LIGHT-CURING (MET)ACRYLATE COMPOSITIONS

Abstract

Photocurable (meth)acrylate compositions for forming features on membrane surfaces and, in particular, on membranes used in osmosis and reverse osmosis applications, such as membrane filters.

Description

2. Brief description of related technology [2] Curable compositions have been widely used for sealing, adhesive, coating and encapsulation applications, to name a few. The choice of backbone type and curable groups is generally selected with reference to the specific end-use application and the environment in which it is intended for use. Polymers having various degrees of unsaturated groups, as well as other functionally crosslinking groups, have been used. [3] For bonding and spacing of reverse osmosis (RO) membranes, commonly used adhesives (i.e., nczrnn / zznz / E / YiAi curable compositions) are two-part room temperature curing polyurethane or epoxy. The two parts must be mixed and applied before the gel time to form parts, which is undesirable for some applications. Light-curing acrylates containing a (meth)acrylate-terminated polybutadiene have been described for protection against membrane folding, but binding to membranes has not been reported. Polybutanediene acrylate oligomers generally have low adhesion to many substrates. Light-curing acrylate-containing polyether-acrylate urethane resins are known to have good hydrolytic stability, but bonding to reverse osmosis membranes is a challenge in alkaline solutions. [4] Even if adequate adhesion is initially achieved between the curable composition and the membrane surface, materials adhered to the membrane surfaces, for example, spacing characteristics, are required in order to maintain good adhesion to the membrane. after curing and during use and maintenance of the membrane. The use and maintenance of, for example, RO membranes requires that the surface of the membrane and the features / spacers that adhere to it be exposed to an aqueous environment. In particular, cleaning of membranes often requires exposure of the membrane to acidic and basic aqueous solutions. Features formed by the cured composition may suffer degradation when in contact with water, particularly in acidic and alkaline solutions, resulting in loss of mass, mechanical strength and adhesion to the membrane during use and maintenance. [5] There is a need for a photocurable (meth)acrylate composition and a process of using said composition to form hydrolytically stable features on the membrane surface, which allows good adhesion of the cured composition to the membrane surface , as well as maintaining good adhesion, mass and mechanical resistance of the cured composition during the use and subsequent maintenance of the membrane. Summary of the invention [6] The present invention provides a photocurable composition that includes: a) a polyether-urethane component functionalized with (meth)acrylate; b) a (meth)acrylate monomer; c) an organic filler; and d) a photoinitiator, wherein, when exposed to UV or visible light, the curable composition forms a cured reaction product, the cured reaction product demonstrating a mass loss of: 1) less than 2% when exposed to acidic aqueous conditions (pH = 1.5) for about 4 weeks at a temperature of about 50°C and / or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for about 4 weeks at a temperature of about 50°C. [7] In another aspect of the present invention, a mixed membrane structure is provided that includes: a) a membrane that includes at least one surface; and b) the cured reaction product of the curable composition described above disposed on at least a portion of at least one surface of the membrane. [8] In another aspect of the present invention, a method is provided for producing a hydrolytically stable cured reaction product comprising the steps of: a) providing a curable composition that includes: i) a polyether-urethane component functionalized with ( meth)acrylate; ii) a (meth)acrylate monomer; iii) an organic filler; and iv) a photoinitiator, and b) exposing the curable composition to a UV or visible light source to form a cured reaction product, wherein hydrolytic stability is demonstrated when the cured reaction product shows a mass loss of: 1) less than 2% when exposed to acidic aqueous conditions (pH = 1.5) for about 4 weeks at a temperature of about 50°C or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for about 4 weeks at a temperature of about 50°C. Detailed description [9] The present invention is directed to photocurable (meth)acrylate compositions, which include: a) a (meth)acrylate functionalized polyether-urethane component; b) a (meth)acrylate monomer; c) an organic filler; and d) a photoinitiator, wherein, when exposed to UV or visible light, the curable composition forms a cured reaction product, the cured reaction product demonstrating a mass loss of: 1) less than 2% when exposed to an acidic aqueous solution (pH = 1.5) for about 4 weeks at a temperature of about 50°C and / or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for about 4 weeks at a temperature of approximately 50°C.

[10] As used herein, hydrolytically stable means that the cured reaction product is resistant to chemical decomposition in the presence of water. This hydrolytic stability is important, particularly in RO membrane applications, because during use and maintenance of such mixed membrane structures, the cured reaction product is exposed (often continuously) to aqueous conditions. Additionally, depending on the specific use of the membrane, the cured reaction product may be exposed to highly acidic and highly basic conditions. For example, cleaning or reconditioning nczrnn / zznz / E / YiAi reverse osmosis membrane filters involves the application of caustic solutions to remove residue and debris trapped in the spacer elements (i.e., features formed by the cured reaction). Therefore, the hydrolytic stability of the cured reaction product may be critical to prolonging the life of these membrane elements and reducing the costs associated with their frequent replacement.

[11] In one aspect of the present invention, the hydrolytic stability of the cured reaction product is demonstrated when the cured reaction product demonstrates minimal mass loss when exposed to aqueous conditions, such as aqueous solutions. As used herein, a minimum mass loss means a loss of less than 5%, less than 4%, less than 3%, less than 2.5%, less than 2%, less than 1.5%, less than 1 %, or less than 0.5% when exposed to aqueous conditions for an extended period of time at elevated temperature. As used herein, an extended period of time means about 0.5 weeks, about 1 week, about 2 weeks, about 3 weeks, about 4 weeks, about 5 weeks, or about 6 weeks. As used herein, an elevated temperature means about 30°C or more, about 35°C or more, about 40°C or more, about 45°C or more, about 50°C or more, about 55°C or higher, about 60°C or higher, or about 70°C or higher.

[12] In aspects of the present invention, aqueous conditions may include acidic aqueous conditions, basic aqueous conditions, and neutral aqueous conditions. As used herein, acidic aqueous conditions means aqueous conditions with a pH of about 3 or less, about 2.5 or less, about 2 or less, about 1.5 or less, or about 1 or less. As used herein, basic aqueous conditions means aqueous conditions with a pH of about 11 or greater, about 11.5 or greater, about 12 or greater, about 12.5 or greater, or about 13 or greater. As used herein, neutral aqueous conditions means aqueous conditions with a pH between about 6 and about 8 or with a pH of about 7.

[13] In one aspect of the present invention, the hydrolytic stability of the cured reaction product is demonstrated when the cured reaction product demonstrates a mass loss of: 1) less than 2% when exposed to acidic aqueous conditions (pH = 1.5) for about 4 weeks at a temperature of about 50°C and / or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for about 4 weeks at a temperature of about 50°C.

[14] In one aspect of the present invention, the cured reaction product has a Shore D hardness of about 20 or greater, preferably about 20 to about 70 or about 40 to about 60.

[15] In one aspect of the present invention, the curable composition has a viscosity of about 10,000 to about 100,000 or about 20,000 to about 80,000 centipoise (at 25°C, 10 s-1).

[16] In one aspect of the present invention, the curable composition has an optimized rheology that is effectively balanced to allow sufficient thixotropy to facilitate deposition and yet maintain its physical structure after deposition and before curing. As used herein, thixotropy means that the substance becomes less viscous when stress is applied (e.g., mixing or stirring) and is more viscous when free of such stress (e.g., under static conditions).

[17] In another aspect of the present invention, the curable composition has a thixotropic index of about 1.5 to about 6 or about 1.5 to about 5. As used herein, the thixotropic index means the ratio of the viscosity (in centipoises) of the curable composition at a speed of s-1a the viscosity (in centipoises) of the curable composition at a speed of 10 s-1 (viscosity at 1 s-1 / viscosity at 10 s-1). Viscosity can be determined using known methods, for example, cone and plate rheometer, parallel plate rheometer or rotational viscometer, such as the Brookfield viscometer.

[18] In one aspect of the present invention, the (meth)acrylate functionalized polyether urethane component is a polyether urethane acrylate oligomer. Suitable polyether acrylate urethane oligomers include, but are not limited to, aliphatic urethane acrylates. Examples of suitable polyether acrylate urethane oligomers include Ebecryl 264, 265, 270, 1258, 4100, 4200, 4220, 4265, 8807, 8810 and 8800-20R (all from Allnex), BR14B, BR-302, BR-344 , BR-345, BR-372, BR-543, BR-571, BR-582, BR 582E8, BR-930D, BR-3042 and BR-3471 (all from Dymax), Genomer 4230, 4217, (all from Rahn ), CN 9004, 9005, 959, 989, 996 and 980 (all from Sartomer). Some other polyether urethane acrylates from urethane acrylate manufacturers such as IGM, Evonik and Kowa can also be used.

[19] In one aspect of the present invention, the urethane acrylate oligomer is a polyethylene glycol diacrylate (the exact structure of polyether urethane acrylate is not known) or a combination thereof.

[20] In a further aspect of the present invention, the nczrnn / zznz / E / YiAi (meth)acrylate functionalized polyether urethane component is present in an amount of about 20% to about 60% by weight or about 30 % to about 50% by weight based on the total weight of the curable composition.

[21] Suitable (meth)acrylate monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, n-butyl meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate , n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, ( phenyl meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate), 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, (meth) diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. In one aspect of the present invention, the (meth)acrylate monomer is polyethylene glycol diacrylate, such as SR 259 (Sartomer polyethylene glycol (200) diacrylate). Suitable multifunctional (meth)acrylates include polyethylene glycol di(meth)acrylates, desirably triethylene glycol di(meth)acrylate, hydroxypropyl (meth)acrylate, bisphenol-Ά di(meth)acrylates, such as ethoxylated bisphenol-A (EBIPA or EBIPMA), and tetrahydrofuran (meth)acrylates and di(meth)acrylates, citronellyl acrylate and citronellyl methacrylate, hexanediol di(meth)acrylate (HDDA or HDDMA), tri(meth)acrylate of trimethylolpropane, tetrahydrodicyclopentadienyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate (ETTA), triethylene glycol diacrylate and triethylene glycol dimethacrylate (TRIEGMA). In one aspect of the present invention, the (meth)acrylate monomer is monofunctional or difunctional acrylate, or a combination thereof.

[22] In one aspect of the present invention, the (meth)acrylate monomer is present in an amount of about 10% to about 60% by weight or about 20% to about 40% by weight. weight based on the total weight of the curable composition.

[23] In another aspect of the present invention, the (meth)acrylate monomer has a viscosity of less than about 1,000 cps or less than about 500 cps.

[24] In one aspect of the present invention, organic fillers include organic thickeners based on hydrophobic polyolefin, thermoplastic polymers such as polyvinyl acetate, polyolefin, nylon fibers and combinations thereof. Suitable organic fillers include polyvinyl chloride powder, polypropylene powder or a combination thereof.

[25] In one aspect of the present invention, the organic filler is present in an amount of 5% to 50% by weight or 15% to 40% based on the total weight of the curable composition.

[26] In aspects of the present invention, the curable composition is a photo-curable or light-curable composition, that is, curable using light such as visible or ultraviolet (UV) light. In aspects of the present invention, the curable composition can be cured using a light source, such as a light bulb or LED that produces visible or UV light.

[27] In a further aspect of the present invention, the photoinitiator may be a UV initiator, a visible light initiator, or a combination of UV and visible light initiators. In one aspect of the present invention, the photoinitiator is a polymeric structure to which at least one chromophore is attached that is excited by radiation in the range of UV light or visible light.

[28] A variety of UV initiators can be employed. UV initiators are generally effective in the range 200 to 400 nm, and particularly in the portion of the spectrum bordering invisible light and the visible portion just beyond, e.g., >200 nm to approximately 390 nm.

[29] Initiators that will respond to UV radiation to initiate and induce cure of the (meth)acryl-functionalized curable component, which are useful in the present invention include, but are not limited to, benzophenone and substituted benzophenones, acetophenone and substituted acetophenones, benzoin and their alkyl esters, xanthone and substituted xanthones, phosphine oxides, diethoxy-acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thio-xanthone, N-methyl diethanolamine-benzophenone, 2 -hydroxy-2-methyl-l-phenyl-propan-l-one, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and mixtures thereof.

[30] Examples of such UV initiators include commercially available initiators from IGM Resins under the trade names OMNIRAD (formerly IRGACURE) and DAROCUR, specifically OMNIRAD 184 (1-hydroxycyclohexyl nczrnn / zznz / E / YiAi phenyl ketone), 907 (2- methyl-l-[ 4-(methylthio)phenyl]-2-morpholino propan-l-one), 369 (2-benzyl-2-N,N-dimethylamino-l-(4morpholinophenyl)-1-butanone), 500 ( the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4,4-trimethylpentyl)phosphine oxide and 2 -hydroxy-2-methyl-l-phenyl-propan-l-one), and 819 [bis(2,4,6-trimethyl-benzoyl)phenylphosphine oxide], and DAROCUR 1173 (2-hydroxy-2-methyl-l-phenyl-l- propane) and 4265 (the combination of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2-hydroxy-2-methyl-lfenyl-propan-l-one); and 2,4,6trimethylbenzoyldiphenylphosphine oxide (commercially available as LUCIRIN TPO from BASF Corp.). Of course, combinations of these materials can also be used here. It is of course understood that some of these photoinitiators classified here as UV photoinitiators have tail absorption in the visible range and therefore fall on the line between UV and visible light curing initiators, but nonetheless They are included here as part of the invention.

[31] Suitable initiators for use in the present invention that will respond to visible light to initiate and induce cure include, but are not limited to, camphorquinone peroxyester initiators, 9-fluorene carboxylic acid peroxyesters, visible light photoinitiators [blue ], dl-camphorquinone, IRGACURE 784DC (photoinitiator based on substituted titanocenes) and combinations thereof.

[32] Other suitable photoinitiator systems include those described in each of the following patents or publications, each of which is incorporated herein by reference in its entirety.

[33] The U.S. Pat. No. 4,505,793 to Tamoto et al., which is incorporated herein by reference, describes photopolymerization initiators that include a combination of a 3-keto substituted coumarin compound and an active halogen compound. Several illustrative compounds are described. Such photopolymerization initiators cure on exposure to light having wavelengths ranging from about 180 nm to 600 nm.

[34] U.S. Pat. No. 4,258,123 to Nagashima et al., which is incorporated herein by reference, describes photoresist compositions that include initiator components that generate a free radical upon irradiation with actinic light. Such components include various triazine compounds, as described in more detail therein.

[35] Additional useful components are described in the following document, which is incorporated herein by reference. European Patent Publication No. EP 0 369 645 Al describes a three-part photoinitiator system including a trihalomethyl substituted s-triazine, a sensitizer compound capable of absorbing radiation in the range of about 300-1000 nm, and an electron donor. . Examples of sensitizing compounds are described, including: ketones; coumarin dyes; xanthene dyes; 3Hxanthene-3-one dyes; acridine dyes; tlazol dyes; thiazine dyes; oxazine dyes; azine dyes; aminoketone dyes; methane and polymethine dyes; porphyrins; polycyclic aromatic hydrocarbons; p-substituted aminostyryl ketone compounds; aminotriaryl methanes; merocyanins; squarylium dyes; and pyridinium dyes. Illustrative donors are also described, including: amines; amides; ethers; ureas; ferrocene; sulfinic acids and their salts; ferrocyanide salts; ascorbic acid and its salts; dithiocarbamic acid and its salts; xanthate salts; salts of ethylenediaminetetraacetic acid; and salts of tetraphenylboronic acid. These initiators are sensitive to both UV light and visible light.

[36] Additional useful components are described in the following document, which is incorporated herein by reference. European Patent Publication No. EP 0 563 925 A1 describes photopolymerization initiators that include a sensitizing compound that is capable of absorbing radiation in the range of about 250-1000 nm and 2-aryl-4,6bis(trichloromethyl)-1, 3, 5-triazine. Examples of sensitizing compounds that are described include: cyanine dye, merocyanine dye, camarin dye, ketocoumarin dye, (thio)xanthene dye, acridine dye, tlazol dye, thiazine dye, oxazine dye, azine, aminoketone dye, squarylium dye, pyridinium dye, (thia)pyrylium dye, porphyrin dye, triaryl methane dye, (poly)methane dye, amino styryl compounds and polycyclic aromatic hydrocarbons. These photopolymerization initiators are sensitive to UV and visible light.

[37] The U.S. Pat. No. 5,395,862 to Neckers et al., which is incorporated herein by reference, describes fluorone photoinitiators, which are sensitive to visible light. Such fluorone initiator systems also include a coinitiator, which is capable of accepting an electron from the excited fluorone species. Illustrative co-initiators are described, including: onium salts, nitrohalomethanes and diazosulfones. The U.S. Patent No. 5,451,343 to Neckers et al., which is incorporated herein by reference, describes fluorone and pyronin-Y derivatives as initiators that absorb light at wavelengths greater than 350 nm. US Patent No. 5,545,676 to Palazzotto et al., which is incorporated herein by reference, describes a three-part photoinitiator system that cures under ultraviolet light or visible light. The three-part system includes an aryllidonium salt, a sensitizing compound, and an electron donor. Examples of iodonium salts include diphenyliodonium salts. Illustrative sensitizers and electron donors for use in the three-part system are also described. Furthermore, the sensitizer is capable of absorbing light in the range of approximately 300-1000 nm.

[38] In another aspect of the present invention, the photoinitiator is present in an amount of about 0.2% to about 5% by weight or about 1% to about 3% by weight based on the total weight of the curable composition.

[39] In a further aspect of the present invention, the curable composition may further include an inorganic filler that is stable in acidic and basic solutions. Inorganic fillers include fumed silica. Silane-treated fumed silica, silicate, aluminum silica, zirconium silicate, feldspar, ferromagnetics, fly ash, glass fibers, jute fiber, mica, quartz, titanium dioxide, and combinations thereof.

[40] In one aspect of the present invention, the inorganic filler is present in amounts of about 0.1% to about 40% or about 1% to about 10% by weight based on the total weight of the curable composition.

[41] Optional additives, such as co-initiators, stabilizers, rheology modifiers, antifoams, inhibitors, oxygen scavenging agents, dyes, colors, pigments, adhesion promoters, plasticizers, hardening agents, reinforcing agents, fluorescent agents, agents humectants, antioxidants and combinations thereof may also be included in the compositions of the present invention.

[42] The present invention is also directed to mixed membrane structures, including: a) a membrane comprising at least one surface and b) the cured reaction product of the curable composition described above arranged on at least a part of at least a membrane surface.

[43] The present invention further relates to methods for producing a hydrolytically stable cured reaction product, which include the steps of: a) providing a curable composition that includes: i) a (meth)acrylate functionalized polyether-urethane component ; ii) a (meth)acrylate monomer; iii) an organic filler; and iv) a photoinitiator, and b) exposing the curable composition to a UV or visible light source to form a cured reaction product, wherein hydrolytic stability is demonstrated when the cured reaction product shows a mass loss of: 1) less than 2% when exposed to acidic aqueous conditions (pH = 1.5) for approximately 4 weeks at a temperature of approximately 50 °C or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for approximately weeks at a temperature of approximately 50°C.

[44] In another aspect of the composite membrane structure of the present invention, the cured reaction product is adhesively bonded to at least a portion of at least one surface of the membrane.

[45] In another aspect of the mixed membrane structure of the present invention, the cured reaction product is arranged on at least a portion of at least one surface of the membrane in a predetermined pattern. In embodiments of the mixed membrane structure of the present invention, the predetermined pattern is selected from the group consisting of stripes, waves, circles, ovals, arcs, squares, rectangles, rhombuses, pentagons, hexagons, stars, chevrons, a random pattern , and combinations thereof.

[46] In one aspect of the present invention, the pattern is formed on the surface of the membrane by known methods, such as printing or deposition of the curable composition on the surface of the membrane followed by curing of the curable composition. The pattern formed on the membrane surface by the methods of the present invention is generally composed of numerous features formed from the cured reaction product. Generally, these features have physical characteristics that make them suitable for providing space between the overlapping layers of the membrane. For example, nczrnn / zznz / E / YiAi features may provide adequate separation between the layers of a spiral reverse osmosis filter membrane to optimize the performance, cleanliness, and life of the reverse osmosis membrane elements that They use membranes with these characteristics. In one aspect of the present invention, the feature pattern may be of a size and shape sufficient to maintain adequate separation of the membrane and expose sufficient surface area of ​​the membrane to ensure effective operation of the membrane.

[47] The surface onto which the curable composition is deposited can include the surface of any suitable membrane for application of the curable composition. In one aspect of the present invention, the surface on which the curable composition is deposited is a membrane surface. As used herein, a membrane means a selective barrier that allows the passage of some substances, but prevents the passage of other substances. In one aspect of the present invention, the membrane is a filter membrane, ie, a membrane for filtering substances from a liquid vehicle, such as water. Filter membranes include reverse osmosis membranes, direct osmosis membranes, microfiltration membranes, ultrafiltration membranes, and nanofiltration membranes. The features composed of the cured composition can be deposited on the active surface of the membrane, or on the nczrnn / zznz / E / YiAi non-active surface of the membrane, or both.

[48] ​​In general, the above description is provided for illustrative and example purposes; The present invention is not necessarily limited thereto. Rather, those skilled in the art will appreciate that further modifications, as well as adaptations for particular circumstances, will be within the scope of the invention as shown and described herein and the appended claims. Examples Materials

[49] The following ingredients were used in the examples described below in Table 1: Table 1 Ingredient Name Class Supplier Polyester-Acrylate Urethane A (Proprietary) Polyester-Acrylate Urethane Henkel CN9024 Polyester-Acrylate Urethane Sartomer CN991 Polyester-Acrylate Urethane Sartomer CN9167US Polyether-Acrylate Urethane Sartomer CN996 Polyether-Acrylate Sartomer Ebecryl 880 7 Polyether Acrylate Urethane Allnex BR582E8 Polyether Acrylate Urethane Dymax Genomer 4230 Polyether Acrylate Urethane Rhan Isobornyl Acrylate (ΙΒΟΑ) Sartomer Acrylate Monomer Genomer 1122 Rahn Acrylate Monomer Isodecyl Acrylate Sartomer Acrylate Monomer Powder polyvinyl chloride ( PVC) Organic filler Formosa Plastics Corporation Polypropylene powder BYK organic filler Zirconium silicate powder Inorganic filler Continental Mineral Processing Aluminum Silicate Powder Inorganic Filler Continental Mineral Processing Aerosil R202 Silane Modified Fumed Silica (Inorganic Filler) Evonik Omnirad 184 UV / Visible (PI) Photoinitiator IGM Omnirad ΤΡΟ UV / Visible (PI) Photoinitiator IGM Omnirad 1173 UV / Visible Photoinitiator ( PI) IGM nczrnn / zznz / E / YiAi

[50] Polyester urethane acrylate A is a flexible urethane polyester acrylate derived from the reaction of a saturated polyester diol and an aliphatic diisocyanate, which is then capped with hydroxy acrylate. Test methods

[51] The following test methods were used in the examples described below. Viscosity and thixotropic index

[52] The viscosities were measured at a shear rate of 1 s-1y 103-1 using a cone and plate rheometer (Antón Paar). The thixotropic index was calculated as the ratio of the viscosities at 1 s-1 and 10 ^1. Chemical resistance: Percent weight change

[53] The photocurable composition was placed between two plastic sheets with a 1-millimeter-thick spacer and light-cured for 30 seconds in a UV chamber with a UV A light intensity of 100 mw / cm2. The cured sheet was cut into a rectangular sample 20 millimeters long and 10 millimeters wide. The sample was then immersed in a pH 1.5 hydrochloric acid solution or a pH 12.5 sodium hydroxide solution for 2 to 4 weeks at 50°C or 80°C.

[54] After immersion, the sample was rinsed with distilled water and dried at 50°C for 4 hours. Percent weight change was calculated as the percentage difference in sample weight before and after immersion. Shore D Hardness

[55] Shore D hardness was measured according to ASTM D2240. The tested material was placed between two PE films and covered with two glass plates to form a 1 mm thick sheet, and then cured with LED light with an intensity of 1.5 W / cm2 on both sides of the glass plate. . The cured sheet was then cut into 4 pieces and then stacked for Shore durometer measurement. Example 1 - Photocurable compositions with various polyether and polyester-urethane oligomers

[56] Photocurable formulations were formulated with various polyether and polyester-urethane oligomers as shown below in Table 2. nczrnn / zznz / E / YiAi Table 2 Ingredient Class Composition / quantity (% by weight) 1-1 1-2 1-3 1-4 1-5 CN 991 Polyesterurethane oligomer 56.4 CN 9024 56.4 Polyester urethane acrylate A 47 Genomer 4230 Polyether urethane oligomer 47 Ebecryl 8807 47 IBOA Acrylate Monomer 26.32 18.8 45.12 21.62 23.5 Genomer 1122 23.5 Isodecyl Acrylate 9.4 16.92 21.62 Omnirad 184 Photoinitiator 0.94 0.94 0.94 0.94 0.94 Omnirad TPO 0.94 0. 94 0.94 0.94 0.94 Aerosil R2 02 Inorganic filler 6 6 6 6 6 Total 100 100 100 100 100

[57] These formulations were cured and tested for rheology, Shore hardness and percent weight change. The results are shown below in Table 3. Table 3 Tested parameter Composition 1-1 1-2 1-3 1-4 1-5 Viscosity ais1 (mPa*s) 127,200 50,030 45,780 160,700 88,870 Viscosity at 10 s-1 (mPa*s) 16,980 8,417 9,304 33,080 13. 950 thixotropic index 7.49 5.94 4.92 4.86 6.37 Shore D Hardness 68 58 37 55 50 Percent weight change pH 1.5 2 weeks of immersion -1.02 -2.58 -0.63 -9.55 -0.37 Percent weight change pH 1.5 4 weeks of -1.12 -3.61 -0.67 -23.68 -0.52 immersion Percent weight change pH 12.5 2 weeks immersion -5.92 -2.26 -1.47 -5.960 -0.83 Percent weight change pH 12.5 4 weeks immersion -28.37 -3.84 -1.50 -8.67 -1.12

[58] These results demonstrate that photocurable compositions employing polyether-urethane acrylate have better hydrolytic stability (chemical resistance) than polyester-urethane acrylates, particularly when immersed in an alkaline solution of pH 12.5. Example 2: Photocurable compositions with various oligomers and urethane fillers

[59] Photocurable formulations were formulated with various urethane oligomers and fillers as shown below in Table 4. For each urethane acrylate oligomer one organic filler and two inorganic fillers were compared. Table 4 Ingredient Composition / amount (% by weight) 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 Polyester Urethane Acrylary A (Polyester UA) 32.5 32.5 32.5 CN 9024 ( Polyester UA) 39 39 39 BR582 E8 (Polyether UA) 32.5 32.5 32.5 Isobornyl acrylate (Monomer) 14.95 13 14.95 14.95 13 14.95 14.95 13 14.95 Genomer 1122 (Monomer) 16.25 11.7 16.25 16.25 11.7 16.25 16.25 11.7 16.25 I rgacure 1171 (PI) 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 Irgacure TPO (PI) 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 Aerosil R2 02 (Inorganic filler) 8 5 8 8 5 8 8 5 8 PVC powder (Organic filler) 30 30 30 Zirconium silicate powder (Inorganic filler) 30 30 30 aluminum (Inorganic filler) 30 30 30 Total 100 100 100 100 100 100 100 100 100

[60] These formulations were cured and tested for rheology, Shore hardness and percent weight change. The results are shown below in Table 5. Table 5 Tested parameter Composition 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 Viscosity at 1 s-1 (mPa»s) 3.278 1.354 3.965 4.054 696 2.027 2.931 1.014 1.756 Viscosity at 10 s~i (mPa»s) 134 197 946 132 88 271 192 121 237 Thixotropic index 24.46 6.87 4.19 30.71 7.91 7.48 15.27 8.38 7.41 Hardness Shore D 60 70 45 63 7 5 50 75 52 Percent -7.03 -1.45 -0.18 -2.37 -2.46 -1.26 -2.87 -2 -1.31 weight change pH 1.5 4 weeks immersion Percent weight change pH 12.5 4 weeks immersion -2.38 -2.25 -1.2 -7.98 -14.19 -4.48 -5.23 -5.00 -2.90 nczrnn / zznz / E / YiAi

[61] Formulations containing polyether acrylate urethane (BR582 E8) (Compositions 2-3, 2-6 and 2-9) had less weight loss than formulations containing polyether acrylate urethane A (Compositions 2- 1, 2-4 and 2-7) and the formulations containing polyester-urethane acrylate (CN 9024) (Compositions 2-2, 2-5 and 2-8) after immersion in the pH 1.5 solution and after of immersion in the pH 12.5 solution. The results are consistent with the conclusions of Example 1. The formulations containing organic filler (polyvinyl chloride powder) (Compositions 2-1, 2-2 and 2-3) had less weight loss than the formulations containing silicate of zirconium and aluminum silicate (Compositions 2-4, 2-5 and 2-6 and 2-7, 2-8 and 2-9, respectively) in solutions of pH 12.5. Example 3: Photocurable compositions with various polyether-urethane oligomers and organic fillers

[62] Photocurable formulations were formulated with various polyether-urethane oligomers and organic fillers as shown in Table 6 below. nczrnn / zznz / E / YiAi Table 6 Ingredient Class Composition / amount (% by weight) 3-1 3-2 3-3 3-4 CN 9167US Polyether-urethane oligomer 33 CN 996 39.6 Genomer 4230 32.5 32.5 IBOA acrylate monomer 18.48 15.18 31.2 31.2 Isodeci acrylate 13.2 9.9 Omnirad 184 photoinitiator 0.66 0.66 0.65 0.65 Omnirad TPO 0.66 0.66 0.65 0.65 Aerosil R202 Inorganic filler 4 4 5 5 Polyvinyl chloride powder Organic Filler 30 30 30 Polypropylene powder 30 Total 100 100 100 100

[63] These formulations were cured and tested for rheology, Shore hardness, and percent weight change. The results are shown below in Table 7. Table 7 Tested parameter Composition 3-1 3-2 3-3 3-4 Viscosity at 1 s-1 (mPa*s) 158,200 200,000 253,200 256,000 Viscosity at 10 s-1 (mPa*s) 29,370 46,790 35,720 34,460 thixotropic index 5. 39 4.26 7.09 7.43 Shore D Hardness 78 65 45 45 Percent weight change pH 1.5 2 weeks immersion -0.30 -0.42 -0.31 -0.33 Percent weight change pH 1.5 4 weeks immersion -0.32 -0.47 -0.47 -0.44 Percent of weight change pH 12.5 2 weeks of immersion -0.48 -0.96 -1.16 -0.62 Percent of weight change pH 12.5 4 weeks of immersion -0.79 -1.32 -1.33 -0.64

[64] These results demonstrate that photocurable compositions using urethane polyether-acrylate and organic fillers have good hydrolytic stability (chemical resistance) after immersion both in the pH 5 1.5 solution at 50°C and after immersion in the pH solution 12.5 at 50°C. nczrnn / zznz / E / YiAi Example 4 - Photocurable Compositions with Various Ratios of Polyether Urethane Oligomer to Acrylate Monomer

[65] Photocurable formulations were formulated with various ratios of polyether urethane oligomer to acrylate monomer as shown below in Table 8. Table 8 Ingredient Class Composition / amount (% by weight) 4-1 4-2 4-3 Genomer 4230 Polyetherurethane oligomer 55 20 37.5 IBOA acrylate monomer 20 55 37.5 Omnirad 184 Photoinitiator 0.5 0.5 0.5 Omnirad TPO 0.5 0.5 0.5 Aerosil R202 Inorganic filler 4 4 4 Polypropylene powder Organic Filler 20 20 20 Total 100 100 100

[66] These formulations were cured and tested for rheology, Shore hardness and percent weight change The results are shown below in Table 9. Table 9 Tested parameter Composition 4-1 4-2 4-3 Viscosity at 1 s-1 (mPa*s) 107,200 22,820 52,880 Viscosity at 10 s-1 (mPa*s) 30,290 3, 672 9,546 thixotropic index 3.54 6.21 5.54 Shore D hardness 24 70 49 Percent weight change pH 1.5 2 weeks of immersion -0.49 -0.11 -0.32 Percent weight change pH 1.5 4 weeks of immersion -0.45 -0.12 -0.30 Percent weight change pH 12.5 2 weeks of immersion -0.56 -0.19 -0.25 Percent weight change pH 12.5 4 weeks of immersion -0.43 -0.16 -0.19

[67] These results demonstrate that photocurable compositions with various ratios of polyetherurethane oligomer to acrylate monomer have good hydrolytic stability (chemical resistance) after immersion in the pH 1.5 solution at 50°C and after immersion in the pH 12.5 solution at 50°C. Example 5: Photocurable compositions with polyether-urethane oligomer and various organic fillers

[68] Photocurable formulations were formulated with polyether-urethane oligomer and various organic fillers as shown below in Table 10. Table 10 nczrnn / zznz / E / YiAi Ingredient Composition / amount (% by weight) Resin 5-1 5-2 5-3 5-4 5-5 5-6 5-7 Genomer 4230 (UA Polyether) 50 47 26 33 40 26 33 40 Isobornyl Acrylate (Monomer ) 48 45.12 24.96 31.68 38.4 24.96 31.68 38.4 Omnirad 184 (PI) 1 0.94 0.52 0.66 0.8 0.52 0.66 0.8 Omnirad (PI) 1 0.94 0.52 0.66 0.8 0.52 0 .66 0.8 Aerosil R202 (Inorganic filler) 6 3 4 5 3 4 5 Polypropylene powder (Organic filler) 45 30 15 PVC powder (Organic filler) 45 30 15 Total 100 100 100 100 100 100 100 100

[69] These formulations were cured and tested for reelection, Shore hardness, and percent weight change. The results are shown below in Table 11. Table 11 Tested parameter Composition Resin 5-1 5-2 5-3 5-4 5-5 5-6 5-7 Viscosity at 1 s-1 (mPats) 729 45,200 1,133,000 92,710 49,600 433,400 125,200 52,750 Viscosity at 10 s'1 ( mPa *s) 695 8,331 246,600 15,600 9,237 46,010 19,370 9,579 thixotrepic index 1.05 5.43 4.56 5.94 5.37 9.42 6.46 5.51 Shore D hardness 25 38 51 48 41 5 0 45 40 Percent weight change pH 1.5 2 weeks of immersion 0.66 0.46 0.18 0.32 0.4 1.24 0.61 0.08 Percent weight change pH 1.5 4 weeks of immersion -0.62 -0.46 -0.21 -0.32 -0.39 1.25 0.60 -0.09 Percent weight change pll 12.5 2 weeks of immersion -0.91 -0.72 -0.20 -0.37 -0.47 1.08 0.37 -0.36 Percent weight change pH 12.5 4 weeks of immersion -0.86 -0.72 -0.22 -0.34 -0.42 1.05 0.26 -0.48 nczrnn / zznz / E / YiAi

[70] These results demonstrate that photocurable compositions without fillers or various organic fillers in different ranges have good hydrolytic stability (chemical resistance) after immersion in the solution 5 of pH 1.5 at 50 ° C and after immersion in the solution pH 12.5 at 50°C. However, the amount of organic filler in the formulation affects the viscosity. In Examples 5-6 and 5-6, the weight change is positive because the filler absorbs water and the water was not completely removed in the specified test method.

[71] These results demonstrate that photocurable compositions with various amounts of organic filler all have good hydrolytic stability (chemical resistance) after immersion in both the pH 15 1.5 solution at 50°C and after immersion in the pH solution 12.5 at 50°C.

Claims

1. A photocurable composition comprising: a) a polyether-urethane component functionalized with (meth)acrylate; b) a (meth)acrylate monomer; c) an organic filler; and d) a photoinitiator, wherein, when exposed to UV or visible light, the curable composition forms a cured reaction product, the cured reaction product exhibiting a mass loss of: 1) less than 2% when exposed to acidic aqueous conditions (pH = 1.5) for approximately 4 weeks at a temperature of approximately 50°C and / or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for approximately 4 weeks at a temperature of approximately 50°C.

2. The photocurable composition according to claim 1, wherein the cured reaction product has a Shore D hardness of approximately 20 or higher.

3. The light-curable composition according to claim 1, wherein the curable composition has a viscosity of approximately 10,000 to approximately 100,000 cps.

4. The photocurable composition according to claim 1, wherein the curable composition has a thixotropic index of approximately 1.5 to approximately 6.

5. The light-curable composition according to claim 1, wherein the (meth)acrylate functionalized polyether-urethane component is present in an amount of approximately 20% to approximately 60% by weight based on the total weight of the curable composition.

6. The photocurable composition according to claim 1, wherein the (meth)acrylate functionalized polyether-urethane component is a polyetheracrylate urethane oligomer.

7. The light-curable composition according to claim 1, wherein the (meth)acrylate monomer is present in an amount of approximately 10% to approximately 60% by weight based on the total weight of the light-curable composition.

8. The photocurable composition according to claim 1, wherein the (meth)acrylate monomer is a polyethylene glycol diacrylate.

9. The photocurable composition according to claim 1, wherein the organic filler is present in an amount of approximately 0.1% to approximately 40% by weight based on the total weight of the curable composition.

10. The light-cured composition according to claim 1, wherein the organic filler is an organic thickener based on hydrophobic polyolefin. nczrnn / zznz / E / YiAi 11. The photocurable composition according to claim 1, wherein the organic filler is selected from the group consisting of polyvinyl chloride powder, polypropylene powder and combinations thereof.

12. The photocurable composition according to claim 1, wherein the photoinitiator is present in an amount of approximately 0.2% to approximately 5% by weight based on the total weight of the curable composition.

13. The photocurable composition according to claim 1, wherein the photoinitiator is a polymeric structure to which at least one chromophore is attached that is excited by radiation in the UV or visible light range.

14. A composite membrane structure comprising: a) a membrane comprising at least one surface; and b) the cured reaction product of the photocurable composition according to claim 1 disposed on at least a portion of at least one surface of the membrane.

15. The composite membrane structure according to claim 14, wherein the cured reaction product is adhesively bonded to at least a portion of at least one surface of the membrane.

16. The membrane structure composed of 37 according to claim 14, wherein the cured reaction product is disposed over at least a portion of at least one surface of the membrane in a predetermined pattern.

17. The composite membrane structure according to claim 16, wherein the predetermined pattern is selected from the group consisting of stripes, waves, circles, ovals, arcs, squares, rectangles, rhombuses, pentagons, hexagons, stars, chevrons, a random pattern, and combinations thereof.

18. A method for producing a hydrolytically stable cured reaction product comprising the steps of: a) providing a curable composition comprising: i) a polyether-urethane component functionalized with (meth)acrylate; ii) a (meth)acrylate monomer; iii) an organic filler; and iv) a photoinitiator, and b) exposing the curable composition to a UV or visible light source to form a cured reaction product, wherein hydrolytic stability is demonstrated when the cured reaction product exhibits a mass loss of: 1) less than 2% when exposed to aqueous acidic conditions (pH = 1.5) for approximately 4 weeks at a temperature of approximately 50°C or 2) less than 3% when exposed to basic aqueous conditions (pH = 12.5) for approximately 4 weeks at a temperature of approximately 50°C.

19. The method according to claim 18, wherein the cured reaction product has a Shore D hardness of approximately 20 or greater.

20. The method according to claim 18, wherein the (met) acrylate functionalized polyether-urethane component is present in an amount of approximately 20% to approximately 60% by weight based on the total weight of the curable composition.

21. The method according to claim 18, wherein the polyether-urethane component functionalized with (met) acrylate is a polyether-urethane acrylate oligomer.

22. The method according to claim 18, wherein the (meth)acrylate monomer is present in an amount of approximately 10% to approximately 60% by weight based on the total weight of the curable composition.

23. The method according to claim 18, wherein the (meth)acrylate monomer is a polyethylene glycol diacrylate.

24. The method according to claim 18, wherein the organic filler is present in an amount of approximately 0.1% to approximately 40% by weight on a nczrnn / zznz / E / YiAi basis to the total weight of the curable composition.

25. The method according to claim 18, wherein the organic filler is an organic thickener based on hydrophobic polyolefin. 5 26. The method according to claim 21, wherein the organic filler is selected from the group consisting of polyvinyl chloride powder, polypropylene powder, and combinations thereof.

27. The method according to claim 10 18, wherein the photoinitiator is present in an amount of approximately 0.2% to approximately 5% by weight based on the total weight of the curable composition.

28. The method according to claim 18, wherein the photoinitiator has a polymeric structure 15 to which at least one chromophore is attached that is excited by radiation in the UV or visible light range.