% to 80% by weight and , more preferably, 45% to 75% by weight.
    In the case of an optionally present elastomeric support layer, the total amount of elastomeric binders can be up to 100% by weight. Typically, it is 75% to 100% by weight, preferably 85% to 100% by weight and, more preferably, 90% to 100% by weight.
    The light-curing relief layer additionally comprises, in a known manner, at least one ethylenically unsaturated compound that is compatible with the binders. Suitable compounds have at least one ethylenically unsaturated double bond and are polymerizable. Therefore, they are referred to below as monomers. Acrylic or methacrylic acid esters or amides with monofunctional or polyfunctional alcohols, amines, aminoalcohols or hydroxyl ethers and hydroxyl esters, fumaric or maleic acid esters, vinyl ethers, vinyl esters or allyl compounds have proved particularly advantageous. Examples of suitable monomers are butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tetradecyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri ( met) acrylate, dioctyl fumarate and N-dodecylmaleimide. Most preferred monomers are monoacrylates, diacrylates and triacrylates and - methacrylates. Of course, it is also possible to use mixtures of two or more different monomers. The nature and quantity of the monomers are selected by those skilled in the art according to the desired properties of the layer. The amount of monomers in the light-curing relief layer a) is, in general, no more than 20% by weight relative to the amount of all constituents and, in general, it is between 3% and 15% by weight.
    In a manner which is known in principle, the light-curing relief layer additionally comprises at least one photoinitiator or a photoinitiator system. Examples of suitable initiators are benzoyl or benzoyl derivatives, such as methylbenzoin or benzoyl ethers, benzyl derivatives, such as benzyl ketals, acylarylphosphine oxides, acrylarylphosphine esters, α-hydroxy ketones, polycyclic quinones or benzophenones. The amount of photoinitiator in the embossing layer is, in general, 0.1% to 5% by weight, relative to the amount of all the constituents of the embossing layer.
    The elastomeric support layer can also comprise the aforementioned ethylenically unsaturated compounds and the aforementioned photoinitiators and, preferably, does not comprise them and is therefore photopolymerizable as the relief formation layer. Generally speaking, the amount of ethylenically unsaturated compounds in the backing layer is 0% to 15% by weight. In general, the amount of photoinitiator in the support layer is 0% to 5% by weight.
    The embossing layer and, optionally, the optional elastomeric support layer may comprise plasticizers. Mixtures of different plasticizers can also be used. Examples of suitable plasticizers include modified and unmodified natural oils and natural resins, such as paraffinic, naphthenic or aromatic high-boiling mineral oils, oligomers or synthetic resins, such as oligo-styrene, high-boiling esters, styrene-butadiene copolymers oligomeric, oligomeric α-methylstyrene / p-methylstyrene copolymers, liquid oligobutadienes, more particularly, those with a molecular weight between 500 and 5,000 g / mol, or acrylonitrile - butadiene oligomeric liquid copolymers or ethylene - propylene - diene oligomeric copolymers. Preference is given to polybutadiene oils, more particularly, those with a molecular weight between 500 and 5,000 g / mol, aliphatic esters with a high boiling point, such as, more particularly, esters of alkylmonocarboxylic and dicarboxylic acids, examples being stearates or adipates and mineral oils. The amount of an optionally present plasticizer is determined by those skilled in the art according to the desired properties of the layer. In general, it will not exceed 50% by weight of the total sum of all the constituents of the photopolymerizable relief layer; in general, it is 0% to 50% by weight, preferably 0% to 40% by weight.
    The thickness of the relief layer is, in general, 0.3 to 7 mm, preferably 0.5 to 6 mm.
    A preferred embodiment uses a styrene-butadiene type binder. Particularly preferred binders are linear, radial or branched block copolymers of the styrene-butadiene type. These block copolymers have an average molecular weight Mw (average weight) of 80,000 to 250,000 g / mol, preferably 80,000 to 150,000 g / mol and, more preferably, 90,000 to 130,000 g / mol, and have a styrene content of 20% to 40% by weight, preferably from 20% to 35% by weight and, more preferably, from 20% to 30% by weight.
    In another preferred embodiment of the invention, the binder is of the styrene-isoprene type. Preferred styrene-isoprene-type binders generally contain 13% to 40%, preferably 13% to 35% and, more preferably, 14% to 30% by weight of styrene.
    The photopolymerizable flexographic printing elements can be produced by methods known in principle to those skilled in the art, such as, for example, by extrusion by melting, casting or laminating in a single-stage or multistage production procedure. Preference is given to its production by means of melt extrusion, in which, first of all, the constituents of the embossing layer are mixed together in a heated extruder. To produce blade-type flexographic printing elements, the photopolymerizable composition can be discharged from the extruder through a slit mold between two films, and the layer assembly can be calendered, the nature of the films being guided by the desired end use. The films in question are films that exhibit good adhesion to the light-curing layer or are readily removable (temporary) films. For the production of blade flexographic printing elements, it is usual to use a well adherent support film and a removable top film. The thickness of the photopolymerizable layer is, in general, 0.4 to 7 mm, preferably 0.5 to 4 mm and, more preferably, 0.7 to 2.5 mm.
    The image formation of the layer that can pass through digital image formation is carried out by means of digital masks. Masks of this type are also known as masks in situ. For this purpose, a layer that can undergo digital imaging is applied first to the photopolymerizable embossing layer. The layer that can undergo digital imaging is preferably an IR-ablative layer, inkjet layer or layer that can be thermographically engraved.
    The layer that can undergo digital imaging is preferably a layer that can be removed using an IR laser (IR removable layer).
    IR-removable layers and masks are opaque in the wavelength of actinic light and typically comprise at least one binder, an IR absorber, such as carbon black, for example, and also an absorber for UV radiation; the function of the IR absorber and the UV absorber can also be performed by only one substance, as is the case, for example, when carbon black is used as an IR absorber, since, in sufficient concentration, carbon black takes the mask layer substantially opaque to UV light. A mask can be engraved on the ablative layer by IR using an IR laser - in other words, at the points where it is found by the laser beam, the layer is decomposed and removed. Irradiation can occur image by image with actinic light through the resulting mask. Examples of the imaging of flexographic printing elements with ablative IR masks are disclosed in EP-A 654 150 or EP-A 1 069 475, for example.
    In the case of inkjet layers, a layer that can be etched with inkjet inks, such as a gelatin layer, is applied. This layer can undergo image formation using inkjet printers. Examples are disclosed in EP-A 1 072 953.
    Thermographic layers are layers that comprise substances that acquire a black color under the influence of heat. Layers of this type comprise, for example, a binder and an organic silver salt, and can be imaged by means of a printer with a thermal head or by means of IR lasers. Examples are disclosed in EP-A 1 070 989.
    In a particular embodiment of the method of the invention, there is a rough UV-transparent layer that comprises a particulate substance between the photopolymerizable embossing layer and the layer that can undergo digital imaging. As a result of the particulate substance, small elevations or cuts are produced on the printing surface, and improve the transfer of ink in the printing operation.
    Therefore, the flexographic printing element comprises, arranged on top of each other, at least • a dimensionally stable support, and • at least one photopolymerizable embossing layer comprising at least one elastomeric binder, an ethylenically unsaturated compound and a photoinitiator , • a rough UV-transparent layer that comprises at least one particulate substance, and • a layer that can undergo digital imaging.
    The particulate substance present in the UV transparent layer is both anchored in the embossing layer, and therefore produces elevations in the embossing layer, and the particulate substance is not anchored, and this leaves it in the embossing layer. , cuts whose size is in the order of the particle diameter of the particulate substance. Generally speaking, the particulate substance has an average particle diameter of 0.5 to 50 μm.
    The UV transparent rough layer is located in direct and intimate contact with the light-curing relief layer, and therefore the roughness is transferred to the printing surface of the flexographic printing element.
    In a first embodiment, the rough substrate layer comprises a) at least one polymeric binder, and b) at least one particulate substance with an average particle diameter of 0.5 - 50 μm.
    If the flexographic printing element is developed using a washing agent, with the unimagined regions of the flexographic printing element being removed with a suitable solvent or solvent mixture, the polymeric binder is soluble or at least dispersible in the washing agent . If the flexographic printing element is thermally developed, with the non-image regions being liquefied in such a way that they can be taken up with a suitable absorbent material, the polymeric binder can be liquefied at the processing temperature up to a limit such that it takes become fluid and can be taken up by the absorbent material.
    Suitable binders include polyamides, examples being nylon and nylon copolymers, polyvinyl alcohols, polyurethanes, urethane copolymers, polyvinylpyrrolidone, polyethylene oxides with a number - average molecular weight of> 100,000 g / mol, ethylene vinyl acetate copolymers, polyia, polyia polyesters, cellulose esters, cellulose ethers and polyolefins.
    The particulate substance can produce cuts in the light-curing relief layer as a result of printing or, because it is anchored in the light-curing relief layer, it can form elevations in the light-curing relief layer.
    Anchoring of the particulate substance in the light-curing relief layer can occur physically or chemically. Physical anchoring can be caused, for example, by the particulate substance with a very irregular shape or that has a large number of small open pores. In this case, while it is in direct contact with the rough transparent UV layer, the photopolymerizable layer can penetrate into the cavities or pores of the particulate substance, thus producing, after polymerization, a mechanical anchorage. Chemical anchoring of the particulate substance in the light-curing relief layer can be carried out, for example, by means of functional groups on the particle surface. Suitable functional groups include ethylenically unsaturated groups or other groups reactive with free radicals, such as allyl groups, amine groups, vinylsilane groups, vinylsiloxane groups or halogen groups.
    As described in EP 1457823 A2, the particulate substance has, in general, an average particle size of> 3 μm according to ASTM D 4483-85. It is preferred that> 60 weight percent of the particulate substance has a particle size of 3 to 15 μm.
    The structure of the particulate substance is preferably inorganic in nature. Suitable particulate substances comprise binding agents with i) a pore volume of> 0.9 ml / g or ii) a BET surface area of> 150 m2 / g or iii) an oil number of> 150 g / 100 g , and it is also possible that two or three of the stated conditions are met. Additional suitable particulate substances are silica and silica-gels, finely dispersed silicon dioxide, zeolites and pigments in the described particle sizes.
    For anchoring the particulate substance on the surface of the photopolymerizable layer, the declared suitable substances can be functionalized with the aforementioned functional groups, functionalization being present, in general, only on the surface of the particles.
    In a second embodiment, the rough UV-transparent layer comprises not only the particulate substance, but also at least one wax. In this case, the rough substrate layer is advantageously produced by applying a polymeric wax dispersion to the layer that can undergo digital image formation. It is preferred not to add any additional binders to the wax.
    Between the layer that can undergo digital imaging and the rough transparent UV layer, there can also be, optionally, intermediate layers, an example being an adhesion-promoting layer.
    With the conventional exposure of the previous technology of a flexographic printing element that has undergone digital imaging that has an additional UV transparent rough layer, with UV tubes or UV lamps, the oxygen that is present and diffuses inside the layer light-curing relief has an inhibitory effect on polymerization, and it does so more directly below the surface of the flexographic printing element. More particularly, a region of the top layer, at a depth of about 30 μm, of the flexographic printing element is incompletely polymerized and, in the course of subsequent development, by solvent washing or thermal development, is removed together with the regions without Image. As a result, the roughness of the rough UV-transparent layer, present in the form of cuts or in the form of anchored particles, which undergoes image formation on the printing surface is largely lost. Then, only very flat structures remain on the printing surface, which can have a wormlike appearance, and whose dimensions no longer coincide with the defined particle sizes of the particulate substance.
    If the exposure method of the invention is employed, the high intensity of the first exposure step at least greatly reduces the oxygen inhibitory effect. As a result, the roughness applied to the surface of the photopolymerizable relief layer by the rough UV transparent layer is substantially retained. A uniformly rough surface of the printing regions is advantageous (increasing the density of the base ink) in terms of uniformity and quantity of the ink transferred to the print media.
    The method of the invention can be carried out by inserting the starting material, first, into a receiving unit, by means of, for example, placing it on a conveyor belt or loading the spool. If the starting material has a protective sheet, then, unless the receiving unit has an automatic removal device, said sheet must be removed.
    In step (A) of the method, the layer that can undergo digital image formation undergoes image formation in an image formation unit using the technology required in each case. The image information is taken directly from a control unit.
    In step (b) of the method, the flexographic printing element that has undergone image formation is irradiated through the exposure unit through the mask that was produced using actinic light - that is, chemically active light.
    In a step (c) of the method, the flexographic printing element that has undergone imaging in the image-by-image manner and has been exposed is developed by means of a suitable solvent or solvent combination. In this case, the unexposed regions, that is, those covered by the mask, in the relief layer are removed, while the exposed regions - that is, reticulated - are retained. In addition, residues of the layer that can undergo digital imaging are removed.
    The solvent or solvent mixture used is guided by the nature of the flexographic printing element employed. If the flexographic printing element has an aqueous, developable photopolymerizable layer, then water or predominantly aqueous solvents can be used. In the case of organically developable flexographic printing elements, particular compatibility is possessed by the washing agents known for flexographic printing plates, which typically consist of mixtures of different organic solvents that interact in an appropriate manner. For example, developers can use fractions of naphthenic or aromatic oil in a mixture with alcohols, such as benzyl alcohol, cyclohexanol or aliphatic alcohols with 5 to 10 carbon atoms, for example, and also, optionally, components additional, such as, for example, alicyclic hydrocarbons, terpenoid hydrocarbons, substituted benzenes, such as diisopropylbenzene, esters with 5 to 12 carbon atoms or glycol ethers, for example. Suitable washing agents are disclosed in EP-A 332 070 or EP A 433 374, for example.
    The development stage is typically carried out at temperatures above 20 ° C. For safety reasons and to reduce the cost and complexity of the development apparatus involved, the temperature when using organic solvents should be 5 ° C to 15 ° C below the melting point of the used washing agent mixture.
    The flexo printing plates can be dried in step (d) of the method. When the flexographic printing element has a PET film support, drying preferably occurs at a temperature of 40 to 80 ° C, more preferably at 50 to 70 ° C. When the dimensionally stable support of the flexographic printing element is a metal support, drying can also occur at higher temperatures, up to about 160 ° C.
    In one step (e) of the method, the resulting flexographic printing plates can, when necessary, be additionally subjected to a post-treatment of unraveling by means of UV-A and / or UV-C light. Generally speaking, a step like this is timely. If irradiation needs to occur with light of different wavelengths, this can occur simultaneously or even in succession.
    Among the individual steps of the method, the flexographic printing element or the flexographic printing plate is transported from one unit to the next. The flexographic printing element or the flexographic printing plate need not be curved in any of the method steps; instead, all steps are traversed with the flat flexo printing element or plate.
    Development can also be carried out by thermal means. In the case of thermal development, no solvent is used. Instead, following the image-to-image exposure, the relief layer is placed in contact with an absorbent material and heated. The absorption material comprises, for example, a porous non-woven fabric, made of nylon, polyester, cellulose or inorganic materials, for example. In the course of thermal development, the flexographic printing element, at least on the surface, experiences an increase in temperature in such a way that the unpolymerized fractions of the embossing layer can become liquid and be taken up by the absorption material. Then, the used absorption material is removed. Details regarding thermal development are disclosed by US 3,264,103, US 5,175,072, WO 96/14603 or WO 01/88615, for example. The mask can optionally be removed in advance using a suitable solvent or, equally, thermally.
    In addition, the apparatus for inline production of flexographic printing plates by means of digital image formation is additionally provided by the present invention, comprising at least: (A) optionally, a unit for digital image formation of the flexographic printing element, (B) a first exposure unit comprising a plurality of LEDs arranged in an array and capable of emitting UV light with an intensity of> 100 mW / cm, (C) a second exposure unit comprising at least one source of UV radiation different from LEDs, preferably a UV tube or UV lamp, (D) a washing unit, (E) a drying unit, (F) optionally, a post-treatment unit, (G) optionally, a distribution unit for the resulting flexo printing plates, and (H) transport units for the flexo printing elements and plates that connect the units (B) to (E) with each other.
    Units (A) through (H) are preferably designed so that the elements and flexo printing plates are processed in a flat state.
    Unit (A) is used for digital image formation of the flexographic printing element. It can comprise two or more functional units of the same type, examples being IR lasers or inkjet print heads for digital imaging. It can have, for example, 5 to 50 functional units. The interaction of a relatively large number of functional units allows faster imaging of the flexographic printing element to be achieved. Due to the action of the functional units in the layer that can undergo digital image formation of the flexographic printing element, a mask is produced in the flexographic printing element. This step is often carried out separately in a unit separate from the device that has units (B) through (H).
    The functional units are typically arranged above the flexographic printing element and then can image the layer that can digitally image as much as possible vertically from above. For the purpose of image formation, it must also be possible for there to be a relative movement between the functional units and the flexographic printing element that must undergo image formation. For this purpose, the plate, the functional units or both can move. It will also be possible, however, that there is, for example, a fixed laser source, with only the laser beam being guided, as a mirror system, for example.
    The nature of the functional units is guided by the nature of the layer that can undergo digital image formation. For imaging the flexographic printing elements with opaque layers ablative by IR, IR lasers are used. These are preferably diode lasers, with no intention that the invention should be restricted to such lasers. In this case, the opaque IR ablative layer is removed where it is found by a laser beam, and the underlying photopolymerizable layer is exposed. In order to prevent the apparatus of the invention from being contaminated with the products of the layer decomposition, the image forming unit, in the case of this modality, must expediently have a suction removal device.
    Image formation using inkjet technology occurs according to the reverse principle. The layer that can undergo digital imaging is transparent, and those places that should not be cross-linked are masked using opaque ink. The functional units, in this way, are inkjet print heads.
    Layers that can undergo thermographic digital imaging are transparent and opaque under the influence of heat. Functional units suitable for recording thermographic layers are IR lasers or thermal printheads, for example.
    It is useful that the imaging unit (A) has a modular construction, therefore, allowing the functional units to be easily switched according to the desired imaging technology.
    The first display unit (B) comprises a plurality of LEDs arranged in an arrangement. It can comprise two or more LED arrays.
    The second exposure unit (C) comprises at least one UV tube or a UV lamp of the type described above. /
    The washing unit (D) comprises a device for treating the exposed flexographic printing element with a suitable washing agent, by spraying or dipping, for example. It additionally typically comprises brushes or movable sponges to accelerate the removal of the unpolymerized polymer. Furthermore, the washing unit typically comprises a device suitable for supplying fresh washing agent and for removing used washing agent.
    The drying unit (E) is used to dry the wet flexographic printing element. It can consist, for example, of a heating chamber or a drying tunnel. Heat can be supplied, for example, by installed heating elements. However, the drying unit can also advantageously have a continuous flow of hot drying gas passing through it. Of course, it is also possible to combine the heating options with each other. The dryer used must be an exhaust air dryer in order to prevent the accumulation of solvent in the gas space. The solvent concentration in the gas space must be below the lower explosion limit. It is also advantageously possible to circulate a continuous flow of drying gas, in which case, the washing agent that escaped from the flexographic printing plate is separated in a suitable device for the purpose, and the exhausted continuous flow of drying gas is separated. returned to the drying unit. The solvent can be removed by means of, for example, condensation at relatively low temperatures or absorption in suitable absorbents.
    The after-treatment unit (F) is not necessary in any case and is therefore only optional. Generally speaking, however, it is opportune to untie the surface of the resulting flexographic printing plate. The post-treatment unit comprises radiation sources suitable for irradiating the flexographic printing plate with UV-A and / or UV-C light.
    The distribution unit (G) is used to distribute the completed flexo printing plate. In its simplest form, this unit can comprise a simple dispensing device, from which the flexo printing plates are taken manually. For example, flexo printing plates can be transported on a conveyor belt in the aftertreatment unit (F). The dispensing unit (D) may alternatively comprise a spool that can hold a relatively large amount of completed flexographic printing elements.
    The transport units (H) associate at least units (B) to (E), but, as and when necessary, they also associate all units (A) to (G), with each other, and provide the transport of elements or flexo printing plates from one unit to the next. It is conceivable that the elements or flexographic printing plates pass through the entire apparatus of the invention in a single transport device. The transport device can be, for example, a conveyor belt, on which a flexographic printing element is placed and is maintained on the belt by means of a suitable maintenance device, such as pins, for example, and guided. Alternatively, the flexographic printing element can also be transported using what is called a transport strip. A transport strip is a rigid maintenance device in which the flexographic printing element is fixed for transport. This fixation can be implemented, for example, by first punching holes inside the flexographic printing element, these holes keeping the flexographic printing element in position with the aid of metal pins on the transport strip. It is also possible to use a clamping mechanism on the transport strap. The transport strip is transported through the entire apparatus of the invention, taking the flexographic printing element with it. The transport strip can be advantageously transported through the entire apparatus of the invention by means of threaded rods driven if the outer sides of the transport strip lead to contours that form a positive lock with the threaded rod.
    The invention is illustrated by the examples that follow. EXAMPLES
    Used flexo printing plates
    The flexographic printing plates used in the following examples were commercially available plates, called digital flexographic printing plates, from the brand nyloflex® (Flint Group), which are marketed under the product name ACE 114 D and also FAC 470 D.
    Digital flexographic printing plates comprise, arranged on top of each other, at least a) a dimensionally stable support (in this case, a PET film) b) a light sensitive elastomeric layer that can be cross-linked image by image by means of radiation actinic c) a layer of the mask that is substantially opaque to UV light, it is also possible that additional interlayers are employed, such as an adhesion promoting layer between a) and b), for example.
    Preliminary exposure of flexographic printing plates
    Flexographic printing plates with transparent UV supports, with a thickness of at least 1 mm, are typically subject to preliminary exposure in their complete area, from the reverse side, in order to generate a two-dimensional polymerized region that adjusts the depth of the relief of the regions without image to a desired degree. As a result, thin isolated positive elements are more effectively anchored and therefore also more stable in the printing operation. Flexographic printing plates with a thickness of 1.14 mm are typically subject to preliminary exposure on the reverse side with UV light until the depth of the relief in the regions without image is 0.5 to 0.7 mm.
    Before the image formation step of the mask, the flexographic printing plates used in the examples were pre-exposed from the reverse side with UV light, for the time indicated in table 1, to define a relief depth of approximately 0.7 mm .
    Digital image formation of flexographic printing plates
    For all of the tests identified in the examples, the digital flexographic printing plates used have been imaged with a test pattern that contains different test elements, including a plurality of halftone values on different screen widths and thin lines, text , negative points and, also, negative lines and manuscript in variable dimensions.
    Image formation of the digital mask was performed using a “nano” laser ablation system from Flexolaser GmbH, the mask resolution used being 2,540 dpi.
    Development of flexographic printing plates
    Solvent-based development of the flexographic printing plates exposed to the image-by-image manner was carried out at the indicated washing speed and with the brush adjustment recommended for the particular type of product, with the aid of a nyloflex® F III washer. The washing agent used was nylosolv® A.
    After the washing operation, the plates that still contain solvent were dried according to the specific product recommendations at 60 - 65 ° C and then re-exposed in the re-exposure unit of a nyloflex® F III exposure device using UVA and UVC light. Reexposure serves, first, to react these monomer and photoinitiator residues that are still reactive and, second, it has the effect of making the surface of the plate less sticky.
    Exposure of flexographic printing plates using UV tubes
    Flexographic printing plates were exposed using UV tubes in the main exposure unit of a nyloflex® F III exposure device, with the UV / A radiation energy at the surface level of the plate, determined using a Kühnast UVA meter, in average, 15 mW / cm2.
    Exposure of flexographic printing plates using UV LED radiation
    The UV LED unit used was a high-performance arrangement consisting of 8 square UV LED modules in a reliable metal housing. Each of these UV LED modules consisted of 5 x 5 individual diode elements, arranged together in a square field of approximately 8x8 mm, thus providing the general arrangement of a UV emission area of approximately 75 x 8 mm. The UV LEDs used had a maximum emission of 365 nm and were operated at a very constant energy level by means of water cooling and an associated control device. UV LED units of this type are available, for example, by Dr. Honle AG (Grafelfing, Germany) under the name “LED UVPowerline”. Examples A1-A5
    First of all, as explained, an IR laser was used to engrave a test pattern on the mask layer of a nyloflex® ACE 114 D flexographic printing plate that was pre-exposed from its reverse side. Due to the remaining mask layer, the regions with no image remain UV opaque, although removing the mask in the image regions enables the light-curing relief layer to be cured by means of actinic radiation.
    In a first stage of exposure, the flexo printing plate prepared in this way was first transported at a uniform speed, by means of a transport device, under a UV LED unit of the type described and, thus, on its front side, the plate was exposed to radiation from the UV LED unit; the exposure speed parameters (transport speed of the plate under the UV LED unit), the distance between the plate surface and the beam source, and the UV dose applied using UV LED can be found in table 1.
    In a second exposure stage, subsequently, the printing plate exposed to UV LED was additionally exposed with UV tubes in a nyloflex® F III exposure system for the period of time indicated in table 1. The total sum of the UV dose of both the exposure steps are also listed in table 1.
    Finally, as explained, the exposed flexographic printing plate, according to the recommended processing parameters specific to the product, was washed in a solvent-based development step, dried and re-exposed. Example A6
    First of all, as explained, an IR laser was used to engrave a test pattern on the mask layer of a nyloflex® flexographic printing plate) FAC 470 D (thickness without top sheet: 4.7 mm) which was pre -exposed from its reverse. Due to the remaining mask layer, the regions without image remain UV opaque, although the removal of the mask in the image regions enables the photopolymerizable relief layer to be cured by means of actinic radiation.
    In a first exposure stage, the flexographic printing plate prepared in this way was first transported at a uniform speed, by means of a transport device, under a UV LED unit of the type described and, thus, on its front side, the board was exposed to radiation from the UV LED unit; the exposure speed parameters (transport speed of the plate under the UV LED unit), the distance between the plate surface and the beam source, and the UV dose applied using UV LED can be found in table 1.
    In a second exposure stage, subsequently, the printing plate exposed to UV LED was additionally exposed with UV tubes in a nyloflex® F III exposure system for the period of time indicated in table 1. The total sum of the UV dose of both the exposure steps are also listed in table 1.
    Finally, as explained, the exposed flexographic printing plate, according to the recommended processing parameters specific to the product, was washed in a solvent-based development step, dried and re-exposed. Example A7
    First of all, a film element was prepared, comprising the following layers, one on top of the other: d) PET film 125 µm thick; c2) a mask layer that can undergo digital image formation approximately 3 μm thick, comprising a polymeric and carbon black binder (identical to the mask layer used in commercially available printing plates from the brand nyloflex®) ', cl) a rough UV-transparent layer comprising a polymeric binder and porous silica particles.
    The UV transparent rough layer was obtained as follows:
    First of all, a solution of 7 parts by weight of Macromelt 6900 was prepared in 90 parts by weight of a solvent mixture (45 parts of n-propanol, 45 parts of toluene, 10 parts of benzyl alcohol) with heating up to 50 ° C. Subsequently, 3 parts by weight of a porous silica gel (Syloid® ED-5 by Grace & Co., mean particle diameter 8.4 - 10.2 μm, pore volume 1.8 ml / were subsequently added to this solution. g). The particulate silica gel was dispersed in the polymer solution for a period of 20 minutes by means of an ULTRA-TURRAX® T 50 disperser at 8,000 rpm. The resulting dispersion was applied to a digital mask layer that was approximately 3 μm thick and located on a 125 μm PET film. The digital mask layer consisted of about 65% Macromelt 6900 and 35% finely divided carbon black. In this way, a film element was produced which had the aforementioned sequence of PET film layer, mask layer and rough substrate layer. The application speed of the rough substrate layer was approximately 5 g / m2.
    In the course of the standard production process of the nyloflex® ACE 170 printing plate, the film element described was supplied by means of extrusion through the upper calender cylinder, to provide an upper flexographic printing element that was composed of the following arranged layers one on top of the other: a) a dimensionally stable PET support film with a thickness of 125 μm and a thin adhesion layer; b) a photopolymerizable elastomeric layer; cl) a rough UV-transparent layer comprising a polymeric binder and porous silica particles, with an application weight of approximately 5 g / m2; c2) a mask layer that can undergo digital image formation approximately 3 μm thick and comprising a polymeric and carbon black binder (identical to the mask layer used in commercially available printing plates from the brand nyloflex®y, d ) a PET protective film 125 μm thick. / First of all, as exposed, an IR laser was used to engrave a test pattern on the mask layer of the flexographic printing element thus produced which was pre-exposed from its reverse side. Due to the remaining mask layer, the regions with no image remain UV opaque, although removing the mask in the image regions enables the light-curing relief layer to be cured by means of actinic radiation.
    In a first stage of exposure, the flexographic printing plate prepared in this way was first transported at a uniform speed, by means of a transport device, under a UV LED unit of the type described and, thus, on its front side, the board was exposed to radiation from the UV LED unit. The exposure speed was 150 mm / min for a distance between the plate surface and the beam source of 5 mm. The UV dose applied through the UV LED was 1.8 J / cm2.
    In a second exposure stage, subsequently, the printing plate exposed to UV LED was additionally exposed with UV tubes in a nyloflex® FIII exposure system for 6 minutes. The total sum of the UV dose of both exposure stages was, therefore, 7.2 J / cm2.
    Finally, the exposed flexographic printing plate, at a washing speed of 270 mm / min, was washed in a solvent-based development step, dried and re-exposed.
    Before and after implementing the method of the invention, photographs were taken of the surface of the flexographic printing element using a recording microscope (from M-Service). The photographs are reproduced in figures 1 and 2. For comparison, a flexographic printing element of this type, after digital image formation, was exposed for 15 minutes with conventional UV / A tubes (15 mW / cm2) in an ambient atmosphere and , in other circumstances, developed with identical parameters. The surface of this conventionally processed flexographic printing element is shown in figure 3.
    In this way, figure 1 shows a photograph of the surface of the flexographic printing element with a relief layer with a rough surface after the ablation of the layer that can undergo digital image formation, but before exposure and development; Figure 2 shows a photograph of the surface of the flexographic printing element with a relief-forming layer with a rough surface after the ablation of the layer that can undergo digital image formation, and after inventive exposure and development; Figure 3 shows a photograph of the surface of the flexographic printing element with a relief-forming layer with a rough surface after the ablation of the layer that can undergo digital image formation, after conventional exposure exclusively with a UVA tube and after development.
    From the photographs, it can be seen that the roughness of the substrate surface after the method of the invention has been carried out can be reproduced on the printing surface, whereas, in the case of exposure through conventional UV / A tubes, the effect inhibitory by oxygen means that the roughness is not transferred to the surface of the printing element. Comparative example B1
    First of all, as explained, an IR laser was used to engrave a test pattern on the mask layer of a nyloflex® ACE 114 D flexographic printing plate that was pre-exposed from its reverse side. Due to the layer of the remaining mask, the regions without image remain UV opaque, while the removal of the mask in the image regions enables the light-curing relief layer to be cured by means of actinic radiation.
    The flexographic printing plate thus prepared was exposed for the time indicated in table 1 exclusively with UV tubes in a nyloflex® FIII exposure system from the front side. Finally, as explained, the exposed flexographic printing plate, according to the recommended processing parameters specific to the product, was washed in a solvent-based development step, dried and re-exposed. Comparative example B2
    First of all, as explained, an IR laser was used to engrave a test pattern on the mask layer of a nyloflex® ACE 114 D flexographic printing plate that was pre-exposed from its reverse side. Due to the layer of the remaining mask, the regions without image remain UV opaque, while the removal of the mask in the image regions enables the light-curing relief layer to be cured by means of actinic radiation.
    In a single exposure step, the flexographic printing plate prepared in this way was transported at a uniform speed, by means of a transport device, below the two UV LED units in series and, thus, on its front side, the plate was exposed to radiation from the two UV LED units; the exposure speed parameters (transport speed of the plate under the UV LED units), the distance between the surface of the plate and the source of the beam, and the UV dose applied using UV LED can be found in table 1.
    Finally, as explained, the exposed flexographic printing plate, according to the recommended processing parameters specific to the product, was washed in a solvent-based development step, dried and re-exposed. Comparative example B3
    First of all, as explained, an IR laser was used to engrave a test pattern on the mask layer of a nyloflex® ACE 114 D flexographic printing plate that was pre-exposed from its reverse side. Due to the layer of the remaining mask, the regions without image remain UV opaque, while the removal of the mask in the image regions enables the light-curing relief layer to be cured by means of actinic radiation.
    The flexographic printing plate thus prepared was exposed in a first stage, for the time indicated in table 1, using UV tubes, in a nyloflex® F III exposure system, from the front side.
    In an additional step, the printing plate was subsequently transported by means of a transport device at a uniform speed under the aforementioned UV LED unit and, therefore, was exposed from the front side with radiation from the UV LED unit; the exposure speed parameters (transport speed of the plate under the UV LED unit), the distance between the plate surface and the beam source, and the UV dose applied using UV LED can be found in table 1. The sum The total UV dose for all exposure steps is also listed in Table 1.
    Finally, as explained, the exposed flexographic printing plate, according to the recommended processing parameters specific to the product, was washed in a solvent-based development step, dried and re-exposed.
    Evaluation of test elements a) Depth of the negative point of 400 μm The depth of the negative point of 400 μm is a measure of the differentiation between regions with and without image in the print. While it is desirable for the printable image elements to be stably formed, the intermediate depth in the non-image regions should be as high as possible, so that, even in a relatively long printing procedure, the non-image regions remain open and not light to defects in the printed image. b) Minimum dimension of the positive elements stably formed (positive point, positive line, screen). The smaller the size of the first stably formed positive elements, the better the resolution of the printing plate and the finer the details that can be reproduced in the printing procedure. Lower stable halftone values, moreover, increase the range of the tonal value and therefore the contrast, especially in the case of tonal value progressions and filtered images. c) 60 μm grid
    The 60 μ grid is a test element that represents thin positive lines crossed in the pattern. In flexographic printing, such elements are critical, since, due to the small width of the element, they are difficult to anchor stably and, at the same time, due to their geometry, are susceptible to the swelling effect of the washing agent.
    If the grid is not fully formed and / or if the grid, although formed as such, nevertheless shows undulating deformation after drying, the grid is evaluated as
    If the grid has only minimal undulation (visible only using a microscope), but is otherwise stably formed, then the grid is evaluated as "o".
    If the grid, although formed with stable anchoring, has a line width on the surface that is less than that specified in the data, the grid is evaluated as “(+)” •
    A grid with complete stable formation and a width that essentially corresponds to the width of the element in the standard data is evaluated as d) Tonal value of the tracking field at 15% at 146 Ipi, measured on the plate. /
    Traces are used for the reproduction of halftones - that is, for the representation of standard regions that do not correspond to 100% in relation to one of the primary colors used in the printing procedure. In this way, colors mixed with different luminosities can be produced.
    In the present case, a so-called "autotypical screening" was used, that is, the filtered area is divided into a fixed number of screening cells. Perceived luminosity and color vary, mainly, through the size of a point in a cell like this (the amplitude).
    The tracking field used has a 15% coverage on standard data. The measured tonal value for this field on the plate surface is a measure of the accuracy of the copy. If the value measured on the plate is less than the data, then it is said that the reduction of the tonal value has occurred. On the one hand, this may be desirable in order to compensate, for example, the increase in tonal value in the actual printing procedure; on the other hand, below a certain tonal value, halftone points are no longer anchored and will no longer be formed. As a result, gray gradations are lost, and the tonal value range on the printout is lower. The effect of reducing the tonal value is known in the context of the exposure of digital flexographic printing plates with UV tubes according to the prior art. The oxygen polymerization inhibiting effect during exposure stops the polymerization of the halftone dots and then the halftone dots on the plate are smaller than specified in the data. However, the degree of this effect depends on the intensity of UV radiation and, therefore, may imply fluctuating tonal values in the event of changes in the intensity of the UV tubes used.
    Ideally, halftone dots on the plate have approximately equal coverage to that in the parent data, but also have sufficient depressions between the individual halftone dots to prevent ink from being deposited in the vicinity of the printing surface in the print. Interpretation of test results
    As can be seen from examples A1-A5 and B2, fine positive elements, such as dots, lines and screens, are well reproduced in the exhibition with intense UVA radiation from UV LEDs. Here, a particularly surprising finding was also that despite the high-intensity UV, there was no undesirably high plate heating> 50 ° C and therefore the dimensional stability of a PET film holder was not affected, despite the fact that a UV high intensity in itself may have suggested higher temperatures from the heat of polymerization that occurred in the crosslinking procedure.
    From the halftone values measured on the plate, moreover, it can be inferred that the tonal value copied on the plate during the use of UV LED radiation, at about 13%, came very close to the parent data of the tonal value 15% at 146 Ipi. This means that exposure occurs with high copy accuracy. At the same time, when using UV LED radiation, the halftone dots on the surface have virtually not been rounded, thus ensuring a more stable and more reproducible printing procedure, since thin, highly rounded halftone dots can lead to enormously different increases in tonal value, depending on the setting in the printing procedure. The small remaining reduction in the tonal value in the copy on the plate, however, is entirely desirable, since there is always a small increase in the tonal value due to the definition of printing in the printing procedure and, therefore, a small reduction in the elements helps to compensate for this increase in printing and then improve the contrast range of the printed image.
    For the formation of certain fine critical elements, such as a 60 μm wide grid of lines, however, a very high dose of UV LED radiation is required. In comparative example B2, about 4.4 J / cm2 of pure UV LED energy is still not sufficient to result in an adequately stable formation of a grid like this. A dose of UV LED of this level, moreover, requires a large number of LED elements in order to obtain acceptable exposure times. In particular, in the case of continuous automated systems (for example, coupled with a downstream washing unit), the ACE 114 D plate used in the examples, with a washing speed of 300 mm / min, would require more than 5 LED strips Serial UV, which would represent a very high cost and, therefore, would take the exposure onerous operation.
    From examples A2 - A5, however, it can be readily inferred that, as long as there is a certain minimum dose of UV LED radiation, even a more economical combination of UV LED radiation and a final downstream exposure with UV radiation from a conventional beam source facilitates the desired copy accuracy. Specifically, at a UV LED dose of> 1 J / cm2, stable elements with an accurate copy are produced on the plate, by suppressing the oxygen inhibition that occurs on exposure with relatively low intensity UV beam sources. If the UV LED dose is too low, on the contrary, there may be cases of fragmentation in thin elements, which, in the printing procedure, leads to fluctuations in the printed image and to defective prints. The example Al illustrates this fact, since the tonal values measured on the plate in data of 15% and 146 Ipi still fluctuate, a fact attributable to cases of fragmentation in the halftone points. Here, the initial dose of UV LED, at <1 J / cm2, is still very low.
    Example A6 illustrates the fact that, even with relatively thick flexographic printing elements, which are used, for example, to print corrugated cardboard or other rough or uneven substrates, an initial exposure with UV LEDs followed by a low energy exposure with tubes UV / A allows reproduction with precise copying of very finely resolved data. The reproduction of a tonal value of 15% with a common 146 Ipi screen produces a tonal value of only 2 - 3% in the case of conventional exposure of the same flexographic printing element with UV / A tubes, on the plate, while the value tonal on the plate in the case of implementation of the method of the invention, at 10.6%, produces a value that is much closer to the ideal value. Furthermore, halftone dots, when the method of the invention is implemented, have defined dot surfaces that are substantially flat.
    Conversely, inverting the sequence - that is, exposure first with a customary UV beam source of relatively low intensity (UVA tubes) and subsequent exposure with high energy UV LED radiation - does not produce the desired effect (comparative example B3), since the inhibition of polymerization by oxygen, once it has occurred, can no longer be reversed by subsequent exposure to high-energy UV radiation - in other words, reproduction in this case is no longer with an accurate copy. Example Al A2 A3 A4 A5 A6 Bl B2 B3
    Board type ACE 114 D ACE 114 D ACE 114 D ACE 114 D ACE 114 D ACE 114 D ACE 114 D ACE 114 D ACE 114 D
    Plate processing
    Preliminary exposure time on reverse face Mon 19 19 19 19 19 115 19 19 19 UV beam source UV LED UV 365 LED UV 365 LED UV 365 LED UV 365 LED UV 365 LED UV 365 tubes UV LED UV 365 LED UV 365 Number of units UV LED in sequence mm 1 1 1 1 1 1 2 1 Time of first / last beam source sec 3 6 6 6 6 11 62 6 Preliminary exposure to UVA tubes min 15 6 UV intensity of LEE) UV mW / cm2 300, 0 300.0 300.0 300.0 300.0 300.0 300.0 300.0 Beam / plate source distance mm 5 5 5 5 5 5 5 5 Exposure speed mm / min 300 150 150 150 150 80 120 150 UV dose of LED J / cm2 0.9 1.8 1.8 1.8 1.8 3.3 4.4 4.4 Secondary exposure to UVA tubes min 6 2 4 6 8 6 UV dose of LEDs & tubes J / cm2 6.3 3.6 5.4 7.2 9.0 8.7 13.5 4.4 7.2 Washing speed mm / min 270 270 270 270 270 80 270 270 270 Exposure properties Depth negative point of 400 μm μm 180 190 185 185 170 135 170 150 180 Minimum stable positive point μm 300 200 200 200 200 300 200 200 200 Minimum stable positive line μm 80 120 80 40 40 100 20 80 60 60 μm grade OO 0 + + 0 (+) - (+) Minimum screen stable at 123 Ipi% 5 5 4 3 4 7 5 3 5 Minimum screen stable at 146 Ipi% 5 6 5 4 5 8 6 3 6 Data of 15% of the halftone value at 146 Ipi% 8-10 13.2 13.0 12.7 12.9 10.6 6.6 13.4 6.2
    权利要求:
    Claims (10)
    [0001]
    1. Method for producing flexographic printing plates using, as a starting material, a photopolymerizable flexographic printing element that comprises at least arranged on top of each other, • a dimensionally stable support, and • at least one relief formation layer photopolymerizable, comprising at least one elastomeric binder, an ethylenically unsaturated compound and a photoinitiator, • optionally, a rough UV-transparent layer comprising at least one particulate substance, • a layer that can undergo digital imaging, and the method comprising at least the following steps: (a) producing a mask by image formation of the layer that can pass through digital image formation, (b) exposing the light-curing relief layer through the mask with actinic light and light-curing the regions of image of the layer, and (c) develop the light-cured layer by washing away the non-photopolymer regions of the relief formation layer with an organic solvent, or by thermal development, characterized by the fact that step (b) comprises two stages of exposure (b-1) and (b-2), in which, in a first step (b-1), exposure with actinic light occurs with an intensity of> 100 mW / cm from a plurality of UV LEDs and, subsequently, in a second step (b-2), exposure occurs with actinic light with an intensity <100 mW / cm from a source of UV radiation other than UV LEDs.
    [0002]
    2. Method according to claim 1, characterized by the fact that the radiation source used in step (b-2) is a UV tube or a UV lamp.
    [0003]
    3. Method according to claim 1 or 2, characterized by the fact that the UV LEDs used in step (b-1) have a maximum emission in the wavelength range of 350 - 405 nm, for example, at 350 nm , 365 nm, 375 nm, 385 nm, 395 nm or 405 nm.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the intensity in the first exposure step (b-1) is> 150 mW / cm.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the intensity in the second exposure step (b-2) is <50 mW / cm.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the radiation dose in the first exposure stage (b-1) is 1 to 4 J / cm and in the second exposure stage (b-2) ) is 2 to 8 J / cm2.
    [0007]
    Method according to any one of claims 1 to 6, characterized in that the layer that can undergo digital imaging is a removable laser layer.
    [0008]
    Method according to any one of claims 1 to 7, characterized by the fact that, between the photopolymerizable embossing layer and the layer that can undergo digital image formation, there is a rough UV transparent layer comprising at least least one particulate substance with an average particle diameter of 0.5-50 μm.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the rough UV-transparent layer comprises a polymeric binder or a wax.
    [0010]
    10. Apparatus for in-line production of flexographic printing plates by means of digital image formation, characterized by the fact that it comprises at least: (A) optionally, a unit for digital image formation of the flexographic printing element, 5 (B ) a first exposure unit comprising a plurality of LEDs arranged in an array and capable of emitting UV light with an intensity of> 100 mW / cm, (C) a second exposure unit comprising at least one different source of UV radiation of the LEDs, preferably a UV tube or UV lamp, (D) a washing unit, (E) a drying unit, (F) optionally, a post-treatment unit, (G) optionally, a distribution to the resulting flexographic printing plates, and (H) transport units for the flexographic printing elements and plates that connect the units (A) to (G) with each other.
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    同族专利:
    公开号 | 公开日
    CN103109233A|2013-05-15|
    DE102010031527A1|2012-01-19|
    US10730283B2|2020-08-04|
    EP2596404B1|2014-07-09|
    JP5876879B2|2016-03-02|
    MX2013000634A|2013-04-03|
    AU2011281789B2|2014-09-11|
    JP2013534324A|2013-09-02|
    US20130242276A1|2013-09-19|
    NZ605851A|2014-12-24|
    ES2510412T3|2014-10-21|
    IL224158A|2016-09-29|
    CA2804841A1|2012-01-26|
    PL2596404T3|2015-01-30|
    US20190022994A1|2019-01-24|
    US10112381B2|2018-10-30|
    EP2596404A1|2013-05-29|
    CA2804841C|2018-09-18|
    AU2011281789A1|2013-02-07|
    DK2596404T3|2014-09-01|
    WO2012010459A1|2012-01-26|
    CN103109233B|2015-06-17|
    BR112013001262A2|2016-05-17|
    HK1185421A1|2014-02-14|
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    法律状态:
    2018-12-26| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-11-03| B09A| Decision: intention to grant|
    2021-01-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102010031527.3|2010-07-19|
    DE102010031527A|DE102010031527A1|2010-07-19|2010-07-19|Process for the preparation of flexographic printing plates comprising the irradiation with UV LEDs|
    PCT/EP2011/061829|WO2012010459A1|2010-07-19|2011-07-12|Method for producing flexographic printing plates using uv-led irradiation|
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