Elastic material prepared from an energy-curable liquid composition

Abstract

Provided is an elastic material having an elongation greater than 150% as measured in accordance with ASTM D638-02a, a resilience greater than 12% as measured in accordance with ASTM D2632-01 (reapproved 2008), and a Shore A hardness of at least 10 as measured by ASTM D2240-15e1. The elastic material is the energy-cured reaction product of a curable composition that is liquid at 25°C. The curable composition includes at least: a) a relatively high molecular weight (meth)acrylate-functionalized oligomer having an average of two or fewer (meth)acrylate functional groups per molecule; b) at least one mono(meth)acrylate-functionalized monomer and / or ethylenically unsaturated nitrogen-containing monomer having a molecular weight less than 500 daltons and a single (meth)acrylate functional group per molecule; and c) at least one multi(meth)acrylate-functionalized monomer having a molecular weight less than 1000 daltons and at least two (meth)acrylate functional groups per molecule.

Description

[Technical Field]

[0001] The present invention relates to a composition that is liquid at room temperature and can harden, particularly by energy curing, to yield an elastic material (elastomer). [Background technology]

[0002] Energy curing (EC) refers to the conversion of a curable composition (sometimes called a "resin") into a polymer using an energy source such as an electron beam (EB), a light source (e.g., a visible light source, a near-ultraviolet light source, an ultraviolet lamp (UV), a light-emitting diode (LED), or an infrared light source) and / or heat. Compositions that can be polymerized by exposure to such an energy source are sometimes called energy-curable compositions. Materials prepared by polymerizing a curable composition with EB or a light source (e.g., visible light, near-ultraviolet light, ultraviolet LED, or infrared light) and / or heat can be considered energy-cured materials.

[0003] Energy curing technology offers the potential to obtain a wide range of material properties. This breadth is evident in the many applications of energy-curable compositions: wood coatings, plastic coatings, glass coatings, metal coatings, finishing films, mechanical performance coatings, durable hard coats, inkjet inks, flexographic printing inks, screen printing inks, overprint varnishes, nail gel resins, dental materials, pressure-sensitive adhesives, bonding adhesives, electronic display components, photoresists, 3D printing resins, and so on. However, the industry continues to strive to reach new "material property spaces" that have been previously unattainable in energy-curable compositions and materials prepared from such compositions. A property space refers to a combination of different material properties under specific constraints. Energy-cured materials with elastomeric properties are attracting considerable interest for specific end applications. However, energy-curable compositions that are liquid at room temperature but can be cured with energy to obtain elastic materials have not been widely explored or developed to date.

[0004] To obtain the elasticity required for an elastomer, the material must: 1) deform under stress and 2) quickly return to its original shape when the stress is removed. In polymer materials, the ability to deform is reduced by cross-linking between polymer chains. Therefore, if there are too many cross-links, elasticity cannot be obtained. On the other hand, cross-linking is necessary for the material to return to its original shape after the stress is removed. For a given composition, there is a cross-link density that provides optimal elasticity. The elongation of the material is similarly greatly influenced by the cross-link density, and elongation decreases with cross-linking. The cross-link density required for resilience is sufficient to significantly limit elongation. Therefore, a decisive issue when formulating an energy-curable composition that can provide an elastic material through curing is to simultaneously obtain high elongation and high elasticity.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Non-Patent Documents

[0006]

Non-Patent Document No. 1

[0007] The present invention relates to a composition that is liquid at room temperature and can harden, particularly by energy curing, to yield an elastic material (elastomer). [Means for solving the problem]

[0008] One aspect of the present invention is an elastic material having an elongation greater than 150% as measured in accordance with ASTM D638-02a, an elasticity greater than 12% as measured in accordance with ASTM D2632-01 (re-approved in 2008), and a Shore A hardness of at least 10 as measured by ASTM D2240-15e1 (unless otherwise specified in the ASTM method, the aforementioned properties are measured at 25°C). The elastic material is an energy-cured reaction product of a curable composition that is liquid at 25°C, the curable composition comprising, essentially consisting of, components a), b), and c), or consisting solely of components a), b), and c). Component a): A (meth)acrylate-functionalized oligomer having an average of 2 or fewer (meth)acrylate functional groups per molecule, in an amount of 43-89.9% by mass based on the total mass of components a), b), and c), wherein the number average molecular weight of component a) as a whole is at least 10,000 daltons, as measured using gel permeation chromatography and standard polystyrene; Component b): Based on the total mass of components a), b), and c), 10 to 55% by mass of monomers functionalized with at least one mono(meth)acrylate having a molecular weight of less than 500 daltons and a single (meth)acrylate functional group per molecule, and / or monomers containing ethylenically unsaturated nitrogen; Component c): Based on the total mass of components a), b), and c), a multi(meth)acrylate functionalized monomer of at least one type having a molecular weight of less than 1000 daltons and at least two (meth)acrylate functional groups per molecule, in an amount of 0.1 to 10% by mass.

[0009] As will be explained in more detail later, the curable composition may optionally contain one or more further components, in particular one or more initiator systems such as photopolymerization initiators. [Modes for carrying out the invention]

[0010] <Definition> In this application, the term "comprise(s) a / an" means "comprise(s) one or more".

[0011] Unless otherwise stated, the mass percentage in a compound or composition is expressed based on the mass of the compound or composition.

[0012] The term "X substantially contains no Y" means that X contains only Y in amounts less than 10% by mass, less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, less than 0.1% by mass, less than 0.01% by mass, or even 0% by mass.

[0013] The term "Cα~Cβ group / linker" (where α and β are integers) refers to a group / linker (linking group) having α to β carbon atoms.

[0014] As used herein, the term “(meth)acrylate functional group” refers to either an acrylate functional group (-OC(=O)-CH=CH2) or a methacrylate functional group (-OC(=O)-C(CH3)=CH2). Unless the phrase “functional group” is used, the term “(meth)acrylate” refers to a compound containing at least one acrylate functional group or at least one methacrylate functional group per molecule. “(meth)acrylate” may also refer to a compound having both at least one acrylate functional group and at least one methacrylate functional group. “Functional value” refers to the number of (meth)acrylate functional groups per molecule. Unless otherwise specified, it does not refer to any functional group other than a (meth)acrylate functional group. For example, a difunctional monomer is understood to mean a monomer having two (meth)acrylate functional groups per molecule. On the other hand, trifunctional alcohols are understood to mean compounds that do not have a (meth)acrylate group and have three hydroxyl groups per molecule.

[0015] The term "oligomer" is understood to refer to an organic substance that has multiple repeating units (e.g., oxyalkylene repeating units) and a polydispersity (Mw / Mn) greater than 1. Monomers are distinct single molecules, whether or not they have multiple repeating units. For example, 2(2-ethoxyethoxy)ethyl acrylate has two oxyethylene repeating units, but this compound is considered a monomer rather than an oligomer because it is a compound with a distinct structure, rather than a mixture of structurally related compounds with a molecular weight distribution (and therefore polydispersity > 1).

[0016] As used herein, the term “elastic material” qualitatively refers to a material having one or more elastomer properties, such as high elongation, high elasticity, high toughness, high resilience, and / or high elastic recovery. Quantitatively, these properties vary depending on the details of the end application of the elastic material. Elongation refers to the total deformation until the specimen breaks. High elongation can be greater than 75%, greater than 150%, greater than 225%, or greater than 300% when tested according to ASTM D638-02a. Elasticity refers to the rebound height of an object bouncing off the surface of the material, expressed as a percentage of the object's original height. High elasticity can be greater than 10%, greater than 20%, greater than 30%, or greater than 40% when tested according to ASTM D2632-01 (re-approved in 2008). Toughness refers to the integral value of the tensile stress-strain curve, and elasticity refers to the maximum deformation that a material can return to its original shape after being stretched. High elasticity can be 100%, 200%, or 300% when tested according to ASTM D638-02a. In addition, a fast recovery rate is also required. These material properties are not unrelated. For example, all other things being equal, higher elongation generally means higher toughness, and good elastic recovery is associated with good resilience.

[0017] The term "diisocyanate" refers to a compound that has two isocyanate groups.

[0018] The term "diol" refers to a compound that has two hydroxyl groups.

[0019] The term "hydroxyl-functionalized (meth)acrylate" refers to a compound containing one hydroxyl group and at least one (meth)acrylate functional group.

[0020] The term "isocyanate group" refers to a group with the formula -N=C=O.

[0021] The term "hydroxyl group" refers to the group with the formula -OH.

[0022] The term "amino group" is -NR a1 R b1 group (in the formula, Ra1 and R b1 (This independently means an alkyl group which may be substituted with H or optionally.)

[0023] The term "alkyl" is derived from the formula -C x H 2x+1 This refers to a monovalent saturated acyclic hydrocarbon group (where x is between 1 and 100). The alkyl group may be linear or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, N-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, and 2-ethylhexyl.

[0024] The term "alkenyl" refers to a monovalent acyclic hydrocarbon group containing at least one C=C double bond. Alkenyls may be linear or branched in structure.

[0025] The term "hydroxyalkyl" refers to an alkyl group that is substituted with at least one hydroxyl group.

[0026] The term "aminoalkyl" refers to an alkyl group that is substituted with at least one amino group.

[0027] The term "alkoxyalkyl" refers to an alkyl group that is substituted with at least one alkoxy group.

[0028] The term "cycloalkyl" refers to a non-aromatic cyclic hydrocarbon group. Cycloalkyls may contain one or more carbon-carbon double bonds. Examples of cycloalkyls include cyclopentyl, cyclohexyl, and isobornyl.

[0029] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom that is a heteroatom selected from O, N, or S.

[0030] The term "aryl" refers to an aromatic hydrocarbon group.

[0031] The term "heteroaryl" refers to an aryl compound having at least one ring atom that is a heteroatom, such as O, N, S, or combinations thereof.

[0032] The term "alkoxy" refers to a group with the formula -O-alkyl.

[0033] The term "alkylaryl" refers to an alkyl group substituted with an aryl group. An example of an alkylaryl group is benzyl(-CH2-phenyl).

[0034] The term "arylalkyl" refers to an aryl group that has been substituted with an alkyl group.

[0035] The term "alkylene" is derived from formula C m H 2m+2 This refers to a linker obtained by removing one hydrogen atom from each bond point of an alkane (where m is between 1 and 200 in the formula).

[0036] The term "oxyalkylene" refers to a linker of the formula -RO- or -OR- (where R is alkylene). Examples of oxyalkylenes include oxyethylene (-O-CH2-CH2-), oxypropylene (-O-CH2-CH(CH3)- or -O-CH(CH3)-CH2-), and oxybutylene (-O-CH2-CH2-CH2-CH2-).

[0037] The term "linker" refers to a polyvalent group. A linker can link at least two parts of a compound. For example, a linker that links two parts of a compound is sometimes called a divalent linker.

[0038] The term "hydrocarbon linker" means a linker having a carbon backbone which may be interrupted by one or more heteroatoms selected from N, O, S, Si, and mixtures thereof. Hydrocarbon linkers may be aliphatic, alicyclic, or aromatic. Hydrocarbon linkers may be saturated or unsaturated. Hydrocarbon linkers may be optionally substituted.

[0039] The term "acyclic compound / group / linker" refers to a compound / group / linker compound that does not contain a ring.

[0040] The term "cyclic compound / group / linker" refers to a compound / group / linker that contains one or more rings.

[0041] The term "aliphatic compound / group / linker" refers to an acyclic compound / group / linker. The compound / group / linker may be linear or branched, saturated or unsaturated. The compound / group / linker may be substituted with one or more groups selected from, for example, alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl, amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R' (each R' independently being a C1-C6 alkyl). The compound group / linker may contain one or more bonds selected from ether, ester, amide, urethane, urea, and combinations thereof.

[0042] The term "alicyclic compound / group / linker" refers to a compound / group / linker containing a non-aromatic ring. The non-aromatic ring may have only carbon atoms as ring atoms (i.e., cycloalkyl), or it may contain carbon atoms and one or more heteroatoms selected from N, O, and S as ring atoms (i.e., heterocycloalkyl). The non-aromatic ring may be substituted with one or more groups as defined for aliphatic compounds and linkers. The non-aromatic ring may contain one or more bonds as defined for aliphatic compounds and linkers.

[0043] The term "aromatic compound / group / linker" refers to a compound / group / linker containing an aromatic ring (i.e., a ring conforming to Hückel's aromaticity rules). The aromatic ring may have only carbon atoms as ring atoms (i.e., aryls such as phenyl), or it may contain a carbon atom and one or more heteroatoms selected from N, O, and S as ring atoms (i.e., heteroaryls). The aromatic ring may be substituted with one or more groups as defined for aliphatic compounds and linkers. The aromatic ring may contain one or more bonds as defined for aliphatic compounds and linkers. Aromatic aliphatic compounds / groups / linkers (i.e., compounds / groups / linkers containing both aromatic and aliphatic moieties) are encompassed within aromatic compounds / groups / linkers.

[0044] The term "saturated compound / group / linker" refers to a compound / group / linker that does not contain any carbon-carbon double or carbon-carbon triple bonds.

[0045] The term "unsaturated compound / group / linker" refers to a compound / group / linker containing a carbon-carbon double bond or carbon-carbon triple bond, especially a carbon-carbon double bond.

[0046] The term "polyol" refers to a compound containing at least two hydroxyl groups.

[0047] The term "polyether polyol" refers to a polyol that contains at least two ether bonds.

[0048] The term "polyester polyol" refers to a polyol that contains at least two ester bonds.

[0049] The term "polycarbonate polyol" refers to a polyol containing at least two carbonate bonds.

[0050] The term "polydiene polyol" refers to a polyol containing at least two units obtained by polymerization of a diene (e.g., butadiene).

[0051] The term "polycaprolactone polyol" refers to a polyol obtained by ring-opening polymerization of ε-caprolactone, which contains at least two units, particularly at least two -[(CH2)5-C(=O)O]- units.

[0052] The term "polyorganosiloxane polyol" refers to a polyol containing at least two organosiloxane bonds. These organosiloxane bonds may, for example, be dimethylsiloxane bonds.

[0053] The term "urethane bond" refers to a -NH-C(=O)-O- or -OC(=O)-NH- bond.

[0054] The term "ester bond" refers to a -C(=O)-O- or -OC(=O)- bond.

[0055] The term "ether bond" refers to an O-bond.

[0056] The term "carbonate bond" refers to an -OC(=O)-O- bond.

[0057] The term "optionally substituted compound / group / linker" means a compound / group / linker that may be optionally substituted with one or more groups selected from halogens, alkyls, cycloalkyls, aryls, heteroaryls, alkoxys, aryloxys, aralkyls, alkaryls, haloalkyls, hydroxyls, thiols, hydroxyalkyls, thioalkyls, thioaryls, alkylthiols, aminos, alkylaminos, isocyanates, nitriles, amides, carboxylic acids, -C(=O)-R'-C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R', and -SO2-NH-R' (each R' is independently an optionally substituted group selected from alkyls, aryls, and alkylaryls).

[0058] As used herein, the term "alkoxylation" refers to a compound in which one or more epoxides, such as ethylene oxide and / or propylene oxide, react with an active hydrogen-containing group (e.g., a hydroxyl group) of a base compound, such as a polyol, to form one or more oxyalkylene moieties. For example, 1 to 25 moles of epoxide may be reacted with 1 mole of the base compound.

[0059] <Elastic materials> The elastic material according to the present invention has an elongation greater than 150% when measured in accordance with ASTM D638-02a, a resilience greater than 12% when measured in accordance with ASTM D2632-01 (re-approved in 2008), and a Shore A hardness of at least 10 when measured according to ASTM D2240-15e1. As will be described in more detail below, these properties can be adjusted and altered as desired by selecting and combining various components of the curable composition used to prepare the elastic material. For example, by changing the type and relative amounts of the substances used as components a), b), and c) of the curable composition, changes in the elongation, resilience, and Shore A hardness of the elastic material obtained from those components can be made. The elongation, resilience, and Shore A hardness can be measured as described in the examples.

[0060] According to certain embodiments, the elastic material may have an elongation greater than 200%, greater than 250%, or greater than 300% when measured in accordance with ASTM D638-02a.

[0061] In other embodiments, the elastic material may have an elasticity greater than 20%, greater than 25%, or greater than 30% when measured in accordance with ASTM D2632-01 (re-approved in 2008).

[0062] The elastic material in other embodiments of the present invention may have a Shore A hardness of at least 15, or at least 20, as measured by ASTM D2240-15e1. The Shore A hardness may be, for example, 100 or less, 90 or less, 80 or less, 70 or less, or 60 or less, as measured by ASTM D2240-15e1. For example, the elastic material may have a Shore A hardness of 20 to 60 as measured by ASTM D2240-15e1.

[0063] In certain embodiments, the elastic material of the present invention may have little or no tack. For example, the elastic material may have a probe tack of 4.4 N or less, 2.2 N or less, or 0.44 N or less when measured in accordance with ASTM D2979-95 using a ChemInstruments® PT-500 Inverted Probe Machine in tension peak mode. The diameter at which the inverted probe of the PT-500 contacts the sample is 0.197 inches as defined in ASTM D2979-95. 4.4 N corresponds to a reading of 1.000 pound on the measuring instrument.

[0064] The curable composition used to prepare the elastic material according to the present invention is characterized by being liquid at room temperature (e.g., 25 °C). For example, the curable composition may have a viscosity at 25 °C of 50,000 centipoise or less, 40,000 centipoise or less, 30,000 centipoise or less, or 20,000 centipoise or less when measured using a Brookfield rotational viscometer. As is known in the art, various ASTM methods (such as ASTM D1084 and ASTM D2556) that are all very similar may be used to measure the viscosity using a Brookfield rotational viscometer with a spindle size selected such that the torque is 50 - 70%. The specific ASTM method will be selected based on, among other possible factors, how viscous the liquid sample is and whether the nature of the liquid is Newtonian or non-Newtonian.

[0065] Component a) The curable composition used to prepare the elastic material according to the present invention contains, as component a), one or more (meth)acrylate-functionalized oligomers having an average of two or fewer (meth)acrylate functional groups per molecule. Any such oligomers known in the art can be used. However, when measured using gel permeation chromatography and calibration standard polystyrene, the number average molecular weight (M n) is at least 10,000 Daltons. Therefore, if the curable composition contains a single such oligomer, its M n M should be at least 10,000 Daltons. In embodiments of the present invention in which the curable composition contains two or more such oligomers, at least one other such oligomer present in the curable composition has an M of at least 10,000 Daltons. n It has the M of multiple oligomers when combined in the proportions used in the curable composition. n If the amount is at least 10,000 Daltons, then one or more of such oligomers have less than 10,000 Daltons. n It is possible to have it.

[0066] According to various embodiments of the present invention, component a) M n is at least 10,000 Daltons, at least 12,500 Daltons, at least 15,000 Daltons, at least 17,500 Daltons, at least 20,000 Daltons, at least 21,000 Daltons, at least 22,000 Daltons, or at least 25,000 Daltons. In particular, M of component a) n This is less than or equal to 100,000 Daltons, less than or equal to 75,000 Daltons, or less than or equal to 50,000 Daltons. For example, M of component a) n This may be 10,000 to 100,000 Daltons, or 12,500 to 75,000 Daltons. In particular, component a) M n This could be 12,000-50,000 Daltons, 12,500-50,000 Daltons, 12,500-40,000 Daltons, 12,500-30,000 Daltons, or 15,000-30,000 Daltons.

[0067] Suitable oligomers for use as component a) in the curable composition of the present invention may be functionalized with acrylate functional groups alone, with methacrylate functional groups alone, or with both acrylate and methacrylate functional groups (for example, oligomers containing both acrylate and methacrylate functional groups in the same molecule can be used). For example, using oligomers with a molar ratio of acrylate functional group to methacrylate functional group of 1:3 to 3:1, 1:2 to 2:1, or 1:1.5 to 1.5:1 may be advantageous under certain circumstances.

[0068] In particular, the oligomer of component a) contains at least one acrylate group.

[0069] Typically, the oligomer may have (meth)acrylate functional groups at one or more of its termini, but it is also possible for the (meth)acrylate functional groups to be positioned along the main chain of the oligomer. The average (meth)acrylate functional value of the oligomer of component a) may generally be 2 or less (i.e., an average of 2 (meth)acrylate functional groups per molecule), but in other embodiments, the average (meth)acrylate functional value may be less than 2, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less. In particular, the average acrylate functional value of the oligomer or component a) may generally be 2 or less (i.e., an average of 2 acrylate functional groups per molecule), but in other embodiments, the average acrylate functional value may be less than 2, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less. Generally, the oligomer or combination of oligomers used as component a) preferably has at least one average (meth)acrylate functional value, and more preferably at least one average acrylate functional value.

[0070] Suitable oligomers include, but are not limited to, epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, (meth)acrylic (meth)acrylate oligomers, and amino (meth)acrylate oligomers. The oligomer structure may contain two or more segmental properties from the above-mentioned oligomer classes. The oligomer may contain both a "hard" segment and a "soft" segment, and may also be a block copolymer. The oligomer may contain regions whose structure is similar to that of common elastomer materials (e.g., polyurethane, polyisoprene, polybutadiene, polyisobutylene), but may not have structural similarity to conventional elastomers.

[0071] In certain embodiments of the present invention, the oligomer may have a relatively low glass transition temperature (Tg) as measured by differential scanning calorimeter. For example, the oligomer may have a Tg of less than 0°C, less than -10°C, less than -20°C, less than -30°C, less than -40°C, less than -50°C, less than -60°C, or less than -70°C.

[0072] Examples of suitable epoxy (meth)acrylate oligomers include reaction products of acrylic acid or methacrylic acid or mixtures thereof with epoxy group-containing compounds such as glycidyl ether or ester. The epoxy (meth)acrylate oligomer may be hydroxyl-functionalized (i.e., containing one or more hydroxyl functional groups in addition to one or two (meth)acrylate functional groups per molecule). Suitable hydroxyl-functionalized epoxy (meth)acrylate oligomers include, but are not limited to, oligomer compounds obtained by the reaction of an epoxy compound (such as an epoxy resin oligomer or other epoxy-functionalized oligomer) with (meth)acrylic acid (introducing both hydroxyl and (meth)acrylate functionality through ring-opening of the epoxy group by (meth)acrylic acid). The starting epoxy compound may have a number average molecular weight of 10,000 daltons or more (so that the epoxy (meth)acrylate oligomer obtained from the compound similarly has a number average molecular weight of at least 10,000 daltons). For example, higher molecular weight oligomers of bisphenol-type epoxy resins can be used. Alternatively, oligomers such as polyoxyalkylene glycol or polybutadiene can be functionalized with one or two epoxy groups, and then the epoxy groups can be reacted with (meth)acrylic acid to obtain suitably high molecular weight epoxy (meth)acrylate oligomers. Suitable examples of hydroxyl-functionalized epoxy (meth)acrylates include aliphatic epoxy (meth)acrylate oligomers that possess both (meth)acrylate functionality and secondary hydroxyl functionality due to ring-opening of the epoxy groups.

[0073] Examples of urethane (meth)acrylate oligomers (also called (meth)acrylate-functionalized polyurethane oligomers) usable in the curable composition of the present invention include urethanes based on aliphatic and / or aromatic polyester polyols and polyether polyols, and aliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates, which are terminally capped with one or two (meth)acrylate terminal groups. Suitable urethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane mono and diacrylate oligomers, aliphatic polyether-based urethane mono and diacrylate oligomers, and aliphatic polyester / polyether-based urethane mono and diacrylate oligomers.

[0074] In various embodiments, urethane (meth)acrylate oligomers may be prepared by reacting an aliphatic and / or aromatic diisocyanate with an OH-terminated polyester polyol (including aromatic, aliphatic, and aliphatic / aromatic polyester polyol mixtures), a polyether polyol (particularly polypropylene glycol and / or polytetramethylene glycol), a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol (particularly polydimethylsiloxane polyol), or a polydiene polyol (particularly polybutadiene polyol), or a combination thereof, to form an isocyanate-functionalized oligomer, and then reacting the oligomer with a hydroxyl-functionalized (meth)acrylate such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate or hydroxyethyl methacrylate, or polycaprolactone (meth)acrylate) to impart one or two terminal (meth)acrylate groups. Other synthetic methods for preparing urethane (meth)acrylate oligomers are well known in the art, and by using any of these methods, oligomers suitable for use in component a) of a curable composition can be prepared according to the present invention.

[0075] Particularly preferred urethane (meth)acrylate oligomers suitable for use in the present invention include oligomers formed by the reaction of a polyol, a diisocyanate, and a hydroxyl-functionalized (meth)acrylate (such as hydroxyalkyl (meth)acrylate or polycaprolactone (meth)acrylate).

[0076] Urethane (meth)acrylate oligomers are given by the following formula (I): [ka] (In the formula, each A is independently a polyol residue; Each R is independently a residue of the diisocyanate; Each B is independently a residue of a hydroxyl-functionalized (meth)acrylate; Each X is independently either H or methyl; n is 1 to 20, preferably 1 to 15, more preferably 1 to 10. It may also contain urethane (meth)acrylate oligomers in accordance with the formula.

[0077] In this specification, the term “diol residue” means the portion between the two hydroxyl groups of a diol. Therefore, A may be a residue of a polyol of the formula OH-A-OH.

[0078] In this specification, the term “diisocyanate residue” means the portion between the two isocyanate groups of a diisocyanate. Therefore, R may be a diisocyanate residue of the formula OCN-R-NCO.

[0079] As used herein, the term “residue of a hydroxyl-functionalized (meth)acrylate” means the portion of a hydroxylated mono(meth)acrylate between the (meth)acrylate functional group and the hydroxyl group. Thus, B may be a residue of a hydroxylated mono(meth)acrylate of the formula CH2=C(X)-(C=O)-OB-OH (where X is H or methyl).

[0080] The urethane (meth)acrylate oligomer may be based on polypropylene glycol. A polypropylene glycol-based urethane (meth)acrylate oligomer refers to a urethane (meth)acrylate oligomer containing oxypropylene units. The oxypropylene units are preferably included in the polyol portion of the urethane (meth)acrylate oligomer. The polyol portion of the urethane (meth)acrylate oligomer may correspond to portion A in formula (I). The hydroxyl-functionalized (meth)acrylate portion preferably contains substantially no oxypropylene units. The hydroxyl-functionalized (meth)acrylate portion of the urethane (meth)acrylate oligomer may correspond to portion B in formula (I).

[0081] The mass content of oxypropylene units in the urethane (meth)acrylate oligomer may be at least 45% based on the total mass of the urethane (meth)acrylate oligomer. In particular, the mass content of oxypropylene units may be 45-95%, 50-95%, 55-95%, 60-95%, 65-95%, 70-95%, 75-95%, 78-95%, or 80-95% based on the total mass of the urethane (meth)acrylate oligomer. The mass content of oxypropylene units can be determined by calculating the mass of oxypropylene units in the compound used to prepare the urethane (meth)acrylate relative to the total mass of the compound used to prepare the urethane (meth)acrylate.

[0082] The polyol used to prepare the urethane (meth)acrylate oligomer may have a number-average molecular weight of at least 2,000 daltons, at least 3,000 daltons, at least 4,000 daltons, or at least 5,000 daltons.

[0083] The polyol used to prepare the urethane (meth)acrylate oligomer is preferably selected from polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polydimethylsiloxane polyols, and polydiene polyols, with polyether polyols being particularly preferred.

[0084] Polyether polyols may have a degree of olefin unsaturation higher than 0.01 meq / g (milliequivalent of olefin per gram of polyether polyol). For example, polyether polyols may have a degree of olefin unsaturation of 0.015 to 0.05 meq / g or 0.02 to 0.05 meq / g. The degree of unsaturation can be determined in accordance with ASTM method D4671-93 "Polyurethane Raw Materials: Determinations of Unsaturation of Polyols".

[0085] The polyether polyol may contain less than 10% by mass, less than 8% by mass, less than 5% by mass, less than 1% by mass, or even 0% by mass of ethylene glycol monomer units, based on the mass of the polyether polyol. Alternatively, the polyether polyol may contain more than 30% by mass, more than 40% by mass, more than 50% by mass, or more than 60% by mass of ethylene glycol monomer units, based on the mass of the polyether polyol.

[0086] The polyether polyol may have a number-average molecular weight of at least 2,000 daltons, at least 3,000 daltons, at least 4,000 daltons, or at least 5,000 daltons.

[0087] The polyether polyol may be selected from a homopolymer or copolymer of polypropylene glycol, a homopolymer or copolymer of polyethylene glycol, and a homopolymer or copolymer of polytetramethylene glycol. Preferably, the polyether polyol is selected from a homopolymer of polypropylene glycol, a homopolymer of polyethylene glycol, and a homopolymer of polytetramethylene glycol, more preferably a homopolymer of polypropylene glycol or a homopolymer of polytetramethylene glycol, and even more preferably a homopolymer of polypropylene glycol.

[0088] The diisocyanate used to prepare the urethane (meth)acrylate oligomer may be aromatic, aliphatic, or alicyclic diisocyanate.

[0089] Examples of suitable diisocyanates having aliphatic residues include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), and 1,12-dodecane diisocyanate.

[0090] Examples of suitable diisocyanates having alicyclic residues include 1,3- and 1,4-cyclohexane diisocyanates, isophorone diisocyanates (IPDI, which corresponds to 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), dicyclohexylmethane-4,4'-diisocyanate (HMDI or hydrogenated MDI), 2,4-diisocyanato-1-methylcyclohexane, and 2,6-diisocyanato-1-methylcyclohexane.

[0091] Examples of suitable diisocyanates having aromatic residues include 4,4'-methylenediphenyl diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), 1,4-benzene diisocyanate, 1,5-naphthalene diisocyanate (NDI), m-tetramethylene xylylene diisocyanate, and 4,6-xylylene diisocyanate.

[0092] In preferred embodiments, the diisocyanate may be an aliphatic or alicyclic diisocyanate, such as a diisocyanate containing a C4-C12 hydrocarbon chain or one or more cyclohexyl groups. More specifically, the diisocyanate may be an alicyclic diisocyanate. Even more specifically, the diisocyanate may be an isophorone diisocyanate.

[0093] Hydroxyl-functionalized (meth)acrylates are given by the following formula: CH2=C(X)-(C=O)-OB-OH (wherein B is a divalent linker; X is either H or methyl. This can be considered equivalent to that.

[0094] Hydroxyl-functionalized (meth)acrylates may have molecular weights (molar masses) of less than 600 g / mol, less than 500 g / mol, less than 400 g / mol, less than 350 g / mol, less than 300 g / mol, less than 250 g / mol, less than 200 g / mol, or less than 150 g / mol.

[0095] In one embodiment, B may correspond to a hydrocarbon linker containing 2 to 50 carbon atoms, particularly 2 to 10 carbon atoms, and more specifically 2 to 6 carbon atoms. The hydrocarbon linker may optionally be substituted with one or more hydroxyl groups. The hydrocarbon linker may optionally be interrupted by one or more oxygen atoms. B may optionally contain one or more oxyalkylene units, particularly three or fewer oxyalkylene units. The oxyalkylene units may be selected from oxyethylene, oxypropylene, oxybutylene, and combinations thereof, preferably oxyethylene, oxybutylene, and combinations thereof. In one embodiment, B may substantially not contain oxypropylene units, and in particular B may substantially not contain oxyalkylene units.

[0096] More specifically, B is given by the following equation: -(Alk-O) p -(L) q -(O-Alk) r - (wherein each Alk is independently ethylene, propylene, or butylene, preferably ethylene or butylene; L is a C2-C20 alkylene, preferably a C2-C10 alkylene, which may be optionally substituted with one or more hydroxyl groups; p and r are independently between 0 and 3, preferably both p and r are 0; q is 0 or 1, preferably 1; This may correspond to the condition that p, q, and r are all not zero, and the sum of p+r is between 0 and 6, preferably between 0 and 3.

[0097] Examples of such hydroxyl-functionalized (meth)acrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, neopentyl glycol monoacrylate, neopentyl glycol monomethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, triethylolpropane monoacrylate, triethylolpropane monomethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Examples include methacrylates, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, tripropylene glycol monoacrylate, tripropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, dibutylene glycol monoacrylate, dibutylene glycol monomethacrylate, tributylene glycol monoacrylate, tributylene glycol monomethacrylate, polybutylene glycol monoacrylate, polybutylene glycol monomethacrylate, alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives of the above compounds, and mixtures thereof.

[0098] The following compounds are particularly preferred: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, neopentyl glycol monoacrylate, neopentyl glycol monomethacrylate.

[0099] In another embodiment, B may be a residue containing an ester bond, particularly at least two ester bonds. In particular, B may be a residue containing a polymerization unit derived from a lactone, particularly caprolactone.

[0100] More specifically, B is given by the following formula: -((CH2)5-CO2) s -R'- (wherein R' is a C2-C8 alkylene, preferably a C2-C6 alkylene, more preferably a C2-C4 alkylene; (s is 1 to 10, preferably 2 to 8, more preferably 3 to 5) This can be considered equivalent to that.

[0101] Hydroxyl-functionalized (meth)acrylates containing polymerization units derived from lactones can be prepared by reacting a lactone (preferably ε-caprolactone) with a hydroxyalkyl mono(meth)acrylate (preferably 2-hydroxyethyl acrylate) followed by ring-opening polymerization of the lactone.

[0102] Examples of polyester (meth)acrylate oligomers include reaction products of acrylic acid or methacrylic acid or mixtures thereof with hydroxyl-terminated polyester polyols. The reaction process can be carried out such that all or some of the hydroxyl groups of the polyester polyol are (meth)acrylicated. Polyester polyols can be produced by polycondensation reactions of polyhydroxyl functional components (particularly diols such as glycols and oligoglycols) and polycarboxylic acid functional compounds (particularly dicarboxylic acids and anhydrides). The polyhydroxyl functional components and polycarboxylic acid functional components may each have linear, branched, alicyclic, or aromatic structures and can be used individually or as a mixture. According to a preferred embodiment, the polyester polyol used to prepare the polyester (meth)acrylate oligomer has a number-average molecular weight of at least 10,000 daltons, at least 12,500 daltons, or at least 15,000 daltons.

[0103] Suitable (meth)acrylic (meth)acrylate oligomers (sometimes referred to in the art as "acrylic oligomers" or "(meth)acrylic oligomers") include oligomers that may be described as having an oligomeric acrylic backbone functionalized with one or two (meth)acrylate groups (which may be present at the end of the oligomer or as pendants to the acrylic backbone). The (meth)acrylic backbone may be a homopolymer, random copolymer, or block copolymer composed of repeating units of (meth)acrylic monomers. The (meth)acrylic monomers may be any monomer (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, and functionalized (meth)acrylates, such as (meth)acrylates having hydroxyl groups, carboxylic acid groups, and / or epoxy groups. (Meth)acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art. For example, a monomer functionalized with at least a portion of a hydroxyl group, a carboxylic acid group, and / or an epoxy group (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) can be oligomerized to obtain a functionalized oligomer intermediate, and then the intermediate can be reacted with one or more (meth)acrylate-containing reaction products to introduce the desired (meth)acrylate functional group.

[0104] According to various embodiments of the present invention, the curable composition used to prepare the elastic material of the present invention comprises, based on the combined mass of components a), b), and c), one or more (meth)acrylate-functionalized oligomers having an average of two or fewer (meth)acrylate functional groups per molecule, totaling 43% to 89.9% by mass (i.e., component a) constitutes 43% to 89.9% of the total mass of components a), b), and c). In certain embodiments, component a) constitutes at least 50% by mass, at least 55% by mass, at least 60% by mass, or at least 65% by mass of the combined components a), b), and c). In other embodiments, component a) constitutes 85% by mass or less, 80% by mass or less, or 75% by mass or less of the combined components a), b), and c). For example, in a particular embodiment, the curable composition may contain such oligomers in an amount of 65-75% by mass, or 70-75% by mass, based on the combined mass of components a), b), and c).

[0105] component b) A curable composition used to prepare an elastic material according to the present invention comprises, as component b), one or more mono(meth)acrylate-functionalized monomers having a molecular weight of less than 500 daltons and a single (meth)acrylate functional group per molecule, and / or one or more ethylenically unsaturated nitrogen-containing monomers.

[0106] A curable composition used to prepare an elastic material according to the present invention may contain, as component b), one or more mono(meth)acrylate-functionalized monomers having a molecular weight of less than 500 daltons and a single (meth)acrylate functional group per molecule. Such compounds are sometimes referred to herein as "monofunctional (meth)acrylate monomer diluents." Any such compounds known in the art may be used.

[0107] Suitable examples of monofunctional (meth)acrylate monomer diluents include: mono(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monoalcohol, dialcohol, or polyol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (phenols including alkylated phenols, etc.); mono(meth)acrylate esters of alkylaryl alcohols (benzyl alcohol, etc.); and mono(meth)acrylate esters of glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol, etc.). Examples include, but are not limited to, mono(meth)acrylate esters; mono(meth)acrylate esters of glycol monoalkyl ethers; mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (where the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (alkoxylated phenols, etc.); caprolactone mono(meth)acrylate; and others.

[0108] Examples of monofunctional (meth)acrylate monomer diluents include tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 2(2-hydroxy)ethyl (meth)acrylate, diethylene glycol methyl ether (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, ethoxylated phenol (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate; cyclic trimethylolpropaneformyl (meth)acrylate, ethoxy Liglycol (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, alkoxylated lauryl acrylate, ethoxylated cetyl / stearyl (meth)acrylate, alkoxylated phenol acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, allyl (meth)acrylate, propoxylated allyl (meth)acrylate, caprolactone (meth)acrylate, polyoxyethylene p-cumylphenyl ether (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, C 12 ~C 14 Examples include, but are not limited to, alkyl (meth)acrylates and behenyl (meth)acrylates.

[0109] The monofunctional (meth)acrylate monomer of component b) has a Hansen solubility parameter distance relative energy difference of at least 3 MPa with the (meth)acrylate-functionalized oligomer of component a). 1 / 2 It may be selected to show the following: For example, the Hansen solubility parameter distance relative energy difference between a monofunctional (meth)acrylate monomer and a (meth)acrylate-functionalized oligomer is 3-10 MPa. 1 / 2 , 3-9 MPa 1 / 2or 3-8 MPa 1 / 2 That's fine.

[0110] The Hansen solubility parameters consist of three parameters representing the forces acting between molecules of a substance (dispersion forces, polar interactions, and hydrogen bonding forces). They can be calculated according to the method proposed by Charles Hansen in his book "Hansen Solubility Parameters, A User's Handbook," 2nd edition (2007), Boca Raton, Fla.: CRC Press. ISBN 978-O-8493-7248-3. According to this method, the three parameters called Hansen parameters are: δ d , δ p , δ h This is sufficient to predict the behavior of the solvent for a given molecule. Parameter δ d This quantifies the energy of intermolecular dispersion forces, i.e., van der Waals forces (unit: MPa). 1 / 2 ). Parameter δ p This represents the energy of the intermolecular dipole interaction (unit: MPa). 1 / 2 ). Finally, the parameter δ h This quantifies the energy derived from intermolecular hydrogen bonds, i.e., the ability to interact via hydrogen bonds (unit: MPa). 1 / 2 The sum of the squares of these three parameters is the Hildebrand solubility parameter (δ). tot This is equivalent to the square of ).

[0111] The three Hansen solubility parameters define a three-dimensional Hansen space. The three Hansen solubility parameters of a material are coordinates in Hansen space. Therefore, the Hansen solubility parameters of a material determine its relative position in Hansen space. The Hansen solubility parameters of a multi-component mixture are a volume-weighted combination of the Hansen solubility parameters of the individual components constituting the mixture. Therefore, a multi-component mixture also has a relative position in Hansen space. The Hansen solubility parameter distance (Ra) is the distance between any two materials in Hansen space. Ra is given by the following equation 1:

number

[0112] According to certain embodiments of the present invention, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the (meth)acrylate functional groups in component b) are acrylate functional groups (the remainder, if any, are methacrylate functional groups). According to one embodiment, all functional groups in component b) are acrylate functional groups.

[0113] According to a particular embodiment of the present invention, component b) comprises at least one high-Tg monofunctional monomer and at least one low-Tg monofunctional monomer. As used herein, “high-Tg monofunctional monomer” refers to a monofunctional (meth)acrylate monomer diluent that, when homopolymerized, produces a polymer having a glass transition temperature (measured by differential scanning calorimetry) higher than 25°C, and “low-Tg monofunctional monomer” refers to a monofunctional (meth)acrylate monomer diluent that, when homopolymerized, produces a polymer having a glass transition temperature (measured by differential scanning calorimetry) lower than 25°C.

[0114] High-Tg monofunctional monomers, for example, when homopolymerized, can produce polymers having a Tg of at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, or at least 75°C. Isobornyl acrylate is an example of a high-Tg monofunctional monomer. Low-Tg monofunctional monomers, for example, when homopolymerized, can produce polymers having a Tg of 10°C or less, at least 0°C, at least -10°C or less, at least -20°C or less, or at least -25°C. 2-(2-ethoxyethoxy)ethyl acrylate is an example of a low-Tg monofunctional monomer. In certain embodiments, the difference in such glass transition temperatures (i.e., the difference between the Tg of the high-Tg monofunctional monomer during homopolymerization and the Tg of the low-Tg monofunctional monomer) is at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, or at least 100°C.

[0115] The relative amounts of high-Tg and low-Tg monofunctional monomers in the curable composition may be varied as desired, for example, depending on the properties of the oligomers also present in the curable composition and the properties (e.g., hardness) required for the elastic material obtained from the curable composition. However, generally, the mass ratio of high-Tg monofunctional monomers to low-Tg monofunctional monomers in the curable composition is preferably 1:10-10:1, 1:5-5:1, 1:4-4:1, 1:3-3:1, or 1:2-2:1. Generally, when all other attributes of the curable composition are kept constant, the Shore A hardness of the elastic material can be increased by increasing the amount of high-Tg monofunctional monomers relative to the amount of low-Tg monofunctional monomers.

[0116] In a preferred embodiment, component b) comprises a monofunctional monomer selected from sterically hindered monofunctional (meth)acrylate monomers, ethylenically unsaturated nitrogen-containing monomers, and mixtures thereof.

[0117] Component b) may contain at least one sterically hindered monofunctional (meth)acrylate monomer. Component b) may contain a mixture of sterically hindered monofunctional (meth)acrylate monomers.

[0118] The sterically hindered monofunctional (meth)acrylate monomer may contain a cyclic moiety and / or a tert-butyl group. The cyclic moiety may be monocyclic, bicyclic, or tricyclic, and may include a crosslinked ring system, a fused ring system, and / or a spiro-ring system. The cyclic moiety may be carbocyclic (all ring atoms are carbon) or heterocyclic (ring atoms consist of at least two elements). The cyclic moiety may be aliphatic, aromatic, or a combination of aliphatic and aromatic. In particular, the cyclic moiety may contain a ring or ring system selected from cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof. More specifically, the cyclic moiety may contain a ring or ring system selected from phenyl, cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl, dicyclopentadienyl, oxylanil, oxetanyl, tetrahydrofuranil, tetrahydropyranil, dioxolanil, dioxanil, dioxanil, dioxapridecanyl, and dioxapridecanyl. The ring or ring system may be optionally substituted with one or more groups selected from hydroxyl, alkoxy, alkyl, hydroxyalkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl.

[0119] In particular, the ring part is given by the following equation: [ka] (In the formula, symbols [ka] This indicates the site where the (meth)acrylate group is bonded. Dashed line connection [ka] This represents a single bond or a double bond; Each ring atom may be optionally substituted with one or more groups selected from hydroxyl, alkoxy, alkyl, hydroxyalkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups. It may correspond to one of the following.

[0120] A particularly preferred ring portion is given by the following equation: [ka] It corresponds to one of them.

[0121] Suitable examples of sterically hindered monofunctional (meth)acrylate monomers include tert-butyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, tricyclodecane methanol mono(meth)acrylate, and tetrahydrofulf Examples include lyl(meth)acrylate, cyclic trimethylolpropaneformyl(meth)acrylate (also called 5-ethyl-1,3-dioxan-5-yl)methyl(meth)acrylate, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, glycerol formal methacrylate, their alkoxylated derivatives, and mixtures thereof.

[0122] Preferred examples of sterically hindered monofunctional (meth)acrylate monomers include tert-butyl (meth)acrylate, isobornyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate (also called 5-ethyl-1,3-dioxan-5-yl)methyl (meth)acrylate), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, glycerol formal methacrylate, their alkoxylated derivatives, and mixtures thereof.

[0123] In particular, sterically hindered monofunctional (meth)acrylate monomers may account for at least 10% by mass, 10-100% by mass, 20-100% by mass, 30-100% by mass, 40-100% by mass, 50-100% by mass, 60-100% by mass, 70-100% by mass, 80-100% by mass, 90-100% by mass, and even 100% by mass of the total mass of component b).

[0124] Component b) may contain an ethylenically unsaturated nitrogen-containing monomer. Component b) may contain a mixture of ethylenically unsaturated nitrogen-containing monomers.

[0125] The presence of ethylenically unsaturated nitrogen-containing monomers can, advantageously, improve the adhesion of the cured material to the substrate on which it is cured.

[0126] Ethylene-unsaturated nitrogen-containing monomers contain ethylenically unsaturated functional groups and nitrogen-containing groups. Ethylene-unsaturated nitrogen-containing monomers may have a molecular weight of less than 500 daltons and a single ethylenically unsaturated functional group per molecule.

[0127] Ethylene-unsaturated functional groups may include groups containing polymerizable carbon-carbon double bonds. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds are generally found in groups selected from acryloyl, methacryloyl, and alkenyl (vinyl, allyl, propen-1-yl, butenyl, pentenyl, hexenyl, etc.), preferably in groups selected from acryloyl, methacryloyl, and vinyl. Carbon-carbon double bonds in aromatic rings or aromatic heterocycles are not considered polymerizable carbon-carbon double bonds.

[0128] The nitrogen-containing group of the monomer may have any preferred chemical configuration. The nitrogen-containing group may have a cyclic or acyclic structure. In many preferred cyclic nitrogen-containing groups, nitrogen is one of the ring atoms of the cyclic structure. Exemplary cyclic groups containing a nitrogen ring atom include, but are not limited to, the pyrrolidonyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, pyridinyl group, pyridadinyl group, pyrimidinyl group, piperidinyl group, pyrazinyl group, piperazinyl group, piperidonyl group, triazinyl group, caprolactamyl group, carbazolyl group, morpholinyl group, and succinimidyl group.

[0129] The ethylenically unsaturated functional group may be directly or indirectly, preferably directly, bonded to the nitrogen atom of the nitrogen-containing group.

[0130] In particular, monomers containing ethylenically unsaturated nitrogen are given by the following formula: [ka] (In the formula, R1 and R2 are independently H, alkyl, aryl, and -C(=O)-R 11 Selected from; or, R1 and R2 may form a 4- to 10-membered ring with the nitrogen atom to which they are bonded; R6 and R7 are independently H, alkyl, aryl, -L3-C(=O)-R 12R6 and R7 may be selected from cycloalkyl, aminoalkyl, and alkoxyalkyl groups; or R6 and R7 may form a 4-10 membered ring with the nitrogen atom to which they are bonded; R3, R4, R5, R8, R9, and R 10 These are independently selected from H, alkyl, and Cl; R 11 and R 12 is independently H or alkyl; L1 is a bond or alkylene, preferably a bond or methylene; L2 and L3 are independently alkylenes; m is 0 or 1, preferably 0.) It may correspond to one of the following.

[0131] The ethylenically unsaturated nitrogen-containing monomer may contain an alkenyl group (particularly a vinyl group or allyl group) bonded to a cyclic nitrogen-containing group, preferably directly bonded to the nitrogen atom that is the ring atom of the cyclic nitrogen-containing group. Suitable examples include N-vinylcarbazole, N-allylcarbazole, N-butenylcarbazole, N-hexenylcarbazole, N-vinylsuccinimide, N-vinylimidazole, N-allyliimidazole, N-vinyl-2-methylimidazole, N-vinyl-2-ethylimidazole, N-vinyl-2-phenylimidazole, N-vinyl-2,4-dimethylimidazole, N-vinylbenzimidazole, N-vinylimidazolin, N-vinyl-2-methylimidazolin, N-vinyl 2-phenylimidazoline, N-vinylpiperidine, N-allylpiperidine, N-vinyl-2-pyrrolidone, N-allylpyrrolidone, N-vinyl-3-methylpyrrolidone; N-vinyl-4-methylpyrrolidone; N-vinyl-5-methylpyrrolidone; N-vinyl-3-ethylpyrrolidone; N-vinyl-3-butylpyrrolidone; N-vinyl-3,3-dimethylpyrrolidone; N-vinyl-4,5-dimethylpyrrolidone; N-vinyl-5,5-dimethylpyrrolidone; N-vinyl-3,3,5-trimethylpyrrolidone Roridone; N-vinyl-5-methyl-5-ethylpyrrolidone; N-vinyl-3,4,5-trimethyl-3-ethylpyrrolidone; N-vinyl-2-piperidone; N-vinyl-6-methyl-2-piperidone; N-vinyl-6-ethyl-2-piperidone; N-vinyl-3,5-dimethyl-2-piperidone; N-vinyl-4,4-dimethyl-2-piperidone; N-vinyl-6-propyl-2-piperidone; N-vinyl-3-octylpiperidone; N-vinylcaprolactam, N-allylcaprolactam, N- Vinyl-7-methyl caprolactam; N-vinyl-7-ethyl caprolactam; N-vinyl-4-isopropyl caprolactam; N-vinyl-5-isopropyl caprolactam; N-vinyl-4-butyl caprolactam; N-vinyl-5-butyl caprolactam; N-vinyl-4-butyl caprolactam; N-vinyl-5-tert-butyl caprolactam; N-vinyl-4-octyl caprolactam; N-vinyl-5-tert-octyl caprolactam; N-vinyl-4-nonyl caprolactam;Examples include, but are not limited to, N-vinyl-5-tert-nonylcaprolactam; N-vinyl-3,7-dimethylcaprolactam; N-vinyl-3,5-dimethylcaprolactam; N-vinyl-4,6-dimethylcaprolactam; N-vinyl-3,5,7-trimethylcaprolactam; N-vinyl-2-methyl-4-isopropylcaprolactam; and N-vinyl-5-isopropyl-7-methylcaprolactam and N-vinylcapryllactam.

[0132] The ethylenically unsaturated nitrogen-containing monomer may contain an alkenyl group (particularly a vinyl group or an allyl group) bonded to an acyclic nitrogen-containing group, preferably directly bonded to the nitrogen atom of the acyclic nitrogen-containing group. Examples include, but are not limited to, N-vinylacetamide; N-propenylacetamide; N-(2-methylpropenyl)acetamide; N-vinylformamide; N-(2,2-dichloro-vinyl)propionamide; N-vinyl-N-methylacetamide; and N-vinyl-N-propylpropionamide.

[0133] The ethylenically unsaturated nitrogen-containing monomer may include a (meth)acryloyl group bonded to a cyclic nitrogen-containing group, preferably directly bonded to the nitrogen atom that is the ring atom of the cyclic nitrogen-containing group. Suitable examples include, but are not limited to, N-(meth)acryloylpyrrolidone; N-(meth)acryloylcaprolactam; N-(meth)acryloylpiperidone; ethyl(meth)acryloylpyrrolidone; methyl(meth)acryloylpyrrolidone; ethyl(meth)acryloylcaprolactam; methyl(meth)acryloylcaprolactam, and 4-(meth)acryloylmorpholine.

[0134] The ethylenically unsaturated nitrogen-containing monomer may also contain a (meth)acryloyl group bonded to an acyclic nitrogen-containing group, preferably a (meth)acryloyl group directly bonded to the nitrogen atom of the acyclic nitrogen-containing group. Examples include (meth)acrylamide, N-methyl(meth)acrylamide; N-ethyl(meth)acrylamide; isopropyl(meth)acrylamide; N,N-diethyl(meth)acrylamide; N-cyclohexyl(meth)acrylamide, N-cyclopentyl(meth)acrylamide; N-butoxymethyl(meth)acrylamide; N,N-dibutyl(meth)acrylamide; N-butyl(meth)acrylamide; diacetone(meth)acrylamide; N-(N,N-dimethylamino)ethyl(meth)acrylamide; N-(N,N-dimethylamino)propyl(meth)acrylamide, N,N-diethyl(meth)acrylamide; N,N-dimethyl(meth)acrylamide; N-octyl(meth)acrylamide; N-decyl(meth)acrylamide; N-dodecyl(meth)acrylamide; N-octadecyl(meth)acrylamide; N-isopropyl Examples include, but are not limited to, methylol(meth)acrylamide; N-tert-butyl(meth)acrylamide; N-isobutyl(meth)acrylamide; N,N,3,3-tetramethylacrylamide; N-methylol(meth)acrylamide; N-[2-hydroxyethyl](meth)acrylamide; N-phenyl(meth)acrylamide; trichloroacrylamide; 2-dimethylaminoethyl(meth)acrylate; 2-diethylaminoethyl(meth)acrylate; 3-dimethylamino-2,2-dimethylpropyl-1-(meth)acrylate; 3-diethylamino-2,2-dimethylpropyl-1-(meth)acrylate; 2-morpholinoethyl(meth)acrylate; 2-tert-butylaminoethyl(meth)acrylate; 3-(dimethylamino)propyl(meth)acrylate; and 2-(dimethylaminoethoxyethyl)(meth)acrylate.

[0135] In particular, the ethylenically unsaturated nitrogen-containing monomer may account for at least 10% by mass, 10-100% by mass, 20-100% by mass, 30-100% by mass, 40-100% by mass, 50-100% by mass, 60-100% by mass, 70-100% by mass, 80-100% by mass, 90-100% by mass, or even 100% by mass of the total mass of component b).

[0136] In a particularly preferred embodiment, component b) contains at least 10% by mass of monofunctional monomers selected from sterically hindered monofunctional (meth)acrylate monomers, ethylenically unsaturated nitrogen-containing monomers, and mixtures thereof. For example, component b) may contain 10-100% by mass, 20-100% by mass, 30-100% by mass, 40-100% by mass, 50-100% by mass, 60-100% by mass, 70-100% by mass, 80-100% by mass, 90-100% by mass, and even 100% by mass of monofunctional monomers selected from sterically hindered monofunctional (meth)acrylate monomers, ethylenically unsaturated nitrogen-containing monomers, and mixtures thereof, based on the total mass of component b).

[0137] Component b) may contain one or more monofunctional (meth)acrylate monomers that function as adhesion promoters. Adhesion promoters are substances that can improve the adhesion of elastic materials obtained from the curable composition to a substrate (particularly the substrate surface). Exemplary (meth)acrylate-functionalized adhesion promoters include, but are not limited to, (meth)acrylated (meth)acrylic acid esters, (meth)acrylated sulfate esters, (meth)acrylated phosphate esters, and any other (meth)acrylated organic acids, (meth)acrylated inorganic acids, and (meth)acrylated silanes.

[0138] According to various embodiments of the present invention, the curable composition used to prepare the elastic material of the present invention contains 10 to 55% by mass of one or more monofunctional (meth)acrylate monomer diluents in total, based on the combined mass of components a), b), and c). That is, component b) may constitute 10 to 55% by mass of the total mass of the combined components a), b), and c). According to a particular embodiment, the curable composition contains at least 12% by mass, at least 15% by mass, or at least 18% by mass, and / or 35% by mass or less, or 30% by mass or less, of monofunctional (meth)acrylate monomer diluents in total. For example, in a particular embodiment, the curable composition may contain 18 to 30% by mass or 18 to 25% by mass of such monofunctional (meth)acrylate monomer diluents in total.

[0139] Ingredient c) The curable composition used to prepare an elastic material according to the present invention contains, as component c), one or more multi(meth)acrylate-functionalized monomers having a molecular weight of less than 1000 daltons and at least two (meth)acrylate functional groups per molecule. Such monomers function as crosslinking agents during the curing of the curable composition to form an elastic material according to an embodiment of the present invention. Any such compounds known in the art can be used. The multi(meth)acrylate-functionalized monomer may have, for example, two, three, four, five, or more (meth)acrylate functional groups per molecule. Preferably, the multi(meth)acrylate-functionalized monomer has two (meth)acrylate functional groups per molecule. The functional groups may consist solely of acrylate functional groups, solely of methacrylate functional groups, or both acrylate and methacrylate functional groups, but in certain embodiments of the present invention, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the (meth)acrylate functional groups in component c) are acrylate functional groups (the remainder being methacrylate functional groups, if present). According to one embodiment, all functional groups in component c) are acrylate functional groups.

[0140] Suitable multi-(meth)acrylate functionalized monomers include (meth)acrylates of polyols and alkoxylated polyols, provided that two or more alcohol groups of the polyol or alkoxylated polyol are esterified with (meth)acrylic acid.

[0141] Component c) may include one or more di(meth)acrylate-functionalized monomers, particularly one or more diacrylate-functionalized monomers, or may consist essentially of the aforementioned monomers, or consist solely of the aforementioned monomers.

[0142] Suitable examples of di(meth)acrylate-functionalized monomers include di(meth)acrylates of ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol (e.g., tetraethylene glycol di(meth)acrylate); di(meth)acrylates of polyethylene glycol (where polyethylene glycol has a number-average molecular weight of 150-250 daltons) (e.g., polyethylene glycol di(meth)acrylate); di(meth)acrylates of 1,4-butanediol (e.g., 1,4-butanediol di(meth)acrylate); and 1,6-hexanediol Examples include (meth)acrylates of bisphenol A (e.g., 1,6-hexanediol di(meth)acrylate); di(meth)acrylates of neopentyl glycol (e.g., neopentyl glycol di(meth)acrylate); di(meth)acrylates of 1,3-butylene glycol (e.g., 1,3-butylene glycol di(meth)acrylate); di(meth)acrylates of ethoxylated bisphenol A containing 1 to 25 oxyethylene units per molecule (e.g., bisphenol A ethoxylated with 1 to 35 equivalents of ethylene oxide and then (meth)acrylicated); and combinations thereof.

[0143] In particular, di(meth)acrylate functionalized monomers include ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, and polyethylene glycol (600) dimethacrylate. Polyethylene glycol (200) diacrylate, 1,12-dodecanediol dimethacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate, methylpentanediol diacrylate, polyethylene glycol (400) diacrylate, ethoxylated 2-bisphenol A dimethacrylate, ethoxylated 3-bisphenol A dimethacrylate, ethoxylated 3-bisphenol A diacrylate, cyclohexanedimethanol dimethacrylate, cyclohexanedimethanol diacrylate, ethoxylated 10 Bisphenol A dimethacrylate, dipropylene glycol diacrylate, acrylic acid ester, ethoxylated 4-bisphenol A dimethacrylate, ethoxylated 6-bisphenol A dimethacrylate, ethoxylated 8-bisphenol A dimethacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, dodecane diacrylate, ethoxylated 4-bisphenol A diacrylate, ethoxylated 10Bisphenol A diacrylate, polyethylene glycol (400) dimethacrylate, NPG-hydroxypivaldihydradipic acid, polypropylene glycol (400) dimethacrylate, metal diacrylate, modified metal diacrylate, metal dimethacrylate, methacrylated polybutadiene, propoxylated neopentyl glycol diacrylate, ethoxylated 30 Bisphenol A dimethacrylate, ethoxylated 30 Bisphenol A diacrylate, alkoxylated neopentyl glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 2-bisphenol A dimethacrylate, dipropylene glycol diacrylate, ethoxylated 4-bisphenol A diacrylate, polyethylene glycol (600) diacrylate, tricyclodecanedimethanol diacrylate, propoxylated 2-neopentyl glycol diacrylate, alkoxylated aliphatic diacrylate, and combinations thereof may be selected.

[0144] In particular, the di(meth)acrylate functionalized monomer may account for at least 20% by mass, 20-100% by mass, 30-100% by mass, 40-100% by mass, 50-100% by mass, 60-100% by mass, 70-100% by mass, 80-100% by mass, 90-100% by mass, or even 100% by mass of the total mass of component c).

[0145] The curable composition may contain 2 to 10% by mass, particularly 3 to 8% by mass, and more particularly 4 to 6% by mass, of the total mass of components a), b), and c), as a di(meth)acrylate-functionalized monomer.

[0146] Component c) may contain one or more (meth)acrylate-functionalized compounds, each containing three or more (meth)acrylate functional groups per molecule.

[0147] A (meth)acrylate-functionalized compound containing three or more (meth)acrylate functional groups per molecule may be a (meth)acrylate ester of a polyol (polyhydric alcohol) or alkoxylated polyol containing three or more hydroxyl groups per molecule, provided that at least three of the hydroxyl groups are (meth)acrylicated.

[0148] Specific examples of suitable polyols include glycerin, alkoxylated glycerin, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, sugar alcohols, and alkoxylated sugar alcohols. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) provided that the resulting product has at least three (meth)acrylate functional groups per molecule. As used herein, the term "alkoxylated" refers to a compound in which one or more epoxides, such as ethylene oxide and / or propylene oxide, react with an active hydrogen-containing group (e.g., a hydroxyl group) of a base compound such as a polyol to form one or more oxyalkylene moieties. For example, 1 to 25 moles of epoxide may be reacted with 1 mole of the base compound.

[0149] Examples of (meth)acrylate-functionalized compounds containing three or more (meth)acrylate functional groups per molecule include: trimethylolpropane triacrylate; propoxylated trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; tris(2-hydroxyethyl) isocyanurate triacrylate; pentaerythritol triacrylate; ethoxylated pentaerythritol triacrylate; propoxylated pentaerythritol triacrylate, glyceryl triacrylate, ethoxylated glyceryl triacrylate, propoxy Examples include silated glyceryl triacrylate; ditrimethylolpropanetetraacrylate; ethoxylated ditrimethylolpropanetetraacrylate; propoxylated ditrimethylolpropanetetraacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; propoxylated pentaerythritol tetraacrylate; dipentaerythritol pentaacrylate; ethoxylated dipentaerythritol pentaacrylate; propoxylated dipentaerythritol pentaacrylate; and combinations thereof.

[0150] Preferred crosslinked monomers may be di-, tri-, or have a higher functional value, preferably bifunctional, but the amount should be adjusted accordingly. Generally, the higher the average functional value of component c), the more preferable it is to use a relatively smaller amount of such crosslinked monomers. When using only bifunctional crosslinked monomers, for example, it is preferable to use an amount of 2 to 10% by mass, particularly 3 to 8% by mass, and more specifically 4 to 6% by mass, based on the total mass of components a), b), and c). As another example, when only trifunctional crosslinked monomers are present in component c), preferred amounts include a range of 0.1 to 4% by mass based on the total mass of components a), b), and c), with even lower amounts being preferable for crosslinked monomers with higher functional values.

[0151] ingredient d) The curable compositions used to prepare the elastic materials according to the present invention may also optionally include an initiator system as component d). The initiator system comprises one or more substances capable of initiating the curing (polymerization) of components a), b), and c) (independently or in cooperation with other substances), typically in response to an external stimulus such as heat or light. For example, the curable composition may include one or more photoinitiators for the purpose of initiating the polymerization of the (meth)acrylate functionalized components of the curable composition upon exposure to light. Photoinitiators are advantageously always included when the curable composition is intended to be polymerized by ultraviolet (UV) or visible light (i.e., cured by a UV bulb or LED). Curable compositions intended to be polymerized by electron beam (EB) typically do not contain photoinitiators. Exemplary curable compositions may contain, for example, 0-20% by mass, 0-15% by mass, 0-10% by mass, or 0-5% by mass of photoinitiators based on the total mass of the curable composition. The curable composition may contain, for example, at least 0.01% by mass, at least 0.05% by mass, at least 0.1% by mass, or at least 0.5% by mass of a photopolymerization initiator, based on the total mass of the curable composition. A preferred photopolymerization initiator is one that can absorb the frequency of light emitted by a desired energy source, as is common knowledge in the art.

[0152] A photopolymerization initiator can be considered any type of substance that, upon exposure to radiation (e.g., chemically active radiation), forms chemical species that initiate the reaction and curing of polymerizable organic materials present in the curable composition. Suitable photopolymerization initiators include free radical photopolymerization initiators. The photopolymerization initiator needs to be selected so as to be readily activated by photons of wavelengths associated with the light irradiation (e.g., ultraviolet, visible light) intended for use in curing the photocurable composition.

[0153] Free radical polymerization initiators are substances that form free radicals upon irradiation.

[0154] Examples of suitable free radical photopolymerization initiators for use in the curable compositions used in the present invention include, but are not limited to, benzoin, benzoin ether, acetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, and triazine compounds. Examples of specific suitable free radical photopolymerization initiators include 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler ketone, 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone, as well as acetophenone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2- Isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, ethyl-p-dimethylaminobenzoate, benzyl ketone, α-hydroxyketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethylketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenyl-propanone, oligomer α-hydroxyketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-4-dimethylaminobenzoate, ethyl(2,4,6-Trimethylbenzoyl)phenyl phosphine, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl phenyl ketone 50 / 50 mixture, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4-benzoyl biphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4' -Bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthene-9-one, dibenzosverenone, 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-H 50 / 50 mixture of droxy-2-methylpropiophenone, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methyl Examples include, but are not limited to, phenophenone, 3-methylbenzophenone, methylbenzoylformate, 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, thioxanthene-9-one, and combinations thereof.

[0155] Component e) The curable composition may optionally contain, as component e), one or more compounds or substances that improve adhesion but are not (meth)acrylate functionalized (i.e., do not have (meth)acrylate functional groups). These additives can improve the adhesion of the curable elastic material obtained from the curable composition to the substrate to which the curable composition was originally attached. Examples of additives that improve substrate adhesion but do not contain reactive (meth)acrylate functional groups include tackifying resins, polymers with inherent adhesion, or components that do not have inherent adhesion but improve substrate adhesion when included as a component of the curable composition. Adhesion-improving components that do not have (meth)acrylate functional groups can be used, for example, in a blending amount of 0 to 30% (w / w).

[0156] In particular, the adhesion-enhancing component may be silane.

[0157] Other optional components The curable composition may optionally contain one or more aerobic inhibitors, anaerobic inhibitors, and / or antioxidants. These additives are typically used to inhibit unwanted premature polymerization during the manufacture of the composition, during storage at high temperatures or for extended periods, during coating, during other times when the composition is exposed to temperatures higher than room temperature, or during any time when the product is accidentally exposed to radiation (such as sunlight) before curing. The curable composition may contain, for example, 0 to 5% by mass of various inhibitors based on the total mass of the curable composition.

[0158] The curable composition may optionally contain one or more non-(meth)acrylate components for the purpose of improving performance, controlling costs, improving processability, or otherwise modifying the properties and attributes of the curable composition and the elastic material prepared from the composition. Examples of additives and fillers include, but are not limited to, linear low-density polyethylene, ultra-low-density polyethylene, low-density polyethylene, high-density polyethylene, any other polyethylene, polypropylene, polyvinyl acetate, ethyl vinyl acetate, polyvinyl butyrate, thermoplastic urethane, EVA graft terpolymer, clay, zeolite, mineral powder, block copolymer, other impact modifiers, engineering polymers such as core-shell particles, organic nanoparticles, and / or inorganic nanoparticles. The curable composition used in the present invention may contain, for example, 0 to 30% by mass of one or more of these additives or fillers based on the total mass of the curable composition.

[0159] Pigments may be included as part of the curable composition. The pigment may be any chemical substance that imparts a visible color to the final elastic material. These chemical substances may include conjugated organic molecules, inorganic substances, or organometallic compounds. The pigment may also have photochromic, electrochromic, or mechanochromic properties and may exhibit photoswitching or other responsive visual effects.

[0160] Exemplary embodiments of the present invention include an elastic material which is a polymerization reaction product of the following curable compositions.

[0161] Components a), b), c), and d): Component a): An acrylate-functionalized polyurethane oligomer based on polypropylene glycol, having an average acrylate functional value of 1-2 in the total mass of components a), b), c), and d), and having a number-average molecular weight of 15,000-25,000 Daltons as measured by gel permeation chromatography using standard polystyrene; Component b): 18 to 30% by mass of at least one mono(meth)acrylate-functionalized monomer selected from the group consisting of isobornyl acrylate, 2(2-ethoxyethoxy)ethyl acrylate, and tetrahydrofurfuryl acrylate, based on the total mass of components a), b), c), and d); Component c): 2 to 6% by mass of 1,6-hexanediol diacrylate based on the total mass of components a), b), c), and d); and Component d): At least one photopolymerization initiator, in an amount of 0.3 to 5% by mass based on the total mass of components a), b), c), and d). A curable composition containing the following:

[0162] Components a), b), c), and d): Component a): A mixture comprising 70-75% by mass of components a), b), c), and d), i) a polypropylene glycol-based acrylate-functionalized polyurethane oligomer having an average acrylate functional value of 1-2 and a number-average molecular weight of 15,000-25,000 Daltons as measured by gel permeation chromatography using standard polystyrene, and ii) a polypropylene glycol-based (meth)acrylate-functionalized polyurethane oligomer containing both acrylate and methacrylate functional groups, having an average (meth)acrylate functional value of 1-2, and a number-average molecular weight of 8,000-15,000 Daltons as measured by gel permeation chromatography using standard polystyrene, wherein i) and ii) are present in a mass ratio of 1:0.8-1:2.5; Component b): 18 to 25% by mass of at least one mono(meth)acrylate-functionalized monomer selected from the group consisting of isobornyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, and tetrahydrofurfuryl acrylate, based on the total mass of components a), b), c), and d); Component c): 3 to 7% by mass of 1,6-hexanediol diacrylate based on the total mass of components a), b), c), and d); and Component d): At least one photopolymerization initiator, in an amount of 0.3 to 5% by mass based on the total mass of components a), b), c), and d). A curable composition containing the following:

[0163] According to various embodiments of the present invention, the curable composition may be characterized by containing one or more of the following components in amounts of less than 10% by mass, less than 5% by mass, less than 1% by mass, less than 0.5% by mass, less than 0.1% by mass, or less than 0.01% by mass, or even 0% by mass, based on the total mass of the curable composition: Growth promoters, which are sulfur-containing compounds, particularly sulfur-containing compounds having a molecular weight of less than 1,000 daltons, as described in U.S. Patent Nos. 6,265,476 and 7,198,576; Oligomers or monomers having ethylenically unsaturated functional groups (i.e., ethylenically unsaturated functional groups other than (meth)acrylate functional groups, such as vinyl groups) and not containing (meth)acrylate functional groups, as described in U.S. Patent No. 6,265,476 and No. 7,198,576; Polythiol compounds having 2 to 6 mercapto groups per molecule, as described in U.S. Patent Application Publication No. 2012 / 0157564A1; Polysiloxanes selected from acryloxyalkyl and methacryloxyalkyl-terminated polydialkylsiloxanes, i.e., (meth)acrylated polysiloxanes as described in U.S. Patent No. 5,268,396; Rubber (elastomer) that does not have (meth)acrylate functional groups; Rubber having (meth)acrylate functional groups that exhibit elastomeric properties in an uncured state; and / or silica.

[0164] The above-mentioned patent documents are incorporated herein by reference in their entirety for all purposes.

[0165] <Preparation of curable composition> Typically, it is desirable to combine the various components of the curable composition and mix them until homogeneous. The manufacturing process can be adjusted based on the characteristics and quantities of the different components used in the curable composition, processability considerations, or other factors considered important for the manufacturing process. For example, components can be added slowly or quickly and at any temperature, individually, or as a premixture with other components of the curable composition, in any order. High temperatures and / or stirring may be required to mix and homogenize the components of the curable composition. Typically, the processing temperature is advantageously maintained below the temperature that would cause premature polymerization of the components of the curable composition.

[0166] <Application / Use of Curable Compositions> According to aspects of the present invention, a curable composition can be applied to a substrate, particularly to one or more surfaces of the substrate. Any means known in the art for coating, depositing, or applying a liquid curable composition may be used here. These methods include, but are not limited to, coating, rolling, extrusion, injection, and spraying. In some cases, the curable composition is heated to a temperature higher than room temperature before being applied to the substrate. In other cases, the curable composition is applied at ambient temperature (e.g., room temperature or about 15°C to about 30°C). The substrate may optionally be pre-treated to improve adhesion to the elastic material obtained by polymerizing the curable composition. The curable composition may be applied with the intention of permanently bonding the elastic material obtained from the composition to the substrate. Alternatively, the substrate may be a non-adhesive material (e.g., a release liner film) such that the substrate can be easily removed or separated from the elastic material after curing. The curable composition may be applied or deposited on top of a previously cured layer of curable composition according to the present invention. Articles composed of the elastic material according to the present invention may be formed by any preferred method such as casting or 3D printing.

[0167] <Curing of curable compositions> According to aspects of the present invention, the compositions described above may be polymerized into a dimensionally stable solid material having elastomer properties. The components of the curable composition may be selected such that the curable composition can be polymerized by exposure to UV or visible radiation from any light source, or to EB. In one embodiment, a layer of the curable composition passes under an energy source on a conveyor line, web, etc. Curing may occur at the manufacturing site, remotely, for example, on-site, at home, or as part of a "do it yourself" application. Curing of a layer of the curable composition may occur while the layer is in contact with a previously cured layer. Curing may be performed as part of a 3D printing method.

[0168] A method for producing an elastic material of the present invention includes a step of curing a curable composition of the present invention. In particular, the curable composition may be cured by exposing the composition to radiation. More particularly, the curable composition may be cured by exposing the composition to an electron beam (EB), a light source (e.g., a visible light source, a near-ultraviolet light source, an ultraviolet lamp (UV), a light-emitting diode (LED) or an infrared light source) and / or heat.

[0169] Curing can be accelerated or promoted by supplying energy to the curable composition, such as by heating it. Therefore, the elastic material can be considered a reaction product of the curable composition formed by curing. The curable composition may be partially cured by exposure to chemically active rays, and further curing can be achieved by heating the partially cured elastic material. For example, the product formed from the curable composition may be heated at a temperature of 40°C to 120°C for 5 minutes to 12 hours.

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

[0171] The substrate to which the curable composition is applied and cured may be any type of substrate. The curable composition according to the present invention may also be formed or cured by a bulk method (for example, the curable composition may be cast into a suitable mold and then cured).

[0172] The elastic material obtained by the method of the present invention may be a coating, adhesive, sealant, molded article, or 3D printed article, and may be a coated or 3D printed article in particular.

[0173] The 3D printed article may be obtained by a method for preparing the 3D printed article, which in particular includes the step of printing the 3D article with the curable composition of the present invention. In particular, the method may include the step of printing the 3D article layer by layer or continuously.

[0174] Multiple layers of the curable composition according to the present invention may be applied to the surface of a substrate; multiple layers may be cured simultaneously (for example, by exposure to a single irradiation of radiation), or each layer may be cured sequentially before the application of additional layers of the curable composition.

[0175] The curable compositions described herein can be used as resins in three-dimensional printing applications. Three-dimensional (3D) printing (also known as additive manufacturing) is a process in which 3D digital models are manufactured by stacking building materials. 3D printed objects are created by sequentially constructing two-dimensional (2D) layers or slices corresponding to cross-sections of a 3D object, using computer-aided design (CAD) data of the object. Stereolithography (SL) is a type of additive manufacturing in which liquid resin is selectively exposed to radiation to cure and form each 2D layer. The radiation can be in the form of electromagnetic waves or electron beams. The most commonly used energy sources are ultraviolet, near-ultraviolet, visible, or infrared light.

[0176] Stereolithography and other photocurable 3D printing methods typically utilize low-intensity light sources to irradiate each layer of photocurable resin to form the desired article. Consequently, the kinetics of photocurable resin polymerization and the green intensity of the printed article are important criteria for determining whether a particular photocurable resin has sufficient green intensity to polymerize (cure) sufficiently upon irradiation and maintain its integrity throughout the 3D printing process and post-processing.

[0177] The curable compositions of the present invention may be used as 3D printing resin formulations, i.e., compositions intended for use in the manufacture of three-dimensional articles using 3D printing technology. Such three-dimensional articles may be self-supporting / self-supporting and may consist essentially of cured compositions according to the present invention, or solely of cured compositions according to the present invention. The three-dimensional articles may also be composite materials comprising at least one component consisting essentially of or solely of the aforementioned curable compositions, and at least one additional component consisting of one or more components other than such cured compositions (e.g., metallic components, thermoplastic components, or inorganic fillers or fiber reinforcements). The curable compositions of the present invention are particularly useful in digital light printing (DLP), but other types of three-dimensional (3D) printing methods can also be carried out using the curable compositions of the present invention (e.g., SLA, inkjet, multijet printing, piezoelectric printing, chemically activated ray curing extrusion, and gel deposition printing). The curable compositions of the present invention can be used in three-dimensional printing operations together with another material that serves as a scaffold or support for articles formed from the curable compositions of the present invention.

[0178] Accordingly, the curable compositions of the present invention are useful in the implementation of various types of three-dimensional fabrication or printing technologies, including methods in which the construction of three-dimensional objects is carried out in a stepwise or layer-by-layer manner. In such methods, layer formation may be carried out by solidification (curing) of the curable composition under the action of exposure to radiation such as visible light, UV, or other chemically active ray irradiation. For example, a new layer may be formed on the top surface of the growing object or on the bottom surface of the growing object. The curable compositions of the present invention can also be advantageously used in methods for manufacturing three-dimensional objects by additive manufacturing, in which the method is carried out continuously. For example, the object may be manufactured from a liquid interface. This type of preferred method is sometimes referred to in the art as “Continuous Liquid Interface (or Interface) Fabrication (or Printing)” (“CLIP”) method. Such methods are described, for example, in International Publication Nos. 2014 / 126830; 2014 / 126834; 2014 / 126837; and Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects," Science Vol. 347, 6228, pp. 1349-1352 (March 20, 2015).

[0179] The curable composition may be supplied by extrusion from the print head rather than from a vat. This type of method is commonly called inkjet or multi-jet 3D printing. One or more UV curing sources mounted immediately behind the inkjet print head cure the curable composition immediately after it is applied to the constructed surface substrate or previously applied layer. In this method, two or more print heads can be used, thereby allowing different compositions to be applied to different areas of each layer. For example, compositions of different colors or different physical properties can be applied simultaneously to produce 3D printed parts of various compositions. In typical use, a support material (which is later removed in post-processing) is deposited simultaneously with the composition used to create the desired 3D printed part. The print head can operate at temperatures from approximately 25°C to approximately 100°C. The viscosity of the curable composition is less than 30 mPa·s at the print head's operating temperature.

[0180] A method for preparing a 3D-printed item may include the following steps: a) A step of bringing a first layer of the curable composition according to the present invention onto a surface (e.g., coating); b) A step of curing the above-mentioned first layer at least partially to obtain a cured first layer; c) The step of bringing a second layer of the curable composition onto the cured first layer (e.g., coating); d) a step of curing the above-mentioned second layer at least partially to obtain a cured second layer adhering to the cured first layer; and e) A process of constructing a three-dimensional article by repeating steps c) and d) a desired number of times.

[0181] After a 3D article is printed, it may be subjected to one or more post-processing steps. These post-processing steps may be performed simultaneously or sequentially and may include one or more of the following steps: removal of any printed support structures; washing with water and / or organic solvents to remove residual resin; and post-curing with heat treatment and / or chemically activated radiation. Post-processing steps may be used to transform a freshly printed article into a finished, functional article ready for use in its intended application.

[0182] <Articles containing elastic materials> The elastic material of the present invention may be permanently attached to a substrate. Alternatively, if the elastic material is removed from the substrate after curing, it may result in a self-supporting article. The elastic material may be in the form of very thin articles (e.g., less than 1 mil thick), thick articles (e.g., more than 1 inch thick), or articles of intermediate thickness. Articles containing the elastic material may be layered products manufactured by alternately curing layers of a curable composition, and then reapplying and curing one or more additional layers of the curable composition. Such multilayer articles include articles with few layers (e.g., two or three layers) and articles with many layers (e.g., more than three layers, as in certain types of 3D printing).

[0183] While embodiments have been described herein in a manner that enables the writing of a clear and concise specification, it will be understood that embodiments are intended and can be combined and separated in various ways without departing from the present invention. For example, it will be understood that all preferred features described herein are applicable to all embodiments of the present invention described herein.

[0184] In some embodiments, the inventions described herein may be interpreted as excluding any elements or method steps that do not substantially affect the fundamental and novel properties of the curable compositions, the materials, products and articles prepared from the compositions, and the methods of preparing and using such curable compositions as described herein. Furthermore, in some embodiments, the inventions may be interpreted as excluding any elements or method steps not expressed herein.

[0185] Although the present invention has been described and explained herein with respect to specific embodiments, the present invention is not intended to be limited to the details shown. Rather, various modifications may be made in detail within the scope of the claims and their equivalents without departing from the present invention. [Examples]

[0186] <Example 1> In Example 1, the relationship between the composition of a curable (e.g., energy-curable) composition (the main components of the composition and their relative proportions) and the properties of the cured material obtained from that composition was examined. Therefore, different curable compositions were qualitatively compared. On the composition side, the variations involved different oligomer bodies and varying proportions of crosslinkable monomers. One objective in these tests was to understand the effect of these changes on the elasticity and hardness of the cured products prepared from the curable compositions.

[0187] Various energy-curable compositions are shown in Table 1. Each composition is based on a formulation containing 75% by mass of oligomer, 20% by mass of isobornyl acrylate, and 5% by mass of Irgacure® 2022 photopolymerization initiator, with various amounts (0-4% by mass) of 1,6-hexanediol diacrylate ("HDDA") added to the base formulation. The oligomers were selected to have various number-average molecular weights and functional values ​​(number of functional groups). Since other chemical components were the same for all samples, Table 1 shows only the chemical properties of the various oligomers used. Approximately 50 g of each energy-curable composition was prepared and mixed at room temperature using a FlackTek® high-speed mixer. Once homogenized, each energy-curable composition was poured separately into an open aluminum mold, and the filled mold was cured by passing it twice under a 600W Fusion D valve at 10 ft / min. This amount of energy exceeded the amount necessary to cure the sample, but it was used to be completely certain that curing was complete. After the reaction, the sample was aged (i.e., post-cured) for one day under ambient conditions prior to testing. Hardness was tested qualitatively by hand; materials that deformed easily were judged to be "too soft," and samples that could not be compressed / bent were judged to be "too hard." Samples with intermediate hardness were considered to qualitatively correspond to materials typically classified as elastomers. Elasticity was tested quantitatively using a Bayshore elasticity tester, but the results were recorded qualitatively. Samples showing less than 10% rebound were judged to have "poor" elasticity, and samples showing more than 10% rebound were considered to have "good" elasticity. Elongation was not measured in this test.

[0188] [Table 1]

[0189] Description of ingredients: Oligomer A: Diadduct of hydrogenated methylene diisocyanate and caprolactone acrylate, average functional value = approximately 2, M n = about 1,000. Oligomer B: Urethane acrylate having a polypropylene glycol main chain, average functional value = approximately 1.8, M n Approximately 20,000 Daltons. Oligomer C: Urethane acrylate having neopentyl glycol / adipic acid main chain, average functional value = approximately 1.5, M n = Approximately 10,000 Daltons. Oligomer D: Urethane acrylate having a hydrogenated polyolefin main chain, average functional value = approximately 2, M n = Approximately 7,000 Daltons. Oligomer E: Urethane acrylate having a hydrogenated polyolefin main chain, average functional value = approximately 2, M n = Approximately 4,000 Daltons. Oligomer F: Urethane acrylate having a polytetramethylene ether glycol main chain, average functional value = approximately 2, M n = Approximately 2,000 Daltons.

[0190] One of the main conclusions drawn from this study is the relationship between crosslinking density and elasticity. All other conditions being equal, a low crosslinking density softened the hardened samples, making them unable to return to their original shape after deformation, or delaying their return. On the other hand, too high a crosslinking density prevented the samples from bending. The comparison of samples 7, 8, and 9 particularly illustrates this trend. Furthermore, the data shows that the amount of crosslinking agent required to obtain moderate hardness and good elasticity depends on the molecular weight and functional value of the oligomer. A third finding was that among the samples classified as "moderate hardness and good rebound," the sample prepared using the oligomer with the highest molecular weight and lowest functional value exhibited the highest rebound.

[0191] <Example 2> This test uses high molecular weight (M) samples, all of which are based on the same resin component: polypropylene glycol. nThe study consisted of 15 samples containing various amounts of low-functional-value urethane acrylate oligomer (the same oligomer as oligomer B (Olig. B) in Example 1), isobornyl acrylate ("IBA"), 2-(2-ethoxyethoxy)ethyl acrylate ("EEEA"), and 1,6-hexanediol diacrylate ("HDDA"). The photopolymerization initiator was Irgacure® 2022, used at 1% by mass in each energy-curable composition. The formulations of each sample are shown in Table 2a.

[0192] For each sample, an energy-curable composition was prepared by combining 60 g of the components at room temperature and then mixing them using a FlackTek high-speed mixer. This energy-curable composition was cured between two 1.6 mm thick glass panels at a line speed of 10 ft / min using a 600 W Fusion D valve. This amount of energy exceeded the amount required to cure the sample, but it was used to be completely certain that curing was complete. After the reaction, the sample was aged (i.e., post-cured) for 1 day under ambient conditions before testing. The test results are shown in Table 2b.

[0193] Each hardened specimen was evaluated in several ways. For each specimen, elongation was measured by stamping three dogbone-shaped tensile bars in accordance with ASTM D638-02a (published in 2002) and testing the bars. Here, the specimen shape was conforming to Type IV shape. The distance between the grips (also known as "crossheads") was 6.35 cm. The initial length of the specimen used for calculating the elongation at break was the length of the elongated part of the specimen (3.3 cm). The strain rate was 2.54 cm / min. The elongations shown in Table 2b are the average values ​​of three repeated tests. Elasticity was tested three times on a Bayshore elasticity tester using ASTM D2632-01 (re-approved in 2008), by cutting five 1.6 mm films into 1 x 1 inch squares, laminating them, and testing them according to ASTM D2632-01 (re-approved in 2008). Since some specimens had slight surface tack, which could interfere with the plunger rebound height, the specimens were covered with thin pieces of plastic film during testing. The elasticity values ​​shown in Table 2b are the average values ​​of three measurements. Hardness was measured using a Shore A durometer. Unlike elongation and elasticity, hardness was measured only once per sample. In addition to these quantitative tests, elastic elongation and elastic recovery were qualitatively evaluated by hand.

[0194] These tests demonstrate that high elongation and elasticity can be achieved simultaneously in energy-curing materials. Although not shown in Table 2b, most of these samples also exhibited good elastic elongation and rapid elastic recovery, which are characteristic of elastomers. Specifically, in most cases, the elastic elongation was qualitatively the same as the elongation at break.

[0195] [Table 2]

[0196] [Table 3]

[0197] <Example 3> Table 3a below contains compositional information, and Table 3b contains cured elastomer property data for 10 additional energy-cured elastomers (and two samples from Example 2 for comparison). Here, a wider variety of oligomers and monomers were used than in the previous examples. Notably, one of the oligomers in Example 3 is a PPG-based urethane (meth)acrylate having both acrylate and methacrylate functional groups. Each formulation contained 1% (w / w) of Irgacure® 2022 photoinitiator, with the exception of sample 39 which contained 5% Irgacure® 1173 as a photoinitiator. The procedures for composition preparation, curing, and testing were the same as in the previous examples. One exception is that in Example 3, hardness was measured in three ways, and the average hardness is shown in Table 3b.

[0198] [Table 4]

[0199] Description of ingredients: "Olig. G" - A urethane acrylate oligomer having a number-average molecular weight of approximately 5,000 Daltons, wherein the main chain of the oligomer contains a polyester based on neopentyl glycol and adipic acid. "Olig. B" - Same as oligomer B in Example 1. "Olig. H" - A urethane (meth)acrylate oligomer having a number-average molecular weight of approximately 11,000 Daltons, wherein the main chain of the oligomer contains polypropylene glycol, the average molar ratio of acrylate to methacrylate functional groups in the oligomer is approximately 1:1, and approximately half of the oligomer molecules have both acrylate and methacrylate functional groups; the average (meth)acrylate functional value = 2. "IBA" - Isobornyl acrylate. "EEEA" - 2(2-ethoxyethoxy)ethyl acrylate. "Monomer mix" - A 1:1 (w / w) mixture of isooctyl acrylate and isodecyl acrylate. "THFA" - Tetrahydrofurfurylacrylate. "HDDA" - 1,6-hexanediol diacrylate. "TCDDMDA" - Tricyclodecanedimethanol diacrylate.

[0200] [Table 5]

[0201] One conclusion that can be drawn from this study is that energy-curable compositions containing larger molecular weight and lower functional value oligomers tend to produce materials with higher elongation, higher elasticity, and softer properties upon curing. Another conclusion is that Example 3 also demonstrates possible strategies for controlling material hardness while maintaining elasticity. Samples 15 and 32 showed that changing the ratio of the two monofunctional monomers altered material hardness, but in both cases, the materials were clearly elastomeric. By comparing samples 23, 35, and 37, another strategy for controlling hardness can be identified: namely, adjusting the ratio of the two high molecular weight, low functional value oligomers. Hardness increases as the proportion of the harder (higher Tg) oligomer increases. However, all three materials maintain very high elasticity.

[0202] <Example 4> Table 4a below contains compositional information, and Table 4b contains cured elastomer property data for additional energy-cured elastomers. The main objective of Example 4 was to demonstrate the properties of curable compositions containing monomers with ethylenically unsaturated nitrogen, and the cured elastomers prepared from these compositions. Some samples contain both ethylenically unsaturated nitrogen-containing monomers and monofunctional (meth)acrylate monomers. Other samples contain ethylenically unsaturated nitrogen-containing monomers but do not contain monofunctional (meth)acrylate monomers.

[0203] [Table 6]

[0204] Description of ingredients: "DMAA" - N,N-dimethylacrylamide "VCAP" - N-vinylcaprolactam "VMOX" - Vinylmethyloxazolidinone "PI 1173" - Irgacure(registered trademark) 1173 "PI 819" - Irgacure(registered trademark) 819

[0205] The second objective of this study was to demonstrate the effect of the selection of photoinitiators on curing properties. In particular, Example 4 included two types of photoinitiators. To compare the two types of photoinitiators, samples 49-58 were designed to have the same composition as samples 39-48, except for the photoinitiator. Sample 39 (see Example 3) was prepared, cured, and tested again for Example 4 to serve as a comparative example for samples 40-48. Similarly, sample 49, which did not contain ethylenically unsaturated nitrogen-containing monomers, was used as a comparative example for samples 50-58.

[0206] Unlike the previous example, Example 4 included a T-peel test to evaluate the adhesion between the cured composition and a substrate coated with the curable composition before curing. Specifically, the liquid composition was applied between two layers of PET film and then energy-cured. The cured film was then cut into 1-inch wide strips before testing. The T-peel test was performed using an Instron tensile testing machine to peel the two layers of PET at a speed of 1 inch / minute. The reported values ​​are in pounds (lb) / inch (in), with higher values ​​corresponding to better adhesion. The latter half of Example 4 (samples 50-58) focused on optimizing substrate adhesion. For this reason, quantitative elasticity and hardness tests were not performed on samples 50-58; instead, these samples were qualitatively evaluated. According to this qualitative test, all cured specimens of samples 40-58 possessed the elasticity and hardness characteristics of elastomers.

[0207] One conclusion that can be drawn from Example 4 is that curable compositions containing ethylenically unsaturated nitrogen-containing monomers produce cured elastomers. This conclusion is valid whether or not the composition also contains monofunctional (meth)acrylate monomers. A second conclusion is that N,N-dimethylacrylamide, when included in a curable composition, enables higher T-type peel strength.

[0208] [Table 7]

Claims

1. An elastic material having an elongation greater than 150% when measured according to ASTM D638-02a, a resilience greater than 12% when measured according to ASTM D2632-01 (re-approved in 2008), and a Shore A hardness of at least 10 when measured according to ASTM D2240-15e1, and the elastic material being liquid at 25°C and comprising the following components a), b) and c): a) A (meth)acrylate-functionalized oligomer having an average of 2 or fewer (meth)acrylate functional groups per molecule in an amount of 43 to 89.9% by mass, based on the total mass of components a), b), and c), and having a number-average molecular weight of at least 10,000 daltons for the entirety of component a) as measured using gel permeation chromatography and standard polystyrene; b) 10 to 55% by mass of components a), b), and c), with a molecular weight of less than 500 daltons and at least one mono(meth)acrylate-functionalized monomer having a single (meth)acrylate functional group per molecule, and / or at least one ethylenically unsaturated nitrogen-containing monomer; and c) Based on the total mass of components a), b), and c), 0.1 to 10% by mass of at least one multi(meth)acrylate functionalized monomer having a molecular weight of less than 1000 daltons and at least two (meth)acrylate functional groups per molecule. It includes, An elastic material which is an energy-cured reaction product of a curable composition comprising component a) a urethane (meth)acrylate oligomer and component b) a mono(meth)acrylate functionalized monomer containing a cyclic moiety and / or a tert-butyl group.

2. The elastic material according to claim 1, wherein the elastic material has a probe tack of 4.4 N or less, 2.2 N or less, or 0.44 N or less when measured in accordance with ASTM D2979-95 using a Chem Instruments® PT-500 Inverted Probe Machine in tension peak mode.

3. The elastic material according to claim 1 or 2, wherein component a) comprises a (meth)acrylate-functionalized oligomer having a glass transition temperature of less than -20°C as measured by differential scanning calorimetry.

4. The elastic material according to any one of claims 1 to 3, wherein component a) comprises a (meth)acrylate-functionalized polyurethane oligomer based on polypropylene glycol.

5. The elastic material according to claim 4, wherein the polypropylene glycol has a number-average molecular weight of at least 2,000 daltons.

6. The elastic material according to any one of claims 1 to 5, wherein the (meth)acrylate-functionalized oligomer includes an oligomer functionalized with both acrylate and methacrylate groups, and / or an oligomer functionalized with only acrylate groups.

7. The elastic material according to any one of claims 1 to 6, wherein component c) comprises at least one compound selected from the group consisting of 1,6-hexanediol diacrylate and tricyclodecanedimethanol diacrylate.

8. The monofunctional (meth)acrylate monomer of component b) has at least 3 MPa １／２ The elastic material according to any one of claims 1 to 7, wherein the Hansen solubility parameter distance relative energy difference between component a) and the (meth)acrylate functionalized oligomer.

9. The elastic material according to any one of claims 1 to 8, wherein component b) comprises at least one compound selected from the group consisting of isobornyl acrylate, 2(2-ethoxyethoxy)ethyl acrylate, and tetrahydrofurfuryl acrylate.

10. The elastic material according to any one of claims 1 to 9, wherein component b) further comprises a monofunctional monomer selected from ethylenically unsaturated nitrogen-containing monomers.

11. The mono(meth)acrylate functionalized monomer containing the cyclic moiety and / or tert-butyl group in component b) is tert-butyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, benzyl(meth)acrylate, isobornyl(meth)acrylate, tert-butylcyclohexyl(meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, dicyclopentadienyl(meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, tetrahydrofurfuryl An elastic material according to any one of claims 1 to 10, selected from (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate (also called (5-ethyl-1,3-dioxan-5-yl)methyl (meth)acrylate), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, glycerol formal methacrylate, alkoxylated derivatives thereof, and mixtures thereof.

12. The elastic material according to any one of claims 1 to 11, wherein component b) comprises an ethylenically unsaturated nitrogen-containing monomer comprising a group selected from acryloyl, methacryloyl, and alkenyl, and a nitrogen-containing group having a cyclic or acyclic structure.

13. A method for producing an elastic material according to any one of claims 1 to 12, comprising the step of energy-curing a curable composition.

14. A method for preparing a 3D printed article, comprising the step of printing the 3D article by energy curing using a curable composition as defined in any one of claims 1 to 12.

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