Coating compositions with improved properties

Abstract

Described are curable compositions, where the composition comprises, consists essentially of, or consists of a monomer of Formula (1) and a monomer of Formula (2), where the molar ratio of the monomer of Formula (1) to the monomer of Formula (2) is at least 1.5:1, and where the curable composition is substantially free of water. Also described are cured compositions, substrates coated with the curable composition, and methods for making the monomers of Formula (1) and Formula (2). The curable compositions can be used as a coating for batteries, particularly for the outer surface of a battery.

Description

Background Technology

[0001] Phosphate monomers have been reported to contribute to the properties of coating compositions for use on a variety of substrates (e.g., US4647638, US6710161, US8318848, US7081488, US9273221, US9303160, and US20210347979). However, the potential impact on such properties due to variations in the spacing between the olefinic (olefinic) unsaturated group at one end of the phosphate monomer and the phosphate moiety at the other end has generally not been reported.

[0002] In this invention, it has been unexpectedly discovered that altering the spacing between the olefinic unsaturated group at one end of the phosphate ester monomer and the phosphate ester portion at the other end of the monomer results in enhanced coating (coating) performance on a substrate, such as a battery. This improved performance enhances the durability and lifespan of substrates containing such coating compositions. Summary of the Invention

[0003] One aspect of the present invention is a curable composition comprising monomers, the monomers comprising monomers (monoesters) of formula (1) and monomers (diesters) of formula (2), substantially composed of monomers (monoesters) of formula (1) and monomers (diesters) of formula (2), or composed of monomers (monoesters) of formula (1) and monomers (diesters) of formula (2).

[0004] (1)

[0005] (2)

[0006] In equations (1) and (2):

[0007] Each R1 is independently H or a C1-C6 alkyl group;

[0008] Each R2 is independently H or a C1-C6 alkyl group;

[0009] Each R3 is independently H or a C1-C6 alkyl group;

[0010] Each X is independently a C1-C6 alkylene group, wherein an N, O, or S atom may be inserted between any two carbon atoms present in the alkylene chain and wherein carbon atoms in the alkylene chain may be substituted by C1-C3 alkyl groups;

[0011] Each R4 is independently either an H or a cation;

[0012] Each R5 is independently either an H or a cation;

[0013] Each n is independently 4 to 7; and

[0014] Each m is independently 1 to 10.

[0015] The molar ratio of the monoester monomer of formula (1) to the diester monomer of formula (2) is at least 1.5:1, and

[0016] The curable composition is essentially water-free.

[0017] Another aspect of the present invention is a cured composition formed from a curable composition as described herein.

[0018] Another aspect of the invention is a substrate comprising, on at least one surface of a substrate, a curable composition or a cured composition as described herein.

[0019] Another aspect of the invention is a method for improving the adhesion and / or corrosion resistance and / or water resistance and / or electrical insulation and / or matting and / or flame retardancy and / or weather resistance of a substrate by applying a curable coating composition to at least one surface of the substrate, the curable coating composition comprising monomers of formula (1) and formula (2) as described herein, substantially composed of monomers of formula (1) and formula (2) as described herein, or composed of monomers of formula (1) and formula (2) as described herein, wherein the molar ratio of monomer of formula (1) to monomer of formula (2) is at least 1.5:1.

[0020] Another aspect of the invention is a battery (e.g., the outer surface of a battery) comprising a curable composition or a cured composition as described herein, wherein each m is independently 2 to 9, wherein the curable composition is applied to the battery or the cured composition is coated onto the battery.

[0021] Another aspect of the invention is the use of a curable composition according to any embodiment described herein for improving the corrosion resistance and / or water resistance and / or adhesion and / or electrical insulation and / or matte finish and / or flame retardancy and / or weather resistance of the surfaces on which the curable composition is applied.

[0022] Another aspect of the invention is the use of the curable composition as described herein as a coating for at least one surface of a substrate. Detailed Implementation

[0023] The term "photochemical light source" refers to an electromagnetic radiation source whose electromagnetic radiation, within the ultraviolet range (100 nm to 400 nm), can induce photochemical reactions. Photochemical radiation can include ultraviolet (UV) light, such as light in the UVB and UVC range, for example, light having wavelengths of 180 nm to 400 nm, such as 200 nm to 400 nm, or 200 nm to 320 nm. In embodiments, the photochemical radiation range can be generated by a mercury bulb, such as an H bulb.

[0024] The term "curable composition" refers to a composition whose properties are altered based on a stimulus. Typically, curable compositions as described herein are cured through polymerization and / or crosslinking. Generally, those curable compositions cure upon the addition of energy to the system, which can be in the form of photochemical light, heat, or both. Typically, when the compounds in the curable composition contain carbon-carbon double bonds, polymerization (curing) involves the reaction of such carbon-carbon double bonds.

[0025] The term "photoinitiator" refers to any type of substance that, upon exposure to radiation (e.g., photochemical radiation), forms a species that initiates the reaction and curing of polymerizable organic substances in a curable composition. Typically, such polymerization (curing) involves the reaction of such carbon-carbon double bonds when the compound present in the reactive component contains carbon-carbon double bonds.

[0026] The term "free radical photoinitiator" refers to a compound that undergoes a photoreaction upon absorbing light, generating reactive free radical species. These reactive species then initiate the curing (polymerization) of the reactive components of a curable composition.

[0027] The term "free radical polymerizable resin" refers to a resin that can polymerize when exposed to free radicals.

[0028] The term "(meth)acrylate group" refers to either an acrylate group or a methacrylate group. An acrylate group corresponds to a group with the formula -OC(=O)-CH=CH2. A methacrylate group corresponds to a group with the formula -OC(=O)-C(CH3)=CH2.

[0029] The term "monofunctional" refers to a compound having a single functional group. For example, a monofunctional (meth)acrylate monomer is a monomer having a single (meth)acrylate group.

[0030] The term "monomer" refers to a molecule having one or more polymerizable functional groups. Monomers have a single molecular weight, typically below 1000 g / mol, preferably from 100 to 950 g / mol. As is generally recognized in the art, commercial products of particular monomers may contain impurities or other chemical species.

[0031] The term "number-average molecular weight" or "M" n "Number-average molecular weight" refers to the statistical average molecular weight of polymer chains in a sample or group. Unless otherwise explicitly stated, the number-average molecular weights reported herein were determined using size exclusion chromatography (SEC).

[0032] The term "oligomer" refers to a molecule having a molecular weight distribution and may or may not have one or more polymerizable functional groups. Oligomers can be the reaction products of two or more monomers and typically have a number-average molecular weight of 500 g / mol or greater, preferably from 500 g / mol to 30,000 g / mol, more preferably from 1,000 g / mol to 8,000 g / mol. Oligomers do not always have a single molecular weight.

[0033] The term "optionally substituted group" means that one or more hydrogen atoms of a group may be independently replaced by a substituent selected from alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylaryl, haloalkyl, hydroxyl, halogen, isocyanate, nitrile, amine, oxo(=O), carboxylic acid, -C(=O)-R', -C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R' and -SO2-NH-R', where each R' is independently an optionally substituted group selected from alkyl, aryl and alkylaryl groups.

[0034] The term "weight%" refers to a percentage by weight. Unless otherwise stated, the weight percentage of the compounds or components in a composition is expressed relative to the weight of the composition.

[0035] monomer

[0036] The compositions of the present invention comprise monomers of formula (1) and monomers of formula (2):

[0037] (1)

[0038] (2)

[0039] In equations (1) and (2):

[0040] Each R1 is independently H or a C1-C6 alkyl group;

[0041] Each R2 is independently H or a C1-C6 alkyl group;

[0042] Each R3 is independently H or a C1-C6 alkyl group;

[0043] Each X is independently a C1-C6 alkylene group, wherein an N, O, or S atom may be inserted between any two carbon atoms present in the alkylene chain and wherein carbon atoms in the alkylene chain may be substituted by C1-C3 alkyl groups;

[0044] Each R4 is independently either an H or a cation;

[0045] Each R5 is independently either an H or a cation;

[0046] Each n is independently 4 to 7; and

[0047] Each m is independently 1 to 10

[0048] The molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1. In embodiments, the molar ratio of the monoester monomer of formula (1) to the diester monomer of formula (2) is at least 1.6:1, for example at least 1.7:1, for example at least 1.8:1, for example at least 1.9:1, for example at least 2.0:1, for example at least 2.2:1, for example at least 2.5:1, for example at least 3.0:1, for example at least 3.5:1, for example at least 4.0:1, for example from 1.5:1 to 4.0:1, for example from 1.5:1 to 3.5:1, for example from 1.5:1 to 3.0:1, for example from 1.5:1 to 2.5:1, for example from 1.5:1 to 2.0:1, for example from 1.5:1 to 1.9:1, for example from 1.5:1 to 1.8:1, for example from 1.5:1 to 1.7:1. In a preferred embodiment, the molar ratio of the monoester monomer of formula (1) to the diester monomer of formula (2) is 1.70:1 to 4:1, 1.75:1 to 4:1, 1.80:1 to 4:1, 1.85:1 to 4:1, 1.90:1 to 4:1, 1.95:1 to 4:1 or 2.0:1 to 4:1.

[0049] In various embodiments of any of the above-listed molar ratios of monomers of formula (1) to monomers of formula (2), the variable “m” in each of formulas (1) and (2) may be independently 1 to 9, for example 2 to 9, for example 3 to 9, for example 4 to 9, for example 2 to 8, for example 3 to 8, for example 4 to 8, for example 2 to 7, for example 3 to 7, for example 4 to 7, for example 2 to 6, for example 3 to 6, for example 4 to 6, preferably between 2 and 7, for example between 2 and 6, more preferably between 2 and 5, for example between 2 and 4.

[0050] In equations (1) and (2), each of R4 and R5 is independently either H or a cation. Examples of suitable cations include metals (e.g., Na). + Li + K + Ca 2+ Ba 2+ etc.), ammonium group (NH4) + ), primary ammonium group (RNH3) + ), secondary ammonium group ((R)2NH2) + ) or tertiary ammonium group ((R)3NH + ), wherein each R is independently a non-hydrogen moiety (e.g., alkyl, heterocyclic, aryl, heteroaryl, etc.).

[0051] In the embodiments, each R4 and R5 of the monomers of formulas (1) and (2) is independently selected from ammonium groups (NH4+). + ), primary ammonium group (RNH3) + ), secondary ammonium group (R2NH2) + ), tertiary ammonium group (R3NH + (where each R is independently a non-hydrogen moiety (e.g., alkyl, heterocyclic, aryl, heteroaryl, etc.)) and a metal (e.g., Na) + Li + K + Ca 2+ Ba 2+ (etc.). In one embodiment, at least one of R4 and R5 is ammonium-based. In another embodiment, at least one of R4 and R5 is metal. In another embodiment, both R4 and R5 are ammonium-based. In another embodiment, both R4 and R5 are metals.

[0052] In formulas (1) and (2), each R1 is independently H or a C1-C6 alkyl group. In a preferred embodiment, each R1 is H or a methyl group.

[0053] In formulas (1) and (2), each R2 is independently H or a C1-C6 alkyl group. In a preferred embodiment, each R2 is H or a methyl group.

[0054] In formulas (1) and (2), each R3 is independently H or a C1-C6 alkyl group. In a preferred embodiment, each R3 is H or a methyl group.

[0055] In formulas (1) and (2), each X is independently a C1-C6 alkylene group, wherein an N, O, or S atom may be inserted between any two carbon atoms present in the alkylene chain. In a preferred embodiment, each X is selected from formula (3) or formula (4):

[0056] -(CR6R'6) e - (3)

[0057] -[(CR7R'7) f -O] g -(CR7R'7) h - (4)

[0058] in:

[0059] Each R6 and R'6 is independently H or a C1-C3 alkyl group;

[0060] Each R7 and R'7 is independently H or methyl;

[0061] e is an integer from 1 to 6;

[0062] f is an integer from 1 to 4;

[0063] g is an integer from 1 to 3;

[0064] h is an integer from 1 to 4; and

[0065] f+g+h≤6.

[0066] In the implementation of the monomer of formula (1), n ​​is 5 and m is 1 to 9.

[0067] In the implementation of the monomer of formula (1), n ​​is 5 and m is 2 to 9.

[0068] In the implementation of the monomer of formula (1), n ​​is 5 and m is 1 to 8.

[0069] In the implementation of the monomer of formula (1), n ​​is 5 and m is 2 to 8.

[0070] In the implementation of the monomer of formula (1), n ​​is 5 and m is 3 to 7.

[0071] In the embodiment of the monomer of formula (1), n ​​is 5 and m is 4 to 6.

[0072] In the implementation of the monomer of formula (2), each n is 5, and each m is the same and is 1 to 9.

[0073] In the implementation of the monomer of formula (2), each n is 5, and each m is the same and is 2 to 9.

[0074] In the embodiment of the monomer of formula (2), each n is 5, and each m is the same and is 1 to 8.

[0075] In the embodiment of the monomer of formula (2), each n is 5, and each m is the same and is 2 to 8.

[0076] In the embodiment of the monomer of formula (2), each n is 5, and each m is the same and is 3 to 7.

[0077] In the embodiment of the monomer of formula (2), each n is 5, and each m is the same and is 4 to 6.

[0078] In the embodiment of the monomer of formula (1), n ​​is 5, m is 1 to 8 and X is -CH2-CH2-.

[0079] In the embodiment of the monomer of formula (1), n ​​is 5, m is 3 to 5 and X is -CH2-CH2-.

[0080] In the embodiment of the monomer of formula (1), n ​​is 5, m is 4 to 6 and X is -CH2-CH2-.

[0081] In the embodiment of the monomer of formula (2), each n is 5, each m is the same and m is 1 to 8, and X is -CH2-CH2-.

[0082] In the embodiment of the monomer of formula (2), each n is 5, each m is the same and is 3 to 7, and each X is -CH2-CH2-.

[0083] In the embodiment of the monomer of formula (2), each n is 5, each m is the same and is 4 to 6, and each X is -CH2-CH2-.

[0084] In the embodiment of the monomer of formula (1), n ​​is 5, m is 4 and X is -CH2-CH2-.

[0085] In the embodiment of the monomer of formula (2), each n is 5, each m is 4 and each X is -CH2-CH2-.

[0086] In embodiments of the present invention, the two (meth)acrylate substituents of formula (2) are identical to each other.

[0087] In embodiments of the present invention, the (meth)acrylate substituents of formula (1) are the same as the two (meth)acrylate substituents of formula (2).

[0088] The monomers of formulas (1) and (2) can be obtained by reacting the caprolactone-modified hydroxylated (meth)acrylate of formula (5) with a phosphating agent (phosphorylating agent):

[0089] (5)

[0090] R1, R2, R3, X, n, and m are defined as above.

[0091] The phosphating agent can be selected from phosphoric acid, polyphosphoric acid, phosphorus pentoxide, phosphoric anhydride, and mixtures thereof. Preferably, the phosphating agent is phosphorus pentoxide.

[0092] The ratio between the phosphorus atomic equivalents of the phosphating agent and the OH group equivalents of the caprolactone-modified hydroxylated (meth)acrylate of formula (5) can be less than 1, preferably 0.40 to 0.95, more preferably 0.45 to 0.90, and even more preferably 0.50 to 0.85.

[0093] The reaction can be carried out in a diluent. The diluent can be a non-reactive diluent such as an organic solvent (e.g., toluene) or a reactive diluent such as a (meth)acrylate-functionalized monomer (e.g., methyl methacrylate or tricyclodecanediethanol diacrylate). The reaction can be carried out by adding caprolactone-modified hydroxylated (meth)acrylate of formula (5) to a reactor comprising a phosphating agent and a diluent. The reaction can be carried out at a temperature below 70°C, preferably below 65°C, more preferably below 60°C. The reaction can be carried out for a period of 30 minutes to 5 hours, preferably 1 hour to 3 hours.

[0094] In the embodiments, the combined amount of the monomers of formula (1) and formula (2) is 0.05 to 10% by weight, for example 0.1 to 10% by weight, for example 0.5 to 10% by weight, for example 1 to 10% by weight, for example 2 to 10% by weight, for example 4 to 10% by weight, for example 5 to 10% by weight, relative to the total weight of polymerizable monomers present in the composition.

[0095] In the embodiments, the combined amount of the monomers of formula (1) and formula (2) is 10 to 100% by weight, for example 10 to 90% by weight, for example 10 to 80% by weight, for example 10 to 70% by weight, for example 10 to 60% by weight, for example 10 to 50% by weight, for example 10 to 40% by weight, for example 10 to 30% by weight, for example 10 to 90% by weight, for example 20 to 100% by weight, for example 20 to 90% by weight, for example 20 to 80% by weight, for example 20 to 70% by weight, for example 20 to 60% by weight, for example 20 to 50% by weight, for example 20 to 40% by weight, for example 30 to 100% by weight, for example 30 to 90% by weight, for example 30 to 80% by weight, for example 30 to 70% by weight, for example 30 to 60% by weight, for example 40 to 100% by weight, for example 40 to 90% by weight, for example 40 to 80% by weight, for example 50 to 100% by weight, relative to the total weight of polymerizable monomers present in the composition.

[0096] Based on the total weight of the composition, the composition may include 0.05 to 95% by weight, particularly 0.5 to 90% by weight, more particularly 1 to 85% by weight, even more particularly 2 to 80% by weight, and still more particularly 5 to 70% by weight of monomers of formulas (1) and (2). In particular, based on the total weight of the composition, the composition may include 2 to 50% by weight, or 2 to 40% by weight, or 2 to 30% by weight, or 2 to 20% by weight of monomers of formulas (1) and (2).

[0097] In addition to the monomers required to be present in formulas (1) and (2), there are no particular limitations on other monomers that may be present in the curable composition, and may include one, two, three, four or more olefinic unsaturated compounds containing at least one polymerizable carbon-carbon double bond (i.e., a carbon-carbon double bond capable of participating in radical polymerization or anionic polymerization, such as reactions initiated by persulfates, peroxides, azo compounds or other conventional radical initiators).

[0098] Therefore, the curable composition may further include at least one olefin unsaturated monomer that is not a monomer of formula (1) or (2), preferably at least two olefin unsaturated monomers.

[0099] In embodiments, the amount of olefinic unsaturated monomers (other than the monomers of formula (1) and formula (2)) also present in the curable composition is 1 to 99% by weight, for example 1 to 95% by weight, for example 1 to 90% by weight, for example 1 to 80% by weight, for example 1 to 75% by weight, for example 1 to 65% by weight, for example 1 to 55% by weight, for example 1 to 45% by weight, for example 1 to 35% by weight, for example 1 to 25% by weight, for example 1 to 15% by weight, for example 5 to 99% by weight, for example 5 to 95% by weight, for example 5 to 90% by weight, for example 5 to 80% by weight, for example 5 to 75% by weight, for example 5 to 65% by weight, for example 5 to 55% by weight, for example 5 to 45% by weight, for example 5 to 35% by weight, for example 5 to 25% by weight, for example 5 to 15% by weight, for example 10 to 99% by weight, for example 10 to 95% by weight, for example 10 to 90% by weight, for example 10 to 80% by weight, for example 10 to 75% by weight. The amount, for example, 10 to 65 wt%, for example, 10 to 55 wt%, for example, 10 to 45 wt%, for example, 10 to 35 wt%, for example, 10 to 25 wt%, for example, 15 to 99 wt%, for example, 15 to 95 wt%, for example, 15 to 90 wt%, for example, 15 to 80 wt%, for example, 15 to 75 wt%, for example, 15 to 65 wt%, for example, 15 to 55 wt%, for example, 15 to 45 wt%, for example, 15 to 35 wt%, for example, 20 to 99 wt%, for example, 20 to 95 wt%, for example, 20 to 90 wt%, for example, 20 to 80 wt%, for example, 20 to 75 wt%, for example, 20 to 65 wt%, for example, 20 to 55 wt%, for example, 30 to 99 wt%, for example, 30 to 95 wt%, for example, 30 to 80 wt%, for example, 30 to 75 wt%, for example, 30 to 65 wt%, relative to the total weight of polymerizable monomers present in the composition.

[0100] In particular, the composition may include (meth)acrylate-functionalized monomers or mixtures of (meth)acrylate-functionalized monomers other than the monomers of formulas (1) and (2) (hereinafter referred to as other (meth)acrylate-functionalized monomers).

[0101] Other (meth)acrylate-functionalized monomers may have 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0102] Other (meth)acrylate-functionalized monomers may include mixtures of (meth)acrylate-functionalized monomers with different degrees of functionality. For example, other (meth)acrylate-functionalized monomers may comprise mixtures of (meth)acrylate-functionalized monomers containing a single acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule.

[0103] In one embodiment, other (meth)acrylate-functionalized monomers include mono(meth)acrylate-functionalized monomers. Mono(meth)acrylate-functionalized monomers can advantageously be used as reactive diluents and reduce the viscosity of the composition.

[0104] Examples of other suitable monomers for mono(meth)acrylate functionalization include, but are not limited to, mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monohydric, dihydric, or polyhydric alcohol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); oligomeric and polymeric diols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol). Mono(meth)acrylates; mono(meth)acrylates of monoalkyl ethers of glycols and oligomeric glycols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is (meth)acrylated); mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates, etc.

[0105] The following compounds are specific examples of monomers suitable for mono(meth)acrylate functionalization in component a): methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; n-hexyl methacrylate; 2-ethylhexyl methacrylate; n-octyl methacrylate; isooctyl methacrylate; n-decyl methacrylate; n-dodecyl methacrylate; tridecyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; 2-hydroxyethyl methacrylate; 2- and 3-hydroxypropyl methacrylate; 2-methoxyethyl methacrylate; 2-ethoxyethyl methacrylate; 2- and 3-ethoxypropyl methacrylate; tetrahydrofurfuryl(meth)acrylate; alkoxylated tetrahydrofurfuryl(meth)acrylate; 2-(2-ethoxy)acrylate Ethoxyethyl acrylate; cyclohexyl acrylate; glycidyl acrylate; isodecanyl acrylate; lauryl acrylate; 2-phenoxyethyl acrylate; alkoxylated phenolic methacrylate; alkoxylated nonylphenol methacrylate; cyclic trimethylolpropane acetal methacrylate; isobornyl acrylate; tricyclodecane methanol methacrylate; tert-butylcyclohexanol methacrylate; trimethylcyclohexanol methacrylate; diethylene glycol monomethyl ether methacrylate; diethylene glycol monoethyl ether methacrylate; diethylene glycol monobutyl ether methacrylate; triethylene glycol monoethyl ether methacrylate; ethoxylated lauryl methacrylate; methoxylated polyethylene glycol methacrylate; hydroxyethyl-butyl carbamate methacrylate; 3-(2-hydroxyalkyl)oxazolidinone methacrylate; and combinations thereof.

[0106] In embodiments, other (meth)acrylate-functionalized monomers may include (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule.

[0107] Examples of suitable (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule include acrylates and methacrylates of polyols. Such polyols can be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acrylate functional groups per molecule.

[0108] Exemplary monomers functionalized with (meth)acrylates per molecule containing two or more (meth)acryloyloxy groups may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene ... Methacrylates; Polytetramethylene glycol di(meth)acrylate; 1,2-Butanediol di(meth)acrylate; 2,3-Butanediol di(meth)acrylate; 1,3-Butanediol di(meth)acrylate; 1,4-Butanediol di(meth)acrylate; 1,5-Pentanediol di(meth)acrylate; 1,6-Hexanediol di(meth)acrylate; 1,8-Octadiol di(meth)acrylate; 1,9-Nonanediol di(meth)acrylate; 1,10-Nonanediol di(meth)acrylate; 1,12-Dodecanediol di(meth)acrylate; Neopentyl glycol Di(meth)acrylate; 2-Methyl-2,4-pentanediol di(meth)acrylate; Polybutadiene di(meth)acrylate; Cyclohexane-1,4-diethanol di(meth)acrylate; Tricyclodecanediethanol di(meth)acrylate; Metallic di(meth)acrylates; Modified metallic di(meth)acrylates; Glyceryl di(meth)acrylate; Glyceryl tri(meth)acrylate; Trimethylolethane tri(meth)acrylate; Trimethylolethane di(meth)acrylate; Trimethylolpropane tri(meth)acrylate; Trimethylolpropane di(meth)acrylate Esters; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane)diacrylate; di(trimethylolpropane)triacrylate; di(trimethylolpropane)tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol)tetraacrylate; di(pentaerythritol)pentaacrylate; di(pentaerythritol)hexa(meth)acrylate; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0109] Preferred monomers present in the curable compositions described herein (other than those of formulas (1) and (2)) include 1,2-dodecanediol dimethacrylate (DDDMA), isobornyl acrylate (IBOA), caprolactone acrylate (CAPA), tricyclodecanediethanol diacrylate (TCDDMA), and mixtures thereof. Such monomers have been observed to enhance the electrical and / or mechanical properties of batteries coated with the compositions of the present invention.

[0110] Based on the total weight of the composition, the composition may include 0 to 95% by weight, particularly 5 to 90% by weight, more particularly 10 to 85% by weight, even more particularly 15 to 80% by weight, and still more particularly 20 to 70% by weight of other (meth)acrylate-functionalized monomers. Specifically, based on the total weight of the composition, the composition may include 5 to 50% by weight, or 10 to 50% by weight, or 15 to 50% by weight, or 20 to 50% by weight, or 25 to 50% by weight of other (meth)acrylate-functionalized monomers.

[0111] The composition may include one or more olefinically unsaturated compounds other than (meth)acrylate-functionalized monomers or oligomers. Examples of such olefinically unsaturated compounds include:

[0112] - Polyvinyl and / or polyallyl monomers (particularly divinylbenzene, 1,4-butanediol divinyl ether, tri(ethylene glycol) divinyl ether, diallyl ether, glyceryl diallyl ether, glyceryl triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl phthalate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, glyoxal bis(diallyl acetal) and mixtures thereof);

[0113] - Vinyl esters of carboxylic acids (particularly vinyl acetate, vinyl propionate, vinyl hexanoate, 2-ethylhexanoate, vinyl octanoate, vinyl nonanoate, vinyl laurate, vinyl stearate, vinyl tert-carbonates and mixtures thereof);

[0114] - Vinyl ethers (particularly vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether and mixtures thereof, ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether);

[0115] - Alicyclic vinyl monomers (especially vinylcyclohexane);

[0116] - Olefins (particularly ethylene, propylene, 1-butene, isobutene, diisobutene, 1-nonene, 1-decene and mixtures thereof);

[0117] - Conjugated dienes (especially butadiene, isoprene, pentadiene, chloride dienes and mixtures thereof);

[0118] - Vinyl aromatic monomers (particularly styrene, α-methylstyrene, tert-butylstyrene, o-, m- and p-methylstyrene, o-, m- and p-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o-, p-dichlorostyrene, o-, p-dibromostyrene, o-, m- and p-methoxystyrene, optionally substituted indene, optionally substituted vinylnaphthalene, acenaphthene, diphenylethylene, vinylanthracene and mixtures thereof);

[0119] - Mono- or dicarboxylic acid monomers, cyclic anhydride monomers and their salts (especially 3-butenoic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, maleic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, itaconic acid, mesocarboxylic acid, citraconic acid, pentenoic acid, mucoconic acid and mixtures thereof);

[0120] - and its alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives;

[0121] - and its mixtures.

[0122] oligomers

[0123] The compositions of the present invention may further comprise (meth)acrylate-functionalized oligomers or mixtures of (meth)acrylate-functionalized oligomers.

[0124] Suitable (meth)acrylate-functionalized oligomers include, for example, polyester (meth)acrylates, polyether (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates (also known as polyurethane (meth)acrylates or urethane (meth)acrylate oligomers) and combinations thereof, as well as their amine-modified and sulfide-modified variants.

[0125] Examples of suitable epoxy (meth)acrylate oligomers include reaction products of acrylic acid or methacrylic acid or mixtures thereof with glycidyl ethers or esters. For example, glycidyl ethers may be polyglycidyl ethers of bisphenols such as bisphenol A or oligomers thereof.

[0126] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation products of acrylic acid or methacrylic acid or mixtures thereof with polyether alcohols, where the polyether alcohol is a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether alcohols can be straight-chain or branched compounds containing ether bonds and terminal hydroxyl groups. Polyether alcohols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or epoxides with starter molecules. Suitable starter molecules include, but are not limited to, water, polyhydroxy functional compounds, polyester polyols, and amines.

[0127] Suitable polyurethane (meth)acrylate oligomers can be prepared by reacting an aliphatic and / or aromatic diisocyanate with an OH-terminated polyester polyol (including aromatic, aliphatic, and mixed aliphatic / aromatic polyester polyols), polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (e.g., polydimethylsiloxane polyol) or polydiene polyol (e.g., polybutadiene polyol) or combinations thereof to form an isocyanate-functionalized oligomer, and then reacting the isocyanate-functionalized oligomer with a hydroxyl-functionalized (meth)acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate to provide terminal (meth)acrylate groups. For example, the polyurethane (meth)acrylate oligomer may contain two, three, four, or more (meth)acrylate functional groups per molecule.

[0128] In a preferred embodiment, the composition comprises one or more oligomers selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyurethane (meth)acrylates, and combinations thereof.

[0129] In a preferred embodiment, the composition comprises one or more oligomers selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyester-based aliphatic urethane di(meth)acrylates, polyether-based aliphatic urethane di(meth)acrylates, polybutadiene-based aliphatic urethane di(meth)acrylates, and combinations thereof. Such oligomers have been observed to enhance the electrical and / or mechanical properties of batteries coated with the compositions of the present invention.

[0130] Based on the total weight of the curable composition, the curable composition of the present invention may comprise 0 to 95% by weight, particularly 5 to 90% by weight, more particularly 10 to 85% by weight, or even more particularly 15 to 80% by weight of (meth)acrylate-functionalized oligomers. Specifically, based on the total weight of the curable composition, the curable composition of the present invention may comprise 5 to 60% by weight, or 10 to 60% by weight, or 15 to 60% by weight, or 20 to 60% by weight of (meth)acrylate-functionalized oligomers.

[0131] Free radical photoinitiators

[0132] The curable composition may include at least one free radical photoinitiator. The free radical photoinitiator is operable to cure a free radical polymerizable resin. Typically, free radical photoinitiators can employ two different modes of action and are classified as Norrish Type I and Norrish Type II photoinitiators based on their mode of action. In some embodiments, the free radical photoinitiator includes a Norrish Type I photoinitiator, a Norrish Type II photoinitiator, or both.

[0133] As used herein, the term "activity" in relation to Norish type I and Norish type II activity is intended to refer to Norish photoinitiation and similar reactions. For example, a photoinitiator with Norish type I activity would be characterized by a photoinitiator that, upon exposure to photochemical radiation within a selected wavelength range, cleaves into a radical fragment of the original photoinitiator. For an initiator with Norish type II activity, exposure to photochemical radiation within a selected wavelength range leads to the formation of a radical species that can abstract hydrogen to generate a second radical species capable of initiating photopolymerization. The mechanisms of Norish type I and Norish type II activity are known to those skilled in the art.

[0134] Suitable classes of free radical photoinitiators for curable compositions as described herein include, but are not limited to, benzoin, benzoin ether, acetophenone, α-hydroxyacetophenone, benzyl ketal, anthraquinone, phosphine oxide, acylphosphine oxide, α-hydroxy ketone, phenyl glyoxylate, α-amino ketone, benzophenone, thioxanthone, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine, benzoyl carbamate, aromatic oxime, metallocene, acylsilyl or acylgermanyl compounds, camphorquinone, their polymeric derivatives, and mixtures thereof.

[0135] Examples of suitable free radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, and michler's ketone. ketone), 2,2-dialkoxybenzophenone, 1-hydroxyphenyl ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetylnaphthalene, benzoinone, α-hydroxy ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenyl ethyl ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-hydroxy-2-methyl-1-phenyl-propanone, oligomeric α-hydroxy ketone, Benzoylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisolein, anthraquinone, anthraquinone-2-sulfonic acid, (benzene)tricarbonylchromium, benzoyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexylphenyl ketone (50 / 50 blend), 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4′-morpholinophenylbutanone, 4,4′-bis(diethylamino)benzophenone, 4,4′-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothiazol-9-one, dibenzocycloheptenone, 4, 4′-Dihydroxybenzophenone, 2,2-Dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4′-dimethylbenzoin, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylacetophenone (50 / 50 blend), 4′-ethoxyacetophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3′-hydroxyacetophenone, 4′-hydroxyacetophenone, 3-hydroxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoylcarbamate, 2-methyl-4'-(methylthio)-2-morpholinophenylacetone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthone-9-one and combinations thereof.

[0136] Preferred free radical photoinitiators include benzophenone (e.g., available from Sartamomer under the trademark Speedcure). TM BP, Speedcure TM 7005 and Speedcure TM Those obtained from 7006), thioxanthone (e.g., available from Sartomer under the trademark Speedcure) TM 7010 and Speedcure TM ITX), α-hydroxyacetophenone, acylphosphine oxides (e.g., available from Sartomer under the trademark Speedcure) TM BPO, Speedcure TM TPO and Speedcure TM TPO-L (obtained) and its combinations.

[0137] In an exemplary embodiment, the free radical photoinitiator is an acylphosphine oxide. As used herein, the term "phosphine oxide" refers to a compound comprising a -P (=O)- group. Acylphosphine oxides may have structure 1

[0138] Structure 1 .

[0139] In an exemplary embodiment, the free radical photoinitiator is acetone, such as acetone having structure 2.

[0140] Structure 2 .

[0141] In an exemplary embodiment, the free radical photoinitiator is a blend of acylphosphine oxide and phenylacetone.

[0142] additive

[0143] The curable compositions of the present invention may further include additives. The curable compositions may include mixtures of additives.

[0144] Specifically, the additives may be selected from antioxidants, UV absorbers, stabilizers, defoamers, solvents, coalescing agents, rheology modifiers, flow or leveling agents, colorants, adhesion promoters, pigments, dispersants, wetting agents, slip additives, fillers, thixotropic agents, matting agents, waxes, neutralizers, biocides, preservatives, organic solvents, or other various additives, including any additives conventionally used in the fields of coatings, sealants, or adhesives.

[0145] In various embodiments, based on the total weight of the curable composition, the curable composition may include one or more of these additives from 0% to 40% by weight, for example, 0.01% to 30% by weight, for example, 0.01% to 25% by weight, for example, 0.01% to 20% by weight, for example, 0.01% to 15% by weight, for example, 0.1% to 40% by weight, for example, 0.1% to 30% by weight, for example, 0.1% to 25% by weight, for example, 0.1% to 20% by weight, for example, 0.5% to 15% by weight, for example, 0.5% to 10% by weight, for example, 0.5% to 5% by weight, for example, 0.5% to 1% by weight.

[0146] Suitable pigments include zinc oxide, antimony oxide, zirconium oxide, chromium oxide, iron oxide, lead oxide, zinc sulfide, zinc barium white, and various forms of titanium dioxide such as anatase and rutile.

[0147] Suitable fillers include alkaline earth metal carbonates such as calcium carbonate, clay minerals, aluminosilicates such as kaolin, andalusite, kyanite and sillimanite, alkaline earth metal sulfates such as calcium sulfate and barium sulfate, talc, aluminum stearate, diatomite, wollastonite, nepheline syenite, alumina, silica and silica, or combinations thereof.

[0148] Suitable wetting agents include alkoxylated surfactants, silicone surfactants, sulfosuccinates, and fluorinated polymers.

[0149] Suitable UV absorbers include benzophenones (e.g., benzophenone and hydroxybenzophenone), benzotriazoles (e.g., hydroxyphenylbenzotriazole), hydroxyphenyltriazines (e.g., oxaloylteaniline), and thioxanone.

[0150] solvent

[0151] The curable compositions of the present invention may include solvents. As used herein, the term “solvent” means a non-reactive organic solvent, that is, a solvent comprising carbon and hydrogen atoms that does not react when exposed to photochemical radiation used to cure the curable compositions described herein.

[0152] In one embodiment, the curable composition includes an organic solvent. In another embodiment, the curable composition is free of or substantially free of organic solvents. Suitable organic solvents include, but are not limited to, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, octane, cyclohexane, or methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, or xylene; halogenated hydrocarbons such as dichloromethane, chloroform, or trichloroethane; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclopentanone, or cyclohexanone; esters such as methyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, or butyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol diethyl ether, tetrahydrofuran, or tetrahydropyran; carbonates such as diethyl carbonate; and combinations thereof. When a solvent is present, in embodiments, the total amount may be 5 to 150% by weight based on the total weight of the polymerizable components.

[0153] Advantageously, the curable compositions of the present invention can be formulated as solvent-free. For example, the curable compositions of the present invention may contain very little or no solvent, for example, less than 10% by weight, less than 5% by weight, less than 1% by weight, or even 0% by weight of solvent based on the total weight of the curable composition.

[0154] water

[0155] In embodiments, the curable composition is substantially free of water (i.e., contains less than 5% by weight relative to the total weight of the curable composition), and water, for example, less than 3% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.2% by weight, less than 0.1% by weight, less than 0.01% by weight, 0 to 4% by weight, 0 to 1% by weight, 0 to 0.5% by weight, 0 to 0.1% by weight, or 0% by weight.

[0156] Preferred implementation methods and formulations (compositions)

[0157] One embodiment is a curable composition (suitable for use in batteries) comprising monomers of formulas (1) and (2) and one or more of 1,2-dodecanediol dimethacrylate (DDDMA), isobornyl acrylate (IBOA), and caprolactone acrylate (CAPA), wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0158] Another embodiment is a curable composition (suitable for use in batteries) comprising monomers of formulas (1) and (2) and one or more oligomers, the oligomers including polyester acrylates, polyester-based aliphatic urethane diacrylates, polyether-based aliphatic urethane diacrylates and polybutadiene-based aliphatic urethane diacrylates, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0159] Another embodiment is a curable composition (suitable for use in batteries) comprising: monomers of formulas (1) and (2); one or more of 1,2-dodecanediol dimethacrylate (DDDMA), isobornyl acrylate (IBOA), and caprolactone acrylate (CAPA); and one or more oligomers, including polyester acrylates, polyester-based aliphatic urethane diacrylates, polyether-based aliphatic urethane diacrylates, and polybutadiene-based aliphatic urethane diacrylates, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0160] Another embodiment is a curable composition (suitable for use in batteries) comprising phosphate monomers of formulas (1) and (2), one or more acrylate oligomers, one or more acrylate monomers other than the monomers of formulas (1) and (2), a photoinitiator, and one or more fillers / additives, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0161] Another embodiment is a curable composition (suitable for use in batteries) comprising 1 to 5% by weight of monomers of formula (1) and formula (2), 20 to 60% by weight of acrylate oligomers, 25 to 50% by weight of acrylate monomers other than those of formula (1) and formula (2), and 0.5 to 3% by weight of a photoinitiator, based on the total weight of the curable composition, wherein the molar ratio of the monomers of formula (1) to the monomers of formula (2) is at least 1.5:1, wherein the curable composition is substantially free of water, and wherein the composition is free of organic solvents, or alternatively, includes one or more organic solvents.

[0162] Another embodiment is a curable composition (suitable for use in batteries) wherein n is 5, X is CH2-CH2, and m is 2 to 9, for example 2 to 8, for example 2 to 7, for example 2 to 6, for example 3 to 9, for example 3 to 8, for example 3 to 7, for example 4 to 9, for example 4 to 8, for example 4 to 7.

[0163] The curable compositions described herein may be compositions that undergo curing via free radical polymerization. In specific embodiments, the curable compositions may be photocurable (i.e., cured by exposure to photochemical radiation, particularly UV, near-UV, visible, infrared, and / or near-infrared radiation).

[0164] The curable compositions of the present invention may be ink compositions, coating compositions, adhesive compositions, sealant compositions, molding compositions, dental compositions, nail polish compositions, or 3D printing compositions.

[0165] End-use applications of the curable compositions include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (e.g., 3D printing resins), molding resins, sealants, composites, antistatic layers, electronic applications, recyclable materials, smart materials capable of detecting and responding to stimuli, packaging materials, personal care products, nail polish, articles for use in agriculture, water or food processing or animal husbandry, and biomedical materials. Therefore, the curable compositions of the present invention can be used in the manufacture of biocompatible articles. Such articles may, for example, exhibit high biocompatibility, low cytotoxicity, and / or low extractability (extractable content).

[0166] The compositions according to the invention can be used in particular to obtain cured products by the following methods.

[0167] Method for preparing cured compositions

[0168] One aspect of the invention relates to a method for preparing a cured composition, comprising curing the curable composition of the invention, preferably by exposing the curable composition to photochemical radiation such as UV, near-UV, visible, infrared and / or near-infrared radiation, and more particularly by exposing the polymerizable composition to an LED light source. The curable composition can also be cured by exposing the photocurable composition to photochemical radiation and heat via any of many well-known conventional techniques.

[0169] Curing can be accelerated or promoted by providing energy to the curable composition, for example, by heating the curable composition. Therefore, a cured composition can be considered a reaction product of a curable composition formed through curing. A curable composition can be partially cured by exposure to photochemical radiation, wherein further curing is achieved by heating the partially cured article. For example, a product formed from a curable composition can be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

[0170] Prior to curing, the curable composition can be applied to the substrate surface by any known conventional method, such as by spraying, jetting, blade coating, roller coating, casting, drum coating, dipping, and combinations thereof. Indirect application using a transfer process can also be used.

[0171] The substrate on which the curable composition is applied and cured can be of any kind. Suitable substrates are detailed below. When used as an adhesive, the curable composition can be placed between two substrates and then cured, thereby binding the substrates together to provide an adhered article. The curable composition according to the invention can also be bulk-formed or cured (e.g., the curable composition can be cast into a suitable mold and then cured).

[0172] The substrate can be ceramic, metallic, mineral, cellulose, animal-based, or polymeric. The substrate can also be a part of the human body, such as teeth or nails.

[0173] The substrate can be porous or substantially non-porous. The substrate can be transparent, translucent, or opaque.

[0174] Examples of ceramic substrates include alumina-based ceramics and zirconia-based ceramics.

[0175] Examples of metallic substrates (metallic substrates) include titanium, gold, silver, copper, brass, aluminum, steel, and bronze.

[0176] Examples of mineral substrates include glass, asbestos, and basalt.

[0177] Examples of cellulose-based materials include plain paper or resin-coated paper (such as polyethylene or polypropylene-coated paper). There is no practical limitation on the type of paper; it includes newsprint, magazine paper, office paper, wallpaper, and higher grammage papers commonly referred to as paperboard, such as white-lined chipboard, corrugated board, and packaging board. Further examples of cellulose-based materials include bamboo, cotton, flax, hemp, jute, lyocell, modal, rayon, raffia, ramie, and sisal.

[0178] Examples of cellulose-based materials include wool, fur, silk, and leather.

[0179] Examples of polymer substrates include polyethylene, polypropylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polylactide, polyamide, polyimide, polyacrylonitrile, polyurethane, acrylonitrile butadiene styrene.

[0180] There are no restrictions on the shape of the substrate, which can be a sheet, film, roll (coil), nonwoven or woven fiber pad or three-dimensional object.

[0181] Specifically, the substrate can be selected from food and beverage packaging, pharmaceutical packaging, textiles, medical devices, food and beverage processing equipment, water pipes, batteries, metal coils (coils) or toys.

[0182] In embodiments, the curable compositions of the present invention, as described herein, are used as coatings for batteries (e.g., batteries for motors or vehicles, such as dielectric batteries), particularly on their outer surfaces. Coatings on battery cells and modules are necessary for a variety of reasons, including providing protection, insulation, and enhancing the overall performance and durability of the battery system. At elevated temperatures and high relative humidity, strong adhesion and flexibility of the battery coating are crucial for several reasons, including, but not limited to: (1) environmental protection, where battery cells and modules are frequently exposed to harsh environmental conditions, such as high humidity and temperature fluctuations, and therefore require protective barriers to protect the batteries from moisture and contaminants, where strong adhesion ensures the coating remains in situ and effectively protects against environmental threats; (2) corrosion resistance, which is required to combat high humidity and elevated temperatures, which can accelerate corrosion and chemical reactions on the surfaces of battery cells and modules, where strong adhesion of the composition creates a barrier that inhibits contact between moisture and contaminants and the metallic (e.g., aluminum) components of the battery, reducing the risk of corrosion; (3) maintaining electrical insulation, where the composition provides electrical insulation in the battery system, where strong adhesion ensures the insulation remains intact, preventing leakage or short circuits that can be caused by the intrusion of moisture or contaminants; and (4) long-term durability, where the operational life of the battery is extended by the presence of the composition. Furthermore, a flexible coating (which is characteristic of the compositions of the present invention) is better configured to withstand the mechanical stresses and temperature variations experienced by the battery throughout its lifespan.

[0183] In one embodiment, the curable composition is used to coat the outer surface of a battery. In other embodiments, the curable composition is used to coat the battery electrodes or battery separator of a lithium-ion battery. The curable composition combines desired performance properties, including ease of application, improved storage stability, flowability, adhesion, electrical insulation, matting, flame retardancy, and weather resistance (including one or more of high and low temperature compatibility, salt spray resistance, and moisture resistance). Notably, the curable composition provides high dielectric strength and high resistivity, which is desirable for application to the outer (outer) surface of the battery, which in this embodiment is a metal such as aluminum.

[0184] Standard tests for batteries coated with the cured form of the curable compositions described herein include: ASTM D257 (surface / volume resistivity), which measures the resistance to leakage current through the body of the insulating material; and ASTM D149, which evaluates the failure of the insulating material under an externally applied field (dielectric breakdown) and the ability of the insulating material or device to withstand high voltages without experiencing destructive electrical breakdown (dielectric tolerance).

[0185] In embodiments, the curable composition is used as a coating for at least one surface of a metal substrate, particularly a metal coil, more particularly a steel coil, or an aluminum coil. Important properties of the metal coated on the coil include weather resistance, water resistance, chemical resistance, scratch resistance, gloss, hardness, flexibility, and resistance to surface delamination (delamination) or cracking when the substrate is bent. The latter properties are important because the coated metal typically undergoes forming steps during the preparation of the end-use article.

[0186] Aspects of the present invention

[0187] The present invention also relates to the following aspects.

[0188] Aspect 1. A curable composition comprising a monoester monomer of formula (1) and a diester monomer of formula (2), substantially composed of a monoester monomer of formula (1) and a diester monomer of formula (2), or composed of a monoester monomer of formula (1) and a diester monomer of formula (2),

[0189] (1)

[0190] (2)

[0191] The molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and the curable composition is substantially free of water.

[0192] In equations (1) and (2):

[0193] Each R1 is independently H or a C1-C6 alkyl group;

[0194] Each R2 is independently H or a C1-C6 alkyl group;

[0195] Each R3 is independently H or a C1-C6 alkyl group;

[0196] Each X is independently a C1-C6 alkylene group, wherein an N, O, or S atom may be inserted between any two carbon atoms present in the alkylene chain and wherein carbon atoms in the alkylene chain may be substituted by C1-C3 alkyl groups;

[0197] Each R4 is independently either an H or a cation;

[0198] Each R5 is independently either an H or a cation;

[0199] Each n is independently 4 to 7; and

[0200] Each m is independently 1 to 10.

[0201] Aspect 2. The curable composition of aspect 1, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.6:1, for example at least 1.7:1, for example at least 1.8:1, for example at least 1.9:1, for example at least 2.0:1, for example at least 2.2:1, for example at least 2.5:1, for example at least 3.0:1, for example at least 3.5:1, for example at least 4.0:1, for example from 1.5:1 to 4.0:1, for example from 1.5:1 to 3.5:1, for example from 1.5:1 to 3.0:1, for example from 1.5:1 to 2.5:1, for example from 1.5:1 to 2.0:1, for example from 1.5:1 to 1.9:1, for example from 1.5:1 to 1.8:1, for example from 1.5:1 to 1.7:1.

[0202] Aspect 3. The curable composition according to aspect 1 or 2, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is 1.70:1 to 4:1, 1.75:1 to 4:1, 1.80:1 to 4:1, 1.85:1 to 4:1, 1.90:1 to 4:1, 1.95:1 to 4:1 or 2.0:1 to 4:1.

[0203] Aspect 4. The curable composition according to any one of aspects 1 to 3, wherein X is selected from -CH2-CH2-, formula (3) or formula (4):

[0204] -(CR6R'6) e - (3)

[0205] -[(CR7R'7) f -O] g -(CR7R'7) h - (4)

[0206] in:

[0207] Each R6 and R'6 is independently H or a C1-C3 alkyl group;

[0208] Each R7 and R'7 is independently H or methyl;

[0209] e is an integer from 1 to 6;

[0210] f is an integer from 1 to 4;

[0211] g is an integer from 1 to 3;

[0212] h is an integer from 1 to 4; and

[0213] f+g+h≤6.

[0214] Aspect 5. A curable composition of any one of Aspects 1 to 4, wherein for the monomers of Formula (1) and Formula (2), m is 1 to 9, for example 2 to 9, for example 3 to 9, for example 4 to 9, for example 2 to 8, for example 3 to 8, for example 4 to 8, for example 2 to 7, for example 3 to 7, for example 4 to 7, for example 2 to 6, for example 3 to 6, for example 4 to 6.

[0215] Aspect 6. A curable composition of any one of Aspects 1 to 5, wherein n is 5 for the monomer of formula (1) and the monomer of formula (2).

[0216] Aspect 7. A curable composition of any one of Aspects 1 to 6, wherein for the monomers of Formula (1) and Formula (2), m is 3 to 7 and n is 5.

[0217] Aspect 8. A curable composition of any one of Aspects 1 to 7, wherein for the monomers of formula (1) and formula (2), m is 3 to 7, n is 5 and X is -CH2-CH2-.

[0218] Aspect 9. A curable composition of any one of Aspects 1 to 8, wherein m is 4 to 6 for the monomers of formula (1) and formula (2).

[0219] Aspect 10. A curable composition of any one of Aspects 1 to 9, wherein m is 4 for the monomer of formula (1) and the monomer of formula (2).

[0220] Aspect 11. A curable composition of any one of aspects 1 to 9, wherein for the monomers of formula (1) and formula (2), m is 4 and n is 5.

[0221] Aspect 12. A curable composition of any one of Aspects 1 to 9, wherein for the monomers of Formula (1) and Formula (2), m is 5 and n is 5.

[0222] Aspect 13. A curable composition of any one of Aspects 1 to 9, wherein for the monomers of formula (1) and formula (2), m is 4, n is 5 and X is -CH2-CH2-.

[0223] Aspect 14. A curable composition of any one of Aspects 1 to 9, wherein for the monomers of Formula (1) and Formula (2), m is 5, n is 5 and X is -CH2-CH2-.

[0224] Aspect 15. A curable composition of any one of Aspects 1 to 14, wherein R4 is an ammonium ion for the monomer of formula (1) and the monomer of formula (2).

[0225] Aspect 16. A curable composition of any one of Aspects 1 to 14, wherein R4 is H for the monomer of formula (1) and the monomer of formula (2).

[0226] Aspect 17. A curable composition of any one of Aspects 1 to 14, wherein R4 is Na for the monomers of formula (1) and formula (2). + Li + K + Ca 2+ Or Ba 2+ .

[0227] Aspect 18. A curable composition of any one of aspects 1 to 17, wherein R5 is an ammonium ion for the monomer of formula (1).

[0228] Aspect 19. A curable composition of any one of aspects 1 to 17, wherein R5 is H for the monomer of formula (1).

[0229] Aspect 20. A curable composition of any one of Aspects 1 to 17, wherein for the monomer of formula (1), R5 is Na. + Li + K + Ca 2+ Or Ba 2+ .

[0230] Aspect 21. The curable composition of any one of Aspects 1 to 20, further comprising one or more olefinically unsaturated monomers selected from: methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; n-hexyl methacrylate; 2-ethylhexyl methacrylate; n-octyl methacrylate; isooctyl methacrylate; n-decyl methacrylate; n-dodecyl methacrylate; tridecyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; 2-hydroxyethyl methacrylate; 2- and 3-hydroxypropyl methacrylate; 2-methoxyethyl methacrylate; 2-ethoxyethyl methacrylate; 2- and 3-ethoxypropyl methacrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethylhexyl)methacrylate (Oxyethoxy)ethyl ester; (Meth)cyclohexyl acrylate; (Meth)glycidyl acrylate; (Meth)isodecyl acrylate; (Meth)lauryl acrylate; (Meth)2-phenoxyethyl acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane acetal (meth)acrylate; (Meth)isobornyl acrylate; tricyclodecane methanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate Esters; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxylated polyethylene glycol (meth)acrylate; hydroxyethyl-butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0231] Aspect 22. The curable composition of any one of Aspects 1 to 21 further comprises one or more olefinically unsaturated monomers selected from: bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; Acrylic esters; Polytetramethylene glycol di(meth)acrylate; 1,2-Butanediol di(meth)acrylate; 2,3-Butanediol di(meth)acrylate; 1,3-Butanediol di(meth)acrylate; 1,4-Butanediol di(meth)acrylate; 1,5-Pentanediol di(meth)acrylate; 1,6-Hexanediol di(meth)acrylate; 1,8-Octadiol di(meth)acrylate; 1,9-Nonanediol di(meth)acrylate; 1,10-Nonanediol di(meth)acrylate; 1,12-Dodecanediol di(meth)acrylate; Neopentyl glycol di( Methacrylates; 2-Methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-diethanol di(meth)acrylate; tricyclodecanediethanol di(meth)acrylate; metal di(meth)acrylates (esters); modified metal di(meth)acrylates (esters); glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate Esters; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane)diacrylate; di(trimethylolpropane)triacrylate; di(trimethylolpropane)tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol)tetraacrylate; di(pentaerythritol)pentaacrylate; di(pentaerythritol)hexa(meth)acrylate; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0232] Aspect 23. The curable composition according to any one of Aspects 1 to 22 further comprises one or more olefinically unsaturated monomers selected from: 1,2-dodecanediol dimethacrylate (DDDMA), isobornyl acrylate (IBOA), caprolactone acrylate (CAPA), tricyclodecanediethanol diacrylate (TCDDMA), and mixtures thereof.

[0233] Aspect 24. The curable composition according to any one of Aspects 1 to 23 further comprises one or more oligomers selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyurethane (meth)acrylates, and combinations thereof.

[0234] Aspect 25. The curable composition of any one of Aspects 1 to 24 further comprises one or more oligomers selected from: polyester (meth)acrylates, polyester-based aliphatic urethane di(meth)acrylates, polyether-based aliphatic urethane di(meth)acrylates and polybutadiene-based aliphatic urethane di(meth)acrylates and combinations thereof.

[0235] Aspect 26. A curable composition of any one of Aspects 1 to 25, wherein the curable composition comprises one or more additives selected from the group consisting of: antioxidants, ultraviolet absorbers, stabilizers, defoamers, solvents, coalescing agents, rheology modifiers, flow or leveling agents, colorants, adhesion promoters, pigments, dispersants, wetting agents, slip additives, fillers, thixotropic agents, matting agents, waxes, neutralizers, biocides, preservatives, organic solvents, and combinations thereof.

[0236] Aspect 27. A curable composition of any one of Aspects 1 to 26, wherein the combined amount of the monomers of Formula (1) and Formula (2) is 0.05 to 95%, 0.5 to 90%, 1 to 85%, 2 to 80%, 5 to 70%, 2 to 50%, 2 to 40%, 2 to 30%, 2 to 20% or 1 to 5%, based on the total weight of the composition.

[0237] Aspect 28. The curable composition of any one of aspects 1 to 27, wherein the combined amount of the monomers of formula (1) and formula (2) is 10 to 100% by weight, for example 10 to 90% by weight, for example 10 to 80% by weight, for example 10 to 70% by weight, for example 10 to 60% by weight, for example 10 to 50% by weight, for example 10 to 40% by weight, for example 10 to 30% by weight, for example 10 to 90% by weight, for example 20 to 100% by weight, for example 20 to 90% by weight, for example 20 to 80% by weight, for example 20 to 70% by weight, for example 20 to 60% by weight, for example 20 to 50% by weight, for example 20 to 40% by weight, for example 30 to 100% by weight, for example 30 to 90% by weight, for example 30 to 80% by weight, for example 30 to 70% by weight, for example 30 to 60% by weight, for example 40 to 100% by weight, for example 40 to 90% by weight, for example 40 to 80% by weight, for example 50 to 100% by weight, relative to the total weight of the polymerizable monomers present in the composition.

[0238] Aspect 29. A curable composition of any one of Aspects 1 to 28, wherein the amount of the olefinically unsaturated monomer (other than the monomer of formula (1) and the monomer of formula (2)) present in the curable composition is 1 to 99 wt%, for example 1 to 95 wt%, for example 1 to 90 wt%, for example 1 to 80 wt%, for example 1 to 75 wt%, for example 1 to 65 wt%, for example 1 to 55 wt%, for example 1 to 45 wt%, for example 1 to 35 wt%, for example 1 to 25 wt%, for example 1 to 15 wt%, for example 5 to 99 wt%, for example 5 to 95 wt%, for example 5 to 90 wt%, for example 5 to 80 wt%, for example 5 to 75 wt%, for example 5 to 65 wt%, for example 5 to 55 wt%, for example 5 to 45 wt%, for example 5 to 35 wt%, for example 5 to 25 wt%, for example 5 to 15 wt%, for example 10 to 99 wt%, for example 10 to 95 wt%, for example 10 to 90 wt%, for example 10 to 80 wt%. For example, 10 to 75% by weight, for example, 10 to 65% by weight, for example, 10 to 55% by weight, for example, 10 to 45% by weight, for example, 10 to 35% by weight, for example, 10 to 25% by weight, for example, 15 to 99% by weight, for example, 15 to 95% by weight, for example, 15 to 90% by weight, for example, 15 to 80% by weight, for example, 15 to 75% by weight, for example, 15 to 65% by weight, for example, 15 to 55% by weight, for example, 15 to 45% by weight, for example, 15 to 35% by weight, for example, 20 to 99% by weight, for example, 20 to 95% by weight, for example, 20 to 90% by weight, for example, 20 to 80% by weight, for example, 20 to 75% by weight, for example, 20 to 65% by weight, for example, 20 to 55% by weight, for example, 30 to 99% by weight, for example, 30 to 95% by weight, for example, 30 to 80% by weight, for example, 30 to 75% by weight, for example, 30 to 65% by weight, relative to the total weight of polymerizable monomers present.

[0239] Aspect 30. A curable composition of any one of Aspects 1 to 29, wherein the curable composition comprises less than 3% by weight of water, such as less than 1% by weight, such as less than 0.5% by weight, such as less than 0.2% by weight, such as less than 0.1% by weight, such as less than 0.01% by weight, such as 0 to 4% by weight, such as 0 to 1% by weight, such as 0 to 0.5% by weight, such as 0 to 0.1% by weight, such as 0% by weight of water, relative to the total weight of the curable composition.

[0240] Aspect 31. A cured composition formed from any one of aspects 1 to 30.

[0241] Aspect 32. A substrate comprising the curable composition described in any one of aspects 1 to 30.

[0242] Aspect 33. A substrate comprising the cured composition of aspect 31.

[0243] Aspect 34. A method for improving the adhesion and / or corrosion resistance and / or water resistance of a curable coating composition applied to at least one surface of a substrate, said method comprising adding a monomer of formula (1) and a monomer of formula (2) as defined in any one of aspects 1 to 30 to the curable coating composition and curing the curable composition.

[0244] Aspect 35. A method for improving the corrosion resistance and / or water resistance of at least one surface of a substrate, the method comprising adding a curable composition of any one of Aspects 1 to 30 to at least one surface, and curing the curable composition.

[0245] Aspect 36. A battery (e.g., the outer surface of a battery), comprising a curable composition of any one of Aspects 1 to 30.

[0246] Aspect 37. A battery (e.g., the outer surface of a battery), comprising the cured composition of aspect 31.

[0247] Aspect 38. A battery (e.g., the outer surface of a battery) comprising a curable composition comprising a monomer of formula (1) and formula (2) as defined in any one of aspects 1 to 30, and one or more of 1,2-dodecanediol dimethacrylate (DDDMA), isobornyl acrylate (IBOA), caprolactone acrylate (CAPA), wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0248] Aspect 39. A battery (e.g., the outer surface of a battery) comprising a curable composition comprising monomers of formula (1) and formula (2) as defined in any one of aspects 1 to 30, and one or more oligomers, the oligomers comprising polyester acrylates, polyester-based aliphatic urethane diacrylates, polyether-based aliphatic urethane diacrylates and polybutadiene-based aliphatic urethane diacrylates, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0249] Aspect 40. A battery (e.g., the outer surface of a battery) comprising a curable composition comprising a monomer of formula (1) and formula (2) as defined in any one of aspects 1 to 30, one or more acrylate oligomers, one or more acrylate monomers other than the monomers of formula (1) and formula (2), a photoinitiator, and one or more fillers / additives, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, and wherein the curable composition is substantially free of water.

[0250] Aspect 41. A battery (e.g., the outer surface of a battery) comprising a curable composition comprising 1 to 5% by weight of monomers of formula (1) and (2) as defined in any one of aspects 1 to 30, 20 to 60% by weight of acrylate oligomers, 25 to 50% by weight of acrylate monomers other than those of formula (1) and (2) and 0.5 to 3% by weight of a photoinitiator, based on the total weight of the curable composition, wherein the molar ratio of the monomers of formula (1) to the monomers of formula (2) is at least 1.5:1, wherein the curable composition is substantially free of water, and wherein the composition is free of organic solvents or alternatively contains one or more organic solvents.

[0251] Aspect 42. Metal coils (e.g., steel coils or aluminum coils) comprising the cured composition of aspect 31.

[0252] Aspect 43. Use of the curable composition of any one of Aspects 1 to 30 for improving corrosion resistance and / or scrub resistance and / or water resistance and / or adhesion and / or electrical insulation and / or matte finish and / or flame retardancy and / or weather resistance on at least one surface of a substrate.

[0253] Aspect 44. Use of the curable composition of any one of Aspects 1 to 30 as a coating for at least one surface of a substrate.

[0254] Aspect 45. Use of aspect 44, wherein the substrate is the surface of the battery, particularly the outer surface of the battery.

[0255] Applications of aspect 46. Applications of aspect 44, wherein the substrate is a metal substrate, particularly a metal coil, and more particularly a steel coil or an aluminum coil.

[0256] Example

[0257] List of components

[0258] The following components are used in the examples.

[0259] SR833S: Sartamomer (Tricyclodecanediethanol Diacrylate)

[0260] HEMA: 2-Hydroxyethyl methacrylate (Aldrich)

[0261] SR170: 2-Hydroxyethyl methacrylate (Sartomer)

[0262] SR506A: Sartamomer (isobornyl acrylate)

[0263] SR9054: 2-Hydroxyethyl methacrylate (Sartomer)

[0264] SR210: Polyethylene glycol dimethacrylate (Sartomer)

[0265] HEA: 2-Hydroxyethyl acrylate (Aldrich)

[0266] CN963: Bifunctional carbamate acrylate (Sartomer)

[0267] CN991: Bifunctional carbamate acrylate (Sartomer)

[0268] Speedcure BPO: Phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (Sartomer)

[0269] Speedcure TPO-L: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (Sartomer)

[0270] Speedcure 73: 2-Hydroxy-2-methyl-1-phenylpropanone (Sartomer)

[0271] PL-460: Liquid photoinitiator (Esstech)

[0272] AEROSIL R805: Fumed Silica

[0273] TiO2: Titanium dioxide

[0274] Talc (Mg3Si4O) 10 (OH)2)

[0275] P2O5: Phosphorus pentoxide (Aldrich)

[0276] method

[0277] Aging test / electrolyte immersion test

[0278] The coated substrates were aged for up to 4 weeks in both an 85°C / 85%RH ambient chamber and by immersion in an electrolyte solution. These aged samples were tested immediately after the aging test. Prior to testing, the coated samples, which had been immersed in an electrolyte solvent mixture containing diethyl carbonate, dimethyl carbonate, and ethylene carbonate in a 1:1:1 ratio, were dried using a cleanroom wipe and alcohol.

[0279] Viscosity test

[0280] The viscosity of each composition was measured at room temperature using a Brookfield rheometer.

[0281] Flexibility test

[0282] According to ISO 1519:2002, the crack resistance of a coating is determined by bending a fully cured coated plate at a 90-degree angle on a tapered mandrel with a diameter of 4 to 34 mm.

[0283] Adhesion test

[0284] The adhesion of the coated resin to the underlying aluminum plate is evaluated using a crosshatch test according to ASTM standard D3359. The crosshatch test is rated on a scale of 0 to 5 (where 5 is the highest level of adhesion strength) provided in the ASTM standard.

[0285] Pencil hardness

[0286] The surface hardness of a material is evaluated using the pencil hardness test as described in ISO 15184:1998.

[0287] Dielectric breakdown test

[0288] The breakdown strength of the cured film was measured using ASTM D-149 standard.

[0289] Volume resistivity test

[0290] Volume resistivity was measured at room temperature using a Keithley 6517B and 8009 clamp according to ASTM D-257 standard.

[0291] Overlap shear test of glass

[0292] Overlap shearing was measured using ASTM C961 standard.

[0293] Synthesis Examples

[0294] Comparative Example 1: Preparation of phosphate ester monomers of formulas (1) and (2) having structures 5 and 6 (m=1)

[0295] 210 gm of phosphorus pentoxide (Aldrich) and 713 gm of toluene were added to a 3L, 4-necked round-bottom flask equipped with an air spray, stirrer, thermocouple, temperature controller, heating mantle, side arm, and feeding funnel. 1113 gm of caprolactone-modified 2-hydroxyethyl methacrylate (with an average molar ratio of caprolactone to 2-hydroxyethyl methacrylate of 1:1) was added over 30 minutes via the feeding funnel with stirring, while maintaining the exothermic flask temperature below 65°C. After the addition of all caprolactone-modified 2-hydroxyethyl methacrylate, stirring was continued for another 2 hours, followed by filtration of the mixture through filter paper to remove unreacted phosphorus pentoxide. Toluene was removed by vacuum distillation at a maximum of 65°C / 15 mm Hg to obtain a mixture of 1323 gm caprolactone-modified 2-hydroxyethyl methacrylate phosphates of structures 5 and 6, with a monoester to diester molar ratio of 1.19:1, as shown by... 31 Measured by p NMR.

[0296]

[0297] The analysis of the product mixture is provided below.

[0298]

[0299] Example 1: Preparation of phosphate ester monomers of formulas (1) and (2) having structures 3 and 4 (m=4)

[0300] 71 gm of phosphorus pentoxide (Aldrich) and 929 gm of toluene were added to a 3L, four-necked round-bottom flask equipped with an air spray, stirrer, thermocouple, temperature controller, heating mantle, side arm, and feeding funnel. 858 gm of caprolactone-modified 2-hydroxyethyl acrylate (with an average molar ratio of caprolactone to 2-hydroxyethyl acrylate of 4:1) was added over 30 minutes with stirring via the feeding funnel, while maintaining the exothermic flask temperature below 60°C. After the addition of all caprolactone-modified 2-hydroxyethyl acrylate, stirring was continued for another 2 hours, followed by filtration of the mixture through filter paper to remove unreacted phosphorus pentoxide. Toluene was removed by vacuum distillation at a maximum of 65°C / 15 mm Hg to obtain a mixture of 929 gm caprolactone-modified 2-hydroxyethyl acrylate phosphates of structures 3 and 4, with a monoester to diester molar ratio of 2.45:1, as shown by... 31 Measured by p NMR.

[0301]

[0302] The analysis of the product mixture is provided below.

[0303]

[0304] Example 2: Preparation of phosphate ester monomers of formulas (1) and (2) having structures 5 and 6 (m=1)

[0305] 16.2 gm of phosphorus pentoxide (Aldrich) and 100 gm of SR833S were added to a 1 L four-necked round-bottom flask equipped with an air spray, stirrer, thermocouple, temperature controller, heating mantle, side arm, and feeding funnel. 83.8 gm of caprolactone-modified 2-hydroxyethyl methacrylate (with an average molar ratio of caprolactone to 2-hydroxyethyl methacrylate of 1:1) was added over 30 minutes with stirring via the feeding funnel, while maintaining the exothermic flask temperature below 60°C. After adding all the caprolactone-modified 2-hydroxyethyl methacrylate, stirring continued for another 2 hours, followed by filtration of the mixture through filter paper to remove unreacted phosphorus pentoxide. The resulting product was a mixture of 200 gm of caprolactone-modified 2-hydroxyethyl methacrylate phosphates with structures 5 and 6, with a monoester to diester molar ratio of 1.89:1, as shown in the figure. 31 Measured by p NMR.

[0306]

[0307] The analysis of the product mixture is provided below.

[0308]

[0309] Example 2A: Preparation of phosphate ester monomers of formulas (1) and (2) having structures 3 and 4 (m=4)

[0310] 71 gm of phosphorus pentoxide (Aldrich) and 929 gm of SR833S were added to a 3L, four-necked round-bottom flask equipped with an air spray, stirrer, thermocouple, temperature controller, heating mantle, side arm, and feeding funnel. 858 gm of caprolactone-modified 2-hydroxyethyl acrylate (with an average molar ratio of caprolactone to 2-hydroxyethyl acrylate of 4:1) was added over 30 minutes with stirring via the feeding funnel, while maintaining the exothermic flask temperature below 60°C. After the addition of all caprolactone-modified 2-hydroxyethyl acrylate, stirring was continued for another 2 hours, followed by filtration of the mixture through filter paper to remove unreacted phosphorus pentoxide. The resulting product was a mixture of 1858 gm of caprolactone-modified 2-hydroxyethyl acrylate phosphates of structures 3 and 4, with a monoester to diester molar ratio of 3.08:1, as shown in the figure. 31 Measured by p NMR.

[0311] The analysis of the product mixture is provided below.

[0312]

[0313] Example 3: Preparation of phosphate ester monomers of formulas (1) and (2) having structures 7 and 8 (m=10)

[0314] 8 gm of phosphorus pentoxide (Aldrich) and 110 gm of toluene were added to a 1 L four-necked round-bottom flask equipped with an air spray, stirrer, thermocouple, temperature controller, heating mantle, side arm, and feeding funnel. Under stirring, 320 gm of a solution comprising 67 wt% caprolactone-modified 2-hydroxyethyl acrylate (where the average molar ratio of caprolactone to 2-hydroxyethyl acrylate is 10:1) and 33 wt% toluene was added over 30 minutes via the feeding funnel, while maintaining the exothermic flask temperature below 60°C. After the addition of all caprolactone-modified 2-hydroxyethyl acrylate, stirring was continued for another 2 hours, followed by filtration of the mixture through filter paper to remove unreacted phosphorus pentoxide. Toluene was removed by vacuum distillation at a maximum of 65°C / 15 mm Hg to obtain a mixture of 218 gm caprolactone-modified 2-hydroxyethyl acrylate phosphates of structures 7 and 8, with a monoester to diester molar ratio of 2.58:1, as shown by... 31 Measured by p NMR.

[0315]

[0316] The analysis of the product mixture is provided below.

[0317]

[0318] Example 4: Formulation (composition) 1 (m=1).

[0319] To evaluate the performance of the compositions of the present invention comprising exemplary monomers of formulas (1) and (2), a curable formulation was prepared comprising epoxy acrylate oligomer, acrylate SR506A, diacrylate SR833S, caprolactone-modified 2-hydroxyethyl methacrylate phosphate of structures 5 and 6 prepared as described in Example 2 at a monoester to diester molar ratio of 1.89:1, TiO2, AEROSIL R805, talc, and SpeedCure BPO and SpeedCure 73 as photoinitiators.

[0320] Comparative Example 4: Comparative formulation Comp 1 (m=1).

[0321] To evaluate the performance of the compositions of the present invention comprising exemplary monomers of formulas (1) and (2), curable formulations were prepared comprising epoxy acrylate oligomers, acrylate SR506A, diacrylate SR833S, caprolactone-modified 2-hydroxyethyl methacrylate phosphates of structures 5 and 6 prepared as described in Comparative Example 1 at a monoester-to-diester molar ratio of 1.19:1, TiO2, AEROSIL R805, talc, and SpeedCure BPO and SpeedCure 73 as photoinitiators.

[0322] Example 5: Formulation 2 (m=4).

[0323] To evaluate the performance of the compositions of the present invention comprising exemplary monomers of formulas (1) and (2), curable formulations were prepared comprising epoxy acrylate oligomers, acrylate SR506A, diacrylate SR833S, caprolactone-modified 2-hydroxyethyl acrylate phosphates of structures 3 and 4 prepared as described in Example 1 at a monoester to diester molar ratio of 2.45:1, TiO2, AEROSIL R805, talc, and SpeedCure BPO and SpeedCure 73 as photoinitiators.

[0324] Example 6: Formulation 3 (m=10).

[0325] To evaluate the performance of the compositions of the present invention comprising exemplary monomers of formulas (1) and (2), curable formulations were prepared comprising epoxy acrylate oligomers, acrylate SR506A, diacrylate SR833S, caprolactone-modified 2-hydroxyethyl acrylate phosphates of structures 7 and 8 as described in Example 3 at a monoester to diester molar ratio of 2.58:1, TiO2, AEROSIL R805, talc, and SpeedCure BPO and SpeedCure 73 as photoinitiators.

[0326] Example 7: Preparation of curable composition.

[0327] To prepare the curable compositions of formulations 1, 2, and 3 of Examples 4, 5, and 6, respectively, epoxy acrylate oligomers, TiO2, AEROSIL R805, and talc were added to Flacktek. ® The polypropylene was mixed in a high-speed mixer cup at 2000 rpm for 2 minutes. TiO2, AEROSIL R805, and talc filler were then dispersed using a three-roll mill. After dispersion, acrylate SR506A, diacrylate SR833S, monomers of formulas (1) and (2), and a photoinitiator were added to the mixture of oligomers and fillers, and the mixture was again mixed in a Flacktek cup for 5 minutes until the solution became homogeneous. The resulting curable compositions are summarized in Table 1 below.

[0328] Table 1

[0329]

[0330] Example 8: Preparation of cured composition.

[0331] The curable composition of the present invention is applied to one or more surfaces of a substrate (e.g., a metal substrate, such as aluminum) that has been sequentially wiped with toluene and acetone, to a thickness of up to 60 μm, using a drawdown bar film applicator. The composition is then cured using a UV-A LED lamp (395 nm) and a fusion lamp (H bulb).

[0332] Example 9: Testing of Formulations 1 to 3 and Comparative Formulation 1

[0333] The test results for formulation 1 are shown in Table 2 below.

[0334] Table 2

[0335]

[0336] The test results for formulation 1 are shown in Table 3 below.

[0337] Table 3

[0338]

[0339] The test results for formulation 2 are shown in Table 4 below.

[0340] Table 4

[0341]

[0342] The test results for formulation 3 are shown in Table 5 below.

[0343] Table 5

[0344]

[0345] The results from Tables 2 to 5 demonstrate that formulations 1, 2, and 3 each exhibited superior adhesion and flexibility after two weeks of application to the surface, with formulations 1 and 2 exhibiting superior adhesion after four weeks, and formulation 2 also exhibiting superior flexibility after four weeks. The comparison with formulations lacking α-phosphate esters shows the improvements in both adhesion and hardness obtained by the present invention. Comparative formulation 1 did not exhibit sufficient flexibility.

[0346] Example 10: Comparative test of glass adhesion.

[0347] The following compositions were tested for lap shear strength against glass: 67 wt% CN963, 15 wt% SR210, 15 wt% SR170, and 3 wt% TPO-L (“Control”); Control + 5 wt% phosphate acrylate SR9054 (“Comparative”); and Control + 8.2 wt% of phosphate monomers of formulas (1) and (2) having structures 5 and 6 in a molar ratio of 1.89 monoester to diester (“Invention”). The Invention compositions exhibited superior adhesion to glass compared to the Comparative compositions (which contain phosphate acrylates without formula (1) or (2)) and the Control. Specifically, the Invention formulation had an lap shear strength of approximately 52,000 psi, while the Comparative and Control formulations had lap shear strengths of 39,500 psi and 20,500 psi, respectively.

[0348] Example 11: Comparative test on the adhesion of steel coils.

[0349] The following composition (based on weight % of the composition) was tested for cross-cut adhesion on steel coil (cold-rolled steel). The composition was applied to cold-rolled steel (CRS) at a rate of 50 micrometers and tested using a solution with 1 J / cm². 2 Curing is performed using a mercury lamp with UVA energy.

[0350]

[0351] Cross-cut adhesion was tested after conditioning at 24°C and 55% relative humidity for 24 hours (ASTM D3359). The cross-cut adhesion of the resulting coating is reported in the table below.

[0352]

[0353] The control coating (without adhesion promoter) showed no adhesion to the steel coil. Compared with the comparative composition (which contains phosphate acrylates without formula (1) or formula (2)), the inventive composition showed superior cross-cut adhesion to the steel coil.

[0354] The invention described herein is intended to cover not only all aspects or exemplary embodiments of the invention, but also all combinations of aspects and embodiments.

Claims

1. A curable composition comprising a monomer of formula (1) and a monomer of formula (2). (1) (2) In equations (1) and (2): Each R1 is independently H or a C1-C6 alkyl group; Each R2 is independently H or a C1-C6 alkyl group; Each R3 is independently H or a C1-C6 alkyl group; Each X is independently a C1-C6 alkylene group, wherein an N, O, or S atom may be inserted between any two carbon atoms present in the alkylene chain and wherein the carbon atoms in the alkylene chain may be substituted by C1-C3 alkyl groups; Each R4 is independently either an H or a cation; Each R5 is independently either an H or a cation; Each n is independently 4 to 7; and Each m is independently 1 to 10. The molar ratio of the monomer of formula (1) to the monomer of formula (2) is at least 1.5:1, preferably at least 1.8:1, more preferably at least 2.0:1, and The curable composition is substantially water-free.

2. The curable composition according to claim 1, wherein the molar ratio of the monomer of formula (1) to the monomer of formula (2) is 1.70:1 to 4:1, 1.75:1 to 4:1, 1.80:1 to 4:1, 1.85:1 to 4:1, 1.90:1 to 4:1, 1.95:1 to 4:1 or 2.0:1 to 4:

1.

3. The curable composition according to claim 1 or 2, wherein X is selected from -CH2-CH2-, formula (3) or formula (4): -(CR6R'6) e - (3) -[(CR7R’7) f -O] g -(CR7R’7) h - (4) in: Each R6 and R'6 is independently H or a C1-C3 alkyl group; Each R7 and R'7 is independently H or methyl; e is an integer from 1 to 6; f is an integer from 1 to 4; g is an integer from 1 to 3; h is an integer from 1 to 4; and f+g+h≤6.

4. The curable composition according to any one of claims 1 to 3, wherein the respective cations of R4 and R5 are independently ammonium-based, primary ammonium-based, secondary ammonium-based, tertiary ammonium-based, or metal-based, and preferably ammonium-based.

5. The curable composition according to any one of claims 1 to 4, wherein n is 5, m is 3 to 5, and X is -CH2-CH2-.

6. The curable composition according to any one of claims 1 to 5 further comprises at least one olefinic unsaturated monomer that is not a monomer of formula (1) or a monomer of formula (2), preferably at least two olefinic unsaturated monomers.

7. The curable composition according to any one of claims 1 to 6 further comprises one or more oligomers selected from the group consisting of epoxy (meth)acrylates, polyester (meth)acrylates, polyurethane (meth)acrylates, and combinations thereof.

8. The curable composition according to any one of claims 1 to 7 further comprises one or more oligomers selected from: epoxy (meth)acrylates, polyester (meth)acrylates, polyester-based aliphatic urethane di(meth)acrylates, polyether-based aliphatic urethane di(meth)acrylates, polybutadiene-based aliphatic urethane di(meth)acrylates, and combinations thereof.

9. The curable composition according to any one of claims 1 to 8, wherein the composition further comprises one or more additives selected from the group consisting of pigments, fillers, dispersants, rheology modifiers, wetting agents, defoamers, organic solvents, coalescing agents, neutralizing agents, and biocides.

10. The curable composition according to any one of claims 1 to 9, further comprising one or more (meth)acrylate oligomers, one or more (meth)acrylate monomers other than the monomers of formula (1) and (2), a photoinitiator, and optionally one or more solvents, fillers, and additives.

11. The curable composition of claim 10, wherein the composition comprises: Based on 20 to 60% by weight of at least one (meth)acrylate oligomer of the total weight of the curable composition, Based on 25 to 50% by weight of (meth)acrylate monomers other than those of formulas (1) and (2) of the total weight of the curable composition, Based on 1 to 5% by weight of the monomers of formula (1) and formula (2) of the total weight of the curable composition, and Based on 0.5 to 3% by weight of photoinitiator of the total weight of the curable composition, Optionally, at least one of a solvent, filler, and additive.

12. A method for improving the corrosion resistance and / or scrub resistance and / or water resistance and / or adhesion and / or electrical insulation and / or matte finish and / or flame retardancy and / or weather resistance of at least one surface of a substrate, the method comprising applying a curable composition as defined in any one of claims 1 to 11 to the at least one surface and curing the curable composition.

13. A cured composition formed from a curable composition according to any one of claims 1 to 11.

14. A battery comprising the cured composition according to claim 13.

15. A metal coil, comprising the cured composition according to claim 13.

16. Use of the curable composition according to any one of claims 1 to 11 as a coating for at least one surface of a substrate.

17. The use according to claim 16, wherein the substrate is the surface of the battery, particularly the outer surface of the battery.

18. The use according to claim 16, wherein the substrate is a metal substrate, particularly a metal coil, more particularly a steel coil or an aluminum coil.

19. Use of the curable composition according to any one of claims 1 to 11 for improving the corrosion resistance and / or water resistance and / or adhesion and / or electrical insulation and / or matte finish and / or flame retardancy and / or weather resistance of the surfaces on which the curable composition is applied.

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