UV curable composition, hard coating and hard coated article

Abstract

The invention relates to a UV curable composition. A curable composition comprising a combination of: a (meth) acrylate-based curable resin composition comprising one or more acrylates having 3 or more acrylate groups, and an oligomer of a (meth) acrylate-based urethane or a (meth) acrylate or a (meth) acrylate-based epoxy resin or a (meth) acrylate-based silicone; and a mixture of a compound having a perfluoropolyether (PFPE) group and a curable moiety and a di (meth) acrylate monomer. Furthermore, the invention relates to a hard coating obtainable by curing the composition; a surface-treated article comprising a hard coating layer on one or more surfaces thereof; and a method of producing the article.

Description

Technical Field

[0001] The present invention relates to a UV curable composition, a hard coating obtainable by curing the composition, an article including the hard coating on a surface, and a method for producing the article. Background Art

[0002] Coatings, including hard coatings, are often used to cover the surface of a substrate to increase the mechanical strength of the substrate, such as scratch or mar resistance. Functional coatings impart specific decorative and / or functional properties to the substrate. For example, functional additives can be incorporated into coating formulations to modify the surface properties of the substrate, such as corrosion resistance, or tactile and wear resistance or the surface energy of the substrate.

[0003] The formulation of the coating depends on the desired function and its desired properties. Generally speaking, the formulation includes a resin component (also called a binder), a solvent and other additives. The coating can be applied to the substrate using well-known techniques and then hardened (cured) by exposure to heat and / or light such as ultraviolet (UV).

[0004] The hardcoat is selected based on the desired properties for the intended use. For example, decorative hardcoats are often required to have a good visual appearance, such as color or gloss, which should remain stable under weather conditions. One known method of protecting the visual appearance of commercial hardcoats is to add UV absorbers and / or hindered amine light stabilizers (HALS).

[0005] On the other hand, for functional hard coatings, the focus is on specific surface properties, such as super lyophobicity (omniophobicity). In this specification, the surface referred to as super lyophobic refers to a surface that repels almost any liquid. Therefore, the super lyophobic hard coating exhibits both hydrophobicity and oleophobicity, and is considered to be easy to clean. However, it has been found that commercially available hard coatings with super lyophobic properties cannot withstand harsh chemical or physical stresses. Specifically, when the super lyophobic hard coating is affected by harsh conditions such as chemical reagents or weather (such as high temperature and / or high humidity), it is observed that the functional surface performance is impaired.

[0006] However, this can be problematic for specific applications, such as easily cleaned hard coatings, which are frequently or permanently subjected to harsh conditions. For example, hard coatings in automotive sensor or display applications need to meet specific criteria, such as super-liquid repellency (i.e., hydrophobicity and oleophobicity), cleaning performance and scratch resistance, as well as exhibiting high durability even under harsh conditions.

[0007] Therefore, there is a need for a composition, preferably a UV curable composition, which can form a hard coating having excellent surface properties in terms of durable surface functionality, especially maintaining super lyophobicity for a long time even if the hard coating is exposed to harsh conditions. Summary of the invention

[0008] Technical Problems to be Solved by the Invention

[0009] In view of the above, an object of the present invention is to provide a UV curable composition capable of forming a hard coating on a surface by curing, the hard coating exhibiting highly durable surface functionality, in particular having super-liquid repellency including water repellency (hydrophobicity) and oil repellency (oleophobicity), and thus being easy to clean even when exposed to adverse conditions such as chemical agents, high temperature and / or high humidity, while also maintaining the usual properties such as visual appearance, high adhesion to the coated substrate and hardness (scratch resistance).

[0010] Solutions for solving technical problems

[0011] The present invention addresses all of the above requirements by satisfying them using a specific combination of components of a UV curable composition capable of forming a hard coating that has never been considered before in the coating art. Thus, the present invention has been accomplished.

[0012] That is, the UV curable composition comprises a combination of the following (a) and (b):

[0013] (a) 75-95 wt% of a (meth)acrylate curable resin composition comprising:

[0014] (i) 40 to 60 wt % of one or more acrylates having 3 or more acrylate groups, based on the total amount of (a); and

[0015] (ii) 40-60 wt% of an oligomer of (meth)acrylate-based urethane, (meth)acrylate acid-based ester, (meth)acrylate epoxy, or (meth)acrylate silicone, based on the total amount of (a); and

[0016] (b) 5-25 wt% of a mixture of:

[0017] (i) 0.5-50.0 wt% of a compound having a perfluoropolyether (PFPE) group and a curable portion, based on the total amount of (b); and

[0018] (ii) 50.0 to 99.5 wt% of at least one di(meth)acrylate monomer represented by the following formula, based on the total amount of (b),

[0019]

[0020] in,

[0021] R' is each independently H, methyl or halogen, and

[0022] X is a straight chain C 2-16 -alkyl, (CH 2 ) n -C 3-16 -cycloalkyl-(CH 2 ) m , wherein n and m are independently integers of 1 to 18, or a linear (poly)alkylene oxide having methylene groups at both ends;

[0023] Wherein (a) does not contain F compounds, and the total amount of (a) and (b) is not less than 80 wt % of the total non-volatile matter in the composition.

[0024] The present invention also provides a hard coating which can be obtained by curing the UV curable composition with ultraviolet light. In addition, the present invention relates to a surface treated article comprising a substrate and the hard coating of the present invention on one or more surfaces thereof; and a method for producing such an article.

[0025] Preferred embodiments of the invention are defined in the accompanying dependent claims and / or in the following detailed description. DETAILED DESCRIPTION

[0026] (UV curable composition)

[0027] The UV curable composition of the present invention comprises:

[0028] (a) 75-95 wt% of a (meth)acrylate curable resin composition comprising:

[0029] (i) 40 to 60 wt % of one or more acrylates having 3 or more acrylate groups, based on the total amount of (a), and

[0030] (ii) 40-60 wt% of an oligomer of (meth)acrylate urethane or (meth)acrylate ester or (meth)acrylate epoxy resin or (meth)acrylate silicone, based on the total amount of (a), and

[0031] (b) 5-25 wt% of a mixture of:

[0032] (i) 0.5 to 50.0 wt% of a compound having a perfluoropolyether group and a curable portion, based on the total amount of (b), and

[0033] (ii) 50.0 to 99.5 wt% of at least one di(meth)acrylate monomer represented by the following formula, based on the total amount of (b),

[0034]

[0035] in,

[0036] R' is each independently H, methyl or halogen, and

[0037] X is a straight chain C 2-16 -alkyl, (CH 2 ) n -C 3-16 -cycloalkyl-(CH 2 ) m , wherein n and m are independently integers of 1 to 18, or a linear (poly)alkylene oxide having methylene groups at both ends;

[0038] Wherein (a) does not contain F compounds, and the total amount of (a) and (b) is not less than 80 wt % of the total non-volatile matter in the composition.

[0039] The nonvolatile matter (hereinafter sometimes abbreviated as "NV") is measured by thermogravimetry.

[0040] (Meth)acrylate curable resin composition (a)

[0041] The content of the (meth)acrylate curable resin composition (a) in the UV curable composition is 75-95 wt % based on the total non-volatile matter in the composition. Preferably, the content of the (meth)acrylate curable resin composition (a) in the UV curable composition is 80-90 wt % based on the non-volatile matter in the UV curable composition.

[0042] The (meth)acrylate curable resin composition (a) comprises (i) one or more acrylates having 3 or more acrylate groups, and the content of (i) one or more acrylates is 40-60 wt % based on the total amount of the (meth)acrylate curable resin composition (a).

[0043] In a preferred embodiment, the acrylate is one or more selected from the following: pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4a), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), tripentaerythritol heptaacrylate (TP7A), tripentaerythritol octaacrylate (TPOA) and trimethylolpropane triacrylate (TMPTA).

[0044] For example, in one embodiment, the acrylate present in the (meth)acrylate curable resin composition (a) may include a combination of PET4A and TMPTA. In another exemplary embodiment, the acrylate present in the (meth)acrylate curable resin composition (a) may include a combination of PET3A, PET4A and TPMTA. In another exemplary embodiment, the acrylate present in the (meth)acrylate curable resin composition (a) may include a combination of PET3A, PET4A, DPPA, DPHA, TPOA and TP7A. However, any suitable combination of esters may be included in the (meth)acrylate curable resin composition (a).

[0045] In addition, the (meth)acrylate curable resin composition (a) contains (ii) 40-60 wt % of at least one of oligomers of (meth)acrylate urethane, (meth)acrylate ester, (meth)acrylate epoxy resin and (meth)acrylate silicone, based on the total amount of the (meth)acrylate curable resin composition (a).

[0046] Preferably, the oligomer is at least one of a (meth)acrylate-based urethane oligomer, a (meth)acrylate-based ester oligomer, and a (meth)acrylate-based epoxy resin oligomer.

[0047] The (meth)acrylate-based curable resin composition (a) may further include one or more polymerizable monomers. Examples of the polymerizable monomers include alkyl vinyl ethers, acryl group-containing monomers, and (meth)acrylate monomers having one or two acrylate groups.

[0048] Examples of the alkyl vinyl ethers include cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, and vinyl pivalate.

[0049] An example of the acryl group-containing monomer is (meth)acryloylmorpholine, such as 4-acryloylmorpholine.

[0050] Examples of the (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, 3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-n-hexyl (meth)acrylate, n-octyl (meth)acrylate, cyclohexyl (meth)acrylate, propylene (meth)acrylate, propylene glycol ... Isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethoxy (meth)acrylate The present invention relates to ethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, neopentyl glycol mono(meth)acrylate, neopentyl glycol diester (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl acrylate, (1,1-dimethyl-3-oxobutyl) (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, glyceryl mono(meth)acrylate, as well as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, silicon (meth)acrylate and alkoxysilyl-containing (meth)acrylate monomers.

[0051] Specific examples of the urethane (meth)acrylate include poly[(meth)acryloyloxyalkyl]isocyanurate represented by, for example, tris(2-hydroxyethyl)isocyanurate-diacrylate.

[0052] Epoxy (meth)acrylates are obtained by adding a (meth)acryloyl group to an epoxy group, and common ones are those obtained by using bisphenol A, bisphenol F, phenol novolac resins or alicyclic compounds as starting materials.

[0053] Examples of the polyol constituting the polyester unit of the polyester (meth)acrylate include 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and dipentaerythritol, and examples of the polyacid include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid and alkenylsuccinic acid.

[0054] Silicone (meth)acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000, which is modified with a (meth)acryloyl group at one or both ends thereof, and examples thereof include the following compounds:

[0055]

[0056] Examples of the alkoxysilyl group-containing (meth)acrylate monomers include 3-(meth)acryloyloxypropyl trichlorosilane, 3-(meth)acryloyloxypropyl trimethoxysilane, 3-(meth)acryloyloxypropyl triethoxysilane, 3-(meth)acryloyloxypropyl triisopropoxysilane (also known as (triisopropoxysilyl)propyl methacrylate (abbreviation: TISMA) and (triisopropoxysilyl)propyl acrylate), 3-(meth)acryloxyisobutyl trichlorosilane, 3-(meth)acryloxyisobutyl triisopropoxysilane, 3-(meth)acryloyloxypropyl ... trichlorosilane), 3-(meth)acryloxyisobutyl triethoxysilane and 3-(meth)acryloxyisobutyl triisopropoxy-3-(meth)acryloxyisobutyltrimethoxysisilane.

[0057] In a preferred embodiment, the curable (meth)acrylate resin composition (a) is a urethane (meth)acrylate resin composition. For example, the curable resin composition (a) comprises one or more of the above-mentioned acrylates (a) (i), and further comprises a (meth)acrylate urethane oligomer, and optionally a polymer and oligomer derived from an acrylate monomer. The resin composition may further comprise other components, such as polysiloxane-urethane-acrylate oligomers.

[0058] Commercially available resin compositions that can be used as the (meth)acrylate curable resin composition (a) in the present invention include UV525 PGM and UV525 M (available from Showa Denko Materials Co., Ltd., Japan), SILFORT*UVHC7400 (available from Momentive Performance Materials GmbH, Germany) and Beamset502H, 504H, 505A-6, 550B, 575CB, 577 and 1402 (available from Arakawa Chemical Industries, Ltd.), Ebecryl 40 (available from Daicel Cytec Co., Ltd.) and HR300 series (available from Yokohama Rubber Co., Ltd.).

[0059] The (meth)acrylate curable resin composition (a) of the present invention does not contain any F-type compound. In the sense of the present invention, this means that it does not contain any fluorine-type ("F-type") compound.

[0060] A mixture of a compound having a perfluoropolyether group and a curable portion and a di(meth)acrylate monomer (b)

[0061] The UV curable composition of the present invention comprises, in addition to (a) a (meth)acrylate-based curable resin, a mixture (b) of (i) a compound having a perfluoropolyether (PFPE) group and a curable portion and (ii) a specific di(meth)acrylate monomer.

[0062] The content of the mixture (b) in the UV curable composition is 5-25 wt % based on the total non-volatile matter in the composition. Preferably, the content of the mixture (b) in the UV curable composition is 10-20 wt % based on the total non-volatile matter in the composition.

[0063] Compound (b)(i) having a perfluoropolyether group and a curable portion

[0064] The compound (b)(i) having a perfluoropolyether (PFPE) group and a curable portion is not particularly limited.

[0065] However, preferably, the curable moiety is a C=C double bond. For example, the curable moiety includes, but is not limited to, allyl, cinnamic acid, sorbic acid, substituted or unsubstituted acryloyl and (meth)acryloyl. For example, a substituted or unsubstituted (meth)acryloyl group can be represented by the formula CH 2 =CX 1 -C(O)- means, where X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom or a C atom which may be optionally substituted by fluorine. 1-10 alkyl.

[0066] The perfluoropolyether group is represented, for example, by the formula:

[0067] -(OC 6 F 12 ) s -(OC 5 F 10 ) t -(OC 4 F 8 ) a -(OC 3 F 6 ) b -(OC 2 F 4 ) c -(OCF 2 ) d -.

[0068] Wherein, in the formula, s, t, a, b, c and d are each independently an integer of 0 or more and 200 or less, and the sum of s, t, a, b, c and d is at least 1. Preferably, s, t, a, b, c and d are each independently an integer of 0 or more and 100 or less. Preferably, the sum of s, t, a, b, c and d is 5 or more, more preferably 10 or more. Preferably, the sum of s, t, a, b, c and d is 200 or less, more preferably 100 or less, such as 10 or more and 200 or less, more specifically, 10 or more and 100 or less. The order of appearance of each repeating unit with subscript s, t, a, b, c or d in brackets is not limited in the formula.

[0069] These repeating units may be straight chain or branched, but are preferably straight chain. 6 F 12 Examples of )-groups include -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 CF2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )- and -(OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-.-(OC 5 F 10 )- group examples include -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )- and -(OCF 2 CF 2 CF 2 CF(CF 3 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-.-(OC 4 F 8)-group can be -(OCF 2 CF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 CF 2 )-、-(OCF 2 CF(CF 3 )CF 2 )-、-(OCF 2 CF 2 CF(CF 3 ))-、-(OC(CF 3 ) 2 CF 2 )-、-(OCF 2 C(CF 3 ) 2 )-、-(OCF(CF 3 )CF(CF 3 ))-、-(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, but preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )-group can be, for example, -(OCF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))-, preferably-(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )-group can be -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-, but preferably -(OCF 2 CF 2 )-.

[0070] In a preferred embodiment, the compound (b)(i) having a PFPE group and a curable moiety comprises an isocyanate or isocyanurate structure.

[0071] In particular, in one embodiment, compound (b)(i) is a compound represented by formula (1):

[0072]

[0073] Where R f1 is C optionally substituted by F 1-16 Alkyl; R F is a divalent perfluoropolyether group; q is 0 or 1; X a is a single bond or a divalent organic group; R A1 Is containing OR Ac The group; R Ac is a (meth)acrylate group; X b is a divalent organic group containing at least two heteroatoms; and R B YesR f1 -X a - or R A1 -X b -.

[0074] In a preferred embodiment, R f1 is substituted by F and can be a straight or branched chain C 1-6 Alkyl, preferably C 1-2 More preferably, R f1 It is a straight chain C 1-6 Alkyl, more preferably C 1-3 alkyl.

[0075] R F is a divalent perfluoropolyether group, which has the same definition as above. For example, in one embodiment, R F It can be represented by one of the following structures (f1), (f2), (f3), (f4), or (f5):

[0076] -(OC 3 F 6 ) d -(f1)

[0077] Wherein, in formula (f1), d is an integer of 1-200;

[0078] -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f2)

[0079] Wherein, in formula (f2), c and d are independently integers of 0-30, e and f are independently integers of 1-200, and the sum of c, d, e and f is an integer of 10-200; the order of appearance of the repeating units with subscripts c, d, e or f in brackets is arbitrary;

[0080] -(R 6 -R 7 ) g- (f3)

[0081] Among them, in formula (f3), R 6 OCF 2 or OC 2 F 4 ; R 7 Selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 A group or a combination selected from these groups, g is an integer from 2 to 100;

[0082] -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f4)

[0083] wherein, in formula (f4), e is an integer from 1 to 200, a, b, c, d and f are independently integers from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of appearance of the repeating units with subscripts a, b, c, d, e or f in brackets is arbitrary in the equation;

[0084] -(OC 6 F 12 ) a -(OC 5 F10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f5)

[0085] Wherein, in formula (f5), f is an integer of 1-200, a, b, c, d and e are independently an integer of 0 or greater and 200 or less, and the sum of a, b, c, d and e, and a, b, c, d, e and f is at least 1, and the order of appearance of the repeating units with subscripts a, b, c, d, e or f in brackets is arbitrary.

[0086] In a preferred embodiment, X a Is composed of -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 -represented by a divalent organic group, wherein X 121 To X 124 are independently H, F, OH or -OSi(OR 121 ) 3 (where each R 121 Independently for C 1-4 Alkyl), X a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- or -NHC(=O)NH-, x1 is an integer of 0-10, y1 is 0 or 1, and z1 is 1-10. More preferably, X 1 It is composed of -(CH 2 ) m22 -represented by a group, wherein m22 is an integer of 1-3.

[0087] In a preferred embodiment, R A1 Yes-R A6 -R A4 -OR AC or -R A6 -R A5 -(OR AC ) 2 , where R A4 It is C1-10 Alkylene, and preferably C 2-6 Alkylene, more preferably C 2-4 Alkylene, R A5 It is trivalent C 1-10 A hydrocarbon group, preferably a trivalent C 4-6 Hydrocarbon, R A6 Is a single bond or -C 1-10 Alkylene-O-, more preferably a single bond, and R Ac As defined above.

[0088] In a preferred embodiment, X b By -X c -X d - indicates that X c is a divalent organic group containing a heteroatom, and X d Yes-CO-NR d2 -、-OCO-NR d2 -、-NR d2 -CO- or -NR d2 COO-, and more preferably -CO-NR d2 -, where R d2 is hydrogen or C 1-6 alkyl.

[0089] In another preferred embodiment, the compound (b)(i) having a PFPE group and a curable portion has an isocyanate structure. In this embodiment, the compound (b)(i) is preferably obtained by reacting (A) a triisocyanate prepared by trimerization of a diisocyanate and (B) a combination of at least two active hydrogen-containing compounds, the combination comprising (B-1) at least one perfluoropolyether having active hydrogen and (B-2) at least one monomer having active hydrogen and a carbon-carbon double bond. The reaction of the triisocyanate (A) with the component (B) yields a perfluoropolyether-containing compound having at least one carbon-carbon double bond.

[0090] In the present invention, "active hydrogen" refers to a hydrogen atom attached to an atom with a higher electronegativity, such as, for example, the hydrogen of a hydroxyl group.

[0091] The triisocyanate (A) may be a triisocyanate prepared by trimerizing a diisocyanate. Examples of diisocyanates for preparing the triisocyanate (A) include diisocyanates with aliphatic bonded isocyanate groups, such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane diisocyanate; and diisocyanates with aromatic bonded isocyanate groups, such as toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluene diisocyanate, and naphthalene diisocyanate.

[0092] In a preferred embodiment, (B-1) has the general formula CYF 2 -[CF 2 ] a -[O(CF 2 ) 3 ] b -[O(CF 2 ) 2 ] c -COC(CF 3 )CF 2 ] d -[OCF 2 ] e -[O(CF 2 ) 2 ] f -[O(CF 2 ) 3 ] g -OCZF-(CF 2 ) h -CH 2 OH, where Y and Z are F or -CF 3 , a is an integer of 1-16, c is an integer of 0-5, b, d, e, f and g are independently an integer of 0-200, and h is an integer of 0-16.

[0093] The monomer (B-2) having active hydrogen and a carbon-carbon double bond is preferably a (meth)acrylate or vinyl monomer having active hydrogen, especially a hydroxyl group. Examples of the monomer (B-2) include: hydroxyethyl (meth)acrylate; aminoethyl (meth)acrylate; HO(CH 2 CH 2 O) i -COC(R)C=CH 2 , where R is H or CH 3 , and i is an integer from 2 to 10; CH 3 CH(OH)CH 2 OCOC(R)C=CH 2 , where R is H, CH 3 or 2-hydroxypropyl (meth)acrylate; CH 3 CH 2 CH(OH)CH 2 OCOC(R)C=CH 2 , where R is H, CH 3 Or 2-hydroxybutyl (meth)acrylate; C 6 H 5 OCH 2 CH(OH)CH 2 OCOC(R)C=CH 2, where R is H, CH 3 or 2-hydroxy-3-phenoxypropyl (meth)acrylate; allyl alcohol; HO(CH 2 ) k CH=CH 2 , where k is 2-20; (CH 3 ) 3 SiCH(OH)CH=CH 2 and styrylphenol.

[0094] The compound (b)(i) having a PFPE group and a curable part has an isocyanate group and can be obtained by known methods, for example the method described in EP 1 411 073 A1.

[0095] In the UV curable composition, the content of the compound (b)(i) having a PFPE group and a curable portion is 0.5-50.0 wt%, preferably 0.5-25.0 wt%, based on the total amount of (b). The compound (b)(i) having a PFPE group and a curable portion is preferably present in an amount of 0.01-5 wt%, preferably 0.1-2 wt%, based on the total NV material of the UV curable composition.

[0096] Commercially available compounds having a PFPE group and a curable portion that can be used as the compound having a PFPE group and a curable portion (b)(i) in the present invention include, for example, OPTOOL DAC HP (available from Daikin Industries, Ltd.).

[0097] Di(meth)acrylate monomer (b)(ii)

[0098] The di(meth)acrylate monomer (b)(ii) may be a diacrylate monomer, a dimethacrylate monomer or an acrylate-methacrylate monomer.

[0099] The di(meth)acrylate monomer (b)(ii) is represented by the following formula,

[0100]

[0101] Wherein, R' is independently H, methyl or halogen, X is a straight chain C 2-16 Alkyl, (CH 2 ) n -C 3-16 -cycloalkyl-(CH 2 ) m , wherein n and m are independently integers of 1 to 18, or a linear (poly)alkylene oxide having methylene groups at both ends.

[0102] The term "straight chain" in the sense of the present invention means that the chain connecting the (meth)acrylates has no branches and that none of the carbon atoms present in the chain carries any substituents other than hydrogen atoms.

[0103] For example, in one embodiment, X can be ethylene (CH 2 CH 2 ), n-propylene (CH 2 CH 2 CH 2 ), n-butylene (CH 2 CH 2 CH 2 CH 2 ), n-pentylene (CH 2 CH 2 CH 2 CH 2 CH 2 ) or n-hexylene (CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 In another embodiment, X may be a (poly) alkylene oxide group having methylene groups at both ends. For example, the alkylene group in the (poly) alkylene oxide group may be an ethylene group or a propylene group.

[0104] Specific examples of the di(meth)acrylate monomer (b)(ii) represented by the above formula include 1,6-hexanediol diacrylate, 1,5-pentanediol diacrylate, 1,4-butanediol diacrylate, 1,3-propylene glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-propylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, esters, poly(ethylene glycol) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, poly(propylene glycol) diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, poly(ethylene glycol) dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, poly(propylene glycol) dimethacrylate, tricyclodecane dimethanol diacrylate (e.g., SR833 S available from Sartomer), (octahydro-4,7-methano-1H-indenediyl)bis(methylene)bismethacrylate (CAS No. 43048-08-04), but are not limited thereto.

[0105] Preferably, in the above formula, each R' is H and X is n-hexylene. That is, component (b) is 1,6-hexanediol diacrylate (HDDA), which corresponds to the formula CH 2 =CH-C(=O)O-(CH 2 ) 6 -OC(=O)CH=CH 2 .

[0106] In the UV curable composition, the content of the di(meth)acrylate monomer (b)(ii) is 50.0-99.5wt%, preferably 75.0-99.5wt%, based on the total amount of (b). The content of the di(meth)acrylate monomer (b) is preferably 1-20wt%, more preferably 10-18wt%, and further more preferably 14-16wt%, based on the total NV material of the UV curable composition.

[0107] The present UV curable composition may also contain other components, which are generally known to be useful additives in resin compositions, including but not limited to solvents, photopolymerization initiators, antioxidants, thickeners, leveling agents, defoamers, antistatic agents, antifogging agents, ultraviolet absorbers, light stabilizers, pigments, dyes, inorganic fine particles such as silica, fillers such as aluminum paste, talc, glass frit and metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

[0108] Preferably, the UV curable composition of the present invention may further include one or more agents, such as (c) an organic solvent, (d) a photopolymerization initiator, (e) a UV absorber (UVA), (f) a hindered amine light stabilizer (HALS), (g) a leveling agent, (h) a defoaming agent and (i) a wetting agent.

[0109] The organic solvent (c) that may be present in the UV curable composition is not particularly limited, but examples include non-fluorinated organic solvents and fluorinated organic solvents, including ketones, esters, amides, sulfoxides, ethers, hydrocarbons, and fluorine-based solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethyl ether, diisopropyl ether, 1-methoxy-2-propanol, tetrahydrofuran, dioxane, toluene, xylene, 1,3-tetrahydrofuran, dioxane, toluene, xylene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene. One of these organic solvents may be used alone, or a combination of two or more organic solvents may be used. For example, the organic solvent includes 1-methoxy-2-propanol (also known as propylene glycol methyl ether, PGME) and / or 1,1,2,2,3,3,4-heptafluorocyclopentane.

[0110] The photopolymerization initiator (d) that may be present in the UV curable composition is not particularly limited as long as it serves as a catalyst for initiating curing (crosslinking reaction) of the curable portion (e.g., carbon-carbon double bonds). The photopolymerization initiator (d) in the UV curable composition of the present invention may be appropriately selected depending on the composition, the type of active energy ray used, or the irradiation intensity (wavelength range, etc.).

[0111] Specifically, examples of the initiator include acetophenones such as acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl dimethyl ketal; benzophenones such as benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropyl benzophenone, acrylate benzophenone and Michler's ketone; thioxanthones such as thioxanthone, chlorothioxanthone, methylthioxanthone, diethylthioxanthone and dimethylthioxanthone; and others such as benzyl, α-acyloxime The photopolymerization initiator (d) may be used alone or in combination of two or more and may be present in any suitable amount, for example, in an amount of 2-5 wt % based on the total non-volatile matter of the UV curable composition.

[0112] A commercially available photopolymerization initiator such as Omnirad 184 (registered trademark) (1-hydroxycyclohexyl-phenyl ketone) or Irgacure 819 (registered trademark) (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) may be used, but the photopolymerization initiator is not limited thereto.

[0113] The UV curable composition may also optionally include (e) a UV absorber (UVA) and / or (f) a hindered amine light stabilizer (HALS). UVA and HALS are not particularly limited, and examples include Tinuvin 400, Tinuvin 405, Tinuvin 479, Tinuvin 152, and Tinuvin 292 (available from BASF), Hostavin 3400, Hostavin 3206, and Hostavin 3070 (available from Clariant), ADK SATB LA-82 and LA-87 (available from ADEKA Corporation), and Ruva-93 (available from Otsuka Chemical Co., Ltd.).

[0114] The UV curable composition may also optionally contain (g) a leveling agent, such as TEGO RAD 2100, 2200N, 2250, TEGO flow 307 and TEGO GLine 432 (available from Evonik).

[0115] In addition, the UV curable composition may further comprise (h) a defoamer such as TEGO Foamex N or TEGO (registered trademark) Airex 971 (available from Evonik), and / or (i) a wetting agent such as TEGO (registered trademark) Glide 432, TEGO (registered trademark) Dispers 652 and TEGO wet 270 (available from Evonik).

[0116] In the UV curable composition of the present invention, the amount of non-volatile matter amounts to 20-50 wt %, preferably 30-45 wt %, more preferably 40 wt %, based on the total amount of the UV curable composition.

[0117] Hard coating

[0118] The present invention also relates to a hard coating which can be obtained by curing the UV curable composition of the present invention with ultraviolet light. Before curing, volatile substances including solvents can be evaporated. The evaporation is preferably carried out in two steps. For example, the evaporation can be carried out in a first step by flashing at room temperature for 2-5 minutes and in a second step by heat treatment at about 60-90° C. for 5-15 minutes.

[0119] The hard coating layer can be obtained by curing the UV curable composition of the present invention using UV light. The curing energy can be appropriately selected according to the formulation of the UV curable composition and can be in the range of 500-10000 mJ / cm 2 In the range of, for example, 1000mJ / cm 2、5000mJ / cm 2 or 7000mJ / cm 2 The curing is preferably carried out in an inert gas atmosphere. The inert gas may preferably be nitrogen (N 2 ).

[0120] The hard coating composition of the present invention is preferably cured by radiation using a mercury lamp.

[0121] The hard coating of the present invention preferably has a water contact angle (WCA) greater than 103°, and / or a n-hexadecane contact angle greater than 55°, and / or a diiodomethane contact angle greater than 83° and / or a surface free energy less than 20mN / m. In particular, a water contact angle greater than 90° indicates that the surface of the hard coating has hydrophobicity. In addition, a n-hexadecane contact angle of 60-80° indicates that the hard coating surface has oleophobicity.

[0122] Surface treatment products

[0123] The present invention also relates to a surface treated article comprising a substrate and the hard coating of the present invention applied to one or more surfaces of the substrate.

[0124] The substrate on which the hard coating can be applied is not particularly limited. Examples of substrates to be treated include plastic substrates, preferably plastic substrates selected from poly(methyl methacrylate) (PPMA), polycarbonate (PC), polyethylene terephthalate (PET) and triacetyl cellulose (TAC).

[0125] The method for producing the surface treated article comprises applying the UV curable composition of the present invention on the surface of the substrate and curing the applied composition preferably under a nitrogen atmosphere. The UV curable composition can be applied to the substrate by common coating methods, such as spraying, roll-to-roll coating, flow coating, dip coating, spin coating, gravure coating, micro gravure coating, die coating and screen printing.

[0126] The present invention also relates to an optical material having a surface treatment layer as an outermost layer.

[0127] In addition to optical materials related to displays, etc., the optical materials preferably include a variety of optical materials as shown in the following examples: for example, cathode ray tubes (CRT; such as televisions, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFD), field emission displays (FED) and the like displays; or protective plates or films for such displays; or those materials obtained by performing anti-reflection film treatment on their surfaces.

[0128] In one embodiment, the article with a surface treatment layer obtained according to the present invention can be, but is not limited to, an optical component. Examples of optical components include lenses of glasses, etc.; front surface protection plates, anti-scattering films, anti-reflection plates, polarizing plates, and anti-glare plates of displays such as PDPs and LCDs; touch panels for devices such as mobile phones and personal digital assistants; optical disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; and optical fibers.

[0129] In one embodiment, examples of articles having a surface treatment layer obtained by the present invention include light detection and ranging (LiDAR) cover parts, sensor parts, instrument panel cover parts, automobile interior parts, etc., especially these parts for automobiles.

[0130] Example

[0131] Hereinafter, examples and comparative examples according to the present invention will be described in detail.

[0132] Preparation of UV curable compositions:

[0133] An exemplary UV curable composition was prepared as follows:

[0134] (1) mixing a (meth)acrylate curable resin composition (a) and a diacrylate monomer (b)(ii);

[0135] (2) diluting (or dispersing) other additives (if any) in an organic solvent;

[0136] (3) dissolving the photoinitiator in an organic solvent;

[0137] (4) diluting the compound (b)(i) having a PFPE group and a curable portion in an organic solvent;

[0138] (5) Mix all the solutions from steps 1 to 4 under stirring.

[0139] For Examples 1-3, the following components were used:

[0140] (a) (Meth)acrylate curable resin composition: UV525 PGM (obtained from Showa Denko K.K., Japan)

[0141] (b) (i) Compound having a PFPE group and a curable portion: DAC-HP (Daikin Industries, Ltd.)

[0142] (b)(ii) Di(meth)acrylate monomer: 1,6-hexanediol diacrylate (HDDA) (SR 238, obtained from Sartomer Arkema Group)

[0143] (c) Solvent: 1-methoxy-2-propanol (PGME)

[0144] (d) Photopolymerization initiator: Irgacure 184 (Omnirad 184)

[0145] Determination of NV content

[0146] The standard method is thermogravimetry, where a certain amount of the composition is heated for a period of time to allow volatile substances such as solvents to evaporate. The residue is then weighed again and the NV content is calculated as follows:

[0147] NV% = (weight after heat aging) / (initial weight) * 100

[0148] Those skilled in the art will appreciate that the temperature and time depend on the boiling points of the solvent and the monomers.

[0149] The proportions of the components mixed in Examples 1-3 are shown in Table 1:

[0150] [Table 1]

[0151]

[0152] Preparation of hard coating:

[0153] According to the above composition examples 1-3, hard coating examples 1 to 3 were prepared on the surface of the substrate as shown below:

[0154] (1) Cleaning the substrate, for example, by wiping with alcohol and then deionizing with ionized air;

[0155] (2) filtering the coating composition through a filtering process to remove insoluble components or any kind of contaminants, such as dust particles, for example, by filtering using a 0.2-5 micron PTFE filter;

[0156] (3) the coating composition is then applied to the substrate by known coating methods, such as flow coating, spray coating, dip coating, rod coating or roll-to-roll coating;

[0157] (4) The solvent is then evaporated in two steps, including flash evaporation at room temperature for 2-5 minutes, followed by a thermal pretreatment at 70-90°C for 5-10 minutes.

[0158] (5) Then in a non-active atmosphere (N 2 ) and expose the coating to UV radiation. The required curing energy depends on the formulation composition and can be between 500-10000 mJ / cm 2 In Examples 1-3 and Comparative Examples 1 and 2, the curing energy is 1000 mJ / cm 2 .

[0159] Furthermore, hard coating layers were prepared in the same manner as in Examples 1 to 3 by using only component (a) (Comparative Example 1) and using only components (a) and (b) (i) (Comparative Example 2), respectively.

[0160] Contact angle measurement

[0161] For the hardcoat obtained, the hydrophobicity and oleophobicity of the hardcoat are evaluated by using a contact angle meter (LSA200, manufactured by Lauda Scientific) to measure the contact angle. In particular, the test liquid for measuring the contact angle is water, n-hexadecane and diiodomethane, to obtain water contact angle (WCA), n-hexadecane contact angle and diiodomethane contact angle. 2 microliters of test liquids are used to carry out contact angle measurement. These values ​​are measured after the preparation of the cured hardcoat (initial contact angle) and after several stress tests as described below.

[0162] Determination of surface free energy

[0163] Surface free energy (SFE) was calculated from the contact angle according to the method of Owens et al. ("OWRK method") described in J. Appl. Polym. Sci 13 (1969), pp. 1741-1747.

[0164] Evaluation of substrate adhesion

[0165] In addition, the adhesion of the hard coating was evaluated by a cross-cut (grid) test. The adhesion level was rated according to the ASTM D3359 classification, where 0B represents the lowest adhesion and 5B represents the highest adhesion.

[0166] Coating hardness evaluation (scratch resistance)

[0167] The hardness (scratch resistance) of the hard coating was evaluated by an Erichsen hardness tester using a 0.75 mm Bosch tip.

[0168] Evaluation of coating chemical resistance

[0169] The chemical resistance of hard coatings is evaluated using two different tests:

[0170] Tolerance to cosmetics (sunscreen) according to VW-PV-3964

[0171] Resistance to alkaline media according to BMW-PR-557

[0172] Coating durability evaluation

[0173] The durability of hard coatings is measured by the following tests:

[0174] Constant humidity condensation environment according to DIN EN ISO 6270-2, test duration 240 hours

[0175] Hydrolysis aging: 72 hours in a climate chamber at (90±2)℃ and (95±1)% relative humidity

[0176] Environmental cycle test: 8 cycles according to test specification VW-PV-1200

[0177] The results obtained in Examples 1-3 and Comparative Examples 1 and 2 are shown in Table 2. In the table, "○" indicates performance improvement, "-" indicates no test, and "×" indicates test failure.

[0178] [Table 2]

[0179]

[0180] *Based on total NV species of the composition.

[0181] As is apparent from the data in Table 2, the hard coating according to the present invention exhibits excellent surface properties even after stress testing and is therefore considered to have high functionality and high durability. In addition, as shown in the NaOH tolerance test and the sunscreen tolerance test, the visual appearance of the hard coating is not impaired after exposure to alkaline media.

[0182] In particular, even after the NaOH resistance test and the hydrolysis test, the water contact angles of Examples 1-3 all exceeded 90°, indicating that the hydrophobic properties of the hard coating were not compromised under harsh conditions. Examples 2 and 3 both showed good to excellent adhesion after the hydrolysis test.

[0183] Surprisingly, after each resistance test, the visual appearance and functional properties including adhesion to substrate, hydrophobicity and oleophobicity of Example 3 were excellent. When the coating was cured under a nitrogen atmosphere, the properties were even further improved.

[0184] In contrast, Comparative Example 1, which does not contain components (b)(i) and (b)(ii), and Comparative Example 2, which does not contain component (b)(ii), both showed reduced hydrophobicity after the NaOH resistance test, and reduced adhesion after hydrolysis. Comparative Example 2 also failed the sunscreen test, with the hard coating showing significant delamination, thereby compromising its functional and visual performance.

[0185] In addition, the hard coatings of Examples 4 and 5 were prepared in the same manner as in Examples 1-3 above, wherein poly(ethylene glycol) diacrylate (PEGDA) was used as component (b)(ii). The evaluation of the water contact angles of the hard coatings of Examples 4 and 5 before and after the NaOH tolerance test and the hydrolysis test was the same as in Examples 1-3 above and Comparative Examples 1 and 2. The compositions and results of Examples 4 and 5 are shown in Table 3 below.

[0186] [Table 3]

[0187]

[0188] * Based on total NV material of the composition

[0189] It is apparent from the above results that Examples 4 and 5 both showed water contact angles greater than 90° after both the NaOH tolerance test and the hydrolysis test. This indicates that the hydrophobic properties of the hard coating were not compromised after being subjected to harsh conditions, thereby demonstrating that the functional surface properties of the hard coating are durable.

Claims

1. A UV-curable composition comprising: (a) 75-95 wt% of a (meth)acrylate curable resin composition comprising: (i) 40 to 60 wt % of one or more acrylates having 3 or more acrylate groups, based on the total amount of (a); and (ii) at least one of oligomers of (meth)acrylate urethane, (meth)acrylate ester, (meth)acrylate epoxy resin and (meth)acrylate silicone in an amount of 40-60 wt % based on the total amount of (a); (b) 5-25 wt% of a mixture of: (i) 0.5-50.0 wt% of a compound having a perfluoropolyether (PFPE) group and a curable portion, based on the total amount of (b); and (ii) 50.0 to 99.5 wt% of at least one di(meth)acrylate monomer represented by the following formula, based on the total amount of (b), in, R' is each independently H, methyl or halogen, and X is a straight chain C 2-16 -alkyl, (CH2) n -C 3-16 -cycloalkyl-(CH2) m , wherein n and m are independently integers of 1 to 18, or a linear (poly)alkylene oxide having methylene groups at both ends; Wherein (a) does not contain F compounds, and the total amount of (a) and (b) is not less than 80 wt % of the total non-volatile matter in the composition.

2. The composition according to claim 1, further comprising one or more organic solvents, photopolymerization initiators, UV-absorbers (UVA), hindered amine light stabilizers (HALS), leveling agents, defoamers and wetting agents.

3. The composition according to claim 1 or 2, wherein the non-volatile matter accounts for 20-50 wt% of the total weight of the composition.

4. The composition of any one of claims 1 to 3, wherein (b)(i) comprises an isocyanate or isocyanurate structure.

5. A composition according to any one of claims 1 to 4, wherein (b)(i) is a compound of formula (1): in, R f1 is C optionally substituted by F 1-16 -alkyl; R F is a divalent perfluoropolyether group; q is 0 or 1; X a It is a single bond or a divalent organic group; R A1 Is containing OR Ac Groups; R Ac is a (meth)acrylate group; X b is a divalent organic group containing at least two heteroatoms; and R B YesR f1 -X a - or R A1 -X b -.

6. The composition according to any one of claims 1 to 4, wherein (b)(i) is obtainable by reacting (A) and (B) below, (A) a triisocyanate prepared by trimerizing a diisocyanate, and (B) a combination of at least two active hydrogen-containing compounds, the combination comprising: (B-1) at least one perfluoropolyether having active hydrogen, and (B-2) At least one monomer having active hydrogen and a carbon-carbon double bond.

7. The composition according to any one of claims 1 to 6, wherein (a)(i) is one or more selected from the group consisting of pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4a), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), tripentaerythritol heptaacrylate (TP7A), tripentaerythritol octaacrylate (TPOA) and trimethylolpropane triacrylate (TMPTA).

8. The composition of claims 1-7, wherein in (b)(ii), each R' is H and X is n-hexylene.

9. A hard coating layer obtainable by curing the UV-curable composition according to any one of claims 1 to 8 with ultraviolet light.

10. The hard coating layer according to claim 9, wherein the curing is performed in an inert gas atmosphere, preferably a nitrogen atmosphere.

11. The hard coating layer according to claim 9 or 10, having (i) a water contact angle greater than 103°, and / or (ii) a n-hexadecane contact angle greater than 55°, and / or (iii) a diiodomethane contact angle greater than 83°, and (iv) optionally a surface free energy of less than 20 mN / m.

12. A surface-treated article comprising a substrate and the hard coating according to any one of claims 9 to 11 on one or more surfaces of the substrate.

13. The surface treatment article according to claim 12, wherein the substrate is a plastic substrate, and preferably a plastic substrate selected from poly(methyl methacrylate) (PPMA), polycarbonate (PC), polyethylene terephthalate (PET) and triacetyl cellulose (TAC).

14. A method for producing a surface-treated article according to claim 12 or 13, comprising applying the composition according to any one of claims 1 to 9 onto the surface of a substrate and curing the applied composition, preferably under a nitrogen atmosphere.

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