Curable compositions based on incompatible reactive components and block copolymers - Patents.com

Abstract

To provide a curable composition that permits systematic adjustment to dimensions, composition and configuration of a structure.SOLUTION: A polymer composition of a nanostructure having a plurality of phases is prepared by curing a composition containing a first reactive component (for example, a hydrophilic reactive component), a second reactive component (for example, a hydrophobic reactive component) and a block copolymer. The first reactive component and the second reactive component express a visible separation at 25°C in the absence of the block copolymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to curable compositions, methods of making and using such compositions, and articles made from such curable compositions and cured compositions. [Background technology]

[0002] The polymerization or curing of various functional monomers and / or oligomers to provide cured compositions or articles such as adhesives, coatings, sealants, moldings, etc., has been studied for many years. For example, (meth)acrylate functionalized monomers / oligomers may be combined, optionally with other ingredients such as photoinitiators, and then exposed to conditions (exposure to a radiation source, e.g., UV light, etc.) that effectively cause the (meth)acrylate functional groups to react with each other and form a polymerized matrix. Typically, such curable compositions are initially liquids (e.g., homogeneous solutions) that are converted to solids as a result of the curing reaction.

[0003] The solid polymeric matrices formed by the reaction of curable monomers and / or oligomers are usually homogeneous, i.e., only a single phase is present. Although the properties and characteristics of such single-phase matrices can be controlled and varied to some extent by selecting and combining different types of reactants and using different curing techniques, there are substantial limitations to what can be achieved due to the fact that the resulting cured product is in the form of a single phase. Therefore, it would be highly desirable to develop a process for producing microphase-separated polymeric systems (i.e., cured compositions composed of two or more polymeric phases or domains that are compositionally distinct from one another) that can be produced starting from the same general types of monomers and oligomers that are typically used to prepare single-phase polymeric systems. Summary of the Invention [Problem to be solved by the invention]

[0004] The inventors of the present invention have thus discovered that block copolymers can be used to direct the structure of specific combinations of polymerizable compounds into structures that are controlled by the phase behavior of the block copolymer. In bulk, the microphases of block copolymers separate on a molecular scale (e.g., 5-100 nm) to produce composites, i.e., ordered nanostructures, with a variety of morphologies depending on the volume fraction of one type of block relative to another type of block and the relative compatibility of the block types. In contrast, radiation-curable monomeric and oligomeric materials do not typically exhibit any order and therefore polymerize into random networks that lack order when cured. It has been found that the addition of block copolymers to certain polymerizable compound systems, as embodied in the present invention, provides an effective mechanism for directing the structure of the polymerizable compounds into ordered morphologies, for example when the polymerizable compounds are cured by exposure to radiation. This allows for systematic control over the size, composition and configuration of the structures in the cured composition. Thus, the present invention allows for the preparation of cured compositions with unique properties that cannot be achieved by known techniques.

[0005] Without wishing to be bound by theory, it is believed that an ordered system forms in the liquid phase prior to curing of the polymerizable compound, at least in part due to the presence of the block copolymer. The curing (polymerization) process is believed to kinetically complement the liquid phase structure.

[0006] The resulting cured composition has a short-range ordered structure as opposed to a long-range ordered structure. The term "short-range ordered" is understood in the art to refer to a material that exhibits order on the nanometer length scale, but is not ordered (i.e., not crystalline) on the sub-nanometer scale. See, e.g., Li et al., "Block copolymer patterns and templates," Materials Today, September 2006, Vol. 9, No. 9, pp. 30-39. [Means for solving the problem]

[0007] According to one embodiment, the present invention provides a curable composition, which exists in an ordered microphase separated state at 25° C., a) a block copolymer comprising at least a first block and a second block, the first block and the second block having different monomer compositions; b) a first reactive component having a higher affinity for the first block of the block copolymer than for the second block of the block copolymer; and c) a second reactive component that has a higher affinity for the second block of the block copolymer than for the first block of the block copolymer; d) the first reactive component and the second reactive component are not completely compatible with each other at 25° C. in the absence of the block copolymer; A curable composition is provided.

[0008] In general, the first and second reactive components are selected to be sufficiently different in chemical structure and properties to be mutually incompatible at the molecular level, such that when mixed at 25° C. in the absence of other materials (such as the block copolymer components of the present invention), the components separate into separate phases visible to the unaided human eye. One approach to achieving the desired dissimilarity is to have one reactive component that is significantly more hydrophilic than the other reactive component. For convenience, the more hydrophilic reactive component may be referred to herein as the “hydrophilic reactive component” and the less hydrophilic reactive component may be referred to herein as the “hydrophobic reactive component”. Incompatibility of the reactive components may also be achieved by selecting reactive components that differ significantly from each other in terms of their polarity or dipole moment or ability to form intermolecular bonds (e.g., through hydrogen bonding). By existing in an ordered microphase separated state, the curable composition has two or more separate domains, each having a different phase and having dimensions on the order of the microscale range. [Brief description of the drawings]

[0009] [Figure 1] 1 illustrates certain illustrative, non-limiting aspects of the present invention. [Diagram 2] 1 illustrates certain illustrative, non-limiting aspects of the present invention. [Diagram 3] 1 illustrates certain illustrative, non-limiting aspects of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] 1, 2 and 3 are representative embodiments of the present invention in which a first reactive component and a second reactive component, which are typically not fully compatible with each other, are mixed with a block copolymer to provide a curable composition that exists in an ordered microphase separated state at 25° C., and, for comparison purposes, a similar monomer mixture that does not contain the block copolymer.

[0011] The compounds present in the reactive component may contain one or more functional groups or moieties per molecule that are capable of reacting (e.g., through a polymerization reaction) when the curable composition is cured. In one embodiment, all reactive compounds are monofunctional, i.e., they each contain only one such functional group or moiety per molecule. However, in other embodiments, the curable composition includes both monofunctional and polyfunctional reactive compounds (compounds that contain two or more reactive functional groups per molecule). Increasing the ratio of polyfunctional reactive compounds to monofunctional reactive compounds in the curable composition typically tends to increase the amount of crosslinking (crosslink density) achieved in the cured composition.

[0012] Each reactive component may be comprised of a single reactive compound, where the reactive compound present in the first reactive component is different from the reactive compound present in the second reactive component, hi other embodiments, one or both of the reactive components may be comprised of two or more reactive compounds that are compatible with each other but incompatible as a mixture with the other reactive component.

[0013] Hydrophilic reactive components As mentioned above, the curable composition of the present invention may include a hydrophilic reactive component. The hydrophilic reactive component is composed of one or more hydrophilic reactive compounds, which may be reactive monomers and / or reactive oligomers. For example, the hydrophilic reactive component may be composed of at least one hydrophilic monomer selected from the group consisting of hydrophilic epoxides, hydrophilic oxetanes, hydrophilic vinyl compounds, hydrophilic (meth)acrylamides, and hydrophilic (meth)acrylate functional compounds (particularly preferred). As used herein, the term "(meth)acrylate" refers to both acrylate (-OC(=O)-CH=CH2) and methacrylate (-OC(=O)-C(CH3)=CH2) functional groups.

[0014] As used herein, the term "reactive" means that the compound contains at least one moiety capable of participating in a polymerization or curing reaction, whereby multiple reactive compound molecules become covalently bonded together to form a polymeric structure. Suitable reactive moieties include sites of ethylenic unsaturation (i.e., carbon-carbon double bonds, C=C). Such sites of ethylenic unsaturation can be provided, for example, by (meth)acryloyl, maleyl, allyl, propenyl and / or vinyl groups. As used herein, the term "(meth)acryloyl" is intended to encompass both methacryloyl and acryloyl.

[0015] The reactive compound may be rendered hydrophilic, typically by containing one or more polar functional groups and / or one or more functional groups capable of participating in hydrogen bonding, such as, for example, hydroxyl groups, carboxylic acid groups, oxyethylene groups, carboxyl (ester) groups, amide groups, etc., and the proportion of such functional groups relative to the total number of carbon atoms in the reactive compound is relatively high.

[0016] According to certain aspects of the invention, the at least one hydrophilic monomer may be selected from the group consisting of acetoxyethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, phosphate (meth)acrylate monomers (e.g., phosphate esters of hydroalkyl (meth)acrylates), mono-(2-(meth)acryloyloxyethyl)succinate, lactone and lactam (meth)acrylates (e.g., those obtained by reacting a hydroxyalkyl (meth)acrylate with one or more (e.g., 1-10) caprolactone or caprolactam equivalents), (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-vinylformamide, (meth)acryloylmorpholine, and diacetone (meth)acrylamide.

[0017] For example, at least one hydrophilic reactive component may comprise at least one half ester, which is a reaction product of a hydroxyalkyl (meth)acrylate with a dicarboxylic acid or a carboxylic anhydride, in which only one of the two carboxyl groups of the dicarboxylic acid or the carboxylic anhydride is esterified. The hydroxyalkyl (meth)acrylate may be selected, for example, from the group consisting of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, and alkoxylated hydroxyalkyl (meth)acrylate (e.g., a hydroxyalkyl (meth)acrylate reacted with one or more epoxide equivalents, such as ethylene oxide or propylene oxide). The dicarboxylic acid or the carboxylic anhydride may be selected, in an exemplary embodiment of the present invention, from the group consisting of succinic acid, succinic anhydride, malonic acid, methylsuccinic acid, and methylsuccinic anhydride. According to a particular aspect of the present invention, at least one hydrophilic reactive component comprises a half ester, which is a reaction product of hydroxyethyl acrylate with succinic acid.

[0018] Suitable hydrophilic reactive monomers can be considered "half esters" of formula (I): HO-C(=O)-R 1 -C(=O)-OR 2-OC(=O)CR 3 =CH2(I) where R 3 is H or CH3, R 1 and R 2 are the same or different and are divalent organic moieties each containing 1, 2, or more carbon atoms; R 1 and R 2 and R preferably contain a total of 10 or less, or 8 or less, carbon atoms. For example, R 1 may be C1-C4 alkylene, for example -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)- or -CH2CH2CH2CH2-, R 2 may be a C2-C4 alkylene, for example -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)- or -CH2CH2CH2CH2-.

[0019] As mentioned above, the ethylenically unsaturated functional groups suitable for use in the present invention include functional groups containing at least one carbon-carbon double bond, particularly functional groups containing a carbon-carbon double bond capable of participating in a reaction (e.g., a free radical reaction) in which at least one carbon of the carbon-carbon double bond becomes covalently bonded to an atom, particularly a carbon atom, in a second molecule. Such a reaction can result in polymerization or curing, whereby the compound containing one or more ethylenically unsaturated functional groups becomes part of a polymerized matrix or polymer chain. The carbon-carbon double bond may be present, for example, as part of an α,β-unsaturated carbonyl moiety, for example, as an α,β-unsaturated ester moiety, such as an acrylate functional group (HC=CH-C(=O)O-) or a methacrylate functional group (HC=C(CH3)-C(=O)O-). Carbon-carbon double bonds may also be present in ethylenically unsaturated functionalities in the form of vinyl groups -CH=CH2 or allyl groups (-CH2-CH=CH2).

[0020] Additional examples of suitable hydrophilic (meth)acrylate functional compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, alkoxylated (e.g., ethoxylated) hydroxyethyl (meth)acrylate and alkoxylated (e.g., ethoxylated) hydroxypropyl (meth)acrylate, N-(meth)acryloylmorpholine, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, triethylene glycol monomethyl ether mono(meth)acrylate, polyethoxyethyl (meth)acrylate, (meth)acrylic acid, maleic acid, half esters of maleic anhydride, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol mono(meth)acrylate, glycerol ... glycidyl ethers of phenols (e.g., cresol) and bisphenols (e.g., bisphenol A), glycidyl ethers of C2-C8 aliphatic alcohols (e.g., monoalcohols and polyols such as butanediol and trimethylolpropane).

[0021] In one embodiment, the hydrophilic (meth)acrylate functional compound is a polyethylene glycol monoacrylate or a mixture of polyethylene glycol monoacrylates. Such polyethylene glycol monoacrylates have the structural formula H2C=CHC(=O)(OCH2CH2) n OH, where n is an integer from 2 to 30 (eg, 4 to 12).

[0022] Examples of suitable hydrophilic epoxides include glycidyl ethers, such as 2-hydroxyethyl glycidyl ether, hydroxypropyl glycidyl ether, alkoxylated (e.g., ethoxylated) hydroxyethyl glycidyl ether, alkoxylated (e.g., ethoxylated) hydroxypropyl glycidyl ether, and the like; glycidyl ethers of polyalkylene glycols, such as polyethylene glycol and polypropylene glycol; glycidyl ethers of polyalkylene glycol monoethers, such as polyethylene glycol monomethyl ether, 2-(2-ethoxyethoxy)ethyl glycidyl ether, triethylene glycol monomethyl ether monoglycidyl ether, and the like; polyethoxyethyl glycidyl ethers, triethylene glycol monomethyl ether monoglycidyl ether, and the like; These include, but are not limited to, glycidyl ethers of methylolpropane and trimethylolethane, such as trimethylolpropane monoglycidyl ether, glycidyl ethers of pentaerythritol, such as pentaerythritol monoglycidyl ether, glycidyl ethers of dipentaerythritol, such as dipentaerythritol monoglycidyl ether, glycidyl ethers of glycerol, such as glycerol monoglycidyl ether, glycidyl ethers of neopentyl glycol, such as neopentyl glycol monoglycidyl ether, glycidyl ethers of sugars and sugar alcohols, urethane glycidyl ethers (both monomers and oligomers), and glycidyl (meth)acrylate.

[0023] Examples of suitable hydrophilic oxetanes include oxetanyl methanol ethers, such as 2-hydroxyethyl oxetanyl methanol ether, hydroxypropyl oxetanyl methanol ether, alkoxylated (e.g., ethoxylated) hydroxyethyl oxetanyl methanol ether and alkoxylated (e.g., ethoxylated) hydroxypropyl oxetanyl methanol ether, 2-(2-ethoxyethoxy)ethyl oxetanyl methanol ether, triethylene glycol monomethyl ether monooxetanyl methanol ether, polyethoxyethyl oxetanyl methanol ether, trimethylolpropane monooxetanyl methacrylate, and urethane oxetanyl methanol ethers (both monomers and oligomers), as well as hydroxyl and carboxylic acid functionalized oxetanes, such as, but not limited to, 3-hydroxyoxetane, oxetane-3-carboxylic acid, oxetane-3-methanol, 3-ethyl-3-hydroxymethyloxetane, and 3-hydroxymethyl-3-methyloxetane.

[0024] Examples of suitable hydrophilic vinyl compounds include, but are not limited to, allyl alcohol, ethylene glycol vinyl ether (2-hydroxyethyl vinyl ether), alkoxylated (e.g., ethoxylated) allyl alcohol, trimethylolpropane monoallyl ether, hydroxypolyethoxyallyl ether, N-vinyl-N-methylacetamide, vinyl phosphonic acid, diethyl vinyl phosphonic acid, phenyl vinyl phosphonic acid, dimethyl vinyl phosphonic acid, di-n-butyl vinyl phosphonic acid, di-isobutyl vinyl phosphonic acid, di-isopropyl vinyl phosphonic acid, 2-aminoethyl vinyl ether, methyl vinyl ether, 2-acetoxyethyl vinyl ether, vinyl pyrrolidone, vinyl caprolactam, and the like.

[0025] Examples of suitable hydrophilic (meth)acrylamides include, but are not limited to, N-iso-propylacrylamide, N-(2-hydroxypropyl)(meth)acrylamide, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and diacetone(meth)acrylamide.

[0026] Examples of suitable phosphate ester (meth)acrylate monomers include those represented by the following formula (II): H2C=CR 1 C(=O)-(-O-(-CR 2 R 3 ) m ) n -OP(=O)(OH)2(II) Examples of compounds include, but are not limited to, compounds corresponding to the formula: 1 is hydrogen or a methyl group, R 2 and R 3 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and m and n independently represent an integer of 1 to 20. Specific examples of suitable phosphate (meth)acrylate monomers include 2-(meth)acryloxyethyl phosphate, 3-(meth)acryloxypropyl phosphate, 2-(meth)acryloxypropyl phosphate, 4-(meth)acryloxybutyl acrylate, diethylene glycol (meth)acrylate phosphate, triethylene glycol (meth)acrylate phosphate, and polyethylene glycol (meth)acrylate phosphate.

[0027] Hydrophobic reactive components As mentioned above, the hydrophobic reactive component is selected to be a reactive compound or mixture of reactive compounds that is not sufficiently compatible with the hydrophilic reactive component at 25° C. in the absence of the block copolymer (i.e., when the components are mixed, the hydrophobic reactive component visibly phase separates from the hydrophilic reactive component). Typically, the hydrophobic reactive component is less polar than the hydrophilic reactive component, but may contain one or more polar functional groups, such as ester groups. In general, the hydrophobicity of the reactive compound can be increased, for example, by including long chain alkyl groups, C5+ alicyclic and / or aromatic rings, and / or by increasing the ratio of total carbon atoms to polar and / or active hydrogen-containing functional groups (e.g., hydroxyl groups, carboxylic acid groups, oxyethylene groups, carboxyl (ester) groups, etc.).

[0028] According to a particular embodiment of the present invention, at least one hydrophobic reactive component comprises at least one C4-C 24 (Meth)acrylate esters of aliphatic mono-alcohols (i.e., C4-C esters esterified with acrylic acid or methacrylic acid) 24 The cycloalkyl group may include aliphatic mono-alcohols). The aliphatic mono-alcohols may be linear or branched in structure. The aliphatic mono-alcohols may be composed of one or more alicyclic rings. The cycloalkyl group may be a monocyclic alkyl group, such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group, or a (substituted or unsubstituted) polycyclic alkyl group, such as an isobornyl group or a tricyclodecyl group. Suitable polycyclic alkyl groups include polycyclic alkyl groups having fused ring systems, polycyclic alkyl groups having bridged ring structures, and polycyclic alkyl groups having both fused ring systems and bridged rings.

[0029] The hydroxyl group of the aliphatic mono-alcohol may be directly substituted on the alicyclic ring or may be substituted on a non-alicyclic organic moiety (e.g., -CH2-) attached to the alicyclic ring. The hydroxyl group of the aliphatic mono-alcohol may be a primary, secondary or tertiary hydroxyl group. In one embodiment of the present invention, the aliphatic mono-alcohol is saturated.

[0030] Examples of suitable aliphatic mono-alcohols include, but are not limited to, n-butanol, sec-butyl alcohol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 3-methyl-3-pentanol, pelargonic alcohol, 1-decanol, aliphatic alcohols (e.g., lauryl alcohol, stearyl alcohol, undecyl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, nonadecyl alcohol, 1-eicosanol, 1-heneicosanol), cyclohexanol, 4-tert-butyl-cyclohexanol, cyclohexaneethanol, cyclohexanemethanol, 4-methylcyclohexanemethanol, menthol, 2-ethoxyethanol, isobornyl alcohol, 2-methyl-2-butanol, 3-methylbutanol, 2-methyl-1-propanol, and the like.

[0031] According to another aspect of the invention, at least one hydrophobic reactive component is a C4-C 24 Contains alkyl acrylate.

[0032] Aromatic (meth)acrylates, including alkylated aromatic (meth)acrylates and aralkyl (meth)acrylates, are also suitable for use in or as the hydrophobic reactive component.

[0033] Alicyclic (meth)acrylates represent another type of (meth)acrylate-functional compound useful as a hydrophobic reactive monomer in the present invention. As used herein, the term "alicyclic (meth)acrylate" refers to a compound that contains at least one alicyclic moiety per molecule and an acrylate or methacrylate functional group that can be directly or indirectly (e.g., through an alkylene group such as -CH2- or -CH2CH2-) bonded to the alicyclic moiety. The alicyclic moiety can be cyclopentyl, cyclohexyl, cyclooheptane, cyclooctyl, etc., can be monocyclic or polycyclic, and / or can be substituted with one or more other groups, such as linear or branched alkyl groups.

[0034] Illustrative examples of compounds suitable for use in the hydrophobic reactive component are n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, 3-methyl-3-pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-amyl (meth)acrylamide, pelargonyl (meth)acrylate, 1-decyl (meth)acrylate, isodecyl (meth)acrylate, aliphatic (meth)acrylates (e.g., lauryl (meth)acrylate, stearyl (meth)acrylate, undecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, hexadecyl (meth)acrylate, nonadecyl (meth)acrylate, 1-eicosanyl (meth)acrylate, 1-heneicosanyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexaneethyl (meth)acrylate, cyclohexanemethyl (meth)acrylate, 4-methylcyclohexanemethyl (meth)acrylate, menthyl (meth)acrylate, isobornyl (meth)acrylate, 2-methyl-2-butanol, 3-methylbutyl (meth)acrylate, 2-methyl-1-propyl (meth)acrylate, phenyl (meth)acrylate, 2-naphthyl (meth)acrylate, benzyl (meth)acrylate, alkylphenyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and the like, and combinations thereof.

[0035] The hydrophobic reactive component may include or be a vinyl aromatic compound, particularly a vinyl aromatic compound that does not have any polar substituents on the aromatic ring. The aromatic ring (e.g., phenyl or naphthenyl ring) may be substituted with one or more alkyl groups, etc. Examples of suitable hydrophobic vinyl aromatic compounds include styrene, α-methylstyrene, vinylnaphthalene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, and 4-tert-butylstyrene, divinylbenzene, vinyltoluene, etc.

[0036] Vinyl alicyclic compounds (e.g., vinylcyclohexane) and long chain olefins (e.g., C6-C such as 1-decene) 24 Olefins) may be used as or in the hydrophobic reactive component.

[0037] In the present invention, hydrophobic (meth)acrylamides, particularly those having relatively long chain alkyl groups substituted on the nitrogen atom, such as C6-C 24 (Meth)acrylamides containing alkyl groups (which may be, for example, linear or branched) may also be used. Hydrophobic (meth)acrylamides suitable for use in the present invention include, but are not limited to, N-(n-decyl)(meth)acrylamide, N-(n-octadecyl)(meth)acrylamide, N-(n-dodecyl)(meth)acrylamide, N-tert-octyl(meth)acrylamide, and the like.

[0038] Amounts of First and Second Reactive Components The relative amounts of the first (e.g., hydrophilic) reactive component and the second (e.g., hydrophobic) reactive component in the curable composition can be easily varied and controlled as desired to obtain a particular ordered structure in the cured composition or in the cured article obtained by curing the curable composition. The curable composition can be, for example, comprised of 10 to 90% by weight of the first (e.g., hydrophilic) reactive component and 90 to 10% by weight of the second (e.g., hydrophobic) reactive component, based on the total weight of the first (e.g., hydrophilic) reactive component and the second (e.g., hydrophobic) reactive component.

[0039] Varying the relative ratios of the first and second reactive components can affect the type of phase structure obtained within the composition when it is cured. For example, the morphology of one phase in the cured composition can be characterized as dispersed spheres, cylinders, galloids, or lamellae, depending on the ratio of the first reactive component to the second reactive component.

[0040] Block Copolymers The curable composition of the present invention comprises at least one block copolymer. Without wishing to be bound by theory, it is believed that the block copolymer assists in the formation of an ordered nanostructured polymer matrix when the incompatible first and second reactive components are cured. The first reactive component may preferentially bind ("solvate") with one of the blocks present in the block copolymer, while the second reactive component may preferentially bind ("solvate") with another of the blocks present in the block copolymer. As a result, the concentration of the first reactive component in a region adjacent to the first block of the block copolymer may be higher than the concentration of the second reactive component in the same region. Similarly, the concentration of the second reactive component in a region adjacent to the second block of the block copolymer (having a different monomer composition than the first block) may be higher than the concentration of the first reactive component in the same region. Thus, the block copolymer may assist in pre-assembling the reactive components in a region in the liquid phase where the affinity (i.e., tendency to bind) corresponding to each type of block and where binding occurs. As an example, in a region where a first reactive component is more hydrophilic than a second reactive component and the block copolymer contains a first block that is more hydrophilic than the second block, the first reactive component will tend to associate more strongly with the first block, while the second reactive component will tend to associate more strongly with the second block. The block copolymer may thus be thought of as functioning in a manner similar to that of a surfactant or soap, with a hydrophilic end that binds strongly with the water phase and a hydrophobic end that binds strongly with the oil phase.

[0041] In certain embodiments, the curable composition is composed of at least one of a diblock copolymer or a triblock copolymer. The structure of the block copolymer can be selected such that the block copolymer comprises two different types of blocks, one type of block having a higher affinity for the first reactive component (e.g., hydrophilic reactive component) than for the second reactive component (e.g., hydrophobic reactive component), and the other type of block having a higher affinity for the second reactive component than for the first reactive component. Thus, when the first reactive component, the second reactive component, and the block copolymer are mixed to form a mixture, the first reactive component can bond to a greater extent with one block of the block copolymer, while the second reactive component can bond to a greater extent with the other block of the block copolymer. Each type of block present in the block copolymer can have a glass transition temperature different from the glass transition temperature of the other type of block. The at least one block copolymer may, for example, comprise at least one block having a glass transition temperature of at least 25° C. and at least one block having a glass transition temperature below 25° C. In other embodiments, the at least one block copolymer may comprise at least one block having a glass transition temperature of at least 50° C. and at least one block having a glass transition temperature below −25° C. “Tg” means the glass transition temperature of the polymer as measured by differential scanning calorimetry (DSC) according to standard ASTM E1356.

[0042] According to various preferred embodiments, the at least one block copolymer comprises at least one block copolymer selected from the group consisting of: a) block copolymers constituted by at least one poly(n-butyl acrylate) block and at least one poly(methyl methacrylate) block, b) block copolymers constituted by at least one polystyrene block and at least one polybutadiene block, and c) block copolymers constituted by at least one polystyrene block and at least one polyisoprene block.

[0043] The overall molecular weight of the block copolymer is not believed to be particularly important. For example, at least one block copolymer may have a number average molecular weight (measured by gel permeation chromatography (GPC)) of 3,000 to 200,000 daltons using polystyrene standards. The polydispersity of the block copolymer may be, for example, 1 to 2, 1 to 1.5, or 1 to 1.3.

[0044] According to one embodiment of the present invention, the curable composition comprises at least one thermoplastic acrylic block copolymer. For example, the curable composition may be represented by the general formula (A): nThe block A may be constituted by at least one thermoplastic acrylic block copolymer having a Tg of less than 20° C. and preferably a methacrylic homopolymer or copolymer having a Tg of more than 50° C., preferably more than 80° C., or a polystyrene or an acrylic / styrene or methacrylic / styrene copolymer. Preferably, A is methyl methacrylate, phenyl methacrylate, benzyl methacrylate or isobornyl methacrylate. Preferably, block A is PMMA or PMMA modified by an acrylic or methacrylic comonomer, and B is an acrylic or methacrylic homopolymer or copolymer having a Tg of less than 20° C., preferably consisting of (in polymerized form) methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or butyl methacrylate, more preferably butyl acrylate.

[0045] Additionally, blocks A and / or B can include other acrylic or methacrylic comonomers with various functional groups known to those skilled in the art, such as acid, amide, amine, hydroxyl, epoxy or alkoxy functional groups. The A block can incorporate monomers such as acrylic acid or methacrylic acid to enhance temperature stability.

[0046] According to various preferred embodiments, the block copolymer may have a structure selected from ABA, AB, A3B2 and A4B3, where A3B2 and A4B3 may have a linear, radial or branched type structure.

[0047] Preferably, the thermoplastic acrylic block copolymer may be selected from the following triblock copolymers: pMMA-pBuA-pMMA, p(MMAcoMAA)-pBuA-p(MMAcoMAA) and p(MMAcoAA)-pBuA-p(MMAcoAA), where MMA=methyl methacrylate, BuA=butyl acrylate, MAA=methacrylic acid, AA=acrylic acid. In one embodiment, the block copolymer is of the type MAM (PMMA-pBuA-PMMA).

[0048] In certain embodiments of the invention, the block copolymer comprises at least one relatively hydrophilic block (e.g., a polyethylene oxide block, a polyhydroxyethyl(meth)acrylate block, a poly(N,N-dimethylacrylamide) block, or a block prepared from one or more of the hydrophilic monomers previously mentioned in connection with the reactive components), and at least one less hydrophilic block (e.g., a polystyrene block, a polycyclohexane block, or a block prepared from one or more of the hydrophobic monomers previously mentioned in connection with the reactive components).

[0049] The components of the curable composition in various embodiments of the present invention may be selected such that the curable composition is comprised of at least a first block and a second block, the first reactive component being comprised of at least one monomer corresponding to at least one monomer present in the polymerized form of the first block, and the second reactive component being comprised of at least one monomer present in the polymerized form of the second block, the first block and the second block having different monomer compositions. In further embodiments, the curable composition is comprised of at least a first block and a second block, the first reactive component being comprised of at least one monomer corresponding to at least one monomer present in the polymerized form of the first block, and the second reactive component being comprised of at least one monomer different from at least one monomer present in the polymerized form of the first block.

[0050] According to certain embodiments, block B may represent 25% to 75%, e.g., 40% to 65%, of the total weight of the block copolymer (wherein, in certain embodiments, block A represents the remainder of the total weight of the block copolymer). Each block B may have, for example, a number average molecular weight of 5,000 g / mol to 200,000 g / mol, e.g., 10,000 g / mol to 50,000 g / mol. The number average molecular weight of each block A may be in such range as well, although the number average molecular weights of blocks A and B may be similar to or different from each other.

[0051] In one embodiment of the invention, the curable composition comprises a PMMA-pBuA-PMMA block copolymer, where each PMMA block has a number average molecular weight of 5000-10,000 g / mol and the pBuA block has a number average molecular weight of 10,000-20,000 g / mol.

[0052] Other types of suitable block copolymers include polyethylene oxide / polypropylene oxide / polyethylene oxide (PEO / PPO / PEO) block copolymers, polyethylene oxide / polypropylene oxide (PEO / PPO) block copolymers, polypropylene oxide / polyethylene oxide / polypropylene oxide (PPO / PEO / PPO) block copolymers, polystyrene / polyethylenebutylene / polystyrene (PS / PEB / PS) block copolymers, polystyrene / polybutadiene / polystyrene (PS / PB / PS) block copolymers, polystyrene / polyethylene oxide (PS / PEO) block copolymers, polyethylene / polyethylene oxide block copolymers, polydimethylacrylamide / poly Examples of block copolymers include, but are not limited to, tributyl acrylate / polydimethylacrylamide block copolymers, segmented polyurethanes (having a plurality of relatively hydrophilic segments, e.g., polyether segments, and a plurality of relatively hydrophobic segments, e.g., urethane segments), poly(dimethylsiloxane / polycaprolactone / polydimethylsiloxane block copolymers, polyamide / polyether block copolymers, polyether / polyester block copolymers, polylactic acid / polyethylene oxide block copolymers, poly(lactide-co-glycolide) / polyethylene oxide block copolymers, polycaprolactone / polyethylene oxide block copolymers, polyethylene oxide / silicone block copolymers, and the like.

[0053] Block copolymers suitable for use in the present invention can be readily prepared using conventional methods known in the art, such as controlled radical polymerization (CRP) or anionic polymerization, or obtained from commercial sources, such as block copolymers sold under the trade name "Nanostrength" from the Arkema Group.

[0054] In various embodiments of the present invention, the curable composition comprises an amount of block copolymer effective to provide a homogeneous and stable curable composition. For example, the amount of block copolymer can be sufficient to provide a curable composition that does not exhibit bulk phase separation of the first (e.g., hydrophilic) and second (e.g., hydrophobic) reactive components at 25° C. after 7 days. According to certain aspects, the curable composition can be comprised of 1 to 40 wt %, or 2 to 20 wt %, of the block copolymer, based on the total weight of the curable composition.

[0055] The curable composition may consist of a first (e.g., hydrophilic) reactive component, a second (e.g., hydrophobic) reactive component, and a block copolymer, without the presence of other types of components. However, in other embodiments, the curable composition may additionally include one or more additional components, as described below. According to certain embodiments, the curable composition may include 0-50 wt%, 0-25 wt%, 0-10 wt%, 0-5 wt%, or 0-1 wt%, based on the total weight of the curable composition, of components other than the first (e.g., hydrophilic) reactive component, the second (e.g., hydrophobic) reactive component, and the block copolymer.

[0056] Photoinitiators When light, such as ultraviolet light, is used to cure the curable composition, it will usually be desirable to formulate the composition to include one or more photoinitiators, however, when electron beam curing or chemical curing is used, the curable composition does not need to contain any photoinitiators.

[0057] Photoinitiators are compounds that undergo a photochemical reaction upon absorption of light to generate reactive species. The generated reactive species then initiate the polymerization of the reactive components of the curable composition, such as the first (e.g., hydrophilic) reactive component and the second (e.g., hydrophobic) reactive component. Generally, when the compounds present in the reactive components contain carbon-carbon double bonds, such polymerization (curing) involves the reaction of such carbon-carbon double bonds. In various embodiments of the present invention, the reactive species may be, for example, a free radical species or anionic species. Suitable photoinitiators include, for example, α-hydroxyketones, phenylglyoxylic acid, benzil dimethyl ketal, α-aminoketones, mono-acylphosphines, bis-acylphosphines, metallocenes, phosphine oxides, benzoin ethers, and benzophenones, and combinations thereof.

[0058] Specific examples of suitable photoinitiators include 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2 benzyanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2 Diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, acetylnaphthalene, ethyl-p-dimethylaminobenzoate, benzyl ketone, α-hydroxyketo, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyl dimethyl ketal, benzyl ketal (2,2-dimethoxy-1,2-diphenylethanone), 1-hydroxycyclohexyl phenyl ketone (hydroxycylclohexyl phenyl ketone), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propanone, oligomeric α-hydroxyketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-4-dimethylaminobenzoate, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzyl, Benzoin Isobutyl Ether, 50 / 50 Blend of Benzophenone / 1-Hydroxycyclohexyl Phenyl Ketone, 3,3',4,4'-Benzophenonetetracarboxylic Dianhydride, 4-Benzoylbiphenyl, 2-Benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-Bis(diethylamino)benzophenone, 4,4'-Bis(dimethylamino)benzophenone, Camphorquinone, 2-Chlorothioxanthen-9-one, Dibenzosuberenone, 4,4'-Dihydroxybenzophenone, 2,2-Dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzyl, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide oxide), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one, and combinations thereof.

[0059] Exemplary combinations of suitable photoinitiators include a blend of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and a blend of 2-hydroxy-2-methyl-1-phenyl-1-propanone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0060] Also useful in the present invention are organometallic titanocene photoinitiators such as Irgacure® 784 bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

[0061] When photoinitiators are used in the curable composition, they can typically be present in a total concentration of up to about 15% by weight, based on the total weight of the curable composition (e.g., a concentration of about 0.1 to about 5% by weight, based on the total weight of the curable composition).

[0062] Inorganic Nanoparticles The curable compositions of the present invention may additionally include one or more types of inorganic nanoparticles, which may or may not contain an organic component (e.g., organically modified inorganic nanoparticles). Such inorganic nanoparticles may be dispersed in one or both of the first (e.g., hydrophilic) reactive component or the second (e.g., hydrophobic) reactive component. Suitable types of inorganic nanoparticles include, for example, silica nanoparticles, alumina nanoparticles, iron oxide nanoparticles, niobia nanoparticles, titania nanoparticles, mixed oxide nanoparticles (e.g., silica / alumina nanoparticles), metal nanoparticles, alloy nanoparticles, zirconia nanoparticles, clay nanoparticles (such as organically modified clay nanoparticles and / or intercalated clay nanoparticles), graphene, and combinations thereof. Inclusion of inorganic nanoparticles in the curable composition and curing such inorganic nanoparticle-containing curable compositions can result in the production of ordered hybrid inorganic polymer composites.

[0063] Candidate inorganic nanoparticles may be defined by their chemical nature as described above, but also by their physical dimensions measured in one of many dimensions, depending on the general geometry of the particle in question. Typical three-dimensional spherical-like particles, such as silica, may be defined by measuring the particle diameter from one edge, perpendicularly through the center of the particle to the opposite edge of the particle. In the case of faceted, dendritic or otherwise geometrically shaped particles, the diameter may be defined by measuring from one facet surface or apex, perpendicularly through the center of the particle to the opposite surface or apex. Where multiple nanoparticles may be aggregated into larger structures, the present description relates to the smallest three-dimensional subunit of such aggregates. For application in the present invention, three-dimensional nanoparticles will have diameters as previously described, ranging from 0.5 nm to 1000 nm, preferably 1.0 to 200 nm, and most preferably 1.0 to 100 nm.

[0064] In the case of sheet-like two-dimensional nanoparticles, the individual particles can be defined as likely to have a thickness of less than 1 nm, and their length and width dimensions can be relatively large, ranging from 1.0 nm to 100 μm, preferably 5.0 nm to 10 μm, and most preferably 10.0 nm to 5 μm. These types of materials usually exist as a stack of multiple "sheets" and can be separated into individual "sheets" or particles by various physical processes or chemical methods known in the art.

[0065] When inorganic nanoparticles are used in the curable composition, typically, the inorganic nanoparticles may be present in a total concentration of up to about 50% by weight, based on the total weight of the curable composition (e.g., a concentration of about 0.1 to about 25% by weight, based on the total weight of the curable composition).

[0066] Other Components of the Curable Composition The curable compositions of the present invention may optionally contain one or more additives instead of or in addition to the above-mentioned components. Such additives include, but are not limited to, antioxidants, UV absorbers, light stabilizers, foam inhibitors, flow control or leveling agents, colorants, pigments, dispersants (wetting agents), slip agents, fillers (other than or in addition to inorganic nanoparticles), thixotropic agents, matting agents, accelerators, adhesion promoters (such as acidic adhesion promoters), thermoplastics and other types of polymers (other than or in addition to the block copolymers mentioned above), waxes or various other additives, including any additives commonly used in coating, sealant, adhesive, molding or ink technology.

[0067] How to use The curable compositions of the present invention are useful as inks (for printing applications such as food packaging), molding resins, 3D printing resins, coatings (e.g., coatings for optical fibers and "soft touch" coatings), sealants and adhesives (e.g., UV curable laminating adhesives, UV curable hot melt adhesives), in addition to other potential applications.

[0068] Cured compositions prepared from the curable compositions described herein may be used, for example, in three-dimensional articles (the three-dimensional article can consist essentially of the cured composition or can consist of the cured composition), coated articles (wherein a substrate is coated with one or more layers of the cured composition), laminated or adhesive articles (wherein a first component of the article is laminated or adhered to a second component by the cured composition), or printed articles (wherein a graphic or the like is imprinted onto a substrate, e.g., a paper, plastic, or metal substrate, using the cured composition).

[0069] The curable compositions may be cured by free radical polymerization or other types of polymerization (eg, anionic or cationic polymerization).

[0070] Curing of the curable composition according to the present invention can be carried out by any suitable method, for example, free radical polymerization, cationic polymerization, and / or anionic polymerization. One or more initiators, such as radical initiators (e.g., photoinitiators, peroxide initiators), may be present in the curable composition. Prior to curing, the curable composition can be applied to the substrate surface by any known conventional method, for example, spraying, knife coating, roller coating, casting, drum coating, dipping, and the like, and combinations thereof. Indirect application using a transfer process can also be used. The substrate can be any commercially reasonable substrate, such as, for example, a high surface energy substrate or a low surface energy substrate, for example, a metal substrate or a plastic substrate, respectively. The substrate can include metal, paper, cardboard, glass, thermoplastics, such as, for example, polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof, composites, wood, leather, and combinations thereof. When used as an adhesive, the composition is placed between two substrates and then cured, whereby the cured composition bonds the substrates.

[0071] Curing may be accelerated or facilitated by providing energy to the composition, for example, by heating the composition and / or by exposing the composition to a radiation source, such as visible or ultraviolet, infrared and / or electron beam radiation. Thus, a cured composition may be considered a reaction product of a curable composition formed by curing.

[0072] The curable compositions of the present invention are particularly suitable for curing with LEDs (light emitting diodes) (e.g., UV LED curing, which uses radiation from a UV LED device) and for use in high speed applications (e.g., coatings).

[0073] Multiple layers of the composition according to the invention may be applied to a substrate surface. The multiple layers may be cured simultaneously (e.g., by exposure to radiation only once) or each layer may be cured sequentially before applying an additional layer of the composition.

[0074] The curable compositions described herein are particularly useful as 3D printing resin formulations, i.e., compositions for use in producing three-dimensional articles using 3D printing technology. Such three-dimensional articles may be free-standing / self-supporting and may consist essentially of the cured curable composition or may consist of the cured curable composition. The three-dimensional article may also be a composite comprising at least one component that consists essentially of or consists of the cured composition as described above, and at least one additional component that consists of one or more materials other than such cured composition (e.g., a metal part or a thermoplastic part).

[0075] The method for producing a three-dimensional article using the curable composition according to the present invention comprises the steps of: a) coating a first layer of a curable composition according to the present invention onto a surface; b) curing the first layer to provide a first cured layer; c) coating a second layer of a curable composition onto the first cured layer; d) curing the second layer to provide a second cured layer adhered to the first cured layer; and e) repeating steps c) and d) as many times as desired to build the three-dimensional article.

[0076] The curing step may be carried out by any suitable means, but in some cases will depend on the components present in the curable composition, and in certain embodiments of the present invention, curing is achieved by exposing the layer to be cured to an effective amount of radiation (e.g., electron beam radiation, ultraviolet radiation, visible light, etc.).

[0077] Thus, in various embodiments, the present invention provides a method for treating a cancer cell comprising: a) coating a first layer of a curable composition according to the present invention in liquid form onto a surface; b) imagewise exposing the first layer to actinic radiation to form a first exposed imaged cross-section, the radiation being of sufficient intensity and duration to cause at least partial curing (e.g., at least 80% or at least 90% curing) of the layer in the exposed areas; c) coating an additional layer of a curable composition onto the previously exposed imaged cross section; d) imagewise exposing the additional layer to actinic radiation to form an additional imaged cross section, the radiation being of sufficient intensity and duration to cause at least partial curing (e.g., at least 80% or at least 90% curing) in the additional layer in the exposed areas and to cause adhesion of the additional layer to the previously exposed imaged cross section; e) repeating steps c) and d) as many times as desired to build the three-dimensional article. The present invention provides a process comprising the steps of:

[0078] According to one aspect of the invention, the block copolymer is a triblock copolymer of the general structure ABA, where the terminal A blocks have a relatively high glass transition temperature (e.g., ≧50° C.), the central B block has a relatively low glass transition temperature (e.g., ≦0° C.), the hydrophilic or hydrophobic reactive component has a higher affinity for the terminal A blocks than the central B blocks and, upon polymerization, produces a polymer with a relatively high glass transition temperature (e.g., ≧50° C.), and the other reactive component has a higher affinity for the central B blocks than the terminal A blocks and, upon polymerization, produces a polymer with a relatively low glass transition temperature (e.g., ≦0° C.). Such curable compositions are expected to be useful, for example, in the manufacture of reinforced, rigid 3D printed products, structural adhesives, and impact resistant films.

[0079] In another aspect of the invention, the block copolymer is a triblock copolymer of the general structure ABA, where the terminal A blocks have a relatively low glass transition temperature (e.g., ≦0° C.), the central B block has a relatively high glass transition temperature (e.g., ≧50° C.), a hydrophilic or hydrophobic reactive component has a higher affinity for the terminal A blocks than the central B blocks and, upon polymerization, produces a polymer with a relatively low glass transition temperature (e.g., ≦0° C.), and the other reactive component has a higher affinity for the central B blocks than the terminal A blocks and, upon polymerization, produces a polymer with a relatively high glass transition temperature (e.g., ≧50° C.). Such curable compositions are expected to be useful, for example, in the production of reinforced elastomeric 3D printed products or packaging adhesives.

[0080] In yet another embodiment of the present invention, the cured composition contains hydrophobic phases or regions as a result of using reactive components comprised of one or more hydrophilic monomers, and the hydrophilic phases or regions are capable of absorbing and retaining water, thereby acting as a sacrificial material.

[0081] According to another aspect, the microphase separated structure achieved by curing the curable compositions of the present invention can increase the fracture of the cured compositions, thereby providing a more tear resistant material.

[0082] In yet other embodiments, components of the hardenable composition may be selected to provide a hydrophilic phase in the hardenable composition that acts as a carrier for the ceramic, e.g., a ceramic dispersion that has been mixed with the hardenable composition.

[0083] The cured composition may also be subjected to further processing after curing to change the properties of the cured composition. For example, if the cured composition contains both hydrophilic and hydrophobic phases, a coating composed of the cured composition may be formed on a substrate surface, after which an etching step may be performed, whereby at least a portion of the hydrophilic phase is selectively removed, leaving behind the hydrophobic phase. Thus, it is believed that etching can change the surface texture and surface feel of the coating, thereby creating a "soft-touch" coating with more favorable or desirable tactile properties.

[0084] Exemplary Aspects of the Invention Various non-limiting aspects of the present invention can be summarized as follows.

[0085] Aspect 1: A curable composition, which exists in an ordered microphase separated state at 25° C., a) a block copolymer comprising at least a first block and a second block, the first block and the second block having different monomer compositions; b) a first reactive component that has a higher affinity for the first block of the block copolymer than for the second block of the block copolymer; c) a second reactive component that has a higher affinity for the second block of the block copolymer than for the first block of the block copolymer; A curable composition consisting of, consisting essentially of, or consisting of, wherein the first reactive component and the second reactive component are not completely compatible with each other at 25° C. in the absence of the block copolymer.

[0086] Aspect 2: The curable composition of aspect 1, wherein the first reactive component is comprised of one or more hydrophilic monomers and the second reactive component is comprised of one or more hydrophobic monomers.

[0087] Aspect 3: The curable composition of aspect 1 or 2, wherein the first reactive component is comprised of, consists essentially of, or consists of at least one hydrophilic monomer selected from the group consisting of hydrophilic epoxides, hydrophilic oxetanes, hydrophilic vinyl compounds, hydrophilic acrylamides, and hydrophilic (meth)acrylate functional compounds.

[0088] Aspect 4: The curable composition of any of Aspects 1-3, wherein the first reactive component is comprised of, consists essentially of, or consists of at least one hydrophilic monomer selected from the group consisting of hydrophilic (meth)acrylate functional compounds.

[0089] Aspect 5: The curable composition of any of Aspects 1-4, wherein the first reactive component is composed of, consists essentially of, or consists of at least one hydrophilic monomer selected from the group consisting of acetoxyethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, phosphate (meth)acrylate monomer, mono-(2-(meth)acroyloxyethyl)succinate, lactone (meth)acrylate, lactam (meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, (meth)acryloylmorpholine, N-vinylformamide, polyethylene glycol (meth)acrylate, and diacetone (meth)acrylamide.

[0090] Embodiment 6: The curable composition of embodiment 4, wherein the at least one hydrophilic monomer comprises, consists essentially of, or consists of a half ester that is the reaction product of a hydroxyalkyl (meth)acrylate or an alkoxylated hydroxyalkyl (meth)acrylate with a dicarboxylic acid or a carboxylic acid anhydride.

[0091] Aspect 7: The curable composition of aspect 6, wherein the hydroxyalkyl (meth)acrylate is selected from the group consisting of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0092] Aspect 8: The curable composition of aspect 6 or 7, wherein the dicarboxylic acid or carboxylic acid anhydride is selected from the group consisting of succinic acid, succinic anhydride, malonic acid, methylsuccinic acid, and methylsuccinic anhydride.

[0093]

[0023] Embodiment 9: The curable composition of embodiment 6, wherein the at least one hydrophilic monomer comprises, consists essentially of, or consists of a half ester that is the reaction product of hydroxyethyl acrylate and succinic acid.

[0094] Aspect 10: The second reactive component is at least one C4-C 24 The curable composition of any of the preceding embodiments, comprising, consisting essentially of, or consisting of a (meth)acrylate ester of an aliphatic mono-alcohol.

[0095] Aspect 11: The second reactive component comprises at least one C4-C 24 11. The curable composition of any of embodiments 1-10, comprising, consisting essentially of, or consisting of an alkyl acrylate.

[0096] Aspect 12: The second reactive component is an aromatic (meth)acrylate, an alicyclic (meth)acrylate, a vinyl aromatic compound, a vinyl alicyclic compound, a C6-C 24 Olefins and C6-C 24 11. The curable composition of any of embodiments 1-10, comprising, consisting essentially of, or consisting of at least one hydrophobic reactive compound selected from the group consisting of (meth)acrylamides containing an alkyl group.

[0097]

[0033] Embodiment 13: The curable composition of any of embodiments 1-12, wherein the block copolymer comprises, consists essentially of, or consists of at least one of a diblock copolymer or a triblock copolymer.

[0098] Embodiment 14: The curable composition of any of embodiments 1-13, wherein the block copolymer comprises at least one block having a glass transition temperature of at least 25° C. and at least one block having a glass transition temperature less than 25° C.

[0099] Embodiment 15: The curable composition of any of embodiments 1-14, wherein the block copolymer comprises at least one block having a glass transition temperature of at least 50° C. and at least one block having a glass transition temperature of less than −25° C.

[0100] Example 16: The curable composition of any of Examples 1-15, wherein the block copolymer is a block copolymer selected from the group consisting of: a) a block copolymer constituted by at least one poly(n-butyl acrylate) block and at least one poly(methyl methacrylate) block, b) a block copolymer constituted by at least one polystyrene block and at least one polybutadiene block, and c) a block copolymer constituted by at least one polystyrene block and at least one polyisoprene block.

[0101] Embodiment 17: The curable composition of any of embodiments 1-16, wherein at least one block copolymer has a number average molecular weight of 3,000 to 200,000 Daltons.

[0102] Embodiment 18: The curable composition of any of embodiments 1 to 17, wherein the curable composition is comprised of 1 to 40 weight percent of the block copolymer, based on the total weight of the curable composition.

[0103] Embodiment 19: The curable composition of any of embodiments 1-18, further comprising at least one photoinitiator.

[0104]

[0041] Embodiment 20: The curable composition of any of embodiments 1-19, further comprising inorganic nanoparticles.

[0105]

[0041] Example 21: The curable composition of example 20, wherein the inorganic nanoparticles are dispersed in one or both of the first reactive component or the second reactive component.

[0106] Aspect 22: The curable composition of aspect 20 or 21, wherein the inorganic nanoparticles are selected from the group consisting of silica nanoparticles, alumina nanoparticles, iron oxide nanoparticles, niobia nanoparticles, titania nanoparticles, mixed oxide nanoparticles, alloy nanoparticles, zirconia nanoparticles, metal nanoparticles, clay nanoparticles, and combinations thereof.

[0107] Aspect 23: The curable composition of any of Aspects 1-22, comprising 10 to 90 weight percent of the first reactive component and 90 to 10 weight percent of the second reactive component, based on the total weight of the first reactive component and the second reactive component.

[0108] Embodiment 24: A method comprising curing the curable composition of any of embodiments 1-23.

[0109] Aspect 25: A cured composition obtained by curing the curable composition of any one of Aspects 1 to 23.

[0110] Aspect 26: Use of the curable composition of any of aspects 1 to 23 as an ink, molding resin, 3D printing resin, coating material, or adhesive.

[0111] Aspect 27: A cured composition comprising: a first set of one or more polymeric regions comprised of a first reactive component in polymerized form; a second set of one or more polymeric regions comprised of a second reactive component in polymerized form; and a block copolymer comprised of at least one block associated with the first set of polymeric regions and at least one block associated with the second set of polymeric regions, wherein the first reactive component and the second reactive component are not completely compatible with each other at 25° C. in the absence of the block copolymer.

[0112] Embodiment 28: A 3D article obtained as a result of curing the curable composition of any one of embodiments 1-23.

[0113] Embodiment 29: The 3D article of claim 28, which is a 3D printed article.

[0114] Although the embodiments have been described herein in a manner that enables a clear and concise specification to be written, it is intended and will be understood that the embodiments can be combined or separated in various ways without departing from the invention. For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0115] In some embodiments, the invention herein may be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the curable composition or the process using the curable composition. Further, in some embodiments, the invention may be construed as excluding any element or process step not expressly recited herein.

[0116] Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown, but rather various changes in details may be made without departing from the invention within the spirit and scope of the claims and equivalents thereto. EXAMPLES

[0117] 1-3 show certain exemplary, non-limiting embodiments of the present invention. Two representative reactive components are shown: polyethylene glycol monoacrylate containing six oxyethylene repeat units (abbreviated as "PEA6") and 4-tert-butylcyclohexyl (meth)acrylate (abbreviated as "Tbchma"). PEA6 is considered to be a hydrophilic monomer, while Tbchma is classified as a hydrophobic monomer. The structures of these monomers are shown in the second column of FIG. 1. Equal weights of PEA6 and Tbchma were placed in a test tube at ambient temperature. As shown in the top photograph in the fourth column of FIG. 1, the monomers exhibited a clear phase separation immediately after stirring / mixing (in the left photograph, taken some time after mixing the monomers and allowing the phases to separate, the meniscus between the two liquid phases is discernible, although difficult to discern). The right photograph, taken immediately after vigorously stirring the mixture, shows a somewhat cloudy mixture as a result of a temporary "emulsification" of the two liquid phases.

[0118] The bottom row of FIG. 1 shows the results observed when the block copolymer is mixed with PEA6 and Tbchma. In this case, the block copolymer is a d-block, designated as "NS-1", containing a block of polymethyl methacrylate ("PMMA") and a block of polybutyl acrylate ("PBA"). A schematic structure of the block copolymer is shown in the second column of FIG. 1. The block copolymer structure is simplified, the ester functional groups are not shown, and the number of repeat units in each block does not necessarily correspond to the number of repeat units in the NS-1 block copolymer actually used. The block shown with pendant groups on the polymer backbone represents the PBA block, while the other block is the PMMA block. In the presence of the NS-1 block copolymer, PEA6 and Tbchma are compatibilized, and upon mixing, a single homogenous liquid phase is observed, as shown in the bottom fourth column of photographs in FIG. 1.

[0119] The third row of Figure 1 provides a depiction illustrating what is believed to be happening at the molecular level in the two different mixtures. Without the block copolymer, an upper phase rich in PEA6 and a lower phase rich in Tbchma are formed. In the presence of the block copolymer (shown in the bottom panel of the third row), the Tbchma molecules tend to preferentially bind to the PBA block of the block copolymer, while the PEA6 molecules tend to preferentially bind to the PMMA block of the block copolymer. The presence of the block copolymer thus helps prevent phase separation of the different monomers on a macroscopic scale.

[0120] FIG. 3 shows different possible arrangements of block copolymers with respect to the Tbchma-rich and PEA6-rich regions. In the first row of FIG. 3, diblock copolymer molecules (shown in schematic form as irregular curves) are shown, where one block of the diblock copolymer has affinity to the Tbchma-rich region and the other block has affinity to the PEA6-rich region. In the second row of FIG. 3, triblock (ABA) copolymer molecules are shown, where the central block has affinity to the PEA6-rich region while the two terminal blocks have affinity to the Tbchma-rich region, whereby the central B block forms an "inner loop" that extends into the PEA6-rich region. In the third row of FIG. 3, a triblock copolymer (BAB) is used, whereby the central A block has a higher affinity to the Tbchma-rich region and the terminal B blocks have a higher affinity to the PEA6-rich region, resulting in the formation of an "outer loop" that extends into the Tbchma-rich region.

[0121] Figure 2 has further information regarding the embodiment according to the invention shown in the bottom row of Figure 1. In particular, the third column of Figure 2 shows a schematic of the possible three-dimensional morphology of domain formation that occurs on the microscale (200 nm to 500 nm) when Tbcma and PEA6 monomers are mixed in the presence of a suitable block copolymer. Figure 2 shows an interconnected lattice formed by one of the monomers in a matrix of another monomer. As described elsewhere in this application, other morphologies are possible, including specific morphologies achieved by variations in the relative amounts of the first and second reactive components, the types of monomers selected for use in the first and second reactive components, the type of block copolymer selected, as well as other factors.

Claims

1. 1. A curable composition comprising: a) a block copolymer comprising at least a first block and a second block, the first block and the second block having different monomer compositions; b) a first reactive component that has a higher tendency to bond to the first block of the block copolymer than to the second block of the block copolymer; c) a second reactive component that has a higher tendency to bond to the second block of the block copolymer than to the first block of the block copolymer; wherein the first reactive component and the second reactive component are incompatible in the absence of the block copolymer, and the first reactive component is comprised of at least one hydrophilic monomer selected from the group consisting of hydrophilic epoxides, hydrophilic oxetanes, hydrophilic vinyl compounds, hydrophilic acrylamides, and hydrophilic (meth)acrylate functional compounds.

2. 10. The curable composition of claim 1, wherein the first reactive component is comprised of at least one hydrophilic monomer selected from the group consisting of hydrophilic (meth)acrylate functional compounds.

3. 2. The curable composition of claim 1, wherein the first reactive component is comprised of at least one hydrophilic monomer selected from the group consisting of acetoxyethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, phosphate (meth)acrylate monomer, mono-(2-(meth)acroyloxyethyl)succinate, lactone (meth)acrylate, lactam (meth)acrylate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, (meth)acryloylmorpholine, N-vinylformamide, polyethylene glycol mono(meth)acrylate, and diacetone (meth)acrylamide.

4. 3. The curable composition of claim 2, wherein the at least one hydrophilic monomer comprises a half ester that is the reaction product of a hydroxyalkyl (meth)acrylate or an alkoxylated hydroxyalkyl (meth)acrylate with a dicarboxylic acid or a carboxylic acid anhydride.

5. 5. The curable composition of claim 4, wherein the hydroxyalkyl (meth)acrylate is selected from the group consisting of hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

6. 5. The curable composition of claim 4, wherein the dicarboxylic acid or carboxylic acid anhydride is selected from the group consisting of succinic acid, succinic anhydride, malonic acid, methylsuccinic acid and methylsuccinic anhydride.

7. 5. The curable composition of claim 4, wherein the at least one hydrophilic monomer comprises a half ester that is the reaction product of hydroxyethyl acrylate and succinic acid.

8. The second reactive component comprises at least one C ４ -C ２４ 10. The curable composition of claim 1 comprising a (meth)acrylate ester of an aliphatic mono-alcohol.

9. The second reactive component comprises at least one C ４ -C ２４ The curable composition of claim 1 comprising an alkyl acrylate.

10. The second reactive component is an aromatic (meth)acrylate, an alicyclic (meth)acrylate, a vinyl aromatic compound, a vinyl alicyclic compound, C ６ -C ２４ Olefins and C ６ -C ２４ 10. The curable composition of claim 1 comprising at least one hydrophobic reactive compound selected from the group consisting of (meth)acrylamides containing alkyl groups.

11. The curable composition of claim 1 , wherein the block copolymer comprises at least one of a diblock copolymer or a triblock copolymer.

12. 10. The curable composition of claim 1, wherein the block copolymer comprises at least one block having a glass transition temperature of at least 25°C and at least one block having a glass transition temperature below 25°C.

13. 2. The curable composition of claim 1, wherein the block copolymer comprises at least one block having a glass transition temperature of at least 50°C and at least one block having a glass transition temperature of less than -25°C.

14. 2. The curable composition of claim 1, wherein the block copolymer is a block copolymer selected from the group consisting of: a) block copolymers constituted by at least one poly(n-butyl acrylate) block and at least one poly(methyl methacrylate) block, b) block copolymers constituted by at least one polystyrene block and at least one polybutadiene block, and c) block copolymers constituted by at least one polystyrene block and at least one polyisoprene block.

15. The curable composition of claim 1, wherein the block copolymer has a number average molecular weight of 3,000 to 200,000 Daltons.

16. The curable composition of any one of claims 1 to 15, wherein the curable composition is constituted by 1 to 40 wt% of the block copolymer, based on the total weight of the curable composition.

17. The curable composition of any of claims 1 to 16, further comprising at least one photoinitiator.

18. The curable composition of any one of claims 1 to 17, further comprising inorganic nanoparticles.

19. 20. The curable composition of claim 18, wherein the inorganic nanoparticles are dispersed in one or both of the first reactive component or the second reactive component.

20. 20. The hardenable composition of claim 18, wherein the inorganic nanoparticles are selected from the group consisting of silica nanoparticles, alumina nanoparticles, iron oxide nanoparticles, niobia nanoparticles, titania nanoparticles, mixed oxide nanoparticles, alloy nanoparticles, zirconia nanoparticles, metal nanoparticles, clay nanoparticles, and combinations thereof.

21. 21. The curable composition of any of claims 1 to 20, comprising 10 to 90 wt. % of the first reactive component and 90 to 10 wt. % of the second reactive component, based on the total weight of the first reactive component and the second reactive component.

22. A method comprising curing the curable composition of any one of claims 1 to 21.

23. A cured composition obtained by curing the curable composition according to any one of claims 1 to 21.

24. Use of the curable composition according to any one of claims 1 to 21 as an ink, a moulding resin, a 3D printing resin, a coating material or an adhesive.

25. 1. A curable composition comprising: a first set of one or more polymeric regions comprised of a first reactive component in polymerized form; a second set of one or more polymeric regions comprised of a second reactive component in polymerized form; and a block copolymer comprised of at least one block associated with the first set of polymeric regions and at least one block associated with the second set of polymeric regions, wherein the first reactive component and the second reactive component are not completely miscible with each other at 25° C. in the absence of the block copolymer, and the first reactive component is comprised of at least one hydrophilic monomer selected from the group consisting of hydrophilic epoxides, hydrophilic oxetanes, hydrophilic vinyl compounds, hydrophilic acrylamides, and hydrophilic (meth)acrylate functional compounds.

26. A 3D article resulting from the curing of the curable composition according to any one of claims 1 to 21.

27. 27. The 3D article of claim 26, which is a 3D printed article.

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