UV-curable composition, hard coat, and article having a hard coat layer

Abstract

The present disclosure relates to a UV curable composition, which comprises a mixture of (meth)acrylate-based curable resin compositions, and includes one or more acrylate esters having 3 or more acrylate groups; and (meth)acrylate-based urethanes or (meth)acrylic acid esters or (meth)acrylate-based epoxies or (meth)acrylate-based silicone oligomers; and a mixture of a compound having a perfluoropolyether (PFPE) group and a curable site and a di(meth)acrylate monomer. Furthermore, the present disclosure relates to a hard coat obtained by curing the composition, and a surface-treated article having the hard coat on one or more surfaces, and a method for producing the article.

Description

[Technical Field]

[0001] The present disclosure relates to UV-curable compositions, hard coats obtained by curing the compositions, articles having a hard coat thereon, and methods for making the articles. [Background technology]

[0002] Coatings, including hard coats, are conventionally used to coat the surface of a substrate to improve the mechanical strength of the substrate, such as abrasion resistance or mar resistance. Functional coatings impart specific decorative and / or functional properties to the substrate. For example, functional additives can be included in the coating to change the surface properties of the substrate, such as corrosion resistance, tactile and abrasion resistance, or surface energy of the substrate.

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

[0004] Hardcoats are selected based on the desired properties for the intended application. For example, decorative hardcoats typically need to have good appearance, such as color or gloss, and be stable to weather conditions. Known methods for protecting the appearance of commercially available hardcoats include the addition of UV absorbers and / or hindered amine light stabilizers (HALS).

[0005] On the other hand, functional hard coats focus on specific surface properties, such as omniphobicity. In this disclosure, a surface referred to as omniphobic refers to a surface that repels virtually all liquids. Therefore, omniphobic hard coats are known to be water- and oil-repellent and easy to wipe clean. However, commercially available hard coats with omniphobic properties have been found to be unable to withstand chemical or physical stress. Specifically, when omniphobic hard coats are exposed to harsh conditions, such as chemical agents or weather (i.e., high temperature and / or high humidity), their functional surface properties deteriorate.

[0006] This can be problematic, however, in certain applications, such as facilitating the wiping of hardcoats that are frequently or permanently exposed to harsh conditions. For example, hardcoats in automotive sensor or display applications must meet certain standards for omniphobicity (i.e., water and oil repellency), wipeability, and abrasion resistance, and must be highly durable even under harsh conditions.

[0007] Therefore, there is a need for compositions (especially UV-curable compositions) that can form hard coats with excellent surface properties, in terms of having durable surface functionality, and in particular, in terms of the hard coats being able to maintain omniphobicity for long periods of time even when exposed to harsh conditions. Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the above, it is an object of the present disclosure to provide a UV-curable composition that can be cured to form a hard coat on a surface, which has durable surface functionality and, in particular, omniphobic properties, including water and oil repellency, so that it can be easily wiped clean even when exposed to harsh conditions such as chemicals, high temperature and / or high humidity, while also maintaining general physical properties such as appearance, good adhesion to the coated substrate, and hardness (abrasion resistance). [Means for solving the problem]

[0009] The present disclosure addresses all of the above requirements and is accomplished by using a specific combination of components in a UV-curable composition that can form a hard coat that has not previously been considered in the coatings art.

[0010] Therefore, the UV-curable composition (a) (i) 40 to 60% by weight, based on the total amount of (a), of one or more acrylate esters having three or more acrylate groups; and (ii) 40 to 60 mass% of a (meth)acrylate-based urethane, a (meth)acrylic acid ester, a (meth)acrylate-based epoxy, or a (meth)acrylate-based silicone oligomer, based on the total amount of (a); 75 to 95 mass% of a (meth)acrylate-based curable resin composition containing (b) (i) a compound having a perfluoropolyether (PFPE) group and a curable site, in an amount of 0.5 to 50% by mass based on the total amount of (b); and (ii) Formula: [ka] [In formula: R' is independently an H atom, a methyl group, or a halogen atom; and X is a linear C 2-16 Alkyl group, (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. At least one di(meth)acrylate monomer represented by the formula (I) is used in an amount of 50.0 to 99.5 mass% based on the total amount of (b). The mixture contains 5 to 25% by mass A composition comprising: (a) does not contain F-based compounds, and The total amount of (a) and (b) is 80% by mass or more based on the total nonvolatile content in the composition.

[0011] The present disclosure further provides a hard coat obtained by curing a UV-curable composition with UV light. The present disclosure also relates to a surface-treated article having a substrate and a hard coat of the present disclosure on one or more surfaces thereof, and a method for making the article.

[0012] Preferred embodiments of the invention are as defined in the accompanying dependent claims and / or the following detailed description.

[0013] MODE FOR CARRYING OUT THE INVENTION [UV curable composition] The UV-curable composition of the present disclosure comprises: (a) (i) 40 to 60% by mass of one or more acrylate esters having three or more acrylate groups, based on the total amount of (a), and (ii) 40 to 60% by mass of (meth)acrylate urethane, (meth)acrylic acid ester, (meth)acrylate epoxy, or (meth)acrylate silicone oligomer based on the total amount of (a) 75 to 95 mass% of a (meth)acrylate-based curable resin composition containing (b) (i) a compound having a perfluoropolyether group and a curable site in an amount of 0.5 to 50.0% by mass relative to the total amount of (b), and (ii) Formula: [ka] [In formula: R' is independently an H atom, a methyl group, or a halogen atom; and X is a linear C 2-16 Alkyl group, (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. and (b) contains 50.0 to 99.5% by mass of at least one di(meth)acrylate monomer represented by the formula: The mixture contains 5 to 25% by mass Contains (a) does not contain F-based compounds, and The total amount of (a) and (b) is 80% by mass or more based on the total nonvolatile content in the composition.

[0014] The nonvolatile content (hereinafter sometimes abbreviated as "NV") is measured by thermogravimetry.

[0015] [(Meth)acrylate-based curable resin composition (a)] The (meth)acrylate-based curable resin composition (a) is contained in the UV-curable composition in an amount of 75 to 95 mass % based on the total nonvolatile content in the composition, and preferably in an amount of 80 to 90 mass % based on the total nonvolatile content in the UV-curable composition.

[0016] The (meth)acrylate-based curable resin composition (a) contains (i) one or more acrylate esters having three or more acrylate groups, in an amount of 40 to 60 mass % based on the total amount of the (meth)acrylate-based curable resin composition (a).

[0017] In a preferred embodiment, the acrylate ester is at least one selected from pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4a), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), tripentaerythritol heptaacrylate (TP7A), tripentaerythritol octaacrylate (TPOA), and trimethylolpropane triacrylate (TMPTA).

[0018] For example, in one embodiment, the acrylate ester contained in the (meth)acrylate-based curable resin composition (a) is a combination of PET4A and TMPTA. In another exemplary embodiment, the acrylate ester contained in the (meth)acrylate-based curable resin composition (a) is a combination of PET3A, PET4A, and TPMTA. In yet another exemplary embodiment, the acrylate ester contained in the (meth)acrylate-based curable resin composition (a) is a combination of PET3A, PET4A, DPPA, DPHA, TPOA, and TP7A. However, any combination of esters may be contained in the (meth)acrylate-based curable resin composition (a).

[0019] Furthermore, the (meth)acrylate-based curable resin composition (a) contains (ii) at least one of a (meth)acrylate-based urethane, a (meth)acrylic acid ester, a (meth)acrylate-based epoxy, and a (meth)acrylate-based silicone oligomer in an amount of 40 to 60 mass % relative to the total amount of the (meth)acrylate-based curable resin composition (a).

[0020] Preferably, the oligomer is at least one selected from a (meth)acrylate-based urethane oligomer, a (meth)acrylic acid-based ester oligomer, and a (meth)acrylate-based epoxy oligomer.

[0021] The (meth)acrylate-based curable resin composition (a) may further contain one or more polymerizable monomers, examples of which include alkyl vinyl ethers, acryloyl group-containing monomers having one or two acrylate groups, and (meth)acrylate monomers.

[0022] Examples of 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.

[0023] Examples of acryloyl group-containing monomers include (meth)acryloylmorpholines such as 4-acryloylmorpholine.

[0024] Examples of (meth)acrylate monomers 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, t-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, ) acrylate, cyclohexyl (meth)acrylate, 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 alcohol, Allyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, neopentyl glycol mono(meth)acrylate, neopentyl glycol di(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl 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, glycerol mono(meth)acrylate, and urethane(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, silicon(meth)acrylate, and alkoxysilane group-containing (meth)acrylate monomers can be mentioned.

[0025] A specific example of the urethane (meth)acrylate is poly[(meth)acryloyloxyalkyl]isocyanurate represented by tris(2-hydroxyethyl)isocyanurate-diacrylate.

[0026] Epoxy (meth)acrylates are obtained by adding a (meth)acrylate group to an epoxy group, common examples being obtained by using bisphenol A, bisphenol F, phenol novolac, or cycloaliphatic esters as starting materials.

[0027] Examples of polyhydric alcohols constituting the polyester unit of polyester(meth)acrylate include 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol, and examples of polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, and alkenylsuccinic acid.

[0028] Silicon (meth)acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 and modified at one or both ends with a (meth)acryloyl group, and examples thereof include the following compounds: [ka] [ka] [ka] Examples include:

[0029] Examples of alkoxysilane group-containing (meth)acrylate monomers include 3-(meth)acryloyloxypropyltrichlorosilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane (also referred to as (triisopropoxysilyl)propyl methacrylate (abbreviated as TISMA) and (triisopropoxysilyl)propyl acrylate), 3-(meth)acryloxyisobutyltrichlorosilane, 3-(meth)acryloxyisobutyltriethoxysilane, and 3-(meth)acryloxyisobutyltriisopropoxy3-(meth)acryloxyisobutyltrimethoxysilane.

[0030] 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-described acrylate esters (a)(i), and further comprises a (meth)acrylate urethane oligomer, and optionally a polymer or oligomer derived from an acrylate monomer. The resin composition may further comprise a component such as a polysiloxane urethane acrylate oligomer.

[0031] Commercially available resin compositions that can be used as the (meth)acrylate resin composition (a) in the present disclosure include UV525 PGM and UV525 M (Showa Denko Materials Co., Ltd., Japan), SILFORT * Examples include UVHC7400 (manufactured by Momentive Performance Materials GmbH, Germany), Beamset502H, 504H, 505A-6, 550B, 575CB, 577, and 1402 (manufactured by Arakawa Chemical Industries, Ltd.), Ebecryl 40 (manufactured by Daicel-Cytec Co., Ltd.), and HR300 series (manufactured by Yokohama Rubber Co., Ltd.).

[0032] The (meth)acrylate resin composition (a) of the present disclosure does not contain any F-based compounds, which, in the sense of the present disclosure, means that it does not contain any fluorine-based ("F-based") compounds.

[0033] [Mixture (b) of a compound containing a perfluoropolyether group and a curable site and a di(meth)acrylate monomer]

[0034] The UV-curable composition of the present disclosure contains, in addition to a (meth)acrylate-based curable resin (a), a mixture (b) of (i) a compound having a perfluoropolyether (PFPE) group and a curable site and (ii) a specific di(meth)acrylate monomer.

[0035] The mixture (b) is contained in the UV-curable composition in an amount of 5 to 25% by mass based on the total nonvolatile content of the composition, and preferably in an amount of 10 to 20% by mass based on the total nonvolatile content of the composition.

[0036] (Compound (b)(i) Having a Perfluoropolyether Group and a Curable Site)

[0037] The compound (b)(i) having a perfluoropolyether (PFPE) group and a curable site is not particularly limited.

[0038] Particularly preferably, the curable moiety is a C=C double bond. For example, the curable moiety includes, but is not limited to, an allyl group, a cinnamic acid group, a sorbic acid group, a substituted or unsubstituted acryloyl group, and a (meth)acryloyl group. For example, a substituted or unsubstituted (meth)acryloyl group can be represented by the formula CH2=CX1-C(O)-, where X1 is a hydrogen atom, a chlorine atom, a fluorine atom, or a C group optionally substituted with a fluorine atom. 1-10 It is an alkyl group.

[0039] The perfluoropolyether group may be, for example, a group represented by the following formula: -(OC6F 12 ) s -(OC5F 10 )t -(OC4F8) a -(OC3F6) b -(OC2F4) c -(OCF2) d - It is expressed as:

[0040] In the formula, s, t, a, b, c, and d each independently represent an integer of 0 to 200. 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 to 100. 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, for example, 10 to 200, more specifically, 10 to 100. The order of occurrence of repeating units enclosed in parentheses with the subscript s, t, a, b, c, or d in the formula is arbitrary.

[0041] These repeating units may be linear or branched, but are preferably linear. For example, -(OCF 12 The )-group may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF2CF(CF3)CF2)-, etc., but is preferably -(OCF2CF2CF2CF2CF2CF2CF2)-. 10The )-group may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, etc., but is preferably -(OCF2CF2CF2CF2CF2)-. The -(OC4F8)- group may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. The -(OC3F6)- group may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. Furthermore, the -(OC2F4)- group may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0042] In a preferred embodiment, the compound (b)(i) having a PFPE group and a curable site has an isocyanate or isocyanurate structure.

[0043] In particular, in one embodiment, compound (b)(i) has the formula (1): [ka] wherein R f1 C optionally substituted with an F atom 1-16 is an alkyl group; 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 OR Ac R is a containing group; Ac is a (meth)acrylate group; X bis a divalent organic group having at least two heteroatoms; and R B is R f1 -X a -or R A1 -X b -It is.

[0044] In a preferred embodiment, R f1 is substituted by an F atom and is a straight or branched chain C 1-6 It may be an alkyl group, preferably C 1-2 More preferably, R f1 is a linear C 1-6 alkyl group, more preferably C 1-3 It is an alkyl group.

[0045] R F is a divalent perfluoropolyether group as defined above. For example, in one embodiment, R F is expressed by one of the following formulas (f1), (f2), (f3), (f4), or (f5). -(OC3F6) d - (f1) [In formula (f1), d is an integer of 1 to 200.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In formula (f2), c and d are independently integers of 0 to 30, e and f are independently integers of 1 to 200, and the sum of c, d, e, and f is an integer of 10 to 200; and the order of occurrence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.] -(R 6 -R 7 ) g - (f3) [In formula (f3), R 6 is OCF2 or OC2F4; R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12or a combination independently selected from these groups, and g is an integer of 2 to 100.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) [In formula (f4), e represents an integer of 1 to 200, a, b, c, d, and f each independently represents an integer of 0 to 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In formula (f5), f represents an integer of 1 to 200, a, b, c, d, and e are independently integers of 0 or more and 200 or less, 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 the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0046] In a preferred embodiment, X a Ha-(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - is a divalent organic group represented by X 121 ~X 124 are independently H, F, OH, or -OSi(OR 121 )3(each R 121 The groups are independently C1-4 alkyl group), and 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 to 10, y1 is 0 or 1, and z1 is 1 to 10. More preferably, X 1 Ha-(CH2) m22 -, and m22 is an integer of 1 to 3.

[0047] In a preferred embodiment, R A1 Ha-R A6 -R A4 -OR AC or -R A6 -R A5 -(OR AC )2 and R A4 is C 1-10 is an alkylene group, preferably C 2-6 is an alkylene group, more preferably C 2-4 is an alkylene group. A5 is a trivalent C 1-10 A hydrocarbon group, preferably a trivalent C 4-6 is a hydrocarbon group, R A6 is a single bond or -C 1-10 -alkylene-O-, more preferably a single bond; R Ac is as described above.

[0048] In a preferred embodiment, X b -X c -X d - represented by X c is a divalent organic group containing a heteroatom, and X d is -CO-NR d2 -, -OCO-NR d2 -, -NR d2 -CO- or -NR d2 COO-, more preferably -CO-NR d2 - and R d2 is a hydrogen atom or C 1-6 It is an alkyl group.

[0049] In another preferred embodiment, the compound (b)(i) having a PFPE group and a curing site has an isocyanate structure. In this embodiment, the compound (b)(i) is preferably obtained by the reaction of (A) a triisocyanate formed by trimerizing a diisocyanate with (B) a combination of at least two active hydrogen-containing compounds, the combination including (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) produces a perfluoropolyether group-containing compound having at least one carbon-carbon double bond.

[0050] In the present disclosure, "active hydrogen" refers to a hydrogen atom that is prone to bond with an electronegative atom, such as the hydrogen atom of a hydroxyl group.

[0051] The triisocyanate (A) may be a triisocyanate produced by trimerizing a diisocyanate. Examples of diisocyanates for preparing the triisocyanate (A) include diisocyanates having aliphatically bonded isocyanate groups such as hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, and dicyclohexylmethane diisocyanate; and diisocyanates having aromatically bonded isocyanate groups such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.

[0052] In a preferred embodiment, (B-1) is a compound of the general formula CYF2-[CF2] a -[O(CF2)3] b -[O(CF2)2] c -COC(CF3)CF2] d -[OCF2] e -[O(CF2)2] f -[O(CF2)3] g-OCZF-(CF2) h Y and Z are F or -CF; a is an integer of 1 to 16; c is an integer of 0 to 5; b, d, e, f, and g are independently integers of 0 to 200; and h is an integer of 0 to 16.

[0053] The monomer (B-2) having an active hydrogen and a carbon-carbon double bond is preferably a (meth)acrylate ester or vinyl monomer having an active hydrogen, particularly preferably a hydroxyl group. Examples of the monomer (B-2) include hydroxyethyl (meth)acrylate, aminoethyl (meth)acrylate, and HO(CH2CHO). i -COC(R)C=CH2 (wherein R is H or CH3, and i is an integer from 2 to 10); CH3CH(OH)CH2OCOC(R)C=CH2 (wherein R is H, CH3, or 2-hydroxypropyl(meth)acrylate); CH3CH2CH(OH)CH2OCOC(R)C=CH2 (wherein R is H, CH3, or 2-hydroxybutyl(meth)acrylate); C6H5OCH2CH(OH)CH2OCOC(R)C=CH2 (wherein R is H, CH3, or 2-hydroxy-3-phenoxypropyl(meth)acrylate); allyl alcohol; HO(CH2) k Examples include CH=CH2 (wherein k is 2 to 20); (CH3)3SiCH(OH)CH=CH2 and styrylphenol.

[0054] The compound (b)(i) having a PFPE group and a curable site having an isocyanate group can be obtained by a generally known method, such as the method described in EP 1 411 073 A1.

[0055] In the UV-curable composition, the compound (b)(i) having a PFPE group and a curable moiety is present in an amount of 0.5 to 50.0 mass%, preferably 0.5 to 25.0 mass%, based on the total amount of (B). The compound (b)(i) having a PFPE group and a curable moiety is present in an amount of preferably 0.01 to 5 mass%, more preferably 0.1 to 2 mass%, based on the total NV substances in the UV-curable composition.

[0056] In the present disclosure, an example of a commercially available compound having a PFPE group and a curable moiety that can be used as the compound (b)(i) having a PFPE group and a curable moiety is OPTOOL DAC HP (manufactured by Daikin Industries, Ltd.).

[0057] [Di(meth)acrylate monomer (b)(ii)] The di(meth)acrylate monomer (b)(ii) may be a diacrylate monomer, a dimethacrylate monomer, or an acrylate-methacrylate monomer.

[0058] The di(meth)acrylate monomer (b)(ii) has the formula: [ka] It is expressed as: In the formula, each R' is independently an H atom, a methyl group, or a halogen atom, and X is a linear C 2-16 Alkyl group, (CH2) n -C 3-16 -Cycloalkyl-(CH2) m (wherein n and m are independently an integer of 1 to 18) or a linear (poly)alkylene oxide group having methylene groups at both ends.

[0059] In the present disclosure, the term "linear" means that the chain connecting the (meth)acrylate is not branched and that the carbon atoms present in the chain do not have any substituents other than hydrogen atoms.

[0060] For example, in one embodiment, X is ethylene (CH2CH2), n-propylene (CH2CH2CH2), n-butylene (CH2CH2CH2CH2), n-pentylene (CH2CH2CH2CH2CH2), or n-hexylene (CH2CH2CH2CH2CH2CH2). In another embodiment, X may be a (poly)alkylene oxide group having methylene groups at both ends. For example, the alkylene in the (poly)alkylene oxide group may be ethylene or propylene.

[0061] 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-propanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-propanediol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly(ethylene glycol) Examples of suitable acrylic acid copolymers include, but are not limited to, 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 manufactured by Sartomer), and (octahydro-4,7-methano-1H-indenediyl)bis(methylene)bismethacrylate (CAS No. 43048-08-04).

[0062] Preferably, in the above, each R' is H and X is n-hexylene. That is, component (b) is 1,6-hexanediol diacrylate (HDDA) represented by the formula CH2=CH-C(=O)O-(CH2)6-OC(=O)CH=CH2.

[0063] In the UV-curable composition, the di(meth)acrylate monomer (b)(ii) is present in an amount of 50.0 to 99.5 mass %, preferably 75.0 to 99.5 mass %, based on the total amount of (b). The di(meth)acrylate monomer (b) is present in an amount of preferably 1 to 20 mass %, more preferably 10 to 18 mass %, and even more preferably 14 to 16 mass %, based on the total NV substances in the UV-curable composition.

[0064] The UV-curable composition may contain other components commonly known as useful additives in resin compositions, including, but not limited to, solvents, photopolymerization initiators, antioxidants, thickeners, leveling agents, antifoaming agents, 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).

[0065] Preferably, the UV-curable composition of the present disclosure may further comprise one or more of: (c) an organic solvent; (d) a photoinitiator; (e) a UV absorber (UVA); (f) a hindered amine light stabilizer (HALS); (g) a leveling agent; (h) an antifoaming agent; and (i) a wetting agent.

[0066] The organic solvent (c) contained in the UV-curable composition is not particularly limited, and examples thereof include non-fluorine-based organic solvents and fluorine-based organic solvents, such as 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, diethyl 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 two or more organic solvents may be used in combination. For example, the organic solvent may include 1-methoxy-2-propanol (also known as propylene glycol methoxy ether, PGME) and / or 1,1,2,2,3,3,4-heptafluorocyclopentane.

[0067] The photopolymerization initiator (d) contained in the UV-curable composition is not particularly limited as long as it functions as a catalyst that initiates the curing (crosslinking reaction) of a curable moiety (e.g., a carbon-carbon double bond). The photopolymerization initiator (d) in the UV-curable composition of the present disclosure can be appropriately selected depending on the components, the type of active energy ray used, or the irradiation intensity (wavelength range, etc.).

[0068] Examples of initiators 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 methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzil dimethyl ketal; benzophenone, benzoyl benzoate, methylbenzoyl Examples of suitable photopolymerization initiators include benzophenones such as benzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylated benzophenone, and Michler's ketone; thioxanthone, chlorothioxanthone, methylthioxanthone, diethylthioxanthone, and dimethylthioxanthone; and others, such as benzyl, α-acyloxime esters, acylphosphine oxides, glyoxylates, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, and anthraquinone. The photopolymerization initiator (d) may be used alone or in combination, in an appropriate amount, such as 2 to 5% by mass, based on the total nonvolatile content of the UV-curable composition.

[0069] Commercially available photoinitiators such as, but not limited to, Omnirad 184® (1-hydroxycyclohexyl-phenyl ketone) or Irgacure 819® (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) can be used.

[0070] The UV-curable composition may further optionally contain (e) a UV absorber (UVA) and / or (f) a hindered amine light stabilizer (HALS). The UVA and HALS are not particularly limited, but may include, for example, Tinuvin 400, Tinuvin 405, Tinuvin 479, Tinuvin 152, and Tinuvin 292 (manufactured by BASF), Hostavin 3400, Hostavin 3206, and Hostavin 3070 (manufactured by Clariant), ADK SATB LA-82 and LA_87 (manufactured by ADEKA Corporation), and Ruva-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0071] The UV-curable composition may further optionally contain (g) a leveling agent, such as TEGO RAD 2100, 2200N, 2250, TEGO flow 307, and TEGO GLine 432 (manufactured by Evonik).

[0072] Additionally, the UV-curable composition may further comprise (h) an antifoaming agent, such as TEGO Foamex N or TEGO® Airex 971 (manufactured by Evonik), and / or (i) a wetting agent, such as TEGO® Glide 432, TEGO® Dispers 652, and TEGO wet 270 (manufactured by Evonik).

[0073] In the UV-curable composition of the present disclosure, the total amount of nonvolatile substances is 20 to 50 mass %, preferably 30 to 45 mass %, and more preferably 40 mass %, relative to the total amount of the UV-curable composition.

[0074] [Hard court] The present disclosure further relates to a hard coat obtained by curing the UV-curable composition of the present disclosure with UV light. Prior to curing, volatile materials, including solvents, may be evaporated. The evaporation is preferably carried out in two stages. For example, the evaporation is carried out by flash evaporation at room temperature for 2 to 5 minutes in the first step, and heat treatment at about 60 to 90°C for 5 to 15 minutes in the second step.

[0075] The hard coat can be obtained by curing the UV-curable composition of the present disclosure using UV light. The curing energy can be appropriately selected depending on the formulation of the UV-curable composition, and is generally in the range of 500 to 10,000 mJ / cm. 2 may be in the range of, for example, 1000 mJ / cm 2 , 5000mJ / cm 2 or 7000mJ / cm 2 The curing is preferably carried out under an inert gas atmosphere, which is preferably nitrogen (N2).

[0076] The hardcoat compositions of the present disclosure are preferably radiation cured using a mercury lamp.

[0077] The hard coat of the present disclosure preferably has a water contact angle (WCA) greater than 103° (>103°), and / or an n-hexadecane contact angle greater than 55° (>55°), and / or a diiodomethane contact angle greater than 83° (>83°), and / or a surface free energy less than 20 mN / m (<20 mN / m). In particular, a water contact angle greater than 90° means that the surface of the hard coat is water-repellent. Furthermore, an n-hexadecane contact angle of 60-80° means that the surface of the hard coat is oil-repellent.

[0078] [Surface treatment items] The present disclosure further relates to a surface treated article comprising a substrate and a hardcoat of the present disclosure disposed on one or more surfaces of the substrate.

[0079] The substrate on which the hard coat is provided is not particularly limited. Specific examples of the substrate to be used include plastic substrates, preferably those selected from poly(methyl methacrylate) (PPMA), polycarbonate (PC), polyethylene terephthalate (PET), and triacetyl cellulose (TAC).

[0080] A method for producing a surface-treated article includes applying (coating) the UV-curable composition of the present disclosure to the surface of a substrate and curing the applied composition, preferably under a nitrogen gas atmosphere. The UV-curable composition may be applied to the substrate by a common coating method such as spray coating, roll-to-roll coating, flow coating, dip coating, spin coating, gravure coating, microgravure coating, die coating, or screen printing.

[0081] The present disclosure further relates to an optical material having a surface treatment layer as its outermost layer.

[0082] Examples of optical materials include optical materials related to displays, etc., such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, TVs and PC monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear-emitting displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs); or protective plates or films for these displays; or those whose surfaces have been treated with an anti-reflection film.

[0083] In one embodiment, the article having the surface treatment layer obtained by the present disclosure may be, but is not limited to, an optical member. Examples of optical members include lenses for eyeglasses, front protective plates for displays such as PDPs and LCDs, anti-shatter films, anti-reflection plates, polarizing plates, and anti-glare plates, touch panel sheets for devices such as mobile phones and personal digital assistants, disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs, and optical fibers.

[0084] In one embodiment, examples of articles having a surface treatment layer obtained by the present disclosure include, for example, a light detection and ranging (LiDAR) cover member, a sensor member, an instrument panel cover member, an automotive interior member, and the like, particularly members for automobiles. [Example]

[0085] Examples and comparative examples based on the present disclosure will be described in detail below.

[0086] Preparation of UV-curable composition An exemplary UV-curable composition was prepared as follows. mixing the (meth)acrylate-based curable resin composition (a) with the diacrylate monomer (b)(ii); Diluting (or dispersing) other additives (if present) with organic solvent; Dissolving the photoinitiator in an organic solvent; diluting the compound (b)(i) having a PFPE group and a curable moiety with an organic solvent; All solutions from steps (1) to (4) are mixed while stirring.

[0087] In Examples 1 to 3, the following components were used: (a) (Meth)acrylate-based curable composition: UV525 PGM (Showa Denko K.K., Japan) (b)(i) Compound having a PFPE group and a curable moiety: DAC HP (Daikin Industries, Ltd.) (b)(ii) Di(meth)acrylate monomer: 1,6-hexanediol diacrylate (HDDA) (SR 238, manufactured by Sartomer Arkema Group) (c) Solvent: 1-methoxy-2-promanol (PGME) (d) Photopolymerization initiator: Irgacure 184 (Omnirad 184)

[0088] Determination of NV amount A standard method is thermogravimetry, in which a certain amount of the composition is heated for a certain period of time to evaporate volatile materials such as solvents, after which the residue is reweighed and the NV content is calculated as follows: NV% = (weight after heat aging) / (initial weight) x 100

[0089] As will be apparent to one skilled in the art, the temperature and time will depend on the boiling points of the solvent and monomers.

[0090] The ratios of the components mixed in Examples 1 to 3 are shown in Table 1.

[0091] [Table 1]

[0092] Preparation of hard coat From Synthesis Examples 1 to 3, hard coat Examples 1 to 3 were provided on the surface of the substrate as shown below.

[0093] (1) The substrate is cleaned, for example, by wiping with alcohol, followed by deionization with ionized air. (2) The coating composition is filtered (for example, using a 0.2-5 μm PTFE filter) through a filtration step to remove contaminants such as insoluble components or dust particles. (3) The coating composition is then coated onto a substrate by a commonly used coating method, such as flow, spray, dip, bar coating, or roll-to-roll. (4) The solvent is then evaporated in two steps, including flashing off at room temperature for 2-5 minutes, followed by thermal pretreatment at 70-90°C for 5-10 minutes. (5) The coating is then UV irradiated under an inert atmosphere (N2). The required curing energy varies depending on the formulation, and as mentioned above, ranges from 500 to 10,000 mJ / cm2. 2 In Examples 1 to 3 and Comparative Examples 1 and 2, the curing energy was 1000 mJ / cm 2It was.

[0094] Furthermore, hard coats were prepared in the same manner as in Examples 1 to 3, using only component (a) (Comparative Example 1) and only components (a) and (b)(i) (Comparative Example 2), respectively.

[0095] Contact angle measurement The water and oil repellency of the resulting hard coats was evaluated by measuring the contact angle using a contact angle meter (LSA200, manufactured by Lauda Scientific). Specifically, the test liquids used to measure the contact angle were water, n-hexadecane, and diiodomethane, and the water contact angle (WCA), n-hexane contact angle, and diiodomethane contact angle were obtained. Contact angle measurements were performed using 2 μL of the test liquid. These values ​​were measured after preparation of the cured hard coat (initial contact angle) and after several stress tests as outlined below.

[0096] Surface free energy measurement The surface free energy (SFE) was calculated from the contact angle based on the method of Owens et al. described in J. Appl. Polym. Sci 13 (1969), pp. 1741-1747 ("OWRK method").

[0097] Adhesion evaluation to substrate Additionally, the adhesion of the hard coat was evaluated by a cross-cut test. The adhesion level was rated according to the ASTM D3359 classification, with 0B meaning the lowest adhesion and 5B meaning perfect adhesion.

[0098] Coating hardness evaluation (friction durability) The hardness (friction durability) of the hard coat was evaluated by an Erichsen hardness tester using a 0.75 mm Bosch tip.

[0099] Evaluation of chemical durability of coatings The chemical durability of the hard coat was evaluated by two different tests. Durability against cosmetics (sunscreen cream) in accordance with VW-PV-3964 Resistance to alkaline media according to BMW-PR-557

[0100] Coating durability evaluation The durability of the hard coat was evaluated by the following test. Compressed air with constant humidity (condensation atmosphere) according to DIN EN ISO 6270-2, test period 240 hours Hydrolysis aging: in a climatic chamber at (90±2)°C and (95±1)% relative humidity, 72 hours Environmental cycle test: 8 cycles using test specification VW-PV-1200

[0101] The results obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 2 below. In the table, "◯" means that the test was passed, "-" means that the test was not performed, and "×" means that the test was not passed. [Table 2]

[0102] As is evident from Table 2, the hard coat according to the present invention has excellent surface properties even after the rub resistance test, and is considered to have both high functionality and high durability. Furthermore, the visual appearance of the hard coat is not damaged even after exposure to alkaline media as shown in the NaOH resistance test and the sunscreen cream test.

[0103] In particular, even after NaOH durability testing and hydrolysis testing, Examples 1-3 all exhibited water contact angles greater than 90°, indicating that the water repellency of the hard coat did not decrease even after exposure to harsh conditions. Both Examples 2 and 3 exhibited good adhesion even after hydrolysis testing.

[0104] Surprisingly, the visual appearance, adhesion to substrates, and water and oil repellency of Example 3 remained excellent after all durability tests performed, and the properties were further improved when cured under a nitrogen atmosphere.

[0105] In contrast, Comparative Example 1, which did not contain components (b)(i) and (b)(ii), and Comparative Example 2, which did not contain component (b)(ii), both exhibited reduced durability after the NaOH durability test and after hydrolysis. Comparative Example 2 also failed to withstand the sunscreen cream test, with the hard coat exhibiting significant delamination, resulting in a loss of both its functional and visual properties.

[0106] Additionally, the hard coats of Examples 4 and 5 were prepared in the same manner as in Examples 1-3 above, using poly(ethylene glycol) diacrylate (PEGDA) as component (b)(ii). Water contact angle evaluations of the hard coats of Examples 4 and 5 before and after the NaOH durability test and hydrolysis test were performed in the same manner as in Examples 1-3 and Comparative Examples 1 and 2 described above. The results of Examples 4 and 5 are shown in Table 3 below.

[0107] [Table 3]

[0108] As can be seen from the above results, both Examples 4 and 5 had water contact angles greater than 90° after the NaOH durability test and the hydrolysis test, indicating that the water repellency properties of the hard coat were not compromised even after exposure to harsh conditions, demonstrating the durability of the functional properties of the hard coat.

Claims

1. (a) (i) 40 to 60% by weight, based on the total amount of (a), of one or more acrylate esters having three or more acrylate groups; and (ii) 40 to 60 mass% of at least one of (meth)acrylate urethane, (meth)acrylic acid ester, (meth)acrylate epoxy, and (meth)acrylate silicone oligomer, based on the total amount of (a). 75 to 95% by mass of a (meth)acrylate-based curable resin composition containing (b) (i) a compound having a perfluoropolyether (PFPE) group and a curable site in an amount of 0.5 to 50.0% by mass based on the total amount of (b); and (ii) Formula: 【Chemistry 1】 [In the formula: R' are each independently an H atom, a methyl group, or a halogen atom; and X is a linear C ２－１６ Alkyl group, (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. and (b) at least one di(meth)acrylate monomer represented by the formula: 5 to 25 mass% of a mixture containing A UV curable composition comprising: (a) does not contain F-based compounds, and the total amount of (a) and (b) is 80% by mass or more based on the total nonvolatile content of the composition; (a)(i) is one or more compounds selected from pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4a), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), tripentaerythritol heptaacrylate (TP7A), tripentaerythritol octaacrylate (TPOA), and trimethylolpropane triacrylate (TMPTA); (b)(i) is a UV-curable composition having an isocyanate or isocyanurate structure.

2. 10. The composition of claim 1, further comprising one or more of an organic solvent, a photoinitiator, a UV absorber (UVA), a hindered amine light stabilizer (HALS), a leveling agent, a defoamer, and a wetting agent.

3. The total amount of nonvolatile components is in the range of 20 to 50% by mass based on the total amount of the composition. The composition according to claim 1 or 2.

4. (b)(i) is a compound of formula (1): 【Chemistry 2】 [In the formula: R ｆ１ is C optionally substituted by an F atom １－１６ is an alkyl group; 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 OR Ａｃ is a containing group; R Ａｃ is a (meth)acrylate group; X ｂ is a divalent organic group having at least two heteroatoms; and R Ｂ is R ｆ１ -X ｄ - or R Ａ１ -X ｂ - is.] The composition according to claim 1 or 2, wherein the compound is represented by the formula:

5. (b)(i) is (A) a triisocyanate obtained by trimerizing a diisocyanate; and (B) A combination of at least two active hydrogen-containing compounds is a compound obtained by the reaction The combination is (B-1) at least one perfluoropolyether having active hydrogen, and (B-2) At least one monomer having an active hydrogen and a carbon-carbon double bond Including, The composition according to claim 1 or 2.

6. The composition of claim 1 or 2, wherein in (b)(ii), each R' is a hydrogen atom and X is n-hexylene.

7. A hard coat comprising a cured product of the UV-curable composition described in claim 1 or 2.

8. (i) a water contact angle greater than 103°; and / or (ii) an n-hexadecane contact angle of greater than 55°; and / or (iii) a diiodomethane contact angle of greater than 83°; and / or (iv) a surface energy of less than 20 mN / m; The hard coat according to claim 7.

9. A surface treated article comprising a substrate and the hard coat of claim 7 on one or more surfaces of the substrate.

10. The surface-treated article according to claim 9 , wherein the substrate is a plastic substrate.

11. A method for producing the surface treated article of claim 9, comprising applying the composition of claim 1 to the surface of a substrate.

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