composition and article coated with rigid coating based on polymethyl methacrylate

专利摘要:
COATED ARTICLE AND COMPOSITION OF HARD COATING BASED ON POLYMETHYL METHACRYLATE. A coating composition is disclosed. The coating composition includes a poly (methyl methacrylate) polymer or copolymer with an average molecular weight of at least 50,000 grams per mole; monomer comprising at least one of an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate, or cycloalkylene dimethacrylate, wherein at least one of an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate, or cycloalkylene dimethacrylate at least 80 weight percent of the monomer; and a stabilizer against ultraviolet light. An article that includes a coating on a substrate surface and a method of making the article are also disclosed. The coating on the substrate surface is obtained by curing the disclosed coating composition.
公开号:BR112014023480B1
申请号:R112014023480-9
申请日:2013-03-14
公开日:2021-03-16
发明作者:Mark A. Strobel；Susannah C. Clear；Raghunath Padiyath；Garry W. Lachmansingh；Sonja S. Mackey；Naiyong Jing
申请人:3M Innovative Properties Company；
IPC主号:

专利说明:

Reference to related deposit requests
[001] This application claims priority over provisional US patent application No. 61 / 614,297 filed on March 22, 2012, the description of which is incorporated by reference in its entirety in the present invention. Federally sponsored research or development statement
[002] The present invention was carried out with government support under the contract number DE-FC36-08GO18027 issued by the Department of Energy. The American government has certain rights in this invention. Background
[003] Polymeric films and other substrates are useful in a wide variety of indoor and outdoor applications. It is often desirable for films and polymeric substrates to have a final surface that is free of ripples, scratches and other imperfections. However, polymeric surfaces can tend, in a way, to be soft and easily scratched or damaged. Abrasive particles blown or otherwise placed can scratch an unprotected polymeric surface, and contact cleaning operations can also similarly damage an unprotected polymeric surface. To overcome these trends, protective coatings are sometimes used on polymeric films and substrates. Ultraviolet light and other radiation curable acrylic coating compositions can be applied to some polymeric surfaces and cured to provide a protective coating, sometimes called a hard coating. summary
[004] The present description features coated compositions that can be applied to polymeric surfaces. The resulting coatings typically adhere well to polymeric substrates even after exposure to accelerated wear by atmospheric agents, which can make them useful, for example, in the field of solar energy conversion. Coating compositions typically provide coatings that are more resistant to abrasion than the polymeric substrates themselves, as determined by measuring opacity after an assessment of abrasion with falling sand. In some embodiments, the coated articles shown in the present invention can be readily cleaned and / or resist dust accumulation.
[005] In one aspect, the present description features a coating composition. The coating composition includes a polymer or copolymer, poly (methyl methacrylate) monomer, and a stabilizer against ultraviolet light. The polymer or copolymer of poly (methyl methacrylate) has an average molecular weight of at least 50,000 grams per mol. The monomer, which can be a single monomer or a mixture of monomers, includes at least one of an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate. Alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate and / or cycloalkylenedimethacrylate provide at least 80 weight percent of the monomer.
[006] In another aspect, the present description features an article including a substrate and a first coating on a substrate surface. The first coating is obtained by curing the coating composition shown in the present invention. In some embodiments, the article additionally includes a second coating disposed on the first coating. In some of these embodiments, the second coating includes particles of silica having an average particle size of up to 500 nanometers.
[007] In another aspect, the present invention provides a method of producing an article. The method includes bringing a surface of a substrate into contact with the coating composition shown in the present invention; removing the organic solvent, if present, from the coating composition; and exposing the coating composition to actinic radiation to provide a first coating on the surface of the polymeric substrate. Typically, in this method, the coating composition includes a photoinitiator.
[008] In some embodiments, from the previously mentioned aspects of the article or method for producing the article, the substrate is a polymeric substrate. In some embodiments, the substrate is a thermoplastic substrate. In some of these embodiments, the substrate includes an acrylic, a polyester, a polycarbonate, a blend of PVDF and PMMA, or a combination thereof.
[009] In this application, terms such as "one", "one", "a (s)" and "o (s)" are not intended only for reference to a single entity, but include the general class in which a specific example can be used for illustration. The terms "one", "one", "a" and "o" are used interchangeably with the term "at least one". The phrases “at least one of” and “comprises at least one of” followed by a list refer to any of the items on the list and to any combination of two or more items on the list. All numeric ranges are inclusive of their extreme points and non-integer values between the extreme points except where specified otherwise.
[010] "Alkyl group", "alkylene" and the prefix "alq-" are inclusive of both straight chain and branched chain groups. "Alkylene" is the divalent form of "alkyl". Unless otherwise specified, alkyl or alkylene groups of the present invention have up to 20 carbon atoms. The cycloalkyl and cycloalkylene groups can be monocyclic or polycyclic and, unless otherwise specified, have 3 to 10 carbon atoms in the ring. Alkyl, alkylene, cycloalkyl and cycloalkylene groups contain only carbon and hydrogen atoms.
[011] The term "solvent" refers to the homogeneous liquid material, which may be a simple compound or a combination of compounds and which may or may not include water, which is capable of at least partially dissolving the coating composition presented herein. invention at 25 ° C.
[012] The term "polymer" refers to a molecule that has a structure that essentially includes the multiple repetition of units derived, real or conceptually, from molecules of low relative molecular mass.
[013] The term "monomer" refers to a molecule of low relative molecular weight that can combine with others to form a polymer, which can be a polymer or acrylic copolymer.
[014] The term "acrylic" refers to acrylic and methacrylic polymers, which can be copolymers produced from one or more acrylates or methacrylates or other vinyl-containing monomers.
[015] The summary above the present description is not intended to describe each modality presented or all the implementations of the present description. The description that follows illustrates more particularly the illustrative modalities. It should be understood, therefore, that the following drawings and description are for illustration purposes only and should not be read in such a way as to unduly limit the scope of this description. Brief description of the drawings
[016] The description can be understood in a more complete way taking into account the detailed description below of the different modalities of the description together with the attached drawings.
[017] Figure 1 is a scanning electron micrograph with a 60,000x magnification of a representative surface of example 1C after accelerated weathering;
[018] Figure 2 is a scanning electron micrograph with a 60,000x magnification of a representative surface of example 1D after accelerated weathering; and
[019] Figure 3 is a scanning electron micrograph with a 60,000x magnification of a representative surface of example 3B after accelerated weathering. Detailed Description
[020] One field in which abrasion-resistant polymeric surfaces can be useful is the field of converting solar energy, in which sunlight is converted into electricity. Concentrated solar energy technology (CSP, also called “solar energy concentration”) uses sunlight aimed at heat transfer fluids that heat up and whose thermal energy is then transferred (for example, by heating) or converted in electricity (for example, through the use of a turbine generator). CSP systems typically use lenses or reflectors to focus a large area of sunlight on a small beam. Concentrated sunlight is then used as a heat source by a conventional powerhouse (for example, a turbine generator powered by water vapor). Concentration or concentrated photovoltaic (CPV) systems include photovoltaic cells or other photovoltaic materials that convert energy within sunlight into electrical energy. The reflective, refractive element, or both reflective and refractive elements are used to concentrate sunlight on cells or photovoltaic materials. The use of reflective and / or refractive materials reduces the amount of more expensive photovoltaic materials needed by the system.
[021] To allow solar energy conversion to be competitive with more traditional sources of electricity, advanced efforts aim to reduce the cost and / or optimize the efficiency of solar energy conversion systems. Mirror sets based on silver polymeric mirror films instead of glass-based mirror systems have the potential to reduce the cost of the system installed in solar fields by 20% or more, but polymeric mirror films may be less abrasion-resistant and less cleanable than its glass-based equivalent.
[022] The ability to effectively clean reflectors and lenses used in solar energy conversion systems without damaging them is important since dirt and surface scratches adversely affect the accuracy of the light's direction from these elements. Examples of adverse effects of dirt and scratched surfaces include decreased specular reflectance from mirror films, loss of light concentration from Fresnel lenses and impaired retro-reflectivity from retro-reflective elements. Losses in specular reflectance are directly converted into revenue losses. It is, therefore, desirable to optimize the durability of the mirror reflectance of the surfaces of polymeric mirror films to approximate the performance of glass-based mirror systems.
[023] The coating compositions according to the present description can typically provide abrasion resistant coatings on polymeric surfaces. Coating compositions typically adhere well to polymeric surfaces, even after exposure to weathering conditions. Additionally, in some embodiments, the coatings are either cleanable or resistant to dust accumulation.
[024] The coating composition according to the present description includes a polymer (PMMA) poly (methyl methacrylate), which can be a homopolymer or copolymer. The PMMA polymer or copolymer has an average molecular weight of at least 50,000 grams per mol. In some embodiments, the PMMA polymer or copolymer has an average molecular weight of at least 75,000 grams per mole, 100,000 grams per mole, 120,000 grams per mole, 125,000 grams per mole, 150,000 grams per mole, 165,000 grams per mole or 180,000 grams per mol. The PMMA polymer or copolymer can have an average molecular weight of up to 500,000 grams per mol, in some embodiments, up to 400,000 grams per mol, and in some embodiments, up to 250,000 grams per mol. It should be understood that in general the PMMA polymer or copolymer is a linear polymer or copolymer. When the PMMA polymer or copolymer has an average molecular weight of at least 50,000 grams per mol, as described in any of the above modalities, it has polymer chains long enough to be interwoven into a diacrylate or dimethacrylate interpenetration network. after curing. Without the desire to be bound by theory, it is believed that any chain cleavage that may occur upon exposure to UV light will not completely deinterlace the PMMA polymer or copolymer chains in the cured coating composition.
[025] Weight average molecular weights can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography (SEC)) using techniques known in the art. In general, the PMMA polymer or copolymer useful for the practice of the present description has the average molecular weight as specified in any of the above modalities as determined by the SEC with 4 columns “PL-GEL” (Polymer Labs, England), 30 x 0.78 cm, in series, with a gel particle diameter of 5 micrometers and a nominal porosity of the individual columns: 500, 103, 104 and 105, respectively. The sample solutions, approximately a concentration of 0.2% (weight / volume), are prepared in distilled tetrahydrofuran, which is also the chromatographic eluant. Before injections, the solutions are filtered through syringe filters with a 0.45 micrometer membrane. The injection volume is 200 microliters, and the flow rate of the eluent is adjusted to 1 cubic centimeter per minute. o-dichloro benzene can be added to polymer solutions as a standard internal flow. The column calibration can be performed with narrow PMMA distribution standards (Polymer Labs, England) and a third order of polynomial equation can be obtained from the regression analysis. By comparing chromatograms obtained from different samples, peak areas can be normalized. This method is described in Lazzari, M. and Chiantore, O. Polímero 41 (2000) 6447-6455.
[026] Useful PMMA copolymers include those produced from a C2-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate in combination with methyl methacrylate. In some embodiments, the PMMA copolymer includes at least one of ethyl acrylate, ethyl methacrylate, butyl acrylate or butyl methacrylate. In some embodiments, the copolymer is produced from starting monomers including methyl methacrylate in a range of 50%, by weight, to 90%, by weight (in some embodiments, from 60 to 85%, by weight) and a C2-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate in a range of 10% by weight to 50% by weight (in some embodiments from 15 to 40% by weight), based on the total weight of the monomers. In some of these embodiments, the C2-C8 alkyl acrylate or methacrylate or C3-C8 cycloalkyl acrylate or methacrylate is ethyl acrylate or n-butyl methacrylate. Useful PMMA copolymers are commercially available, for example, from the Dow Chemical Company, Midland, Mich., Under the trade name “PARALOID” and from Lucite International, Inc., Memphis, Tenn., Under the trade name “PERSPEX ”And“ ELVACITE ”. In the Polymer article described above, a copolymer available under the trade name “PARALOID B44” from the Dow Chemical Company is reported as a copolymer produced from 70.3 mol percent methyl methacrylate, 28 mol percent ethyl acrylate and about one mole percent butyl methacrylate and as having an average molecular weight of 105,000 grams per mole. Also in this article, a copolymer available under the trade name “PARALOID B48N” from the Dow Chemical Company is reported as a copolymer produced from 74.5 mol percent methyl methacrylate and 25.5 mol percent butyl acrylate and as having an average molecular weight of 184,000 grams per mol. In some embodiments, employing a copolymer of methyl methacrylate and n-butyl methylacrylate in the coating compositions presented in the present invention improves the abrasion resistance of the coating composition, as evidenced by the reduced opacity after exposure to sand fall, described in Examples, below (for example, in a comparison between Example 2 and Example 1B).
[027] Given the relatively high molecular weights of the PMMA polymer or copolymer in the coating composition presented in the present invention, the PMMA polymer or copolymer in the coating compositions presented in the present invention would not be considered a "macromer" like those described in the application US Patent No. WO 98/27171 (Christian). In addition, the PMMA polymer or copolymer is typically non-functional. That is, the PMMA polymer or copolymer does not typically contain reactive functional groups such as carboxylic acids, sulfonic acids, amino groups and polymerizable carbon-carbon double bonds.
[028] The coating composition according to the present description includes an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate. Alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenediimethacrylate can conveniently be a liquid at room temperature. Alkylene diacrylate or dimethacrylate is typically a C2-C10 alkylene diacrylate or dimethacrylate or a C4-C6 cycloalkylene diacrylate or dimethacrylate with no substituents on the alkylene or cycloalkylene group. The alkylene group in the diacrylate or dimethacrylate, by definition, does not include any heteroatoms or functional groups that interrupt the carbon chain, and the cycloalkylene group in the diacrylate or dimethacrylate, by definition, does not include any heteroatoms in the ring. The alkylene group can be straight or branched. Without sticking to the theory, it is believed that branching to the alkylene group can result in a cured coating, which has a lower modulus, which can increase the abrasion resistance of cured coating compositions in some embodiments. Examples of useful difunctional acrylates and methacrylates include hexane diol diacrylate, hexane diol dimethacrylate, neopentyl glycol diacrylate and neopentyl glycol dimethacrylate.
[029] The coating compositions shown in the present invention have been found to have good adhesion to polymeric substrates after curing even in the absence of alkoxy groups in acrylic monomers. In contrast, some protective coatings and curable inks rely on alkyleneoxy groups for adhesion or flexibility (see, for example, US patent No. 7,943,681 (Lee et al.) And US patent application No. 2008/0026334 (Williamson et al.) Alkoxy groups in cured coatings may have a tendency to oxidize over time when exposed to UV light. Consequently, alkylene or cycloalkylene diacrylates or dimethacrylates are not prepared from alkoxylated diols and are free from ethylene-oxy and propylene-oxy groups.
[030] Alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate and / or cycloalkylenedimethacrylate provide at least 80 weight percent of the monomer in the coating compositions shown in the present invention. In some embodiments, alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate and / or cycloalkylenedimethacrylate provide at least 85, 90, 95, 96, 97, 98, 99 or even 100 weight percent of the monomer. In other words, monomers (for example, acrylic monomers) in addition to alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate and / or cycloalkylenedimethacrylate constitute no more than (for example, less than) 20, 15, 10, 5, 4, 3 , 2 or 1 weight percent, based on the total weight of the monomer in the coating composition. In some embodiments, the coating composition can be considered to be substantially free of monomers (for example, acrylic monomers) in addition to alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate and / or cycloalkylenedimethacrylate. In some embodiments, the monomer in the coating composition can be considered to consist of an alkylene diacrylate, an alkylene dimethacrylate, a cycloalkylene diacrylate, a cycloalkylenediimethacrylate, or a combination thereof.
[031] The coating compositions presented in the present invention therefore do not have significant amounts of monofunctional acrylates or methacrylates. A "significant" amount of monofunctional acrylate or methacrylate is an amount that can reduce crosslink density and reduce abrasion resistance. A "significant" amount of monofunctional acrylate or methacrylate can be considered to be more than about 15 weight percent based on the total weight of the monomer in the coating composition. In some embodiments, the monomer includes no more than 15, 10, 5, 4, 3, 2 or 1 weight percent of monofunctional acrylate or methacrylate, based on the total weight of the monomer in the coating composition.
[032] The coating compositions presented in the present invention also lack significant amounts of tri-, tetra- or highly functional acrylates or methacrylates. A "significant" amount of tri-, tetra- or highly functional acrylate or methacrylate is an amount that can cause the cured composition to be brittle, have very high modulus, or can result in unreacted acrylic or methacrylic functional groups in the cured composition , any of which may compromise the weathering performance of the coating compositions. A "significant" amount of tri-, tetra- or highly functional acrylates or methacrylates can be considered to be more than about 10 weight percent based on the total weight of the monomer in the coating composition. In some embodiments, the monomer includes no more than 7.5, 5, 4, 3, 2 or 1 percent, by weight, of tri-, tetra- or highly functional acrylates or methacrylates, based on the total weight of the monomer in the coating composition.
[033] When the modulus of the coating is very high, a module incompatibility after exposure to the environment can cause cracking or delamination. An illustration of a high modulus coating is provided in Illustrative Example 1, below. After exposing just one cycle to an atmospheric wear device, a high modulus coating prepared from only 1,6-hexane diol diacrylate and photoinitiator was promptly removed from a PMMA substrate using Adhesion Assessment described in the Examples, below. In addition, Illustrative Example 2 illustrates that a coating prepared from penta-acrylate available from Sartomer USA, LLC (Exton, Penn.) Under the trade name “SR-9041” has more opacity through wear by atmospheric agents than o Illustrative Example 1, which may be a result of unreacted acrylate groups. Such results can be considered typical for highly cross-linked coatings, such as those that would result if significant amounts of tri-, tetra- or highly functional acrylates or methacrylates were used in the coating compositions presented in the present invention.
[034] In some embodiments, the coating prepared from the coating composition shown in the present invention has an elongation of less than 50% (in some embodiments, less than 25% or less than 10%). The coating compositions, in any of their modalities, generally do not include urethane acrylates, which tend to lower the modulus and increase the elongation, or do not include more than 10, 5, 3 or 1 weight percent of an urethane acrylate, based on the total weight of the monomer in the coating composition. In addition, by definition, alkylene or cycloalkylene diacrylates or dimethacrylates are not prepared from urethanes and are free of urethane and urea groups.
[035] In the coating compositions shown in the present invention, a variety of monomer ratios comprising at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate for the polymer or poly (methyl methacrylate) copolymer. In any of the PMMA polymer or copolymer modalities or the monomer described above, the ratio of the weight of the monomer comprising at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate and the weight of the polymer or copolymer of poly ( methyl methacrylate) can be in a range of 0.75: 1 to 15: 1. In addition, in any of the aforementioned modalities, the monomer can be present in the composition in a range of 20 percent by weight to 90 percent by weight (in some embodiments, 20 percent by weight to 80 percent percent, by weight, or 23 percent, by weight, to 75 percent, by weight), based on the total weight of the non-volatile components of the composition. The PMMA polymer or copolymer can be present in the composition in a range of 2 percent by weight to 40 percent by weight (in some embodiments, 4 percent by weight, less than 40 percent, in weight, such as up to 39, 38 or 37 weight percent) based on the total weight of the non-volatile components of the composition. In some embodiments, for example, the embodiments in which the coating composition contains no charge, the ratio of the weight of the monomer, which comprises at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene or cycloalkylenedimethacrylate, and the weight of the polymer or poly (methyl methacrylate) copolymer has a range of 0.75: 1 to 5: 1, 1: 1 to 4: 1 or 1.5: 1 to 3: 1. In any of these modalities, the monomer can be present in the composition in a range of 40 percent by weight to 90 percent by weight (in some modalities 41, 42, 43, 44 or 45 percent by weight , at 90 or 80 percent by weight), based on the total weight of the non-volatile components of the composition, and the PMMA polymer or copolymer can be present in the composition in a range of 20 percent, by weight, at 40 percent. percent by weight (in some embodiments, 20 percent by weight, less than 40 percent by weight, such as up to 39, 38 or 37 percent by weight) based on the total weight of the non-volatile components of the composition. In some embodiments, for example, the embodiments in which the coating composition includes filler as described in further detail below, the weight ratio of the monomer, which comprises at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate and the The weight of the polymer or poly (methyl methacrylate) copolymer is in a range of 0.75: 1 to 15: 1, 0.75: 1 to 12.5: 1 or 1: 1 to 10: 1.
[036] The coating compositions according to the present disclosure adhere well to polymeric substrates and, in some embodiments, are apparently resistant to the harmful effects of the thermal expansion incompatibility coefficient or moisture expansion incompatibility coefficient, which can occur through exposure to wear by atmospheric agents. In some embodiments, for example, the modalities where the ratio of the weight of the monomer, which comprises at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenedimethacrylate and the weight of the PMMA polymer or copolymer is in a range of 1: 1 to 10: 1, the coating composition according to the present disclosure adheres surprisingly well to polymeric substrates (for example, acrylic substrates).
[037] The coating composition according to the present description includes a stabilizer against UV light. The stabilizer can be a UV absorber (UVA), a hindered amine-based photostabilizer (HALS) or a combination thereof. A UVA is typically a compound capable of absorbing or blocking electromagnetic radiation at wavelengths less than 400 nanometers (nm) while remaining substantially transparent at wavelengths greater than 400 nm. UVAs are known to those skilled in the art as being able to dissipate the light absorbed energy from UV rays as heat by reversible intramolecular proton transfer. Such compounds can interfere with the physical and chemical processes of photoinduced degradation. UVAs are typically included in the coating compositions presented in the present invention in an amount sufficient to absorb at least 70% (in some embodiments, at least 80%, or more than 90% of UV light in the 180 nm wavelength region) at 400 nm). Typically, it is desirable for UVA to be highly soluble in polymers, highly absorbent, photopermanent and thermally stable in the temperature range of 200 ° C to 300 ° C. UVA can also be highly suitable if it can be copolymerized with the monomers in the coating composition presented in the present invention through free radical polymerization. In some embodiments, the stabilizer in the coating composition shown in the present invention is a red shifted UVA (RUVA). RUVAs typically have enhanced spectral coverage in the long-wave UV region, allowing it to block from high-wavelength UV light that can cause yellowing in polymers. HALS are typically compounds that can remove free radicals, which can be caused by photodegradation.
[038] Any class of UVA can be useful. Examples of useful classes include benzophenones, benzotriazoles, triazines, cinnamates, cyanoacrylates, ethylene dicyans, oxanilide silicylates and para-aminobenzoates. Suitable UVAs include triazines (for example, hydrophenyl substituted triazines, such as 2- (4,6-diphenyl-1-3,5-triazin-2-yl) -5- [(hexyl) oxy] phenol and 2-hydroxyphenyl- s-triazine), hydroxybenzophenones, and benzotriazoles (for example, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3, 5-di-alpha-cumylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzothiazole, 5-chloro-2- (2-hydroxy- 3,5-di-tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-alpha-cumil- 5-tert-octylphenyl) - 2H-benzotriazole, and 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole). Suitable HALS include bis (2,2,6,6-1- (octyloxy) -4-piperidinyl) decanedioic acid ester. Suitable UVAs and HALS include those available, for example, from BASF, Florham Park, NJ, USA, under the trade names “TINUVIN” and “CHIMASSORB”.
[039] In any of the aforementioned embodiments, the coating composition according to the present description can include a free radical initiator. The free radical initiator can be a thermal initiator, such as an azo compound (for example, 2,2'-azo bis isobutyryl nitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), or azo-2- acid cyanovaleric), a hydroperoxide (for example, cumene, tert-butyl or tercamyl hydroperoxide), a dialkyl peroxide (for example, di-tert-butyl or dicumylperoxide), a peroxyester (for example, tert-butyl perbenzoate or peroxyphthalate) di-tert-butyl), and a diacylperoxide (for example, benzoyl peroxide or lauryl peroxide). The free radical initiator may advantageously also be a photoinitiator. Examples of useful photoinitiators include benzoyl ethers (for example, benzoyl methyl ether or benzoyl butyl ether); acetophenone derivatives (for example, 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone); 1-hydroxy cyclohexyl phenyl ketone; and acylphosphine oxide derivatives and acylphosphonate derivatives (eg bis (2,4,6-trimethyl benzoyl) phenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, isopropoxyphenyl-2,4,6- oxide trimethylbenzoylphosphine, or dimethyl pivaloylphosphonate). In some embodiments, the photoinitiator is not a hexa-arylbi-imidazole photoinitiator. In some embodiments, the photoinitiator does not contain an oxime ester functional group. Several photoinitiators are available, for example, from BASF under the trade name “IRGACURE”. When the coating composition shown in the present invention includes a photoinitiator, the coating composition can be applied to a substrate and then exposed to light (e.g., UV light) to form a cured coating on the surface of the substrate.
[040] The coating compositions according to the present description may contain organic solvent. Any solvent that can dissolve the PMMA polymer or copolymer can be useful. Non-volatile components (ie, components other than solvent) can be present in the solvent at any suitable concentration. For example, non-volatile components can be present in a range of about 5 percent to about 90 percent, by weight, from about 30 percent to about 70 percent, by weight, or about 40 percent to 65 percent, by weight, based on the total weight of the coating composition). Illustrative examples of suitable solvents include aliphatic and alicyclic hydrocarbons (for example, hexane, heptane, and cyclohexane), aromatic solvents (for example, benzene, toluene and xylene), ethers (for example, diethyl ether, glyme, diglyme and isopropyl diether), esters (for example, ethyl acetate and butyl acetate), alcohols (for example, ethanol, isopropyl alcohol, and 1-methoxy-2-propanol), and ketones (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone). In some embodiments, the solvent comprises at least one of methyl ethyl ketone, acetone, ethyl acetate, 1-methoxy-2-propanol, isopropanol and toluene. It is also possible, in some embodiments, that the coating compositions are essentially free of organic solvent. That is, the coating compositions can contain less than 5 percent solvent, by weight, based on the total weight of the coating composition.
[041] With or without organic solvent, the coating compositions according to the present description are typically homogeneous solutions or dispersions that are capable of providing PMMA and monomer polymer or copolymer interpenetration networks after crosslinking. In other words, in a coating composition disclosed in the present invention, neither the PMMA polymer or copolymer nor the monomer, which comprises at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate, or cycloalkylenedimethacrylate, is already substantially cross-linked (for example , before being applied to a substrate and cured). The PMMA polymer or copolymer is capable of being dissolved in an organic solvent or monomer and therefore can generally be considered as a linear polymer. And it must be understood that the terms diacrylate and dimethacrylate in reference to the monomer refer to compounds that still have their reactive functional groups and are not yet polymerized.
[042] In some embodiments, the coating composition according to the present disclosure includes inorganic particles, which can be inorganic oxide particles. Inorganic oxide particles include a single oxide, such as silica, a combination of oxides, such as silica and aluminum oxide, or a core of an oxide of one type (or a core of a material other than a metal oxide) on which an oxide of another type is deposited. Examples of suitable inorganic oxide particles include silica, zirconia, titanium oxide, antimony oxides, alumina, tin oxides, combinations thereof or mixed metal oxides thereof. In some embodiments, the coating composition shown in the present invention includes silica (in some embodiments, having an average particle size of up to 500 nanometers).
[043] Inorganic particles (for example, silica, zirconia, titanium oxide, antimony oxides, alumina, tin oxides, combinations of these or mixed metal oxides of these), in any of the modalities in which they are included, may have an average particle size of up to 500 nanometers (nm), which can be in a range of 5 nm to 500 nm, 10 nm to 300 nm, 5 nm to 100 nm, or 5 nm to 20 nm. The “average particle size” refers to the maximum cross-sectional dimension of a particle and, in the case of spherical particles, it can refer to the diameter. The average particle size of inorganic oxide particles can be measured using transmission electron microscopy to count the number of inorganic particles with a given diameter. The inorganic particles can have a substantially monodisperse size distribution or a polymodal distribution obtained by mixing two or more substantially monodispersed distributions.
[044] Inorganic oxide particles are often supplied in the form of a sol containing a colloidal dispersion of inorganic oxide particles in a liquid medium. The sun can be prepared using a variety of techniques and in a variety of ways, including hydrosols (in which water serves as a liquid medium), organosols (in which organic liquids serve as a liquid medium), and mixed suns (in which the liquid medium contains both water and an organic liquid), for example, as described in US Patent No. 5,648,407 (Goetz et al.); 5,677,050 (Bilkadi et al.) And 6,299,799 (Craig et al.). Aqueous suns (for example, amorphous silica) can be used. Suns typically contain at least 2% by weight (% by weight), at least 10% by weight, at least 15% by weight, at least 25% by weight, and often at least 35% by weight of colloidal particles of inorganic oxide, based on the total weight of the sun. The amount of colloidal particles of inorganic oxide is typically not more than 50% by weight (for example, not more than 45% by weight). The particle size can be determined, for example, by selecting a specific sun. Alternatively, inorganic particles can be introduced having a range of particle sizes obtained by grinding the particles of inorganic oxides to a desired size range. Inorganic oxide particles are typically non-aggregated (substantially discontinuous), as aggregation can result in optical dispersion (opacity) or precipitation of inorganic oxide particles or gelation.
[045] Inorganic particles, including those described in any of the modalities, are typically treated with the surface treatment agent. Surface treated inorganic oxide particles (for example, those having an average particle size of up to 500 nm) can provide a stable dispersion in the coating composition. In some embodiments, the surface of the inorganic particles can be functionalized with acrylate or methacrylate, as described, for example, in US patent No. 5,677,050 (Bilkadi et al.), Which allows the surface treatment on the particles to react with the monomer in the coating composition shown in the present invention. The covalent bonding of the monomer can result in a more resistant and more homogeneous polymer / particle network.
[046] In general, a surface treatment agent has a first end that will attach to the surface of the particle (for example, covalently, ionically or through strong physisorption) and a second end that confers compatibility of the particle with the monomer and / or PMMA polymer or copolymer and / or reacts with the monomer during curing. The type of treatment agent (for example, alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes and titanates) can be selected based on, in part, the chemical nature of the metal oxide surface. For example, silanes are useful for silica and other silica fillers. In general, the inorganic oxide particles are treated with the surface treatment agent before the inorganic oxide particles are incorporated into the coating composition shown in the present invention. The amount of surface modifier useful for treating inorganic oxide particles depends on several factors, such as particle size, particle type, molecular weight of the modifier and type of the modifier. In some embodiments, approximately a single layer of modifier is attached to the surface of the particle. The fixing procedure or reaction conditions required also depend on the surface modifier used. For example, silanes can be combined with silica or other silica fillers at elevated temperatures under acidic or basic conditions for approximately one to 24 hours. The surface modification can also be carried out according to the methods described in US patent No. 7,101,616 (Arney et al.). A combination of surface treatment agents can be useful. For example, combinations of the surface modifying agent can result in lower viscosity of the coating composition containing the inorganic particles with the modified surface.
[047] In some embodiments, the surface treatment agent (s) for the inorganic particles in the coating compositions presented in the present invention comprises (m) at least one of 3- (methacryloyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- (methacryloyloxy) propiltrietoxisilano, 3- (methacryloyloxy) propilmetildimetoxisilano, 3- (acriloiloxipropil) metildimetoxisilano, 3- (methacryloyloxy) propildimetiletoxisilano, 3- (methacryloyloxy) propildimetiletoxisilano, vinildimetiletoxisilano, vinilmetildiacetoxisilano, vinilmetildietoxisilano, viniltriacetoxisilano, vinyltriethoxysilane, viniltri-isopropoxisilano, vinyltrimethoxysilane , vinyltriphenoxysilane, vinyltri-t-butoxysilane, vinyltris-isobutoxysilane, vinyltri-isopropenoxysilane, vinyltris (2-methoxyethoxy) silane or mercaptopropyltrimethoxysilane. In some embodiments, a combination of such a surface treatment agent, which can react with the monomer in the coating composition shown in the present invention, and a surface treatment agent, which has a non-reactive end (for example, propyltrimethoxysilane or hexyltrimethoxy silane) can be useful.
[048] In some embodiments, where inorganic particles include silica particles that have an average size of up to 500 nm (including any of the size ranges described above), silica particles are surface-modified silica particles having functional groups acrylate or methacrylate on their surfaces, and if the modified surface silica particles have acrylate functional groups on their surfaces, the monomer comprises at least one of alkylene diacrylate or cycloalkylene diacrylate, and if the silica particles with modified surface have functional groups methacrylate on their surfaces, the monomer comprises at least one among alkylene dimethacrylate or cycloalkylene dimethacrylate. Without sticking to the theory, it is believed that when the reactive monomer acrylate or methacrylate corresponds to the silica particles, more covalent bonds between the cured coating and the silica particles occur, depending on the reaction conditions (for example, due to the comparable kinetics of monomer polymerization and surface treatment). As a result, the effects of thermal expansion and humidity can be less pronounced in these modalities, better performance in wear by atmospheric agents can be achieved.
[049] In some embodiments, where inorganic particles include silica particles having an average size of up to 500 nm (including any of the size ranges described above), the silica particles have surface modified with PMMA. For example, a surface-modified silica particle with methacrylate or acrylate prepared as described above can be combined with methyl methacrylate monomer and a free radical initiator in a suitable heated solvent or exposed to light to provide a silica particle of PMMA with modified surface. Free radical initiators such as those widely known and used in the art can be used to initiate the polymerization of components. Examples of free radical initiators include azo compounds (for example, 2,2'-azo bis isobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), or azo-2-cyanovaleric acid), hydroperoxides (eg cumene, tert-butyl or tert-amyl hydroperoxide), dialkyl peroxides (for example, di-tert-butyl or dicumyl peroxide), peroxyesters (for example, tert-butyl perbenzoate or di-tert-peroxyphthalate butyl), diacyl peroxides (eg benzoyl peroxide or lauryl peroxide). Temperature and solvent for a particular use can be selected by those skilled in the art based on considerations such as the solubility of the reagents, the temperature required for the use of a particular initiator and the desired molecular weight. In general, suitable temperatures are in the range of about 30 ° C to about 200 ° C (in some embodiments, from about 40 ° C to about 100 ° C, or even about 50 ° C to about 80 ° C). The PMMA grafted on the silica particles is compatible with the PMMA polymer or copolymer and the monomers. As a result, coatings produced from coating compositions, including PMMA-grafted silica particles, are stable after wear by extended atmospheric agents, and, in some embodiments, have good resistance to abrasion.
[050] In some embodiments, coatings produced from coating compositions, including silica particles grafted with PMMA, are more stable after wear by extended atmospheric agents than coatings produced from coating compositions, including those surface-modified silica particles with methacrylic groups. For example, Figure 1 shows a scanning electron micrograph of Example 1C, which is a cured coating that includes silica particles that have had the surface modified with methacrylic groups after being exposed to a total UV of 746 MJ / m2. By comparison, Figure 3 shows a scanning electron micrograph of Example 3A, which is a cured coating that includes silica particles grafted with PMMA, after being exposed to a total UV of 746 MJ / m2. In addition, the water contact angle measurements for Example 3A decreased much less than the water contact angles for Example 1C after exposure to a total UV of 746 MJ / m2 or more.
[051] For any of the embodiments of the coating composition according to the present disclosure described above, the coating composition may include an acrylic copolymer containing silicone. The silicone-containing acrylic copolymer can be a copolymer of a silicone acrylate or methacrylate and a C1-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate, for example. The silicone-containing acrylic copolymer can be a copolymer of a C1-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate, for example, and a silicone-containing chain transfer agent (for example, a mercaptane). When a silicone chain transfer reagent is used, the resulting copolymer may contain more acrylic alkyl side chains (e.g., PMMA) than when a silicone acrylate or methacrylate monomer is used in the polymerization. The acrylate or methacrylate containing silicone or the chain transfer agent containing silicone may have an average molecular weight of at least 1000 (in some embodiments, at least 2000, 2500, 5000 or 7500) grams per mol and up to about 20,000 ( in some embodiments, up to 17,500 or 15,000) grams per mol. In some embodiments, the silicone-containing chain transfer agent is a mercapto-functional silicone having the following formula:

[052] where x is in a range of 50 to 150, and y is in a range of 1 to 10. Functional mercapto silicones having this structure can be obtained commercially, for example, from Shin-Etzu Silicones of America (Akron , Ohio, USA) under the trade name “KF-2001”, which is reported to have a molecular weight of 8000 grams per mole and an equivalent mercapto group weighing about 1,900 grams per mole. In some modalities, silicone acrylate is represented by the formula
[053] CH2 = C (CH3) -C (O) -O- (CH2) 3-Si (CH3) 2- [OSi (CH3) 2] nO-Si (CH3) 2- (CH2) 3- CH3 with a molecular weight of about 10,000 g / mol. Such silicone acrylates can be prepared by the method described in US Patent No. 4,728,571 (Clemens et al.), And some are commercially available, for example, available from Shin-Etsu Silicones of America, Inc, Akron, Ohio, USA, under the trade name “X-22-2406”. Still other silicone acrylates include silicone polyether acrylates available, for example, from Evonik Tego Chemie GmbH, Essen Germany, under the trade name “TEGO RAD 2250”.
[054] Acrylic copolymers containing silicone useful in some embodiments of the coating compositions presented here can be prepared, for example, by combining a chain transfer agent containing acrylate silicone or a silicone methacrylate and a C1-C8 acrylate or methacrylate alkyl or a C3-C8 cycloalkyl acrylate or methacrylate in a suitable solvent and heating or photopolymerizing in the presence of a free radical initiator. Examples of useful thermal free radical initiators include azo compounds (for example, 2,2'-azo bis isobutyryl nitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), or azo-2-cyanovaleric acid), hydroperoxides (eg, cumene, tert-butyl or tert-amyl hydroperoxide), dialkyl peroxides (eg, di-tert-butyl or dicumyl peroxide), peroxyesters (eg, tert-butyl perbenzoate or di-peroxyphthalate) tert-butyl), diacyl peroxides (eg benzoyl peroxide or lauryl peroxide). Temperature and solvent for a particular use can be selected by those skilled in the art based on considerations such as the solubility of the reagents, the temperature required for the use of a particular initiator and the desired molecular weight. In general, suitable temperatures are in the range of about 30 ° C to about 200 ° C (in some embodiments, from about 40 ° C to about 100 ° C, or even about 50 ° C to about 80 ° C). For ease of incorporation into the coating composition shown in the present invention, it may be desirable for the acrylic copolymer containing silicone to have an inherent viscosity in the range of 0.15 to 0.50 dL / g, as determined by a Cannon-Fenske viscometer. In embodiments where the coating composition contains an acrylic copolymer containing silicone, the resulting coating is typically more easily cleaned than a control, in which the acrylic copolymer containing silicone is not included, as assessed by the provided "cleanability" assessment method in the Examples, below. For example, a comparison between Example 1E, which includes the copolymer of PMMA and HDDA, with Example 4 or Example 5, which includes the same copolymer of PMMA and HDDA together with an acrylic monomer containing silicone, the amount of opacity measured for Example 1E increases more after the “cleanability” assessment than the amount of opacity measured for Example 4 or Example 5.
[055] In some embodiments, the coating compositions presented in the present invention that have an acrylic monomer containing silicone provide an angle of contact with water of at least 90 degrees, in some embodiments, at least 95 degrees or 100 degrees prior to exposure to any accelerated weathering.
[056] The coating compositions can also include other additives, depending on the desired application of the coating. Optional additives include dyes, slip modifiers, defoaming agents, flow control agents or other rheology, antioxidants, photoinitiator stabilizers, gloss agents, fungicides, bactericides, leveling agents, antistatic agents and dispersants, for example. In some embodiments, for example, in embodiments in which an optically transparent coating is desired, the coating compositions do not include dyes, such as pigments.
[057] The present description presents a substrate coated with the coating composition as in any of the modalities described above. The substrate can be a polymeric film or sheet. Typical polymeric materials include acrylics, polyesters, polycarbonates, cyclic olefin copolymers, silicones and fluoropolymers. Additional examples of polymeric materials include polyester (eg, polyethylene terephthalate, polybutylene terephthalate), cyclic olefin copolymer (COC), fluoropolymers (eg, ethylene tetrafluoroethylene, polyvinylidene fluoride (PVDF), and THV), polycarbonate, carbonate, polycarbonate of allyl diglycol, polyacrylates such as polymethyl methacrylate, polystyrene, polysulfone, polyether sulfone, homoeppoxy polymers, epoxy addition polymers with polydiamines, polydithols, polyethylene copolymers, fluorinated surfaces, cellulose esters and butyl acetate (eg. In some embodiments, the substrate is flexible and produced from polyesters (for example, polyethylene terephthalate (PET)), cyclic olefin copolymer (COC), polyolefins (for example, PP (polypropylene) or PE (polyethylene) ), or PVC (polyvinyl chloride). In some embodiments, the substrate comprises PMMA. In some embodiments, the substrate comprises PET. In some embodiments, the substrate is a blend of an acrylic polymer and another polymer (for example, PVDF). In some embodiments, the substrate is a multilayer optical film (that is, having an optical layer stack), for example, such as those described in US Patent No. App. US No. 2009/0283144 (Hebrink et al.) And 2012/0011850 (Hebrink et al.). In some of these modalities, the multilayer optical film reflects at least a large portion of the average light across the wavelength range that corresponds to the width of the absorption range of a selected photovoltaic cell and does not reflect a large portion of the light that is outside the width of the absorption range of the photovoltaic cell. In other embodiments, the multilayer optical film can be combined with a metal layer to provide a broadband reflector. In some embodiments, the substrate is a mirror film, which may have a polymer layer (or layers) and a metal layer. In some of these embodiments, the polymer layer is a PMMA layer. In some of these embodiments, the coating composition is applied to the PMMA layer. In some of these embodiments, the substrate is a Fresnel lens (for example, an acrylic Fresnel lens). In some of these embodiments, the substrate is a dark film. In some of these embodiments, the substrate is a retroreflective sheet.
[058] The substrate can be made into a film using conventional filmmaking techniques, such as extruding the substrate resin into a film and the optional uniaxial or biaxial orientation of the extruded film. Suitable commercial films include polymethyl methacrylate (PMMA) films available, for example, under the trade name "SOLATUF" from Rowland Industries, Wallingford, CT, and polycarbonate (PC) films under the trade name "BAYFOL" or "MAKROFOL ”Available from Bayer Material Science.
[059] For any of the substrate modalities described above, the main surface of the polymeric substrate to be coated with the coating composition presented in the present invention can be treated to optimize adhesion to the coating. Useful surface treatments include electrical discharge in the presence of an appropriate reactive or non-reactive atmosphere (for example, plasma, luminescent discharge, corona discharge, dielectric barrier discharge, or atmospheric pressure discharge); chemical pre-treatment; pretreatment with UV flash lamp; or flame pretreatment. The primer can be applied while the substrate is being produced or in a separate process. In some embodiments, the substrate is treated with a corona before the coating composition shown in the present invention is applied. In some of these modalities, the corona treatment is a corona treatment with nitrogen at any suitable power (for example, 0.5 joules / square centimeter). Corona treatment with nitrogen can be carried out, for example, as described in US Patent No. 7,442,442 (Strobel et al.).
[060] To produce a coated article according to the present disclosure, a surface of the polymeric substrate, which can be treated (for example, corona treated) as described above, is brought into contact with a coating composition shown in the present invention. . The surface of the polymeric substrate can be contacted with the use of conventional coating techniques, for example, brush, bar, cylinder, cleaning cloth, canvas, gravure, spray or immersion coating techniques. In some embodiments, the coating composition shown in the present invention is provided on the surface of the polymeric substrate using the microgravure coating.
[061] The coating composition can be applied to the polymeric substrate in any thickness useful to provide a continuous coating. That is, in general, it is desirable that the coating forms a layer on the polymeric substrate, so that the layer does not have any breaks or gaps in the area where it is coated, which can be the entire surface of the substrate. In some embodiments, the coating composition is applied, so that the coating (after any drying described below) has a thickness of at least 8 micrometers. In some embodiments, the thickness of the coating on the substrate can be at least 10, 15 or 20 micrometers and up to about 50 micrometers.
[062] In embodiments where the coating composition includes organic solvents, the solvent can be at least partially removed by drying. Drying can be carried out at room temperature over time, or an elevated temperature can be useful. In some embodiments, an article that has been brought into contact with the coating composition shown in the present invention can be dried at a temperature of at least 50 ° C, 60 ° C, 70 ° C or 80 ° C, up to a temperature of about 120 ° C, depending on the temperature limits of the selected substrate. When the coated article is produced by continuous film processing, the film can be directed through an oven having a series of temperature zones, which can be at the same temperature or at higher temperatures in succession.
[063] In many embodiments, the coating composition shown in the present invention can be cured to provide a coating on the surface of the polymeric substrate by exposing the coating composition to actinic radiation. In some embodiments, a photoinitiator as described above is present, and the coating composition is irradiated with ultraviolet radiation from a lamp, in some embodiments, in an inert atmosphere, such as nitrogen. If electron beam radiation is used for healing, a photoinitiator does not need to be used. The amount of actinic radiation useful for curing depends on several factors including the amount and type of reagents involved, the energy source, the speed of the mat, the distance from the energy source and the thickness of the coating composition. Ultraviolet radiation can be useful to provide about 0.1 to about 10 Joules per square centimeter of total energy exposure, and useful amounts of electron beam radiation provide a total energy exposure in a range of less than 1 megarad to 100 megarads or more (in some modalities, in a range of 1 to 10 megarads). Exposure times can range from less than about a second to ten minutes or more.
[064] In some embodiments, the coating composition shown in the present invention can be cured to provide a coating on the surface of the polymeric substrate by heating the substrate with the applied coating composition. In these embodiments, a thermal free radical initiator as described above is present, and the coating composition is heated, in some embodiments, in an inert atmosphere, such as nitrogen. The temperature and solvent for a specific coating composition can be selected by those skilled in the art based on considerations, such as the temperature required to use a specific initiator, the desired molecular weight and the temperature limits of the substrate. In general, suitable temperatures are in the range of about 30 ° C to about 120 ° C (in some embodiments, from about 40 ° C to about 100 ° C, or even about 50 ° C to about 80 ° C).
[065] In some embodiments of articles coated in accordance with the present description, there are the first and second coatings on the substrate. The first coating is prepared from the coating compositions according to any of the coating compositions described above, and the second coating can be on top of the first coating. The second coating can be useful, for example, to enhance the cleanability of the coated article or to provide the coated article with self-cleaning properties.
[066] In some embodiments, the second coating comprises particles of silica that have an average particle size of up to 500 nm, 300 nm, 150 nm or 100 nm. For example, silica nanoparticles can range from 1 nm to 500 nm, 1 nm to 300 nm, 1 nm to 100 nm, 2 nm to 40 nm or 2 nm to 25 nm. The second coating can be applied from a second coating composition, which, in some embodiments, includes an aqueous continuous liquid phase and dispersed silica particles. In some embodiments, for example, in embodiments in which at least a portion of the silica particles have a size in the range of 2 nm to 40 nm, these silica coating compositions, when acidified, can be coated directly on the first coating relatively more hydrophobic presented in the present invention, without the need for organic solvents or surfactants, although in other embodiments, such solvents and surfactants may be useful. The second coating compositions can be coated on the first coating, for example, when they are acidified with HCl at a pH = 2 to 3, and even to 5 in some embodiments. However, the second coating compositions can slip on the first coating at a neutral or basic pH. Without wishing to stick to the theory, it is believed that silica particle agglomerates are formed through acid-catalyzed siloxane bonding in combination with protonated silanol groups on the particle surfaces, and these agglomerates can be applied as a coating on the first coating.
[067] Aqueous silica sols, including a variety of colloidal sizes, are commercially available as described above. Useful silica particles can be spherical or non-spherical. The useful non-spherical silica particles are available, for example, in aqueous suspension under the trade name “SNOWTEX” from Nissan Chemical Industries (Tokyo, Japan). In some embodiments, the second coating composition may have an average particle size of less than 40 nm. In some embodiments, the second coating composition may have an average particle size of less than 100 nm. Mixtures of silica particles sized in different sizes can be useful. For example, at least a portion of the silica particles may have an average particle size in the range of 2 nm to 40 nm (in some embodiments, 2 nm to 25 nm), and other silica particles may be present (for example , having an average particle size of up to 150 nm or 100 nm).
[068] The second coating composition typically contains an acid that has a pKa (H2O) of <3.5, <2.5, or in some embodiments less than 1. Useful acids include both organic and organic acids. inorganic, and examples include oxalic acid, citric acid, H2SO3, H3PO4, CF3CO2H, HCl, HBr, HI, HBrO3, HNO3, HClO4, H2SO4, CH3SO3H, CF3SO3H and CH3SO2OH. In some embodiments, the acid is selected from the group consisting of HCl, HNO3, H2SO4, H3PO4 and combinations thereof. In some embodiments, a mixture of an organic and inorganic acid can be useful.
[069] The second compositions can be coated over the first coating using conventional coating techniques, such as brush, bar, cylinder, cleaning cloth, canvas, rotogravure, spray or immersion coating techniques. The second coating composition generally contains between about 0.1 and 10% by weight of solids. For any of the coating methods for the second coating composition, the thickness of the wet coating can be, for example, in the range of 0.5 to 300 micrometers, or 1 to 250 micrometers. The thickness of the second dry coating depends on the specific composition being coated, but, in general, the average thickness of the dry composition thickness is between 0.002 and 5 micrometers, in some embodiments, between 0.005 and 1 micrometer. The thicknesses of the dry coating layer can be higher, as high as a few microns or even as high as 100 microns in thickness, depending on the application. However, the second thinner coatings still provide useful resistance to dust accumulation, as described in Illustrative Example 3, below.
[070] In some embodiments, an article that has been brought into contact with the second coating composition can be oven dried at a temperature of at least 50 ° C, 60 ° C, 70 ° C or 80 ° C and up to 120 ° C depending on the temperature limits of the selected substrate. When the coated article is produced by continuous film processing, the film can be directed through an oven having a series of temperature zones, which can be at the same temperature or at higher temperatures in succession. In general, the article that has been coated with the second coating composition is heated for a time of up to 30 minutes, up to 20 minutes, up to 10 minutes, or up to 5 minutes. The substrate surface can then be cooled quickly, or variations in heating and cooling can be used to quench the substrate.
[071] In some embodiments, the second coating composition may include a surfactant. In some embodiments, the second coating composition may include a coupling agent such as a tetraalkoxy compound (for example, tetraethylorthosilicate) or an oligomeric coupling agent (for example, poly (detoxoxysiloxane). In some embodiments, the coating composition comprises an organic polymer binder. For example, the coating composition may comprise a polymeric latex, such as aliphatic polyurethane. In another example, the coating composition may comprise a water-soluble copolymer of acrylic acid and an acrylamide, or a salt thereof. The weight ratio of the silica particles to the polymer-based binder is generally at least 1: 1, and in specific examples it ranges from 4: 1 to 9: 1. of organic polymer, the pH of the second coating composition can be 5 or more.
[072] In some embodiments, the articles presented in the present invention, which have a second coating including silica particles with an average particle size of up to 500 nm, 300 nm, 150 nm or 100 nm, provide an angle of contact with water up to 20 degrees, in some modalities, up to 15 degrees or 10 degrees. Additional details about useful second coating compositions including silica particles that have an average particle size of up to 500 nanometers and methods of applying them can be found, for example, in US International Patent Applications No. 2012/047867 ( Brown et al.) And 2012/047877 (Brown et al.), Both of which are incorporated herein by way of reference.
[073] A common problem in desert locations is the accumulation of dust on the exposed surfaces of the optical components of a solar energy system. Airborne desert dust typically and substantially comprises particles with diameters less than 100 micrometers, and often substantially comprises particles with diameters less than 50 micrometers. Dust typically reduces optical performance by causing incident light to be scattered, rather than being concentrated or reflected by the solar optical component to the intended solar energy conversion device. Typically, over a period of time, the electricity produced by the solar energy system decreases as dust accumulates, resulting in losses of 5 to 40% compared to the cleaning system originally installed. As the projected output for the installation increases, losses due to dust are increasingly unacceptable. For larger installations, operators may be forced to clean their optical surfaces, often using methods that require the use of water. Water is expensive and scarce in most places in the desert. Thus, there is a need to provide solar optical components that will maintain optical performance in the presence of desert dust. As suggested by Illustrative Example 3, below, articles coated with a first coating and a second coating shown in the present invention can maintain their optical properties upon exposure to dust, indicating that dust does not tend to accumulate in these articles. Furthermore, as shown in Example 6, below, the second coating adheres unexpectedly well to the first coating, even after exposure to wear by atmospheric agents.
[074] In some embodiments, the coating compositions and coatings thereof according to the present description are transmissible to visible and infrared light. The term "transmissive to visible and infrared light", as used here, can mean having an average transmission relative to the visible and infrared portion of the spectrum of at least about 75% (in some embodiments, at least about 80, 85, 90, 92, 95, 97 or 98%) measured along the normal axis. In some embodiments, the coating compositions and / or coatings thereof have an average transmission over a range of 400 nm to 1400 nm of at least about 75% (in some embodiments, at least about 80, 85, 90, 92, 95, 97 or 98%). Some modalities of the invention
[075] In a first embodiment, the present description features a coating composition comprising:
[076] a polymer or copolymer of poly (methyl methacrylate) having an average molecular weight of at least 50,000 grams per mol;
[077] monomer comprising at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate, or cycloalkylene dimethacrylate, with at least one of alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylene dimethacrylate at least 80 weight, of the monomer; and
[078] a stabilizer against ultraviolet light.
[079] In a second embodiment, the present description presents the coating composition of the first embodiment, where the polymer or copolymer of poly (methyl methacrylate) has an average molecular weight of at least 75,000 grams per mol.
[080] In a third embodiment, the present description presents the coating composition of the first or second embodiment, where the polymer or copolymer of poly (methyl methacrylate) has an average molecular weight of at least 100,000 grams per mol or at least 120,000 grams per mol.
[081] In a fourth embodiment, the present description presents the coating composition of any of the first to third embodiments, where the polymer or copolymer of poly (methyl methacrylate) is poly (methyl methacrylate) or a copolymer of methacrylate of methyl and at least one of a C2-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate.
[082] In a fifth embodiment, the present description presents the coating composition of the fourth embodiment, where the polymer or copolymer of poly (methyl methacrylate) is a copolymer of methyl methacrylate and at least one of ethyl acrylate, methacrylate of ethyl, butyl acrylate or butyl methacrylate.
[083] In a sixth embodiment, the present description presents the coating composition of any of the first to fifth embodiments, where the monomer comprises at least one of a C2-10alkylene diacrylate, C2-10alkylene dimethacrylate, C4-6cycloalkylene diacrylate or C4 - 6cycloalkylenediimethacrylate.
[084] In a seventh embodiment, the present description presents the coating composition of any of the first to sixth embodiments, where the monomer comprises at least one of 1,6-hexane diol diacrylate, 1,6-hexane diol dimethacrylate or neopentyl dimethacrylate glycol.
[085] In an eighth embodiment, the present description presents the coating composition of any of the first to seventh embodiments, which further comprises an acrylic copolymer containing silicone.
[086] In a ninth embodiment, the present description presents the coating composition of any of the first to eighth embodiments, which further comprises inorganic filler.
[087] In a tenth embodiment, the present description presents the coating composition of any of the first to eighth modalities, which further comprises silica particles that have an average particle size of up to 500 nanometers, 300 nanometers, 150 nanometers or 100 nanometers.
[088] In an eleventh modality, the present description presents the coating composition of the eleventh modality, where the silica particles are particles of silica with modified surface that have functional groups of acrylate or methacrylate on their surfaces.
[089] In a twelfth modality, the present description presents the coating composition of the eleventh modality, in which if the modified surface silica particles have functional acrylate groups on their surfaces, the monomer comprises at least one among alkylene diacrylate or cycloalkylene diacrylate, and where if the surface-modified silica particles have functional groups of methacrylate on their surfaces, the monomer comprises at least one of dimethyl acrylate or cycloalkylene dimethacrylate.
[090] In a thirteenth modality, the present description presents the coating composition of the thirteenth modality, where the silica particles are modified with poly (methyl methacrylate).
[091] In a fourteenth embodiment, the present description presents a coating composition of any one of the first to the thirteenth modalities, where the ratio between the monomer, which comprises at least one among alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylenediimethacrylate, and the poly (methyl methacrylate) polymer or copolymer is in the range of 0.75: 1 to 10: 1.
[092] In a fifteenth embodiment, the present description features a coating composition of any one of the first to fourteenth embodiments, which further comprises organic solvent.
[093] In a sixteenth embodiment, the present description features a coating composition of the fifteenth embodiment, where the organic solvent comprises at least one among methyl ethyl ketone, 1-methoxy-2-propanol, isopropanol, toluene, acetone or ethyl acetate.
[094] In a seventeenth modality, the present description presents a coating composition of any one of the first to the sixteenth modalities, where the stabilizer against ultraviolet light comprises at least one among a benzotriazole, a benzophenone, a triazine or a hindered amine photostabilizer.
[095] In an eighteenth embodiment, the present description features a coating composition of any of the first to seventeenth embodiments, which further comprises a photoinitiator.
[096] In a nineteenth modality, the present description features a coating composition of any of the first to eighteenth modalities, where a coating composition does not comprise a hexa-arylbi-imidazole photoinitiator, and / or where a composition coating agent does not comprise a photoinitiator containing an oxime ester functional group.
[097] In a twentieth embodiment, the present description features an article comprising a substrate and a first coating on a surface of the substrate, where the first coating is obtained by curing a coating composition of any of the first to tenth- ninth modalities.
[098] In a twenty-first modality, the present description presents the article of the twenty modality, where the substrate is a polymeric substrate.
[099] In a twenty-second modality, the present description presents the article of the twenty or twenty-first modality, where the substrate is a thermoplastic substrate that comprises at least one among an acrylic, a polyester, a polycarbonate, or a blend of polyvinylidene fluoride and poly (methyl methacrylate).
[0100] In a twenty-third modality, the present description presents the article of any one of the twenty-second to twenty-second modalities, where the surface of the substrate is initiated.
[0101] In a twenty-fourth modality, the present description presents the article of the twenty-third modality, where the substrate surface is treated with a nitrogen corona.
[0102] In a twenty-fifth modality, this description presents the article of any of the twenty-fourth to twenty-fourth modalities, where the substrate is an acrylic mirror film, a multilayer optical film, a lens, retroreflective lamination, or a dark film.
[0103] In a twenty-sixth modality, the present description presents the article of the twenty-fifth modality, where the substrate is an acrylic mirror film or a multilayer optical film.
[0104] In a twenty-seventh embodiment, the present description presents the article of any of the twenty-seventh to twenty-sixth embodiments, which additionally comprises a second coating disposed on the first coating, where the second coating comprises particles of silica that have a size particle average of up to 500 nanometers, 300 nanometers, 150 nanometers or 100 nanometers.
[0105] In a twenty-eighth modality, the present description presents the article of the twenty-seventh modality, where at least a portion of the silica particles have an average particle size of up to 40 nm.
[0106] In a twenty-ninth modality, the present description presents the article of any of the twenty to twenty-eighth modalities, where the first coating has a thickness of at least 8 micrometers.
[0107] In a thirtieth modality, the present description presents the article of any of the twenty to twenty-ninth modalities, where the first coating is transmissive to visible and infrared light.
[0108] In a thirty-first modality, the present description presents the article of any of the twenty to thirty th modalities, where the article is exposed to sunlight.
[0109] In a thirty-second modality, the present description presents a method for the manufacture of an article, the method that comprises:
[0110] placing a substrate surface in contact with a coating composition of any of the first to nineteenth modalities;
[0111] removing the organic solvent, if present, from the coating composition; and
[0112] exposing a coating composition to actinic radiation to provide a first coating on the substrate surface.
[0113] In a thirty-third embodiment, the present description presents the method of the thirty-second embodiment, which further comprises physically or chemically initiating the substrate surface before bringing the substrate surface into contact with a coating composition.
[0114] In a thirty-fourth modality, the present description presents the method of the thirty-second or thirty-third modality, where the substrate is a polymeric substrate.
[0115] In a thirty-fifth modality, the present description presents the method of any of the thirty-second to thirty-fourth modalities, where the substrate is a thermoplastic substrate, which comprises at least one among an acrylic, a polyester, a polycarbonate or a blend of polyvinylidene fluoride and poly (methyl methacrylate).
[0116] In a thirty-sixth modality, the present description presents the method of any of the thirty-second to thirty-fifth modalities, where the substrate is an acrylic mirror film, a multilayer optical film, a lens, retroreflective lamination or a dark film.
[0117] In a thirty-seventh modality, the present description presents the method of any of the thirty-second to thirty-sixth modalities, where the substrate is an acrylic mirror film and / or comprises poly (methyl methacrylate).
[0118] In a thirty-eighth modality, the present description presents the method of the thirty-seventh modality, which additionally comprises starting the substrate with a nitrogen corona treatment.
[0119] In a thirty-ninth embodiment, the present description presents the method of any of the thirty-second to thirty-eighth modalities, which further comprises bringing the first coating into contact with a second coating composition, where the second coating composition The coating has a pH of up to 5 and comprises water and silica particles that have an average particle size of up to 500 nanometers, 300 nanometers, 150 nanometers or 100 nanometers dispersed in the water.
[0120] In a fortieth modality, the present description presents the method of the thirty-ninth modality, where at least some of the silica particles have an average particle size of up to 40 nanometers.
[0121] In a forty-first modality, the present description presents the method of the thirty-ninth or fortieth modality, which further comprises drying the second coating composition to remove at least part of the water.
[0122] In order for this description to be more fully understood, the following examples are presented. It should be understood that these examples are for illustrative purposes only, and should not be construed as limiting the description in any way. EXAMPLES
[0123] Except where otherwise specified, all parts, percentages, ratios, etc., cited in the examples and elsewhere in this specification are given by weight and all reagents used in the examples have been obtained or are available from suppliers for chemicals in general, such as the Sigma-Aldrich Company, Saint Louis, Missouri, USA, or can be synthesized by conventional methods. Materials


Preparation of PMMA-grafted silica
[0124] The grafted samples were prepared by combining Sol B (6.9 grams (g) of 44% of the solids in 1-methoxy-2-propanol), methyl methacrylate (27.0 g), radical initiator free “VAZO 67” (0.15 g), and 2-butanone (66.1 g) in a glass bottle. The flask was purged with nitrogen and sealed. The flask of the solution was turned in a water bath at 65 ° C for 24 hours (h). The solution bottle was left to cool naturally to room temperature (22 ° C). The solids were determined to be 30.75% by weight of loss of samples maintained for 60 minutes (min) at 105 ° C. Acrylic copolymer A containing silicone
[0125] An acrylic silicone copolymer was prepared combining mercapto-functional silicone “KF-2001” (22.5 g), methyl methacrylate (67.5 g), free radical initiator “VAZO 67” (0.45 g ) and ethyl acetate (210 g) in a glass bottle. The flask was purged with nitrogen and sealed. The flask of the solution was turned in a water bath at 65 ° C for 60 h. The solution bottle was left to cool naturally to room temperature (22 ° C). The solids were determined to be 29.6%, by weight, of loss of samples maintained for 60 min at 105 ° C. The inherent viscosity (IV) was measured by conventional means using a Cannon-Fenske viscometer No. 50 in a water bath controlled at 27 ° C to measure the flow time of 10 milliliters (mL) of the polymer solution ( 0.5 g of polymer per deciliter in tetrahydrofuran) and determined as 0.18 deciliters per gram (dL / g). Acrylic copolymer B containing silicone
[0126] An acrylic silicone copolymer was prepared by combining silicone methacrylate “SiMac” (22.5 g), methyl methacrylate, (MMA, 67.5 g), free radical initiator “VAZO 67” (0.45 g ) and ethyl acetate (210 g) in a glass bottle. The flask was purged with nitrogen and sealed. The flask of the solution was turned in a water bath at 65 ° C for 60 h. The solution bottle was left to cool naturally to room temperature (22 ° C). The solids were determined to be 29.1%, by weight, of loss of samples maintained for 60 min at 105 ° C. The inherent viscosity (IV) was measured by conventional means using a Cannon-Fenske viscometer No. 50 in a water bath controlled at 27 ° C to measure the flow time of 10 ml of the polymer solution (1.0 g of polymer per deciliter in tetrahydrofuran) and determined as 0.25 dL / g. Assessment methods
[0127] Opacity measurements were made on PMMA film coated before and after an abrasion treatment (with sand fall, as detailed in ASTM D968 - 05e1). The coated PMMA films attached to the glass were subjected to the following evaluations before and after wear by atmospheric agents: tests of contact angle with sessile water, transmission, opacity and adhesion. The samples attached to the glass were prepared as follows. The adhesive obtained from the 3M company under the trade name “3M 8171 OPTICALLY CLEAR ADHESIVE” was laminated to a glass plate, and then the uncoated side of the PMMA film was laminated to the adhesive with a ball applicator to ensure that there were no air bubbles trapped at each interface. Exposure to weathering by weathering
[0128] For wear by atmospheric agents, the films were exposed in a wear device by atmospheric agents according to a high irradiance version of ASTM G155 tested in Cycle 1 at a slightly higher temperature. The radiation from the source of the xenon arc was adequately filtered in order to provide an excellent adaptation to the ultraviolet portion of the solar spectrum. The samples were tested before any exposure to these conditions of wear by accelerated atmospheric agents, and then removed at total UV dosing intervals of 373 MJ / m2 for evaluation. Optical properties
[0129] Opacity (% O) and transmission (% T) were measured using a Haze-Gard Plus (BYK-Gardner USA, Columbia, MD, USA). Angle of contact with water
[0130] Water contact angles were measured with a static contact angle measuring device (VCA-2500XE available from AST Products (Billerica, MA, USA) using deionized water as received filtered through a filtration system obtained from Millipore Corporation (Billerica, MA, USA). Drop volumes were about 5 μL for static measurement. Abrasion resistance
[0131] The samples were scraped according to ASTM D968 - 05e1 using a sand drop abrasion tester - Model 820 (Taber Industries, North Tonawanda, NY, USA). Accession
[0132] The samples were carved with a utility blade and then a 2.54 cm (one inch) piece of 3M ™ “MAGIC TAPE 810” was applied to the coating over the carved region. The tape was then gently removed from the substrate, and the sample was inspected for evidence of removal of the PMMA substrate coating. Cleanability
[0133] Mounted glass samples were used to assess the cleanability of certain coatings. The initial transmission and measurement of opacity was performed as described above. The samples were then challenged in a dirt test with SPUT slurry. The SPUT slurry was placed inside an acrylic tank measuring 81 cm (32 inches (in.)) X 38 cm (15 in.) X 27 cm (10.5 in.) And kept agitated using a shovel anchor installed on an air mechanism. It was sprayed on the test panels for 2 seconds with a pressure gauge of 1.38 x 105 Pa (20 psig) using a “3M BODY SCHUTZ ™ APPLICATOR GUN” (available from 3M, part no. 08997) with the nozzle tip 74 cm (29 in.) From the front surface of the panel. After dirtying the panel, it was removed and subjected to vertical drying for 5 minutes at 50 ° C. The cycle was repeated twice more. After the third drying step, the panel was loaded into a separate clean water tank measuring 84 cm (33 in.) X 41 cm (16 in.) X 36 (14 in.) And sprayed using water pressure 4.14 x 105 Pa (60 psig) and deionized water for 5 seconds with the tip of the nozzle 81 cm (32 in.) from the front surface of the panel and without any mechanical rubbing. The sample was subjected to a final drying step at 50 ° C.
[0134] After this washing procedure, transmission and opacity were measured at three locations in the sample and quantified. Dry dust test
[0135] One side of 70 mm (2.75 in.) By 69 mm (2.70 in.) Clear glass, 2 mm thick was masked with black tape. Then, the sample was mounted on the glass on the opposite side of the black tape, using a cylinder to eliminate air bubbles. The initial and final gloss measurements were taken from the sample at 20 and 60 degree angles with a micro-TRI-gloss μ gloss meter (BYK-Gardner USA, Columbia, MD, USA). After the initial reading was recorded, the sample was transferred into a plastic container with a tight-fitting lid, and about 10 grams of the Arizona Dust Test was added. The sample was covered and shaken manually and horizontally for 1 minute. Then, the sample was removed from the container and the excess dust was removed by touching the sample in a vertical orientation on the bench. After the excess dust was removed, the final gloss measurement was recorded. Comparative examples Comparative example 1 (EC 1)
[0136] The PMMA film that has been treated with a 0.5 J / cm2 nitrogen corona treatment as described in US Patent No. 7,442,442 (Strobel et al.) Has been subjected to evaluations described in “Evaluation methods” above. The results are shown in Tables 2 to 4. A 60,000x scanning electron micrograph was taken from a representative surface for the PMMA film after exposure to accelerated wear by atmospheric agents of 1119 MJ / m2. After 1119 MJ / m2, alveolar corrosion was observed on the surface, but most of the surface was quite flat. This worn film was shown to be transparent and colorless to the naked eye for all the exposure intervals outlined in Table 2. Before and after the cleanability assessment, the measured transmission was 91.6% and 86.7%, respectively, and the opacity was 0.6% and 27%, respectively. Comparative example 2 (EC 2)
[0137] Sodium-calcium glass was tested by cleaning with acetone to provide Comparative Example 2. Comparative Example 2 was evaluated for abrasion resistance according to the Evaluation Method above. The results are shown in Table 4. Comparative Example 2 was also assessed for its cleanability using the Assessment Method above. Before and after the assessment for cleanability, the transmission was 91.8% and 90.0%, respectively, and the opacity was 0.4% and 14.7%, respectively. Illustrative example 1 (EI 1)
[0138] The coating solution was prepared by combining HDDA, stabilizers, ethyl and methyl ketone (MEK) and 1-methoxy-2 propanol according to the formulation mentioned in Table 1. The components were mixed in dark containers, which were placed on a shaker until all components were dissolved and homogeneously mixed. The PMMA film was treated with a 0.5 J / cm2 nitrogen corona treatment as described in US Patent No. 7,442,442 (Strobel et al.). The coating of the hard coating was made 15 cm (6 in.) Wide. The coating was applied by reverse microgravure coating with 27.6 lines per centimeter (lpcm) (70 lines per inch (lpi)) with a knurled cylinder to achieve a coating thickness of 25 microns (1 mil). The film moved at 6 meters per minute (m / min) (20 feet per minute (fpm)) through a 3 m (10 feet) oven with three successive temperature zones: 60 ° C, 70 ° C and 80 ° C, respectively. After removing the solvent, the dry coating was exposed to a UV curing of “D” lamp of the UV Fusion System (Gaithersburg, Maryland) at a 70% power setting to provide Comparative Example 2 The samples from this film were evaluated in accordance with the “Assessment Methods” above. The results are shown in Tables 2 to 5. A 60,000x scanning electron micrograph was taken from a representative sample after exposure to accelerated wear by atmospheric agents of 1119 MJ / m2. After 1119 MJ / m2, alveolar corrosion was observed on the surface, but most of the surface was quite flat, although not as flat as in Comparative Example 1. This worn film was transparent and colorless to the naked eye for all exposure intervals outlined in Table 2. As noted in Table 5, this formulation does not retain adhesion to the PMMA substrate after exposure to accelerated wear by atmospheric agents. Illustrative example 2 (EI 2)
[0139] Illustrative Example 2 was prepared according to the method of Illustrative Example 1 with the following modifications. The components were penta-acrylate “SR-9041” (45%), photoinitiator “IRGACURE 184” (0.4%), photoinitiator “IRGACURE 819” (0.4%), “TINUVIN 928” UVA available from BASF ( 3.0%), HALS “TINUVIN 123” (0.4%), MEK (22.5%) and PM (28.1%). The composition was coated and cured on a PET substrate instead of a PMMA substrate. A sample of Illustrative Example 2 was evaluated for opacity before and after exposure to wear by atmospheric agents according to the evaluation methods described above. The initial opacity was 2%, and after a dose of 820 MJ / m2 of exposure to full UV, the opacity measured for Illustrative Example 2 was 100%. For comparison, another coating composition was prepared using the same formulation except for the use of HDDA instead of “SR-9041” penta-acrylate. The composition was also coated and cured on a PET substrate and evaluated for opacity before and after exposure to wear by atmospheric agents. The initial opacity was 0.6%, and after a dose of 820 MJ / m2 of total UV exposure, the measured opacity was 4.4%. Examples 1A to 1E
[0140] The amounts of the components shown in Table 1 for Examples 1A to 1E were combined in dark containers, which were mixed on a stirrer until all components were dissolved and homogeneously mixed. For the "silica dispersions" of Examples 1A to 1E, "Sol B" colloidal silica solutions were used. The PMMA film was treated with a 0.5 J / cm2 nitrogen corona treatment as described in US Patent No. 7,442,442 (Strobel et al.). The coating of the Examples coating was made 15 cm (6 in.) Wide. The coating was applied through reverse microgravure coating with a 27.6 lpcm (70 lpi) with knurled cylinder to achieve a coating thickness of 25 microns (1 mil). The film moved at 6 m / min (20 fpm) through a 3 m (10 ft) oven with three successive temperature zones: 60 ° C, 70 ° C and 80 ° C, respectively. After removing the solvent, the dry coating was exposed to a UV curing of lamp "D" of the UV Fusion System at a 70% power setting to provide Examples 1A to 1E. The samples of this film were evaluated according to the “Evaluation Methods”, above. The results are shown in Tables 2 to 5. A 60,000x scanning electron micrograph of a representative surface for Example 1C after an exposure to accelerated wear by atmospheric agents of 746 MJ / m2 is illustrated in Figure 1. An electron micrograph a 60,000x sweep was taken from a representative surface for Example 1D after exposure to weathering by 1119 MJ / m2 and is shown in Figure 2. After 1119 MJ / m2, no honeycomb corrosion was observed in Example 1D, and most of the surface was quite flat, although not as flat as in Comparative Example 1. Examples 1A, 1B and 1C exhibited color to the naked eye after 1119 MJ / m2 of exposure. Examples 1D and 1E, which did not contain colloidal silica, were transparent and colorless to the naked eye after all the exposure intervals described in Table 2. Before and after the cleanability assessment, the measured transmission of Example 1E was 91.7 % and 87.3%, respectively, and the measured opacity was 0.4% and 27.3%, respectively. Example 2
[0141] Example 2 was prepared and evaluated according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX 2 for coating. Example 2 was transparent and colorless to the naked eye after all the exposure intervals evaluated in Table 2. Examples 3A and 3B
[0142] Examples 3A and 3B were prepared and evaluated according to the methods of Examples 1A to 1C, except the use of the formulations shown in Table 1 for EX3A and EX3B for coating. Dispersions of grafted silica from PMMA, prepared as described above, were used instead of "SOL B". The 60,000x scan electron micrographs were taken from a representative surface for Examples 3A and 3B after exposure to accelerated wear by atmospheric agents of 746 MJ / m2. Both surfaces were quite flat after exposure. The surface of Example 3A after weathering is shown in Figure 3. After 1492 MJ / m2 of total UV dose, Examples 3A and 3B were colorless and transparent to the naked eye. Example 4
[0143] Example 4 was prepared and evaluated according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX4 for coating. The "silicone" was acrylic copolymer A containing silicone, prepared as described above. After 1492 MJ / m2 of exposure to wear by atmospheric agents, the samples were colorless and transparent. Before and after the cleanability assessment, the measured transmission of Example 4 was 91% and 88%, respectively, and the measured opacity was 0.4% and 13%, respectively. Example 5
[0144] Example 5 was prepared and evaluated according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX5 for coating. The "silicone" was acrylic copolymer B containing silicone, prepared as described above. Before and after the cleanability assessment, the measured transmission of Example 5 was 91% and 87.7%, respectively, and the measured opacity was 0.6% and 11.3%, respectively. Example 6
[0145] Example 6 was prepared and evaluated according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX6 for coating. Then, a dispersion of aqueous silica from a 50:50 weight percent mixture of Nalco 8699: Nalco 1050 colloidal silica was prepared as 10% (w / w) of the solids in water and adjusted to pH 2 to 3 with nitric acid. This coating dispersion was coated as a second layer on top of the first coating. The coating dispersion was applied through the reverse microgravure coating with a 78.7 lpcm (200 lpi) with knurled cylinder with the engraving cylinder speed set to 5.5 meters per minute (18 feet per minute), directing a thickness 1 micrometer dry coating. The coated film moved at 3 meters per minute (10 feet per minute) through a 3 meter (10 feet) oven with three successive temperature zones each setting of 80 ° C. After the second coating was applied, the samples of this film were evaluated according to the “Evaluation Methods”, above. The results are shown in Tables 2 to 5. Example 7
[0146] Example 7 was prepared according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX7 for coating. HDDMA was used instead of HDDA. For the coating of the film, the three successive temperature zones were kept constant at 80 ° C in each zone, and the UV curing was carried out at a power setting of 90%. The initial opacity was measured, and the opacity was measured again after evaluating the abrasion resistance using the evaluation methods described above. The results are shown in Table 4. Example 8
[0147] Example 8 was prepared according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX8 for coating. NGDMA was used instead of HDDA. For the coating of the film, the film was moved at 3 m / min (10 feet / min) through a 3 m (10 ft) oven with 3 successive temperature zones, which were kept constant at 80 ° C in each zone, and UV curing was performed at a power setting of 85%. The initial opacity was measured, and the opacity was measured again after assessing the abrasion resistance using the test methods described above. The results are shown in Table 4. Example 9
[0148] Example 9 was prepared according to the methods of Examples 1A to 1E, except the use of the formulation shown in Table 1 for EX 9 for coating. TDDA was used instead of HDDA. A coated sample was evaluated for opacity before and after being evaluated for abrasion resistance according to the evaluation method above, and the results are shown in Table 4, below. The contact angle with the water was also measured according to the evaluation method above, and the results are shown in Table 3, below. Illustrative example 3
[0149] A first coating on a substrate for Illustrative Example 3 was prepared according to the method of Illustrative Example 1, except that the following formulation was used: Sol B (39.6%), HDDMA (18.6%) , photoinitiator “IRGACURE 184” (0.2%), photoinitiator “IRGACURE 819” (0.2%), UVA “TINUVIN 479” (2.0%), HALS “TINUVIN 123” (0.4%), MEK (23.4%) and PM (15.6%), with all percentages being percentages by weight. For the coating of the film, the three successive temperature zones were kept constant at 80 ° C in each zone, and the UV curing was performed at a power setting of 90%. An aqueous silica dispersion was prepared from a 50:50 weight percent mixture Nalco 8699: Nalco 1050 silica in 5% (w / w) solids at pH 2.5, adjusted with nitric acid. This coating dispersion was coated as a second coating on top of the first coating. The coating dispersion was applied through the reverse microgravure coating with a 59 lpcm (150 lpi) knurled cylinder with the engraving cylinder speed set to 5.5 meters per minute (18 feet per minute), directing a coating thickness dry from 100 nm to 150 nm. The coated film was moved at 3 meters per minute (10 feet per minute) through a 3 meter (10 feet) oven with three successive temperature zones each setting of 90 ° C. An angle of contact with water measured after the second coating was applied was <10 using the evaluation method described above. The "adhesion" assessment method described above was used on a sample after the second coating was applied, and the coatings were found to adhere. After an application of a dirt challenge as described in the Dry Dust Test, Illustrative Example 3 exhibited a drop of 6.1 units of brightness when measured at 20 degrees, and a drop of 6.7 units of brightness when measured at 60 degrees. By comparison, a sample having only the first coating of Illustrative Example 3 exhibited a drop of 21.4 units of brightness when measured at 20 degrees, and a drop of 64.6 units of brightness when measured at 60 degrees. The optical properties were also measured for Illustrative Example 3 after the Dry Dust Test. Illustrative Example 3 exhibited a 0.1% drop in transmittance and a 1.3% increase in opacity after the dry Dirt challenge. By comparison, a sample having only the first coating of Illustrative Example 3 exhibited a 4.0% drop in transmittance and a 15.2% increase in opacity after the dry Dirt challenge. Table 1 formulations (% w / w)


[0150] The polymer was the “PARALOID B44” copolymer for all Examples, except for Example 2, which used the “PARALOID B48N” copolymer. 2The initiators were “IRGACURE 184” and “IRGACURE 819”. Table 2 opacity

Table 3 Table data: angle of sessile contact of water
Table 4 Measurement of opacity after the abrasion test with falling sand
Table 5 Adhesion before and after accelerated weathering by atmospheric agents

[0151] This description is not limited to the modalities described above, but is intended to be controlled by the limitations established in the following claims, as well as by any equivalents thereof. This description can be properly practiced in the absence of any element not specifically presented in this document.

权利要求:
Claims (10)
[0001]
1. Coating composition, CHARACTERIZED by the fact that it comprises: a polymer or copolymer of poly (methyl methacrylate) having an average molecular weight of at least 50,000 grams per mol; monomer comprising at least one of an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylene dimethacrylate, wherein the at least one of an alkylene diacrylate, alkylene dimethacrylate, cycloalkylene diacrylate or cycloalkylene dimethacrylate provides at least 80 percent by weight; and a stabilizer against ultraviolet light, wherein the stabilizer comprises at least one of a UV absorber or a hindered amine-based photostabilizer.
[0002]
2. Coating composition according to claim 1, CHARACTERIZED by the fact that the poly (methyl methacrylate) polymer or copolymer has an average molecular weight of at least 75,000 grams per mol.
[0003]
Coating composition according to claim 1 or 2, CHARACTERIZED by the fact that the polymer or copolymer of poly (methyl methacrylate) is poly (methyl methacrylate) or a copolymer of methyl methacrylate and at least one among a C2-C8 alkyl acrylate or methacrylate or a C3-C8 cycloalkyl acrylate or methacrylate.
[0004]
Coating composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that the monomeric alkylene diacrylate or a monomeric alkylene dimethacrylate comprises at least one of 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate or neopentyl glycol dimethacrylate.
[0005]
Coating composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that it additionally comprises an acrylic copolymer containing silicone.
[0006]
Coating composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that it additionally comprises an acrylic monomer containing silicone.
[0007]
Coating composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that it additionally comprises at least one of an organic solvent or a photoinitiator.
[0008]
Coating composition according to any one of claims 1 to 7, CHARACTERIZED by the fact that the stabilizer against ultraviolet light comprises at least one of a benzotriazole, a benzophenone, a triazine or a hindered amine-based photostabilizer.
[0009]
9. Article, CHARACTERIZED by the fact that it comprises a polymeric substrate and a first coating on a surface of the polymeric substrate, wherein the first coating is obtained by curing the coating composition, as defined in any one of claims 1 to 8.
[0010]
10. Article according to claim 9, CHARACTERIZED by the fact that the polymeric substrate is a thermoplastic comprising at least one of an acrylic, a polyester, a polycarbonate or a blend of polyvinylidene fluoride and poly (methyl methacrylate) .

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CN104540905B|2017-12-19|

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DK2828345T3|2017-01-02|

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WO2013142239A1|2013-09-26|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2021-01-05| B09A| Decision: intention to grant|

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2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261614297P| true| 2012-03-22|2012-03-22|

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US61/614,297|2012-03-22|

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PCT/US2013/031249|WO2013142239A1|2012-03-22|2013-03-14|Polymethylmethacrylate based hardcoat composition and coated article|

---