Elastic material prepared from a curable liquid composition

Abstract

The present invention relates to an elastic material having high rebound elasticity, which is an energy-curing material obtained from a composition containing a specific urethane (meth)acrylate containing oxybutylene units. [Solution] The elastic material of the present invention is an elastic material having rebound elasticity of more than 10%, particularly more than 15%, and more specifically more than 20%, as measured in accordance with JIS K 6255:1996, and the elastic material is an energy curing reaction product of a curable composition comprising the following components a) and b): a) at least one urethane (meth)acrylate having a number average molecular weight of at least 4,700 g / mol and containing oxybutylene units, in an amount of 30 to 90% by mass, particularly 40 to 90% by mass, and more particularly 50 to 90% by mass, based on the total mass of components a) and b), and at least one (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule, in an amount of 10 to 70% by mass, particularly 10 to 60% by mass, and more particularly 10 to 50% by mass, based on the total mass of components a) and b), with one or two (meth)acrylate functional groups per molecule.

Description

[Technical Field]

[0001] The present invention relates to an elastic material having high rebound elasticity, which is an energy-cured material obtained from a composition containing a specific urethane (meth)acrylate containing oxybutylene units. [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, a light source (e.g., visible light, near-ultraviolet light, ultraviolet LED, or infrared light) and / or heat can be considered energy-cured materials (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. For certain end applications, elastic energy-curable materials are attracting considerable interest. However, energy-curable compositions capable of obtaining elastic materials through energy curing have not been widely explored or developed to date.

[0004] To obtain the rebound elasticity required for elastomers, the material must 1) deform under stress and 2) quickly return to its original shape when the stress is removed. In polymer materials, crosslinking between polymer chains reduces the ability to deform. Therefore, too much crosslinking will result in a loss of rebound elasticity. On the other hand, crosslinking may be necessary for the material to return to its original shape after stress removal. For a given composition, there is an optimal crosslinking density that yields the best rebound elasticity. The elongation of the material also depends heavily on the crosslinking density, and crosslinking reduces elongation. The crosslinking density required for rebound is sufficient to significantly limit elongation. Therefore, the critical challenge when formulating energy-curable compositions that can produce elastic materials through curing is to simultaneously obtain high elongation and high rebound elasticity. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 6,265,476 [Patent Document 2] U.S. Patent No. 7,198,576 [Patent Document 3] U.S. Patent Application Publication No. 2012 / 0157564A1 [Patent Document 4] U.S. Patent No. 5,268,396 [Patent Document 5] International Publication No. 2014 / 126830 [Patent Document 6] International Publication No. 2014 / 126834 [Patent Document 7] International Publication No. 2014 / 126837 [Non-patent literature]

[0006] [Non-Patent Document 1] Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects," Science Vol. 347, No. 6228, pp. 1349-1352 (March 20, 2015). [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention relates to an elastic material having high rebound elasticity, which is an energy-cured material obtained from a composition containing a specific urethane (meth)acrylate containing oxybutylene units. [Means for solving the problem]

[0008] Summary of the present invention One aspect of the present invention is an elastic material having rebound elasticity greater than 10%, particularly greater than 15%, and more specifically greater than 20%, as measured in accordance with JIS K 6255:1996. The elastic material comprises the following components a) and b): Component a): At least one urethane (meth)acrylate having a number average molecular weight of at least 4,700 g / mol and containing oxybutylene units, which is 30 to 90% by mass, particularly 40 to 90% by mass, more particularly 50 to 90% by mass based on the total mass of components a) and b); Component b): At least one (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule, which is 10 to 70% by mass, particularly 10 to 60% by mass, more particularly 10 to 50% by mass based on the total mass of components a) and b) It is an energy curing reaction product of a curable composition containing the same.

[0009] As will be described in more detail later, the curable composition may optionally contain one or more additional components, particularly an initiator system such as one or more photoinitiators.

[0010] The present invention also relates to a method for producing an elastic material of the present invention by curing the curable composition defined herein.

Mode for Carrying Out the Invention

[0011] Detailed description of aspects of the present invention definition In the present application, the term "comprise(s) a / an" means "comprise(s) one or more".

[0012] Unless otherwise indicated, the mass% in a compound or composition is expressed based on the mass of the compound or composition.

[0013] The term "X substantially does not contain Y" means that X contains 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, and even 0% by mass of Y.

[0014] The term "Cα~Cβ group" (where α and β are integers) refers to a group having α to β carbon atoms.

[0015] The term "elastic material" qualitatively refers to a material possessing one or more elastomer properties, such as high elongation, high rebound elasticity, high elasticity, and / or high elastic recovery. Furthermore, elastic materials may also possess appropriate toughness. Quantitatively, these properties vary depending on the details of the end application of the elastic material. Elongation refers to the total deformation until the sample breaks. High elongation may be greater than 200%, greater than 300%, greater than 400%, or greater than 500% when measured according to the method defined herein. Rebound 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 rebound elasticity may be greater than 10%, greater than 15%, greater than 20%, greater than 30%, or greater than 40% when measured according to the method defined herein. 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 even after being stretched. High elasticity, as tested according to ASTM D882-18, can be over 100%, over 200%, or over 300%. In addition, a fast rebound velocity is also required. These material properties are not unrelated. For example, all other things being equal, higher elongation generally means lower toughness, and good elastic recovery is associated with good rebound elasticity.

[0016] 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 having 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 explicitly stated, it does not refer to any functional group other than the (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, a trifunctional alcohol is understood to mean a compound that does not have (meth)acrylate groups but has three hydroxyl groups per molecule. Further details are omitted, but it is understood that "monomer" and "oligomer" refer to (meth)acrylate monomer and (meth)acrylate oligomer, respectively.

[0017] The term "monomer" refers to a compound having a number-average molecular weight of less than 1,000 g / mol, particularly between 100 and 950 g / mol.

[0018] The term "oligomer" refers to a compound having a number-average molecular weight of 1,000 g / mol or more, particularly between 1,050 and 20,000 g / mol.

[0019] The term "mono(meth)acrylate monomer" refers to a monomer that has a single (meth)acrylate functional group.

[0020] The term "di(meth)acrylate monomer" refers to a monomer that has two (meth)acrylate functional groups.

[0021] The term "urethane (meth)acrylate" refers to compounds containing urethane bonds and (meth)acrylate functional groups. Such compounds are sometimes called urethane (meth)acrylate oligomers.

[0022] The term "urethane bond" refers to a -NH-C(=O)-O- or -OC(=O)-NH- bond.

[0023] The term "ester bond" refers to a -C(=O)-O- or -OC(=O)- bond.

[0024] The term "ether bond" refers to an O-bond.

[0025] The term "carbonate bond" refers to an -OC(=O)-O- bond.

[0026] The term "amide bond" refers to a -C(=O)-NH- or -NH-C(=O)- bond.

[0027] The term "urea bond" refers to the -NH-C(=O)-NH- bond.

[0028] The term "diol" refers to a compound that has two hydroxyl groups.

[0029] The term "hydroxyl group" refers to the -OH group.

[0030] The term "diisocyanate" refers to a compound that has two isocyanate groups.

[0031] The term "isocyanate group" refers to the -N=C=O group.

[0032] The term "amine" is -NR a R b It means base, and here R a and R b These are independently H or C1-C6 alkyl groups.

[0033] The term "hydroxylated mono(meth)acrylate" refers to a compound having a single (meth)acrylate functional group and one or more hydroxyl groups.

[0034] The term "oxyalkylene" refers to a divalent group of the formula -RO- or -OR- (where R is a dialkylene). Examples of oxyalkylenes include oxyethylene, oxypropylene, and oxybutylene.

[0035] The term "oxyethylene unit" refers to the -(O-CH2-CH2)- unit.

[0036] The term "oxypropylene unit" refers to the -(O-CH(CH3)-CH2)- and / or -(O-CH2-CH(CH3))- unit.

[0037] The term "oxybutylene unit" refers to the -(O-CH2-CH2-CH2-CH2)-, -(O-CH(CH3)-CH2-CH2)-, -(O-CH2-CH(CH3)-CH2)-, -(O-CH2-CH2-CH(CH3))-, -(O-CH(C2H5)-CH2)-, -(O-CH2-CH(C2H5))-, and / or -(O-CH(CH3)-CH(CH3))- units. Oxybutylene units may be derived from 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and / or 1,4-butanediol (also called tetramethylene glycol), preferably 1,4-butanediol. In particular, "oxybutylene unit" refers to the -(O-CH2-CH2-CH2-CH2)- unit.

[0038] The term "aliphatic compound / group" means a non-aromatic acyclic compound / group, which may be substituted as such. The compound / group may be linear or branched, saturated or unsaturated. The compound / group may contain one or more bonds selected from ethers, esters, amides, urethanes, ureas, and combinations thereof.

[0039] The term "alicyclic compound / group" means a non-aromatic cyclic compound / group. The compound / group may be substituted with one or more groups as defined in the term "aliphatic." The compound / group may contain one or more bonds as defined in the term "aliphatic."

[0040] The term "aromatic compound / group" means a compound / group containing an aromatic ring (meaning conforming to Hückel's rules of aromaticity), in particular a compound / group containing a phenyl group. The compound / group may be substituted with one or more groups as defined in the term "aliphatic." The compound / group may contain one or more bonds as defined in the term "aliphatic."

[0041] The term "acyclic compound / group" refers to a compound / group that does not contain a ring.

[0042] The term "cyclic compound / group" refers to a compound / group containing one or more rings.

[0043] The term "dialkylene" refers to a divalent group obtained by removing two hydrogen groups from an alkane. "C2-C8 dialkylene" refers to a diaryle having 2 to 8 carbon atoms. Examples of suitable diaryles include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, and hexylene.

[0044] The term "alkane" is derived from formula C n H 2n+2 This refers to saturated acyclic compounds. Alkanes may be linear or branched in shape.

[0045] The term "hydrocarbyl" refers to a monovalent or divalent group containing carbon and hydrogen atoms. Hydrocarbyls may be linear or branched, saturated or unsaturated, cyclic or acyclic. C2-C100 hydrocarbyl refers to a hydrocarbyl having 2 to 100 carbon atoms. Hydrocarbyls may be optionally substituted. Hydrocarbyls may be optionally interrupted by one or more heteroatoms selected from O, N, S, and Si.

[0046] The term "optionally substituted compound / group" means a compound / group that may be substituted with one or more groups selected from alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylaryl, haloalkyl, hydroxy, halogen, isocyanate, nitrile, amine, carboxylic acid, -C(=O)-R'-C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R' and -SO2-NH-R' (each R' is independently selected from alkyl, aryl, and alkylaryl groups, and may be substituted).

[0047] The term "alkyl" is derived from the formula -C n H 2n+1 This refers to a monovalent saturated acyclic hydrocarbon group. Alkyl groups may be linear or branched. "C1-C20 alkyl" means an alkyl group having 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0048] The term "hydroxyalkyl" refers to an alkyl group that is substituted with at least one hydroxyl group.

[0049] The term "cycloalkyl" refers to a non-aromatic cyclic hydrocarbon group. Cycloalkyls may contain one or more carbon-carbon double bonds. "C3-C8 cycloalkyl" refers to a cycloalkyl group having 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0050] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom that is a heteroatom selected from O, N, or S.

[0051] The term "aryl" refers to an aromatic hydrocarbon group. "C6-C12 aryl" refers to an aryl group having 6 to 12 carbon atoms.

[0052] The term "heteroaryl" refers to an aryl molecule having at least one ring atom that is a heteroatom, such as O, N, S, or combinations thereof. "C5-C9 heteroaryl" refers to a heteroaryl molecule having 5 to 9 carbon atoms.

[0053] The term "alkoxy" refers to a group with the formula -O-alkyl.

[0054] The term "alkylaryl" refers to an alkyl group substituted with an aryl group. "C7-C20 alkylaryl" refers to an alkylaryl group having 7 to 20 carbon atoms. An example of an alkylaryl group is benzyl(-CH2-phenyl).

[0055] The term "arylalkyl" refers to an aryl group that has been substituted with an alkyl group.

[0056] The term "haloalkyl" refers to an alkyl group that is substituted with one or more halogen atoms.

[0057] The term "halogen" refers to an atom selected from Cl, Br, and I.

[0058] The term "ethylenically unsaturated compound" refers to a compound containing a polymerizable carbon-carbon double bond. 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 acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and combinations thereof, preferably selected from acrylates, methacrylates, and vinyls, more preferably selected from acrylates and methacrylates. The carbon-carbon double bond of a phenyl ring is not considered a polymerizable carbon-carbon double bond.

[0059] 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.

[0060] Elastic materials The elastic material of the present invention has a rebound elasticity of greater than 10%, particularly greater than 15%, and more specifically greater than 20%. The elastic material may have a rebound elasticity of greater than 20%. In particular, the elastic material may have a rebound elasticity of greater than 22%, greater than 25%, greater than 30%, or greater than 35%. For example, the elastic material may have a rebound elasticity of 21-60%, 25-55%, 30-50%, or 35-45%. In an alternative embodiment, the elastic material may have a rebound elasticity of greater than 10% to 20%, for example, 11-20%, 12-20%, 14-20%, or 15-20%. The rebound elasticity can be measured in accordance with JIS K 6255:1996.

[0061] In one embodiment, the elastic material may have an elongation greater than 300%, greater than 350%, greater than 400%, or greater than 450%. For example, the elastic material may have an elongation of 350-1,500%, 400-1,400%, or 450-1,300%. The elongation can be measured in accordance with JIS K 7127:1999.

[0062] The elastic material may have a Shore A hardness of at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45. The Shore A hardness may be, for example, 100 or less, 90 or less, 80 or less, 70 or less, or 60 or less. For example, the elastic material may have a Shore A hardness of 15-90, 20-80, 25-70, 30-60, or 35-55. The Shore A hardness can be measured in accordance with JIS K 6253-3:2012.

[0063] The curable composition used to prepare the elastic material according to the present invention may, advantageously, be a liquid at room temperature (e.g., 25°C) under normal pressure (e.g., 100 kPa). As used herein, the term “liquid” means a composition that flows by its own mass. For example, the curable composition may have a viscosity at 60°C of 20,000 mPa·s or less, 10,000 mPa·s or less, 8,000 mPa·s or less, or 5,000 mPa·s or less. Viscosity can be measured with a Brookfield rotational viscometer.

[0064] As will be explained 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) and b) of the curable composition, changes in the elongation, rebound elasticity and / or Shore A hardness of the elastic material obtained from these components can be produced.

[0065] Component a) The curable composition used to prepare the elastic material of the present invention includes, as component a), a urethane (meth)acrylate containing oxybutylene units. Component a) may also include a mixture of urethane (meth)acrylates containing oxybutylene units.

[0066] The mass content of oxybutylene units in urethane (meth)acrylate may be at least 45% based on the total mass of urethane (meth)acrylate. In particular, the mass content of oxybutylene units may be 45-95%, 50-95%, 55-95%, 60-95%, 65-95%, 70-95%, 75-95%, 78-95%, 80-95%, or 80-90% based on the total mass of urethane (meth)acrylate. The mass content of oxybutylene units can be determined by calculating the mass of oxybutylene units in the compounds used to prepare the urethane (meth)acrylate relative to the total mass of the compounds used to prepare the urethane (meth)acrylate.

[0067] Urethane (meth)acrylate contains urethane bonds. In one embodiment, urethane (meth)acrylate contains an average of two or more urethane bonds per molecule. For example, urethane (meth)acrylate may contain an average of 1.8 to 10, 1.9 to 5, or 2 to 3 urethane bonds per molecule. In a particularly preferred embodiment, urethane (meth)acrylate may contain an average of two urethane bonds per molecule.

[0068] The urethane (meth)acrylate contains (meth)acrylate functional groups. In a preferred embodiment, the urethane (meth)acrylate of component a) does not have more than two (meth)acrylate functional groups on average per molecule. In particular, the urethane (meth)acrylate contains at least one acrylate functional group.

[0069] A suitable urethane (meth)acrylate 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, a urethane containing both acrylate and methacrylate functional groups in the same molecule can be used). For example, using a urethane (meth)acrylate with a molar ratio of acrylate functional groups to methacrylate functional groups 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.

[0070] Typically, a urethane (meth)acrylate may have (meth)acrylate functional groups at one or more ends of the molecule, but it is also possible for the (meth)acrylate functional groups to be located along the main chain of the molecule. The average (meth)acrylate functional value of component a) of the urethane (meth)acrylate may generally be up to 2 (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.

[0071] The number-average molecular weight (Mn) of the urethane (meth)acrylate used as component a) is at least 4,700 g / mol. The Mn of component a) can be measured using gel permeation chromatography and calibration polystyrene as described herein. The Mn of component a) may also be measured as a whole. Therefore, if component a) contains a single urethane (meth)acrylate, its Mn should be at least 4,700 g / mol. In embodiments of the present invention in which component a) contains two or more urethane (meth)acrylates, one or more such compounds may have a Mn of less than 4,700 g / mol, provided that at least one other such compound present in component a) has a Mn of at least 4,700 g / mol, and the Mn of the multiple urethane (meth)acrylates combined in the proportions used in component a) is at least 4,700 g / mol.

[0072] According to various embodiments of the present invention, the Mn of component a) may be at least 5,000 g / mol, at least 5,500 g / mol, at least 6,000 g / mol, at least 6,500 g / mol, or at least 7,000 g / mol. In particular, the Mn of component a) may be 50,000 g / mol or less, 30,000 g / mol or less, 25,000 g / mol or less, 20,000 g / mol or less, 18,000 g / mol or less, or 15,000 g / mol or less. For example, the Mn of component a) may be 4,700 to 50,000 g / mol, 5,000 to 30,000 g / mol, 5,500 to 25,000 g / mol, 6,000 to 20,000 g / mol, 6,500 to 18,000 g / mol, or 7,000 to 15,000 g / mol. In a particularly preferred embodiment, the Mn of component a) may be 5,500 to 20,000 g / mol, 5,500 to 18,000 g / mol, or 5,500 to 15,000 g / mol.

[0073] In one embodiment, the urethane (meth)acrylate of component a) may have a relatively low glass transition temperature (Tg) when measured by differential scanning calorimeter. For example, the urethane (meth)acrylate 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.

[0074] A particularly preferred urethane (meth)acrylate suitable for use as component a) is the following general formula (I): [ka] (In the formula, each A is independently a diol residue, and at least one A contains an oxybutylene unit; Each R is independently a residue of the diisocyanate; Each B is independently a residue of a hydroxylated mono(meth)acrylate; Each X is independently either H or methyl; n is 1 to 9, preferably 1 to 4, more preferably 1 to 2, and even more preferably n is 1. Examples of compounds having this feature include

[0075] In particular, each A is independently a diol residue containing an oxybutylene unit.

[0076] In this specification, the term “diol residue” means the portion between the two hydroxyl groups of a diol. At least one A may be a residue of a diol of the formula HO-A-OH (where A contains an oxybutylene unit). In particular, each A is a residue of a diol of the formula HO-A-OH (where A contains an oxybutylene unit). When a mixture of diols is used, A may correspond to A1 or A2, where A1 is a residue of the diol HO-A1-OH and A2 is a residue of the diol HO-A2-OH, provided that at least one of A1 and A2 contains an oxybutylene unit. A, A1, and A2 preferably do not contain urethane bonds.

[0077] In one embodiment, at least one A, in particular each A, may be a diol residue containing 2 to 200, particularly 10 to 100, and more specifically 13 to 50 oxybutylene units. In particular, the diol may have a number-average molecular weight of at least 1,100 g / mol, more specifically 1,200 to 5,000 g / mol, or 1,400 to 4,000 g / mol.

[0078] At least one A, in particular each A, may be a diol residue further comprising oxyalkylene repeating units other than oxybutylene units, such as oxyethylene units and / or oxypropylene units.

[0079] At least one A, in particular each A, may correspond to a poly(oxyalkylene) containing an oxybutylene unit and, optionally, an oxyethylene and / or oxypropylene unit. For example, at least one A, in particular each A, may correspond to the following: -(Alk'-O)b-Alk'- (In the formula, each Alk' is independently a linear or branched C2-C4 dialkylene, provided that at least a portion of the -Alk'- units are C4-dialkylenes, and in particular, at least a portion of the -Alk'- units are -(CH2)4-; b is 2-200, especially 10-100, and more specifically 13-50. It may be equivalent to this.

[0080] At least one A, in particular each A, may contain at least 50% by mass, at least 55% by mass, at least 60% by mass, at least 65% by mass, at least 70% by mass, at least 75% by mass, at least 80% by mass, at least 85% by mass, at least 90% by mass, at least 95% by mass, at least 98% by mass, at least 99% by mass, or 100% by mass of oxybutylene repeating units, based on the total mass of oxyalkylene repeating units (i.e., oxybutylene, oxyethylene, and oxypropylene repeating units).

[0081] In a particularly preferred embodiment, at least one A, especially each A, may be a residue of polytetramethylene ether glycol, especially a residue of polytetramethylene ether glycol having a number average molecular weight of at least 1,100 g / mol, or 1,200 to 5,000 g / mol, or 1,400 to 4,000 g / mol. The residue of polytetramethylene ether glycol has the following formula: -[(CH2)4 - O] b -(CH2)4 - (where b is 2 to 200, especially 10 to 100, more specifically 13 to 50) and can be represented by

[0082] As used herein, the term "residue of diisocyanate" means the portion between the two isocyanate groups of the diisocyanate. Thus, R may be a residue of a diisocyanate of the formula OCN - R - NCO. In one embodiment, R may be a residue of an aromatic, aliphatic, or alicyclic diisocyanate. In particular, R may be a residue of an aliphatic or alicyclic diisocyanate such as a C4 - C12 hydrocarbon chain or an isocyanate containing one or more cyclohexyl groups. More specifically, R may be a residue of an alicyclic diisocyanate. Even more specifically, R may be a residue of isophorone diisocyanate.

[0083] Examples of suitable diisocyanates having aliphatic residues are 1,4 - tetramethylene diisocyanate, 1,5 - pentamethylene diisocyanate (PDI), 1,6 - hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), 1,12 - dodecane diisocyanate.

[0084] 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.

[0085] 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.

[0086] In the present invention, the term "hydroxylated mono(meth)acrylate residue" refers to the portion between the (meth)acrylate functional group and the hydroxyl group in a hydroxylated mono(meth)acrylate. Therefore, 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).

[0087] In one embodiment, B may be a residue of a hydroxylated mono(meth)acrylate having a molecular weight of less than 600 g / mol, less than 550 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.

[0088] B may correspond to C2-C100 hydrocarbyl. C2-C100 hydrocarbyl may optionally be substituted with one or more hydroxyl groups. C2-C100 hydrocarbyl may optionally be interrupted by one or more oxygen atoms. In particular, C2-C100 hydrocarbyl may contain oxyalkylene units, especially at least two oxyalkylene units. The oxyalkylene units may be selected from oxyethylene, oxypropylene, oxybutylene, and combinations thereof.

[0089] 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 not substantially contain oxypropylene units, and in particular B may not substantially contain oxyalkylene units.

[0090] More specifically, B is given by equation -(Alk-O) p -(L) q -(O-Alk) r - (In the formula, each Alk is independently a linear or branched C2-C4 dialkylene, preferably ethylene or butylene; L is a C2-C20 hydrocarbyl, preferably a C2-C10 dialkylene, which may be optionally substituted with one or more hydroxyl groups: (Under the condition that p, q, and r are all not 0, p and r are independently 0 to 20, preferably 1 to 15, more preferably 2 to 10; q is 0 or 1, preferably 1) It may be equivalent to this.

[0091] In a preferred embodiment, p and r are independently between 0 and 3. In a particularly preferred embodiment, the sum of p + r is between 0 and 3, and more preferably 0.

[0092] Examples of such hydroxylated mono(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.

[0093] Particularly preferred are the following compounds: 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, and neopentyl glycol monomethacrylate.

[0094] 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.

[0095] More specifically, B is given by formula ((CH2)5-CO2) m -R1- (wherein R1 is a C2-C8, preferably C2-C6, more preferably C2-C4 dialkylene; m is 1 to 10, preferably 2 to 8, more preferably 3 to 5. It may be equivalent to this.

[0096] Hydroxylated mono(meth)acrylates containing polymerization units derived from lactones can be prepared by reacting a lactone (preferably ε-caprolactone) with a hydroxyalkyl mono(meth)acrylate, followed by ring-opening polymerization of the lactone.

[0097] The urethane (meth)acrylate of component a) may be a reaction product of one or more diols, one or more diisocyanates, and one or more hydroxylated mono(meth)acrylates. Oxybutylene units may typically be present in the diols. When a mixture of diols is used, oxybutylene units may typically be present in at least one of the diols, particularly in each diol.

[0098] The equivalent ratio R of the diol to the hydroxylated mono(meth)acrylate may be 0.5 to 3, particularly 0.6 to 2.5, more specifically 0.7 to 2, even more specifically 0.8 to 1.8, and even more specifically 1 to 1.5.

[0099] The equivalent ratio R is given by the following formula:

number

[0100] When using a mixture of diols, n OH_ジオール This corresponds to the sum of the moles of each diol.

[0101] n: Number of moles of OH groups in a hydroxyl group-containing compound OH The following equation:

number

[0102] In particular, component a), urethane (meth)acrylate, is produced in the following process: i) A step of reacting a diisocyanate with a hydroxylated mono(meth)acrylate to form an isocyanate functionalized compound; and ii) A step of reacting the adduct obtained in step i) with a diol containing an oxybutylene unit, or a mixture of diols in which at least one of the diols contains an oxybutylene unit. It can be obtained by a method that includes [a specific method].

[0103] The diisocyanate used in this method may be the diisocyanate of formula OCN-R-NCO (where R is as described above). The hydroxylated mono(meth)acrylate may be the hydroxylated mono(meth)acrylate of formula CH2=C(X)-(C=O)-OB-OH (where B and X are as described above). The diol may be the diol of formula HO-A-OH as described above.

[0104] The curable composition used to prepare the elastic material of the present invention contains 30 to 90% by mass, particularly 40 to 90% by mass, and more specifically 50 to 90% by mass, of urethane (meth)acrylate (i.e., component a)) having a number average molecular weight of at least 4,700 g / mol and containing oxybutylene units, based on the total mass of components a) and b). The curable composition used to prepare the elastic material of the present invention may also contain 50 to 90% by mass, of urethane (meth)acrylate (i.e., component a)) having a number average molecular weight of at least 4,700 g / mol and containing oxybutylene units, based on the total mass of components a) and b). In certain embodiments, the amount of component a) in the curable composition is at least 55% by mass, at least 60% by mass, at least 65% by mass, or at least 70% by mass, based on the total mass of components a) and b). In other embodiments, the amount of component a) in the curable composition is 85% by mass or less, 80% by mass or less, or 75% by mass or less, based on the total mass of components a) and b). For example, in a particular embodiment, the curable composition may contain 55-85% by mass, 60-80% by mass, or 65-75% by mass of component a), based on the total mass of components a) and b). In an alternative embodiment, the curable composition may contain 30-49% by mass, 35-49% by mass, or 40-49% by mass of component a), based on the total mass of components a) and b).

[0105] component b) A curable composition used to prepare an elastic material according to the present invention comprises, as component b), a (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule. Component b) may also comprise a mixture of (meth)acrylate monomers having one or two (meth)acrylate functional groups per molecule.

[0106] Suitable (meth)acrylate monomers for use as component b) 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, it is possible to use a (meth)acrylate monomer containing both acrylate and methacrylate functional groups in the same molecule, or a mixture containing acrylate monomer and methacrylate monomer).

[0107] 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.

[0108] The (meth)acrylate monomer used as component b) may be selected from mono(meth)acrylate monomers, di(meth)acrylate monomers, and mixtures thereof.

[0109] In one embodiment, component b) comprises a mono(meth)acrylate monomer. Component b) may also comprise a mixture of mono(meth)acrylate monomers.

[0110] Suitable examples of mono(meth)acrylate monomers include mono(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or cyclic, and may be a monoalcohol 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.); mono(meth)acrylate esters of oligomer glycols (diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, polyethylene glycol, polypropylene glycol, and polybutylene glycol, etc.); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligomer glycols (monomethyl or monoethyl ethers of glycols and oligomer glycols, etc.); alkoxylation (e.g., ethoxylation and Examples include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (or propoxylated) (where the aliphatic alcohol may be linear, branched, or cyclic, and may be a monoalcohol or a polyol, provided that only one hydroxyl group in 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.

[0111] Examples of mono(meth)acrylate monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, methoxydiethylene glycol monoacrylate, methoxydiethylene glycol monomethacrylate, ethoxydiethylene glycol monoacrylate, ethoxydiethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, methoxytriethylene glycol monoacrylate, methoxytriethylene glycol monomethacrylate, ethoxytriethylene glycol monoacrylate, ethoxytriethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and methoxypolyethylene Polyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, ethoxypolyethylene glycol monoacrylate, ethoxypolyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, 2-ethoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, polycaprolactone acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2-phenoxyethyl acrylate, phenyl acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate (or CTFA), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylate (or IPGA), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate (or IPGMA), (2-ethyl-2-methyl-1,3-Dioxolan-4-yl)methyl acrylate, glycerol formal methacrylate (or Glyfoma), 2-[[(butylamino)carbonyl]oxy]ethyl acrylate, octyl / decyl acrylate, cetyl / stearyl acrylate, cetyl / stearyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, iso-decyl acrylate, iso-decyl methacrylate, dodecyl acrylate, tridecyl acrylate, tri Decyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, heptadecyl acrylate, propylheptyl acrylate, dodecyl methacrylate, benzyl acrylate, cyclohexyl acrylate, 2-carboxyethyl acrylate, 2-hydroxy Examples include propyl methacrylate, 2-hydroxyethyl methacrylate, acryloylmorpholine, 2-phenoxyethyl methacrylate, tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tricyclodecane methanol monoacrylate, glycidyl acrylate, glycidyl methacrylate, nonylphenol acrylate, allyl acrylate, allyl methacrylate, para-cumylphenyl ether acrylate, alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives of the above compounds, and mixtures thereof.

[0112] Component b) may contain a mono(meth)acrylate monomer having a glass transition temperature (Tg) greater than 20°C. Such monomers are sometimes called "hard monomers." Conversely, mono(meth)acrylate monomers having a Tg less than 20°C are called soft monomers. The Tg of a monomer corresponds to the Tg of the corresponding homopolymer, as measured by differential scanning calorimeter.

[0113] The hard monomer may have a Tg of at least 40°C, at least 50°C, at least 60°C, at least 70°C, or at least 75°C.

[0114] Suitable hard monomers include tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tricyclodecane methanol monoacrylate, and mixtures thereof.

[0115] In particular, hard 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). Component b) may also contain sterically hindered mono(meth)acrylate monomers. The sterically hindered mono(meth)acrylate monomers may contain a cyclic moiety and / or a tert-butyl group. The cyclic moiety may be monocyclic, bicyclic, or tricyclic, and may include bridging ring systems, fused ring systems, and / or spirocyclic systems. 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 include a ring or ring system selected from cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof. More specifically, the cyclic moiety may include a ring or ring system selected from phenyl, cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl, dicyclopentadienyl, oxylanil, oxetanyl, tetrahydrofuranil, tetrahydropyranil, dioxolanil, dioxanil, dioxapridecanyl, and dioxapriderundecanyl. The ring or ring system may optionally be substituted with one or more groups selected from hydroxyl, alkoxy, alkyl, hydroxyalkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl.

[0116] In particular, the ring part is given by the following equation: [ka] (In the formula, symbols [ka] The dashed line indicates the site of bonding to the part containing the (meth)acrylate group. [ka] (wherein ) represents a single or 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.

[0117] In particular, sterically hindered mono(meth)acrylate monomers include a moiety containing an aliphatic ring, especially a cyclic moiety containing an aliphatic ring selected from cyclohexane, tricyclodecane, tetrahydrofuran, bornane, 1,3-dioxolane, and 1,3-dioxane.

[0118] Examples of sterically hindered mono(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, tricyclodecanemethanolmono(meth)acrylate, tetrahydrofurfuryl( These include 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.

[0119] Specific examples of sterically hindered mono(meth)acrylate monomers include tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate (or CTFA), (2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylate (or IPGA), and (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate. These include (or IPGMA), (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl acrylate, glycerol formal methacrylate (or Glyfoma), 3,5,5-trimethylcyclohexyl acrylate, 3,5,5-trimethylcyclohexyl methacrylate, tricyclodecane methanol monoacrylate, tricyclodecane methanol monomethacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate.

[0120] In a preferred embodiment, component b) comprises a mono(meth)acrylate monomer selected from isobornyl acrylate, tert-butylcyclohexyl acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate (or CTFA), tetrahydrofurfuryl acrylate, and mixtures thereof.

[0121] In particular, the sterically hindered mono(meth)acrylate 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).

[0122] In one embodiment, component b) may comprise a mixture of a hard monomer and a soft monomer. The hard monomer may be as defined above. The soft monomer may have a Tg of 10°C or less, 0°C or less, -10°C or less, -20°C or less, or -25°C or less. In a particular embodiment, such a difference in glass transition temperatures (i.e., the difference between the Tg of the hard monomer and the Tg of the soft 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.

[0123] The relative amounts of hard monomers and soft monomers in the curable composition may be varied as desired, for example, depending on the properties of the urethane (meth)acrylate 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 hard monomers to soft monomers in the curable composition can preferably be 1:10 to 10:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, or 1:2 to 2:1. Generally, if 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 hard monomer relative to the amount of soft monomer.

[0124] In one embodiment, component b) comprises a di(meth)acrylate monomer. Component b) may also comprise a mixture of di(meth)acrylate monomers.

[0125] Suitable di(meth)acrylate monomers include (meth)acrylates of diols and alkoxylated diols. If an average of two hydroxyl groups in the polyol or alkoxylated polyol are esterified with (meth)acrylic acid, then (meth)acrylates of polyols and alkoxylated polyols having an average of more than two hydroxyl groups per molecule can be used.

[0126] Suitable examples of di(meth)acrylate monomers include di(meth)acrylates of ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol (e.g., tetraethylene glycol di(meth)acrylate). Examples include: 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); (meth)acrylates of 1,6-hexanediol (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 1-25 oxyethylene units per molecule (e.g., bisphenol A ethoxylated with 1-35 equivalents of ethylene oxide and then (meth)acrylicated); and combinations thereof.

[0127] Examples of di(meth)acrylate monomers include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, and 1,5-pentene Tandiol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, triethylolpropane diacrylate, triethylolpropane dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, polybutadiene diacrylate, polybutadiene dimethacrylate, 3-methyl-1,Examples include, but are not limited to, 5-pentanediol diacrylate, cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, metal diacrylate, modified metal diacrylate, metal dimethacrylate, modified metal dimethacrylate, alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives of the above compounds, and mixtures thereof.

[0128] The curable composition used to prepare the elastic material of the present invention contains 10 to 70% by mass, particularly 10 to 60% by mass, and more specifically 10 to 50% by mass, of (meth)acrylate monomers having one or two (meth)acrylate functional groups per molecule (i.e., component b)), based on the total mass of components a) and b). The curable composition used to prepare the elastic material of the present invention may also contain 10 to 50% by mass, of (meth)acrylate monomers having one or two (meth)acrylate functional groups per molecule (i.e., component b)), based on the total mass of components a) and b). In certain embodiments, the amount of component b) in the curable composition is at least 12% by mass, at least 15% by mass, at least 20% by mass, or at least 30% by mass, based on the total mass of components a) and b). In other embodiments, the amount of component b) in the curable composition is 45% by mass or less, or 40% by mass or less, based on the total mass of components a) and b). For example, in a particular embodiment, the curable composition may contain 15-45% by mass, 20-40% by mass, or 30-40% by mass of component b) based on the total mass of components a) and b). In an alternative embodiment, the curable composition may contain 51-70% by mass, 51-65% by mass, or 51-60% by mass of component b) based on the total mass of components a) and b).

[0129] Advantageously, the amount of di(meth)acrylate monomer in component b) may be kept relatively low, so that component b) is mainly composed of mono(meth)acrylate monomers. In fact, if the amount of di(meth)acrylate monomer in component b) is too high, excessive crosslinking may reduce the elastic properties of the resulting material.

[0130] In a preferred embodiment, the mono(meth)acrylate monomer constitutes at least 80% by mass, at least 85% by mass, at least 90% by mass, at least 95% by mass, at least 98% by mass, at least 99% by mass, or at least 99.5% by mass, or 100% by mass of the total mass of component b).

[0131] components a) and b) and other curing components c) The curable composition used to prepare the elastic material according to the present invention may contain curable component c) other than components a) and b). The curable composition may also contain a mixture of curable component c) other than components a) and b).

[0132] The curable component c) consists of any ethylenically unsaturated compound present in the composition other than urethane (meth)acrylate having a number average molecular weight of at least 4,700 g / mol and containing oxybutylene units, and (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule.

[0133] The curable component c) may include monomers, oligomers and mixtures thereof, in particular (meth)acrylate monomers, (meth)acrylate oligomers and mixtures thereof.

[0134] In one embodiment, the curable component c) includes a (meth)acrylate oligomer.

[0135] Suitable oligomers include, but are not limited to, epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers other than component a), 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), or it may not contain regions that are structurally similar to conventional elastomers.

[0136] 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. Epoxy (meth)acrylate oligomers may also be hydroxy-functional (i.e., containing one or more hydroxyl groups in addition to one or two (meth)acrylate functional groups per molecule). Suitable hydroxy-functional 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 (where both hydroxyl and (meth)acrylate functionality are introduced by ring-opening of the epoxy group by (meth)acrylic acid). The starting epoxy compound may be, for example, a bisphenol-type epoxy resin. Alternatively, epoxy (meth)acrylate oligomers can be obtained by functionalizing an oligomer such as polyoxyalkylene glycol or polybutadiene with one or two epoxy groups, and then reacting the epoxy groups with (meth)acrylic acid. Suitable examples of hydroxy-functional epoxy (meth)acrylates include aliphatic epoxy (meth)acrylate oligomers that possess both (meth)acrylate functionality and secondary hydroxy functionality through ring-opening of the epoxy group.

[0137] Examples of urethane (meth)acrylate oligomers usable in the curable composition of the present invention include aliphatic and / or aromatic polyester polyols and polyether polyols, as well as urethanes based on 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.

[0138] 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), a polycarbonate polyol, a polycaprolactone polyol, a polydimethylsiloxane polyol, or a polybutadiene polyol, or a combination thereof, to form an isocyanate-functionalized oligomer, and then reacting the oligomer with a hydroxy-functionalized (meth)acrylate such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate or hydroxyethyl methacrylate) to impart one or two terminal (meth)acrylate groups.

[0139] Particularly preferred urethane acrylate oligomers suitable for use in the present invention include oligomers formed by the reaction of a polyol, a diisocyanate, and (meth)acrylic acid or a hydroxyalkyl (meth)acrylate.

[0140] 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 polyhydroxy functional components (particularly diols such as glycols and oligoglycols) and polycarboxylic acid functional compounds (particularly dicarboxylic acids and anhydrides). The polyhydroxy 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.

[0141] 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 ends of the oligomer or hanging (pendanted) from 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 monomer may be any monomer (meth)acrylate such as C1-C6 alkyl (meth)acrylates, or a functionalized (meth)acrylate such as a (meth)acrylate having a hydroxyl group, a carboxylic acid group, and / or an epoxy group. (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.

[0142] Suitable (meth)acrylate oligomers include amine-modified derivatives of the aforementioned (meth)acrylate oligomers. Such products can be obtained by Michael addition of some of the (meth)acrylate functional groups of the (meth)acrylate oligomer with a secondary amine.

[0143] The curable component c) may contain a (meth)acrylate monomer that has more than two (meth)acrylate functional groups per molecule, typically three or more (meth)acrylate functional groups per molecule.

[0144] A (meth)acrylate monomer 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)acrylated.

[0145] Specific examples of suitable polyols include glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sugar alcohols, alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives of the above compounds, and mixtures thereof. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) if the resulting product contains at least three (meth)acrylate functional groups per molecule.

[0146] Examples of (meth)acrylate monomers containing three or more (meth)acrylate functional groups per molecule include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, tris(2-hydroxyethyl) isocyanurate trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, glyceryl triacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives of the above compounds, and mixtures thereof.

[0147] The amount of curable component c) may be kept relatively small so that the curable composition mainly consists of components a) and b).

[0148] In a preferred embodiment, components a) and b) constitute at least 90% by mass, at least 95% by mass, or at least 99% by mass, or 100% by mass, of the total amount of curable components (i.e., components a), b) and c)) present in the curable composition.

[0149] Initiator system - component d) The curable compositions used to prepare the elastic materials according to the present invention may also optionally include an initiator system (also called 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. In one embodiment, the curable composition may contain 0.01 to 10% by mass, or 0.05 to 5% by mass, or 0.1 to 2% 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.

[0150] A photopolymerization initiator can be considered any type of substance that, upon exposure to radiation (e.g., light), 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 to be used to cure the photocurable composition.

[0151] Free radical photoinitiators can employ two different modes of action and are classified into Norrish type I and Norrish type II photoinitiators based on their mode of action. Norrish type I photoinitiators cleave upon exposure to radiation, generating radical species capable of initiating polymerization of unsaturated compounds. Norrish type II photoinitiators are compounds that do not undergo fragmentation upon exposure to radiation, and typically, polymerization of the radical chain does not begin unless a co-initiator is present. Upon exposure to radiation, the interaction between the type II photoinitiator and the co-initiator generates radical species, which can initiate polymerization of UV-curable resins. Some radical photoinitiators may have two different photoactive moieties and exhibit both Norrish type I and Norrish type II activity. In this case, upon exposure to radiation, one portion may cleave into two radical fragments, while the other portion may be converted to a radical by atomic abstraction.

[0152] 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, α-hydroxyacetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, acylphosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formate, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymer derivatives thereof, and mixtures thereof.

[0153] 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. 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-hydroxycycline Rohexyl phenyl 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)phenylphosphine, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)trical Bonylchromium, benzyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexylphenyl ketone 50 / 50 mixture, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4-benzoyl biphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone, 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-hydroxy-2-methylpropiophenone 50 / 50 mixture, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-H Examples include, but are not limited to, droxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthene-9-one, and combinations thereof.

[0154] Additives - Component e) The curable composition used to prepare the elastic material according to the present invention may also contain an additive (also called component e). The curable composition may also contain a mixture of additives.

[0155] In particular, additives may be selected from adhesion enhancers, sensitizers, amine synergies, antioxidants / light stabilizers, light blocking / absorbing agents, polymerization inhibitors, foaming inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip agents, fillers, chain transfer agents, thixotropes, matting agents, impact modifiers, waxes, mixtures thereof, and any other additives conventionally used in coatings, sealants, adhesives, moldings, 3D printing, or ink technologies.

[0156] In one embodiment, the composition may contain an additive that improves adhesion but is not (meth)acrylate functionalized (i.e., does not contain (meth)acrylate functionality). This additive can improve the adhesion of the elastic material obtained from the curable composition to the substrate (especially the substrate surface). Examples of additives that improve adhesion but do not contain reactive (meth)acrylate functional groups include polymers with inherent adhesive properties such as tackifying resins and tack, or components that do not have inherent adhesive properties but improve adhesion when included as a component of the curable composition. Adhesion-improving additives that do not contain (meth)acrylate functional groups can be used, for example, in amounts of 0 to 30% (w / w).

[0157] The curable composition may contain a sensitizer and / or an amine synergistic agent. A sensitizer may be introduced into the curable composition of the present invention to broaden the sensitivity of the photopolymerization initiator to longer wavelengths. For example, the sensitizer may be capable of absorbing light of longer or shorter wavelengths than the photopolymerization initiator, transferring that energy to the photopolymerization initiator, and returning it to its ground state. Examples of suitable sensitizers include benzophenone, anthracene, thioxanthone (2-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone), xanthone, anthrone, anthraquinone (2-ethylanthraquinone), dibenzosverone, and carbazole. The concentration of the sensitizer in the curable composition varies depending on the photopolymerization initiator used. However, typically, the curable composition is formulated to contain 0% to 5% by mass, particularly 0.1% to 3% by mass, and more specifically 0.5% to 2% by mass, of the total mass of the curable composition, as a sensitizer.

[0158] An amine synergist may be introduced into the curable composition of the present invention to act synergistically with the Norrish type II photopolymerization initiator and / or to reduce oxygen inhibition. The amine synergist is typically a tertiary amine. When used with the Norrish type II photopolymerization initiator, the tertiary amine provides an active hydrogen donor site to the excited triple state of the photopolymerization initiator, thereby generating a reactive alkyl-amino radical, which can subsequently initiate polymerization. The tertiary amine can also reduce the effect of oxygen on curing by converting the non-reactive peroxy species produced by the reaction of oxygen with free radicals into a reactive alkyl-amino radical. If the composition contains a cationic polymerizable compound, the amine synergist may not be present. Examples of suitable amine synergists include low molecular weight tertiary amines (i.e., having a molecular weight of less than 200 g / mol), such as triethanolamine and N-methyldiethanolamine. Other types of amine synergies include aminobenzoates or amine-modified acrylates (acrylic amines formed by Michael addition of a secondary amine to some of the acrylate groups of acrylate-functionalized monomers and / or oligomers). Examples of aminobenzoates include ethyl-4-(N,N'-dimethylamino)benzoate (EDB) and 2-n-butoxyethyl 4-(dimethylamino)benzoate (BEDB). Examples of commercially available amine-modified acrylate oligomers include CN3705, CN3715, CN3755, CN381, and CN386, available from Arkema. Polymeric or multi-amino types are also preferred. The concentration of the amine synergy in the curable composition varies depending on the type of compound used. However, typically, the curable composition is formulated to contain 0% to 25% by mass, particularly 0.1% to 10% by mass, and more specifically 0.5% to 5% by mass, of the amine synergy based on the total mass of the curable composition.

[0159] The curable composition may contain stabilizers. Stabilizers may be introduced into the curable composition of the present invention to provide sufficient storage stability and shelf life. The term “stabilizer” includes aerobic inhibitors and / or antioxidants. Advantageously, one or more such stabilizers are present at each step of the method used to prepare the curable composition to protect against unwanted reactions during processing of the ethylenically unsaturated components of the curable composition, for example, during the manufacture of the composition, during storage of the composition at high temperatures or for extended periods, during coating, during other times when the composition is exposed to temperatures above room temperature, or during any time when the product is accidentally exposed to radiation (such as sunlight) before curing. As used herein, the term “stabilizer” means a compound or substance that delays or prevents the reaction or curing of photocurable functional groups present in the composition in the absence of light. However, it would be advantageous to select an amount and type of stabilizer such that the composition remains curable when exposed to light (i.e., the stabilizer does not interfere with the radiation curing of the composition). Typically, stabilizers effective for the purposes of the present invention would be classified as free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions). In the present invention, any of the stabilizers known in the art related to (meth)acrylate functionalized compounds can be used. Quinones correspond to a particularly preferred type of stabilizer that can be used in connection with the present invention. As used herein, the term “quinone” includes both quinones and hydroquinones, as well as ethers such as monoalkyl, monoallyl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a preferred stabilizer that can be used. Other stabilizers known in the art, such as BHT and its derivatives, phosphite compounds, phenothiazine (PTZ), triphenylantimony, and tin(II) salts, can also be used. The concentration of the stabilizer in the curable composition will vary depending on the specific stabilizer or combination of stabilizers selected for use, the desired degree of stabilization, and the susceptibility of the components in the curable composition to degradation in the absence of the stabilizer. However, typically, the curable composition is formulated to contain 5 to 5,000 ppm of stabilizer.

[0160] The curable composition may optionally contain non-(meth)acrylate components, such as fillers, processing aids, or enhancers, 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 fillers, processing aids, or enhancers 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, rubber, thermoplastic urethane, EVA graft terpolymer, dry fumed silica, precipitated silica, surface-modified silica, 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.

[0161] 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.

[0162] The curable composition may contain a light-blocking agent (sometimes called a light-absorbing agent). The introduction of a light-blocking agent is particularly advantageous when the curable composition is used as a resin in a three-dimensional printing method involving the photocuring of the curable composition. The light-blocking agent may be any such substance known in the art of three-dimensional printing, including, for example, non-reactive pigments and dyes. The light-blocking agent may be, for example, a visible light-blocking agent or a UV light-blocking agent. Examples of suitable light-blocking agents include, but are not limited to, titanium dioxide, carbon black, and organic ultraviolet absorbers, such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, hydroxyphenyltriazine, Sudan I, bromothymol blue, 2,2'-(2,5-thiophendiyl)bis(5-tert-butylbenzoxazole) (marketed under the trade name "Benetex OB Plus"), and benzotriazole ultraviolet absorbers. The amount of light-blocking agent may be varied as desired or appropriate for a particular application. Generally, when a curable composition contains a light-blocking agent, the light-blocking agent is present at a concentration of 0.001 to 10% by mass, based on the mass of the curable composition.

[0163] Advantageously, the curable compositions of the present invention may be formulated to be solvent-free, i.e., free from any non-reactive volatile substances (substances with a boiling point of 150°C or less at atmospheric pressure). For example, the curable compositions of the present invention may contain little to no non-reactive solvents based on the total mass of the curable composition, for example, less than 10%, less than 5%, less than 1%, or even 0% non-reactive solvents. As used herein, the term non-reactive solvent means a solvent that does not react when exposed to the light used to cure the curable compositions described herein.

[0164] composition Exemplary embodiments of the present invention include an elastic material which is a polymerization reaction product of the following curable compositions.

[0165] The following components a), b), and c): Component a): 60-70% urethane (meth)acrylate having a number-average molecular weight of at least 4,700 g / mol and containing oxybutylene units; Component b): 30-40% mono(meth)acrylates, especially sterically hindered mono(meth)acrylate monomers, more particularly isobornyl acrylates; Component c): 0.3-5% photopolymerization initiator; A curable composition comprising, wherein % is a mass % based on the total mass of components a), b), and c).

[0166] The following components a), b), and c): Component a): Urethane (meth)acrylate, which is a reaction product of 60-70% polytetramethylene glycol having a number average molecular weight of at least 1,100 g / mol, one or more diisocyanates, and one or more hydroxylated mono(meth)acrylates; Component b): 30-40% mono(meth)acrylates, especially sterically hindered mono(meth)acrylate monomers, more particularly isobornyl acrylates; Component c): 0.3-5% photopolymerization initiator; A curable composition comprising, wherein % is a mass % based on the total mass of components a), b), and c).

[0167] 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 that 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 Nos. 6,265,476 and 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)acrylicated polysiloxanes as described in U.S. Patent No. 5,268,396; - Rubber (elastomer) that does not contain (meth)acrylate functional groups; - Rubber containing (meth)acrylate functional groups that has elastomeric properties in an uncured state; and / or - Silica.

[0168] Preparation of curable compositions Typically, it would be desirable to combine the various components of the curable composition and mix them until homogeneous. The manufacturing process can be adjusted based on the identity and quantity 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.

[0169] In particular, a curable composition may be obtained by preparing a urethane (meth)acrylate according to component a) as defined above. A (meth)acrylate monomer according to component b) as defined above may be added during and / or after the preparation of the urethane (meth)acrylate.

[0170] 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.

[0171] Curing of curable composition According to aspects of the present invention, the compositions described above may be polymerized into dimensionally stable solid materials having elastomer properties. The components of the curable composition can 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 is passed 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.

[0172] 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 specifically, 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.

[0173] 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 light, 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.

[0174] 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.

[0175] 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 as a bulk (for example, the curable composition may be cast in a suitable mold and then cured).

[0176] 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.

[0177] 3D printed articles may be obtained using a method for preparing 3D printed articles, which in particular includes the step of printing the 3D article using 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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 or comprise a cured composition according to the present invention. The three-dimensional articles may also be composite materials consisting essentially of or comprising at least one component comprising the curable compositions described above, and at least one additional component (e.g., a metallic component, a thermoplastic component, or an inorganic filler or fiber reinforcement) comprising one or more materials other than such cured compositions. 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, photocuring 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 functions as a scaffold or support for articles formed from the curable compositions of the present invention.

[0182] Accordingly, the curable compositions of the present invention are useful in implementing 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 light irradiation. For example, a new layer may be formed on the top surface or the bottom surface of the object being created. 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 a “continuous liquid interface (or interface) product (or print)” (“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).

[0183] The curable composition may be supplied by ejection 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 composition immediately after it is applied to the surface substrate on which the curable composition is built or to a 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 produce 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.

[0184] A method for preparing a 3D printed article 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 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 first cured layer (e.g., coating); d) a step of curing the 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.

[0185] After a 3D article is printed, it may be subjected to one or more post-processing steps. These post-processing steps, either simultaneous or sequential, may be one or more of the following: removal of any printed support structures; washing with water and / or organic solvents to remove residual resin; and post-curing using heat treatment and / or light. Post-processing steps may be used to transform the freshly printed article into a final, functional article ready for use in its intended application.

[0186] Articles containing elastic materials The elastic material of the present invention may be permanently attached to a substrate. Alternatively, the elastic material can be removed from the substrate after curing to provide a self-standing article. The elastic material may be in the form of a very thin article (e.g., less than 1 mil thick) or a thick article (e.g., more than 1 inch thick). An article containing the elastic material may be a layered product 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).

[0187] While embodiments have been described herein in a manner that enables the writing of a clear and concise specification, it is intended and to be understood that embodiments 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 aspects of the present invention described herein.

[0188] In some embodiments, the inventions described herein may be interpreted as excluding any elements or process steps that do not substantially affect the basic and novel properties of the curable compositions, the materials, products and articles prepared from the compositions, and the methods for producing and using such curable compositions as described herein. Furthermore, in some embodiments, the inventions may be interpreted as omitting any elements or process steps not expressed herein.

[0189] Although the present invention is illustrated and described 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 without departing from the present invention, within the scope and area of ​​equivalents of the claims. [Examples]

[0190] Materials and methods The following compounds were used in the examples.

[0191] [Table 1]

[0192] In this application, the following method was used.

[0193] Curing method The resin was mixed with 5% by mass of Irgacure 184 based on the mass of the resin. This mixture was coated onto a 100 μm PET film using #10 to #50 coated wire rods. The coated substrate was subjected to a saturation of 400 to 1,000 mJ / cm². 2 The material was cured at a speed of 15 m / min using a UV curing device equipped with an Hg lamp.

[0194] Tensile test (elongation) In accordance with JIS K 7127:1999, the elongation at break (machine direction) was measured for hardened specimens (dumbbell No. 5) with a thickness of 30-100 μm. The distance between the grips was 8 cm. The length of the first specimen used for calculating the elongation at break was the length of the elongated part of the specimen (2.5 cm). The strain rate was 2 cm / min.

[0195] Rebound speed The rebound velocity was measured by manually measuring the rebound time after stretching the hardened sample (Dumbbell No. 5) to twice its original size. The thickness of the hardened film was 30-50 μm. The rebound velocities were classified based on the rebound speed and time. The order of rebound velocities is as follows: 5>4>>3>>>>>>2>>>1 1: No recovery 2: Almost no recovery 3: Slow, over 1.0 second 4: Fast, less than 1.0 second 5: Very fast, less than 0.5 seconds

[0196] Shore A hardness In accordance with JIS K 6253-3:2012, the Shore A hardness of a 3 mm thick hardened sample was measured using a Shore A hardness tester.

[0197] Rebound elasticity The rebound elasticity was measured according to JIS K 6255:1996, "Physical testing methods for molded products of thermosetting polyurethane elastomers." The measurements were performed on hardened cylindrical samples with a diameter of 30 mm and a height of 12.5 mm. The pendulum test method was used. Each sample was tested three times at 25°C.

[0198] number average molecular weight The number-average molecular weight was determined by gel permeation chromatography (GPC) using standard polystyrene. The GPC measurement conditions are as follows. Model: High-performance liquid chromatograph Lachrom Elite, manufactured by Hitachi High-Technologies Corporation. Column: SHODEX GPC KF-G / -401HQ / -402.5HQ / -403HQ (4.6×250mm) Eluent:THF Flow rate: 0.45 mL / min Temperature: 40℃ Sample injection volume and concentration: 5 μL, 10 mg / mL Detection: RI (Differential Refractometer) System for collecting and processing data: Hitachi EZChrom Elite, Ltd.

[0199] viscosity Viscosity was measured at 60°C using a Brookfield rotational viscometer. Various ASTM methods (such as ASTM D1084 and ASTM D2556), all very similar, may be used to measure viscosity using a Brookfield rotational viscometer with a spindle size selected to achieve a torque of 50–70%, as is well known in the art. The specific ASTM method will be selected based on the viscosity of the liquid sample and whether the liquid is a Newtonian or non-Newtonian fluid, among other possible factors.

[0200] Mass content of oxybutylene units The mass content of oxybutylene units in urethane (meth)acrylate can be determined by calculating the mass (grams) of oxybutylene units in the compounds used to prepare the urethane (meth)acrylate relative to the total mass (grams) of the compounds used to prepare the urethane (meth)acrylate. For example, if urethane (meth)acrylate is obtained by reacting a diol, a diisocyanate, and a hydroxylated mono(meth)acrylate, and oxybutylene units are present only in the diol, the mass content of oxybutylene units (%OB) is given by the following formula:

number

[0201] If the diol is polytetramethylene glycol, then OB ジオール is m ジオール This corresponds to OB. When using a mixture of diols, ジオール m is the mass of oxybutylene units in a mixture of diols. ジオール is the mass of the mixture of diols.

[0202] Example 1: Preparation of a curable composition (comparative example) 19.4 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 8.15 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 37.25 grams of PTMG1 were added to the mixture. After the addition of PTMG1 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 500 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 2,700 g / mol and a mass content of 57% oxybutylene units.

[0203] Example 2: Preparation of a curable composition (comparative example) 15.7 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 6.6 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 42.5 grams of PTMG2 were added to the mixture. After the addition of PTMG2 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 600 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 4,500 g / mol and a mass content of 66% oxybutylene units.

[0204] Example 3: Preparation of the curable composition of the present invention 12.4 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 5.2 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 47.2 grams of PTMG3 were added to the mixture. After the addition of PTMG3 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 750 mPa·s at 60°C. The final resin contains 65% by mass of urethane acrylate and 35% by mass of IBOA. This urethane acrylate has a manganese content of 5,800 g / mol and a mass content of 73% oxybutylene units.

[0205] Example 4: Preparation of the curable composition of the present invention 9.5 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 4.0 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 51.3 grams of PTMG4 were added to the mixture. After the addition of PTMG4 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 1,500 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 7,900 g / mol and a mass content of 79% oxybutylene units.

[0206] Example 5: Preparation of the curable composition of the present invention 7.0 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.95 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 54.85 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 3,000 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 9,000 g / mol and a mass content of 85% oxybutylene units.

[0207] Example 6: Preparation of the curable composition of the present invention 7.0 grams of IPDI, 15.0 grams of CTFA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.95 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 54.85 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of CTFA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 2,000 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of CTFA. The urethane acrylate had a manganese content of 8,100 g / mol and a mass content of 85% oxybutylene units.

[0208] Example 7: Preparation of the curable composition of the present invention 7.0 grams of IPDI, 15.0 grams of TBCHA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.95 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 54.85 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of TBCHA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 2,520 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of TBCHA. The urethane acrylate had a manganese content of 8,500 g / mol and a mass content of 85% oxybutylene units.

[0209] Example 8: Preparation of the curable composition of the present invention 5.4 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.3 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 57.1 grams of PTMG6 were added to the mixture. After the addition of PTMG6 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 4,300 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 14,200 g / mol and a mass content of 88% oxybutylene units.

[0210] Example 9: Preparation of a curable composition (comparative example) 6.8 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.85 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 55.15 grams of PPG were added to the mixture. After the addition of PPG was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 220 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 8,600 g / mol and a mass content of 0% oxybutylene units.

[0211] Example 10: Preparation of a curable composition (comparative example) 6.5 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.72 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 55.58 grams of PBD were added to the mixture. After the addition of PBD was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 2,000 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 8,900 g / mol and a mass content of 0% oxybutylene units.

[0212] Example 11: Preparation of the curable composition of the present invention 6.3 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 2.23 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 56.27 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 3,850 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 10,600 g / mol and a mass content of 82% oxybutylene units.

[0213] Example 12: Preparation of the curable composition of the present invention 7.78 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 4.08 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 52.94 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 1,850 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 7,600 g / mol and a mass content of 77% oxybutylene units.

[0214] Example 13: Preparation of the curable composition of the present invention 9.20 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 5.8 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 49.8 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 1,000 mPa·s at 60°C. The final resin contained 65% by mass of urethane acrylate and 35% by mass of IBOA. The urethane acrylate had a manganese content of 6,700 g / mol and a mass content of 72% oxybutylene units.

[0215] Example 14: Preparation of the curable composition of the present invention 10.7 grams of IPDI, 15.0 grams of IBOA, 0.1 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1,000 mL reactor. 7.5 grams of HEA were added dropwise while sparging with dry air, and the mixture was reacted at 50-60°C for 2 hours. The mixture was then heated to 75°C, and 46.6 grams of PTMG5 were added to the mixture. After the addition of PTMG5 was complete, 20.0 grams of IBOA were added to the mixture. The final resin was a colorless, transparent substance with a viscosity of 700 mPa·s at 60°C. The final resin contains 65% by mass of urethane acrylate with a Mn content of 5,300 g / mol, and 35% by mass of IBOA. The urethane acrylate has a Mn content of 5,300 g / mol and a mass content of 57% oxybutylene units.

[0216] Example 15: Properties of hardened materials The resins obtained in Examples 1 to 10 were cured according to the curing method described above. The rebound modulus, rebound velocity, elongation, and Shore A hardness of the materials cured according to the method described herein were measured.

[0217] [Table 2]

[0218] The resin of the present invention yielded a cured material with superior elongation, moderate hardness, higher rebound elasticity, and higher rebound velocity compared to the cured material obtained with the comparative resin.

Claims

1. An elastic material having rebound elasticity greater than 10%, particularly greater than 15%, and more specifically greater than 20%, as measured in accordance with JIS K 6255:1996, and the elastic material having the following components a) and b): a) At least one urethane (meth)acrylate having a number-average molecular weight of at least 4,700 g / mol and containing oxybutylene units, in an amount of 30 to 90% by mass, particularly 40 to 90% by mass, and more particularly 50 to 90% by mass, based on the total mass of components a) and b); b) 10 to 70% by mass, particularly 10 to 60% by mass, and more particularly 10 to 50% by mass, of the total mass of components a) and b), of at least one (meth)acrylate monomer having one or two (meth)acrylate functional groups per molecule. An elastic material which is an energy curing reaction product of a curable composition containing [a specific component].

2. The elastic material according to claim 1, wherein the mass content of oxybutylene units in the urethane (meth)acrylate is at least 45% based on the total mass of the urethane (meth)acrylate, and in particular, the mass content of oxybutylene units is 45-95%, 50-95%, 55-95%, 60-95%, 65-95%, 70-95%, 75-95%, 78-95%, 80-95%, or 80-90% based on the total mass of the urethane (meth)acrylate.

3. The elastic material according to claim 1 or 2, wherein component a) comprises a urethane (meth)acrylate having two or more urethane bonds per molecule on average.

4. The elastic material according to any one of claims 1 to 3, wherein component a) comprises a urethane (meth)acrylate having at least one acrylate functional group.

5. The elastic material according to any one of claims 1 to 4, wherein component a) comprises a urethane (meth)acrylate having an average of two or fewer (meth)acrylate functional groups per molecule.

6. The elastic material according to any one of claims 1 to 5, wherein component a) comprises a urethane (meth)acrylate having a number average molecular weight of 4,700 to 50,000 g / mol, 5,000 to 30,000 g / mol, 5,500 to 25,000 g / mol, 6,000 to 20,000 g / mol, 6,500 to 18,000 g / mol, or 7,000 to 15,000 g / mol.

7. The elastic material according to any one of claims 1 to 6, wherein component a) comprises a urethane (meth)acrylate having a number average molecular weight of 5,500 to 20,000 g / mol, 5,500 to 18,000 g / mol, or 5,500 to 15,000 g / mol.

8. Component a) is given by the following equation (I): 【Chemistry 1】 (In the formula, Each A is independently a diol residue, and at least one A contains an oxybutylene unit; Each R is independently a diisocyanate residue; Each B is independently a residue of a hydroxylated mono(meth)acrylate; Each X is independently either H or methyl; n is 1 to 9, preferably 1 to 4, more preferably 1 to 2, and even more preferably n is 1. An elastic material according to any one of claims 1 to 7, comprising a urethane (meth)acrylate having the following properties.

9. The elastic material according to any one of claims 1 to 8, wherein component a) comprises a urethane (meth)acrylate which is a reaction product of one or more diols, one or more diisocyanates, and one or more hydroxylated mono(meth)acrylates, and at least one of the diols comprises an oxybutylene repeating unit.

10. The elastic material according to claim 8 or 9, wherein the diol is polytetramethylene ether glycol.

11. The elastic material according to any one of claims 8 to 10, wherein the diol has a number-average molecular weight of at least 1,100 g / mol, particularly 1,200 to 5,000 g / mol, or 1,400 to 4,000 g / mol.

12. The elastic material according to any one of claims 8 to 11, wherein the diisocyanate is an aliphatic or alicyclic diisocyanate, particularly an alicyclic diisocyanate, and more particularly an isophorone diisocyanate.

13. Component b) has a glass transition temperature T above 20°C ｇ An elastic material according to any one of claims 1 to 12, comprising a mono(meth)acrylate monomer having, more particularly, tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, trimethylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tricyclodecane methanol monoacrylate, and mixtures thereof, and more particularly, isobornyl acrylate.

14. The elastic material according to any one of claims 1 to 13, wherein component b) comprises a sterically hindered mono(meth)acrylate monomer, particularly a sterically hindered mono(meth)acrylate monomer containing a cyclic moiety and / or a tert-butyl group.

15. 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, tricyclodecane methanol mono (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate ((5-ethyl-1,3-di (Also called oxan-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; in particular, tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, (5-ethyl-1,3 (Dioxan-5-yl) methyl acrylate (or CTFA), (2,2-dimethyl-1,3-dioxolan-4-yl) methyl acrylate (or IPGA), (2,2-dimethyl-1,3-dioxolan-4-yl) methyl methacrylate (or IPGMA), (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl acrylate, glycerol formal methacrylate (or Glyfoma), 3,5,5-trimethylcyclohexyl acrylate, 3,5,5-trimethylcyclohexyl methacrylate, tri- An elastic material according to any one of claims 1 to 14, comprising clodecanemethanol monoacrylate, tricyclodecanemethanol monomethacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate, more particularly isobornyl acrylate, tert-butylcyclohexyl acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate (or CTFA), tetrahydrofurfuryl acrylate, and a sterically hindered mono(meth)acrylate monomer selected from mixtures thereof.

16. The elastic material according to any one of claims 1 to 15, wherein component b) contains at least 80% by mass, at least 85% by mass, at least 90% by mass, at least 95% by mass, at least 98% by mass, at least 99% by mass, or at least 99.5% by mass, or 100% by mass, of the total mass of component b), a mono(meth)acrylate monomer.

17. Component b) has a glass transition temperature T higher than 20°C, with a ratio of 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 100% by mass, based on the total mass of component b). ｇ An elastic material according to any one of claims 1 to 16, comprising a mono(meth)acrylate monomer having the following properties.

18. The elastic material according to any one of claims 1 to 17, wherein component b) contains 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 100% by mass of sterically hindered mono(meth)acrylate monomer, based on the total mass of component b).

19. The elastic material according to any one of claims 1 to 18, wherein components a) and b) together constitute at least 90% by mass, at least 95% by mass, at least 99% by mass, or 100% by mass of the total amount of curable components present in the curable composition.

20. The elastic material according to any one of claims 1 to 19, wherein the curable composition further comprises an initiator system, in particular an initiator system comprising a photopolymerization initiator.

21. The elastic material according to any one of claims 1 to 20, wherein the curable composition further comprises an additive.

22. The elastic material according to any one of claims 1 to 21, wherein the curable composition is liquid at 25°C.

23. The elastic material according to any one of claims 1 to 22, wherein the viscosity of the curable composition at 60°C is measured by a Brookfield rotational viscometer and is 20,000 mPa·s or less, 10,000 mPa·s or less, 8,000 mPa·s or less, or 5,000 mPa·s or less.

24. The elastic material according to any one of claims 1 to 23, wherein the elastic material has an elongation of greater than 300%, greater than 350%, greater than 400%, or greater than 450% as measured in accordance with JIS K 7127:1999.

25. The elastic material according to any one of claims 1 to 24, wherein the elastic material has a rebound elasticity greater than 22%, greater than 25%, greater than 30%, or greater than 35% as measured in accordance with JIS K 6255:1996.

26. The elastic material according to any one of claims 1 to 25, wherein the elastic material has a Shore A hardness of at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45 as measured in accordance with JIS K 6253-3:2012.

27. A method for producing an elastic material according to any one of claims 1 to 26, comprising the step of curing a curable composition according to any one of claims 1 to 23.

28. The method according to claim 27, wherein the method is for preparing a 3D printed article, and the method comprises the step of printing a 3D article, particularly layer by layer or continuously, using a curable composition according to any one of claims 1 to 23.

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