OA21413A

OA21413A - Cationic UV-LED radiation curable protective varnishes for security documents.

Info

Publication number: OA21413A
Application number: OA1202300411
Authority: OA
Inventors: Patrick Veya; Jean Garnier; Pierre-Yves HOFSTETTER
Original assignee: Sicpa Holding Sa
Priority date: 2021-04-01
Filing date: 2022-03-29
Publication date: 2024-06-05

Abstract

The present invention relates to the technical field of varnishes for protecting security documents, such as banknotes, against premature detrimental influence of soil and/or moisture upon use and time. In particular, the present invention provides a cationic UV-LED radiation curable protective varnish comprising : a) from about 65 wt-% to about 90 wt-% of either a cycloaliphatic epoxide, or a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than the cycloaliphatic epoxide; b) from about 1 wt-% to about 10 wt-% of a diaryl iodonium salt; c) from about 0.01 wt-% to about 5 wt-% of a nonionic surfactant; and d) a photosensitizer of general formula (I), wherein the weight percents are based on the total weight of the cationic UV-LED curable protective varnish, and a process for coating a security document with said cationic UV-LED radiation curable protective varnish.

Description

CATIONIC UV-LED RADIATION CURABLE PROTECTIVE VARNISHES FOR SECURITY DOCUMENTS

FIELD OF THE INVENTION

The présent invention relates to the technical field of vamishes for protecting security documents, such as banknotes, against prématuré detrimental influence of soil and/or moisture 10 upon use and time.

BACKGROUND OF THE INVENTION

With the constantly improving quality of color photocopies and printings and in an attempt to 15 protect security documents such as banknotes, value documents or cards, transportation tickets or cards, tax banderais, and product labels against counterfeiting, falsifying or illégal reproduction, it has been the conventional practice to incorporate varions security features in these documents. Typical examples of security features include security threads, Windows, fibers, planchettes, foils, patches, decals, holograms, watermarks, security features obtained from security inks 20 comprising security materials such as magnetic pigments, UV absorbing pigments, IR absorbing pigments, optically variable pigments, light polarizing pigments, luminescent pigments, conductive pigments and surface-enhanced Raman spectroscopy particles.

It is known to provide security documents, in particular banknotes, with dirt-repellent protective 25 coatings to extend their life and fitness for circulation. Protective coatings are protective layers facing the environment of the document, which are obtained from thermally (solvent-containing) curable vamishes, radiation-curable vamishes, or combinations thereof.

European patent application publication number EP0256170A1 proposes a protective layer 30 consisting essentially of cellulose ester or cellulose ether for coating a currency paper printed with an ink containing 1-10% by weight of micronized wax. The protective layer is obtained by applying on the surface of the currency paper a solvent-containing vamish by spraying, dipping or roller coating, and curing said vamish with a current ofhot air.

The increasing sensitivity of the public to environmental concems, as well as the necessaiy responsiveness of the Chemical industry to environmental régulations, hâve motivated the industiy to develop radiation curable protective vamishes (i.e. vamishes that are cured either by UV-visible light radiation, or by électron beam radiation) that contain no or a significantly 5 reduced amount of organic solvent (volatile organic components, VOC). Besides being more environmentally friendly than the solvent-containing protective vamishes, the radiation curable protective vamishes enable the manufacture of protective coatings having increased Chemical and physical résistance and are expediently cured, thereby decreasing the manufacturing time of the security documents coated with a radiation curable protective vamish.

For example, US patent application publication number US20070017647A1 describes a dirtrepellent protective layer for extending the life time and fitness for circulation of security documents, wherein said dirt-repellent protective layer comprises at least two lacquer layers, a first lower lacquer layer being formed by a physically drying lacquer layer applied directly on 15 the paper substrate serving for closing the paper substrate pores, and a second upper lacquer layer, which protects the substrate from physical and Chemical influences. US20070017647A1 spécifiés that in order to provide the second upper lacquer layer with high Chemical and physical résistance a UV radiation curing lacquer, such as a radically crosslinking or a cationically crosslinking curing lacquer, is used. No spécifie examples of radically crosslinking or 20 cationically crosslinking UV radiation curing lacquer are disclosed.

Free-radically UV radiation curable coatings, which are cured by free radical mechanisms consisting of the activation of one or more free radical photoinitiators able to liberate free radicals upon the action of radiation, in particular of UV light, which in tum initiate the 25 polymerization so as to fonn a cured layer, suffer from insufficient adhesion properties, a limited physical résistance and undesirably high levels of shrinkage during curing. Cationic UV radiation curable coatings, which are cured by cationic mechanisms consisting of the activation by UV-Vis light of one or more cationic photoinitiators, which liberate cationic species, such as acids, which in tum initiate the polymerization of the monomer so as to form a cured binder, 30 exhibit increased adhesion and mechanical résistance when compared to free-radically UV radiation curable coatings.

The use of a cationic UV-Vis radiation curable protective vamish comprising cationically curable compounds and fluorinated compounds for imparting soil résistance to a security 35 document has been disclosed by the international patent application publication number

WO2014067715A1. The cationic UV-Vis radiation curable protective vamish described therein is applied by screen printing or flexography printing and cured by exposure to UV light emitted by a standard mercury UV-lamp.

Mercury lamps require a high amount of energy, need efficient and costly heat dissipation Systems, are prone to ozone formation and hâve a limited lifespan. With the aim of providing solutions that are less costly, require less intervention and are more environmentally friendly, lamps and Systems based on UV-LEDs hâve been developed for curing inks and vamishes. Contrary to medium-pressure mercury lamps that hâve émission bands in the UV-A, UV-B and 10 UV-C régions of the electromagnetic spectrum, ÜV-LED lamps émit radiation in the

UV-A région. Moreover, current UV-LED lamps émit quasi monochromatic radiation, i.e. only émit at one wavelength, such as 365 nm, 385 nm, 395 nm or 405 nm.

UV-curing efficiency of a vamish or ink layer dépends inter alia on the overlap of the émission 15 spectrum of the irradiation source used for said curing and the absorption spectrum of the photoinitiator comprised in said vamish or ink. Accordingly, curing of cationic UV radiation curable coating or ink layers comprising conventionally used cationic photoinitiators with UVLED lamps suffers from a reduced curing efficiency as a resuit of the poor overlap of the émission spectrum of the UV-LED lamp with the absorption of the conventionally used 20 photoinitiators, thus leading to slow or poor curing or curing defects.

Cationic UV-LED radiation curable compositions hâve been described in the literature. Said cationic UV-LED radiation curable compositions contain a cationic photoinitiator in combination with a photosensitizer, which absorbs the energy of the light emitted by the UV25 LED lamp and acts as donor by transferring the energy to the cationic photoinitiator.

International patent application publication number. W02006093680A1 discloses a hot-melt cationic formulation curable by UV-LED exposure. The cationic formulation contains a mixture of cationically curable monomers, propylene carbonate, 2.5 wt-% of a thioxanthenium sait photoinintiator and 2 wt-% of isopropyl thioxanthone (ITX) photosensitizer. International 30 patent application publication number W02007017644A1 describes a cationic inkjet ink curable by exposure to a UV-LED source emitting at 395 nm. The exemplified cationic inkjet inks comprise 36.25 wt-% of epoxy UVR-6105, 33.5 wt-% of di-oxetane, 11.25 wt-% propylene carbonate, 3 wt-% of di-tolyl iodonium hexafluorophosphate as a photoinitiator, and 1 wt-% of a sensitizer, such as isopropyl-thioxanthone (ITX), l-chloro-4-propoxy-9H-thioxanthen-9-one 35 (CPTX) and di(butoxy)anthracene (DBA). W02007017644A1 teaches that the UV-LED radiation dose required to cure the ink may be significantly decreased by doubling the amounts of photoinitiator and sensitizer, while maintaining the ratio of 3 : 1 between the wt-% of photoinitiator and the wt-% of sensitizer. Because of the photoinitiation System used in the cationic LED-curable radiation inks known in the art, and in particular the amount of sensitizer, 5 such as isopropyl-thioxanthone (ITX), l-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX) and di(butoxy)anthracene (DBA), required for achieving a good curing, the cationic LED-curable radiation inks known in the art exhibit high fluorescence upon excitation with UV light, in particular upon excitation with UV light having a wavelength of 254 nm or 3 66 nm.

It is well known that UV light excitable luminescent security features hâve been widely used in the field of security documents, in particular for banknotes, to confer said security documents additional eovert security features, wherein the protection of said security documents against counterfeit and illégal reproduction relies upon the concept that such features typically require specialized equipment and knowledge for their détection. UV light excitable luminescent 15 security features include for example UV light excitable luminescent libers, UV light excitable luminescent threads, UV light excitable luminescent patches, stripes or foils (wherein at least a part of said patches, stripes or foils shows luminescence upon excitation with UV light) and printed UV light excitable luminescent features. Said printed UV light excitable luminescent features include luminescent numbering (printed by letterpress), printed patches (printed by 20 letterset), as well as luminescent features printed by offset. As security documents generally contain UV light excitable luminescent security features, which are covered by a protective coating obtained from a protective vamish, the photoinitiation Systems known in the art are not acceptable for being used in protective vamishes for security documents because upon excitation with UV light having a wavelength such as 254 nm or 366 nm, the high levels of fluorescence 25 exhibited by the protective coating impair the machine détection and/or human récognition of the

UV light excitable luminescent security features.

Thus, there remains a need for a cationic UV-LED radiation curable protective vamish for providing at high speed (i.e. industrial speed) a protective coating for security documents, which 30 , extends their life and fitness for circulation, wherein said cationic UV-LED radiation curable vamish exhibits optimal curing properties and, after being cured, low fluorescence in response to 254 nm excitation and 366 nm excitation that does not impair the machine détection and/or human récognition of luminescent security features excitable by UV light, in particular with UV light having a wavelength such as 254 nm or 366 nm, contained by the coated security 35 documents.

SUMMARY OF THE INVENTION

Accordingly, it is the object of the présent invention to provide a cationic UV-LED radiation 5 curable protective vamish for coating at high speed (i.e. industrial speed) security documents in order to extend their life and fitness for circulation, wherein said cationic UV-LED radiation curable vamish exhibits optimal curing properties, and after being cured low fluorescence in response to excitation by UV light, such as 366 nm excitation and 254 nm excitation. This is achieved by the cationic UV-LED radiation curable protective vamish claimed herein, wherein 10 said protective vamish comprises:

a) from about 65 wt-% to about 90 wt-% of either a cycloaliphatic epoxide, or a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than the cycloaliphatic epoxide;

b) from about 1 wt-% to about 10 wt-%, preferably from about 2 wt-% to about 15 5 wt-%, more preferably about 3 wt-% of a diaryl iodonium sait;

c) from about 0.01 wt-% to about 5 wt-% of a non-ionic surfactant; and

d) a photosensitizer of general formula (I)

A¹ and A² are independently of each other selected from hydrogen and a moiety of the following structure:

O O

-L¹- is selected from

and

-L²- is selected from

ni and n2 are integers higher than or equal to 0;

and either m représente 0;

B represent hydrogen;

C is selected from hydrogen,

and

A³ and A⁴ are independently of each other selected from hydrogen and a moiety of the following structure:

O

-L³- and -L⁴- are independently of each other selected from

and n3, and n4 are integers higher than or equal to 0, wherein the sum nl+n2 is comprised between 2 and 8;

the sum nl+n2+n3 is comprised between 3 and 12; and the sum nl+n2+n3+n4 is comprised between 4 and 16;

or m represents 1 ;

: A³, A⁴, A⁵ and A⁶ are independently of each other selected from hydrogen and a moiety of the following structure:

-L³-, -L⁴-, -L⁵- and -L⁶- are independently of each other selected from

and n3, n4, n5 and n6 are integers higher than or equal to 0, wherein the sum nl+n2+n3 is comprised between 3 and 12;

the sum nl+n2+n3+n4 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n6 is comprised between 5 and 15;

the sum nl+n2+n3+n5 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n5 is comprised between 5 and 15;

the sum nl+n2+n3+n4+n5+n6 is comprised between 6 and 18;

wherein the cationic UV-LED radiation curable protective vamish comprises a concentration of the moiety

O

(2-keto-thioxanthone) présent in the photosensitizer of general formula (I) from about 1.3 mmol to about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective vamish;

the weight percents (wt-%) being based on the total weight of the cationic UV-LED radiation curable protective vamish.

Preferably, the photosensitizer contained by the cationic UV-LED radiation curable protective vamish according to the présent invention is a compound of general formula (I-b)

(I-b) ..............

wherein

A¹, A², C, ni, n2, -L¹- and -L²- hâve the meanings defined herein. More preferably, the photosensitizer contained by the cationic UV-LED radiation curable protective vamish according 20 to the présent invention is a compound of general formula (I-b), wherein C représente

with A³, n3 and -L³- having the meanings described herein.

The cationic UV-LED radiation curable protective vamish claimed and described herein is 25 curable by exposure to UV light, preferably by exposure to one or more wavelengths of between about 365 nm and about 405 nm, more preferably by exposure to UV light at 365 nm and/or 385 nm and/or 395 nm, emitted by a UV-LED light source. Hence, another aspect according to the présent invention is directed to a process for coating a security document comprising a substrate and one or more security features applied on or inserted into a portion of the substrate, wherein 5 said process comprises the following steps:

i) applying, preferably by a printing method selected from flexography printing, inkjet printing, and screen printing, the cationic UV-LED radiation curable protective vamish claimed and described herein on a surface of the substrate and/or a surface of the one or more security features of the security document so as to form a vamish layer; and ii) curing the vamish layer by exposure to UV light emitted by a UV-LED source so as to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document. The coating process according to the présent invention is environmentally friendly and enables the manufacture in an expédient manner (i.e. industrial speed) of dirt-repellent protective coatings for security documents that show acceptable levels of fluorescence in response to excitation by UV light, such as 366 nm excitation and 254 nm excitation.

A further aspect according to the présent invention is directed to a security document comprising a substrate, one or more security features applied on or inserted into a portion of the substrate, 20 and a protective coating covering a surface of the substrate and/or a surface of the one or more security features of the security document, wherein the protective coating is obtained by the coating process claimed and described herein.

DETAILED DESCRIPTION

Définitions

The following définitions are to be used to interpret the meaning of the ternis discussed in the description and recited in the daims.

As used herein, the article a/an” indicates one as well as more than one and does not necessarily limit its referent noun to the singular.

As used herein, the term “about” means that the amount or value in question may be the spécifie 10 value designated or some other value in its neighborhood. Generally, the term “about” denoting a certain value is intended to dénoté a range within ± 5% of the value. As one example, the phrase “about 100” dénotés a range of 100 ± 5, i.e. the range from 95 to 105. Preferably, the range denoted by the term “about” dénotés a range within ± 3% of the value, more preferably ± 1 %. Generally, when the term “about” is used, it can be expected that similar results or effects 15 according to the invention can be obtained within a range of ±5% of the indicated value.

As used herein, the term “and/or” means that either ail or only one of the éléments of said group may be présent. For example, “A and/or B” means “only A, or only B, or both A and B”. In the case of “only A”, the term also covers the possibility that B is absent, i.e. “only A, but not B”.

The term “comprising” as used herein is intended to be non-exclusive and open-ended. Thus, for instance a solution comprising a compound A may include other compounds besides A. However, the term “comprising” also covers, as a particular embodiment thereof, the more restrictive meanings of “consisting essentially of ’ and “consisting of’, so that for instance “a 25 solution comprising A, B, and optionally C” may also (essentially) consist of A, and B, or (essentially) consist of A, B, and C.

Where the présent description refers to “preferred” embodiments/features, combinations of these “preferred” embodiments/features are also deemed to be disclosed as long as the spécifie 30 combination of “preferred” embodiments/features is technically meaningful.

As used herein, the term “one or more” means one, two, three, four, etc.

The ternis “UV-LED radiation curable”, “UV-LED radiation curing”, “UV-LED curable” and 35 “UV-LED curing” refer to radiation-curing by photo-polymerization under the influence of one or more radiations having a wavelength comprised between about 365 nm and about 405 nm, such as 365 nm and/or 385 nm and/or 395 nm emitted by one or more UV-LED sources.

The term “cationic UV-LED radiation curable vamish” dénotés a vamish, which is cured by 5 cationic mechanisms activated by one or more radiations having a wavelength comprised between about 365 nm and about 405 nm, such as 365 nm and/or 385 nm and/or 395 nm emitted by one or more ÜV-LED sources.

As used herein, a “2-keto-thioxanthone moiety” or a” 2-keto-9Z7-thioxanthen-9-one” refers to a 10 moiety having the following structure:

O O

Surprisingly, it has been found that a cationic UV-LED radiation curable protective vamish 15 comprising:

b) from about 1 wt-% to about 10 wt-%, preferably from about 2 wt-% to about

5 wt-%, more preferably about 3 wt-% of a diaryl iodonium sait;......... .....

c) from about 0.01 wt-% to about 5 wt-% of a non-ionic surfactant; and

d) a photosensitizer of general formula (I)

(I) wherein in the general formula (I)

ni and n2 are integers higher than or equal to 0; and either m represents 0;

B represent hydrogen;

C is selected from hydrogen,

and

or m represents 1 ;

B is selected from ethyl, and

C is selected from

and

A³, A⁴, A⁵ and A⁶ are independently of each other selected from hydrogen and a moiety of the following structure: .

and n3, n4, η5 and η6 are integers higher than or equal to 0, wherein the sum nl+n2+n3 is comprised between 3 and 12;

the sum nl+n2+n3+n4 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n6 is comprised between 5 and 15;

the sum nl+n2+n3+n5 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n5 is comprised between 5 and 15;

the sum nl+n2+n3+n4+n5+n6 is comprised between 6 and 18;

wherein the cationic UV-LED radiation curable protective vamish comprises a concentration of the moiety ° ⁰ (2-keto-thioxanthone) présent in the

photosensitizer of general formula (I) from about 1.3 mmol to about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective vamish, the weight percents being based on the total weight of the cationic UV-LED radiation curable protective vamish, exhibits optimal curing properties, and following curing, shows levels of fluorescence in response to excitation by UV light, such as 366 nm excitation and 254 nm excitation, that are acceptable in the field of security documents. The use of a photoinitiation System containing a diaryl iodonium sait as a cationic photoinitiator and a photosensitizer of general formula (I) containing one or more 2-keto-thioxanthone moieties, wherein the concentration of 2-ketothioxanthone moiety présent in the photosensitizer of general formula (I) in the cationic UVLED curable protective vamish is of between about 1.3 mmol and about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said 2-keto-thioxanthone moiety per 100 g of cationic UV-LED curable protective vamish, ensures that the cationic UV-LED curable protective vamish exhibits optimal curing properties and provides protective coatings with levels of fluorescence in response to excitation by UV light, such as 366 nm excitation and 254 nm excitation, acceptable for the fîêld of security documents.

The cationic UV-LED radiation curable protective vamish. claimed and described herein comprises

d) a photosensitizer of general formula (I)

O o

-L²- is selected from

and either and ni and n2 are integers higher than or equal to 0;

m represents 0;

B represent hydrogen;

C is selected from hydrogen,

A⁴

A³

G.

.0

A³ n3 and

O

or m represents 1;

B is selected from ethyl, and

A³, A⁴, A⁵ and A^{6 * * * 10} are independently of each other selected from hydrogen and a moiety of the following structure:

and n3, n4, n5 and n6 are integers highcr than or cqual to 0, wherein the sum nl+n2+n3 is comprised between 3 and 12;

the sum nl+n2+n3+n4 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n6 is comprised between 5 and 15;

the sum nl+n2+n3+n5 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n5 is comprised between 5 and 15;

the sum nl+n2+n3+n4+n5+n6 is comprised between 6 and 18;

and a concentration of the moiety ^s (2-keto-thioxanthone) présent in the photosensitizer of general formula (I) from about 1.3 mmol to about 4.7 mmol, preferably from about 1,45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective 5 vamish.

As the cationic UV-LED radiation curable protective vamish comprises a concentration of the 2-keto-thioxanthone moiety présent in the photosensitizer from about 1.3 mmol to about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 10 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective vamish, the corresponding amount (wt-% based on the total weight of the cationic UV-LED radiation curable protective vamish) of photosensitizer of general formula (I) contained by said vamish can be easily calculated on the basis of the molar concentration of the 2-keto-thioxanthone moiety in a photosensitizer of general formula (I) (mmol 2-keto15 thioxanthone moiety / g of photosensitizer of general formula (I)). The molar concentration of the 2-keto-thioxanthone moiety in a photosensitizer of general formula (I) (mmol 2-keto. thioxanthone moiety / g of photosensitizer) is equal to the sulfur molar concentration in said photosensitizer of general formula (I) (mmol sulfur / g of photosensitizer), which can be determined by Energy Dispersion X-Ray Fluorescence (ED-XRF) using the signal of the sulfur 20 atom contained by the 2-keto-thioxanthone moiety. The ED-XRF measurement may be conducted by the internai standard addition technique with a spectrometer Spectro XEFOS by using a 9/7-thioxanthen-9-one (thioxanthone) containing compound of a known structure, for example 2-isopropyl-9/7-thioxanthen-9-one (ITX), as an internai standard.

In a preferred embodiment according to the présent invention, m represents 0 and B represents hydrogen. Thus, a cationic UV-LED curable protective vamish containing a photosensitizer of general formula (I-a)

C

(I-a), wherein A¹, A², C, ni, n2, -L¹- and -L²- hâve the meanings defined herein, is preferred.

In an alternative preferred embodiment according to the présent invention, m represents 1. Hence, the cationic UV-LED radiation curable protective vamish claimed and described herein may contain a photosensitizer of general formula (I-d)

(I-d) wherein A¹, A², B, C, -L¹-, -L²-, ni and n2 hâve the meanings defined herein.

An especially preferred embodiment according to the présent invention relates to a cationic UVLED radiation curable protective vamish as claimed and described herein, wherein m represents 1 and B represents ethyl. Hence, a cationic UV-LED radiation curable protective vamish as claimed and described herein containing a photosensitizer of general formula (I-b)

C

(I-b) wherein A¹, A², C, ni, n2, -L¹- and -L²- hâve the meanings defined herein, is especially preferred.

A further preferred embodiment according to the présent invention relates to a cationic UV-LED radiation curable protective vamish as claimed and described herein, wherein m represents 1 and B represents

, wherein -L⁵-, n5 and A⁵ hâve the meanings defined herein. Hence, a cationic UV-LED radiation curable protective vamish as claimed and described herein containing a photosensitizer of general formula (I-c)

(I-c) wherein A¹, A², A⁵, C, ni, n2, n5, -L¹-, -L²- and -L⁵- hâve the meanings defined herein, is also preferred.

'x ^A³

Preferably, C represents ⁿ , wherein -L³-, n3 and A³ hâve the meanings defined herein. Thus, a cationic UV-LED radiation curable protective vamish as claimed and described herein containing a photosensitizer of general formula (I), (I-a), (I-b), (I-c) or (I-d), '' ^A³ • '^^L3^3 wherein C represents ⁿ and -L³-, n3 and A³ hâve the meanings defined herein, is preferred. Especially preferred is a cationic UV-LED radiation curable protective vamish as claimed and described herein containing a photosensitizer of general formula (I-e)

O A³

(I-e), wherein A¹, A², A³, -L¹-, -L²-, -L³-, ni, n2 and n3 hâve the meanings defined herein.

Preferably -L¹- represents

and -L²-, -L³-, -L⁴-, -L^s- and L⁶represent

Thus, a cationic UV-LED curable protective vamish comprising a photosensitizer of general formula (I), (I-a), (I-b), (I-c), (I-d) or (I-e), wherein -L¹represents and -L²-, -L³-, -L⁴-, -L⁵- and -L⁶- represent ''' is preferred.

A particularly preferred embodiment according to the présent invention is directed to a cationic UV-LED curable protective vamish comprising a photosensitizer of general formula (I-f)

(i-f), wherein A¹, A², A³, ni, n2 and n3 hâve the meanings defined herein. In the general formula (If), one or more, preferably two or more of the A¹, A², and A³ represent a 2-keto-thioxanthone moiety of the following structure:

O O

The cationic UV-LED curable protective vamish may comprise a mixture of photosensitizers of general formula (I), (I-a), (I-b), (I-c), (I-d), (I-e) or (I-f), with the proviso that the vamish contains a concentration of the 2-keto-thioxanthone moiety from about 1.3 mmol to about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective vamish. A particularly preferred cationic UV-LED curable protective vamish according to the présent invention comprises a photosensitizer of general formula (I-f), wherein A¹, A², and A³ are 2-keto-thioxanthone moieties, a photosensitizer of general formula (I-f), wherein A¹ and A² are 2-keto-thioxanthone moieties, and A³ represents hydrogen, and a photosensitizer of general formula (I-f), wherein A¹ is a 2-keto-thioxanthone moiety and A² and

A³ represent hydrogen, and is characterized by a concentration of the 2-keto-thioxanthone moiety from about 1.3 mmol to about 4.7 mmol, preferably from about 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, of said moiety per 100 g of cationic UV-LED radiation curable protective vamish.

In a further preferred embodiment according to the présent invention, -L¹- represents ^and L^2-, -L³-, -L⁴-, -L⁵- and -L⁶represent

The photosensitizer of general formula (I), (I-a), (I-b), (I-c), (I-d), (I-e), and (I-f) preferably has a weight average molecular weight (Mw) higher than or equal to about 700 g/mol eq PS, more preferably higher than or equal to 900 g/mol eq PS, wherein said weight average molecular weight is determined by gel perméation chromatography (GPC) according to thè OECD (Organisation for Economie Coopération and Development) test method 118, wherein a Malvem Viskotek GPCmax is used and wherein a calibration curve (log(molecular mass) = f(retention volume)) is established using six polystyrène (PS) 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 TDA 302 comprising a differential refractometer, a viscosimeter and a double-angle light scattering detector (7° and 90°). For this spécifie measurement, only the differential refractometer is used. Two columns Viskotek TM4008L (column length 30.0 cm, internai diameter 8.0 mm) were coupled in sériés. The stationary phase was made of a styrene-divinylbenzene copolymer with a particle size of 6 μτη and a maximum pore size of 3000 Â. During the measurements, the température was fixed at 35°C and the samples contain 10 mg/mL of the compound to be analyzed and being dissolved in THF (Acros, 99.9%, anhydrous). As described in the Examples herebelow, the samples are independently injected at a rate of 1 ml/min. The molecular mass of the compound is calculated from the chromatogram as a polystyrene-equivalent weight average molecular weight (PS eq Mw), with a

95% confidence level and the average of three measurements of the same solution, using the following formula:

_ ΣΓ-χΗ,μ/ ...... ............~.......

^w Σ?₌₁Ηι where H, is the level of the detector signal from the baseline for the rétention volume Vi, Mi is the molecular weight of the polymer fraction at the rétention volume V, and n is number of data points. Omnisec 5.12 as supplied with the device is used as a software.

Preferably, the concentration of the 2-keto-thioxanthone moiety in the cationic UV-LED curable protective vamish is from from about 1.3 mmol to about 4.7 mmol, preferably from about . 1.45 mmol to about 4.5 mmol, more preferably from about 1.6 mmol to about 4.25 mmol, especially preferably from about 1.6 mmol to about 2.9 mmol, such as from about 1.63 mmol to about 2.9 mmol, 2-keto-thioxanthone moiety per 100 g cationic UV-LED curable protective vamish.

The cationic UV-LED curable protective vamish claimed and described herein comprises b) from about 1 wt-% to about 10 wt-%, preferably from about 2 wt-% to about 5 wt-%, more preferably about 3 wt-% of a diaryl iodonium sait.

As used herein, the tenu “diaryl iodonium sait” refers to a cationic photoinitiator containing a diaryl iodonium as cationic moiety and any suitable anionic moiety including, but not limited to BF4^-(tetrafluoroborate, CAS Nr 14874-70-5), B(C6F5)U(tetrakis(pentafluorophenyl)borate, CAS Nr 47855-94-7), PFô^- (hexafluorophosphate, CAS Nr 16919-18-9), AsFô^- (hexafhioroarsenate,

CAS Nr . 16973-45-8), SbF6^-(hexafluoroantimonate,

CAS Nr 17111-95-4), CFsSCh^- (trifluoromethanesulfonate, CAS Nr 37181-39-8), (CH3C6H4)SO3^_(4-methylbenzenesulfonate, CAS Nr 16722-51-3), (C4F9)SO₃ ^_ (1,1,2,2,3,3,4,4,4nonafluoro-l-butanesulfonate, CAS Nr 45187-15-3), (CFjjCCh^- (trifluoroacetate, CAS Nr 14477-72-6), (C₄F9)CO₂ ^_ (2,2,3,3,4,4,5,5,5-nonafluoro-l-pentanoate, CAS Nr 45167-47-3), and (CFsSOijsC (tris(trifluoromethylsulfonyl)methide,

CAS Nr 130447-45-9).

The two aryl groups of the diaryl iodonium cationic moiety may be independently of each other substituted by one όγ more linear or branched alkyl groups (such as for example methyl, ethyl, 20 isopropyl, isobutyl, tertbutyl, undecyl, dodecyl, tridecyl, tetradecyl etc.) that are optionally substituted by one or more halogens and/or one or more hydroxy groups; one or more alkyloxy groups that are optionally substituted by one or more halogens and/or one or more hydroxy groups; one or more nitro groups; one or more halogens; one or more hydroxy groups; or a combination thereof. Examples of diaryl iodonium cationic moiety as described herein include 25 bis(4-dodecylphenyl)iodonium (CAS Nr 71786-69-1), bis[4-(l,l-dimethylethyl) phenyl]iodonium (CAS Nr 61267-44-5), (4-isopropylphenyl)(4-methylphenyl)iodonium (CAS Nr 178233-71-1), bis(4-methylphenyl)iodonium (CAS Nr 46449-56-3), (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium (CAS Nr 344562-79-4), bis(2,4dimethylphenyl)]iodonium (CAS Nr 78337-07-2), bis(3,4-dimethylphenyl)]iodonium 30 (CAS Nr 66482-57-3), (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium (CAS Nr 758629-51-5), bis[(4-(2-methylpropyl)phenyl]iodonium (CAS Nr 157552-66-4), bis(4-butylphenyl]iodonium (CAS Nr 76310-29-7), bis(2,4,6-trimethylphenyl)iodonium (CAS Nr 94564-97-3), bis(4-hexylylphenyl]iodonium (CAS Nr 249300-48-9), bis(4-decylphenyl)iodonium (CAS Nr 137141-44-7), (4-decylphenyl)(435 undecylphenyl)iodonium (CAS Nr 167997-83-3), bis(4-undecylphenyl)iodonium (CAS Nr 167997-61-7), bis(4-tridecylphenyl)iodonium (CAS Nr 124053-08-3), bis(4-tetradecylphenyl)iodonium (CAS Nr 167997-63-9), bis(4-hexadecylphenyl)iodonium (CAS Nr 137141-41-4), bis(4-heptadecylphenyl)iodonium (CAS Nr 144095-91-0), bis(4-octadecylphenyl)iodonium (CAS Nr 202068-75-5), (4-decylphenyl)(45 dodecylphenyl)iodonium (CAS Nr 167997-67-3), (4-decylphenyl)(4-tridecylphenyl)iodonium (CAS Nr 167997-77-5), (4-decylphenyl)(4-tetradecylphenyl)iodonium (CAS Nr 167997-81-1), (4-dodecylphenyl)(4-undecylphenyl)iodonium (CAS Nr 167997-71-9), (4-dodecylphenyl)(4tridecylphenyl)iodonium (CAS Nr 167997-69-5), (4-dodecylphenyl)(4-tetradecylphenyl) iodonium (CAS Nr 167997-65-1), (4-tridecylphenyl)(4-undecylphenyl)iodonium 10 (CAS Nr 167997-73-1), (4-tetradecylphenyl)(4-undecylphenyl) iodonium (CAS Nr 167997-79-7), (4-tetradecylphenyl)(4-tridecylphenyl)iodonium (CAS Nr 167997-75-3), j>-(octyloxyphenyl) phenyliodonium (CAS Nr 121239-74-5), [4-[(2hydroxytetradecyl)oxy]phenyl]phenyliodonium (CAS Nr 139301-14-7), phenyl[3(trifluoromethyl)phenyl]iodonium (CAS Nr 789443-26-1), bis(4-fluorophenyl)iodonium (CAS 15 Nr 91290-88-9); (4-nitrophenyl)phenyliodonium (CAS Nr 46734-23-0), and (4nitrophenyl)(2,4,6-trimethylphenyl)iodonium (CAS Nr 1146127-10-7).

Preferably, the diaryl iodonium sait is of a compound of general formula (II)

wherein

R¹ - R¹⁰ are independently of each other selected from hydrogen, a Ci-Cis-alkyl group, and Ci-Ci2-alkyloxy group; and

An^- is an anion selected from BF4”, B(CôF5)4^-, PFô”, AsFô”, SbFô^-, CF3SO3^-, (CEBCôFUjSCh^-, (C4F9)SO3^-, (CF₃)CO2^-, (C4F9)CO2~, and (CFsSCEfiC’, preferably selected from BF4-, B(C6Fs)4^-, 25 PFô~, AsFé^-, SbFô^-, and CF3SO3 .

The terni “Ci-Ci8-alkyl group” as used herein refers to a saturated linear or branched-chain monovalent hydrocarbon radical of one to eighteen carbon atoms (Ci-Cis). Examples of Ci-Cis-alkyl groups include, but are not limited to methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (z-Pr, wo-propyl, -CH(CH3)2), 1-butyl (n-Bu, 5 n-butyl, -CH2CH2CH2CH3), 2-methyl- 1-propyl (z-Bu, z-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, sbutyl, -CH(CH3)CH₂CH3), 2-methyl-2-propyl (/-Bu, Z-butyl, -C(CH₃)₃), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH₂CH3), 3-pentyl (-CH(CH₂CH₃)2), 2-methyl2-butyl (-C(CH₃)2CH₂CH3), 3-methyl-2-butyl (-CH(CH₃)CH(CH3)₂), 3-methyl-1-butyl (-CH2CH₂CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH₃)CH₂CH3), 1-hexyl 10 (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH₂CH2CH3), 3-hexyl (-CH(CH2CH₃)(CH2CH₂CH3)), 2-methyl-2-pentyl (-C(CH3)2CH₂CH₂CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH₂CH3), 4-methyl-2-pentyl (-CH(CH3)CH₂CH(CH₃)2), 3-methyl-3-pentyl (-C(CH3)(CH₂CH3)2), 2-methyl-3-pentyl (-CH(CH₂CH3)CH(CH₃)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH₃)2), 3,3-dimethyl-2-butyl .(-CH(CH₃)C(CH3)₃), 1-heptyl (-CH₂(CH2)₅CH3), 15 1-octyl (-CH2(CH₂)₆CH3), 1-nonyl (-CH2(CH₂)₇CH3), 1-decyl (-CH₂(CH₂)8CH3), 1-undecyl (-CH2(CH₂)₉CH3) and 2-dodecyl (-CH2(CH2)ioCH₃).

The terni Ci-Ci2-alkyloxy means a Ci-Ci2-alkyl group (i.e. a saturated linear or branched-chain monovalent hydrocarbon Tadical of one to twelve carbon atoms (C1-C12)), which is linked to the 20 rest of the molécule through an oxygen atom.

Preferably, in general formula (II) the substituents R¹, R², R⁴, R⁵, R⁶, R⁷, R⁹ and R¹⁰ represent hydrogen. Hence, a preferred cationic photoinitiator is a compound of general formula (Il-a)

l⁺ An

R³ (Π-a) wherein

An' has the meaning defined herein; and

R³ and R⁸ are independently of each other selected from hydrogen, a Ci-Ci8-alkyl group, and a

Ci-Ci2-alkyloxy group, preferably selected from hydrogen and a Ci-Ci8-alkyl group, more '

preferably selected from hydrogen and a Ci-Ci2-alkyl group, and especially preferably selected from a Ci-C₄-alkyl group.

Preferably, in general formulae (II) and (Π-a), the anion An^-represents PFô’.

Particularly suitable diaryl iodonium salts of généra formula (II) and (ΙΙ-a) are commercially available known under the name DEUTERON UV 1240 (CAS Nr 71786-70-4), DEUTERON UV 1242 (mixture of CAS Nr 71786-70-4 and CAS Nr 68609-97-2), DEUTERON UV 2257 (mixture of CAS Nr 60565-88-0 and CAS Nr 108-32-7), DEUTERON UV 1250 (mixture of 10 branched bis-((Cio-Ci3)alkylphenyl)-iodoniumhexafluoroantimonate and CAS Nr 68609-97-2), and DEUTERON UV 3100 (mixture of branched bis-((C7-Cio)alkylphenyl)-iodonium hexafluorophosphate and CAS Nr. 68609-97-2), ail available from DEUTERON, OMNICAT 250 (CAS Nr 344562-80-7), OMNICAT 440 (CAS Nr 60565-88-0), and OMNICAT 445 (mixture of CAS Nr 60565-88-0 and CAS Nr 3047-32-3), ail available from IGM Resins, 15 SpeedCure 937 (CAS Nr 71786-70-4), SpeedCure 938 (CAS Nr 61358-25-6) and SpeedCure 939 (CAS Nr 178233-72-2), ail available from Lambson.

The cationic UV-LED curable protective vamish according to the présent invention comprises 20 a) from about 65 wt-% to about 90 wt-%, preferably from about 70 wt-% to about wt-% of either a cycloaliphatic epoxide, or a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than the cycloaliphatic epoxide.

Preferably, the cationic UV-LED curable protective vamish claimed and described herein 25 comprises from about 65 wt-% to about 90 wt-%, preferably from about 70 wt-% to about 90 wt-% of a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than the cycloaliphatic epoxide. More preferably, the cationic UV-LED curable protective vamish claimed and described herein comprises from about 70 wt-% to about 90 wt-% of a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than 30 the cycloaliphatic epoxide, wherein the cycloaliphatic epoxide is présent in an amount of at least 70 wt-%, the weight percents being based on the total weight of the cationic UV-LED radiation curable protective vamish.

As well known to the skilled person, a cycloaliphatic epoxide is a cationically curable monomer containing at least a substituted or unsubstituted epoxycyclohexyl residue:

o:

Preferably, the cycloaliphatic epoxide described herein comprises at least one cyclohexane ring, and at least two epoxide groups. More preferably, the cycloaliphatic epoxide is a compound of general formula (III):

wherein -L- represents a single bond or a divalent group comprising one or more atoms. The cycloaliphatic epoxide of general formula (III) is optionally substituted by one or more linear or branched alkyl radicals containing from one to ten carbon atoms (such as methyl, ethyl, 77-propyl, z-propyl, π-butyl, z-butyl, s-butyl, /-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, n-propyl, and z-propyl).

In the general formula (ΓΠ), the divalent group -L- may be a straight- or branched-chain alkylene group comprising from one to eighteen carbon atoms. Examples of said straight- or branched-chain alkylene group include without limitation methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, and trimethylene group. .

In the general formula (ΙΠ), the divalent group -L- may be a divalent alicyclic hydrocarbon group or cycloalkydene group, such as 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

In the general formula (ΠΙ), -L- may be a divalent group comprising one or more oxygencontaining linkage groups, wherein said oxygen-containing linkage groups are selected from the group consisting of -C(=O)-, -OC(=O)O-, -C(=O)O-, and -O-. Preferably, the cycloaliphatic epoxide is a cycloaliphatic epoxide of general formula (ΙΠ), wherein -L- is a divalent group comprising one or more oxygen-containing linkage groups, wherein said oxygencontaining linkage groups are selected from the group consisting of -C(=O)-, -OC(=O)O-, -C(=O)O-, and -O-, and more preferably a cycloaliphatic epoxide of general formula (ΙΠ-a), (III-b), or (ΠΙ-c), as defrned below:

(ΠΙ-a) wherein

Li can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, π-propyl, z-propyl, n-butyl, z-butyl, s-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, zz-propyl, and z-propyl);

L2 can be the same, or different in each occurrence and is a linear or branched alkyl radical 10 containing from one to ten carbon atoms (such as methyl, ethyl, n-propyl, z-propyl, /z-butyl, z-butyl, Δ'-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, n-propyl, and z-propyl); and h and h are independently of each other integers comprised between 0 and 9, preferably comprised between 0 and 3, and more preferably 0;

(ΠΙ-b) wherein

Li can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, zz-propyl, z-propyl, n-butyl, 20 z-butyl, .y-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, n-propyl, and z-propyl);

L2 can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, n-propyl, z-propyl, zz-butyl, z-butyl, 5-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three 25 carbon atoms (such as methyl, ethyl, /z-propyl, and z-propyl); and li and I2 are independently of each other integers comprised between 0 and 9, preferably comprised between 0 and 3, and more preferably 0;

-L3- is a single bond or a linear or branched divalent hydrocarbon group containing from one to ten carbon atoms, and preferably containing from three to eight carbon atoms, such as alkylene groups including trimethylene, tetramethylene, hexamethylene, and 2-ethylhexylene, and cycloalkylene groups such as 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4cyclohexylene group, and cyclohexylidene group;

(ΠΙ-c) wherein

Li can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to three carbon atoms, such as methyl, ethyl, π-propyl, and z-propyl;

L2 can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to three carbon atoms, such as methyl, ethyl, n-propyl, and z-propyl; and and h are independently of each other integers comprised between 0 and 9, preferably comprised between 0 and 3, and more preferably 0. -................ ........—..........

Preferred cycloaliphatic epoxides of general formula (Ill-a) include, but are not limited to: 3,420 epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methyl-cyclohexanecarboxylate, and 3,4-epoxy-4-methylcyclohexylmethyl-3,4-epoxy-4-methylcyclohexanecarboxylate.

Preferred cycloaliphatic epoxides of general formula (Ill-b) include, but are not limited to: bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)pimelate, and bis(3,4epoxycyclohexylmethyl)sebacate.

A preferred cycloaliphatic epoxide of general formula (III-c) is 2-(3,4-epoxycyclohexyl-5,55 spiro-3,4-epoxy)cyclohexane-meta-dioxane.

Further cycloaliphatic epoxides include a cycloaliphatic epoxide of general formula (IV-a) and a cycloaliphatic epoxide of general formula (IV-b), which are optionally substituted by one or more linear or branched alkyl groups containing from one to ten carbon atoms (such as methyl, 10 ethyl, w-propyl, z-propyl, zz-butyl, z-butyl, .v-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, zz-propyl, and z-propyl)

(IV-b).

The cycloaliphatic epoxides described herein may be hydroxy modified or (meth)acrylate modified. Examples are commercially available under the name Cyclomer A400 (CAS: 6463020 63-3) and Cyclomer M100 (CAS number: 82428-30-6) by Dâiccl Corp., or ΤΤΛ 15 and TTA16

46by TetraChem/Jiangsu.

The one or more cationically curable monomers other than the cycloaliphatic epoxide described herein are selected from the group consisting of: vinyl ethers, propenyl ethers, cyclic ethers other 25 than a cycloaliphatic epoxide, including epoxides other than a cycloaliphatic epoxide, oxetanes, and tetrahydrofuranes, lactones, cyclic thioethers, vinyl thioethers, propenyl thioethers, hydroxyl-containing compounds, and mixtures thereof, preferably from the group consisting of: vinyl ethers, cyclic ethers other than a cycloaliphatic epoxide, particularly oxetanes, and mixtures thereof.

Vinyl ethers are known in the art to accelerate curing and reduce tackiness, thus limiting the risk of blocking and set-off when the coated sheets are put in stacks just after coating. They also improve the physical and Chemical résistance of the protective coating, and enhance its flexibility and its adhesion to the substrate, which is particularly advantageous for coating plastic 5 and polymer substrates. Vinyl ethers also help reducing the viscosity of the vamish, while strongly co-polymerizing with the vamish vehicle. Examples of preferred vinyl ethers to be used in the cationic UV-LED radiation curable protective vamish claimed herein include methyl vinyl ether, ethyl vinyl ether, n-propyl Vinyl ether, n-butyl vinyl ether, rio-butyl vinyl ether, ethylhexyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, isopropyl vinyl ether, tertio butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, 4-(vinyloxy methyl)cyclohexylmethyl benzoate, 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, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, 1, 4-butanediol 15 divinyl ether, 1,6-hexanediol divinyl ether, 4-(vinyloxy)butyl benzoate, bis[4-(vinyl oxy)butyl]adipate, bis[4-(vinyloxy)butyl]succinate, bis[4-(vinyloxymethyl) cyclohexylmethyl] glutarate, 4-(vinyloxy)butyl stéarate, trimethylolpropane trivinyl ether, propenyl ether of propylene carbonate, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, ethylene glycol butylvinyl ether, dipropylene glycol divinyl ether, triethylene glycol divinyl 20 ether, triethylene glycol methyl vinyl ether, triethylene glycol monobutyl vinylether, tetraethylene glycol divinyl ether, poly(tetrahydrofuran) divinyl ether, polyethyleneglycol-520 methyl vinyl ether, pluriol-E200 divinyl ether, tris[4-(vinyloxy)butyl]trimellitate, l,4-bis(2vinyloxyethoxy) benzene, 2,2-bis(4-vinyloxyethoxyphenyl)propane, bis[4(vinyloxy)methyl]cyclohexyl] methyl] terephthalate, bis[4-(vinyloxy)methyl]cyclohexyl]methyl] isophthalate. Suitable vinyl ethers are commercially sold by BASF under the désignation EVE, IBVE, DDVE, ODVE, BDDVE,

DVE-2, DVE-3, CHVE, CHDM-di, HBVE. The one or more vinyl ethers described herein may be hydroxy modified or (meth)acrylate modified (for example: VEEA, 2-(2vinyloxyethoxy)ethyl acrylate from Nippon Shokubai (CAS: 86273-46-3)).

The use of epoxides other than a cycloaliphatic epoxide in the cationic UV-LED radiation curable protective vamish claimed and described herein aids in accelerating curing and reducing tackiness, as well as in reducing the viscosity of the vamish, while strongly co-polymerizing with the vamish vehicle. Preferred examples of an epoxide other than a cycloaliphatic epoxide as 35 described herein include, but are not limited to, cyclohexane dimethanol diglycidylether, poly(ethyleneglycol) diglycidyl ether, poly(propyleneglycol) diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, bisphenol-A diglycidyl ether, neopentylglycol diglycidylether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, butyl glycidyl ether, /2-tert-butyl phenyl glycidyl ether, hexadecyl glycidyl 5 ether, 2-ethyl-hexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, Ci2/Ci4-alkyl glycidyl ether, Cia/Cis-alkyl glycidyl ether and mixtures thereof. Suitable epoxides other than a cycloaliphatic epoxide are commercially sold by EMS Griltech under the trademark Grilonit® (e.g. Grilonit® V51-63 or RV 1806).

A preferred embodiment according to the présent invention is directed to a cationic UV-LED radiation curable protective vamish as claimed and described herein comprising:

a) from about 65 wt-% to about 90 wt-%, preferably from about 70 wt-% to about 90 wt-%, of a mixture of a cycloaliphatic epoxide and one or more oxetanes.

Oxetanes are known in the art to accelerate curing and reduce tackiness, thus limiting the risk of blocking and set-off when the printed sheets are put in stacks just after coating. They also help reducing the viscosity of the vamish, while strongly co-polymerizing with the vamish vehicle. Preferred examples of oxetanes include trimethylene oxide, 3,3-dimethyloxetane, trimethylolpropane oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-[(2-ethylhexyloxy) methyl]oxetane, 3,3-dicyclomethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, bis ([l-ethyl(3oxetanyl)]methyl) ether, 1,4-bis [3-ethyl-3-oxetanyl methoxy)methyl]benzene, 3,3-dimethyl-2(pmethoxy-phenyl)-oxetane, 3-ethyl-[(tri-ethoxysilyl propoxy)methyl]oxetane, 4,4-bis(3-ethyl-3oxetanyl)methoxymethyl]biphenyl and 3,3-dimethyl-2(p-methoxy-phenyl) oxetane. The one or more oxetanes described herein may be hydroxy modified (for example: Curalite™Ox from

Perstorp (CAS Nr: 3047-32-3)) or (meth)acrylate modified (for example: UVi-Cure S170 from Lambson (CAS Nr: 37674-57-0)).

The cationic UV-LED radiation curable protective vamish claimed and described herein comprises

c) from about 0.01 wt-% to about 5 wt-%, preferably from about 0.05 wt-% to about 30 3 wt-%, more preferably from about 0.1 wt-% to about 2 wt-%, even more preferably from about

0.2 wt-% to about 1 wt-%, of a non-ionic surfactant.

As well known to a skilled person, a non-ionic surfactant contains a hydrophilic moiety and a hydrophobie moiety and carries no charge. Preferably, the non-ionic surfactant used in the cationic UV-LED curable protective vamish claimed and described herein has a molecular weight of between about 200 g/mol and about 3000 g/mol, and/or contains one or more functional groups selected from hydroxyl and epoxide groups. More preferably, the non-ionic surfactant is selected from a non-ionic fluorinated surfactant and a non-ionic silicone surfactant.

As used herein the terni “non-ionic fluorinated surfactant” includes non-ionic perfluoropolyether surfactants and non-ionic fluorosurfactants.

As used herein, the terni “non-ionic perfluoropolyether surfactant” dénotés a non-ionic surfactant 10 comprising a perfluoropolyether backbone and one or more, preferably two or more, terminal functional groups selected from the group consisting of: hydroxyl, epoxide, acrylate, méthacrylate and trialkoxysilyl, preferably selected from the group consisting of hydroxyl and epoxide. Preferably, the non-ionic perfluoropolyether surfactant is characterized by an average molecular weight (M_n) below about 2000 [g/mol]. As used herein, a perfluoropolyether 15 backbone dénotés a residue of a perfluoropolyether polymer comprising randomly distributed recurring units selected from perfluoromethyleneoxy (-CF2O-) and perfluoroethyleneoxy (-CF2-CF2O-). The perfluoropolyether residue is connected to the terminal functional group directly or via a spacer selected from methylene(oxyethylene), 1,1-difluoroethylene(oxyethylene), methylene-di(oxyethylene), l,l-difluoroethylene-di(oxyethylene), methylene20 tri(oxyethylene), l,l-difluoroethylene-tri(oxyethylene), methylene-tetra(oxyethylene), 1,1difluoroethylene-tetra(oxyethylene), methylene-penta(oxyethylene), 1,1-difluoroethylenepenta(oxyethylene), and a linear or branched hydrocarbon group, optionally fluorinated at the carbon atom connecting the spacer to the perfluoropolyether residue, containing one or more urethane groups, or one or more amide groups, and optionally one or more cyclic moieties, 25 including saturated cyclic moieties (such as cyclohexylene) and aromatic cyclic moieties (such as phenylene). Preferably, the non-ionic perfluoropolyether surfactant is functionalized with one or more hydroxyl and/or epoxide functional groups.

Preferably, the non-ionic perfluoropolyether surfactant is a compound of general formula (V) 30 having an average molecular weight (M_n) from about 1200 [g/mol] to about 2000 [g/mol] ₂cf₂o-)4cf₂o)--CF₂-S%FG²) 'S ' ' t \ /f (V) wherein f and e are independently of each other integers selected from 1, 2 and 3;

( FG¹)-S¹-CF₂O—f-CF e

FG¹ and FG² are terminal functional groups selected independently of each other from the group consisting of:

-OH, -OC(O)CH=CH₂,

-OC(O)C(CH₃)=CH₂, and-Si(OR²⁰)₃;

R20 is a Ci-C4alkyl group;

-S¹- represents a single bond or a spacer selected from:

wherein

wherein j¹ is an integer comprised between 1 and 12, preferably between 4 and 10;

Ls can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, zz-propyl, z-propyl, n-butyl, z-butyl, 5-butyl, ί-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, zz-propyl, and z-propyl);

Le can be the same, or different in each occurrence and is a linear or branched alkyl radical 15 containing from one to ten carbon atoms (such as methyl, ethyl, zz-propyl, z-propyl, n-butyl, z-butyl, s-butyl, ί-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, zz-propyl, and z-propyl);

Is and le are independently of each other integers comprised between 0 and 4, preferably comprised between 0 and 1; and

-J³- is selected from -O-, -CH2-, -CH(CH3)-, and -C(CH3)2-;

-J²- is selected from '1 ---^^0-·· z’V , ί ^b ;

a is an integer comprised between 1 and 6, preferably between 1 and 3; and b is an integer comprised between 1 and 6, preferably between 2 and 4;

-S²- represents a single bond or a spacer selected from

wherein

-J⁴- is selected from

wherein j⁴ is an integer comprised between 1 and 12, preferably between 4 and 10;

L? can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, zz-propyl, z-propyl, zz-butyl, z-butyl, s-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three 5 carbon atoms (such as methyl, ethyl, π-propyl, and z-propyl); .

Ls can be the same, or different in each occurrence and is a linear or branched alkyl radical containing from one to ten carbon atoms (such as methyl, ethyl, zz-propyl, z-propyl, zz-butyl, z-butyl, ό-butyl, Z-butyl, hexyl, octyl, and decyl), and preferably containing from one to three carbon atoms (such as methyl, ethyl, n-propyl, and z-propyl);

I7 and Is are independently of each other integers comprised between 0 and 4, preferably comprised between 0 and 1 ; and

-J⁶- is selected from -O-, -CH₂-, -CH(CH₃)-, and -C(CH₃)₂-;

-J⁵- is selected from

wherein r is an integer comprised between 1 and 6, preferably between 1 and 3; and w is an integer comprised between 1 and 6, preferably between 2 and 4;

and wherein s and t are integers chosen so that the average molecular weight (M_n) of the compound of general formula (V) is from about 1200 [g/mol] to about 2000 [g/mol]........- ......Preferably, in general formula (V), FG¹ and FG² represent independently of each other -OC(O)CH=CH₂, or -OC(O)C(CH₃)=CH₂;

-S¹-représente

-S²- représente

O

, wherein b has the meaning defined herein; and

O

, wherein w hae the meaning defined herein.

More preferably, in general formula (V), FG¹ and FG² represent -OH;

-S¹- represents a single bond or

, wherein a has the meaning defîned herein;

-S²- represents a single bond or

, wherein r has the meaning defîned herein; and the sum of o and r is comprised between 3 and 9.

Also preferably, in general formula (V), FG¹ and FG² represent -Si(OR^{15 * * * * 20})3;

R²⁰ is a Ci-C4alkyl group, preferably an ethyl group;

-S¹- represents

O

, wherein b has the meaning defîned herein; and

-S²- represents

, wherein w has the meaning defîned herein. Thus, a preferred perfluoropolyether surfactant is a compound of general formula (V-a)

(V-a) wherein b and w are integers comprised between 1 and 6, preferably between 2 and 4;

s is a integer of between 2 and 6; and q is an integer of between 2 and 4.

Particularly suitable examples of non-ionic perfluoropolyether surfactant are commercially available under the name Fluorolink® E10H, Fluorolink® MD700, Fluorolink®. MD500 Fluorolink® AD1700, Fluorolink® E-series, and Fluorolink® S10 from Solvay.

As used herein the terni “non-ionic fluorosurfactant” refers to a non-ionic surfactant containing a perfluoroalkyl chain CF3(CF₂)_X, wherein x is an integer from 2 to 18. Preferably, the non-ionic fluorosurfactant is characterized by an average molecular weight (M_n) from about 200 [g/mol] to about 2000 [g/mol].

Preferably, the non-ionic fluorosurfactant is a compound of general formula (VI)

CF3(CF₂)x(CH2)yE (VI) wherein x is an integer from 2 to 18;

y is an integer from 0 to 8; and

E is selected from

R R and -OSi(OR²⁰)₃, wherein z is an integer from 0 to 15;

R can be the same, or different in each occurrence, and is selected from hydrogen and methyl;

and

R²⁰ is a Ci-C4alkyl group. In the general formula (VI), R preferably represents hydrogen.

A non-ionic fluorosurfactant of general formula (Vl-a)

CF₃(CF2)x(CH2)y(CR2CR2O)zH (Vl-a)..... ......................

wherein x is an integer from 2 to 18;

y is an integer from 0 to 8;

z is an integer from 0 to 15; and

R can be the same, or different in each occurrence, and is selected from hydrogen and methyl, preferably hydrogen is especially preferred. Non-ionic fluorosurfactants of general formula (Vl-a) are commercially available under the name CHEMGUARD S550-100 or CHEMGUARD S550, CHEMGUARD S222N, CHEMGUARD S559-100 or CHEMGUARD S559, ail commercialized by CHEMGUARD; Capstone™ FS-31, Capstone™ FS-35, Capstone™ FS-34,

Capstone™ FS-30, Capstone™ FS-3100, ail commercialized by Chemours.

A non-ionic fluorosurfactant of general formula (Vl-b) CF₃(CF2)x(CH2)_yOSi(OR²⁰) (Vl-b), wherein x is an integer from 2 to 18;

y is an integer from 0 to 8; and

R²⁰ is a Ci-C4alkyl group, is also preferred. Non-ionic fluorosurfactants of general formula (Vl-b) are commercially available under the name Dynasylan F8261 and Dynasylan F8263 commercialized by Evonik.

A non-ionic fluorosurfactant of general formula (VI-c)

F F (VI-c), wherein x is an integer from 2 to 18;

y is an integer from 0 to 8; and

R²¹ is selected from hydrogen and a methyl group, is also preferred. Examples of non-ionic fluorosurfactants of general formula (VI-c) include, but are not limited to: \H,ÏH,2H,2Hperfluorooctyl acrylate (Sigma-Aldrich), 177,lZ/’,2Z/',2H-perfluorooctyl méthacrylate (Sigma20 Aldrich), lÆ,lÆ-perfluorooctyl acrylate (Sigma-Aldrich), l//,177-perfluorooctyl methaciylate (Sigma-Aldrich), ΙΗ,ΙΗ-perfluoroheptyl acrylate (Sigma-Aldrich) and 177,127-perfluoroheptyl méthacrylate (Sigma-Aldrich).

As used herein a non-ionic silicone surfactant refers to a non-ionic surfactant comprising a 25 silicone backbone containing randomly distributed recurring units selected from di(methyl)siloxane (-(CHafrSiO-) and/or methyl-(C2-Cio-alkyl)-siloxane (-(CH3)(C2-Cio-alkyl)SiO-), wherein one or more methyl groups and/or C2-Cio-alkyl groups may be independently of each other substituted by an aryl group, a polyester, optionally presenting a terminal functional group selected from hydroxyl, epoxide, and (meth)acrylate, a polyether, such 30 as polyalkylene glycol, including polyethylene glycol and polypropylene glycol, optionally presenting a terminal functional group selected from hydroxyl, epoxide and (methjacrylate, a hydroxyl group, an epoxide group, or a (methjacrylate group, and/or wherein the silicone backbone may be connected directly or via a spacer to a terminal functional group selected from a hydroxyl group, an epoxide group, and a (meth)acrylate group. The silicone backbone described herein may be connected to an aliphatic urethane acrylate or to a fluorine-containing aliphatic urethane acrylate. Preferably, the non-ionic silicone surfactant is characterized by an 5 average molecular weight lower than about 3000 [g/mol],

Non-ionic silicone surfactants include, but are not limited to poly-methyl-alkyl-siloxane, such as BYK-077 and BYK-085 commercialized by BYK, polyester-modified poly-dimethyl-siloxane, such as BYK 310 commercialized by BYK, polyether-modified poly-dimethyl-siloxane, such as

BYK-377, BYK-333, BYK-345, BYK-346 and BYK-348 commercialized by BYK, polyestermodified poly-methyl-alkyl-siloxane, such as BYK-315 commercialized by BYK, polyethermodified poly-methyl-alkyl-siloxane, such as BYK-341, BYK-320 and BYK-325 commercialized by BYK, hydroxy-functional poly-dimethyl-siloxane, such as TEGOMER® HSI-2311 commercialized by Evonik, polyester-modified hydroxy-functional poly-dimethyl15 siloxane, such as BYK-370 and BYK-373 commercialized by BYK, polyether-modified hydroxy-functional poly-dimethyl-siloxane, such as BYK-308 commercialized by BYK, polyether-polyester modified hydroxy-functional poly-dimethyl-siloxane, such as BYK-375 commercialized by BYK, epoxy-functional poly-dimethyl-siloxane, such as TEGOMER® E-Si 2330 commercialized by Evonik, acryloxy-functional poly-dimethyl-siloxane, such as

TEGOMER® V-SI 2250 and TEGO® Rad 2700 commercialized by Evonik, polyester-modified acrylic functional poly-dimethyl-siloxane, such as BYK-371 commercialized by BYK, polyether-modified acrylic functional poly-dimethyl-siloxane, such as TEGO® Rad 2100 and TEGO® Rad 2500 commercialized by Evonik, silicone-modified aliphatic urethane acrylate, such as SUO-S3000 and SUO-S600NM commercialized by Polygon, silicone- and fluorine25 modified aliphatic urethane acrylate, such as SUO-FS500 commercialized by Polygon.

To facilitate the security documents storing, stacking and grasping, in particular banknotes storing, stacking and grasping, the cationic UV-LED radiation curable protective vamish claimed and described herein may contain a matting agent, which provides a matt protective coating with a better grip. Moreover, a matt protective coating has the advantage of retaining the users' accustomed perception of security documents by the sense of touch, and causes much less reflection than a glossy protective coating, thereby, enabling machine checking and authentication of security documents with the optical sensors customarily used. The matting agent may be présent in an amount from about 1 wt-% to about 12 wt-%, the weight percents (wt-%) being based on the total weight of the cationic UV-LED radiation curable protective vamish.

As well known to the skilled person, the use of matting agents should be avoided in the cationic 5 UV-LED radiation curable protective vamishes intended for production of glossy protective coatings that can be useful for example for protecting the surface of an overt security feature présent in a security document. A cationic UV-LED radiation curable protective vamish as claimed and described herein, which is free of matting agents, provides a glossy protective coating, which is conspicuous and draws the layperson's attention to the security feature covered 10 by the glossy lacquer, thereby aiding the unexperienced users to easily find the security feature on the security document. Such cationic UV-LED radiation curable protective vamish can be applied directly on the surface of a security feature présent in a security document. Furthermore, such matting agent free cationic UV-LED radiation curable protective vamish may be useful for producing glossy discontinuons protective coatings for security documents as described in the 15 international patent application publication number W02011120917A1, which présent a matt protective coating applied directly on the surface of the security document and a glossy protective coating, which partially covers the surface of the matt protective coating.

The matting agent is preferably selected from inorganic particles and resin particles. Examples of 20 inorganic particles and resin particles include, but are not limited to thermoplastic polymer matting agents, such as thermoplastic polymer microspheres and micronized polyolefin waxes, calcium carbonate matting agents, such as core/shell microparticles comprising a calcium carbonate core and a hydroxyapatite shell, sold under the tradename Omyamatt® 100 by Omya, aluminium oxide matting agents, aluminosilicate matting agents, and amorphous Silicon dioxide 25 particles having a porous structure, such as fiimed amorphous Silicon dioxide particles, precipitated amorphous Silicon dioxide particles and amorphous Silicon dioxide particles obtained from the sol-gel process. .

Preferably, the matting agent is selected from amorphous Silicon dioxide particles having a 30 porous structure including organic surface treated amorphous Silicon dioxide particles. Such matting agent présents low refractive index resulting in good transmission properties.

The matting agent is preferably characterized by a D50 value in the range of from about 1 pm to about 25pm, preferably from 2pm to about 15pm, more preferably between about 3pm and 35 about 10 pm, as determinedby laser diffraction.

Suitable amorphous Silicon dioxide particles having a porous structure are commercially available under the name Syloid® from Grâce (such as Syloid® C906, Rad 2105, 7000, ED30), Acematt® from Evonik (such as Acematt® OK412, OK500, OK520, OK607, OK900, 3600, TS

100), PPG Lo-Vel® from PPG (such as PPG Lo-Vel® 66, 2023, 8100, 8300), Gasil® from PQ

Corporation (such as Gasil® UV55C, UV70C, HP210, HP240, HP380, HP860).

The cationic UV-LED radiation curable protective vamish may contain up to 10 wt-% of an organic solvent, the weight percents being based on the total weight of the cationic UV-LED radiation curable protective vamish. Preferably, the organic solvent is présent in an amount from about 1 wt-% to about 7.5 wt-%, more preferably from about 2 wt-% to about 5 wt-%. Preferably, the organic solvent is a polar organic solvent selected from alcohols, glycols, glycol ethers, glycol esters and cyclic carbonates, preferably having a boiling point higher than about 80°C, more preferably higher than about 100°C.

The cationic UV-LED radiation curable protective vamish claimed and described herein may further contain one or more additives including without limitation antifoaming agents, defoaming agents, UV absorbers, anti-sedimentation stabilizers, antimicrobial agents, virucidal agents, biocidal agents, fungicides, and combinations thereof.

.

The cationic UV-LED radiation curable protective vamish described and claimed herein may be prepared by mixing either the cycloaliphatic epoxide, or the mixture of the cycloaliphatic epoxide and the one or more cationically curable monomers other than the cycloaliphatic epoxide, with the organic solvent when présent, the one or more additives when présent, the.......

matting agent when présent, the non-ionic surfactant, the photosensitizer of general formula (I) and the diaryl iodonium sait. Preferably, the solid ingrédients of the cationic UV-LED radiation curable protective vamish are dispersed in the mixture of the liquid ingrédients contained by said protective vamish. The non-ionic surfactant, the photosensitizer of general formula (I) and the diaryl iodonium sait may be added to the mixture either during the dispersing or mixing step of ail other ingrédients, or at a later stage (i.e. just before the application of the cationic UV-LED radiation curable protective vamish on a surface of a substrate of a security document and/or on a surface of one or more security features of a security document) simultaneously, or in sequence.

Preferably the cationic UV-LED radiation curable protective vamish is a flexography printing vamish, an inkjet printing vamish, or a screen printing vamish, more preferably a flexography printing vamish.

In a preferred embodiment, the cationic UV-LED radiation curable protective vamish is a flexography printing vamish. Flexography printing preferably uses a unit with a doctor blade, . preferably a chambered doctor blade, an anilox roller and plate cylinder. The anilox roller advantageously has small cells whose volume and/or density détermines the curable vamish application rate. The doctor blade lies against the anilox roller, and scraps off vamish surplus at the same time. The anilox roller transfers the vamish to the plate cylinder, which finally transfers the vamish to the substrate. Spécifie design might be achieved using a designed photopolymer plate. Plate cylinders can be made from polymeric or elastomeric materials. Polymers are mainly used as photopolymer in plates and sometimes as a seamless coating on a sleeve. Photopolymer plates are made from light-sensitive polymers that are hardened by ultraviolet (UV) light.

Photopolymer plates are eut to the required size and placed in an UV light exposure unit. One side of the plate is completely exposed to UV light to harden or cure the base of the plate. The plate is then tumed over, a négative of the job is mounted over the uncured side and the plate is further exposed to UV light. This hardens the plate in the image areas. The plate is then processed to remove the unhardened photopolymer from the nonimage areas, which lowers the plate surface in these nonimage areas. After processing, the plate is dried and given a postexposure dose of UV light to cure the whole plate. Préparation of plate cylinders for flexography is described in Printing Technology, J. M. Adams and P.A. Dolin, Delmar Thomson Leaming, 5th Edition, pages 359-360. To be suitable to be printed by flexography, the cationic UV-LED radiation curable protective vamish must hâve a viscosity in the range of about 50 to about 500 mPas at 25°C measured using a Brookfîeld viscometer (model “DV-I Prime) equipped with a spindle S21 at 100 rpm for measuring viscosities comprised between 100 mPas and 500 mPas at 25°C, or using a rotational viscosimeter DHR-2 from TA Instruments (cone-plane geometry, diameter 40 mm) for viscosities below 100 mPas at 25°C and 1000 s'¹.

In a further preferred embodiment according to the présent invention, the cationic UV-LED radiation curable protective vamish is an inkjet printing vamish, preferably a drop-on-demand (DOD) inkjet printing vamish. Drop-on-demand (DOD) printing is a non-contact printing process, wherein the droplets are only produced when required for printing, and generally by an éjection mechanism rather than by destabilizing a jet. Depending on the mechanism used in the printhead to produce droplets, the DOD printing is divided in piezo impulse, thermal jet and valve jet. To be suitable for DOD inkjet printing, the cationic UV-LED radiation curable protective vamish must hâve low viscosity of less than about 20 cP at jetting température and a surface tension lower than about 45 N/m.

In a still preferred embodiment according to the présent invention, the cationic UV-LED radiation curable protective vamish is a screen printing vamish. As well known to those skilled in the art, screen printing (also referred in the art as silkscreen printing) is a printing technique that typically uses a screen made of woven mesh to support an ink-blocking stencil. The attached stencil forms open areas of mesh that transfer vamish as a sharp-edged image onto a substrate. A 10 squeegee is moved across the screen with ink-blocking stencil, forcing vamish past the threads of the woven mesh in the open areas. A signifîcant charaeteristic of screen printing is that a greater thickness of the vamish can be applied on the substrate than with other printing techniques. Screen printing is therefore also preferred when vamish deposits with the thickness having a value between about 10 to 50 μηι or greater are required which cannot (easily) be achieved with other printing techniques. Generally, a screen is made of a piece of porous, fïnely woven fabric called mesh stretched over a frame of e.g. aluminum or wood. Currently most meshes are made of man-made materials such as synthetic or Steel threads. Preferred synthetic materials are nylon or polyester threads.

In addition to screens made on the basis of a woven mesh based on synthetic or métal threads, screens hâve been developed out of a solid métal sheet with a grid of holes. Such screens are prepared by a process comprising of electrolytically forming a métal screen by forming in a first electrolytic bath a screen skeleton upon a matrix provided with a separating agent, stripping the formed screen skeleton from the matrix and subjecting the screen skeleton to an electrolysis in a second electrolytic bath in order to deposit métal onto said skeleton.

There are three types of screen printing presses, namely flat-bed, cylinder and rotary screen printing presses. Flat-bed and cylinder screen printing presses are similar in that both use a fiat screen and a three-step reciprocating process to perfonn the printing operation. The screen is first 30 moved into position over the substrate, the squeegee is then pressed against the mesh and drawn over the image area, and then the screen is lifted away from the substrate to complété the process. With a flat-bed press the substrate to be printed is typically positioned on a horizontal print bed that is parallel to the screen. With a cylinder press the substrate is mounted on a cylinder. Flat-bed and cylinder screen printing processes are discontinuons processes, and consequently limited in speed which is generally at maximum 45 m/min in web or 3’000 sheets/hour in a sheet-fed process.

Conversely, rotary screen presses are designed for continuons, high speed printing. The screens 5 used on rotary screen presses are for instance thin métal cylinders that are usually obtained using the electrofonning method described hereabove or made of woven Steel threads. The open-ended cylinders are capped at both ends and fitted into blocks at the side of the press. During printing, the vamish is pumped into one end of the cylinder so that a fresh supply is constantly maintained. The squeegee is fixed inside the rotating screen and squeegee pressure is maintained 10 and àdjusted to allow a good and constant print quality. The advantage of rotary screen presses is the speed which can reach easily 150 m/min in web or 10’000 sheets/hour in a sheet-fed process.

Screen printing is further described for example in The Printing Ink Manual, R.H. Leach and RJ. Pierce, Springer Edition, 5^th Edition, pages 58-62, in Printing Technology, J. M. Adams and 15 P.A. Dolin, Delmar Thomson Leaming, 5^th Edition, pages 293-328 and in Handbook of Print

Media, H. Kipphan, Springer, pages 409-422 and pages 498-499.

The cationic UV-LED radiation curable protective vamish claimed and described herein is curable by exposure to UV light, preferably by exposure to one or more wavelengths of between 20 about 365 nm and about 405 nm, more preferably by exposure to UV light at 365 nm and/or 385 nm and/or 395 nm, emitted by one or more UV-LED light sources. As well-known by the person skilled in the art, the cationic UV-LED radiation curable protective vamish claimed and described herein is also suitable for curing using medium-pressure mercury lamps.

Another aspect according to the présent invention relates to a process for coating a security document comprising a substrate and one or more security features applied on or inserted into a portion of the substrate, wherein said process comprises the following steps:

i) applying, preferably by a printing method selected from flexography printing, inkjet printing, and screen printing, the cationic UV-LED radiation curable protective vamish claimed 30 and described herein on a surface of the substrate and/or a surface of the one or more security features of the security document so as to form a vamish layer; and ii) curing the vamish layer by exposure to UV light emitted by a UV-LED source so as to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document.

Preferably, at least one of the one or more security features applied on or inserted into a portion of the substrate of the security document to be coated is a UV light excitable luminescent security feature i.e. a security feature that emits light in response to excitation by UV light, in particular to UV light having a wavelength of 254 nm or 366 nm.

Preferably, step ii) described herein consists of exposing the vamish layer to one or more wavelengths of between about 365 nm and about 405 nm emitted by one or more UV-LED sources so as to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document. Typically, commercially available UV-LED sources use one or more wavelengths, such as for example 365 nm, 385 nm, 395 nm and 405 nm. Preferably, step ii) described herein consists of exposing the vamish layer to a single wavelength between 365 nm and 405 nm, such as for example 365 nm, 385 nm, 395 nm or 405 nm, emitted by a UV-LED source so as to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document. The vamish layer is preferably exposed to UV light at a dose of at least 150 mJ/cm², more preferably at a dose of at least 200 mJ/cm², and especially preferably at a dose of at least 220 mJ/cm² so as to cure the vamish layer and to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document. As described hereafter, the dose may be measured using a UV Power Puck® II radiometer from EIT, Inc., U.S.A.

As used herein, the terni ”substrate” includes any security document substrate into a portion of which a security feature can .be inserted and/or to which a security feature can be applied. Security document substrates include without limitation, papers or other fïbrous materials such as cellulose, paper-containing materials, plastics and polymers, composite materials and mixtures or combinations thereof. Typical paper, paper-like or other fïbrous materials are made from a variety of fibers including without limitation abaca, cotton, linen, wood pulp, and blends thereof. As well known to those skilled in the art, cotton and cotton/linen blends are preferred for banknotes, while wood pulp is commonly used in non-banknote security documents. Typical examples of plastics and polymers include polyolefins, such as polyethylene (PE) and polypropylene (PP), polyamides, polyesters such as poly(ethylene terephthalate) (PET), poly(l,4-butylene terephthalate) (PBT), poly(ethylene 2,6-naphthoate) (PEN) and polyvinylchlorides (PVC). Typical examples of composite materials include without limitation multilayer structures or laminates of paper and at least one plastic or polymer material, such as those described hereabove. The substrate of the security document may be printed with any desired signs, including any symbols, images and patterns, and/or may include one or more security features, including luminescent security features.

A further aspect according to the présent invention is directed to a security document comprising a substrate, one or more security features applied on or inserted into a portion of the substrate and a protective coating covering a surface of the substrate and/or a surface of the one or more security features of the security document, wherein the protective coating is obtained by the coating process claimed and described herein comprising the following steps:

i) applying, preferably by a printing method selected from flexography printing, inkjet printing, and screen printing, more preferably by flexography printing, the cationic UV-LED radiation curable protective vamish claimed and described herein on a surface of the substrate and/or a surface of the one or more security features of the security document so as to form a vamish layer; and ii) curing the vamish layer by exposure to UV light emitted by a UV-LED source so as to form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document.

The security document according to the présent invention may comprise on one of its sides a protective coating-ffee région of between about 5 and about 15% of the substrate surface, wherein the percentages are based on the total surface of the security document. Preferably, said protective coating-ffee région is présent on at least one edge or corner of the substrate. The protective coating-free région may be used for example for numbering the security document. If the security document is a banknote, the coating-free région may be additionally used for adsorbing a staining (indelible) ink used for protecting banknotes against theft and robbery as described in the international patent application publication no. WO2013127715A2.

A further aspect according to the présent invention is directed to a protective coating for a security document comprising a substrate, and one or more security features applied on or inserted into a portion of the substrate, wherein the protective coating is obtained from the cationic UV-LED radiation curable protective vamish claimed and described herein. Specifically, the above-mentioned protective coating is obtained by:

i) applying, preferably by a printing method selected from flexography printing, inkjet printing, and screen printing, more preferably by flexography printing, the cationic UV-LED radiation curable protective vamish claimed and described herein on a surface of the substrate and/or a surface of the one or more security features of the security document so as to form a vamish layer; and ii) curing the vamish layer by exposure to UV light emitted by a UV-LED source so as to 5 form a protective coating covering the surface of the substrate and/or the surface of the one or more security features of the security document.

Preferably, at least one of the one or more security features applied on or inserted into a portion of the substrate of the security document to be coated is a UV light excitable luminescent 10 security feature i.e. a security feature that emits light in response to excitation by UV light, in particular to UV light having a wavelength of 254 nm or 366 nm.

As used herein, the tenu “security document” refers to a document having a value such as to render it potentially liable to attempts at counterfeiting or illégal reproduction and which is 15 usually protected against counterfeit or fraud by at least one security feature. Typical examples of security documents include without limitation banknotes, deeds, tickets, checks, vouchers, fiscal stamps and tax labels, agreements and the like, identity documents such as passports, identity cards, visas, bank cards, crédit cards, transaction cards, access documents, entrance tickets and the like.

EXAMPLES

The présent invention is now described in more details with reference to non-limiting examples.

The examples and comparative examples below provide more details for the préparation of the 25 cationic UV-LED radiation curable protective vamishes according to the invention.

Photosensitizers

Table IA

Commercial Name (Supplier)

Structure, CAS No, and molecular weight

SI

Genopol* TX2 (Rahn)

S2

OMNIPOLTX (IGM Resins)

with the sum nl+n2+n3 being from 3 to 12 and

and/or

A³ = hydrogen; and/or

O o

A² = A³ = hydrogen. CASNr: 2055335-46 918 ± 12 g/mol eq. PS

CAS Nr: 813452-37-8

761 ± 17 g/mol eq. PS

S3	Genocure* ITX (Rahn)	⁰ 1 CAS Nr: 5495-84-1 254.35 (SciFinder)
S4	Speedcure CPTX (Lambson)	Cl O CAS Nr : 142770-42-1 304.79 (SciFinder)
S5	Anthracure® UVS-1331 (Kawasaki Kasei)	CAS Nr : 76275-14-4 322.45g/mol (SciFinder)

Weight average molecular weight measurement

The weight average molecular weight of the oligomeric photosensitizers S1-S2 was 5 independently determined by GPC (gel perméation chromatography) according to the method described below (based on the OECD test method 118):

A Malvem Viskotek GPCmax was used. The device was equipped with an isocratic pump, a degasser, an autosampler and a triple detector TDA 302 comprising a differential refractometer, a viscosimeter and a double-angle light scattering detector (7° and 90°). For this spécifie 10 measurement, only the differential refractometer was used. A calibration curve (log(molecular mass) = f(retention volume)) was established using six polystyrène standards (with molecular masses ranging from 472 to 512000g/mol). Two columns Viskotek TM4008L (column length 30.0 cm, internai diameter 8.0 mm) were coup UV-LED in sériés. The stationary phase was made of a styrene-divinylbenzene copolymer with a particle size of 6 pm and a maximum pore size of 3000 Â. During the measurement, the température was fïxed at 35°C. The analyzed samples contained 10 mg/mL of the investigated compounds dissolved in THF (Acros, 99.9%, anhydrous) and were injected at a rate of 1 mL/min. The molecular mass of the compounds was 5 calculated from the chromatogram as a polystyrene-equivalent weight average molecular weight (PS eq Mw), with a 95% confidence level and the average of three measurements of the same solution, using the following formula:

. Σ? ·//.··/, ” Σ=1Η<

where Hi is the level of the detector signal from the baseline for the rétention volume H, Mi is the 10 molecular weight of the compound fraction at the rétention volume Vi and n is number of data points. Omnisec 5.12 as provided with the device was used as a software. The PS eq M_wmeasured for SI and S2 are indicated in Table IA hereabove.

Sulfur molar concentration in the thioxanthone-based photosensitizers SI - S4

The sulfur molar concentration (mmol sulfur/g photosensitizer) corresponds to the molar concentration of the reactive thioxanthone-based moiety (mmol reactive thioxanthone-based moiety/g photosensitizer) and is used to ensure that ail thioxanthone-based photosensitizers are 20 used at équivalent molar concentration of the reactive thioxanthone-based moiety.

Détermination of the sulfur molar concentration in the oligomeric photosensitizers S1-S2 by EDXRF ..... .....

The sulfur molar concentration in the oligomeric photosensitizers SI and S2 was determined by 25 ED-XRF (Spectro XEPOS) using the internai standard addition technique and the sulfur atom signal. For each of the oligomeric photosensitizers S1-S2 of Table IA, three 50 mL solutions at 2 mg/mL of the corresponding photosensitizer in acetonitrile (Sigma-Aldrich, 99.9%) were prepared. From each solution, 5 mL samples were collected and increasing amounts of a 5 mg/mL solution of Genocure ITX (Rahn, 99.3% according to certificate of analysis) in 30 acetonitrile were added. Each sample was completed to 10 mL with acetonitrile. The following solutions hâve been obtained and are provided in Table IB.

Table IB

Level	Solution S1-S2 [mL]	Solution ITX [mL]	Acetonitrile [mL]
0	5	0	5
1	5	1	4
2	5	3	2
3	5	4	1

Each sample was independently submitted to an ED-XRF measurement (Spectro XEPOS) and a spectrum was recorded. A blank measurement (pure acetonitrile) was deduced from ail spectra. For each sériés of samples (triplicate measurement), the measured fluorescence intensity at 5 2.31keV (S Καί peak) was displayed as a fonction of the molar concentration (mmol/ml) of the sulfor contained by the added Genocure ITX and a linear régression was performed. The absolute value of the x-intercept of the régression line indicated the sulfor molar concentration présent at level 0 in each sample. Average values (average of three measurements) are provided in Table IC. The corresponding average value was used to détermine the sulfor molar 10 concentration in each of the oligomeric photosensitizers S1-S2 (mmol sulfor/g photosensitizer) and to calculate the amount (wt-%) of oligomeric photosensitizers S1-S2 to be added for the préparation of the examples and comparative examples. For the thioxanthone photosensitizers S3-S4, the sulfor molar concentration [mmol/g] was directly calculated from their known molecular structure.

Table IC summarizes the determined (photosensitizers SI and S2) and calculated (photosensitizers S3 and S4) sulfiir molar concentration (mmol sulfor/g photosensitizer) corresponding to the molar concentration of the reactive thioxanthone-based moiety (mmol reactive thioxanthone-based moiety/g photosensitizer).

Table IC

Photosensitizer

Reactive thioxanthone-based moiety

Sulfor molar concentration (mmol sulfiir / g photosensitizer )

Concentration reactive thioxanthonebased moiety (mmol reactive thioxanthonebased moiety/ g

			photosensitizer)
SI		1.70	1.70
\|
\_s/
S2	ω y —O O 4	2.40	2.40
S3	° Ί	3.93	3.93
S4	Cl 0		3.28	3.28

Cationic photoinitiators

Table 1D

	Commercial Name (Supplier)	Structure, CAS No, and molecular weight
PI	Omnicat 440 (IGM Resins)	ju lX 4,4’-dimethyl-diphenyl iodonium (CAS Nr: 60565-	F^\|^F F J hexafluo 88-0)	rophosphate
P2	Speedcure938 (Lambson)	iQT [Qi bis(4-tert-butylphenyl)iodonium (CAS Nr: 61358-	F ^F\U^FF^\|^F . F aexafluoi 25-6)	rophosphate
P3	Speedcure 992 (Lambson)	F Ί * . Γ F Ί ' ^F\l/^F , ^F\l/^F F 1 F F \| F core οχηχο ο ό ό 50wt-% propylene carbonate (CAS Nr: 108-32-7) + 50wt% mixture of sulfonium, diphenyl[(phenylthio)phenyl]-, hexafhiorophosphate(l-) (1:1) (68156-13-8) and sulfonium, S,S'-(thiodi-4,l-phenylene)bis[S,S-diphenyl-, hexafluorophosphate(l-) (1:2) (CAS Nr: 74227-35-3)

Other ingrédients

Table 1E

Ingrédient

Commercial name (supplier)

Chemical name

		(CAS number)
Cycloaliphatic epoxide	Uvacure 1500 (Allnex)	7-oxabicyclo[4.1,0]hept-3-ylmethyl 7oxabicyclo[4.1,0]heptane-3-carboxylate (CAS Nr: 2386-87-0)
Oxetane	Curalite™<yx. (Perstorp)	3-ethyloxetane-3-methanoi (CAS Nr: 3047-32-3)
Antifoam agent	TEGO® AIREX 900 (Evonik)	Siloxanes and Silicones, di-Me, reaction products with silica (CAS Nr: 67762-90-7)
Surfactant	BYK®-330 (BYK)	50% active ingrédient (polyether modified polydimethylsiloxane; CAS Nr: not available) + 50% 2-methoxy-l-methylethyl acetate CAS Nr: 108-65-6)
Matting agent	ACEMATT®TS 100 (Evonik)	Silica, amorphous, fumed, crystal-free (CAS Nr: 112945-52-5)
Solvent	n-butanol (BRENNTAG)	Butan-l-ol (CAS Nr: 71-36-3)

Préparation of the cationic UV-LED radiation curable protective varnishes (El - E5 and Cl -C9) and protective coatings obtained thereof

Al. Préparation of cationic UV-LED radiation curable protective varnishes (El - E5) according to the invention and comparative experiments (Cl - C9) (Table 2A)

100g of each of the cationic UV-LED radiation curable protective varnishes El - E5 and the comparative varnishes Cl - C9 were prepared by first pre-mixing the two first ingrédients (cycloaliphatic epoxide and oxetane) of Table 2A using a Dispermat (model CV-3) (10 min at 1000 rpm), then adding and dispersing the matting agent during about 15 minutes at 1500 rpm and finally adding the other ingrédients and mixing further the so-obtained mixture during about 10 minutes at 1000 rpm. The cationic UV-LED radiation curable protective varnishes El - E5 hâve viscosity properties that render them suitable for flexography printing and screen printing.

A2. Préparation of protective coatings

The vamishes El - E5 and Cl - C9 were independently applied by hand on a piece of fïduciary polymer substrate (Guardian™ by CCL Secure) using a hand-coater unit with a n°0 bar (RK5 print) to furnish a vamish layer having a size of approximately 5 cm x 10 cm and a thickness of about 4qm. Subsequently, each of the vamish layers was cured, under controlled relative humidity, by exposing said vamish layer two times at a speed of 150 m/min to UV light under a UV-LED curing unit LUV20 emitting at 385nm from IST Metz GmbH (100% lamp power with a 70% duty cycle and a nominal lamp-to-sample distance of 20mm leading to an approximate 10 total delivered dose of 220 mJ/cm² . The dose was measured by passing a Powerpuck II apparatus under the UV-LED in similar conditions to the cured samples (same speed and same distance between lamp and sample/detector). The doses are given for a UV-A2 range, selected by a spécifie filter in the apparatus (370-415nm). The conditions used for curing the coated substrates are similar to the curing conditions expected in an industrial environment.

Table 2A. Composition of the cationic UV-LED radiation curable protective vamishes El - E5 and Cl - C9

Ingrédient	Commercial name	Cl	El	E2	E3	E4	E5	C2	C3	C4	Cf

Cycloaliphatic epoxide	Uvacure 1500 .	72.3 . '2	71.9 4	71.9 4	71.5 5	70.9 0	70.4 0	69.9 0	72.8 0	72.2 3	72. 0
Oxetane	Curalite™Ox	15.05
Antifoam agent	TEGO® AIREX 900	0.30
Surfactant	BYK®-330	0.50
Matting agent	ACEMATT® TS 100	5.25
Solvent	M-butanol	3.00
Diaryliodonium photoinitiator	Omnicat 440 (PI)	3.00	3.00		3.00	3.00	3.00	3.00	3.00	3.00	3.0
	Speedcure 938* (P2)			3.00
Triarylsulphoniu m photoinitiator	Speedcure 992 (P3)
Thioxanthone photosensitizer	Genopol* TX-2 (SI)	0.58	0.96	0.96	1.35	2.00	2.50	3.00
	Omnipol TX (S2)						....... . ·	. — ..	0.1	0.67
	Speedcure CPTX (S3)										0.1
	Genocure* ITX (S4)
Alternative photosensitizer	Anthracure® UVS- 1331 (S5)
Concentration reactive thioxanthonebased moiety [mmol/100g)^a	0.99	1.63	1.63	2.30	3.40	4.25	5.10	0.24	1.61	0.3

^a) Concentration of the reactive thioxanthone-based moiety in the vamish (mmol reactive thioxanthone-based moiety / 100 g vamish)

A3. Assessment of the curing performance of the cationic UV-LED radiation curable protective varnishes El - E5 and comparative varnishes Cl - C9 using the MEK rub test The protective coatings obtained as described at item A2 above were stored in the dark for 24 hours. After that period, the deep cure performance of each protective coating, which is 5 indicative of the curing properties of the vamish used for obtaining said protective vamish, was assessed by the following procedure:

- a cotton swab was dipped in methyl ethyl ketone (MEK) 99.5% (Brenntag);

- each protective coating was rubbed 50 times with the cotton swab, on an area of approx. 0.5cm by 5cm, using a gentle pressure of the hand and after30 seconds, the rubbed area was visually assessed. The results of the visual assessment summarized in Table 2B were classifïed as foliows:

“poor”: the MEK rub test results in the partial or total removal of the protective vamish, which indicates that the curing of the protective coating is insufficient, and the vamish présents poor curing properties), “acceptable”: the MEK rub test is visually détectable, there is no removal of the of the protective coating, which indicates that the curing of the protective coating is acceptable, and the vamish présents acceptable curing properties), “optimal”: the MEK rub test is not visually détectable, which indicates that the curing of the protective coating is optimal, and the vamish présents optimal curing properties.

Varnishes with optimal curing properties under the herein described curing conditions are suitable to be used for the industrial production of protective coatings for security documents.

Table 2B. Results of the MEK rub test

Varnis h

Cl

El

E2

E3

E4

E5

C2

C3

C4

C5

C6

C7

C8

C9

Relativ e humidit y [%rH]

47

42

47

38

45

38

45

38

45

29

Curing a)

poor

optimal

poor

optimal

poor

optimal

poor

optimal

^a) curing as determined by the MEK rub test after 24 h.

A4. Evaluation of the fluorescence exhibited by the protective coatings exhibiting optimal curing properties as determined by the MEK rub test

The fluorescence exhibited by the protective coatings obtained from vamishes exhibiting optimal curing properties as determined by the MEK rub test i.e. the protective coatings obtained from the cationic UV-LED radiation curable protective vamishes El — E5 and comparative vamishes C2, C4, C6, C8 and C9 was assessed using the method described hereafter. Table 2C présents the fluorescence results.

The residual fluorescence of the protective coatings was assessed using a Fluorolog II (Spex) device at 254 nm and 366 nm, using the following parameters: Detector: R928/0115/0381

Angle: 30°

Position: front face

Excitation slit: 2 nm (254 nm) and 2 nm (366 nm)

Intégration time: 0.1 sec

Covered wavelength: 400-700 nm (incrément 1 nm)

Détection slit: 1 nm (254 nm) and 1 nm (366 nm), UV-fîlter (400nm and below) to avoid détection of excitation light

From the obtained spectrum, the intensity maximum of fluorescence was determined and the obtained value was reported as an absolute value in photons/sec., as shown in Table 2C.

The absolute intensity at maximum fluorescence (in photons/sec.) measured for each protective coating obtained from the cationic UV-LED radiation curable protective vamishes El - E5 25 according to the présent invention and the comparative vamishes with optimal curing properties (C2, C4, C6, C8, C9) was compared to the absolute intensity at maximum fluorescence of comparison standards (STI - ST4). Said comparison standards hâve been prepared with a cationic vamish for curing under standard mercury lamps, with compounds that are considered by skilled people as exhibiting low intrinsic fluorescence and/or able to generate only a minimal 30 amount of fluorescent dégradation products upon curing. The comparison standards (STI - ST4) were prepared at the same time as the protective coating for which they serve as comparison standard.

The residual fluorescence of the comparison standards (STI - ST4) was measured at the same time as the residual fluorescence of the protective coating for which they serve as comparison 35 standard.

L9 . 1

Table 2C. composition of the standard cationic protective vamish that is UV-Vis curable with

Hg lamps (used to produce the comparison standards STI - ST4)

Ingrédient	Commercial name	[wt-%]
Cycloaliphatic epoxide	Uvacure® 1500	69.45
Oxetane	Curalite™Çrx.	15.05
Antifoam agent	TEGO® AIREX 900 (Evonik)	0.30 .
Surfactant	BYK®-330	0.50
Matting agent	ACEMATT® TS 100	5.25
Solvent	n-butanol	3.00
Cationic photoinitiator	Speedcure 992	6.45

The standard cationic protective vamish described in Table 2C was applied to a piece of 5 fiduciary polymer substrate (Guardian™ by CCL Secure) using a hand-coater unit with a n°0 bar (RK-print) to form a vamish layer having a size of approximately 5 cm x 10 cm and a thickness of about 4pm. The vamish layer was cured at controlled relative humidity by exposing said vamish layer two times at a speed of 100 m/min to UV-Vis light under a mercury lamp unit (IST Metz GmbH; two lamps: iron-doped mercury lamp + mercury lamp), generating the comparison 10 standards

ST1-ST4.

Aller storage in the dark for 24 h, the curing of each independent comparison standard STI - ST4 was evaluated using the MEK rub test described at item A3 above. The comparison 15 standards STI - ST4 showed an optimal curing. .......

Table 2D displays the absolute intensity at maximum fluorescence of the protective coatings obtained from the vamishes El - E5, C2, C4, C6, C8, C9 and the absolute intensity at maximum fluorescence (in photons/sec.) of the corresponding comparison standards (STI — 20 ST4), as well as the ratio between the absolute intensity at maximum fluorescence of each of the protective coatings and the absolute intensity at maximum fluorescence of the corresponding comparison standard STI - ST4 {relative fluorescence value).

Table 2D. Results of the fluorescence measurements

Varnish		^E1	E2	E3	E4	E5	C2	C4	C6	C8	C9
Comparison standard		STI	ST2	STI	STi	STI	STI	ST3	ST4	ST4	ST3
Fluorescence @366nm [photons/sec]	Comparison standard	3.5E+05	3.9E+05	3.5E+05	3.5E+05	3.5E+05	3.5E+05	4.6E+05	4.1E+05	4.1E+05	4.6E+05
Protective coating	3.2E+05	3.0E+05	4.2E+05	4.7E+05	4.7E+05	6.1E+05	8.7E+05	4.3E+05	9.6E+05	3.3E+06 ! . '
Relative fluorescence value	0.9	0.8	1.2	1.3	1.3	1.7	1.9	1.1	2.4	7.2
Fluorescence @254nm [photons/sec]	Comparison standard	2.9E+05	3.0E+05	2.9E+05	2.9E+05	2.9E+05	2.9E+05	4.2E+05	4.2E+05	4.2E+05	4.2E+05
Protective coating	3.7E+05	3.2E+05	4.4E+05	4.5E+05	4.2E+05	5.0E+05	2.5E+06	8.5E+05	1.6E+06	5.0E+06
Relative fluorescence value	1.3	1.1	1.5	1.6	1.5	1.7	6.0	2.0	3.8	11.9

The fluorescence of the protective coatings obtained from the cationic UV-LED radiation curable protective vamishes El - E5 according to the présent invention and comparative 5 vamishes C2, C4, C6, C8 and C9 was also visually assessed using a CAMAG UV Cabinet 4 (equipped with two UV tubes at 254 nm and 366 nm, 8 W each). The visual perception was correlated with the measured relative fluorescence value determined as described above. Table 2E summarizes the corrélations between the visual perception and the measured relative fluorescence value.

Table 2E

Relative fluorescence value at 254/366nm	Visual perception
< 1.3	Low fluorescence, close to comparison standard
1.3-1.6	Acceptable fluorescence
>1.6	Too high fluorescence

Protective vamishes are usually applied on the whole surface and on both sides of the security document. Hence, protective coatings exhibiting a relative fluorescence higher than 1.6 (compared to the comparison standards STI - ST4) tend to make the visual observation and/or machine readability of luminescent security features présent in said security document diffîcult or even impossible.

As shown by the experiments conducted with the protective vamishes E1-E5 according to the 5 présent invention, cationic UV-LED radiation curable protective vamishes comprising a photosensitizer of general formula (I) and a concentration of 2-keto-thioxanthone moiety from about 1.3 mmol to about 4.7 mmol per 100g of protective vamish, exhibit both an optimal curing performance and a low to acceptable fluorescence both at 254 nm and 366 nm. Cationic UVLED radiation curable protective vamishes comprising a photosensitizer of general formula (I), 10 but a concentration of 2-keto-thioxanthone moiety lower than about 1.3 mmol per 100g of protective vamish, such as comparative vamish Cl, show a poor curing performance. Cationic UV-LED radiation curable protective vamishes comprising a photosensitizer of general formula (I), but a concentration of 2-keto-thioxanthone moiety higher than 4.7 mmol per 100g of protective vamish, such as comparative vamish C2, hâve a good curing performance, but yield 15 protective coatings exhibiting a too high fluorescence.

As shown by the experiments conducted with the comparative vamishes C3, C5 and C7, vamishes containing a thioxanthone containing photosensitizer other than a photosensitizer of general formula (I) as described herein in low amounts suffer from poor curing properties and 20 resuit in insuffïciently cured coatings using curing conditions suitable for industrial coating processes.

As shown by the experiments conducted with the comparative vamishes C4, C6 and C8, cationic UV-LED radiation curable protective vamish comprising a reactive thioxanthone-based moiety 25 containing photosensitizer other than a photosensitizer of general formula (I), wherein the concentration of the reactive thioxanthone-based moiety is within the claimed range, hâve a good curing performance but generate a protective coating exhibiting too high fluorescence, particularly at 254nm.

As shown by the experiments conducted with the comparative vamish C9, a cationic UV-LED radiation curable protective vamish comprising an sulfonium photoinitiator instead of a diaryl iodonium photoinitiator and 9, 10-dibutoxyanthracene as photosensitizer hâve a good curing performance, but yield protective coatings showing extremely high fluorescence.

L

Cationic UV-LED radiation curable protective vamishes exhibiting a too high fluorescence, particularly a relative fluorescence value higher than about 1.6 as measured hereabove, are not suitable to be applied on security documents, since they render the machine detectability of underlying luminescent security features présent on said security documents difficult or even 5 impossible.

Claims

1-8, wherein the diaryl iodonium sait is of general formula (II)

R³ (II) wherein

15 R¹ - R¹⁰ are independently of each other selected from hydrogen, a Ci-Cis-alkyl group, and Ci-Ci2-alkyloxy group; and

An’ is an anion selected from BFU, B(C6Fs)4^-, PFô^-, AsFô~, SbFô^-, CF₃SO₃“, (CH₃C6H4)SO₃“, (C4F₉)SO₃-, (CF₃)CO₂“, (C4F₉)CO₂·, and (CF₃SO₂)₃C-,

1-7, wherein the concentration of the moiety

O O

in the cationic UV-LED curable protective vamish is from about 1.6 mmol to about 2.9 mmol per 100 g cationic UV-LED curable protective vamish.

1-6, wherein

C represents

wherein A³ and n3 hâve the meanings defined in claim 1, and -L³- has the meaning as defined in any one of claims 1-3.

5

1. A cationic UV-LED radiation curable protective vamish comprising:

2. The cationic UV-LED radiation curable protective vamish according to claim 1, wherein

-L¹- represents

and -L²-, -L³-, -L⁴-, -L⁵- and -L⁶represent

3. The cationic UV-LED radiation curable protective vamish according to claim 1, wherein

-L¹- represents represent

and -L²-, -L³-, -L⁴-, -L⁵- and -L⁶-

4. The cationic UV-LED radiation curable protective vamish according to any one of the claims 1-3, wherein the photosensitizer is ôf general formula (I-a)

C

(I-a) wherein

A¹, A², C, ni and n2 hâve the meanings defïned in daim 1, and

-L¹- and -L²- hâve the meanings as defïned in any one of daims 1-3.

5 5. The cationic UV-LED radiation curable protective vamish according to any one of the daims 1-3, wherein the photosensitizer is of general formula (I-b)

(I-b) wherein

5 protective vamish.

5 and n3, n4, n5 and n6 are integers higher than or equal to 0, wherein the sum nl+n2+n3 is comprised between 3 and 12;

the sum nl+n2+n3+n4 is comprised between 4 and 16;

the sum nl+n2+n3+n4+n6 is comprised between 5 and 15;

the sum nl+n2+n3+n5 is comprised between 4 and 16;

5 a) from about 65 wt-% to about 90 wt-% of either a cycloaliphatic epoxide, or a mixture of a cycloaliphatic epoxide and one or more cationically curable monomers other than the cycloaliphatic epoxide;

b) from about 1 wt-% to about 10 wt-%, preferably from about 2 wt-% to about 5 wt-%, more preferably about 3 wt-% of a diaryl iodonium sait;

6 The cationic UV-LED radiation curable protective vamish according to any one of the 15 daims 1-3, wherein the photosensitizer is of general formula (I-c)

(I-c) wherein

A¹, A², A⁵, C, ni, n2 and n5 hâve the meanings defïned in daim 1, and

20 -L¹-, -L²- and -L⁵- hâve the meanings as defïned in any one of daims 1-3.

7 . The cationic UV-LED radiation curable protective vamish according to any one of daims

8. The cationic UV-LED radiation curable protective vamish according to any one of claims

9. The cationic UV-LED radiation curable protective vamish according to any one of claims

10. The cationic UV-LED radiation curable protective vamish according to any one of the claims 1-9, wherein the one or more cationically curable monomers other than the cycloaliphatic epoxide are selected from the group consisting of: vinyl ethers, propenyl ethers, cyclic ethers other than a cycloaliphatic epoxide, lactones, cyclic thioethers, vinyl thioethers, propenyl thioethers, hydroxyl-containing compounds, and mixtures thereof.

10 A¹, A², C, ni and n2 hâve the meanings defïned in daim 1, and

-L¹- and -L²- hâve the meanings as defïned in any one of daims 1-3.

10 the sum nl+n2+n3+n4+n5 is comprised between 5 and 15;

the sum nl+n2+n3+n4+n5+n6 is comprised between 6 and 18;

wherein the cationic UV-LED radiation curable protective varnish comprises a concentration of the moiety

présent in the photosensitizer of general formula (I) from about 1.3 mmol to about 4.7 mmol of said moiety per 100 g of cationic UV-LED radiation curable protective vamish;

the weight percents being based pn the total weight of the cationic UV-LED radiation curable

10 c) from about 0.01 wt-% to about 5 wt-% of a non-ionic surfactant; and

d) a photo sensitizer of general formula (I)

(I) .

wherein in the general formula (I)

15 A¹ and A² are independently of each other selected from hydrogen and a moiety of the following structure:

O O

-L²- is selected from

and either and ni and n2 are integers higher than or equal to 0;

m represents 0;

B represent hydrogen;

C is selected from hydrogen.

A³ and n3

A⁴

O

A³

O

-L³- and -L⁴- are independently of each other selected from

and .0 and n3, and n4 are integers higher than or equal to 0, wherein the sum nl+n2 is comprised between 2 and 8;

15 or m represents 1;

L

A³, À⁴, A⁵ and A^{6 * * * 10} are independently of each other selected from hydrogen and a moiety of the following structure:

-L³-, -L⁴-, -L⁵- and -L⁶- are independently of each other selected from

11. The cationic UV-LED radiation curable protective vamish according to any one of the daims 1 - 10, wherein the vamish is selected from a flexography printing vamish, an inkjet printing vamish, and a screen printing vamish. .

12. A process for coating a security document comprising a substrate and one or more security features applied on or inserted into a portion of the substrate, wherein said process comprises the following steps:

i) applying, preferably by a printing method selected from inkjet printing, flexography 15 printing, and screen printing, the cationic UV-LED radiation curable protective vamish according to any one of the daims 1 - 11 on a surface of the substrate and/or a surface of the one or more security features of the security document so as to form a vamish layer; and ii) curing the vamish layer by exposure to UV light emitted by a UV-LED source so as to form a protective coating covering the surface of the substrate and/or the surface of the one or 20 more security features of the security document.

13. A security document comprising a substrate, one or more security features applied on or inserted into a portion of the substrate, and a protective coating covering a surface of the 25 substrate and/or a surface of the one or more security features of the security document, wherein the protective coating is obtained by the process according to claim 12.

14. The security document according to claim 13, wherein the security document is selected 30 from banknotes, deeds, tickets, checks, vouchers, fiscal stamps, tax labels, agreements, and identity documents, such as passports, identity cards, visas, bank cards, crédit cards, transaction cards, access documents, and entrance tickets.