Method and article for applying primer for self-assembled layer

Abstract

A method of manufacturing an article is described, the method comprising providing a substrate; applying the primer layer to the substrate; wherein the primer layer comprises the reaction product of a polymerizable resin comprising at least one monomer having at least two ethylenically unsaturated groups; and applying a plurality of layers deposited by layer-by-layer self-assembly to the primer layer. Described is an article comprising a substrate; a primer layer disposed on the substrate; wherein the primer layer comprises the reaction product of a polymerizable resin comprising at least one monomer having at least two ethylenically unsaturated groups; and an ionically bonded polymer matrix disposed on the primer layer.

Description

Summary of the Invention

[0001] In one embodiment, a method of manufacturing an article is described, the method comprising providing a substrate; applying a primer layer to the substrate; wherein the primer layer comprises a reaction product of a polymerizable resin, the polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and applying a plurality of layers deposited by layer-by-layer self-assembly to the primer layer.

[0002] In another embodiment, an article is described comprising a substrate; a primer layer disposed on the substrate; wherein the primer layer comprises a reaction product of a polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and a plurality of layers deposited by layer-by-layer self-assembly disposed on the primer layer.

[0003] In another embodiment, an article is described comprising a substrate; a primer layer disposed on the substrate; wherein the primer layer comprises a reaction product of a polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and an ionicly bonded polymer matrix of at least two different organic polymers.

[0004] In some embodiments, the plurality of layers comprises at least one polycationic polymer and at least one polyanionic polymer. In some embodiments, the primer layer has a thickness of less than 1 micrometer, 750 nm, 500 nm, or 250 nm. Attached Figure Description

[0005] Figure 1 A cross-sectional view of an illustrative article 500 is shown, which includes a substrate 550 and a plurality of layers 510 disposed on the substrate 550 and deposited by layer-by-layer self-assembly. Figure 2 As shown in the cross-sectional view of the exemplary article 501, the exemplary article includes a substrate 551, which includes an adhesive 560 and a plurality of layers disposed on the adhesive 560 and deposited by layer-by-layer self-assembly. Figure 3 This is a cross-sectional view of an embodiment of multiple bilayer 510 deposited by layer-by-layer self-assembly. Detailed Implementation

[0006] As used in this application: "Polymer" means organic polymers and copolymers (i.e., polymers formed from two or more monomers or comonomers, such as terpolymers), as well as copolymers or polymers in the form of miscible blends formed by, for example, co-extrusion or reactions (e.g., transesterification). Polymers include block polymers, random polymers, graft polymers, and alternating polymers.

[0007] Polyelectrolytes are organic polymers whose repeating units contain electrolyte groups. These electrolyte groups can dissociate in aqueous solutions (water), causing the polymer to become charged. Therefore, polyelectrolytes exhibit properties similar to electrolytes (salts) and polymers (high molecular weight compounds), and are sometimes referred to as polysalts. Like salts, their solutions are conductive. Strong polyelectrolytes possess a persistent charge over a wide pH range (e.g., polymers containing quaternary ammonium or sulfonic acid groups). Weak polyelectrolytes have a pH-dependent level of charge (e.g., polymers containing primary, secondary, or tertiary amines, or carboxylic acids). "Polycationic" refers to a polyelectrolyte that carries a positive charge in an aqueous solution (water); "Polyanionic" refers to a polyelectrolyte that carries a negative charge in aqueous solution (water); Detailed Explanation refer to Figure 1 An illustrative comparative article 500 includes a substrate 550 and a plurality of layers 510 disposed on the substrate 550.

[0008] refer to Figure 2 The exemplary article 501 of the present invention includes a substrate 551 and a plurality of layers 510. An adhesive 560 is disposed between the substrate 551 and the plurality of layers 510.

[0009] The primer 560 typically has a thickness of no more than 10 micrometers, 9 micrometers, 8 micrometers, 7 micrometers, 6 micrometers, 5 micrometers, 4 micrometers, 3 micrometers, 2 micrometers, or 1 micrometer. In some embodiments, the primer has a thickness of at least 25 nm, 50 nm, 75 nm, or 100 nm. In some embodiments, the primer has a thickness of less than 1 micrometer, 750 nm, 500 nm, or 250 nm.

[0010] The primer improves adhesion between the substrate and the multiple layers 510. Adhesion can be determined using various techniques, such as the tape test described in the embodiments below. The inclusion of the primer results in a smaller percentage of damaged surface area of ​​the multiple layers 510 (e.g., layer-by-layer coating) when evaluated using a tape test compared to a control, which is the same substrate and multiple layers without the primer. In some embodiments, the percentage of damaged surface area of ​​the multiple layers 510 (e.g., layer-by-layer coating) when evaluated using a tape test is less than 35%, 30%, 25%, 30%, 15%, 10%, 5%, or 1%.

[0011] Multiple layers disposed on a substrate include at least two layers deposited by a process commonly referred to as a “layer-by-layer self-assembly process.” This process is typically used for the electrostatic assembly of films or coatings of oppositely charged polyions, such as polyelectrolytes, but other functionalities such as hydrogen bond donors / acceptors, metal ions / ligands, and covalently bonded portions can be driving forces for film assembly. Typically, this deposition process involves exposing a substrate with a surface charge to a series of liquid solutions or baths. This can be achieved by immersing the substrate in a liquid bath (also known as dip coating), spraying, spin coating, roll coating, inkjet printing, etc. Exposure to a first polyelectrolyte (bath) liquid solution with an opposite charge to the substrate causes rapid adsorption of charged material near the substrate surface. This establishes a concentration gradient and draws more polyelectrolyte from the bulk solution to the surface. Further adsorption occurs until enough layers have developed to mask the underlying charge and reverse the net charge on the substrate surface. This exposure time is typically on the order of minutes to achieve mass transfer and adsorption. The substrate is then removed from the first polyionic liquid solution (e.g., a bath) and subsequently exposed to a series of water rinse baths to remove any physically entangled or loosely bound polyelectrolytes. Following these rinse (e.g., bath) liquid solutions, the substrate is then exposed to a second polyelectrolyte liquid solution having an opposite charge to the first polyionic (e.g., bath) liquid solution. Adsorption occurs again because the surface charge of the substrate is opposite to that of the second (e.g., bath) liquid solution. Continued exposure to the second polyionic (e.g., bath) liquid solution causes a reversal of the surface charge of the substrate. Subsequent rinses can be performed to complete the cycle. This series of steps is referred to as building a layer pair, also known herein as a deposited “bilayer,” and can be repeated as needed to further add additional layer pairs to the substrate.

[0012] Examples of suitable processes include those described in US 8,234,998 by Krogman et al.; US 2011 / 0064936 by Hammond-Cunningham et al.; and US 8,313,798 by Nogueira et al. Additional layer-by-layer dip coating can be performed using the StratoSequence VI dip coating robot (nanoStrata Inc., Tallahassee, FL).

[0013] refer to Figure 3 The multiple layers 510 deposited by layer-by-layer self-assembly include one or more bilayers, which include a polycationic (e.g., polyelectrolyte) monolayer 512 and a polyanionic (e.g., polyelectrolyte) monolayer 513.

[0014] Suitable polyelectrolytes include polycationic polymers (i.e., polycations), such as linear and branched poly(ethyleneimine), poly(allylamine hydrochloride) (PAH), polyethyleneamine, deacetylated chitosan, polyaniline, polypyrrole, polyamide, poly(vinylbenzyltrimethylamine), polydiallyldimethylammonium chloride, poly(dimethylamine methacrylate), and poly(methacrylamide)propyltrimethylammonium chloride.

[0015] Suitable polyanionic polymers include, but are not limited to, poly(vinyl sulfate), poly(vinyl sulfonate), poly(acrylic acid) (PAA), poly(methacrylic acid), poly(styrene sulfonate), dextran sulfate, heparin, hyaluronic acid, carrageenan, carboxymethyl cellulose, alginate, and sulfonated tetrafluoroethylene-type fluoropolymers, such as Nafion. ® Poly(vinylphosphonic acid), and poly(vinylphosphonic acid).

[0016] The molecular weight of the polyelectrolyte can vary in the range of about 1,000 g / mol to about 1,000,000 g / mol. In some embodiments, the molecular weight (Mw or Mn) of the polyelectrolyte is at least 5,000 g / mol; 10,000 g / mol; 15,000 g / mol; 20,000 g / mol or 25,000 g / mol. In some embodiments, the molecular weight (Mw or Mn) of the polyelectrolyte is not greater than 100,000 g / mol; 75,000 g / mol; or 50,000 g / mol.

[0017] Multiple layers deposited by layer-by-layer self-assembly may optionally also contain organic light-absorbing compounds, organic light-stabilizing compounds, or combinations thereof dispersed within and preferably covalently bonded to the polyelectrolyte, as described in US 9,902,869, which is incorporated herein by reference.

[0018] Typically, the thickness and number of bilayers are selected using self-assembled layers with the minimum total thickness and / or the minimum number of layer-by-layer deposition steps to achieve desired (e.g., optical, barrier, or protective) properties. In some embodiments, the thickness of the bilayers, the number of bilayers per stack, the number of stacks, and the thickness of each stack are selected using self-assembled layers with the minimum total thickness and / or the minimum number of layer-by-layer deposition steps to achieve desired optical properties. The thickness of each bilayer is typically in the range of about 1 nm to 100 nm. The number of bilayers per stack is typically in the range of about 1 to 200. In some embodiments, the number of bilayers per stack is at least 2, 5, 10, 20, or 30. The number of stacks is typically at least 1, 2, 3, or 4, and no greater than 20, 19, 18, 17, or 15. The thickness of the stacks is typically at least 25 nm, 35 nm, 45 nm, 55 nm, 65 nm, 75 nm, or 85 nm, and no greater than 5, 6, 7, 8, 9, or 10 micrometers. In some embodiments, the thickness of the stack is no greater than 500 nm, 400 nm, 300 nm, 250 nm, 200 nm, or 150 nm. In other embodiments, the number of bilayers is selected to achieve a desired transmittance combined with mechanical durability. In this embodiment, the thickness and number of bilayers can be close to their maximum values. Furthermore, this embodiment can utilize a single stack with low or high refractive index, which can be matched to the index of the substrate or coating to which it is applied. In a typical embodiment, the resulting stack can be characterized as a polymer matrix of ionically bonded at least two organic polymers.

[0019] The substrate 550 is typically a plate or continuous film having a thickness of at least 20, 30, 40, or 50 micrometers to 1 cm, 2 cm, 3 cm, 4 cm, or 5 cm. In more typical embodiments, the substrate thickness is no greater than 30 mm, 20 mm, or 10 mm. Alternatively, thinner substrates may be used for embodiments where the substrate is reinforced by a carrier such as a removable liner.

[0020] In some embodiments, substrate 550 is an inorganic substrate, such as glass. In other embodiments, substrate 550 is an organic polymer material. In other embodiments, the substrate is a composite or multilayer substrate that may contain both organic polymer materials and inorganic materials.

[0021] Suitable organic polymer (e.g., membrane) materials include homopolymers, copolymers, blends, multilayer films including multilayer optical films, and multilayer composites of any polymer materials, including, for example, polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate glycol), polycarbonates, allyl diethylene glycol carbonates, acrylic polymers (e.g., polymethyl methacrylate (PMMA)), polystyrene, polysulfone, polyethersulfone, epoxy polymers, epoxy addition polymers with polydiamines and / or polydithiols, polyamides (e.g., nylon 6 and nylon 6,6), polyimides, polyolefins (e.g., polyethylene and polypropylene including low-density polyethylene), olefin copolymers (e.g., polyethylene copolymers), polyurethanes, polyureas, cellulose esters (e.g., cellulose acetate, cellulose triacetate, and cellulose butyrate), fluoropolymers, cyclic olefin copolymers (e.g., polyethylene / norbornene copolymers), and combinations thereof.

[0022] Inorganic substrates include, for example, insulators / dielectrics, semiconductors, or conductors. Inorganic substrates (e.g., dielectrics) can be amorphous or crystalline and include, for example, glasses (e.g., float glass, soda lime glass, borosilicate glass), quartz, fused silica, sapphire, yttrium oxide, and other transparent ceramics. Inorganic substrates (e.g., semiconductors) include, for example, silicon, germanium, Group III / V semiconductors (e.g., gallium arsenide), Group II / VI semiconductors, Group IV / VI semiconductors, or Group IV semiconductors (e.g., silicon carbide). Inorganic substrates (e.g., conductors) include, for example, transparent conductive oxides (TCOs), such as indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO); or metals, such as gold, silver, aluminum, copper, iron, or alloys such as stainless steel.

[0023] Before applying the primer to the substrate, the substrate is usually corona-treated or otherwise surface-treated to provide a negative charge on the surface of the substrate.

[0024] The primer is applied to a surface-treated (i.e., charged) substrate. In some embodiments, the primer comprises a polymerizable resin combined with an organic solvent to form a diluted solution. In some embodiments, the amount of the organic solvent is typically at least 10%, 20%, 30%, or 40% by weight. In some embodiments, the amount of the organic solvent is no more than 70%, 65%, or 60% by weight. In other embodiments, the polymerizable resin may be solvent-free.

[0025] In some implementations, polymerizable resins are typically applied as a diluted solution, such as by spin coating onto a surface (e.g., corona-treated), drying, and then curing by exposure to photochemical radiation. Polymerizable resins can also be applied using other techniques, such as wire-wound (e.g., Mayer) bars, cut-out bars, doctor blades, or inkjet printing.

[0026] Polymerizable resins contain a variety of olefinically unsaturated monomers. The term olefinically unsaturated refers to the vinyl group and "(meth)acrylaldehyde" group of methacrylate, acrylate, methacrylamide, acrylate, or acrylamide. The molecular weight of olefinically unsaturated monomers is typically no greater than 5000 g / mol, 2500 g / mol, 2000 g / mol, 1500 g / mol, or 1000 g / mol.

[0027] Unlike applying a pre-formed polymer (e.g., an acrylic polymer) layer to a substrate, it is presumed that the monomers can partially dissolve and thus penetrate into the surface of the organic polymer substrate. Upon curing, the polymerizable resin composition or primer layer can be characterized as a polymer. When the polymerizable resin contains more than 50% by weight of (meth)acrylic acid monomers, the polymer can be characterized as a (meth)acrylic polymer.

[0028] In some embodiments, the polymerizable resin comprises at least one monomer having at least two or three olefinically unsaturated (e.g., (meth)acrylate) groups. In some embodiments, the monomer has no more than six, five, four, or three olefinically unsaturated (e.g., (meth)acrylate) groups. In some embodiments, the monomer is free of aromatic moieties and may be characterized as aliphatic or alicyclic. It has been found that polymerizable resins comprising about 80 wt% ethoxylated (3)bisphenol and 16 wt% N,N-dimethylacrylamide (DMA) and a photoinitiator do not improve the adhesion of PDAC and PSS bilayers to PMMA substrates. However, such polymerizable resins are expected to be suitable primers for other substrates.

[0029] Examples of usable polyfunctional (meth)acrylates include, but are not limited to, di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, tricyclodecanediethanol diacrylate, 2-phenoxyethyl acrylate, poly(ethylene glycol) di(meth)acrylate, polybutadiene di(meth)acrylate, polyurethane di(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, and mixtures thereof.

[0030] In some embodiments, the monomer does not contain cyclic groups and the molecular weight of each olefinically unsaturated (e.g., (meth)acrylate) group is not greater than 100 g / mol, such as in the case of pentaerythritol triacrylate or hexanediol diacrylate.

[0031] In other embodiments, the monomer comprises an alicyclic group containing more than 6 carbon atoms, such as in the case of tricyclodecanediethanol diacrylate.

[0032] In some embodiments, the amount of monomer having at least two or three olefinically unsaturated groups is at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% of the olefinically unsaturated monomers of the polymerizable resin. Thus, the cured polymerizable resin contains polymeric units of such monomers at the same concentration.

[0033] The polymerizable resin of the primer typically contains polar monomers. Representative polar monomers include, for example, acid-functionalized monomers, hydroxyl-functionalized monomers, nitrogen-containing monomers, and combinations thereof.

[0034] In some embodiments, the polymerizable resin of the primer layer contains at least 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of polar monomers. In some embodiments, the polymerizable resin contains no more than 20 wt%, 15 wt%, or 10 wt% of polar monomers. Therefore, the cured polymerizable resin contains polymeric units of the same concentration of such monomers.

[0035] Available acid-functionalized monomers include, but are not limited to, those selected from: olefinically unsaturated carboxylic acids, olefinically unsaturated sulfonic acids, olefinically unsaturated phosphonic acids, and mixtures thereof. Examples of such compounds include those selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citrate, maleic acid, oleic acid, β-carboxyethyl (meth)acrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof.

[0036] Representative examples include N-vinylpyrrolidone; N-vinylcaprolactam; acrylamide; mono- or di-N-alkyl substituted acrylamide; tert-butylacrylamide; dimethylaminoethylacrylamide; and N-octylacrylamide.

[0037] Representative hydroxyl-functionalized monomers include 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate.

[0038] Polar monomers may include single acid functional monomers, single hydroxyl functional monomers, single nitrogen-containing monomers, combinations of one type of monomers, or combinations of different types of monomers.

[0039] In some implementations, the polar monomer is acrylic acid, N,N-dimethylacrylamide (DMA), or a combination thereof.

[0040] Monomers such as pentaerythritol triacrylate or hexanediol diacrylate and tricyclodecanediethanol diacrylate can be characterized as high Tg monomers, i.e., (meth)acrylate monomers with a Tg greater than 0 °C when reacting to form homopolymers. High Tg monomers more typically have a Tg greater than 25 °C, 50 °C, or 100 °C.

[0041] In some embodiments, the polymerizable resin of the primer layer comprises one or more low-Tg (meth)acrylate monomers, i.e., those that react to form a homopolymer with a Tg content of 100%. g (Meth)acrylate monomers with a temperature not exceeding 0°C. In some embodiments, the low-Tg monomers have a Tg not exceeding -5°C or -10°C. The Tg of these homopolymers is typically greater than or equal to -80°C, greater than or equal to -70°C, greater than or equal to -60°C, or greater than or equal to -50°C. Including low-Tg monomers can improve the conformability of the base coat.

[0042] Low Tg monomers can have the formula H2C=CR 1 C(O)OR 8 , where R 1 It is H or methyl, and R 8 It is an alkyl group having 1 to 22 carbons or a heteroalkyl group having 2 to 20 carbons and 1 to 6 heteroatoms selected from oxygen or sulfur. The alkyl or heteroalkyl group can be straight-chain, branched, cyclic, or a combination thereof.

[0043] Representative low-Tg monomers include, for example, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylbutyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2-pentyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, isotriadecyl acrylate, octadecyl acrylate, and dodecyl acrylate. Low-Tg heteroalkyl acrylate monomers include, but are not limited to, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate.

[0044] In some embodiments, the polymerizable resin of the primer layer comprises at least one low-Tg monomer having an alkyl group containing 6 to 20 carbon atoms. In some embodiments, the low-Tg monomer has an alkyl group containing 7 or 8 carbon atoms. Exemplary monomers include, but are not limited to, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, isodecanyl (meth)acrylate, and lauryl (meth)acrylate. In some embodiments, the monomer is an ester of (meth)acrylate with an alcohol derived from a renewable source (such as 2-octyl (meth)acrylate).

[0045] The polymerizable resin of the primer layer may optionally contain a high Tg mono(meth)acrylate monomer.

[0046] Representative high-Tg monofunctional (meth)acrylate alkyl ester monomers include, for example, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, stearate methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isoborneol acrylate, isoborneol methacrylate, norborneol acrylate, phenoxyethyl acrylate, benzyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, and propyl methacrylate or combinations thereof.

[0047] The thermograms (Tg) of homopolymers of various monomers are known and reported in various handbooks. The Tg of some exemplary monomers are reported by reference in WO 2016 / 094277, which is incorporated herein by reference.

[0048] In some embodiments, the polymerizable resin of the primer layer comprises at least 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt% of a monofunctional (meth)acrylate monomer. In some embodiments, the polymerizable resin of the primer layer comprises no more than 50 wt%, 45 wt%, 40 wt%, 35 wt%, 30 wt%, 25 wt%, or 20 wt% of a monofunctional (meth)acrylate monomer. The monofunctional (meth)acrylate monomer can be a low-Tg monomer, a high-Tg monomer, or a combination thereof. Therefore, the cured polymerizable resin comprises polymeric units of such monomers at the same concentration.

[0049] The polymerizable resin of the primer may optionally contain additives that provide improved adhesion, as demonstrated by the tape tests further described in the examples. Common additives include polymerizable or non-polymerizable additives such as ultraviolet light absorbers (UVA) containing benzotriazole, benzophenone, or triazine groups, hindered amine light stabilizers (HALS), and combinations thereof, in amounts ranging from about 2% to 10%. In other embodiments, the polymerizable resin of the primer does not contain such light absorbers (UVA) and hindered amine light stabilizers (HALS).

[0050] The polymerizable composition of the primer can be polymerized by various techniques, but preferably by solvent-free radiation polymerization, including processes using electron beams, gamma radiation, and especially ultraviolet radiation. In this (e.g., ultraviolet radiation) embodiment, methacrylate monomers are typically used sparingly or not at all. Therefore, the primer may contain 0 or no more than 10 wt%, 5 wt%, or 1 wt% polymerizable units of monomers having methacrylate groups.

[0051] When a polymerizable composition of a primer is cured by photocuring, the polymerizable composition typically contains a photoinitiator. Available photoinitiators include benzoin ethers, such as benzoin methyl ether and benzoin isopropyl ether; substituted acetophenones, such as those traded under the names IRGACURE 651 or ESACURE. KB-1 photoinitiator is a 2,2-dimethoxy-2-phenylacetophenone photoinitiator purchased from Sartomer Co., West Chester, PA, USA, as well as dimethylhydroxyacetophenone; substituted α-keto alcohols, such as 2-methyl-2-hydroxyacetone; aromatic sulfonyl chlorides, such as 2-naphthalene-sulfonyl chloride; photooximes, such as 1-phenyl-1,2-propanedione-2-(O-ethoxy-carbonyl)oxime; mono- or diacylphosphine oxides, such as LUCIRIN TPO or OMNIRAD 819. Suitable photoinitiators are typically present in amounts from 0.1% to 1.0% by weight.

[0052] The polymerizable resin is transparent enough to be activated by ultraviolet radiation with maximum UVA in the 280 nm to 425 nm range, allowing the monomer components to polymerize. UV light sources can be of various types. Low-intensity sources, such as black lights, typically provide up to 0.1 mW / cm². 2 Or 0.5mW / cm 2 (mW / cm²) to 10mW / cm² 2Intensity within the range (measured according to procedures approved by the National Institute of Standards and Technology, such as, for example, using a UVIMAP UM 365 LS radiometer manufactured by Electronic Instrumentation & Technology, Inc., Sterling, VA). High-intensity light sources typically provide greater than 10 mW / cm². 2 15mW / cm 2 Or 20mW / cm 2 The range is up to 450mW / cm 2 Or even greater intensity. In some implementations, high-intensity light sources provide up to 500 mW / cm². 2 600mW / cm 2 700mW / cm 2 800mW / cm 2 900mW / cm 2 Or 1000mW / cm 2 The intensity of the UV light used to polymerize the monomer components can be provided by various light sources, such as light-emitting diodes (LEDs), black lights, medium-pressure mercury lamps, or combinations thereof. The monomer components can also be polymerized using higher-intensity light sources available from Fusion UV Systems Inc., Gaithersburg, MD, USA. The UV exposure time for polymerization and curing can vary depending on the intensity of the light source used. For example, complete curing with a low-intensity light process can be completed with an exposure time ranging from approximately 30 to 300 seconds, while complete curing with a high-intensity light source can be completed with a shorter exposure time ranging from approximately 5 to 20 seconds. Partial curing using a high-intensity light source can typically be completed with an exposure time ranging from approximately 2 to approximately 5 or 10 seconds.

[0053] In some embodiments, both the substrate and the multiple layers deposited by layer-by-layer self-assembly (i.e., a polymer matrix of ionically bonded at least two organic polymers) are transparent to visible light (400 nm to 700 nm) and typically exhibit at least 85% or 90% transmittance.

[0054] Organic polymer films with high visible light transmittance, including UV, IR and visible light reflective films, can be used in architectural applications, greenhouse applications, window films, paint protection films, solar power generation applications, lighting, door and window products (i.e., products that fill openings in buildings, such as windows, doors, skylights or curtain walls, such as curtain walls designed to allow light to pass through), solar tube products and other daylighting systems for transmitting sunlight into interiors, as well as other applications.

[0055] In other embodiments, the substrate described herein can be used for commercial graphic films (e.g., films for billboards, building exteriors, signage, automobiles, rail vehicles, etc.), traffic signs, and protective films such as automotive wrapping films.

[0056] As described in WO2015-095317, multiple layers deposited by layer-by-layer self-assembly typically do not contain polyelectrolytes alternating with inorganic oxide nanoparticles containing phosphorus-containing surface treatment agents. When the bilayer contains inorganic nanoparticles, the concentration of the inorganic nanoparticles is typically at least 30% by weight of the total amount of the dried bilayer or self-assembled layer. However, it is anticipated that a portion of the layer may contain inorganic oxide particles. Furthermore, it may be advantageous to coat the final bilayer surface with a coating containing inorganic oxide nanoparticles (e.g., a hard coating). In these embodiments, multiple layers and articles deposited by layer-by-layer self-assembly of at least two organic polymers, ion-bonded polymer matrix, typically contain less than 25%, 20%, 15%, 10%, 5%, 1%, or 0.5% by weight of inorganic nanoparticles.

[0057] The following embodiments further illustrate the advantages and implementations of this disclosure; however, the specific materials and quantities mentioned in these embodiments, as well as other conditions and details, should not be construed as undue limitation of this disclosure. Unless otherwise specified or obvious, all materials are commercially available or known to those skilled in the art.

[0058] Example

[0059] Preparation of base adhesive

[0060] In a 4 oz amber-colored wide-mouth jar, add 24.92 g (83 wt% solids) of SR444, 3.91 g (13 wt% solids) of DMA, 1.17 g (3.9 wt% solids) of Esacure One, and 30.00 g of carbitol (2-(2-ethoxyethoxy)ethanol). After mixing, seal the jar and shake vigorously until the contents are thoroughly mixed and the initiator is completely dissolved. Then allow the jar to stand and allow any entrained air bubbles from the shaking to degas. This composition will serve as the base primer formulation and will be referred to as Primer A.

[0061] Prepare other primer compositions as detailed in the table below.

[0062]

[0063] Apply the primer coating to the polymer substrate using a spin coater.

[0064] The primer solution was applied to the polymer substrate sample using a Laurell Technologies Corp. WS-400-B8NPP / Lite / AS spin coater. The sample was mounted on a 2-inch circular vacuum chuck. The spin coater was then programmed to rotate at 4,000 RPM for 2 minutes with an acceleration of 1032. The primer solution was spread over the entire sample using a pipette. The cap was closed, and the spin coater was started. When the spin coating process was complete, the substrate was transferred to an aluminum tray and placed in an oven to dry at 80°C for 3 minutes. The sample was then cured twice using a Heraeus melting processor with an H-bulb at 25 ft / min and 100% power. The total exposure for each sample was 1230 mJ / cm³. 2 UVA, 948mJ / cm 2 UVB, 231.0 mJ / cm 2 UVC and 1462mJ / cm 2 UVV.

[0065] Preparation of (PDAC / PSS) solution for layer-by-layer deposition

[0066] In a 1.75” x 4.75” x 5.5” rectangular container, 2.24 g of PDAC and 117 g of NaCl25 were mixed into 385 g of deionized water to form a homogeneous 0.2 wt% PDAC solution.

[0067] In another 1.75” x 4.75” x 5.5” rectangular container, 3.35 g of PSS and 117 g of NaCl25 were mixed into 384 g of deionized water to form a homogeneous 0.2 wt% PSS solution. In another 1.75” x 4.75” x 5.5” rectangular container, 0.5 g of Acid Blue dye was mixed into 500 g of deionized water to form a 0.1 wt% dye solution.

[0068] All polymer substrate surfaces prepared for layer-by-layer deposition were treated five times with a handheld corona processor, Model BD-20AC, from Electro-Technic Products, Chicago, IL, USA. Therefore, the corona-treated substrates were compared with the same corona-treated substrates with an undercoat.

[0069] A layer-by-layer deposition process was performed by first exposing the sample to a cationic (PDAC) solution via immersion and immediately removing it, then rinsing the sample with deionized water and drying it with compressed air in the chamber. The same procedure was then performed on the sample with anionic (PSS) solution, followed by rinsing with deionized water and drying with compressed air in the chamber. The sample was sequentially exposed to cationic and anionic solutions to form deposited bilayers, and this process was repeated until 10 bilayers were deposited.

[0070] Once 10 double layers were completed, the sample was exposed again to a cationic (PDAC) solution for a similar rinsing and drying process. The sample was then exposed to an acid blue dye solution for 1 minute, followed by a similar rinsing and drying process. The blue dye was present to visually determine if the layer-by-layer coating had been damaged by the tape.

[0071] Tape test used to visually quantify the adhesion of layer-by-layer coatings to a substrate.

[0072] A 1” strip of 3M Company 232 masking tape (3M Company, St. Paul, MN) was laminated onto the coated portion of the sample using small overhang tabs. A rubber roller was then passed back and forth across the sample five times while applying pressure to ensure good lamination of the masking tape. The edges of the sample were marked with a black permanent marker to indicate the area being tested. Next, the masking tape was slowly peeled off at a 90° angle, starting from the overhang tabs.

[0073] The process was repeated a second time in the same marked test area to further attempt to remove any poorly adhered coating. After the second tape test, the sample was imaged and the extent to which the coating area was affected by scratching, abrasion, or complete removal was assessed. This assessment was quantified by applying a grid to the test area in the image. As previously defined, a red square was indicated for any point where the coating was affected. A white square was used to indicate that there was not enough sample / substrate to fill half of that square's area. The percentage of the surface area affected by the tape was calculated by dividing the number of red squares by (the total number of squares in the grid minus the number of white squares).

[0074] Tables 5 and 6 below list the substrate, base coat, and test results.

[0075]

[0076] Preparation of (PAH / PAA) solution

[0077] In a 1.75” x 4.75” x 5.5” rectangular container, 3.33 g of PAH was mixed into 497 g of deionized water to form a homogeneous 0.1 wt% PAH solution. Using a calibrated pH probe, HCl was added dropwise until the pH of the PAH solution reached 7.5. In another 1.75” x 4.75” x 5.5” rectangular container, 4.00 g of PAA was mixed into 496 g of deionized water to form a homogeneous 0.2 wt% PAA solution. Using a calibrated pH probe, sodium hydroxide was added dropwise until the pH of the PAA solution reached 3.5. In yet another 1.75” x 4.75” x 5.5” rectangular container, 0.5 g of Acid Blue dye was mixed into 500 g of deionized water to form a 0.1 wt% dye solution.

[0078] (PAH / PAA) sediments

[0079] The same procedure used for deposition (PDAC / PSS) is also used for (PAH / PAA), however, the number of bilayers is increased to 12. After completing the 12th bilayer, the sample to be coated is immersed in PAH again, then rinsed and dried, and then immersed in Acid Blue dye. The final LbL structure is (PAH / PAA). 12.5 / Acid Blue dye. Table 7 lists the samples prepared with (PAH / PAA) coating.

[0080]

[0081] Tape testing and evaluation

[0082] The tape test was performed in the same manner as described above; however, evaluating the samples was difficult because the dye's staining strength on the coating was not as good as (PDAC / PSS). Instead, the transmittance of the coating before and after the tape test was measured using a BYK haze-gard i instrument from Wesel, Germany. Example 20 showed 92% transmittance before and after the tape test, indicating that the coating was unaffected by the tape test. Example 21 showed approximately 91.5% transmittance before the tape test but 93.3% after, indicating that the sample performed worse than Example 20.

Claims

1. A method for manufacturing an article of articles, the method comprising: Provide a base; Apply the base coat to the substrate; The primer layer comprises a reaction product of a polymerizable resin, the polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and Multiple layers are deposited by layer-by-layer self-assembly and applied to the base coat.

2. The method of claim 1, wherein the polymerizable resin is cured by exposure to photochemical radiation.

3. The method of claim 2, wherein the polymerizable resin is cured before, after, or in combination thereof, the plurality of layers are applied.

4. The method according to claims 1 to 3, wherein the plurality of layers comprises at least one polycationic polymer and at least one polyanionic polymer.

5. The method according to claims 1 to 4, wherein the substrate is an inorganic material, an organic polymer material, or a combination thereof.

6. The method according to claims 1 to 5, wherein the substrate comprises an organic polymer selected from the group consisting of polyolefins, polyesters and acrylic polymers.

7. The method of claim 6, wherein the organic polymer comprises an alicyclic or aromatic moiety.

8. The method according to claims 1 to 7, wherein the base coat has a thickness of less than 1 micrometer, 750 nm, 500 nm or 250 nm.

9. The method according to claims 1 to 8, wherein the polymerizable resin comprises at least one non-aromatic monomer having at least two (meth)acrylate groups.

10. The method according to claims 1 to 9, wherein the polymerizable resin comprises at least one monomer having at least three (meth)acrylate groups.

11. The method according to claims 1 to 10, wherein the polymerizable resin further comprises at least one polar monomer, the at least one polar monomer comprising an acidic monomer and a (meth)acrylamide monomer.

12. The method according to claims 1 to 11, wherein the polymerizable resin further comprises at least one mono(meth)acrylate monomer.

13. An article of manufacture, said article comprising: Base; A base adhesive layer disposed on the substrate; The primer layer comprises a reaction product of a polymerizable resin, the polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and Multiple layers are deposited by self-assembly layer by layer, the multiple layers being disposed on the base coat.

14. An article comprising: Base; A base adhesive layer disposed on the substrate; The primer layer comprises a reaction product of a polymerizable resin, the polymerizable resin comprising at least one monomer having at least two olefinically unsaturated groups; and An ion-bonded polymer matrix disposed on the substrate.

15. The article of claim 14, wherein the ion-bonded polymer matrix comprises at least two different organic polymers.

16. The article of claim 14 to 15, wherein the polymer matrix is ​​crosslinked.

17. The article of manufacture according to claims 14 to 16, further characterized by claims 2 to 12.

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