OA17326A - Protective coatings for security documents. - Google Patents
Protective coatings for security documents. Download PDFInfo
- Publication number
- OA17326A OA17326A OA1201500143 OA17326A OA 17326 A OA17326 A OA 17326A OA 1201500143 OA1201500143 OA 1201500143 OA 17326 A OA17326 A OA 17326A
- Authority
- OA
- OAPI
- Prior art keywords
- radiation curable
- protective
- curable protective
- compounds
- radiation
- Prior art date
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- 239000011253 protective coating Substances 0.000 title claims abstract description 4
- 230000001681 protective Effects 0.000 claims abstract description 107
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 25
- 239000011241 protective layer Substances 0.000 claims abstract description 7
- 239000002689 soil Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 52
- 239000000758 substrate Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
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- 238000000034 method Methods 0.000 claims description 13
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical class [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to the field of the protection of security documents, in particular banknotes, against premature detrimental influence of soil and/or moisture upon use and time. In particular, it relates radiation curable protective varnishes comprising one or more cationically curable compounds and one or more di-hydroxyl-terminated perfluoropolyether compounds of the general formula H0(CH2CH20)c-CH2-CF20-(CF2-CF2-0)a-(CF20)bCF2-CH2-(0CH2CH2)dOH, wherein a and b independently are integers in a range between 0 and 50, wherein a + b > 1, and wherein c and d may be the same or different and are in the range of 1-20, and their uses for providing a protective coating or layer on a security document.
Description
Protectlve coatlnqs for security documents
FIELD OF THE INVENTION [001] The présent Invention relates to the field of the protection of security documents, In particular banknotes, agalnst prématuré detrlmental influence of sol! and/or molsture upon use and time.
BACKGROUND OF THE INVENTION [002] With the constantly improving quality of color photocopies and printlngs and In an attempt to protect security documents such as banknotes, value documents or cards, transportation tickets or cards, tax banderais, and product labels agalnst counterfelting, falslfylng or Illégal reproduction, It has been the conventional practice to incorporate various security means In these documente. Typlcal examples of security means Include security threads or stripes, Windows, fibers, planchettes, foils, decals, holograms, watermarks, security Inks comprislng optically variable pigments, magnetic or magnetizable thin film Interférence pigmente, Interferon ce-coated particles, thermochromie pigments, photochromie pigments, luminescent, Infrared-absorbîng, ultravlolet-absorblng or magnetic compounds.
[003] Solling materials like molsture or any dirt are known to affect not only the appearance but also the mechanical performance and thus the llfetime of security documente and in particular banknotes. Indeed, solling remains the main reason for classifying banknotes as unfit for circulation thus leading to the extraction and destruction of soiled banknotes from circulation. In addition to molsture and dirt, sébum (oily sécrétion consisting of fat, keratln and cellular materials), as for example squalene (common lipld produced by human skln cells) and proteins are an Important source of contamination and solling component of security documents, In particular banknotes. Indeed, due to the Interaction with human fingers, fingerprint deposits accumula te on the surface of the security document and form a layer of aged soil.
[004] It has been a practice to protect security documente with vamlshes. With the alm of Increasing Ote durability and cleanllness and thus the circulation llfetime of security documents, In particular banknotes, it has been a conventional practice to protect the security document agalnst soillng, espedally molsture and dirt, with a protective vamish so as to provide a protective vamlshed document In addition to the Increased durability of the document Itself, protecting the surface of a banknote simultaneously Incroases the durability and résistance of overt (Le. visible to the unalded human eye) and covert (i.e. visible or détectable
I only with the help of an Instrument) security features.
[005] Protective vamishes consist of layer(s) or coating(s) faclng the environment of the document The protective vamish may consist of waterbased vamishes or UV-curable vamishes. Information about the vamlshing of 5 banknotes can for Instance be found In the followtng papers:
Tom Buitelaar, De Nederiandsche Bank NV, Amsterdam, the Netherlands, Effects of Banknote vamlshing, Currency Conférence CSI, Sydney 1999;
Hans A. M. de Heij, De Nederiandsche Bank NV, Amsterdam, the Netherlands, The design methodology of Dutch banknotes, IS&T/SPIEs 12m International
Symposium on Electronlc Imaging, Optical Security and Counterfeit Deterrence Techniques III, San José, Calif., USA (Jan. 27-28,2000), Proceedlngs of SPIE vol. 3973, pp. 2-22;
Frank Wettsteln, Cash Division, Swiss National Bank, Berne and Hubert Ueb, Environmental Unit Swiss National Bank, Zurich, Life cycle assessment (LCA) 15 of Swiss banknotes, Quarteriy Bulletin 3/2000 of the Swiss National Bank,
September 2000;
Tom Buitelaar, De Nederiandsche Bank NV, Amsterdam, the Netherlands, Circulation Fitness Management, Banknote 2003 Conférence, Washington D.C., Feb. 3,2003;
Bank of England Tests Durability In Circulation Trials, Currency News, March 2012, Vol. 10, No 3, pp. 5.
[006] EP-B O 256 170 discloses a paper currency printed with ink and coated with a protective layer, wherein the ink contains 1-10 wt-% of mlcronized wax and the protective coating consiste for a major part of cellulose ester or ether.
[007] US 2002/0127339 discloses a method for ftnlshlng valuable printed paper sheets, sald method consisting of partly or entirely covering the sheets with a vamish used for Increaslng the durability of said sheets.
[008] WO 2002/094577 discloses a long-lived security paper comprising a security element and a protective layer with a mat surface which is recessed in 30 the région of the security element The disdosed security paper comprises recessed areas which may be provided with a protective lacquered layer made of brilliant vamish.
[009] US 2007/0017647 disdoses a security paper having a fiat substrate provided at least partly with a dirt-repellent protective layer for extending the life 35 time and fitness for drculation. The dlsclosed protective layer comprises at least two lacquer layers, a first lower lacquer layer being formed by a physically drylng lacquer layer applied to the substrats and a second upper lacquer layer which protects the substrate from physlcal and chemlcal Influences.
[010] WO 2006/021856 discloses a method for protectlng banknotes and securlty papers from prématuré wear due to the handllng that they undergo, and thus prolonglng thelr lifetime. The dlsdosed method comprises a lacquering step which consiste in deposlting a protective layer on the surface of the securlty document [011] WO 2008/054581 discloses a soit and/or moisture résistant secure document and a method for produclng such a secure document The dlsclosed 10 method employs a slze press or other similar device to force a soit and/or moisture résistant formulation Info the pores of the substrate and to remove excess formulation from opposlng surfaces thereof.
[012] EP-B1 932 678 discloses a method for applying a protectlng layer of parylene on security documents, In particular banknotes so as to Increase thelr 15 résistance to soiling, wetting and mechanlcal damage.
[013] Whereas protective vamlshes may comprise surface addltives such as for example polymerizable compounds or polymeric additives conslsting of siloxane or silicone-contalning compounds to further Increase anti-solling properties of security documents, In particular banknotes, comprising said vamlshes, the 20 protective vamlshes that are commonly used may suffer from a poor oil, fat or grease and waterrepellency thus reduclng the durability and circulation lifetime of the security document [014] A need remalns for providlng a hlgh quallty protective vamish exhlblting, 25 when applied to a security document, In particular a banknote, an Increased performance in circulation, in particular increased soit release characteristics and an increased résistance agalnst prématuré detrimental influence of soit upon use and time by increaslng oil, fat or grease and moisture/water repellency.
SUMMARY [015] It has been surprislngly found that the above mentioned problems can be overcome by radiation curable protective vamishes comprising one or more cationically curable compounds and one or more dl-hydroxyt-terminated perfluoropolyether compounds of the general formula HO-(CH2CH2O)c-CHr CFiO-CCFi-CFrOMCFîOX-CFrCHHOCHiCHîVOH wherein a and b Independently are Integers In a range between 0 and 50, wherein a+ b 21, and wherein c and d may be the same or different and are In the range of 1-20.
[016] Also described and dalmed thereln are security documents comprising a 5 substrate and a radiation cured coatlng made of the radiation curable protective vamlsh described hereln.
[017] Also described and clalmed thereln are processes for maklng a security document and security documents obtained thereof. The processes comprise a) a step of applying on a substrate the radiation curable protective vamlsh 10 described hereln so as to forrn a wet coatlng and b) a step of radiation curing said radiation curable protective vamlsh so as to form a radiation cured coating.
[018] Also described and clalmed therein are uses of the one or more dlhydroxyl-terminated perfluoropolyether compounds described hereln for the manufacture of a radiation curable protective vamlsh described hereln, and 15 methods for Imparting soit résistance to a security document comprising a substrate, said method comprising a step of applying the radiation curable protective vamlsh described hereln onto said substrate and radiation curing said radiation curable protective vamlsh.
[019] The radiation curable protective vamishes according to the présent 20 Invention and security documents -comprising said vamishes exhlblt a combination of Improved anti-soillng characteristics, in particular water/molsture, and/or oîl, fat or grease repellency, Improved anti-soillng performance upon use, time and exposure to environment and Improved anti-fingerprint properties.
PETAI LEP DESCRIPTION [020] The followlng définitions are to be used to interpret the meanlng of the terms discussed In the description and redted In the daims.
[021] As used hereln, the artide ”a” Indicates one as well as more than one and does not necessarily limit its réfèrent noun to the singular.
[022] As used hereln, the term about means that the amount or value In question may be the value designated or some other value about the same. The phrase Is Intended to convey that slmilar values withln a range of ±5% of the indlcated value promote équivalent results or effects according to the Invention. [023] As used hereln, 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 shall mean only A, or only B, or both A and B’.
[024] As used herein, the term protective vamlsh refera to any type of vamîsh, coating or llke protective matériel that may be applied onto the surface of a printed document by a printlng or coating process and Is capable of protectlng sald document agalnst solling by providing anti-solllng characteristics, in 5 particular water/molsture, and/or οΠ, fat or grease repellency, Improved antisoiling performance upon use, time and exposure to environment and improved anti-fingerprint properties.
[025] The term composition· refera to any composition whlch is capable of formlng a coating or a layer on a solld substrate and whlch can be applied 10 preferentially but not excluslvely by a printing method.
[026] The term “curing or curable refera to processes Including the drylng or solldifylng, reacting or polymerizatlon of the applied composition or protective vamlsh In such a manner that It can no longer be removed from the surface onto whlch It Is applied. Examples of curing mechanlsms comprise physlcal curing 15 (e.g. removal of volatile components such as solvents by heating) and chemical curing (e.g. cross-llnklng of prepolymera).
[027] Described herein are radiation curable protective vamlshes comprising one or more cationlcally curable compounds and one or more di-hydroxyl· 20 terminated perfluoropolyether compounds of the general formula HO(CH2CH20)c-CH2-CF20-{CFrCF2-O).-(CF20)b-CF2-CH2-(0CH2CH2)<rOH, whereln a and b Independentiy are Integera In a range between 0 and 50, whereln a + b a 1, and whereln c and d may be the same or different and are In the range of 1-20, preferably 1-10, and more preferably 1-6. Protective vamlshes are prepared 25 from compositions in the form of a liquid or pasty state whlch is capable of formlng a layer or a coating on a solid substrate affer curing and/or hardenlng. The radiation curable protective vamlshes described herein are particularly suitable for protecting security documents, In particular banknotes, agalnst prématuré detrimental influence of soil and/or molsture upon use and time.
[028] Radiation curable protective vamishes may be cured by UV-visible llght radiation (hereafter referred as UV-Vls-curable) or by électron beam radiation (hereafter referred as EB). Radiation curing advantageously leads to very fast curing processes and hence drastically decreases the préparation time of security documents comprising radiation cured protective vamishes. Radiation 35 curable compositions are known in the art and can be found In standard textbooks such as the sériés Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, published In 7 volumes In 1997-1998 by John Wiley & Sons In association with SITA Technology Llmited.
[029] Preferably, the radiation curable protective vamishes according to the présent Invention are UV-Vis light curable protective vamishes (hereafter referred 5 as UV-Vis curable protective vamishes). The radiation curable protective vamishes described herein comprise one or more cationlcally curable compounds. Cationlcally curable compounds are cured by cationlc mechanisms consisting of the activation by energy of one or more photolnitiators which liberate cationlc specles, such as acids, which In tum initiate the polymerization 10 of the compound so as to form a blnder. Preferably, the one or more cationlcally curable compounds are présent In the radiation curable protective vamish In an amount from about 70 to about 90 wt-%, the welght percents belng based on the total welght of the radiation curable protective vamish.
[030] Preferably, the one or more cationlcally curable compounds are selected 15 from the group consisting of vinyl ethers, propenyl et h ers, cyclic ethers such as epoxldes, oxetanes, tetrahydrofuranes, lactones, cyclic thiœthers, vinyl and propenyl thiœthers, hydroxyl-contalnlng compounds and mixtures thereof, preferably cationlcally curable compounds selected from the group consisting of vlnyt ethers, propenyl ethers, cyclic ethers such as epoxldes, oxetanes, 20 tetrahydrofuranes, lactones and mixtures thereof.
[031] Typical examples of epoxldes Include without limitation glycldyl ethers, βmethyl glyddyl ethers of aliphatic or cycloaliphatic dlols or polyols, glyddyl ethers of diphenols and polyphenols, glycldyl esters of polyhydric phénols, 1,4butanediol digtycldyl ethers of phenolformaldehyde (e.g. novolak), resordnol 25 digfycidyl ethers, alkyl glyddyl ethers, glycldyl ethers comprising copolymers of acryllc esters (e.g. styrene-glycldyl méthacrylate or methyl methacrylate-glyddyl acrylate), polyfunctlonal liquld and solld novolak glyddyl ethers resins, polyglyddyt ethers and poly([J-methylglyddyl) ethers, poly(N-glyddyl) compounds, poly(S-glyddyl) compounds, epoxy resins In which the glyddyl 3 0 groupe or β-methyl glyddyl groupe are bonded to hetero atoms of different types, glyddyl esters of carboxyllc acids and polycarboxylic acids, limonene monoxide, epoxidized soybean oil, blsphenol-A and bisphenol-F epoxy resins. Examples of • suitable epoxldes are disdosed, for example, In EP-B 2 125 713. Methods for preparing epoxldes are well-known In the art and do not hâve to be dîscussed 35 hère In detail.
[032] Suitable examples of aromatic, allphatlc or cycloaüphatic vinyl ethers Include wfthout limitation compounds having at least one, preferably at least two, vlnyl ether groupe in the molécule. Examples of preferred vlnyt ethers Include wlthout limitation trlethylene glycol dlvlnyl ether, 1,4-cyclohexanedlmethanol 5 dlvlnyl ether, 4-hydnoxybutyl vlnyl ether, propenyl ether of propylene carbonate, dodecyl vlnyl ether, tert-butyl vlnyl ether, tert-amyl vlnyl ether, cydohexyl vinyl ether, 2-ethylhexyl vlnyl ether, ethyfene glycol monovinyl ether, butanedlol monovinyl ether, hexanediol monovinyl ether, 1,4-cyclohexanedlmethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol dlvlnyl ether, 10 ethylene glycol butyMnyt ether, butane-1,4-diol dlvlnyl ether, hexanediol dîvlnyl ether, diethylene glycol dlvlnyl ether, trlethylene glycol dlvlnyl ether, trlethylene glycol methylvlnyl ether, tetraethylene glycol dlvlnyl ether, pluriol-E-200 dlvlnyl ether (from BASF), polytetrahydrofuran dlvlnyl ether-290, trlmethylolpropane trivlnyl ether, dipropyfene glycol dlvlnyl ether, octadecyl vlnyl ether, (4-cyclohexyl15 methy!eneoxyethene)-glutarlc acid methyl ester and (4-butoxyethene)-lsophthalic acid ester. Methods for preparing vlnyl ethers are well-known In the art and do not hâve to be dlscussed hère In detail.
[033] Examples of hydroxy-containfng compounds include wlthout limitation polyester polyois such as for example polycaprolactones or polyester adipate 20 polyois, glycols and polyether polyois, castor oïl. hydroxy-functional vinyl and acryflc reslns, cellulose esters, such as cellulose acetate butyrate, and phenoxy reslns. Further examples of suitable catlonlcally curable compounds are disclosed in EP-B 2 125 713 and EP-B 0 119 425. Methods for preparing hydroxyl-contalnlng compounds are well-known In the art and do not hâve to be 25 discussed hère In detail.
[034] Altematively, the binder of the radiation curable protective vamishes described herein is a hybrid binder and may be prepared from a mixture of one or more cationically curable compounds and one or more radically curable compounds, wherein the one or more cationically curable compounds are 30 preferably présent In the mixture In an amount from about 85 to about 95 wt-% and the one or more radically curable compounds are preferably présent In the mixture in an amount from about 5 to about 15 wt-%, the weight percents belng based on the total weight of the mixture of the one or more cationically curable compounds and the one or more radically curable compounds. Preferably, the 35 one or more cationically curable compounds and the one or more radically curable compounds are présent in the radiation curable protective vamish In an amount from about 70 to about 90 wt-%, the welghtpercents being based on the total welght of the radiation curable protective vamlsh.
[035] Radically curable compounds to be used in such a hybrid blnder of the présent Invention are cured by free radical mechanlsms conslsting of the 5 activation by energy of one or more photoinitiators which libéra te free radlcals which in tum initiate the polymerization so as to form the binder. Preferably, the radically curable compounds are selected from (methjacrylates, preferably selected from the group conslsting of epoxy (methjacrylates, (meth)acrylated olls, polyester and polyether (methjacrylates, allphatic or aromatic urethane 10 (methjacrylates, silicone (methjacrylates, acrylic (methjacrylates and mixtures thereof. The term (methjacrylate In the context of the présent Invention refera to the acrylate as well as the correspondlng méthacrylate. The blnder of the radiation curable protective vamlshes described herein may be prepared with addltlonal vlnyl ethers and/or mon orne rie acrylates, thelr ethoxyfated équivalents 15 and mixtures thereof. Sultable monomeric acrylates may be selected from the group conslsting of 2(2-ethoxyethoxy)ethyl (methjacrylate, 2-phenoxyethyl (methjacrylate, C12/C14 alkyl (methjacrylate, C16/C18 alkyl (methjacrylate, caprolactone (methjacrylate, cydic trimethylolpropane formai acrylate, ethoxyfated nonylphenol acrylate, isobomy! (methjacrylate, isodecyl acrylate, 20 lauryl (methjacrylate, stearyl (methjacrylate, octyldecyl (methjacrylate. tridecyl (methjacrylate, methoxy poly(ethylene glycolj (methjacrylate, polypropylene glycol (methjacrylate, tetrahydroforfuryl (methjacrylate, 1,3-butylene glycol di(methjacry1ate, 1,4-butanedlol dl(methjacry1ate, 1,6-hexanediol di(methjacrylate, alkoxylated dl(meth)acrylate, esterdiol dlacrylate, ethoxyfated 25 blsphenol A dl(methjacrylate, ethylene glycol dlfmethjacrylate, dlethyfene glycol dl(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol dl(methjacrylate, dipropyleneglycol di(meth)acry1ate, tripropylene glycol di(methjacrylate, polyethylene glycol di(meth)acryiate, neopentyl glycol dlfmethjacrylate, trfcyclodecane dimethanol dl(methjacrylate, trimethylolpropane 30 tri(meth)acrylate, ethoxyfated trimethylolpropane trifmethjacrylate, ethoxyfated glyceryl tri(methjacry1ate, propoxylated trimethylolpropane trifmethjacrylate, propoxylated glyceryl tritmethjacrylate, pentaerythritol tri(methjacrylate, ethoxyfated pentaerythritol tri- and tetra(methjacrylate, propoxylated pentaerythritol trifmethjacrylate, trimethylolpropane trimethacrytate, tris (235 hydroxy ethylj isocyanurate triacrylate, ditrimethylolpropane tetra(methjacrylate, trimethylolpropane tri(methjacrylate, dlpentaerythritol penta(methjacryfate, pentaerythritol tetra(meth)acrylate, dlpentaerythritol tetra(methjacrylate, dïpentaerythritol penta(meth)acrylate and dïpentaerythritol hexa(meth)acry1ate as well as mixtures thereof. More preferably, the one or more reactive diluents are selected from the group consistlng of 2-phenoxyethyl acrylate, Isodecyl acrylate, 1,4-butanediol di(meth)aarylate, 1,6-hexanedlol dl(meth)acrylate, diethylene 5 glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropyieneglycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glyco! di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and thelr ethoxylated équivalents as well as mixtures thereof. StHI more preferably, the one or more 10 reactive diluents are selected from the group conslsting of trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PTA), tripropyleneglycol diacrylate (TPGDA), dipropyieneglycol diacrylate (DPGDA), 1,6-hexanedlol dlacrylate (HDDA) and mixtures thereof and thelr ethoxylated équivalents (ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate, ethoxylated 15 tripropyleneglycol diacrylate, ethoxylated dipropyieneglycol diacrylate and ethoxylated hexanediol diacrylate). When présent, the monomeric acryiates are preferably présent in an amount from about 5 to about 15 wt-%, the welght percent being based on the total welght of the radiation curable protective varnish. (Meth)acryfates suitable for the présent invention and methods for 20 manufacturing them are well-known In the art Many (methjacrylates are commercially avallable.
[036] UV-Vis eu ring of a monomer, oligomer or prepolymer requlres the presence of one or more photolnltiators and may be achleved in a number of ways. As known by those skilled In the art the one or more photolnltiators are 25 selected according to their absorption spectra and are selected to fit with the émission spectra of the radiation source. Depending on the monomers, oligomers or prepolymers used to prépare the binder comprised In the radiation curable protective vamishes described herein, different photoinitiators mlght be used.
[037] Suitable examples of cationlc photoinitiators are known to those skilled In the art and include without limitation onium salts such as organlc iodonlum salts (e.g. dlaryl lodoinlum salts), oxonium (e.g. triaryfoxonlum salts) and sulphonlum salts (e.g. triarylsulph onium salts).
[038] Suitable examples of free radical photoinitiators are known to those skilled 35 In the art and Include without limitation acetophenones, benzophenones, alphaaminoketones, alpha-hydroxyketones, phosphine oxides and phosphine oxide dérivatives and benzyldimethyl ketals. Other examples of useful photoinitiators can be found In standard textbooks such as Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Volume III, Photoinitiators for Free Radical CaÜonlc and Anlonlc Polymerizatlon’, 2nd édition, by J. V. Crivello & K. Dietliker, edlted by G. Bradley and published In 1998 by John Wiley & Sons In 5 association with SITA Technology Llmlted.
[039] It may also be advantageous to Include a sensitlzer In conjunction with the one or more photoinitiators In order to achleve efficient curing. Suitable examples of photosensitizers are known to those skilled In the art and include wlthout limitation IsopropyMhioxanthone (ITX), 1-chloro-2-propoxy-thloxanthone 10 (CPTX), 2-chloro-thloxanthone (CTX) and 2,4-diethyl-thioxanthone (DETX) and mixtures thereof. Altematively, the photosensitizers described herein may be used In an ollgomeric or polymeric form. When présent, the one or more photosensitizers are preferably présent In an amount from about 0.1 to about 15 wt-%, more preferably about 0.5 to about 5 wt-%, the welght percents belng 15 based on the total welght of the radiation curable protective vamlshes.
[040] The one or more photoinitiators comprised In the radiation curable protective vamlshes are preferably présent In an amount from about 0.1 to about 20 wt-%, more preferably about 1 to about 15 wt-%, the welght percents belng based on the total welght of the radiation curable protective vamlshes.
[041] Altematively, dual-cure compositions may be used as blnders of the vamish of the présent Invention; these compositions combine thermal drying and radiation curing mechanisms. Typically, such compositions are similar to radiation curing compositions but indude a volatile part constituted by water or by a solvent These volatile constituents are evaporated first uslng hot air or IR 25 driers, and UV drying 1s then applied for completing the hardenlng process.
Suitable dual-cure composition are known In the art and do not hâve to be described In detail here.
[042] The radiation curable protective vamish according to the présent invention comprises as essential component one or more di-hydroxyl-termlnated 30 perfluoropolyether compounds of the general formula HO-tCHîCH^X-CHr
CFîO-fCFz-CFî-OK-tCFaOJb-CFrCHriOCHîCHïi.rOH, wherein a and b Independently are Integers in a range between 0 and 50, wherein a + b 2 1, and wherein c and d may be the same or different and are In the range of 1-20, preferably 1-10, and more preferably 1-6. The one or more dFhydroxyl35 terminated perfluoropolyether compounds described herein are preferably comprised in the radiation curable protective vamish according to the présent invention In an amount from about 0.1 to about 5 wt-%, more preferably In an amount from about 0.5 to about 4 wt-%, the weight percent being based on the total weight of the radiation curable protective varnlsh.
According to a preferred embodlment of the présent Invention, the one or more dl-hydroxyktermlnated perfluoropolyether compounds are selected from the group of compounds of the above formula, wherein a + b 2 2, and Independently are Integers In a range between 1 and 50, and wherein c and d may be the same or different and are in the range of 1-20, preferably 1-10, and more preferably 16. Those dl-hydroxyl-termlnated perfluoropolyether compounds are commerclally available under the trademark Fluorollnk® E10 or E10-H from SOLVAY Solexis, Italy. The di-hydrcxykterminated perfluoropolyether compounds used in the présent Invention may be prepared from a perfluoropolyether dlmethylester precursor, which may be obtalned by methods known in the art, e.g. as described In US-3,847,978, In paiflcular col. 11, example D, and col. 17, example 11. Sald perfluoropolyether dlmethylester precursor may be reduced to the correspondlng dlmethylol precursor by methods known In the art, e.g. as described In US3,972,856, col. 4. The thus obtalnable dlmethylol precursor may be alkoxylated by methods known In the art, e.g. as described in US-4,775,653, and US5,057,628. According to the scheme described in e.g. those documents, which are expllcitiy Incorporated by référencé, the compounds suitable for the présent Invention may be prepared.
[043] The one or more dihydroxyMerminated perfluoropolyether compounds described hereln, hâve a weight average molecular weight (Mw) between about 100 and about 5000, more preferably between about 500 and about 3000. Unless stated otherwise, weight average molecular weight Is determlned by gel perméation chromatography (GPC).
[044] The one or more di-hydroxyHerminated perfluoropolyether compounds described hereln hâve preferably a fluorine content In a range from about 50 to about 70 wt-%, more preferably from about 55 to about 65 wt-%, the weight percent being based on the total weight of the one or more dihydroxyl-termlnated perfluoropolyether compounds.
[045] Although most of the above dkhydroxyl-terminated perfluoropolyether compounds described hereln are In llquld form, one or more solvents may be added to the radiation curable protective varnlshes to fadlitate the mlxing or dlsperslng of sald compounds in the varnlsh. Suitable solvents Include without limitation éthanol, propanol, isopropanol, butanol, isobutanol, glycols, glycol ether (such as for example 1-methoxy-2-propanol (propylene glycol methyl ether) or dipropylene glycol (mono)methyt ether), tetrahydrofuran, toluene, hexane, cydohexane, heptane, methylene chloride and/or mixtures thereof. When présent, the solvent(s) Is preferably présent In an amount from about 1 to about 10 wt-%, the weight percent belng based on the total weight of the radiation curable protective vamlsh.
[046] The radiation curable protective vamlshes described herein may be transparent or slightly colored or tinted and may be more or less glossy.
[047] The radiation curable protective vamlshes may further comprise one or more security feature substances, preferably selected from the group consisting of UV, Visible or IR-absorblng materials, luminescent materials, forensic markers, taggants and combinations thereof. Suitable examples of such security feature substances are dlsciosed In U.S. Pat No. 6,200,628.
[048] The radiation curable protective vamlshes described herein may further comprise one or more additives Includlng without limitation compounds and materials which are used for adjusting physlcal, rheologlcal and chemical parameters of the protective vamlsh such as the vlscosity (e.g. solvents and surfactants), the conslstency (e.g. anti-settling agents, fillers and plastidzers), the foaming properties (e.g. antifoamlng agents), the lubricating properties (waxes), UV stability (photostabllizers) and adhesion properties, etc. The radiation curable protective vamlshes described herein may further comprise one or more additives selected from the group consisting of antimicroblal agents, vlrucidal agents, blocidal agents, fungtddes and combinations thereof. Additives described herein may be présent In the radiation curable protective vamlshes dlsciosed herein In amounts and In forms known In the art, Induding In the form of so-called nano-mate riais where at least one of the dimensions of the partides is In the range of 1 to 1000 nm.
[049] Also described herein are radiation curable protective vamlshes comprislng:
a) one or more cationlcally curable compounds, preferably selected from the group consisting of vinyl ethers, propenyl ethers, cyclic ethers and mixtures thereof such as those as described herein, preferably In an amount from about 70 to about 90 wt-%, the weight percents belng based on the total weight of the radiation curable protective vamlsh;
b) the one or more di-hydroxyl-termlnated perfluoropolyether compounds described herein, preferably an amount from about 0.1 to about 5 wt-%, more preferably In an amount from about 0.5 to about 4 wt-%, the weight percent belng based on the total weight of the radiation curable protective vamish;
c) one or more cationic photolnltiators preferably selected from the group conslsting of onium salts, oxonium salts, sulphonlum salts and mixtures thereof, preferably In an amount from about 0.1 to about 20 wt-%, more preferably about 1 to about 15 wt-%, the welght percents belng based on the total welght of the radiation curable protective vamish; and
d) optionally one or more additives such as those described herein.
[050] Also described herein are radiation curable protective vamlshes comprising:
a) a mixture, preferably In an amount from about 70 to about 90 wt-%, the welght percents belng based on the total welght of the radiation curable protective vamish, of one or more cationlcally curable compounds, preferably selected from the group conslsting of vinyl ethers, propenyl ethers, cyclic ethers and mixtures thereof such as those as described herein, and one or more radlcally curable compounds such as those described herein; preferably the one or more cationlcally curable compounds are présent In an amount from about 85 to about 95 wt-% and the one or more radlcally curable compounds are présent in an amount from about 5 to about 15 wt-%, the weight percent belng based on the total welght of the mixture of the one or more cationlcally curable compounds and the one or more radlcally curable compounds;
b) the one or more di-hydroxyl-termlnated perfluoropolyether compounds described herein, preferably an amount from about 0.1 to about 5 wt-%, more preferably in an amount from about 0.5 to about 4 wt-%, the weight percent being based on the total weight of the radiation curable protective vamish;
c) a mixture, preferably In an amount from about 0.1 to about 20 wt-%, more preferably about 1 to about 15 wt-%, the weight percents being based on the total welght of the radiation curable protective vamish, of one or more catlonlc photolnltiators preferably selected from the group conslsting of onium salts, oxonium salts, sulphonlum salts and mixtures thereof and one or more free radical photoinltiators preferably selected from the group conslsting of acetophenones, benzophenones, alpha-amlnoketones, alpha-hydroxyketones, phosphine oxides, phosphine oxide dérivatives, benzyldimethyl ketals and mixtures thereof; and
d) optionally one or more additives such as those described herein.
[051] The radiation curable protectlve vamlshes described herein may be prepared by dlsperslng or mlxlng the one or more dl-hydroxy-terminated perfluoropolyether compounds, the one or more photolnitiators when présent, the 5 one or more additives when présent In the presence of the cationlcally curable compounds and the radically curable compounds when présent The one or more di-hydroxy-terminated perfluoropolyether compounds and the one or more photolnitiators when présent may be added to the mixture elther during the disperslng or mlxlng step of ail other Ingrédients or may be added slmultaneously 10 or in sequence at a later stage, l.e. after the formation of the llquld inks.
[052] The radiation curable protectlve vamlshes described herein are partlculariy sultable for protecting security documents agalnst prématuré detrimental Influence of soit, oll, fat grease and/or molsture/water upon use and time. Security documents are usually protected by several security features 15 whlch are chosen from different technology fields, manufactured by different suppliera, and embodied in different constitutlng parts of the security document Security documents comprise one or more security features. As used herein, the terni ‘security feature refera to any element on a security document for the purpose of determlnlng its authenticity and protecting it agalnst counterfeits. 20 Typlcal examples of security features include without limitation cholesteric liquld crystal polymère and pigments, iridescent pigments, thin-film Interférence pigments, multilayer thin-film Interférence pigments, Interference-Jayer coated particles, holographie films and pigments, thermochromie pigments, photochromie pigments, ultraviolet-absorblng luminescent compounds, Infrared25 absorblng compounds, magnetic compounds, forensic markere and taggants as well as threads, Windows, fibera, planchettes, foils, and decals. To break the protection of the security document, the counterfeiter would need to obtain ali of the Implled materials and to get access to ail of the requlred processlng technology, whlch Is a hardly achlevable task.
[053] Examples of security documents include without limitation value documents and value commercial goods. Typlcal example of value 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, transactions cards, 35 access documents, entrance tickets and the like. The term “value commercial good” refers to packaging material, In particular for pharmaceutical, cosmetics, electronics or food industry that may comprise one or more security features in order to warrant the content of the packaging like for Instance genulne drugs. Example of these packaging material Include without limitation labels such as authentlcatlon brand labels, tamper evidence labels and seals. Preferably, the security document accord In g to the présent Invention Is selected from the group conslsting of banknotes, identlty documents such as passports, identity cards, driving llcenses and the like and more preferably banknotes.
[054] The présent Invention provides security documents, preferably banknotes, compristng a substrate and a radiation cured coating made of the radiation curable protective vamlsh described herein. Preferably, the substrate Is selected from the group conslsting papers or other fibrous materials such as cellulose, paper-contalnlng materials, plastics and polymers, composite materials and mixtures or combinations thereof. Typlcal paper, paper-like or other fibrous materials are made from a varlety of fibers Indudlng without limitation abaca, cotton, linen, wood pulp, and blends thereof. As is well known to those skllled in the art, cotton and cotton/linen blends are preferred for banknotes, while wood pulp is commonly used In non-banknote security documents. Typlcal examples of plastics and polymers include polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides, polyesters such as poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), poly(ethylene 2,6-naphthoate) (PEN) and polyvinylchlorides (PVC). Typlcal examples of composite materials Indude without limitation multilayer structures or lamlnates of paper and at least one plastic or polymer material such as those described hereabove. The radiation curable protective vamlsh described herein Is particulariy sultable for the protection of porous substrates. With the alm of further Increaslng the security level and the résistance against counterfeiüng and Illégal reproduction of security features and security documents, the substrate may contain watermarks, security threads, fibers, planchettes, Windows, folls, decals, coatings and combinations thereof.
[055] The one or more security features of the security document, preferably the banknote, described herein mlght be présent either In the substrate or on the surface of the substrate or a combination of both. When présent on the surface of the substrate, the one or more security features are preferably applled or added by any coating or printing method known In the art indudlng without limitation engraved steel plate (also referred In the art as Intagllo), sllkscreen, offset, letterpress, flexo, gravure, Ink-jet printing, roll-, slit-, spray- and powder coating. For applying a foil or decal, the generaily known methods of heat- or cold-stamplng might be used. Should the security document preferably the banknote, according to tho présent invention comprise one or more security features as described above on the surface of the substrate, the protective va mis h would Increase the durabillty and résistance of those security features. In such as case, the protective vamlsh Is elther In direct contact with one or more security features or in direct contact with the substrate or Is in direct contact with both the one or more security features and the substrate.
[056] The security document according to the présent invention preferably comprises a radiation cured coating made of the radiation curable protective vamish described herein combining a surface energy less than or equal to about 10 25 mN/m, preferably between about 10 and about 25 mN/m, and a dispersive surface energy less than or equal to about 18 mN/m, preferably between about 5 and about 18 mN/m. Surface energles are determlned at 24±1 C and a relative humldity of 50% according to the Owen-Wendt-Rabel-Kaelbe (OWRK) method (Owens D. K. and Wendt R. C., 1969, J. Appl. Polym. Sd. 13,1741) by static 15 angle measurement using the sessile drop method. Surface energles are determlned through contact angle measurements by using delonlsed water, dilodomethane and ethylene glycol as test llqulds. Surface energles are calculated by using the Owen-Wendt-Rabel-Kaelbe (OWRK) theory. Typically, surface energles can be determlned by using Contact Angle Measuring Systems 20 such as those sold by Krüss.
[057] Also described herein are processes for making the security documents, preferably the banknotes, according to the présent Invention and security documents, preferably banknotes, obtalned therefrom. The security documents, preferably the banknotes, according to the présent Invention are prepared from 2 5 sheets or rolls of substrate materials. Downstream the application or Insertion of a background, patterns, designs and/or one or more security features when présent, the radiation curable protective vamlsh described herein Is applled. The application of the radiation curable protective vamlsh might be provided elther befare the numbering process or after the numbering process.
[058] The security document according to the présent invention may be prepared by a process comprising the steps ot
a) applying on the substrate described herein the radiation curable protective vamlsh described herein, preferably the UV-Vis radiation curable protective vamish, so as to form a wet coating, and
b) radiation curing, preferably UV-Vis curing, the radiation curable protective vamish so as to form a radiation cured coating.
[059] Preferably, the applying step a) Is a printing process selected from the group conslsting of screen and flexo printing and more preferably by a printing method selected from the group conslsting of flexo printing so as to ensure a constant protectlve vamlsh thickness.
[060] Typtcal amounts of the radiation curable protectlve vamlsh that are applled to security documents, preferably banknotes, are of the order of 1.5 to 3.0 grams per m2 dry welght preferably from 1.8 to 2.5 grams per m2 dry welght Wherever présent, the radiation cured coating made of the radiation curable protectlve vamlsh described herein has preferably an average thickness below 5 10 μτη (microns) and preferably between about 1 and about 3 pm (microns).
[061] Also described herein are uses of the radiation curable protectlve vamlsh described herein for providing a protectlve coating or layer on a security document such as those described herein.
[062] Also described herein are methods for Impartlng soil résistance to a security document comprising a substrate such as those described herein, sald method comprising the step of applying the radiation curable protectlve vamlsh described herein, preferably by a printing process selected from the group conslsting of screen and flexo printing and more preferably by a printing method selected from the group conslsting of flexo printing onto sald substrate and radiation curing, preferably UV-Vis curing, sald radiation curable protectlve vamlsh.
[063] Screen printing (also referred In the art as silkscreen printing) is a stencil process whereby an ink Is transferred to a surface through a stencil supported by a fine fabric mesh of sllk, syntheüc fibers or métal threads stretched tightly on a 25 frame. The pores of the mesh are block-up In the non-image areas and teft open
In the Image area, the Image carrier belng called the screen. Screen printing mlght be flat-bed or rotary. During printing, the frame Is supplled with the ink which is flooded over the screen and a squeegee Is then drawn across It, thus forcing the Ink through the open pores of the screen. At the same tlme, the 30 surface to be printed Is held in contact with the screen and the Ink is transferred to it Screen printing is further described for example in The Printing ink manuai, R.H. Leach and R.J. Plence, Springer Edition, 581 Edition, pages 58-62 and In Printing Technology, J. M. Adams and PA. Dolln, Delmar Thomson Leamlng, δ1” Edition, pages 293-328.
[064] Flexography preferably uses a unit with a doctor blade, preferably a chambered doctor blade, an anilox relier and plate cyllnder. The anllox roller advantageously has small cells whose volume and/or density détermines the ink application rate. The doctor blade lies against the anilox roller, and scraps off surplus Ink at the same time. The anilox roller transfers the ink to the plate cylinder whlch finally transféra the ink to the substrate. Spécifie design mlght be achleved using a deslgned photopolymer plate. Plate cylindera can be made from polymeric or elastomeric materials. Polymère are mainly used as photopolymer In plates and sometlmes as a seamless coating on a sleeve. Photopolymer plates are made from light-sensltive polymère that are hardened by ultraviolet (UV) light Photopolymer plates are eut to the requlred 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 1s then tumed over, a négative of the job Is mounted over the uncured slde 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 nonlmage areas, whlch lowere the plate surface in these nonlmage areas. After processlng, the plate is dried and given a post-exposure dose of UV light to cure the whole plate. Préparation of plate cylindera for flexography is described In Printing Technology, J. M. Adams and PA Dolin, Delmar Thomson Leamlng, 5lh Edition, pages 359-360.
[065] Due to their hlgh émulsion lifetime, the radiation curable protective vamlshes according to the présent Invention do not requlre any pre-treatment such as an addlttonal mlxlng step, before their application on a security document The radiation curable protective vamishes according to the présent invention are particularly sultable for protectlng security documents thus leading to security documents exhibiting increased anti-soillng properties upon use, Ame and exposure to spécifie conditions such as molsture and dirt of the environment as well as human skin and human sweat/sebum. Indeed, due to the interaction with human fingera, fingerprint deposits accumulate on the surface of the security document and form a layer of aged soit Moreover, the radiation curable protective vamishes according to the présent invention are particularly suitable for Increaslng the anti-soillng characteristics of security documents for use In tropical countries havtng hlgh level of relative humldlty and/or température.
EXAMPLES [066] The présent invention is now described In greater detail with respect to non-limiting examples.
Table 1
| α ξ | 2 rj CO | 3 | CD | * « | «î »· | S | en O | CO | T» s | |||||
| 2 «ο | tn S * | m X CD | m N | <0 ό | tf3 | O | CO s | |||||||
| Ο 5 | 1 | CD N | ® | m | p | m CM | en ό | « <O | 3 CM | |||||
| 8 | | ο r- CD | <n p «ri | ç CO | S | «*? O | « | en | r* S | ||||||
| «1 | ο Ώ | <D N | 4) | «ri | «n | m | c*> c | «n CO | Mt | en CD CM | ||||
| 2 | tn o tri | tn X CD | «n | « ό | «0 | CO | P*w CM | |||||||
| C6 wt-% | Ο b· <D | CD CM | ® | r m | «î | c*» | CO Q | «n CO | b* CM | |||||
| 8 S | 8 cri | m CD | CO | CO ό | 8 «ri | en | 3 CM | |||||||
| Μ | 3 3 | <D | CD | g; m | Uï | «0 ô | CO ό | «η cri | S CM | |||||
| ο îf ° ϊ | m o> <0 | 8 ri | Z m V cri | tf> O | CO a | «n | en | en r— CM | ||||||
| CM <f ο ? | 2 S | CD <N | CO | «ri | Ifl | CO ό | 10 cri | 3 CM | ||||||
| - * U ? | S O r* | 8 «ri | 10 < cri | CO ό | » | en | O 3 | |||||||
| Ingradients _______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________1 | S CS £· fi I I Jf 8 en î i «h s 3 Γ 8. « Sj s -fi «»: •ο 4ί Σ5 8 > S th |ïï. | H s | I O L· 8* s ’ ( ffl “* il | U 2· ç S g 8 >* V * IS H g g h | c 5 a g « € 8 £ 6 8 1 £ E 3 8 € c 3 2 * 1 fi £ B £ E » | g ® -Il fiel 1 s “ 5 S. « | £ 2 g Λ CM è· 1 î 5 δ i « 5» ® | i* î ® CM 8 J | I i a e ί I fil | ! 1 Ιέ. 1 * “ en 1 -2· £. ° 2 S H o m i 8 H | 8 | 1 g. a 8 § £ O t g ? •e U I * 1 « - £ S 8 3 I | o i! 5? I s I 4 g UJ II n p g H | ? X 9 - £ s jj τ I s Mi s ; * b! ui ± * g Q g g m | z g τ * x i Js Q. > ω 1 -g -r c 3 î «s J 1 sΐΗ & : ï, ni SB = îH h *J g g Hî | 8 a B I £ ? 8 | I S M II ! f U = $ ë É fi S si | 8 =| a S I * 1 8 I p h 3 LF 2 1 y g < OO fi fi I fi i | ? 8. e & e | S. e, & I |
[067] 500g of each radiation curable protective vamish C1-C10 and E1-E2 were prepared by first pre-mlxlng the three first Ingrédients of Table 1 and the matting agent (about 15 minutes at 1500 rpm) and then adding the other Ingrédients of Table 1 and mlxlng the so-obtalned mixture (about 10 addltlonal minutes at 1000 rpm). About 24 hours after the mlxlng, vlscoslty was adjusted by adding elther the mattlng agent or the Isopropanol so as to obtaln a vlscoslty between 200 and 300 mPa s. Mlxlng was performed at room température with a 10.0 cm disperslng blade. No température élévation due to friction was notlceable by hand contact with steel mlxlng containers. The viscoslties glven In Table 1 were measured on 9 g of the radiation curable protective vamish C1-C10 and E1-E2 at25°C on a Brookfield machine (model DV-l Prime”, small sample adapter, spindle SC4-21 at 100 rpm).
[068] The radiation curable protective vamlshes were Independently applled to a polymer substrata (Guardlari* supplied by Securency) so as to form a wet coating having a thlckness of 2-3 μπι (microns) by a laboratory pilot flexo prlnting unit (N. Schlâfli Maschlnen) with an anilox (1601/m, 8 cnrp/m2) and a rubber prlnting cylinder of 65-75 Shores.
[069] UV-curing the radiation curable protective vamlshes so as to form a radiation cured coating was performed with an on-llne UV dryer (system VPC-20 supplied by GEW) comprising a standard mercury UV lamp (ref 14957) at a power of 100% (160W/cm) and a conveyor speed of50 m/mln.
[070] The surface energy of the radiation cured protective vamlshes was detemnined from static contact angle measurements with a standard sessile drop arrangement using a Krüss DSA100 instrument Contact angles of water, ethylene glycol and dllodomethane deposlted on the radiation cured coatings were measured to détermine the surface energy. Ail measurements were taken at 24±1C and a relative humldlty of 50%. Contact angles glven In Table 2 having been measured 24 hours after the préparation of the radiation cured protective vamishes and consist of average values of three measurements. Contact angles glven In Table 3 having been measured one month (conditioning conditions: at 20-25’C and a relative humldlty of 50-70%), after the préparation of the radiation cured protective vamishes and consist of average values of three measurements. Contact angles were determlned with a constant drop volume of 3.0 μΙ_ for water and ethylene glycol and 1.5 pL for diiodomethane.
[071] The surface energies were calculated by using the Owen-Wendt-Rabel-Kaelbe (OWRK) theory. The followîng reference values were used for calculations (Contact Angles, Work of Adhesion, and Interfadal Tensions at a Dissolving Hydrocarbon Surface; G.Strôm, M.Frederiksson, P.Stenlus; J. Coll. Interf. Sel. 10,119/2,352-361):
water (72.80 mN/m, dispersive: 21.80 mN/m, polan 51.00 mN/m), ethylene glycol (47.70 mN/m, dispersive: 30.90 mN/m, Polar: 16.80 mN/m), diiodomethane (50.80 mN/m, dispersive: 50.80 mN/m, Polar: 0.00 mN/m.
Table 2: contact angle values and surface energles measured one dav after préparation of the protective vamishes
| Contact angle [*] | Surface anergy rfmN/m] | R2 | |||||
| water | ethylene glycol | diiodomethane | yritoparatv· | γΡθί·Τ | T | (OWRK plot) | |
| et | 67.8 | 37.7 | 33.0 | 39.0 | 7.6 | 46.8 | 0.9438 |
| C2 | 672 | 37.1 | 322 | 39.3 | 7.8 | 47.1 | 0.9425 |
| C3 | 73.7 | 48.6 | 44.3 | 33.9 | 6.5 | 40.4 | 0.9404 |
| C4 | 73.5 | 48.0 | 45,7 | 33.8 | 6.8 | 40.6 | 0.9611 |
| C5 | 97.6 | 80.6 | 70.6 | 202 | 1.8 | 220 | 0.8537 |
| CS | 98.9 | 62.8 | 67.6 | 2t2 | 1.2 | 225 | 0.7275 |
| C7 | 99.7 | 79.8 | 68.3 | 21.8 | 1.1 | 229 | 0.8430 |
| C8 | 972 | 77.7 | 66.6 | 22.8 | 1.5 | 24.1 | 0.8559 |
| C9 | 73.4 | 48.5 | 67.3 | 25.3 | 10.3 | 35.6 | 0.9970 |
| C10 | 74.4 | 47.8 | 67.7 | 23.7 | 10.7 | 34.4 | 0.9987 |
| E1 | 1027 | 85.5 | 89.8 | 12.4 | 27 | 15.1 | 0.9950 |
| E2 | 101.0 | 84.5 | 89.0 | 12.8 | 3.1 | 15.7 | 0.9909 |
Table 3: contact angle values and surface energles measured one month after préparation of the protective vamishes
| Contact angle [’] | Surface energy y(mNhn] | R1 | |||||
| water | ethylene glycol | diiodomethane | parafe» | yPOtaf | T | (OWRK plot) | |
| Cl | 60.0 | 35.3 | 49.1 | 31.3 | 142 | 45.8 | 0.9700 |
| C2 | 61.4 | 402 | 49.7 | 30.4 | 13.8 | 442 | 0.9581 |
| C3 | 67.1 | 522 | 61.9 | 23.9 | 13.5 | 37.4 | 0.9577 |
| C4 | 60.4 | 492 | 592 | 24.4 | 16.9 | 41.3 | 0.9452 |
| C5 | 83.5 | 65.9 | 642 | 23.4 | 5.5 | 28.9 | 0.9393 |
| ce | 90.3 | 68.4 | 65.7 | 23.7 | 3.2 | 26.9 | 0.9619 |
| C7 | 99.6 | 79.6 | 69.8 | 212 | 1.3 | 225 | 0.8782 |
| C8 | 97.3 | 77.9 | 65.8 | 22.9 | 1.4 | 24.3 | 0.8352 |
| C9 | 73.0 | 48.9 | 74.4 | 20.2 | 132 | 33.4 | 0.9996 |
| C10 | 75.5 | 52.0 | 70.8 | 21.7 | 10.8 | 325 | 0.9974 |
| E1 | 1012 | 83.7 | 928 | 11.5 | 3.5 | 15.0 | 1.0000 |
| E2 | 100.7 | 84.7 | 93.7 | 10.9 | 3.9 | 14.8 | 0.9985 |
[072] As expressed by their high contact angles with water, the protective vamishes comprising the ethoxylated fluor-based surfacing agents (E1 and E2) exhibited hlgh repellence agalnst aqueous media, said repellence belng sllghüy better than co-polymerlzable slllconebased agent (C5-C8). Moreover, their repellency toward unpolar media was slgnlflcantly better than any of the other examples provided (as expressed by the contact angles obtalned using dilodomethane). Moreover, the protective vamishes comprising the dl-hydroxyl-termlnated ethoxylated perfluoropolyether compounds (E1 and E2) exhibited a slgnlflcantly higher repellency towards both polar and unpolar media in comparison with the comparative dlhydroxyl-termlnated perfluoropolyether compounds (C9 and C10). The combination of both polar and unpolar repellencies provided by the présent invention is a key to the advantages provided by the addition of ethoxylated fluor-based surfaclng agents In the protective vamishes. In line with the observed repellencies, the protective vamishes according to the présent invention (E1 and E2) hâve partlculariy low surface energles compared to the comparative exemples C1-C10.
[073] In addition to their hlgh repellency towards both polar and unpolar media, said repellencies being expressed by contact angle values of water and diiodomethane respectively, the protective vamishes according to tire présent invention (E1 and E2) advantageously did not exhibit a significant decrease of both their repellencies upon time. Indeed, the protective vamishes according to the présent invention (E1 and E2) are the only examples that combine high contact angle values of water and diiodomethane and good rétention of said contact angle values upon time. Whereas the comparative examples C7 and C8 exhibited high contact angles of water and good rétention of said contact angle values upon time, comparative examples C7 and C8 suffered from low contact angle values of diiodomethane.
Claims (16)
1. A radiation curable protective vamlsh comprislng one or more catlonlcally curable compounds and one or more dl-hydroxyl-termlnated perfluoropolyether compounds of the general formula HO-(CH2CH2O)c-CHrCF2O-(CF2-CF2-O)a-(CF20)l)-CF2-CHr(0CH2CH2)rfOH whereln a and b independently are Integers in a range between 0 and 50 and whereln a + b£ 1, and whereln c and d may be the same or different and are In the range of 1-20.
2. The radiation curable protective vamlsh accordlng to daim Ibelng UV-VIs-curable protective vamlshes.
3. The radiation curable protective vamlsh accordlng to any precedlng daim, whereln the one or more cationlcally curable compounds are selected from the group consisting of vlnyl ethers, propenyl ethers, cycllc ethers and mixtures thereof.
4. The radiation curable protective vamlsh accordlng to any precedlng clalm, further comprislng one or more cationlc photolnltiators selected from the group consisting of onium salts, oxonium salts, sulphonium salts and mixtures thereof, preferably In an amount from about 0.1 to about 20 wt-%, the weight percents belng based on frie total weight of the radiation curable protective vamlsh.
5. The radiation curable protective vamlsh accordlng to any preceding claim, whereln the one or more dl-hydroxyl-terminated perfluoropolyether compounds are présent In an amount from about 0.1 to about 5.0 wt-%, the weight percents belng based on the total weight of the radiation curable protective vamlsh.
6. The radiation curable protective vamlsh accordlng to any preceding daim, whereln the one or more di-hydroxyl-termlnated perfluoropolyether compounds hâve weight average molecular weight (Mw) between about 500 and about 3000.
7. The radiation curable protective vamlsh accordlng to any precedlng claim further comprislng one or more radically curable compounds.
8. The radiation curable protective vamlsh according to daim 7, whereln the one or more cationlcally curable compounds are présent in an amount from about 85 to about 95 wt-% and the one or more radically curable compounds are présent in an amount from about 5 to about 15 wt-%, the weight percent belng based on the total weight of the mixture of the one or more cationlcally curable compounds and the one or more radically curable compounds.
9. The radiation curable protective vamlsh accordlng to daim 7 or 8 further comprising one or more free radical photolnitiators.
10. A security document comprislng a substrate and a radiation cured coating obtalned by radiation curing of a radiation curable protective vamish reclted in any one of daims 1 to 9.
11. The security document according to daim 10, whereln the substrate Is selected from the group consisting papers or other fibrous materials, paper-contalning materials, plastics and polymère, composite materials and mixtures or combinations thereof.
12. The security document according to daim 10 or 11, whereln the radiation cured coating made of the radiation curable protective vamish has a surface energy less than or equal to about 25 mN/m and a disperelve surface energy less than or equal to about 18 mN/m.
13. A process for making a security document comprislng a) a step of applying on a substrate the radiation curable protective vamish redted In any one of daims 1 to 9 so as to form a wet coating and b) a step of radiation curing sald radiation curable protective vamish so as to form a radiation cured coating.
14. A use of the radiation curable protective vamish redted In any one of daims 1 to 9 for provldlng a protective coating or layer on a security document
15. A method for impartlng soil résistance to a security document comprislng a substrate, sald method comprislng a step of applying the radiation curable protective vamish redted in any one of daims 1 to 9 onto sald substrate and radiation curing sald radiation curable protective vamish.
16. A use of the one or more dl-hydroxyl-termlnated perfluoropolyether compounds redted in any one of daims 1 to 10 for the manufacture of a radiation curable protective vamish according to any one of daims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12190376.9 | 2012-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA17326A true OA17326A (en) | 2016-05-23 |
Family
ID=
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