UV-LED radical curing offset printing ink and printing method

Abstract

The present invention relates to the field of UV-LED radically curable inks for offset printing of security documents. In particular, the present invention relates to a UV-LED radically curable offset printing ink for offset printing onto a substrate or security document, the UV-LED radically curable ink having a viscosity in the range of about 2.5 to about 25 Pa s at 40°C and 1000 s-1, and comprising a radically curable (meth)acrylate compound, one or more photoinitiators of formula (I), one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds, amine-modified polyether-based acrylates, and combinations thereof, and one or more fillers and / or extenders.

Description

Detailed Description of the Invention

[0001] [Field of the Invention]

[0001] The present invention relates to the field of protection of security documents against counterfeiting and illegal duplication. In particular, the present invention relates to the field of UV-LED radically curable offset printing inks and to a method for producing features or patterns on security documents.

[0002] [Background of the invention]

[0002] With the continuing improvement of color copying and printing quality, and in an attempt to protect security documents such as banknotes, value documents or cards, transport tickets or cards, tax banderols and product labels that do not have reproducible effects from counterfeiting, alteration or illegal duplication, it has been conventional practice to incorporate various security measures in and on these documents. Typical examples of security measures include security threads, windows, fibers, planchettes, foils, decals, holograms, watermarks, optically variable pigments, magnetic or magnetizable thin film interference pigments, interference coating particles, thermochromic pigments, photochromic pigments, security inks containing luminescent compounds, infrared absorbing compounds, ultraviolet absorbing or magnetic compounds.

[0003]

[0003] It is known in the art to apply ink to security documents in multiple printing steps, including different printing methods using low viscosity inks such as screen printing inks, flexographic printing inks, and gravure printing inks, and high viscosity or pasty inks such as offset printing inks, intaglio printing inks, and letterpress printing inks.

[0004]

[0004] Offset printing methods consist of indirect methods in which the ink is first transferred from the printing plate to a blanket cylinder and then to the substrate. Offset printing methods are either wet offset methods or dry offset methods. Wet offset methods exploit the difference in surface energy between the image and non-image areas of the printing plate. The image areas are oleophilic, while the non-image areas are hydrophilic. Thus, the oil-based ink used in the method tends to adhere to the image areas of the printing plate and to be repelled from the non-image areas. Wet offset printing is typically carried out by supplying both a dampening solution (also called dampening fluid in the art) and an oleophilic ink to the surface of the printing plate, causing the image areas to preferentially accept the ink and the non-image areas to preferentially accept the dampening solution, and then transferring the ink deposited on the image areas to the substrate via the printing cylinder. The dry offset method is a method in which the blanket cylinder is covered with a metal-backed photopolymer that forms a relief carrying the motif to be printed. The ink adheres to the relief and is then transferred to the substrate via the printing cylinder. In this case, no dampening solution is required.

[0005]

[0005] It is known in the art that offset printing is the first step to produce printed features, usually as background designs on security documents. Drying of offset inks involves either an oxidation process (i.e. the ink contains an oxidative drying agent, which reacts with oxygen in the air to produce free radicals that initiate the polymerization process of the ink matrix) or a radiation curing process, especially a UV curing process (i.e. the ink contains a photoinitiator, which interacts with light to produce free radicals that initiate the polymerization of the ink matrix). Oxidative drying is a slow process, whereas UV curing is almost instantaneous. Because security printing is an expensive multi-step method requiring multiple intermediate drying steps, UV radical curable offset printing inks are usually preferred in the field. UV radical curable offset printing inks are applied as thin layers with a thickness of about 0.5 μm to about 3 μm (in the cured state) to produce features on security documents.

[0006]

[0006] Offset inks may be applied to both sides of a substrate to print features as background designs for security documents (Simultan process), and the curing steps may be performed simultaneously or sequentially. Typical industrial printing speeds are about 8000 sheets / hour to about 12'000 sheets / hour.

[0007]

[0007] Set-off occurs when the ink does not dry and cure quickly and efficiently. Set-off occurs when a printing ink that is not sufficiently dried or cured adheres at least partially to the back of the printing substrate placed on top as it leaves the printing press during lamination of the printing substrate (see, for example, U.S. Pat. No. 4,604,952). This is a particular problem when printing features on security documents, especially banknotes, because the documents typically have multiple overlapping or partially overlapping features that are applied in subsequent steps. If a previously applied feature, such as a background image or a graphic pattern, is not sufficiently dried or cured, not only is the entire multi-step printing method delayed, but the features so obtained may still suffer from set-off or marking due to set-off in the machine during subsequent printing or process operations.

[0008]

[0008] In conventional banknote printing methods, offset ink is applied during one of the first steps of the overall multi-step printing method, where offset printing is followed by other printing steps including intaglio printing and screen printing. If a feature or pattern is printed on a security document such as a banknote by an offset printing method and said feature or pattern suffers from poor surface hardening properties, the subsequent printing step may be delayed or offset may occur. Therefore, since the intaglio printing press applies very high pressure to the printing substrate, it is important that the offset ink is completely dried or cured before the start of the other printing step to avoid offset problems, especially when the subsequent step is an intaglio printing step.

[0009]

[0009] UV radical curable inks are cured by a free radical mechanism consisting of the activation of one or more photoinitiators which, under the action of radiation, in particular UV light, liberate free radicals and thus are capable of initiating polymerization to form a cured layer. Known free radical photoinitiators include, for example, acetophenone, benzophenone, alpha-aminoketones, alpha-hydroxyketones, phosphine oxides and phosphine oxide derivatives, and benzyl dimethyl ketal.

[0010]

[0010] UV energy is typically provided by mercury lamps, particularly medium pressure mercury lamps, which require large amounts of energy, require efficient and expensive heat dissipation systems, are prone to ozone formation, and have a limited life span.

[0011]

[0011] In order to provide a cheaper, less interventionist and more environmentally friendly solution, UV-LED-based lamps and systems for curing inks and coatings have been developed. In contrast to medium pressure mercury lamps, which have emission bands in the UV-A, UV-B and UV-C regions of the electromagnetic spectrum, UV-LED lamps emit radiation in the UV-A region. Furthermore, current UV-LED lamps emit quasi-monochromatic radiation, i.e., only at one wavelength, such as 365 nm, 385 nm, 395 nm or 405 nm.

[0012]

[0012] The UV curing efficiency of a coating or ink layer depends, inter alia, on the overlap of the emission spectrum of the radiation source used for said curing and the absorption spectrum of the photoinitiator contained in the coating or ink. Thus, UV curing of coatings or ink layers containing conventionally used free radical photoinitiators with UV-LED lamps suffers from reduced curing efficiency resulting from a poor overlap of the emission spectrum of the lamp with the absorption of conventionally used free radical photoinitiators, which leads to slow or poor curing or curing defects.

[0013]

[0013] Photoinitiators with absorption spectra that correspond approximately to the emission wavelengths of currently available UV-LED radiation sources include alpha-aminoketones, thioxanthones, ketocoumarins, bis[4(dimethylamino)phenyl]methanone derivatives (also called Michler's ketones) and acylphosphines. However, alpha-aminoketones and Michler's ketones have presented health and / or environmental concerns in recent years. Ketocoumarins, also known as highly fluorescent, have low curing efficiency and are mainly experimental and / or development products.

[0014]

[0014] Acylphosphine photoinitiators are widely used for curing with UV-LED radiation sources due to their red-shifted absorption spectrum (maximum absorption wavelength around 370 nm). They are known to exhibit low fluorescence. However, acylphosphine photoinitiators can still suffer from slow curing performance, especially slow surface curing performance, and are known to be particularly sensitive to oxygen inhibition, making them less efficient for curing thin layers.

[0015]

[0015] The currently used thioxanthone derivatives have a maximum absorption wavelength of about 370 nm to about 410 nm. However, and in contrast to acylphosphine oxides, the currently used thioxanthones suffer from fluorescence.

[0016]

[0016] As mentioned above, UV radical curable offset printing inks are used in the field of protection of security documents, valuable documents and articles against counterfeiting and illegal duplication, to be applied to security documents as a thin layer in the form of printed features or patterns. It is well known that in the field of security documents, especially for banknotes, luminescent security features are widely used to give said security documents additional covert security features, where the protection of said security documents against counterfeiting and illegal duplication relies on the concept that such features typically require dedicated equipment and knowledge to detect them. Luminescent security features include for example luminescent fibers, luminescent threads, luminescent patches, stripes or foils (at least a part of said patches, stripes or foils is luminescent), and printed luminescent features. The printed features include luminescent numbering (printed by letterpress), printed patches (printed by letterset), and luminescent features printed by offset at the same time and using the same printing press as the one usually used to generate security features as background design of security documents.

[0017]

[0017] Since the security document further comprises, in addition to the offset printed features, luminescent security features, in particular printed luminescent security features, either on the same side or opposite the offset printed features, in order to avoid adverse effects on machine detection and / or human perception of the luminescent security features, it is required that said offset printed features do not exhibit fluorescence themselves, that they do not exhibit fluorescence through the substrate to which they are applied, and that they do not exhibit fluorescence due to contact between two printed security documents due to contamination.

[0018]

[0018] Thus, there remains a need for a UV-LED radically curable offset printing ink and method for printing features on security documents at high speeds (i.e., industrial speeds), wherein the UV-LED curable offset printing ink exhibits good curing properties and, after the ink is cured, enables the production of printed features that exhibit low or no fluorescence.

[0019] [Summary of the invention]

[0019] It is therefore an object of the present invention to overcome the deficiencies of the prior art discussed above. This invention relates to a method for offset printing features on a substrate, comprising the steps of: -1 A UV-LED radical curable offset printing ink having a viscosity in the range of about 2.5 to about 25 Pa s at 200° C., i) about 10 wt.% to about 80 wt.% of one or more radically curable (meth)acrylate compounds; ii) about 4 wt.% to about 20 wt.% of one or more photoinitiators of formula (I):

[0020] [ka] wherein Q has the following formula (IIa), (IIb) or (IIc):

[0021] [ka] (In the formula, n is 1 or more, and R1 are the same or different. 、C 1~C3 Alkylene groups, R2 is selected from the group consisting of hydrogen and C1-C3 alkyl groups, the sum of a+b+c is 3 to 12, and the sum of d+e+f+g is 4 to 16); iii) about 1 wt.% to about 15 wt.% of one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds having a weight average molecular weight of at least 400 g / mol eq PS, amine-modified polyether-based acrylates having a weight average molecular weight of at least 400 g / mol eq PS, and combinations thereof; and iv) from about 1 wt.% to about 30 wt.% of one or more inorganic pigments and / or one or more organic pigments, and v) about 0.5 wt.% to about 10 wt.% of one or more fillers and / or extenders wherein the weight percentage is based on the total weight of the UV-LED radically curable offset printing ink.

[0022]

[0020] The UV-LED radically curable offset printing inks described herein are particularly suitable for being cured by exposure to UV light from a UV-LED light source, preferably one or more wavelengths from about 355 nm to about 415 nm. A method for printing one or more features on a substrate by an offset printing method, comprising the steps of applying the UV-LED radically curable offset printing inks described herein by offset printing to form an ink layer, and applying a UV-LED radically curable offset printing ink of at least 150 mJ / cm2. 2 , preferably at least 200 mJ / cm 2 and curing the ink layer with a UV-LED source.

[0023] Also described herein are features consisting of a cured ink layer made from the UV-LED radically curable offset printing ink described herein. Described herein are uses of the features described herein for the protection of security documents, value documents or articles against counterfeiting or fraud, and security documents, value documents or articles comprising one or more printed features described herein.

[0024] Also described herein is a security document including a substrate as described herein and one or more printed features as described herein.

[0025]

[0023] Also, at 40°C and 1000s -1 % to about 25 Pa s, wherein the UV-LED radically curable offset printing ink is provided with one or more photoinitiators as described herein in an amount of about 1 wt.% to about 20 wt.%, preferably in an amount of about 5 wt.% to about 15 wt.%, more preferably in an amount of about 8 wt.% to about 12 wt.%, and one or more amino-containing compounds as described herein in an amount of about 1 wt.% to about 15 wt.%, for producing a UV-LED radically curable offset printing ink having a viscosity in the range of about 2.5 to about 25 Pa s at 100° C., The use described herein is suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material, the photochromic material being suitable for printing a photochromic material [Brief description of the drawings]

[0026] [Figure 1] It represents a banknote comprising a substrate (1), different security features (2-9) including features printed by offset, said features covering more than 70% of the total surface of the security document. Detailed Description

[0027] definition The following definitions clarify the meaning of terms used in this specification and claims.

[0028]

[0025] As used herein, the indefinite article "a" denotes one and more than one and does not necessarily limit its referent noun to the singular.

[0029]

[0026] As used herein, the term "about" means that the subject amount, value, or limit may be the specified particular value or some other value in its vicinity. In general, the term "about" referring to a value is intended to indicate a range within ±5% of the value. For example, the phrase "about 100" indicates a range of 100±5, i.e., a range of 95 to 105. In general, when the term "about" is used, it can be expected that similar results or effects according to the present invention may be obtained within a range of ±5% of the specified value. However, a specific amount, value, or limit supplemented with the term "about" is intended herein to disclose the exact amount, value, or limit itself, i.e., without the supplement "about".

[0030]

[0027] As used herein, the term "and / or" means that all or only one of the elements of the group may be present. For example, "A and / or B" is intended to mean "A only, or B only, or both A and B." In the case of "A only," the term also encompasses the possibility that B is absent, i.e., "A only and not B."

[0031] As used herein, the term "one or more" means one, two, three, four, etc.

[0032]

[0029] As used herein, the term "comprising" is intended to be non-exclusive and open-ended. Thus, for example, an ink comprising compound A may comprise other compounds besides A. However, the term "comprising" also encompasses the more restrictive meanings of "consisting essentially of" and "consisting of" as specific embodiments thereof, so that, for example, an "ink comprising compound A" may also consist (essentially) of compound A.

[0033]

[0030] When this specification refers to "preferred" embodiments / features, combinations of these "preferred" embodiments / features shall also be considered to be disclosed, so long as such combinations make technical sense.

[0034]

[0031] As used herein, the term UV (ultraviolet) is intended to mean radiation having wavelength components in the UV portion of the electromagnetic spectrum, typically between 200 nm and 400 nm.

[0035]

[0032] The term "security document" refers to a document that is protected against counterfeiting or fraud, typically by at least one security feature. Examples of security documents include, without limitation, value documents and value items.

[0036]

[0033] Descriptions of specific embodiments of the present invention are presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and, of course, many modifications and variations are possible in light of the above teachings. The exemplary embodiments have been chosen and described to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to best utilize the invention and its various embodiments, with various modifications as may be suited to the particular uses contemplated.

[0037]

[0034] The present invention provides a UV-LED radically curable offset printing ink for producing (printing) one or more features on a security document by an offset printing method. The present invention further provides a printed feature consisting of a cured ink layer made from a UV-LED radically curable offset printing ink as described herein, and a security document comprising one or more printed features as described herein. The UV-LED radically curable offset printing ink as described herein is applied by an offset printing step, said offset printing may be a wet printing method or a dry offset printing method.

[0038]

[0035] The one or more radically curable (meth)acrylate compounds of the UV-LED radically curable offset printing inks described herein undergo curing upon exposure to UV light emitted from a UV-LED light source, preferably one or more wavelengths from about 355 nm to about 415 nm, more preferably 365 nm and / or 385 nm and / or 395 nm, in the presence of one or more photoinitiators described herein and one or more amino-containing compounds described herein. As known by those skilled in the art, the UV-LED radically curable offset printing inks described herein may also be suitable for curing using medium pressure mercury lamps.

[0039]

[0036] The UV-LED radically curable offset printing ink described herein can be cured at 40°C and 1000s -1 The viscosity values ​​given herein are measured on a Haake Roto-Visco RV1 with a cone of 2 cm at 0.5° and a linear velocity increase of 30 seconds from 0 to 1000 seconds. -1 It is measured in.

[0040]

[0037] The UV-LED radically curable offset printing ink described herein comprises a radically curable (meth)acrylate compound. The radically curable (meth)acrylate compound described herein is present in an amount of about 10 wt.% to about 80 wt.%, preferably about 20 wt.% to about 80 wt.%, more preferably about 30 wt.% to about 80 wt.%, and even more preferably about 50 wt.% to about 80 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink described herein.

[0041]

[0038] Radically curable compounds are cured by a free radical mechanism consisting of the activation by energy of one or more photoinitiators, which liberate free radicals and thus initiate polymerization to form the layer or coating.

[0042]

[0039] The described radically curable (meth)acrylate compounds preferably consist of one or more radically curable (meth)acrylate oligomers and one or more radically curable (meth)acrylate monomers. The term "(meth)acrylate" in the context of the present invention refers to the acrylate as well as the corresponding methacrylate.

[0043]

[0040] The radically curable (meth)acrylate oligomer described in this specification is preferably selected from the group consisting of epoxy (meth)acrylates, (meth)acrylated oils, (meth)acrylated epoxidized oils, polyester (meth)acrylates, aliphatic or aromatic polyurethane (meth)acrylates, polyacrylic acid (meth)acrylates, polyacrylate ester (meth)acrylates, and mixtures thereof, and more preferably selected from the group consisting of epoxy (meth)acrylates, polyester (meth)acrylates, aliphatic or aromatic polyurethane (meth)acrylates, and mixtures thereof.

[0044]

[0041] The radically curable oligomer described herein is preferably a (meth)acrylate oligomer, which may be branched or essentially linear, and the one or more (meth)acrylate functional groups may be terminal groups and / or pendant side groups attached to the oligomer backbone, respectively. Preferably, the radically curable oligomer is selected from the group consisting of (meth)acrylic oligomers, urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether-based (meth)acrylate oligomers, epoxy (meth)acrylate oligomers and mixtures thereof, more preferably selected from polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers and mixtures thereof.

[0045]

[0042] Suitable examples of epoxy (meth)acrylate oligomers include, but are not limited to, aliphatic epoxy (meth)acrylate oligomers, particularly mono(meth)acrylate, di(meth)acrylate and tri(meth)acrylate, and aromatic epoxy (meth)acrylate oligomers. Suitable examples of aromatic epoxy (meth)acrylate oligomers include bisphenol-A (meth)acrylate oligomers, such as bisphenol-A mono(meth)acrylate, bisphenol-A di(meth)acrylate and bisphenol-A tri(meth)acrylate, and alkoxylated (such as ethoxylated and propoxylated) bisphenol-A (meth)acrylate oligomers, such as alkoxylated bisphenol-A mono(meth)acrylate, alkoxylated bisphenol-A di(meth)acrylate and alkoxylated bisphenol-A tri(meth)acrylate, and ethoxylated bisphenol-A diacrylate is particularly suitable.

[0046]

[0043] The radically curable (meth)acrylate monomers described herein are preferably selected from the group consisting of mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, hexa(meth)acrylates and mixtures thereof.

[0047]

[0044] Preferred examples of mono(meth)acrylates include 2(2-ethoxyethoxy)ethyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, C12 / C14 alkyl(meth)acrylate, C16 / C18 alkyl(meth)acrylate, caprolactone(meth)acrylate, cyclic trimethylolpropaneformal(meth)acrylate, nonylphenol(meth)acrylate, isobornyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, octyldecyl(meth)acrylate, and the like. di(meth)acrylate, tridecyl (meth)acrylate, methoxypoly(ethylene glycol) (meth)acrylate, polypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, alkoxylated di(meth)acrylates, ester diol di(meth)acrylates, and mixtures thereof.

[0048]

[0045] Preferred examples of di(meth)acrylates include bisphenol A di(meth)acrylate, alkoxylated (e.g., ethoxylated and propoxylated) bisphenol A di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and mixtures thereof.

[0049]

[0046] Preferred examples of tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated, etc.) trimethylolpropane tri(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated, etc.) glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkoxylated pentaerythritol tri(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated, etc.) pentaerythritol tri(meth)acrylate, and mixtures thereof.

[0050]

[0047] Preferred examples of tetra(meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated (e.g., ethoxylated and propoxylated) pentaerythritol tetra(meth)acrylate, and mixtures thereof, preferably selected from the group consisting of ditrimethylolpropane tetra(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, and mixtures thereof.

[0051]

[0048] In embodiments where the UV-LED radically curable offset printing inks described herein are applied by a dry offset printing method, the UV-LED radically curable offset printing inks described herein comprising the (meth)acrylate compounds described herein may further comprise one or more vinyl ethers and / or their ethoxylated equivalents. Examples of preferred vinyl ethers are methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ethylhexyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, isopropyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, 4-(vinyloxymethyl)cyclohexylmethylbenzoate, phenyl vinyl ether, methylphenyl vinyl ether, methoxyphenyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-hexanediol monovinyl ether, 3-amino-1-propanol vinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-Hexanediol divinyl ether, 4-(vinyloxy)butyl benzoate, bis[4-(vinyloxy)butyl]adipate, bis[4-(vinyloxy)butyl]succinate, bis[4-(vinyloxymethyl)cyclohexylmethyl]glutarate, 4-(vinyloxy)butyl stearate, trimethylolpropane trivinyl ether, propenyl ether of propylene carbonate, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, dipropylene glycol divinyl ether, triethylene glycol divinyl ether, triethylene glycol methyl vinyl ether, triethylene glycol monobutyl ether, tetraethylene glycol divinyl ether, poly (tetrahydrofuran)divinyl ether, polyethylene glycol-520 methyl vinyl ether, pluriol-E200 divinyl ether, tris[4-(vinyloxy)butyl]trimellitate, bis[4-(vinyloxy)butyl]1,6-hexanediyl biscarbamate, 1,4-bis(2-vinyloxyethoxy)benzene, 2,2-bis(4-vinyloxyethoxyphenyl)propane, bis[4-(vinyloxy)methyl]cyclohexyl]methyl]terephthalate, bis[4-(vinyloxy)methyl]cyclohexyl]methyl]isophthalate, bis[4-(vinyloxy)butyl](4-methyl-1,3-phenylene)biscarbamate, and bis[4-vinyloxy)butyl](methylenedi-4,1-phenylene)biscarbamate. Suitable vinyl ethers are marketed by BASF under the names EVE, IBVE, DDVE, ODVE, BDDVE, DVE-2, DVE-3, CHVE, CHDM-di, HBVE. When present, the one or more vinyl ethers and / or their ethoxylated equivalents are present in an amount of about 1 wt.% to about 5 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0052] The UV-LED radically curable offset printing inks described herein comprise one or more photoinitiators as described herein, said one or more photoinitiators consisting of a thioxanthone derivative linked to a residue via an ester bond in the 2-position, i.e. the UV-LED radically curable offset printing inks described herein comprise one or more photoinitiators of formula (I):

[0053] [ka] wherein Q has the following formula (IIa), (IIb) or (IIc):

[0054] [ka] (wherein n is greater than 1, and R1 are the same or different from each other. 、C 1~C3 Alkylene Groups (i.e. Methylene, ethylene, 1- propylene, 2- propylene) and R2 is selected from the group consisting of hydrogen and a C1-C3 alkyl group (i.e., methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, isopropyl, -CH(CH3)2)), and the sum of a+b+c is 3 to 12, and the sum of d+e+f+g is 4 to 16). Includes.

[0055] The photoinitiator or photoinitiators of formula (I) preferably have a weight average molecular weight (MW) of about 900 g / mol eq PS or more, said weight average molecular weight being determined by GPC (gel permeation chromatography) according to OECD test method 118, a Malvern Viskotek GPCmax is used, and a calibration curve (log(molecular mass)=f(retention volume)) is made using six polystyrene standards (with molecular masses ranging from 472 to 512000 g / mol). The device is equipped with an isocratic pump, a degasser, an autosampler and a triple detector TDA302 including a differential refractometer, a viscometer and a dual angle light scattering detector (7° and 90°). For this particular measurement, only the differential refractometer is used. Two columns Viskotek TM4008L (column length 30.0 cm, internal diameter 8.0 mm) are connected in series. The stationary phase was made of styrene-divinylbenzene copolymer with a particle size of 6 μm and a maximum pore size of 3000 Å. During the measurements, the temperature was fixed at 35° C. and the samples contained 10 mg / mL of the product to be analyzed dissolved in THF (Acros, 99.9%, anhydrous). As described in the examples below, the samples were injected independently at a rate of 1 ml / min. The molecular mass of the compound was calculated as the polystyrene equivalent weight average molecular weight (PSeqM) using a 95% confidence level and an average of three measurements of the same solution, using the following formula: W ) is calculated from the chromatogram as:

[0056]

number

[0057] According to a preferred embodiment, the UV-LED radically curable offset printing ink described herein comprises one or more photoinitiators of formula (I), in which n is equal to 1, 2 or 3, Q has formula (IIb), and the sum of a+b+c is between 3 and 12. According to a more preferred embodiment, the UV-LED radically curable offset printing ink described herein comprises one or more photoinitiators of formula (I), in which n is equal to 1, 2 or 3, Q has formula (IIb), and the sum of a+b+c is between 3 and 12, and R1 are identical; ethylene It is based on

[0058] According to a further preferred embodiment, the UV-LED radically curable offset printing ink described herein comprises one or more photoinitiators of formula (I), in which n is equal to 1 (see formula IIb-1), 2 (see formula (IIb-2)) or 3 (see formula (IIb-3)), Q has formula (IIb), the sum of a+b+c is between 3 and 12, R1 are identical and are ethylene groups and R2 are ethyl groups:

[0059] [ka] It is.

[0060] A particularly suitable photoinitiator of formula (I) is sold by Rahn under the name Genopol® TX-2.

[0061]

[0054] The one or more photoinitiators described herein are present in an amount of about 4 wt.% to about 20 wt.%, preferably in an amount of about 5 wt.% to about 15 wt.%, and more preferably in an amount of about 8 wt.% to about 12 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0062] It should further be understood that the present invention also extends to compounds in which one or more of the atoms have been replaced by an isotopic variant, e.g., one or more hydrogen atoms are 2 H or 3 H and / or one or more carbon atoms may be replaced by 14 C or 13 It may be replaced by C.

[0063]

[0056] The UV-LED radically curable offset printing ink described herein comprises about 1 wt.% to about 15 wt.%, preferably about 2 wt.% to about 12 wt.%, of one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds having a weight average molecular weight of at least 400 g / mol eq PS, amine-modified polyether-based acrylates having a weight average molecular weight of at least 400 g / mol eq PS, and combinations thereof, the weight average molecular weight being measured as described herein, and the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink. The amino-containing compounds act as hydrogen donors. However, due to their rather high hydrophilicity, the compounds are known in the art to adversely affect the performance of UV-curable inks when wet offset methods are used (i.e., amines tend to make normally oleophilic inks hydrophilic, which in turn contaminate the non-image areas of the printing plate).

[0064] The aminobenzoate compound or compounds described herein have a weight average molecular weight of at least 400 g / mol eq PS, preferably at least 700 g / mol eq PS, and more preferably at least 900 g / mol eq PS.

[0065] According to one embodiment, the one or more aminobenzoate compounds described herein comprise one or more tertiary amines, preferably one or more 4-dialkylaminobenzoate groups, most preferably one or more 4-dimethylaminobenzoate groups. The one or more aminobenzoate compounds described herein are preferably polyether-based compounds derived from alkoxylated (e.g., ethoxylated and propoxylated) glycerol or alkoxylated (e.g., ethoxylated and propoxylated) pentaerythritol. Suitable examples of the one or more aminobenzoate compounds are represented by the following formula (III):

[0066] [ka] (In the formula, m is greater than 1 and preferably 1 to 4, and the sum of h+i+j+k is 3 to 12.) has.

[0067] A particularly suitable aminobenzoate compound is sold by Lambson under the name SpeedCure 7040.

[0068]

[0060] The one or more amine-modified polyether-based acrylates described herein have a weight average molecular weight of at least 400 g / mol eq PS, preferably at least 700 g / mol eq PS, more preferably at least 900 g / mol eq PS. Preferably, the one or more amine-modified polyether-based acrylates described herein have a high viscosity (such as a viscosity value of more than 500 mPas, preferably more than 1000 mPas at 20-25°C) and a high acrylate functionality (e.g., the number of acrylate groups per molecule, in particular an acrylate functionality of more than 2, preferably more than 3). According to one embodiment, the one or more amine-modified polyether-based acrylates described herein are prepared by reaction of a small portion (approximately 2-15 wt.%) of the acrylate double bonds of the polyether acrylate with an amine (Radiation curing, P. Glockner, Vincentz, 2008, p. 66-67). The amine is preferably a primary or secondary alkyl or cycloalkylamine, or an aliphatic cyclic secondary amine, such as pyrrolidine, piperidine, or piperazine. Particularly suitable polyether acrylates have an acrylate functionality of at least 3. Corresponding examples include ethoxylated or propoxylated glycerol triacrylate, ethoxylated or propoxylated trimethylolpropane triacrylate, ethoxylated or propoxylated pentaerythritol tetraacrylate, etc. Suitable amine-modified polyether-based acrylates are sold by Allnex under the name Ebecryl® 80, by Genomer Chemicals under the name Brembourg, by ... * It is sold by Rahn under the names 3457 and 3480, by IGM Resins under the name Photomer® 5662, and by DSM Resins under the names Neorad™ P-82 and Agisyn™ 701.

[0069] The amount of one or more amino-containing compounds described herein (particularly one or more aminobenzoate compounds described herein and one or more amine-modified polyether-based acrylates described herein) and one or more photoinitiators of formula (I) described herein is preferably selected such that the molar ratio between the nitrogen of one or more amino-containing compounds described herein (particularly one or more aminobenzoate compounds described herein and one or more amine-modified polyether-based acrylates described herein) and the thioxanthone moiety of one or more photoinitiators of formula (I) described herein is preferably comprised between about 0.1 and about 1, more preferably between about 0.2 and about 0.8, and even more preferably between about 0.4 and about 0.6. The preferred ranges described herein are particularly suitable for embodiments in which the UV-LED radically curable offset printing inks described herein are applied by a wet offset printing method.

[0070]

[0062] The UV-LED radically curable offset printing ink described herein further comprises one or more inorganic pigments and / or one or more organic pigments described herein, wherein said one or more inorganic pigments and / or one or more organic pigments described herein are present in an amount of about 1 wt.% to about 30 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0071]

[0063] Typical examples of organic and inorganic pigments include, but are not limited to, CI Pigment Yellow 12, CI Pigment Yellow 42, CI Pigment Yellow 93, CI Pigment Yellow 110, CI Pigment Yellow 147, CI Pigment Yellow 173, CI Pigment Orange 34, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Red 9, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 67, CI Pigment Red 122, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 170, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 185, CI Pigment Red 202, CI Pigment Red 224, CI Pigment Brown 6, CI Pigment Brown 7, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Brown 23, CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 60, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Black 7, CI Pigment Black 11, CI Pigment White 4, CI Pigment White 6, CI Pigment White 7, CI Pigment White 21, CIPigment White 22, antimony yellow, lead chromate, lead chromate sulfate, lead molybdate, ultramarine blue, cobalt blue, manganese blue, chromium oxide green, hydrated chromium oxide green, cobalt green, cerium sulfide, cadmium sulfide, cadmium sulfoselenide, zinc ferrite, bismuth vanadate, Prussian blue, mixed metal oxide, azo, azomethine, methine, anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, thiazineindigo, dioxazine, iminoisoindoline, iminoisoindolinone, quinacridone, flavanthrone, indanthrone, anthrapyrimidine, and quinophthalone pigments. When present, the inorganic pigments, organic pigments, or mixtures thereof described herein are preferably present in an amount of about 0.1 wt.% to about 45 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0072] According to a preferred embodiment, the inorganic pigment or pigments described herein and / or the organic pigment or pigments described herein independently have a particle size of 5 μm or less, preferably 3 μm or less, as measured using a granulometry gauge (such as an Erichsen Model 232 granulometer, scale 0-15 μm) according to ISO 1524:2013. The granulometry tests are carried out directly on the ready-to-use ink, i.e., ink containing all ingredients and prepared and milled as described in Examples E1-E2 and Comparative Examples C1-C4 below.

[0073]

[0065] The UV-LED radically curable offset printing ink described in this specification further comprises one or more fillers and / or extenders in an amount of about 0.5 wt.% to about 10 wt.%, preferably about 0.5 to about 5 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink. The one or more fillers and / or extenders are preferably selected from the group consisting of carbon fibers, talc, mica (muscovite), wollastonite, clays (calcined clay and china clay), kaolin, carbonates (e.g., calcium carbonate, sodium aluminum carbonate), silicates (e.g., magnesium silicate, aluminum silicate), sulfates (e.g., magnesium sulfate, barium sulfate), titanates (e.g., potassium titanate), alumina hydrate, silica (including fumed silica), montmorillonite, graphite, anatase, rutile, bentonite, vermiculite, zinc oxide, zinc sulfide, wood flour, quartz flour, natural fibers, synthetic fibers, and combinations thereof. The one or more fillers and / or extenders are more preferably selected from the group consisting of carbon fibers, talc, mica, wollastonite, clay, kaolin, carbonates, silicates, sulfates, titanates, alumina hydrate, silica, montmorillonite, graphite, bentonite, vermiculite, wood flour, quartz flour, natural fibers, synthetic fibers, and combinations thereof. The one or more fillers and / or extenders are even more preferably selected from the group consisting of carbonates (e.g., calcium carbonate, sodium aluminum carbonate), silica, talc, clay, and mixtures thereof.

[0074]

[0066] The UV-LED radically curable offset printing ink described herein may further comprise one or more waxes, preferably selected from the group consisting of synthetic waxes, petroleum waxes, and natural waxes. The one or more waxes are preferably selected from the group consisting of amide waxes, erucamide waxes, paraffin waxes, polyethylene waxes, polypropylene waxes, fluorocarbon waxes, polytetrafluoroethylene waxes, Fischer-Tropsch waxes, silicone fluids, beeswax, candelilla wax, montan wax, carnauba wax, and mixtures thereof, more preferably selected from the group consisting of paraffin waxes, polyethylene waxes, fluorocarbon waxes, polytetrafluoroethylene waxes, carnauba wax, and mixtures thereof. When present, the one or more waxes are preferably present in an amount of about 0.1 to about 5 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0075]

[0067] The UV-LED radically curable offset printing inks described herein may further comprise one or more phosphine oxides as coinitiators. Suitable examples of phosphine oxides include, without limitation, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; ethyl(2,4,6-trimethylbenzoyl)phenylphosphineate; phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; substituted acyl-phosphine oxides sold by Lambson as Speedcure XKm; a mixture of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methylpropiophenone, a mixture of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methylpropiophenone, a mixture of ethyl(2,4,6-trimethylbenzoyl)phenylphosphineate and 2-hydroxy-2-methylpropiophenone. When comprising one or more phosphine oxides as described herein, the UV-LED radically curable offset printing ink preferably comprises from about 6 wt.% to about 25 wt.%, preferably from about 10 wt.% to about 20 wt.%, of a combination of one or more photoinitiators of formula (I) as described herein and one or more phosphine oxides as described herein, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0076]

[0068] The UV-LED radically curable offset printing ink described herein may further comprise one or more machine-readable materials selected from the group consisting of magnetic materials, IR absorbing materials, and mixtures thereof. As used herein, the term "machine-readable material" refers to a material that exhibits at least one unique characteristic detectable by a device or machine, such as, for example, a CCD or CMOS sensor, a magnetic detector (if the machine-readable material has magnetic properties) or an IR camera (if the machine-readable material has IR absorbing properties), and may be included in a security feature made from the UV-LED radically curable offset printing ink described herein to provide a means of authenticating said security feature using a specific device for detection and / or authentication of said security feature. The one or more machine-readable materials described herein are present in an amount of about 1 wt.% to about 60 wt.%, preferably about 5 wt.% to about 40 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0077]

[0069] Magnetic materials exhibit certain detectable magnetic properties of the ferromagnetic or ferrimagnetic type and include permanent magnetic materials (hard magnetic materials with a coercive force Hc>1000 A / m) and magnetizable materials (soft magnetic materials with a coercive force Hc≦1000 A / m according to IEC 60404-1 (2000)). Typical examples of magnetic materials are iron, nickel, cobalt, manganese and their magnetic alloys, carbonyl iron, chromium dioxide CrO2, magnetic iron oxides (e.g. Fe2O3; Fe3O4), magnetic ferrites M(II)Fe(III)2O4 and hexaferrites M(II)Fe(III). 12 O 19 , magnetic garnet M(III)3Fe(III)5O 12 (Yttrium iron garnet Y3Fe5O 12etc.), as well as magnetic isostructural substitutes and particles thereof that are permanently magnetized (e.g., CoFe2O4). Magnetic pigment particles comprising a magnetic core material surrounded (coated) by at least one layer of another material, such as those described in WO 2010 / 115986 A2, can also be used in the present invention. When present, the one or more magnetic materials are preferably present in an amount of about 5 to about 60 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0078]

[0070] Infrared (IR) absorbing materials, i.e., materials that absorb in the near infrared (NIR) range of the electromagnetic spectrum, most commonly in the wavelength range of 700 nm to 2500 nm, are widely known and used as marking materials in security applications to impart additional covert security elements to printed documents that aid in their authentication. For example, security features having IR absorbing properties are implemented on banknotes used by automated currency processing devices (automated teller machines, vending machines, etc.) in banking and retail applications for the recognition of a given currency note and confirmation of its authenticity, particularly to distinguish it from copies made by color copiers. IR absorbing materials include IR absorbing inorganic materials, glasses that contain substantial amounts of IR absorbing atoms or ions or entities that exhibit IR absorption as a cooperative effect, IR absorbing organic materials, and IR absorbing organometallic materials (complexes of cation(s) and organic ligand(s) where either or both of the distinct cations and / or distinct ligands together have IR absorbing properties). Typical examples of IR absorbing materials include, inter alia, carbon black, quinone-diimmonium or aminium salts, polymethines (e.g., cyanines, squaraines, croconines), phthalocyanine or naphthalocyanine type (IR absorbing π systems), dithiolenes, quaterylenediimides, metal (e.g., transition metal or lanthanide) phosphates, lanthanum hexaboride, indium tin oxide, antimony tin oxide in nanoparticulate form, and doped tin(IV) oxide (cooperative properties of SnO4 crystals). IR absorbing materials including transition element compounds, whose infrared absorption is the result of electronic transitions within the d-shell of transition element atoms or ions, such as those described in WO 2007 / 060133 A2, can also be used in the present invention. When present, the one or more IR absorbing materials are preferably present in an amount of about 1 to about 40 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink.

[0079]

[0071] The UV-LED radically curable offset printing inks described herein may further comprise one or more markers and / or taggants.

[0080]

[0072] The UV-LED radically curable offset printing inks described herein may further comprise one or more UV stabilizers, in particular to stabilize said inks during their storage. Representative examples of suitable UV stabilizers include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-t-butylcatechol, 4-t-butyl-phenol, 2,6-di-t-butyl-4-methyl-phenol (BHT), pyrogallol, phenothiazine (PTZ), 2,4-diazabicyclo[2.2.2]octane (DABCO), copper(II) salts (e.g., copper(II) phenoxide, copper(II) acetylacetonate, copper(II) gluconate, copper(II) tartrate, copper(II) acetate, copper(II) carbamate, copper(II) thiocarbamate, copper(II) dithiocarbamate, or copper(II) dimethyldithiocarbamate, etc.), copper(I) salts (e.g., copper(I) chloride or copper(I) acetate, etc.), tris[N-(hydroxyl- κ O)-N-(nitroso- κ O) benzeneaminato]-aluminum, and mixtures thereof. When present, the one or more UV stabilizers described herein are present in the UV-LED radically curable offset printing ink in an amount of about 0.1 wt.% to about 5 wt.%, preferably about 0.5 wt.% to about 2 wt.%, the weight percentage being based on the total weight of the UV-LED radically curable offset printing ink described herein.

[0081]

[0073] As known to those skilled in the art, the UV-LED radically curable offset printing inks described herein may further comprise one or more solvents and / or diluents.

[0082]

[0074] The UV-LED radically curable offset printing ink described herein may further comprise one or more inactive resins (i.e., resins that do not participate in the polymerization reaction). The inactive resin may be used to adjust the viscosity of the radically curable offset printing ink described herein to reduce the glass transition temperature of the ink layer prepared by the radically curable offset printing ink described herein or to increase the adhesion of the ink layer prepared by the radically curable offset printing ink described herein. The one or more inactive resins are preferably selected from the group consisting of hydrocarbons (e.g., styrene-based hydrocarbon resins, etc.), acrylics (e.g., acrylic copolymers, etc.), styrene allyl alcohols, phenolic resins, rosin-modified resins, ketone resins, alkyd resins, and mixtures thereof. When present, the one or more inactive resins described herein are present in the UV-LED curable wet offset printing inks described herein in an amount of from about 0.1 wt.% to about 10 wt.%, preferably from about 0.5 wt.% to about 2 wt.%, the weight percentage being based on the total weight of the UV-LED curable wet offset printing inks described herein.

[0083]

[0075] The UV-LED radically curable offset printing inks described herein may further comprise additives including, but not limited to, one or more of the following components: coinitiators, anti-settling agents, defoamers, surfactants, and other processing aids known in the offset ink art, and combinations thereof. The additives described herein can be present in the UV-LED curable wet offset printing inks described herein in amounts and forms known in the art, including in the form of so-called nanomaterials, where at least one of the particle dimensions is in the range of 1-1000 nm.

[0084]

[0076] The UV-LED radically curable offset printing ink may be applied by the offset printing method described herein for printing features on security documents at high speed, said UV-LED curable offset printing ink exhibits good curing properties and allows to produce printed features after being cured, said printed features exhibiting low or no fluorescence. Advantageously, this allows ink manufacturers to take advantage of this background low or no fluorescence and produce low or no fluorescent inks and low or no fluorescent print features. Also described herein is a composition comprising the UV-LED radically curable offset printing ink described herein and one or more luminescent materials. By taking advantage of the low or no fluorescence of the UV-LED radically curable offset printing ink, it is possible to formulate a composition comprising one or more luminescent materials described herein, where the luminescent characteristics of said composition are deliberately chosen freely, since no masking or interference occurs between the UV-LED radically curable offset printing ink components and the incorporated luminescent materials. In other words, UV-LED radically curable offset printing inks can be used to produce compositions and security features with targeted fluorescent properties (i.e. fluorescent properties that are predictable and not altered by the components / materials of the UV-LED radically curable offset printing ink itself).In other words, the combination of one or more radically curable (meth)acrylate compounds as described herein, one or more photoinitiators of formula (I) as described herein, one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds as described herein, amine-modified polyether-based acrylates and combinations thereof, one or more inorganic pigments and / or one or more organic pigments as described herein, one or more fillers and / or extenders as described herein and optional additives in the UV-LED radically curable offset printing inks as described herein allows the production of low or non-fluorescent inks and low or non-fluorescent printed features per se, or a composition comprising one or more luminescent compounds, and by incorporating the luminescent materials as described herein, allows the production of low or non-fluorescent printed security features with controlled and desired luminescent properties, wherein the luminescent properties of said luminescent compounds are not substantially altered or masked by the UV-LED radically curable offset printing inks as described herein. Furthermore, due to the low or non-fluorescence of the UV-LED radically curable offset printing inks, the amount of one or more luminescent materials described herein can be reduced, thus reducing manufacturing and production costs.

[0085]

[0077] Typical examples of luminescent materials include, without limitation, inorganic pigments (such as inorganic host crystals or glasses doped with luminescent ions), organic and organometallic (complex materials of luminescent ion(s) and organic ligand(s)) compounds. When present, the one or more luminescent materials that are inorganic pigments are preferably present in the composition comprising the UV-LED radically curable offset printing ink described herein in an amount of about 1 to about 40 wt.%, the weight percentage being based on the total weight of the composition described herein. When present, the one or more luminescent materials that are organic compounds are preferably present in the composition comprising the UV-LED radically curable offset printing ink described herein in an amount of about 1 to about 20 wt.%, the weight percentage being based on the total weight of the composition described herein. The luminescent compound is capable of absorbing a specific type of energy that acts on the luminescent compound and subsequently emitting at least part of this absorbed energy as electromagnetic radiation. The luminescent compound is detected by exposure to light of a specific wavelength and analyzing the emitted light. Down-converting luminescent compounds absorb electromagnetic radiation at a higher frequency (shorter wavelength) and at least partially re-emit it at a lower frequency (longer wavelength). Up-converting luminescent compounds absorb electromagnetic radiation at a lower frequency and at least partially re-emit it at a higher frequency. Light emission from luminescent materials arises from excited states of atoms or molecules. The radiative decay of such excited states has a characteristic decay time, which is material dependent and can range from 10 to 200 . -9It may range from seconds up to hours. Both fluorescent and phosphorescent compounds are suitable for the present invention. In the case of phosphorescent compounds, measurements of the decay characteristics are also made and can be used as machine-readable features. Luminescent compounds in pigment form are widely used in inks (see US6565770, WO2008 / 033059A2, and WO2008 / 092522A1). Examples of luminescent compounds include, among others, sulfides, oxysulfides, phosphates, vanadates, etc. of non-luminescent cations doped with at least one luminescent cation selected from the group consisting of transition metal ions and rare earth ions; rare earth oxysulfides and rare earth metal complexes, such as those described in WO2009 / 005733A2 or US7108742. Examples of inorganic compound materials include, without limitation, La2O2S:Eu, ZnSiO4:Mn, and YVO4:Nd.

[0086]

[0078] The UV-LED radically curable offset printing inks described herein are typically prepared by a process comprising the steps of dispersing, mixing and / or grinding all the materials described herein, i.e. one or more photoinitiators of formula (I) described herein, one or more amino-containing compounds described herein, one or more inorganic pigments and / or one or more organic pigments described herein, one or more fillers and / or extenders described herein, if present one or more waxes described herein, and one or more additives, if present, in the presence of a (meth)acrylate compound described herein, thereby forming a pasty composition. The one or more photoinitiators described herein may be added to the ink during the dispersing / mixing / grinding steps of all the other materials or may be added at a later stage.

[0087]

[0079] Also disclosed herein are intaglio printing inks (also referred to in the art as "engraved steel die" or "copperplate" printing inks) and letterpress printing inks comprising the materials described herein, in particular comprising i) one or more photoinitiators of formula (I) as described herein, and ii) one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds having a weight average molecular weight of at least 400 g / mol eq PS, amine-modified polyether-based acrylates having a weight average molecular weight of at least 400 g / mol eq PS, and combinations thereof.

[0088] As described herein, a process for producing the printed features described herein includes the steps of: a) applying a UV-LED radically curable offset printing ink described herein by offset printing to form an ink layer; and b) curing the ink layer with a UV-LED source at a concentration of at least 150 mJ / cm. 2 , preferably at least 200 mJ / cm 2 and curing the ink layer, the dose of which can be measured using a UV Power Puck® II radiometer from EIT, Inc., USA, as described below.

[0089]

[0081] The UV-LED radically curable offset printing ink described herein is applied by an offset printing step, said offset printing may be a wet printing method or a dry offset printing method.

[0090]

[0082] Also described herein is a method in which the UV-LED radically curable offset printing inks described herein are applied to both sides of the substrate described herein by offset printing as described herein to form ink layers on both sides, i.e., the same UV-LED radically curable offset printing inks are used on both sides. Also described herein is a method in which two types of UV-LED radically curable offset printing inks described herein are applied to both sides of the substrate described herein by offset printing as described herein to form ink layers on both sides, i.e., two different UV-LED radically curable offset printing inks are used on both sides.

[0091]

[0083] Preferably, step b) described herein consists of exposing the ink layer to one or more wavelengths between 355 and 415 nm. Typically, commercially available UV-LED sources use one or more wavelengths, such as 365 nm, 385 nm, 395 nm and 405 nm. According to one embodiment, step b) described herein consists of exposing the ink layer to a single wavelength between 355 and 415 nm.

[0092]

[0084] The process described herein is particularly suitable for producing one or more printed features on a substrate suitable as a substrate for a security document. The one or more printed features described herein may be continuous or non-continuous.

[0093]

[0085] According to an embodiment, one or more features described herein are used as background features or patterns (either on one or both sides) on a substrate or security document on which other inks or security features are subsequently printed or processed. This means that on top of one or more features printed by the offset printing method described herein with the UV-LED radically curable offset printing inks described herein, further features are printed or applied in one or more further printing or application runs, such that the further features at least partially overlap the one or more features printed by the offset method described herein. Figure 1 shows a non-fluorescent fiduciary substrate (1), for example a cellulosic or polymeric substrate, a background design (10) consisting of printed features prepared by applying and curing the UV-LED radically curable offset printing inks described herein by the offset printing steps described herein, and further security elements (2-9). Said security elements (2-9) include, without limitation, letterpress printed serial numbers (2), security threads (3), fluorescent or phosphorescent patches (4), intaglio security features (5), transparent windows (6), numbers (7), fluorescent security fibers (8), and printed luminescent security elements (9). The fluorescent fibers (8) are incorporated into the substrate during its preparation, and the fluorescent or phosphorescent patches (4) may be applied in a separate process or printed in a subsequent step. The printed luminescent security elements (9) may be based on compositions described herein and comprising the UV-LED radically curable offset printing inks described herein and one or more luminescent materials described herein, and may be offset printed during the same printing step as the background design made from the UV-LED radically curable offset printing inks described herein.

[0094] According to one embodiment, one or more printing features consisting of a cured ink layer as described herein and made from a UV-LED radically curable offset printing ink as described herein have a total surface (i.e. the sum of all surfaces of one or more printing features as described herein) of about 50% or more, preferably about 60% or more, even more preferably about 70% or more, the % being based on the total surface of the substrate on which said one or more printing features are present. One or more printing features may be applied to one or both sides of the substrate as described herein. If both sides of the substrate contain one or more printing features as described herein, the percentages as described herein, i.e. about 50% or more, preferably about 60% or more, even more preferably about 70% or more, may be the same on both sides or may be different on both sides.

[0095]

[0087] Typical examples of substrates include, without limitation, fiber-based substrates, preferably substrates based on cellulose fibers, such as paper, paper-containing materials, polymer-based substrates, composite materials (e.g. substrates obtained by lamination of paper layers and polymer films), metal or metallized materials, glass, ceramics, and combinations thereof. Typical examples of polymer-based substrates are substrates made from ethylene or propylene-based homo- and copolymers, such as polypropylene (PP) and polyethylene (PE), polycarbonate (PC), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). As known to those skilled in the art, polymer-based substrates do not exhibit fluorescence. Typical examples of composite materials include, without limitation, multi-layer structures (e.g. laminates) of at least one paper layer and at least one polymer film, including polymers such as those mentioned above, as well as paper-like substrates based on a mixture of cellulose fibers and synthetic polymer fibers. In one preferred embodiment, the features are printed on a substrate selected from offset paper and fiduciary paper. Offset paper is made from wood pulp cellulose, which has properties that make the paper suitable for offset printing, including dimensional stability, curl resistance, high surface strength, a clean surface, and a high level of moisture resistance. Typically, offset paper has a basis weight of 30 g / m 2 ~250g / m 2 , preferably 50 g / m 2 ~150g / m 2 It is of the following.

[0096]

[0088] Credit paper (also called security paper in the art) is produced from lignin-free cotton pulp cellulose. Further properties of credit paper compared to offset paper include enhanced mechanical resistance (especially resistance to tearing and abrasion), resistance to staining and treatment against degradation by microorganisms (bacteria, viruses and fungi). The mechanical resistance of credit paper can be enhanced by introducing synthetic fibers into the paper (cotton-based) pulp and the anti-stain performance can be improved by coating or printing an anti-stain polymer layer before printing or applying the banknote features. Usually a biocide treatment is combined with an anti-stain treatment. Typically credit paper has a weight of 50-150 g / m 2 , preferably 80 to 120 g / m 2 The sheet has a basis weight of 1.0 g.

[0097]

[0089] Furthermore, the use of credit paper instead of offset paper adds an additional element of anti-counterfeiting protection, since the credit paper is produced on special papermaking machines that are only available to manufacturers of security paper, and the supply chain is protected, preventing the credit paper from being diverted to counterfeiters. In contrast to plain writing paper, credit paper does not contain optical brighteners. The optical brighteners are used to give plain writing paper a whiter and brighter appearance, but at the same time they exhibit a strong blue fluorescence on exposure to UV light, while credit paper remains relatively dark under similar illumination. Papers without optical brighteners are not available outside the realm of security, which means that bright blue fluorescence under UV light is already a sign of counterfeiting (Optical Document Security, 3rd Edition, 2005, Artech House, 3.2.5 p.71).

[0098]

[0090] According to one embodiment, the substrate described herein is a non-fluorescent substrate, preferably a non-fluorescent polymer-based substrate, or credit paper lacking optical brighteners.

[0099]

[0091] The term "security document" refers to a document that has such value that counterfeiting or illegal duplication attempts are potentially high, and that is typically protected against counterfeiting or fraud by one or more features. Examples of security documents include, without limitation, documents of value and items of value. Typical examples of documents of value include, without limitation, bank notes, titles, tickets, cheques, vouchers, revenue stamps and tax labels, agreements, etc., identity documents such as passports, ID cards, visas, bank cards, credit cards, transaction cards, entrance passes, security badges, admission tickets, transport tickets or titles, etc.

[0100]

[0092] The term "goods of value" refers to packaging materials, especially for the pharmaceutical, cosmetic, electronics or food industries, which may include one or more features to ensure that the contents of the package are authentic, e.g., authentic drugs. Examples of these packaging materials include, without limitation, labels such as brand authentication labels, tax banderols, tamper evidence labels and seals. The security documents described herein may further include one or more additional layers or coatings either under or over the printed features described herein. For example, if the adhesion between the substrate and the printed features consisting of the cured ink layer made from the UV-LED radically curable offset printing ink described herein is insufficient due to substrate material, surface irregularities, or surface inhomogeneities, an additional layer, coating, or undercoat may be applied between the substrate and the printed features, as known to those skilled in the art.

[0101]

[0093] In order to further increase the level of security and resistance to counterfeiting and illegal duplication of security documents, the substrate may contain watermarks, security threads, fibers, planchets, luminescent compounds, windows, foils, decals, coatings and combinations thereof.

[0102]

[0094] The substrate described herein onto which the UV-LED radically curable offset printing inks described herein are applied may comprise an inherent part of the security document or alternatively the UV-LED radically curable offset printing inks described herein are applied to a supplementary substrate such as, for example, a security thread, security stripe, foil, decal or label and are subsequently transferred to the security document in a separate step.

[0103]

[0095] Also described herein is the use of one or more photoinitiators described herein for producing a UV-LED radically curable offset printing ink described herein, wherein said UV-LED radically curable offset printing ink is suitable for printing one or more features on a security document. EXAMPLES

[0104]

[0096] The present invention will now be described in more detail with reference to non-limiting examples. The following examples provide further details regarding the preparation of UV-LED radically curable printing inks and the use of photoinitiators and amino-containing compounds according to the present invention and comparative data.

[0105] Photoinitiators and Amino-Containing Compounds

[0106] [Table 1]

[0107] [Table 2]

[0108] Concentration of thioxanthone moieties in photoinitiators P1-P3: Determination by ED-XRF The molar concentration of the thioxanthone moiety was determined by ED-XRF (Spectro XEPOS) using the signal of the sulfur atom. For each of the photoinitiators P1-P3 in Table 1A, three 50 mL solutions of 2 mg / mL of the corresponding photoinitiator in acetonitrile (Sigma-Aldrich, 99.9%) were prepared. For each solution, 5 mL samples were collected and increasing amounts of a 5 mg / mL solution of Genocure ITX (Rahn, 99.3% according to the certificate of analysis) in acetonitrile were added. Each sample was made up to 10 mL with acetonitrile. The following solutions were obtained and are shown in Table 1B:

[0109] [Table 3]

[0110] Each sample was independently subjected to ED-XRF measurement (Spectro XEPOS) and a spectrum was recorded. A blank measurement (pure acetonitrile) was extrapolated from all spectra. For each series of samples (triplicate measurements), the fluorescence intensity measured at 2.31 keV (S Kα1 peak) was plotted as a function of the concentration of ITX added and a linear regression was performed. The x-intercept of the regression line (abscissa at the origin) indicated the concentration of thioxanthone moiety present at level 0 in each sample. The average values ​​(average of three measurements) are shown in Table 1A. The corresponding average values ​​were used to determine the thioxanthone concentration in each of the photoinitiators P1 to P3 in mmol / g and to calculate the amount of photoinitiator P1 to P3 added for the preparation of the examples and comparative examples.

[0111] [Table 4]

[0112] Nitrogen concentrations in amino-containing compounds S1-S3: Determination by potentiometric titration The nitrogen molar concentrations of amino-containing compounds S1-S3 in Table 1C were obtained by potentiometric titration with perchloric acid. For each compound S1-S3, three 50 mL samples were prepared at 3 mg / mL in dichloromethane (Acros, 99.99%). 5 mL of each sample was transferred to a volumetric flask and made up to 50 mL with dichloromethane. These solutions were titrated with a 0.01 M solution of perchloric acid in glacial acetic acid, prepared by mixing 9 parts of glacial acetic acid (Sigma-Aldrich, 99%) with 1 part of perchloric acid solution (Sigma-Aldrich, 0.1 mol / L in glacial acetic acid). The titrations were performed using a Metrohm Titrando 905 equipped with a Conductivity Meter 826 and a Solvotrode electrode for non-aqueous solutions (saturated LiCl in ethanol). The inflection points were determined graphically. The average values ​​(in mmol / g) of triplicate measurements are shown in Table 1C.

[0113] Weight average molecular weight measurement The weight average molecular weights of the photoinitiators P1 and P3 and the amino-containing compounds S2 and S3 were determined independently by GPC (gel permeation chromatography) according to the method described below (based on OECD test method 118): A Malvern Viskotek GPCmax was used. The device was equipped with an isocratic pump, a degasser, an autosampler and a triple detector TDA302 including a differential refractometer, a viscometer and a dual angle light scattering detector (7° and 90°). For this particular measurement, only the differential refractometer was used. A calibration curve (log(molecular mass)=f(retention volume)) was made using six polystyrene standards (with molecular masses ranging from 472 to 512000 g / mol). Two columns Viskotek TM4008L (column length 30.0 cm, internal diameter 8.0 mm) were connected in series to the UV-LED. The stationary phase was made of styrene-divinylbenzene copolymer with a particle size of 6 μm and a maximum pore size of 3000 Å. The temperature was fixed at 35° C. during the measurements. Analytical samples contained 10 mg / mL of the investigated compound dissolved in THF (Acros, 99.9%, anhydrous) and were injected at a rate of 1 mL / min. The molecular mass of the compound was calculated from the chromatograms as polystyrene equivalent weight average molecular weight (PSeqMW) with a 95% confidence level and an average of three measurements of the same solution using the following formula:

[0114]

number

[0115] UV-LED radically curable offset printing inks containing color pigments and the resulting printed features (C1-C4 and E1-E2)

[0116] [Table 5] [Table 6]

[0117] UV-LED radically curable offset printing inks containing colored and luminescent pigments and the resulting printed features (C5-C8 and E3-E4)

[0118] [Table 7] [Table 8]

[0119]

[0101] The UV-LED radically curable offset printing inks of Table 2A were prepared and the efficiency of photoinitiators P1-P4 (Table 1A) and amine synergists S1-S3 (Table 1C) to cure the ink printed layer was evaluated and their impact on the residual fluorescence of the printed and cured layer was evaluated.

[0120]

[0102] The UV-LED radically curable offset printing inks of Table 2B were prepared to evaluate the efficiency of photoinitiators P1, P3 and P4 (Table 1A) and amine synergist S2 (Table 1C) to cure the ink printed layers, and to evaluate their influence on the measured luminescence of the printed and cured layers containing either a fluorescent pigment (RADGLO VSFX02 UV GREEN) or a phosphorescent pigment (LUMILUX GREEN CD 140 FS 52155 (Honeywell)). The aim was to determine whether the residual fluorescence of the printed and cured layers due to the presence of the photoinitiators (P1, P3 and P4, Table 1A) adversely affects the luminescence signal of the luminescent pigment.

[0121] The UV-LED radically curable offset printing inks of Tables 2A-B were prepared independently by mixing the materials listed in Tables 2A-B, except for the photoinitiators P1-P4, in a SpeedMixer™ (DAC 150 SP CM31 from Hauschild Engineering) at room temperature. The resulting pastes were milled independently in a SDY300 triple roll mill with three passes (first pass at 5 bar pressure, second and third passes at 11 bar pressure).

[0122]

[0104] Photoinitiators P1 to P4 were added independently to the pastes thus obtained and the inks thus obtained were mixed in a Speedmixer™ (DAC 150 SP CM31 from Hauschild Engineering) at a speed of 2500 rpm for 3 minutes at room temperature, milled in a Loher mill (3 x 50 revolutions with a load of 7.5 kg) and mixed again in the Speedmixer™ for 3 minutes.

[0123]

[0105] The viscosity values ​​of the UV-LED radical curable offset printing inks in Tables 2A to 2B were measured at 40°C and 1000 s. -1 Haake Roto-Visco RV1, cone 2cm 0.5°, linear velocity increase 30 seconds, 0~1000sec -1 The results are shown in Tables 2A-B.

[0124] Curing Efficiency

[0106] The UV-LED radically curable offset printing inks of Tables 2A-B were printed independently onto a credit paper polymer substrate (Guardian™, CCL Secure) as features (4.5 cm x 23 cm) using a Prufbau with a pressure of 1000 N (T=22°C, RH=54%).

[0125]

[0107] The obtained printed layer was subjected to irradiation with a UV-LED-UV lamp (LUV3 385 nm, IST) at a dose of about 200 mJ / cm 2 The exposure dose was determined according to the following details: The irradiation source (LUV3 385 nm, IST) was switched on. A Power Pack II radiometer (EIT, Inc., USA) was placed on the conveyor belt of the irradiation equipment designed to receive the samples to be irradiated. A Power Pack equipped with four filters (UVA, UVB, UVC and UVA2) was irradiated by the irradiation source at different belt speeds. Only the dose obtained in the UVA2 region was retained. Approximately 200 mJ / cm 2 The conveyor belt speed to obtain an irradiation of about 36 m / min was determined (average of two measurements).

[0126]

[0108] Using a UV-LED-UV lamp (LUV3 385 nm, IST), the printed features were printed at 36 m / min (approximately 200 mJ / cm 2 The exact amount of printed and cured layer was calculated for each sample by weighing the substrate before and after printing and curing. The weight of the printed and cured layer for all printed features was 1 g / m 2 It was ±3%.

[0127] For each sample, the curing test was carried out by placing one blank substrate (i.e. unprinted substrate) on the front side of the substrate carrying the printed and cured layer and by subjecting the assembly so formed to a counter pressure of 3.4 bar at 65° C. using an ORMAG Intaglio Proof Press. The substrate carrying the printed and cured layer and the blank substrate were separated and the optical density of the blank substrate was checked for ink transfer (offset). Two blanks were prepared in order to define two possible extremes of the curing behavior. The first blank, defining the maximum efficiency (100% curing efficiency), was obtained by measuring the optical density of a sample of unprinted substrate, while the lowest efficiency (0% curing efficiency) was defined by measuring the optical density of a sample obtained by counter pressure of a completely uncured ink layer (no passage under the UV-LED-UV lamp) immediately after printing. The maximum optical density (corresponding to 0% curing efficiency) was calculated as OD max while the minimum optical density (corresponding to 100% curing efficiency) is defined as OD minThe actual curing efficiency (curing efficiency for each sample in %) was defined as OD,

[0128]

number

[0129]

[0110] Table 3 shows the results of the curing efficiency of the printed layer obtained with the UV-LED radically curable offset printing inks of Tables 2A-B.

[0130] [Table 9]

[0131] As shown in Table 3, comparative offset printing inks 4, 7 and 8 (C4, C7 and C8), which contained phosphine oxide as a photoinitiator, suffered from extremely poor curing performance.

[0132] As shown in Table 3, comparative offset printing ink 3 (C3), which is of formula (I) and contains a thioxanthone photoinitiator having a weight average molecular weight (MW) higher than 900 g / mol eq PS, but contains a benzoate compound having a lower molecular weight than 400 g / mol eq PS (specifically a molecular weight of 277.4 as provided by the supplier) as the amino-containing compound, suffered from moderate curing performance.

[0133] As shown in Table 3, the comparative offset printing inks 1, 2, 5 and 6 (C1, C2, C5 and C6), i.e. inks which are different from formula (I) and which comprise a thioxanthone photoinitiator of formula (I) having a weight average molecular weight (MW) lower than 900 g / mol eq PS and which comprise an amine-modified polyether-based acrylate compound having a molecular weight higher than 400 g / mol eq PS (in particular about 4000 g / mol eq PS) as the amino-containing compound, showed moderate or good curing performance, whereas the offset printing inks according to the invention (E1 to E4), i.e. inks which are of formula (I) and which comprise a thioxanthone photoinitiator having a weight average molecular weight (MW) higher than 900 g / mol eq PS and which comprise an amine-modified polyether-based acrylate compound having a molecular weight higher than 400 g / mol eq PS (in particular about 4000 g / mol eq PS) as the amino-containing compound, showed moderate or good curing performance. Inks containing either the benzoate compound with PS) showed good curing performance.

[0134] Fluorescence measurements The UV-LED radically curable offset printing inks of Tables 2A-B were printed in a Prufbau at 800 N on a credit paper cotton substrate (BNP paper from Louisenthal, 100 g / m 2 The resulting printed layer was printed at 200 mJ / cm 2 The printed and cured layers were independently cured by a UV-LED-UV lamp (LUV3 385 nm, IST) at a dose of 10 ... 2 It was ±3%.

[0135]

[0115] The fluorescence of printed and cured layers made from the inks in Tables 2A-B was evaluated using the methods described below. The results of the fluorescence tests are presented in Tables 4A-B.

[0136] Front side fluorescence (C1-C8 and E1-E4)

[0116] The residual fluorescence of the printed and cured layers was assessed using a Fluorolog II (Spex) device at 254 nm and 365 nm using the following parameters: - Detector: R928 / 0115 / 0381 - Angle: 30° - Location: Surface - Excitation slits: 2nm (254nm) and 1.2nm (365nm) - Wavelengths covered: 400~700nm (in 1nm increments) - Detection slits: 1 nm (254 nm) and 0.6 nm (365 nm).

[0137]

[0117] The fluorescence spectrum of one blank substrate (i.e., unprinted substrate) was first measured. The fluorescence spectrum of the printed and cured layer was then recorded. From the obtained spectrum, the maximum intensity of the fluorescence was determined and the fluorescence of the blank substrate at the same wavelength was extrapolated, and the obtained value was reported together with the corresponding wavelength. This corresponds to the maximum fluorescence of the front side (printed side).

[0138] The front side luminescence of the printed and cured layers made from the inks of Table 2B was evaluated to determine the effect of the residual fluorescence of the printed and cured layers on the intrinsic luminescence intensity of the added luminescent compounds. A CAMAG UV Cabinet 4 (equipped with two UV tubes, 254 nm and 366 nm, each of 8 W) was used to observe the perceived color of the printed and cured security features with the naked eye. The measured luminescence intensity and observed color are reported in Table 4B. Backside fluorescence (C1-C4 and E1-E2) Each of the printed and cured layers was placed on one equally sized blank substrate (i.e., unprinted substrate) such that the printed side (the "front" side in Table 4) was in contact with the blank substrate. Both were kept between two glass plates (20 cm x 15 cm x 3 mm) and the assembly was placed horizontally in an oven at 60°C and 50% relative humidity for 72 hours. Two fluorescence measurements were then performed as described herein: Fluorescence on the backside of the printed layer: the results (average of three measurements at three different points on the backside) are shown in Table 4 as "Backside of printed sample"; Fluorescence of the backside of the unprinted sample: The results (average of three measurements at three different points on the backside) are shown in Table 4 as "backside of the unprinted sample" and represent the migration of the fluorescent compound from the printed layer of one sheet to the backside of the sheet placed on top of it.

[0139]

[0120] In all cases, the fluorescence spectrum of a blank substrate (ie, unprinted substrate) was measured first and the results were extrapolated from the fluorescence of the printed and cured layer.

[0140] [Table 10]

[0141] [Table 11]

[0142]

[0121] As shown in Table 4A, printed features made from comparative offset printing ink 4 (C4), which contains a phosphine oxide as a photoinitiator, exhibited very low fluorescence on the front and backside.

[0143]

[0122] As shown in Table 4A, printed features made from comparative offset printing ink 3 (C3), which contains a thioxanthone photoinitiator of formula (I) but a benzoate compound having a lower molecular weight than 400 g / mol eq PS (specifically, a molecular weight of 277.4 as provided by the supplier) as the amino-containing compound, exhibited low fluorescence.

[0144]

[0123] As shown in Table 4A, the printed features made from comparative offset printing inks 1 and 2 (C1 and C2), i.e. inks which, unlike formula (I), contain a thioxanthone photoinitiator of formula (I) having a weight average molecular weight (MW) lower than 900 g / mol eq PS and contain an amine-modified polyether-based acrylate compound having a molecular weight higher than 400 g / mol eq PS (in particular about 4000 g / mol eq PS) as the amino-containing compound, are not suitable as they show strong fluorescence on the front side. As shown in Table 4A, printed features made from comparative offset printing ink 2 (C2), i.e. an ink comprising a thioxanthone photoinitiator of formula (I) having a weight average molecular weight (MW) lower than 900 g / mol eq PS, unlike formula (I), and comprising an amine-modified polyether-based acrylate compound having a molecular weight higher than 400 g / mol eq PS (in particular, about 4000 g / mol eq PS) as the amino-containing compound, exhibited strong fluorescence not only on the front and backside of the printed features, but also on the backside of the blank substrate (unprinted substrate).

[0145]

[0124] As shown in Table 4A, printed features made from offset printing inks according to the present invention (E1 and E2), i.e. inks of formula (I) and comprising a thioxanthone photoinitiator having a weight average molecular weight (MW) higher than 900 g / mol eq PS, and comprising either an amine-modified polyether-based acrylate compound having a molecular weight higher than 400 g / mol eq PS (in particular about 4000 g / mol eq PS) as the amino-containing compound, or a benzoate compound having a molecular weight higher than 400 g / mol eq PS (in particular about 1000 g / mol eq PS) as the amino-containing compound, showed low fluorescence on the front and back sides.

[0146]

[0125] As shown in Tables 3 and 4A, the UV-LED radically curable offset printing inks according to the present invention (E1 and E2) combined good curing performance on the front and back side and enabled the production of features exhibiting low fluorescence, while the comparative inks either suffered from very poor or poor curing performance or resulted in features suffering from fluorescence.

[0147]

[0126] As shown in Table 4B, the luminescent printed features made from the comparative offset printing inks C7 and C8 (containing phosphine oxide photoinitiators) showed a strong green luminescent signal of the added luminescent compound (C7: fluorescent pigment; C8: phosphorescent pigment). In other words, the blue residual fluorescence of the printed and cured layers resulting from the inks containing the phosphine oxide photoinitiators did not adversely affect the signal of the added luminescent pigment.

[0148] As shown in Table 4B, the luminescent printed features made from the comparative offset printing inks C5 and C6 (which have a structure different from formula (I) and contain thioxanthone with a weight average molecular weight (MW) lower than 900 g / mol eq PS and contain amine-modified polyether-based acrylate compound with a molecular weight higher than 400 g / mol eq PS (specifically about 4000 g / mol eq PS)) showed blue luminescent signals essentially originating from the strong residual fluorescence of the printed and cured layer. In other words, the green luminescent signals originating from the added luminescent compounds (C5: fluorescent pigment; C6: phosphorescent pigment) were hidden by the strong residual fluorescence of the printed and cured layer, and the luminescent signals of the added luminescent compounds were very difficult to detect.

[0149] As shown in Table 4B, luminescent printed features made from offset printing inks according to the present invention (E3 and E4), i.e. inks of formula (I) and containing a thioxanthone photoinitiator with a weight average molecular weight (MW) lower than 900 g / mol eq PS and containing an amine-modified polyether-based acrylate compound with a molecular weight higher than 400 g / mol eq PS (in particular about 4000 g / mol eq PS), showed strong green luminescent signals of the added luminescent compounds (E3: fluorescent pigment; E4: phosphorescent pigment). In other words, the blue residual fluorescence of the printed and cured layers obtained from inks containing a thioxanthone photoinitiator with a structure according to formula (I) and a weight average molecular weight (MW) lower than 900 g / mol eq PS did not adversely affect the signal of the added luminescent pigment.

[0150]

[0129] As shown in Tables 3 and 4B, the UV-LED radically curable offset printing inks according to the present invention (E3 and E4) combined good curing performance and enabled the production of luminescent security features exhibiting a strong luminescent signal from the added luminescent (fluorescent or phosphorescent) pigment, while the comparative inks (C5-C8) either suffered from poor curing performance or suffered from strong residual fluorescence in the printed and cured layer, resulting in luminescent security features where accurate detection of the intrinsic luminescent signal of the added luminescent pigment was very difficult.

Claims

1. 40° C. and 1000 s for offset printing features on a substrate －１ A UV-LED radically curable offset printing ink having a viscosity in the range of 2.5 to 25 Pa s at 200° C., wherein the UV-LED radically curable offset printing ink comprises: i) 10 wt. % to 80 wt. % of one or more radically curable (meth)acrylate compounds consisting of one or more radically curable (meth)acrylate oligomers and one or more radically curable (meth)acrylate monomers; the radically curable (meth)acrylate oligomer is selected from the group consisting of epoxy (meth)acrylates, (meth)acrylated oils, (meth)acrylated epoxidized oils, polyester (meth)acrylates, aliphatic or aromatic polyurethane (meth)acrylates, polyacrylic acid (meth)acrylates, polyacrylate ester (meth)acrylates, and mixtures thereof; The radical curable (meth)acrylate monomer is one or more radical curable (meth)acrylate compounds selected from the group consisting of mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, hexa(meth)acrylates, and mixtures thereof. ii) 4 wt. % to 20 wt. % of one or more photoinitiators of formula (I): 【Chemistry 1】 wherein Q has the following formula (IIa), (IIb) or (IIc): 【Chemistry 2】 【Chemistry 3】 (Wherein, n is 1 or more, R1 are the same or different, C １ ~C ３ alkylene groups, R2 being selected from the group consisting of hydrogen and C １ ~C ３ alkyl groups, the sum of a+b+c is 3 to 12, and the sum of d+e+f+g is 4 to 16). iii) 1 wt. % to 15 wt. % of one or more amino-containing compounds selected from the group consisting of aminobenzoate compounds having a weight average molecular weight of at least 400 g / mol eq PS, amine-modified polyether-based acrylates having a weight average molecular weight of at least 400 g / mol eq PS, and combinations thereof; iv) 1 wt. % to 30 wt. % of one or more inorganic pigments and / or one or more organic pigments; v) 0.5 wt. % to 10 wt. % of one or more fillers and / or extenders selected from the group consisting of carbon fiber, talc, mica, wollastonite, clay, kaolin, carbonates, silicates, sulfates, titanates, alumina hydrate, silica, montmorillonite, graphite, bentonite, vermiculite, wood flour, quartz flour, natural fibers, synthetic fibers, and combinations thereof; vi) one or more light-emitting materials wherein the weight percentage is based on the total weight of the UV-LED radically curable offset printing ink.

2. The one or more photoinitiators are of formula (I) and Q is of the following formula (IIb-1), (IIb-2) or (IIb-3): 【Chemistry 4】 where n is equal to 1, 2, or 3, and the sum of a+b+c is from 3 to 12.

2. The UV-LED radically curable offset printing ink of claim 1, comprising:

3. 3. The UV-LED radically curable offset printing ink according to claim 1 or 2, wherein the one or more amino-containing compounds are selected from the group consisting of aminobenzoate compounds having a weight average molecular weight of at least 700 g / mol eq PS, amine modified polyether based acrylates having a weight average molecular weight of at least 700 g / mol eq PS, and combinations thereof.

4. 4. A UV-LED radically curable offset printing ink according to any one of claims 1 to 3, wherein the one or more amino-containing compounds are selected from the group consisting of amino-containing compounds including aminobenzoate compounds.

5. The one or more amino-containing compounds have the formula (III): 【Chemistry 5】 (wherein m is greater than 1 and the sum of h+i+j+k is 3 to 12).

5. The UV-LED radically curable offset printing ink according to claim 4, wherein the compound is selected from the group consisting of aminobenzoate compounds having the formula:

6. 6. A UV-LED radically curable offset printing ink according to any one of claims 1 to 5, wherein the one or more inorganic pigments and the one or more organic pigments independently have a particle size of 5 μm or less as measured using a granulometry gauge.

7. 7. A UV-LED radically curable offset printing ink according to any one of claims 1 to 6, further comprising one or more waxes selected from the group consisting of paraffin waxes, polyethylene waxes, fluorocarbon waxes, polytetrafluoroethylene waxes, carnauba waxes, and mixtures thereof.

8. 1. A method for printing features onto a substrate by an offset printing process, comprising: a) applying the UV-LED radically curable offset printing ink according to any one of claims 1 to 7 by offset printing to form an ink layer; and b) at least 150 mJ / cm ２ exposing the ink layer to UV light at a dose of 0.05 to 0.5% by weight and curing the ink layer with a UV-LED source; A method comprising:

9. The method of claim 8, wherein step b) comprises exposing the ink layer to one or more wavelengths between 355 nm and 415 nm.

10. 40°C and 1000s －１ % to 25 Pa s, comprising one or more photoinitiators according to claim 1 or 2 in an amount of 4 wt. % to 20 wt. % and one or more amino-containing compounds according to claim 1, 3, 4 or 5 in an amount of 1 wt. % to 15 wt. %, % of one or more inorganic pigments and / or one or more organic pigments, 0.5 wt. % to 10 wt. % of one or more fillers and / or extenders, and one or more luminescent materials, the weight percentages being based on the total weight of the UV-LED radically curable offset printing ink.

11. A printing feature comprising an ink layer which is a cured product of the UV-LED radically curable offset printing ink according to any one of claims 1 to 7.

12. A security document comprising a substrate and one or more printed features according to claim 11.

13. 13. The security document of claim 12, wherein the one or more printed features have a total surface of 50% or more, the percentage being based on the total surface of the substrate on which the one or more printed features are present.

14. A security document according to claim 12 or 13, wherein the substrate is a non-fluorescent substrate.

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