Curable compositions and uses thereof

Abstract

Mixtures of one or more (meth)acrylate-functionalized compounds and one or more reactive comonomers, such as 1,1-diester-1-alkenes (e.g., methylene malonate), 1,1-diketo-1-alkenes, 1-ester-1-keto-1-alkenes, and / or catonates, are used to prepare curable compositions with desirable attributes, such as rapid cure rates and improved physical properties.

Description

[Technical field]

[0001] The present invention relates to curable compositions. In particular, the present invention relates to compositions based on mixtures of (meth)acrylate functionalized compounds and reactive comonomers (e.g., 1,1-diester-1-alkenes, 1,1-diketo-1-alkenes, 1-ester-1-keto-1-alkenes and / or icatonates (including methylene malonates and / or methylene beta-diketones)) that can be cured by exposure to radiation (e.g., ultraviolet radiation). The curable compositions are useful as coatings, inks, adhesives, molding resins and 3D printing resins, among other applications. [Background technology]

[0002] Radiation curable compositions based on various types of (meth)acrylate-functionalized compounds (i.e., compounds containing one or more acrylate and / or methacrylate functional groups per molecule, including both monomers and oligomers) have been known for many years and are widely used in many applications, such as in the formulation of coatings, sealants, adhesives, inks, inks for 3D printing, molding resins, etc. In general, methacrylate-functionalized compounds are typically used to improve the physical properties of the cured formulation (e.g., higher strength, higher glass transition temperature, higher chemical resistance), while acrylate-functionalized compounds are typically used to promote faster reaction rates (i.e., faster curing speed when the radiation-curable composition is exposed to radiation). Rapid curing is highly desirable in many end applications, as it increases productivity and thereby provides other benefits. At the same time, however, the physical properties of the cured composition should desirably continue to meet certain minimum performance requirements. Increasing the proportion of acrylate-functionalized compounds in the radiation-curable formulation can increase the cure speed, but this often comes at the expense of compromising to some degree the physical properties of the cured product that are achieved if only the methacrylate-functionalized compounds are present. Many low functionality acrylate / methacrylate resins (i.e., resins with a low number of (meth)acrylate groups per mole) exhibit slow cure speeds using conventional radiation sources, especially when using long wavelength LED curing systems. Additionally, acrylate-functionalized compounds (especially acrylate-functionalized monomers) tend to be more irritating and pose greater health hazards compared to their methacrylate-functionalized counterparts.

[0003] It is therefore desirable to develop radiation curable compositions that can reduce the content of acrylate-functionalized compounds while still providing high cure rates and suitably high physical properties to the cured products obtained therefrom.

[0004] It has been discovered that the cure properties of compositions based on (meth)acrylate-functionalized compounds can be advantageously controlled or modified by including in such compositions one or more reactive monomers (comonomers) in which the carbon atom (C=C) moiety that is part of an alkene is disubstituted with a carbonyl-containing substituent, such as a ketone, ester, or amide group. In particular, it has been found that formulations based on a combination of one or more methacrylate-functionalized compounds and one or more such reactive comonomers (e.g., methylene malonate) exhibit much faster cure when exposed to UV light compared to similar formulations based on a combination of a methacrylate-functionalized compound and an acrylate-functionalized compound. The faster cure rate means that reactive comonomer-containing formulations reach their rheological gel point (i.e., solidify) at substantially lower UV exposure. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, the incorporation of such reactive comonomers helps improve the cure kinetics and physical properties of radiation curable formulations based on (meth)acrylate-functionalized compounds, with distinct synergistic effects resulting from the presence of such comonomers. [Means for solving the problem]

[0006] According to one aspect of the present invention, a) Structure R a R b C=CHR c (In the formula, R a and R b are the same or different, -C(=O)XR d , -CH 2 C(=O)XR e , and -C(=O)R f is selected from, where R a and R b Both are -CH 2 C(=O)XR e each X is independently O or NR i And each Ri is independently selected from H or an organic group; R c is H or C1 or C2 alkyl, and each R d and R e is independently selected from H, an alkali metal, or an organic group; each R f is an organic group; or R d , R e Or R f two of which together with the atoms to which they are attached form a ring; b) at least one (meth)acrylate-functionalized compound; A curable composition is provided comprising:

[0007] The curable compositions according to the present invention can be cured (e.g., using radiation) to provide a cured composition. The curable compositions can thus be used as adhesives, sealants, inks, 3D printing resins or molding resins to make various types of articles, such as three dimensional printed or 3D articles that are part of the present invention. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 shows the results observed by DSC, where cumulative enthalpy is plotted versus UV exposure time. [Diagram 2] FIG. 2 shows the results observed by FTIR, where the % conversion of starting material is plotted versus UV exposure time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Comonomer a) The curable compositions of the present invention comprise one or more comonomers a) which may be generally characterized as compounds containing a reactive carbon-carbon double bond (i.e., an ethylenically unsaturated site), wherein one of the carbon atoms participating in the carbon-carbon double bond is substituted with two C=O (carbonyl)-containing groups, such carbon atom of the carbon-carbon double bond being either directly bonded to a carbon atom of the C=O moiety of each of the two C=O-containing groups, or directly bonded to a carbon atom of the C=O moiety of one of the two C=O-containing groups and bonded to a carbon atom of the C=O moiety of the other C=O-containing group via an intermediate -CH 2 Indirectly bonded via a - group (C=C-CH 2 (producing a -C(=O)- moiety). The other carbon atoms involved in the carbon-carbon double bond are unsubstituted (terminal methylene groups, C=CH 2 or C 1 Or C 2 Alkyl-substituted (alkene group C=CHCH 3 or C=CCH 2 CH 3 result).

[0010] Reactive comonomers useful in the present invention have the general structure R a R b C=CHR c wherein R a and R b are the same or different, -C(=O)XR d , -CH 2 C(=O)XR e , and -C(=O)R f is selected from, where R a and R b Both are -CH 2 C(=O)XR e each X is independently O or NR i And each R i is independently selected from H or an organic group; R c is H or C1 or C2 alkyl, and each R d and R eare independently selected from H, an alkali metal, or an organic group (wherein the organic group may be, for example, an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclyl group, an alkylheterocyclyl group, an aryl group, an aralkyl group, an alkaryl group, a heteroaryl group, an alkheteroaryl group, or a polyoxyalkylene group); f are independently selected from organic groups (e.g., alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, oxyalkylene, or polyoxyalkylene groups); or R d , R e Or R f Two of the R's form a ring together with the atoms to which they are attached. d , R e or R f When is an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclyl group, an alkylheterocyclyl group, an aryl group, an aralkyl group, an alkaryl group, a heteroaryl group, an alkheteroaryl group, or a polyoxyalkylene group, such groups may be substituted with one or more substituents. For example, any of the substituents known in the art of organic chemistry may be present, including halo, nitro, cyano, alkoxy, hydroxy, and the like, and combinations thereof, provided that such substituents do not interfere with the ability of the comonomer to co-cure with the (meth)acrylate-functionalized compound.

[0011] Suitable types of reactive comonomers useful in the present invention include, but are not limited to, 1,1-diester-1-alkene, 1,1-diketo-1-alkene, 1-ester-1-keto-1-alkene, 1,1-diamide-1-alkene, 1-amide-1-keto-1-alkene, 1-amide-1-ester-1-alkene, and / or ikatanate. In certain aspects of the present invention, the comonomer may be selected from the group consisting of methylene malonate (which may be considered a type of 1,1-diester-1-alkene), methylene acetylacetonate (which may be considered a type of 1-ester-1-keto-1-alkene), methylene beta-diketone (which may be considered a type of 1,1-diketo-1-alkene), and itaconate. In one embodiment of the present invention, only one type of reactive comonomer is present in the curable composition. In such an embodiment, the curable composition may include only a single specific compound as the comonomer component. However, it is also possible for the curable composition to include a combination of two or more comonomer compounds of the same type (e.g., two or more specific methylene malonate compounds) as the comonomer component. In other embodiments, the curable composition includes two or more reactive comonomers (e.g., both methylene malonate and methylene beta-diketone).

[0012] Terminal methylene-containing compounds have at least one methylene (=CH 2 ) group, where the carbon atom to which such methylene group is attached is substituted, for example, by two ester groups (-C(=O)OR), two ketone groups (-C(=O)R) or both an ester group and a ketone group, where R is an organic group such as alkyl or cycloalkyl (described in more detail below).

[0013] According to one particular embodiment of the present invention, the one or more methylene malonates have the structure (I):

[0014] [ka] (Wherein, R and R′ are independently C 1 -C15 Alkyl, C 2 -C 15 Alkenyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, Heteroaryl-(C 1 -C 15 alkyl), or alkoxy-(C 1 -C 15 alkyl), which are each C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; Or, R and R', together with the atoms to which they are attached, are C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1-C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 The curable composition is present as a comonomer a) having a 5- to 7-membered heterocyclic ring optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester.

[0015] In one embodiment of the present invention, the curable composition comprises at least one methylene malonate of structure (I), wherein one or both of R and R' are or include cycloalkyl groups, which may be substituted or unsubstituted. When both R and R' are or include cycloalkyl groups, the cycloalkyl groups may be the same or different from each other. The cycloalkyl group may be directly bonded to an oxygen atom of the ester group or indirectly bonded to such an oxygen atom (e.g., -CH 2 - or other alkylene groups.

[0016] A cycloalkyl group may be a monocyclic alkyl group (substituted or unsubstituted), such as a cyclopentyl, cyclohexyl, or cycloheptyl group, or a polycyclic alkyl group (substituted or unsubstituted), such as an isobornyl or tricyclodecyl group. Suitable polycyclic alkyl groups include polycyclic alkyl groups having fused ring systems, polycyclic alkyl groups having bridged ring systems, and polycyclic alkyl groups having both fused and bridged ring systems.

[0017] Illustrative, non-limiting examples of methylene beta-diketones useful as comonomers in the curable compositions of the present invention include compounds where R and R′ in structure (I) above are as follows:

[0018] R = t-butyl, R' = methyl; R=R'=ethyl; R = isopropyl, R' = methyl; R = phenyl, R' = methyl; R=R'=phenyl; R=R'=n-propyl; R=2-thiophene, R'=trifluoromethyl; R=t-butyl; R'=trifluoromethyl; R = n-hexyl, R' = trifluoromethyl; R=R'=isopropyl; R = methyl, R' = bromomethyl; R=2-furanyl, R'=trifluoromethyl; R = n-propyl, R' = trifluoromethyl; R = ethyl, R' = trifluoromethyl; R = methyl, R' = dichloromethyl; R = phenyl, R' = difluoromethyl; R=R'=chloromethyl; R = methyl, R' = difluoromethyl; R = methyl, R' = chlorodifluoromethyl; R = methyl, R' = dichloromethyl; R = 4-chlorophenyl, R' = difluoromethyl; R = methyl, R' = chloromethyl; R = 2,4-dichlorophenyl, R' = trifluoromethyl; R = 2,4-dimethoxyphenyl, R' = methyl; R=R'=isobornyl; R=R'=cyclohexyl; R = ethyl, R' = isobornyl; R=ethyl, R′=cyclohexyl; and R=4-methoxyphenyl, R'=methyl.

[0019] Specific exemplary methylene malonates include, but are not limited to, the following compounds: diethyl methylene malonate (R=R'=ethyl), di-n-hexyl methylene malonate (R=R'=n-hexyl), di-isobornyl methylene malonate (R=R'=isobornyl), ethyl isobornyl methylene malonate (R=ethyl, R'=isobornyl), and dicyclohexyl methylene malonate (R=R'=cyclohexyl).

[0020] Methylene malonate monomers are well known in the art and are described, along with methods for their synthesis, in the following exemplary patent documents, the entire disclosures of each of which are incorporated herein by reference for all purposes: U.S. Pat. Nos. 2,313,501; 2,330,033; 3,221,745; 3,523,097; 3,557,185; 3,758,550; 3,975,422; 4,049,698; 4,056,543; and 4,160,864. No. 4,931,584; No. 5,142,098; No. 5,550,172; No. 6,106,807; No. 6,211,273; No. 6,245,933; No. 6,420,468; No. 6,440,461; No. 6,512,023; No. 6,610,078; No. 6,699,928; No. 6,750,298; U.S. Patent Publication No. 2004 / 0076601; and International Patent Publication Nos. WO / 2012 / 054616A2 and WO2012 / 054633A2.

[0021] In one embodiment, the curable composition has the structure (II):

[0022] [ka] (In the formula, R 1 and R 2 is independently C 1 -C 15 Alkyl, C 2 -C 15 Alkenyl, halo-(C 1 -C 15 Alkyl), C3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy-(C 1 -C 15 alkyl), which are each C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; Or, R 1 and R 2 together with the atoms to which they are attached, C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 The compound includes one or more methylene beta-diketone monomers having a 5-7 membered heterocycle optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester.

[0023] Illustrative, non-limiting examples of methylene beta-diketones useful as comonomer a) in the curable compositions of the present invention are represented by R 1 and R 2 The present invention includes compounds in which:

[0024] R 1 = t-Butyl, R 2 = methyl; R 1 =R 2 = ethyl; R 1 = isopropyl, R 2 = methyl; R 1 = phenyl, R 2 = methyl; R 1 =R 2 = phenyl; R 1 =R 2 = n-propyl; R 1 = 2-thiophene, R 2 = trifluoromethyl; R 1 = t-Butyl; R 2 = trifluoromethyl; R 1 = n-hexyl, R 2 = trifluoromethyl; R 1 =R 2 = isopropyl; R 1 = methyl, R 2 = bromomethyl; R 1 = 2-furanyl, R 2= trifluoromethyl; R 1 = n-propyl, R 2 = trifluoromethyl; R 1 = ethyl, R 2 = trifluoromethyl; R 1 = methyl, R 2 = dichloromethyl; R 1 = phenyl, R 2 = difluoromethyl; R 1 =R 2 = chloromethyl; R 1 = methyl, R 2 = difluoromethyl; R 1 = methyl, R 2 = chlorodifluoromethyl; R 1 = methyl, R 2 = dichloromethyl; R 1 = 4-chlorophenyl, R 2 = difluoromethyl; R 1 = methyl, R 2 = chloromethyl; R1=2,4-dichlorophenyl, R 2 = trifluoromethyl; R 1 = 2,4-dimethoxyphenyl, R 2 = methyl; R 1 =R 2 = isobornyl; R 1 =R 2 = cyclohexyl; R 1 = ethyl, R 2 = isobornyl; R 1 = ethyl, R 2 = cyclohexyl; and R 1 = 4-methoxyphenyl, R 2 =Methyl.

[0025] Methods for making such methylene beta-diketone compounds are known in the art and include those methods described in US2014 / 0275400A1, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

[0026] A further class of reactive comonomers that may be used in the curable compositions of the present invention are R a -C(=O)OR d and R b -C(=O)R f and R c is H, methyl or ethyl; a R b C=CHR c Such compounds are alkene beta-ketoesters or 1-ester-1-keto-1-alkene or R c When R is H, it may be referred to as a methylene beta-keto ester or methylene acetylacetonate. Compounds of this type are known in the art and are described, for example, in US 2014 / 0288230, the disclosure of which is incorporated herein by reference in its entirety for all purposes. Specific illustrative examples of methylene beta-keto esters suitable for use in the present invention include, but are not limited to, c is H and R a -C(=O)OR d and R b -C(=O)R f and R d and R f A structure R such that a R b C=CHR c This includes compounds of the formula:

[0027] R d = methyl, R f = t-butyl; R d = ethyl, R f = phenyl; R d = ethyl, R f = n-propyl; R d = ethyl, Rf = methyl; R d =R f = methyl; R d = ethyl, R f = isopropyl; R d =R f = ethyl; R d =R f = cyclohexyl; R d =R f = isobornyl; R d = isobornyl, R f = ethyl; R d = cyclohexyl, R f = ethyl; R d = ethyl, R f = benzyl; R d = ethyl, R f = chloromethyl; R d = ethyl, R f = thiophene; R d = ethyl, R f = furanyl; R d = methyl, R f = chloromethyl; R d = cyclopentylmethyl, R f = phenyl; R d = ethyl, R f = difluoromethyl; R d = tetrahydrofuranylmethyl, R f = phenyl; R d = ethyl, R f = 1-Bromo-ethyl; R d = ethyl, R f = cyclohexyl; R d = isopropyl, R f = chloromethyl; Rd = ethyl, R f = cyclopentyl; R d = 2-Methoxyethyl, R f = methyl; R d =-CH 2 CH 2 OC(=O)CH 3 , R f = methyl; R d = furanylmethyl, R f = methyl; and R d = Benzyl, R f = methyl;

[0028] The curable composition of the present invention may include one or more itaconates. An itaconate or a combination of two or more different itaconates may be utilized by itself as a reactive comonomer component of the curable composition. However, in other embodiments, one or more itaconates may be present in combination with one or more other types of reactive comonomers as a reactive comonomer component of the curable composition (e.g., one or more itaconates + one or more methylenemalonates). Itaconates are represented by the formula HOC(=O)CH 2 C(=CH 2 It is characterized as a diester of itaconic acid having the structure: )C(=O)OH.

[0029] The appropriate itaconate is R g OC(=O)CH 2 C(=CH 2 )C(=O)OR h may correspond to the structure, g and R h are the same or different organic groups. Suitable organic groups include alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, oxyalkylene and polyoxyalkylene groups, which may be substituted or unsubstituted. For example, R g and R his C 1 -C 15 Alkyl, C 2 -C 15 Alkenyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy-(C 1 -C 15 alkyl), each of which may be independently selected from, for example, C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 The appropriate R may be optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. g and R h Specific examples of groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopentyl, cyclohexyl, cyclohexylmethyl (Cyc-CH 2 -, Cyc = cyclohexyl), phenyl, benzyl, 2-phenylethyl and isobornyl.

[0030] Illustrative, non-limiting examples of suitable itaconates include dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-isobutyl itaconate, dicyclohexyl itaconate, alkyl poly(oxyethylene) itaconates, bis(hexafluoroisopropyl) itaconate, diphenyl itaconate, dibenzyl itaconate, ethyl isobornyl itaconate, ethyl cyclohexyl itaconate, and the like, and combinations thereof.

[0031] (Meth)acrylate-functionalized compounds b) The curable compositions of the present invention are further characterized by comprising at least one (meth)acrylate-functionalized compound b). The (meth)acrylate-functionalized compound b) may be described as an organic compound having one or more (meth)acrylate functional groups per molecule. As used herein, the term "(meth)acrylate" refers to both acrylate and methacrylate functional groups. The (meth)acrylate-functionalized compounds suitable for use in the present invention may generally be described as ethylenically unsaturated compounds (compounds containing at least one α,β-unsaturated ester moiety) that contain at least one carbon-carbon double bond alpha to an ester group, particularly a carbon-carbon double bond that can participate in free radical or anionic reactions, particularly reactions initiated by ultraviolet radiation or electron beam radiation. Such reactions can result in polymerization or curing, whereby the (meth)acrylate-functionalized compound becomes part of a polymerized matrix or polymer chain. In various embodiments of the present invention, the (meth)acrylate-functionalized compounds may contain one, two, three, four, five, or more (meth)acrylate functional groups per molecule. Combinations of (meth)acrylate-functionalized compounds containing different numbers of (meth)acrylate groups may be utilized in the curable compositions of the present invention.

[0032] Thus, the curable compositions of the present invention comprise one or more (meth)acrylate functional compounds capable of undergoing free radical and / or anionic polymerization (curing) initiated by exposure to ultraviolet or electron beam radiation. As used herein, the term "(meth)acrylate" refers to methacrylate (-OC(=O)-C(CH 3 )=CH 2 ) and acrylates (-OC(=O)-CH=CH 2 (Meth)acrylate functionalized compounds may be oligomers or monomers, or a combination of oligomers and monomers.

[0033] For example, any of the following types of (meth)acrylate-functionalized compounds may be used in the curable compositions of the present invention, either in combination with one or a methylene-containing compound as a comonomer: monomers such as (meth)acrylate esters of aliphatic monoalcohols, (meth)acrylate esters of alkoxylated aliphatic monoalcohols, (meth)acrylate esters of aliphatic polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic ring-containing alcohols, and (meth)acrylate esters of alkoxylated aromatic ring-containing alcohols; and oligomers such as epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates (including amine- and sulfide-modified derivatives thereof); and combinations thereof.

[0034] Suitable (meth)acrylate-functionalized oligomers include, for example, polyester (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates (sometimes referred to as polyurethane (meth)acrylate or urethane (meth)acrylate oligomers), and combinations thereof, as well as amine- and sulfide-modified versions thereof.

[0035] Exemplary polyester (meth)acrylates include the reaction products of acrylic acid or methacrylic acid or mixtures thereof with hydroxyl-terminated polyester polyols. The reaction step may be carried out so that the polyester (meth)acrylates are left with a significant concentration of residual hydroxyl groups, or may be carried out so that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated. The polyester polyols may be made by polycondensation reactions of polyhydroxyl-functional components (particularly diols) with polycarboxylic acid-functional compounds (particularly dicarboxylic acids and anhydrides). To prepare polyester (meth)acrylates, the hydroxyl groups of the polyester polyols are then partially or fully esterified by reaction with (meth)acrylic acid, (meth)acryloyl chloride, (meth)acrylic anhydride, and the like. The polyester (meth)acrylates may also be synthesized by reacting hydroxyl-containing (meth)acrylates, such as hydroxyalkyl (meth)acrylates (e.g., hydroxyethyl acrylate), with polycarboxylic acids. The polyhydroxyl-functional and polycarboxylic acid-functional components may each have a linear, branched, alicyclic or aromatic structure and may be used individually or in mixtures.

[0036] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic acid or methacrylic acid, or mixtures thereof, with glycidyl ethers or esters.

[0037] Exemplary polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic acid or methacrylic acid or mixtures thereof with polyetherols, which are polyether polyols. Suitable polyetherols may be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols may be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-propylene oxide, butene oxide, tetrahydrofuran, and combinations thereof) with initiator molecules. Suitable initiator molecules include water, hydroxyl-functional materials, polyester polyols, and amines. Polyetherols may also be obtained by condensation of diols, such as glycols.

[0038] Urethane (meth)acrylates (sometimes referred to as "polyurethane (meth)acrylates") that can be used in the curable compositions of the present invention include urethanes based on aliphatic and / or aromatic polyester polyols, polyether polyols, and polycarbonate polyols, as well as aliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates capped with (meth)acrylate end groups.

[0039] In various embodiments, urethane (meth)acrylates can be prepared by reacting an aliphatic and / or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with an OH-terminated polyester polyol (including aromatic, aliphatic, and mixed aliphatic / aromatic polyester polyols), polyether polyols, polycarbonate polyols, polycaprolactone polyols, polydimethylsiloxane polyols, or polybutadiene polyols, or combinations thereof, to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate, such as hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate, to provide terminal (meth)acrylate groups. For example, the urethane (meth)acrylate may contain two, three, four, or more (meth)acrylate functional groups per molecule. As known in the art, other addition sequences may be practiced to prepare polyurethane (meth)acrylates. For example, a hydroxyl-functionalized (meth)acrylate may be first reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which is then reacted with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, polybutadiene polyol, or a combination thereof. In yet another embodiment, a polyisocyanate may first be reacted with a polyol, including any of the aforementioned types of polyols, to obtain an isocyanate-functionalized polyol, which is then reacted with a hydroxyl-functionalized (meth)acrylate to produce a polyurethane (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0040] Any of the above types of oligomers can be modified with amines or sulfides (e.g., thiols) according to procedures known in the art. Such amine- and sulfide-modified oligomers can be prepared, for example, by reacting a relatively small amount (e.g., 2-15%) of (meth)acrylate functional groups present in the base oligomer with an amine (e.g., a secondary amine) or a sulfide (e.g., a thiol), where the modifying compound adds to the carbon-carbon double bond of the (meth)acrylate in a Michael addition reaction.

[0041] Illustrative examples of suitable monomeric (meth)acrylate-functionalized compounds include (meth)acrylated mono- and polyols (polyalcohols) and (meth)acrylated alkoxylated monoalcohols and polyols. The monoalcohols and polyols may be aliphatic (containing one or more alicyclic rings) or may contain one or more aromatic rings (as in the case of phenol or bisphenol A). "Alkoxylation" refers to the addition of one or more ether moieties (e.g., -CH) to the monoalcohol or polyol prior to esterification to introduce one or more (meth)acrylate functional groups. 2 CH 2 It means that the base monoalcohol or polyol is reacted with one or more epoxides, such as ethylene oxide and / or propylene oxide, to introduce a hydroxyl group (-O-) to one or more hydroxyl groups of the monoalcohol or polyol. For example, the amount of epoxide reacted with the monoalcohol or polyol may be from about 1 to about 30 moles of epoxide per mole of monoalcohol or polyol. Examples of suitable monoalcohols include, but are not limited to, linear, branched and cyclic C 1 -C 54 Monoalcohols include monoalcohols, which may be primary, secondary or tertiary alcohols. For example, monoalcohols include C 1 -C 7 In another embodiment, the monoalcohol is 8 -C 24It may be an aliphatic monoalcohol (e.g., lauryl alcohol, stearyl alcohol). Examples of suitable polyols include glycols (diols), such as ethylene glycol, 1,2- or 1,3-propylene glycol, or 1,2-, 1,3- or 1,4-butylene glycol, neopentyl glycol, trimethylolpropane, triethylolpropane, pentaerythritol, glycerol, and other organic compounds containing two, three, four or more hydroxyl groups per molecule.

[0042] Representative, non-limiting examples of suitable monomeric (meth)acrylate functionalized compounds include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, long chain aliphatic di(meth)acrylates (generally represented by the formula H 2 C=CRC(=O)-O-(CH 2 ) m -OC(=O)CR'=CH 2where R and R' are independently H or methyl and m is an integer from 8 to 24), alkoxylated (e.g., ethoxylated, propoxylated) hexanediol di(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) neopentyl glycol di(meth)acrylate, dodecyl di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol Licor di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) trimethylolpropane tri(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) glyceryl tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, alkoxylated lauryl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, dicyclopentadienyl (meth)acrylate, diethylene glycol methyl ether (meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) nonylphenol (meth)acrylate acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, octyldecyl (meth)acrylate (also known as stearyl (meth)acrylate), tetrahydrofurfuryl (meth)acrylate, tridecyl (meth)acrylate, triethylene glycol ethyl ether (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentadiene di(meth)acrylate, phenoxyethanol(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, tetradecyl(meth)acrylate, cetyl(meth)acrylate, hexadecyl(meth)acrylate, behenyl(meth)acrylate, diethylene glycol ethyl ether(meth)acrylate, diethylene glycol butyl ether(meth)acrylate, triethylene glycol methyl ether(meth)acrylate, dodecanediol di(meth)acrylate ) acrylate, dipentaerythritol penta / hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) glyceryl tri(meth)acrylate, and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and combinations thereof.

[0043] The relative proportions of reactive comonomer a) and (meth)acrylate-functionalized compound b) utilized in the curable composition can be appropriate depending on the particular components selected and the desired properties of the curable composition and the cured composition obtained therefrom. For example, in various embodiments of the present invention, based on the combined total weight of reactive comonomer a) (which may be a single reactive comonomer a) or a combination of two or more different reactive comonomers a)) may be 1 to 99% or 10 to 90% by weight, and correspondingly, the total weight of (meth)acrylate-functionalized compound b) (which may be a single (meth)acrylate-functionalized compound b) or a combination of two or more different (meth)acrylate-functionalized compounds b)) may be 1 to 99% or 10 to 90% by weight.

[0044] Photoinitiator c) If the curable composition is to be cured using light, such as ultraviolet light, it is generally desirable to formulate the composition to include c) one or more photoinitiators. However, if electron beam or chemical curing is used, the curable composition need not include any photoinitiators.

[0045] Photoinitiators are compounds that undergo a photoreaction upon absorption of light to generate reactive species. The generated reactive species then initiate the polymerization of reactive components of the curable composition, such as (meth)acrylate-functionalized compounds. Generally speaking, such polymerization (curing) involves the reaction of carbon-carbon double bonds present in such components. In various embodiments of the present invention, the reactive species may be, for example, a free radical species or an anionic species. In one embodiment of the present invention, the photoinitiator may be a photobase generator, such as α-aminoacetophenone.

[0046] Suitable photoinitiators include, for example, alpha-hydroxyketones, phenyl glyoxylates, benzil dimethyl ketals, alpha-aminoketones, mono-acylphosphines, bis-acylphosphines, metallocenes, phosphine oxides, benzoin ethers, and benzophenones, and combinations thereof.

[0047] Specific examples of suitable photoinitiators include, but are not limited to, 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, alpha-methylbenzoin, alpha-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, 2-methyl-1-[4-(methylthio) (O)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, benzophenone / 1-hydroxycyclo Hexyl Phenyl Ketone, 50 / 50 Blend, 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, 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)cyclopentadienyliron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.

[0048] 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.

[0049] If a photoinitiator is used in the curable composition, the photoinitiator may 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 from about 0.1 to about 5% by weight, based on the total weight of the curable composition).

[0050] Other Ingredients The curable compositions of the present invention may optionally contain one or more additives instead of c) or in addition to components a), b) and c) above. Such additives include, but are not limited to, antioxidants, UV absorbers, light stabilizers, defoamers, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fillers, thixotropic agents, matting agents, thermoplastics such as acrylic resins that do not contain free radically polymerizable functional groups, waxes, or various other additives including any of the additives conventionally utilized in coating, sealant, adhesive, molding or ink technology.

[0051] Curing and Use of the Curable Composition The curable compositions of the present invention are useful as inks (for graphic arts applications, including for food packaging), molding resins, 3D printing resins, coatings (e.g., optical fiber coatings), sealants and adhesives (e.g., UV curable laminating adhesives, UV curable hot melt adhesives), among other possible applications.

[0052] Cured compositions prepared from the curable compositions described herein may be used, for example, in three-dimensional articles (the three-dimensional article may consist essentially of or consist of the cured composition), coated articles (wherein a substrate is coated with one or more layers of the cured composition), laminated or bonded articles (wherein a first component of the article is laminated or bonded to a second component by the cured composition), or printed articles (wherein a graphic or the like is imprinted onto a substrate such as a paper, plastic, or metal substrate using the cured composition).

[0053] The hardenable composition may be subjected to curing using free radical polymerization or other types of polymerization (eg, anionic or cationic polymerization).

[0054] Curing of the curable composition according to the present invention may be carried out by any suitable method, such as free radical polymerization, cationic polymerization and / or anionic polymerization. One or more initiators, such as free radical initiators (e.g., photoinitiators, peroxide initiators), may be present in the curable composition. Prior to curing, the curable composition may be applied to the substrate surface in any known conventional manner, for example, by spraying, knife coating, roller coating, casting, drum coating, dipping, and the like, and combinations thereof. Indirect application using a transfer process may also be used. The substrate may be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, for example, a metal substrate or a plastic substrate, respectively. The substrate may include metal, paper, cardboard, glass, thermoplastics, such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof, composites, wood, leather, and combinations thereof. When used as an adhesive, the composition may be placed between two substrates and then cured, thereby bonding the substrates together with the cured composition.

[0055] 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 source of radiation, such as visible or UV light, infrared radiation, and / or electron beam radiation, etc. Thus, a cured composition may be considered the reaction product of a curable composition formed by curing.

[0056] The curable compositions of the present invention are particularly well suited for curing using LED (light emitting diode) curing (e.g., UV LED curing using radiation from a UV LED device) and for use in high speed applications (such as coatings).

[0057] Multiple layers of a composition according to the present invention may be applied to a substrate surface and the multiple layers may be cured simultaneously (e.g., by exposure to a single dose of radiation) or each layer may be cured sequentially prior to application of an additional layer of the composition.

[0058] The curable compositions described herein are particularly useful as 3D printing resin formulations, i.e. compositions intended for use in the manufacture of three-dimensional articles using 3D printing techniques. Such three-dimensional articles may be free-standing / self-supporting and may consist essentially of or consist of the cured curable compositions. The three-dimensional articles may also be composites comprising at least one component consisting essentially of or consisting of the aforementioned cured compositions, and at least one additional component (e.g., a metal component or a thermoplastic component) comprising one or more materials other than such cured compositions.

[0059] The method of making a three-dimensional article using the curable composition according to the present invention comprises the steps of: a) coating a surface with a first layer of a curable composition according to the present invention; b) curing the first layer to provide a cured first layer; c) coating a second layer of a curable composition onto the cured first layer; d) curing the second layer to provide a cured second layer adhered to the cured first layer; e) repeating steps c) and d) as many times as necessary to build a three-dimensional article. Includes.

[0060] The curing step can be carried out by any suitable means, which in some cases will depend on the components present in the curable composition, but 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, UV radiation, visible light, etc.).

[0061] Thus, in various embodiments, the present invention provides a method for treating a cancer cell comprising: a) coating a surface with a first layer of a curable composition in liquid form according to the present invention; 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) of 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 necessary to build a three-dimensional article. The present invention provides a method comprising:

[0062] Various exemplary aspects of the present invention can be summarized as follows.

[0063] Aspect 1: a) Structure R a R b C=CHR c (In the formula, R a and R b are the same or different, -C(=O)XR d , -CH 2 C(=O)XR e , and -C(=O)R f is selected from, where R a and R b Both are -CH 2 C(=O)XR e each X is independently O or NR i And each R i is independently selected from H or an organic group; R c is H or C1 or C2 alkyl, and each R d and R e is independently selected from H, an alkali metal, or an organic group; each R f is an organic group; or Rd , R e Or R f two of which together with the atoms to which they are attached form a ring; b) at least one (meth)acrylate-functionalized compound; 1. A curable composition comprising, consisting essentially of, or consisting of:

[0064] Aspect 2: Each R d , R e , R f and R g is independently selected from an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclyl group, an alkylheterocyclyl group, an aryl group, an aralkyl group, an alkaryl group, a heteroaryl group, an alkheteroaryl group, an oxyalkylene group, or a polyoxyalkylene group, which may be substituted or unsubstituted.

[0065] Aspect 3: The curable composition of aspect 1 or 2, comprising at least one comonomer selected from the group consisting of 1,1-diester-1-alkene, 1,1-diketo-1-alkene, 1-ester-1-keto-1-alkene, and itaconate.

[0066] Aspect 4: R a and R b Both are -C(=O)OR d and R c The curable composition of any one of embodiments 1 to 3, comprising at least one comonomer a) where

[0067] Aspect 5: R a and R b Both are -C(=O)R f and R c The curable composition of any one of embodiments 1 to 3, comprising at least one comonomer a) where

[0068] Aspect 6: R a -C(=O)OR d and R b -C(=O)R fand R c The curable composition of any one of embodiments 1 to 3, comprising at least one comonomer a) where

[0069] Aspect 7: R a -C(=O)OR d and R b Ga-CH 2 C(=O)OR e and R c The curable composition of any one of the preceding embodiments, comprising at least one comonomer a) where

[0070] Embodiment 8: The curable composition of embodiments 1-3, comprising at least one methylene malonate as comonomer a).

[0071] Embodiment 9: as comonomer a), a compound of structural formula (I)

[0072] [ka] wherein R and R' are the same or different and are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, oxyalkylene and polyoxyalkylene groups, which may be substituted or unsubstituted, or R and R' taken together form a 5-7 membered ring or heterocycle, which may be substituted or unsubstituted.

[0073] Aspect 10: R and R′ are the same and C 1 -C 15 Alkyl and C 5 -C 12 The curable composition of embodiment 9, wherein the alkyl group is selected from the group consisting of cycloalkyl.

[0074] Embodiment 11: The curable composition of embodiments 1-3 and 8-10, wherein the at least one comonomer a) comprises at least one methylene malonate selected from the group consisting of dicyclohexyl methylene malonate, diisobornyl methylene malonate, ethyl isobornyl methylene malonate, dihexyl methylene malonate, and diethyl methylene malonate.

[0075] Aspect 12: Structure (II)

[0076] [ka] (In the formula, R 1 and R 2 is independently C 1 -C 15 Alkyl, C 2 -C 15 Alkenyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy-(C 1 -C 15 alkyl), which are each C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C1 -C 15 Alkoxy, C 1 -C 15 optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; Or, R 1 and R 2 together with the atoms to which they are attached, C 1 -C 15 Alkyl, halo-(C 1 -C 15 Alkyl), C 3 -C 12 Cycloalkyl, halo-(C 3 -C 12 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 Alkyl), aryl, aryl-(C 1 -C 15 Alkyl), Heteroaryl, C 1 -C 15 Alkoxy, C 1 -C 15 The curable composition of embodiments 1-3, comprising one or more methylene beta-diketone monomers having a 5- to 7-membered heterocycle optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester.

[0077] Aspect 13: The curable composition of any of Aspects 1-12, wherein the at least one (meth)acrylate-functionalized compound b) comprises at least one (meth)acrylate-functionalized compound selected from the group consisting of (meth)acrylate esters of aliphatic (non-alkoxylated) monoalcohols, (meth)acrylate esters of alkoxylated aliphatic monoalcohols, (meth)acrylate esters of aliphatic (non-alkoxylated) polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic (non-alkoxylated) alcohols, (meth)acrylate esters of alkoxylated aromatic alcohols, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, and amine- and sulfide-modified derivatives thereof, and combinations thereof.

[0078] Embodiment 14: The curable composition of any of embodiments 1-13, wherein the at least one (meth)acrylate-functionalized compound b) comprises at least one (meth)acrylate-functionalized compound selected from the group consisting of isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, polyether aliphatic urethane acrylate, and polycarbonate urethane acrylate.

[0079] Embodiment 15: The curable composition of any of embodiments 1-14, comprising from about 1% to about 99% by weight in total of comonomer a), and from about 1% to about 99% by weight in total of (meth)acrylate-functionalized compound b), based on the total weight of comonomer a) and (meth)acrylate-functionalized compound b).

[0080] Aspect 16: The curable composition of any of Aspects 1-15, comprising about 10% to about 90% by weight in total of comonomer a), and about 10% to about 90% by weight in total of (meth)acrylate-functionalized compound b), based on the total weight of comonomer a) and (meth)acrylate-functionalized compound b).

[0081] Embodiment 17: The curable composition of any of Embodiments 1-16, further comprising c) at least one photoinitiator.

[0082] Aspect 18: A cured composition obtained by curing the curable composition according to any one of Aspects 1 to 17.

[0083] Embodiment 19: A method of making a cured composition comprising curing a curable composition according to any of embodiments 1-17.

[0084] Embodiment 20: The method of embodiment 19, wherein the curable composition is exposed to radiation.

[0085]

[0041] Embodiment 21: The method of embodiment 19 or 20, wherein the curable composition is exposed to ultraviolet radiation or electron beam radiation.

[0086] Embodiment 22: A method of making a three-dimensional article, comprising: a) coating a surface with a first layer of a curable composition according to any of aspects 1-17; b) curing the first layer to provide a cured first layer; c) coating a second layer of a curable composition onto the cured first layer; d) curing the second layer to provide a cured second layer adhered to the cured first layer; e) repeating steps c) and d) as many times as necessary to build a three-dimensional article. The method includes:

[0087] Aspect 23: The method of aspect 22, wherein the curing step is carried out by exposing the layer of the curable composition to radiation.

[0088] Aspect 24: Use of the curable composition according to any of aspects 1 to 17 in a coating, such as an optical fiber coating, an adhesive, such as a UV curable laminating adhesive or a UV curable hot melt adhesive, a sealant, an ink, a 3D printing resin or a molding resin.

[0089] Embodiment 25: Use of the curable composition of embodiments 1 to 17 in the production of a 3D article.

[0090] Embodiment 26: A 3D article obtained by use of a curable composition according to embodiments 1 to 17.

[0091] Although embodiments have been described herein to enable a clear and concise specification to be set forth, 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.

[0092] In some embodiments, the invention herein may be construed as excluding any element or method step that does not materially affect the basic and novel characteristics of the curable composition or the method of using the curable composition. Further, in some embodiments, the invention may be construed as excluding any element or method step not specified herein.

[0093] Although the invention has been illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown, but rather, various modifications of the details may be made within the sphere and range of equivalents of the claims without departing from the invention. EXAMPLES

[0094] A series of formulations as listed in Tables 1 and 2 were prepared and their photocuring properties were investigated using DSC (Differential Scanning Calorimetry) and FTIR (Fourier Transform Infrared) techniques.

[0095] For the photo-DSC test, a drop of the formulation was placed in an open aluminum pan, which was then placed in the DSC instrument. The DSC instrument was then operated in isothermal mode at 25°C and the formulation was subjected to a 1 second UV light impulse (stopped after seven 1 second impulses). The heat flow was allowed to return to the baseline before the next light impulse was applied. The enthalpy (surface under the corresponding peak) was then calculated. The evolution of the cumulative enthalpy over time was compared between the different formulations and the state of the sample in the pan (solid or liquid, etc.) was assessed at the end of the test.

[0096] For light FTIR testing, a background spectrum was measured before each sample was cured. A drop of the formulation was deposited on the FTIR crystal, which was then periodically exposed to 1 second UV light impulses. FTIR spectra were recorded after 1, 2, 3, 4, 5, and 10 seconds of UV light exposure (multiple 1 second impulses). A final 20 second UV light impulse was then applied and another FTIR spectrum was recorded. -1 The height of the absorbance peak was recorded. The physical state of the sample (solid, liquid, etc.) at the end of the test was also recorded.

[0097] The following components were used in the formulations. In each case, the formulations further contained 0.5 wt% of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) photoinitiator. In formulations containing two reactive components, the components were present in equal weight amounts (50 / 50). All monomers, oligomers, and initiators were mixed in the reported proportions and homogenized between room temperature (approximately 21° C.) and 60° C. for 48 hours.

[0098] "SR506": Sartomer SR506 (isobornyl acrylate).

[0099] "DCHMM": dicyclohexylmethylenemalonate.

[0100] "SR423": Sartomer SR423 (isobornyl methacrylate).

[0101] [Table 1]

[0102] [Table 2]

[0103] FIG. 1 shows the results observed by DSC, where cumulative enthalpy is plotted versus UV exposure time.

[0104] FIG. 2 shows the results observed by FTIR, where the % conversion of starting material is plotted versus UV exposure time.

[0105] The data presented in Figures 1 and 2 suggest that the presence of methylene malonate monomer substantially increases the rate of both double bond conversion (reaction) and formation of solid articles compared to formulations containing only methacrylate monomers or a combination of acrylate and methacrylate monomers (but without methylene malonate monomer). Thus, the incorporation of methylene malonate monomer into (meth)acrylate-based curable compositions serves to improve the curing properties of such curable compositions, thereby making such curing processes faster and / or more efficient.

[0106] A further series of formulations were prepared having the compositions shown in Table 3. The amount of each component in the formulation is expressed as a weight percent based on the total weight of the listed components. Each formulation further included a photoinitiator. The components used were as follows:

[0107] "CN9023": Sartomer CN9023 Polyether Aliphatic Urethane Acrylate (M n = approximately 2500 Daltons).

[0108] "CN8881": Sartomer CN8881 Polycarbonate Urethane Acrylate (M n = approximately 1800 Daltons).

[0109] "DEMM": diethyl methylene malonate.

[0110] "DHMM": dihexylmethylenemalonate.

[0111] "DCHMM": dicyclohexylmethylenemalonate.

[0112] "SR506": Sartomer SR506 (isobornyl acrylate).

[0113] "SR833": Sartomer SR833 (tricyclodecane dimethanol diacrylate).

[0114] "SR454": Sartomer SR454 (ethoxylated (3EO) trimethylolpropane triacrylate).

[0115] [Table 3]

[0116] Table 4 lists the viscosity of each formulation in the uncured state and various mechanical properties of each formulation after light curing.

[0117] [Table 4] TIFF0007663319000009.tif137170

[0118] The addition of DCHMM to (meth)acrylate formulations results in higher viscosities but better mechanical properties (especially tensile strength, elongation, and modulus) than similar formulations containing isobornyl acrylate. Isobornyl acrylate is also known to have a noticeable odor that is absent in DCHMM. Despite the odor, isobornyl acrylate is known to have a high T gDue to their low functionality, they are widely used as reactive diluents in (meth)acrylate formulations, which make them relatively strong and stiff at room temperature, yet still have high T g This achieves a final material that is relatively softer than (meth)acrylic formulations having

Claims

1. a) Structure R ａ R ｂ C=CHR ｃ (In the formula, R ａ and R ｂ are the same or different, -C(=O)ORd and -C(=O)R ｆ is selected from R ｃ is H or C1 or C2 alkyl, each Rd is independently selected from H, an alkali metal, or an organic group; ｆ is an organic group; or R ｄ and Rf together with the atoms to which they are attached form a ring; b) at least one (meth)acrylate-functionalized compound; Including, 10% to 90% by weight in total of comonomer a) and 10% to 90% by weight in total of (meth)acrylate-functionalized compound b), based on the total weight of comonomer a) and (meth)acrylate-functionalized compound b), the at least one (meth)acrylate-functionalized compound b) comprises at least one (meth)acrylate-functionalized compound selected from the group consisting of (meth)acrylate esters of alkoxylated aliphatic monoalcohols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of alkoxylated aromatic alcohols, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, and amine- and sulfide-modified derivatives thereof, and combinations thereof; Curable composition.

2. Each R ｄ 2. The curable composition of claim 1, wherein Rf and Rf are independently selected from alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, oxyalkylene or polyoxyalkylene groups, which may be substituted or unsubstituted.

3. 3. The curable composition according to claim 1, comprising at least one comonomer a) selected from the group consisting of 1,1-diester-1-alkenes, 1,1-diketo-1-alkenes and 1-ester-1-keto-1-alkenes.

4. As comonomer a), 【Chemistry 1】 4. The curable composition according to any one of claims 1 to 3, comprising at least one methylene malonate corresponding to the formula: wherein R and R' are the same or different and are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, oxyalkylene and polyoxyalkylene groups, which may be substituted or unsubstituted, or R and R' taken together form a 5-7 membered ring or heterocycle, which may be substituted or unsubstituted.

5. 5. The curable composition according to claim 1, wherein the at least one comonomer a) comprises at least one methylene malonate selected from the group consisting of dicyclohexyl methylene malonate, diisobornyl methylene malonate, ethyl isobornyl methylene malonate, dihexyl methylene malonate and diethyl methylene malonate.

6. Structure (II) 【Chemistry 2】 (In the formula, R １ and R ２ is independently C １ -C １５ Alkyl, C ２ -C １５ Alkenyl, halo-(C １ -C １５ Alkyl), C ３ -C １２ Cycloalkyl, halo-(C ３ -C １２ cycloalkyl), heterocyclyl, heterocyclyl-(C １ -C １５ alkyl), aryl, aryl-(C １ -C １５ alkyl), heteroaryl or heteroaryl-(C １ -C １５ alkyl), or alkoxy-(C １ -C １５ alkyl), each of which is C １ -C １５ Alkyl, halo-(C １ -C １５ Alkyl), C ３ -C １２ Cycloalkyl, halo-(C ３ -C １２ cycloalkyl), heterocyclyl, heterocyclyl-(C １ -C １５ alkyl), aryl, aryl-(C １ -C １５ Alkyl), heteroaryl, C １ -C １５ Alkoxy, C １ -C １５ optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; Or, R １ and R ２ together with the atoms to which they are attached, C １ -C １５ Alkyl, halo-(C １ -C １５ Alkyl), C ３ -C １２ Cycloalkyl, halo-(C ３ -C １２ cycloalkyl), heterocyclyl, heterocyclyl-(C １ -C １５ alkyl), aryl, aryl-(C １ -C １５ Alkyl), heteroaryl, C １ -C １５ Alkoxy, C １ -C １５ 4. The curable composition of claim 1, comprising one or more methylene beta-diketone monomers having a 5-7 member heterocyclic ring optionally substituted with alkylthio, halo, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester.

7. 7. The curable composition according to any of claims 1 to 6, wherein the at least one (meth)acrylate-functionalized compound b) comprises at least one (meth)acrylate-functionalized compound selected from the group consisting of isobornyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, polyether aliphatic urethane acrylate and polycarbonate urethane acrylate.

8. A cured composition obtained by curing the curable composition according to any one of claims 1 to 7.

9. A method of making a cured composition comprising curing the curable composition of any one of claims 1 to 7.

10. 1. A method of making a three-dimensional article, comprising: a) coating a surface with a first layer of the curable composition according to any one of claims 1 to 7; b) curing the first layer to provide a cured first layer; c) coating a second layer of the curable composition onto the cured first layer; d) curing the second layer to provide a cured second layer adhered to the cured first layer; e) repeating steps c) and d) as many times as necessary to build up the three-dimensional article. The method includes:

11. Use of the curable composition according to any of claims 1 to 7 in coatings such as optical fibre coatings, adhesives such as UV curable laminating adhesives or UV curable hot melt adhesives, sealants, inks, 3D printing resins or moulding resins.

12. Use of the curable composition according to any of claims 1 to 7 in the production of a 3D article.

13. 3D article obtainable by use of the curable composition according to any of claims 1 to 7.

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