Thiol masterbatch compositions and methods of making ultraviolet curable compositions

Abstract

A thiol masterbatch composition for preparing a UV curable composition is provided, the thiol masterbatch composition comprising at least 70% by weight of a thiol compound, and at least one stabilizer. A kit for providing an ultraviolet curable composition includes: a first portion including a thiol masterbatch composition therein; and a second portion separate from the first portion and including a (meth) acrylate composition therein. A method of making a UV curable composition includes combining a thiol masterbatch composition and a (meth) acrylate composition.

Description

Technical Field

[0001] The present disclosure relates to a mercaptan masterbatch composition. The mercaptan masterbatch composition comprises a mercaptan compound and at least one stabilizer. The present disclosure also relates to a kit for providing an ultraviolet (UV) curable composition and a method for preparing an ultraviolet (UV) curable composition. Background Art

[0002] Ultraviolet (UV) curable compositions, such as mercaptan-(meth)acrylate formulations, can be used in a variety of applications such as UV curable nail gels, printing, coatings, and 3D printing and manufacturing. However, mercaptan-(meth)acrylate formulations have certain limitations during storage, such as premature polymerization. For example, mercaptan-(meth)acrylate formulations without a suitable stabilizer may gel when exposed to elevated temperatures (e.g., during transit or storage). Due to performance requirements, this difficulty limits their applications.

[0003] Stabilizers can be added to mercaptan-(meth)acrylate formulations to improve stability. However, developing a stabilizer package that improves stability in a variety of mercaptan-(meth)acrylate formulations while maintaining desirable performance properties can be challenging. Accordingly, there is a need for mercaptan masterbatch compositions that can be added to (meth)acrylate compositions, and methods for preparing ultraviolet (UV) curable compositions that promote desirable performance properties and long-term stability even at elevated temperatures.

[0004] Embodiments of the mercaptan masterbatch compositions, kits for providing ultraviolet (UV) curable compositions, and methods for preparing ultraviolet (UV) curable compositions disclosed herein overcome the disadvantages associated with reduced stability of ultraviolet (UV) curable compositions. Summary of the Invention

[0005] A first aspect disclosed herein is a mercaptan masterbatch composition for preparing an ultraviolet (UV) curable composition, the mercaptan masterbatch composition comprising at least 70 weight percent of a mercaptan compound, based on the total weight of the mercaptan masterbatch composition, and at least one stabilizer. The mercaptan compound can be selected from primary mercaptans, secondary mercaptans, or combinations thereof. When at least 50 weight percent of the mercaptan compound is a primary mercaptan, based on the total weight of the mercaptan compound, the mercaptan masterbatch composition can comprise at least 22,000 parts per million (ppm) of the stabilizer, based on the total weight of the mercaptan masterbatch composition. When less than 50 weight percent of the mercaptan compound is a primary mercaptan, based on the total weight of the mercaptan compound, the mercaptan masterbatch composition can comprise at least 10,000 parts per million (ppm) of the stabilizer, based on the total weight of the mercaptan masterbatch composition.

[0006] Another aspect disclosed herein is a kit for providing an ultraviolet curable composition. The kit includes a first part that includes a thiol masterbatch composition, wherein the thiol masterbatch composition includes at least 70 wt% thiol compound, based on the total weight of the thiol masterbatch composition, and at least one stabilizer. The kit further includes a second part that is separate from the first part and that includes a (meth)acrylate composition, the (meth)acrylate composition including a (meth)acrylate monomer, a (meth)acrylate oligomer, and a photoinitiator.

[0007] Another aspect disclosed herein is a method for preparing an ultraviolet curable composition. The method can include combining a thiol masterbatch composition with a (meth)acrylate composition to obtain an ultraviolet curable composition. The thiol masterbatch composition includes at least 70 wt% thiol compound, based on the total weight of the thiol masterbatch composition, and at least one stabilizer. The (meth)acrylate composition includes a (meth)acrylate monomer, a (meth)acrylate oligomer, and a photoinitiator.

[0008] This summary is intended to introduce a series of concepts that are further described in the specific embodiments. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

[0009] Additional features and advantages of the described embodiments will be set forth in the detailed description that follows. The additional features and advantages of the described embodiments will be readily apparent to those skilled in the art from the detailed description, or can be recognized by practicing the described embodiments (including the detailed description and the claims). Detailed Embodiments

[0010] Definitions

[0011] As used herein, the term "comprising" can mean "comprising one or more".

[0012] Unless otherwise indicated, weight percentages in compounds or compositions are expressed relative to the weight of the compound or composition, respectively.

[0013] The term "thiol masterbatch composition" refers to a mixture including thiols.

[0014] The term "ultraviolet curable composition" refers to a composition that can be cured upon exposure to ultraviolet radiation to form a cured product.

[0015] The term "thiol compound" refers to an organic sulfur compound having the form R-SH, where R represents an organic substituent.

[0016] The term "primary mercaptan" refers to a compound in which -SH is attached to a carbon atom, and the carbon atom to which -SH is attached is attached to another carbon atom.

[0017] The term "secondary mercaptan" refers to a compound in which -SH is attached to a carbon atom, and the carbon atom to which -SH is attached is attached to two other carbon atoms.

[0018] The term "(meth)acrylate" refers to acrylate or methacrylate. The term "acrylate" refers to acryloyloxy (-O-C(=O)-CH=CH2). The term "methacrylate" refers to methacryloyloxy (-O-C(=O)-C(CH3)=CH2).

[0019] As used herein, the term "monomer" refers to a molecule having one or more polymerizable functional groups. A monomer has a single molecular weight, typically less than 1000 g / mol, preferably 100 to 950 g / mol. As recognized, commercial products of a particular monomer may contain impurities or other chemical substances.

[0020] As used herein, the term "oligomer" refers to a molecule having a molecular weight distribution and typically having one or more polymerizable functional groups. An oligomer can be the reaction product of two or more monomers, and generally has a number average molecular weight greater than or equal to 500 g / mol, preferably 500 g / mol to 30,000 g / mol, more preferably 1,000 g / mol to 8,000 g / mol.

[0021] The term "reactive diluent" refers to a chemical compound that can reduce the viscosity of the material to which it is added and participate in crosslinking upon curing.

[0022] The term "non-reactive diluent" refers to a chemical compound that can reduce the viscosity of the material to which it is added and does not participate in crosslinking upon curing.

[0023] As used herein, the term "stabilizer" refers to a compound or material that can increase the stability of the mercaptan masterbatch composition or the ultraviolet curable composition described herein.

[0024] The term "radical scavenger compound" refers to a chemical compound or material that removes or inactivates radical products.

[0025] The term "hydroperoxide decomposing agent compound" refers to a chemical compound or material that decomposes hydroperoxide compounds.

[0026] The term "hydrogen donor compound" refers to a chemical compound or material that includes extractable hydrogen.

[0027] The terms "mass fraction" and "weight fraction" are used interchangeably herein and, for the embodiments or examples of this document, shall be considered equivalent to each other.

[0028] The term "photoinitiator" can be considered any type of substance that, upon exposure to radiation (such as actinic radiation), forms substances that initiate the reactions and curing of the polymerizable organic substances present in a curable composition.

[0029] Method for preparing an ultraviolet curable composition

[0030] In some embodiments, an ultraviolet curable composition is prepared. The method for preparing the ultraviolet curable composition may include combining a thiol masterbatch composition with a (meth)acrylate composition to form an ultraviolet curable composition.

[0031] The thiol masterbatch composition in the method may include any embodiment of the thiol masterbatch composition described in the present disclosure and can be used alone or in any combination.

[0032] The (meth)acrylate composition in the method may include any embodiment of the (meth)acrylate composition described in the present disclosure and can be used alone or in any combination.

[0033] The weight ratio of the thiol masterbatch composition to the (meth)acrylate composition can be adjusted according to the desired properties of the ultraviolet curable composition (such as curing time, stability, and storage conditions), or according to the desired properties of the cured product formed by curing the ultraviolet curable composition (such as gel strength, oxygen inhibition on the surface, and shrinkage rate).

[0034] In some embodiments, the weight ratio of the thiol masterbatch composition to the (meth)acrylate composition in the ultraviolet curable composition can be 1:1 to 1:20, 1:1 to 1:15, 1:1 to 1:10, 1:1 to 1:9, 1:1 to 1:8, 1:1 to 1:7, 1:1 to 1:5, 1:1 to 1:4, 1:1 to 1:3, 1:1 to 1:2, 1:2 to 1:20, 1:2 to 1:15, 1:2 to 1:10, 1:2 to 1:9, 1:2 to 1:8, 1:2 to 1:7, 1:2 to 1:5, 1:2 to 1:4, 1:2 to 1:3, 1:3 to 1:20, 1:3 to 1:15, 1:3 to 1:10, 1:3 to 1:9, 1:3 to 1:8, 1:3 to 1:7, 1:3 to 1:5, 1:3 to 1:4, 1:4 to 1:20, 1:4 to 1:15, 1:4 to 1:10, 1:4 to 1:9, 1:4 to 1:8, 1:4 to 1:7, 1:4 to 1:5, or any and all subranges formed by any of these endpoints.

[0035] Thiol masterbatch composition

[0036] In some embodiments, the thiol masterbatch composition comprises a thiol compound and at least one stabilizer. In some embodiments, the thiol masterbatch composition consists of, or consists essentially of, a thiol compound and a stabilizer.

[0037] Thiol compounds of the thiol masterbatch composition

[0038] In some embodiments, the thiol compound is selected from primary thiols, secondary thiols, or combinations thereof. In some embodiments, the thiol compound is a primary thiol. In other embodiments, the thiol compound is a secondary thiol.

[0039] In some embodiments, based on the total weight of the thiol compound, the thiol compound comprises at least 5 weight percent (wt%) of primary thiol, such as at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt%, or at least 95 wt% of primary thiol.

[0040] Examples of suitable primary thiols include, but are not limited to, any polythiol-functional molecule, oligomer, or polymer. Some polythiols have the formula R-(SH) n , where n is at least 2, and preferably from 2 to 4, and R is an aliphatic or aromatic organic group with a valence of n. Some examples include: ethylene glycol bis(mercaptoacetate), 2,2′-(ethylenedioxy)diethanethiol, 1,6-hexanedithiol, tetraethylene glycol dithiol, hexa(ethylene glycol) dithiol, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis-mercaptoacetate, 1,2-propanediol (3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, ethylene glycol dimercaptoacetate, ethoxylated trimethylolpropane tris(3-mercaptopropionate) 700 (ETTMP700), ethoxylated trimethylolpropane tris(3-mercaptopropionate) 1300 (ETTMP1300), propylene glycol 3-mercaptopropionate 800 (PPGMP800), propylene glycol 3-mercaptopropionate 2200 (PPGMP2200), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(mercaptoacetate), pentaerythritol tetra(mercaptoacetate).

[0041] In some embodiments, based on the total weight of the thiol compound, the thiol compound comprises at least 5 wt% secondary thiol, such as at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 50 wt%, at least 70 wt% or at least 95 wt% secondary thiol.

[0042] Examples of suitable secondary thiols include, but are not limited to, the secondary thiol versions of any of the primary thiol examples above. The secondary thiol can be any polythiol functional molecule, oligomer or polymer. The available polythiols have the formula R-(SH) n n, where n is at least 2, and preferably 2 to 4, and R is an aliphatic or aromatic organic group with a valence of n. Some examples include: ethylene glycol bis(3-mercaptobutyrate), 1,2-propanediol (3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate) and / or trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptomethylbutyrate), 1,3,5-tris[2-(3-mercaptobutyryloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,4-bis(1-mercaptoethyl)benzene, bisphenol A bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane or combinations thereof.

[0043] In some embodiments, the thiol compound can include any of the thiol compounds disclosed herein. In some embodiments, the thiol compound is selected from pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate) or combinations thereof. In some embodiments, the thiol compound is selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate) and combinations thereof. In some embodiments, the thiol compound comprises pentaerythritol tetra(3-mercaptopropionate). In some embodiments, the thiol compound is pentaerythritol tetra(3-mercaptopropionate). In some embodiments, the thiol compound comprises pentaerythritol tetra(3-mercaptobutyrate). In some embodiments, the thiol compound is pentaerythritol tetra(3-mercaptobutyrate).

[0044] The amount of the thiol compound in the thiol masterbatch composition can vary depending on the desired properties of the ultraviolet curable composition comprising the thiol masterbatch composition, such as polymerization rate, mechanical properties, tack-free and shrinkage rate.

[0045] In some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may comprise at least 70 wt% of a thiol compound. For example, in some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may comprise at least 72 wt%, at least 75 wt% or at least 80 wt% of a thiol compound. In some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may contain from 70 wt% to 99 wt% of a thiol compound. Without wishing to be bound by any particular theory, it is believed that a thiol masterbatch composition comprising a large amount of a thiol compound (e.g., at least 70 wt% of a thiol compound) can be added to a (meth)acrylate composition in order to provide a sufficient concentration of the thiol compound in the ultraviolet curable composition formed by the combination of the thiol masterbatch composition and the (meth)acrylate composition.

[0046] It should be understood that when the thiol masterbatch composition comprises more than one discrete type of thiol compound, the weight fraction of the thiol compound in the thiol masterbatch composition is equal to the sum of the individual weight fractions of each discrete type of thiol compound in the thiol masterbatch composition.

[0047] Stabilizers of the thiol masterbatch composition

[0048] In some embodiments, the thiol masterbatch composition comprises at least one stabilizer, at least two stabilizers or at least three stabilizers. In some embodiments, the stabilizer may comprise a radical scavenging compound, a hydroperoxide decomposing compound, a hydrogen donor compound or a combination thereof.

[0049] Examples of suitable radical scavenging compounds may include phenolic antioxidants such as butylated hydroxytoluene, methoxyphenol, hydroquinone, 4-tert-butylcatechol, α-tocopherol, pyrogallol, N-nitroso-N-phenylhydroxylamine aluminum salt, ethyl gallate, propyl gallate, octyl gallate, dodecyl gallate, 2,4,5-trihydroxybutyrophenone, catechol and combinations thereof.

[0050] Examples of suitable hydroperoxide decomposing compounds may include compounds based on organophosphorus, organoantimony, organotin or organobismuth. The hydroperoxide decomposing compound may be selected from any typical phosphite, phosphate, phosphonate or antimonate, such as phosphorous acid, triphenyl phosphite, triphenylphosphine, triphenylantimony, tris(2,4-di(tert)butylphenyl) phosphite, tri-p-tolylphosphine, m-tritolylphosphine, phenylphosphonic acid and diphenyl(p-tolyl)phosphine, diphenylisodecyl phosphite, poly(dipropylene glycol) phenyl phosphite, spirophosphite, distearyl pentaerythritol diphosphite, compounds such as Irgaphos® chemicals from Ciba / BASF and combinations thereof.

[0051] Examples of suitable hydrogen donor compounds can include acidic compounds having a pKa between 1 and 5, such as phosphoric acid, phosphorous acid, oxalic acid, p-toluenesulfonic acid, ascorbic acid, barbituric acid, diphenylphosphinic acid, and combinations thereof.

[0052] In some embodiments, the thiol masterbatch composition can comprise at least one stabilizer selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, or phosphite esters. In some embodiments, the thiol masterbatch composition can comprise at least one stabilizer selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, or combinations thereof. In some embodiments, at least one stabilizer can be selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, phosphite esters, and combinations thereof. In some embodiments, at least one stabilizer can be selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, and combinations thereof. In some embodiments, the stabilizer can be selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, phosphite esters, and combinations thereof. In some embodiments, the stabilizer can be selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, and combinations thereof.

[0053] In some embodiments, based on the total weight of the stabilizer, at least 50 wt% of the stabilizer can be dissolved in the thiol masterbatch composition. For example, in some embodiments, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or even 100 wt% of the stabilizer is dissolved in the thiol masterbatch composition. Without wishing to be bound by any particular theory, it is believed that a higher solubility of the stabilizer in the thiol masterbatch composition can increase the solubility of the stabilizer in the ultraviolet curable composition formed by combining the thiol masterbatch composition with a (meth)acrylate composition.

[0054] The amount of stabilizer in the thiol masterbatch composition can vary depending on the desired properties of the thiol masterbatch composition, such as the solubility of the stabilizer and the reactivity of the thiol compound, or the desired properties of the ultraviolet curable composition comprising the thiol masterbatch composition, such as stabilizer concentration, stability, and storage conditions.

[0055] In some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may include any one of one or more stabilizers in an amount of 10 parts per million (ppm) to 100,000 ppm by weight. For example, in some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may include 10 ppm to 75,000 ppm, 10 ppm to 50,000 ppm, 10 ppm to 25,000 ppm, 1,000 ppm to 100,000 ppm, 1,000 ppm to 75,000 ppm, 1,000 ppm to 50,000 ppm, 1,000 ppm to 25,000 ppm, 5,000 ppm to 100,000 ppm, 5,000 ppm to 75,000 ppm, 5,000 ppm to 50,000 ppm, 5,000 ppm to 25,000 ppm, 10,000 ppm to 100,000 ppm, 10,000 ppm to 75,000 ppm, 10,000 ppm to 50,000 ppm, 10,000 ppm to 25,000 ppm, 15,000 ppm to 25,000 ppm, or 20,000 to 25,000 ppm of any one of one or more stabilizers.

[0056] In some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may include a total amount of stabilizers in an amount of 10 ppm to 200,000 ppm. For example, in some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may include 1,000 ppm to 150,000 ppm, 1,000 to 100,000 ppm, 1,000 to 75,000 ppm, 10,000 ppm to 150,000 ppm, 10,000 to 100,000 ppm, 10,000 to 75,000 ppm, 22,000 ppm to 150,000 ppm, 22,000 to 100,000 ppm, 22,000 to 75,000 ppm, 30,000 to 150,000 ppm, 30,000 to 100,000 ppm, 30,000 to 75,000 ppm, 50,000 to 150,000 ppm, 50,000 to 100,000 ppm, or 50,000 to 75,000 ppm of the total amount of stabilizers.

[0057] It should be understood that when the thiol masterbatch composition includes more than one discrete type of stabilizer, the weight fraction of the stabilizer in the thiol masterbatch composition is equal to the sum of the individual weight fractions of each discrete type of stabilizer in the thiol masterbatch composition.

[0058] In embodiments where at least 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 22,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, in embodiments where at least 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. In embodiments where at least 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise from 22,000 ppm to 200,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0059] In embodiments where at least 70% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 22,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, in embodiments where at least 70% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. In embodiments where at least 70% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise from 22,000 ppm to 200,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0060] In embodiments where at least 90% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 22,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, in embodiments where at least 90% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. In embodiments where at least 90% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise from 22,000 ppm to 200,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0061] In embodiments where less than 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain at least 10,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, when less than 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain at least 12,000 ppm, at least 15,000 ppm, at least 20,000 ppm, at least 22,000 ppm, at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. In embodiments where less than 50% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain from 10,000 ppm to 100,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0062] In embodiments where less than 30% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain at least 10,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, when less than 30% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain at least 12,000 ppm, at least 15,000 ppm, at least 20,000 ppm, at least 22,000 ppm, at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. In embodiments where less than 30% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may contain from 10,000 ppm to 100,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0063] In embodiments where less than 10% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 10,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition. For example, when less than 10% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise at least 12,000 ppm, at least 15,000 ppm, at least 20,000 ppm, at least 22,000 ppm, at least 25,000 ppm, at least 30,000 ppm, at least 35,000 ppm, at least 40,000 ppm, at least 45,000 ppm, or even at least 50,000 ppm of a stabilizer. In embodiments where less than 10% of the thiol compounds in the thiol masterbatch composition are primary thiols, the thiol masterbatch composition may comprise from 10,000 ppm to 100,000 ppm of a stabilizer, based on the total weight of the thiol masterbatch composition.

[0064] Additional components of the thiol masterbatch composition

[0065] In some embodiments, the thiol masterbatch composition may include a diluent. In some embodiments, the diluent may be a non-reactive diluent, a reactive diluent, or a combination thereof. In other embodiments, the thiol masterbatch composition does not include a diluent. Without wishing to be bound by any particular theory, it is believed that a diluent may be included in the thiol masterbatch composition to increase the concentration of the stabilizer dissolved in the thiol masterbatch composition.

[0066] Examples of suitable non-reactive diluents may include, but are not limited to, solvents and plasticizers such as toluene, methyl acetate, butyl acetate, ethyl acetate, methyl ethyl ketone, dimethyl carbonate, mineral oil, phthalates, and combinations thereof.

[0067] Examples of suitable reactive diluents can include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, diethylene glycol methyl ether (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, ethoxylated phenyl (meth)acrylate, propoxylated phenyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, ethoxylated nonylphenyl (meth)acrylate, propoxylated nonylphenyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, methoxypolyethylene glycol (350) mono(meth)acrylate, methoxypolyethylene glycol (550) mono(meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, ethoxylated triglycol (meth)acrylate, bisphenol A diallyl ether, ethylene glycol diallyl ether, ethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, and combinations thereof. In some embodiments, the diluent is a polar monofunctional (meth)acrylate monomer that can be used to dissolve the stabilizer.

[0068] In some embodiments, the diluent can comprise (meth)acrylate monomers, including acrylate monomers and methacrylate monomers. In some embodiments, based on the total weight of the diluent, the diluent can comprise at least 50 wt% of (meth)acrylate monomers. For example, in some embodiments, based on the total weight of the diluent, the diluent can comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of (meth)acrylate monomers.

[0069] In some embodiments, the diluent comprises methacrylate monomers. In some embodiments, the diluent is a methacrylate monomer. In some embodiments, based on the total weight of the diluent, the diluent can comprise at least 50 wt% of methacrylate monomers. For example, in some embodiments, based on the total weight of the diluent, the diluent can comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of methacrylate monomers.

[0070] In some embodiments, the diluent comprises acrylate monomers. In some embodiments, the diluent is an acrylate monomer. In some embodiments, based on the total weight of the diluent, the diluent may comprise at least 50 wt% acrylate monomers. For example, in some embodiments, based on the total weight of the diluent, the diluent may comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or at least 99 wt% acrylate monomers.

[0071] In some embodiments, the diluent is monofunctional. In other embodiments, the diluent may be polyfunctional, where individual monomer units contain two or more reactive sites that participate in crosslinking upon curing. Examples of monofunctional monomer units may include 2-hydroxyethyl methacrylate. Examples of polyfunctional monomer units may include divalent monomer units such as polyethylene glycol (200) di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, and combinations thereof.

[0072] The weight fraction of the diluent in the thiol masterbatch composition will vary depending on the amount of stabilizer and the solubility of the stabilizer in the thiol masterbatch composition. The weight fraction of the diluent in the thiol masterbatch composition may vary depending on the desired properties of the thiol masterbatch composition (such as viscosity or stabilizer concentration).

[0073] In some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may comprise from 0 wt% to 25 wt% diluent. For example, in some embodiments, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition may comprise from 0 wt% to 20 wt%, from 0 wt% to 15 wt%, from 0 wt% to 10 wt%, from 0 wt% to 5 wt%, including from 5 wt% to 20 wt%, from 5 wt% to 15 wt% or from 5 wt% to 10 wt% diluent.

[0074] It should be understood that when the thiol masterbatch composition comprises more than one discrete type of diluent, the weight fraction of the diluent in the thiol masterbatch composition is equal to the sum of the individual weight fractions of each discrete type of diluent in the thiol masterbatch composition.

[0075] Properties of the thiol masterbatch composition

[0076] In some embodiments, the thiol masterbatch composition may have improved properties, such as a high concentration of stabilizer, increased stability, and resistance to premature polymerization.

[0077] The viscosity of the thiol masterbatch composition can be monitored to demonstrate the stability and resistance to premature polymerization of the thiol masterbatch composition.

[0078] In some embodiments, the initial viscosity of the thiol masterbatch composition can be from 10 centipoise (cps) to 4,000 cps, such as from 20 cps to 200 cps.

[0079] The thiol masterbatch composition can be aged, heated, or both aged and heated to demonstrate the stability of the thiol masterbatch composition.

[0080] In some embodiments, when the thiol masterbatch composition is aged for at least 28 days, the difference between the final viscosity and the initial viscosity of the thiol masterbatch composition can be 10,000 cps or lower. For example, in some embodiments, the difference between the final viscosity and the initial viscosity of the thiol masterbatch composition can be 8,000 cps or lower, 5,000 cps or lower, 4,000 cps or lower, 3,000 cps or lower, 2,000 cps or lower, 1,000 cps or lower, 500 cps or lower, or even 100 cps or lower.

[0081] In some embodiments, when the thiol masterbatch composition is heated at a temperature of at least 60 degrees Celsius (°C) or higher for at least 28 days, the difference between the final viscosity and the initial viscosity of the thiol masterbatch composition can be 10,000 cps or lower. For example, in some embodiments, the final viscosity of the thiol masterbatch composition can be 8,000 cps or lower, 5,000 cps or lower, 4,000 cps or lower, 3,000 cps or lower, 2,000 cps or lower, 1,000 cps or lower, 500 cps or lower, or even 100 cps or lower lower than the initial viscosity of the thiol masterbatch composition before heating.

[0082] Without wishing to be bound by any particular theory, it is believed that a thiol masterbatch composition can be prepared such that when it is added to a (meth)acrylate composition, the combination exhibits improved stability and resistance to premature polymerization.

[0083] (Meth)acrylate composition

[0084] In some embodiments, the (meth)acrylate composition can comprise a (meth)acrylate monomer, a (meth)acrylate oligomer, and a photoinitiator.

[0085] (Meth)acrylate monomers of the (meth)acrylate composition

[0086] In some embodiments, the (meth)acrylate monomers of the (meth)acrylate composition may include methacrylate monomers and acrylate monomers, such as trimethacrylate and diacrylate.

[0087] In some embodiments, the (meth)acrylate monomers of the (meth)acrylate composition are monofunctional. In other embodiments, the (meth)acrylate monomers of the (meth)acrylate composition may be polyfunctional, wherein the individual monomer units contain two or more active sites that participate in crosslinking upon curing.

[0088] In some embodiments, the (meth)acrylate monomers may comprise a mixture of (meth)acrylate monomers.

[0089] The molecular weight of the (meth)acrylate monomers may be less than 1,000 g / mol, particularly 100 to 550 g / mol, more particularly 200 to 500 g / mol.

[0090] Suitable (meth)acrylate monomers may include, but are not limited to: mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be straight-chain, branched-chain or cycloaliphatic, and may be a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric diols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol); mono(meth)acrylates of monoalkyl ethers of diols and oligomeric diols; mono(meth)acrylates of alkoxylated (such as ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be straight-chain, branched-chain or cycloaliphatic, and may be a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono(meth)acrylates of alkoxylated (such as ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylate, etc.The following compounds are specific examples of mono(meth)acrylate monomers applicable to the curable compositions of the present invention: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated nonylphenol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, tert-butylcyclohexanol (meth)acrylate, trimethylcyclohexanol (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, ethoxylated lauryl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, hydroxyethyl-butylcarbamate (meth)acrylate, 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate, and combinations thereof.

[0091] (Meth)acrylate monomers may include (meth)acrylate monomers having two or more (meth)acrylate groups per molecule. Examples of suitable (meth)acrylate monomers having two or more (meth)acrylate groups per molecule include acrylates and methacrylates of polyols (organic compounds having two or more, for example 2 to 6 hydroxyl groups per molecule). Specific examples of suitable polyols include C2-20 alkylene glycols (diols having C2-10 alkylene groups may be preferred, where the carbon chain may be branched; for example, ethylene glycol, trimethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenol and hydrogenated bisphenol, and their alkoxylated (for example, ethoxylated and / or propoxylated) derivatives), diethylene glycol, glycerol, alkoxylated glycerol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, bis-trimethylolpropane, alkoxylated bis-trimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornenedimethanol, alkoxylated norbornenedimethanol, norbornanedimethanol, alkoxylated norbornanedimethanol, polyols containing an aromatic ring, cyclohexane-1,4-dimethanol ethylene oxide adduct, bisphenol ethylene oxide adduct, hydrogenated bisphenol ethylene oxide adduct, bisphenol propylene oxide adduct, hydrogenated bisphenol propylene oxide adduct, cyclohexane-1,4-dimethanol propylene oxide adduct, sugar alcohols and alkoxylated sugar alcohols. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) provided that they have at least two (meth)acrylate functional groups per molecule. As used herein, the term "alkoxylated" refers to a compound containing one or more alkylene oxide moieties (for example, ethylene oxide and / or propylene oxide moieties). The alkylene oxide moiety corresponds to the general formula -R-O-, where R is a divalent aliphatic moiety, such as -CH2CH2- or -CH2CH(CH3)-. For example, an alkoxylated compound may contain 1 to 30 alkylene oxide moieties per molecule.

[0092] Exemplary (meth)acrylate monomers containing two or more (meth)acrylate groups per molecule may include ethoxylated bisphenol A di(meth)acrylate; triethylene glycol di(meth)acrylate; ethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; 1,4-butanediol diacrylate; 1,4-butanediol dimethacrylate; diethylene glycol diacrylate; diethylene glycol dimethacrylate; 1,6-hexanediol diacrylate; 1,6-hexanediol dimethacrylate; neopentyl glycol diacrylate; neopentyl glycol di(meth)acrylate; polyethylene glycol (600) dimethacrylate (where the number in parentheses after "polyethylene glycol" is the approximate average molecular weight of the polyethylene glycol portion); polyethylene glycol (200) diacrylate; 1,12-dodecanediol dimethacrylate; tetraethylene glycol diacrylate; triethylene glycol diacrylate; 1,3-butanediol dimethacrylate; tripropylene glycol diacrylate; polybutadiene diacrylate; methylpentanediol diacrylate; polyethylene glycol (400) diacrylate; ethoxylated (2) bisphenol A dimethacrylate (where the number in parentheses after "ethoxylated" is the average number of alkylene oxide moieties per molecule); ethoxylated (3) bisphenol A dimethacrylate; ethoxylated (3) bisphenol A diacrylate; cyclohexanedimethanol dimethacrylate; cyclohexanedimethanol diacrylate; ethoxylated (10) bisphenol A dimethacrylate; dipropylene glycol diacrylate; ethoxylated (4) bisphenol A dimethacrylate; ethoxylated (6) bisphenol A dimethacrylate; ethoxylated (5) bisphenol A dimethacrylate; alkoxylated hexanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; dodecanediacrylate; ethoxylated (4) bisphenol A diacrylate; ethoxylated (10) bisphenol A diacrylate; polyethylene glycol (400) dimethacrylate; polypropylene glycol (400) dimethacrylate; metal diacrylate; modified metal diacrylate; metal dimethacrylate; polyethylene glycol (1000) dimethacrylate; methacrylated polybutadiene; propoxylated (2) neopentyl glycol diacrylate (where the number in parentheses after "propoxylated" is the average number of alkylene oxide moieties per molecule); ethoxylated (30) bisphenol A dimethacrylate; ethoxylated (30) bisphenol A diacrylate; alkoxylated neopentyl glycol diacrylate; polyethylene glycol dimethacrylate; 1,3-butanediol diacrylate; ethoxylated (2) bisphenol A dimethacrylate; dipropylene glycol diacrylate; ethoxylated (4) bisphenol A diacrylate; polyethylene glycol (600) diacrylate; polyethylene glycol (1000) dimethacrylate; tricyclodecanedimethanol diacrylate; propoxylated neopentyl glycol diacrylate, such as propoxylated (2) neopentyl glycol diacrylate; diacrylate of alkoxylated aliphatic alcohol; trimethylolpropane trimethacrylate;Trimethylolpropane triacrylate; Tris(2-hydroxyethyl)isocyanurate triacrylate; Ethoxylated(20) trimethylolpropane triacrylate; Pentaerythritol triacrylate; Ethoxylated trimethylolpropane triacrylate; Propoxylated(3) trimethylolpropane triacrylate; Ethoxylated(6) trimethylolpropane triacrylate; Propoxylated(6) trimethylolpropane triacrylate; Ethoxylated, trimethylolpropane triacrylate; Alkoxylated trifunctional acrylate; Trifunctional methacrylate; Trifunctional acrylate; Propoxylated(3) glycerol triacrylate; Propoxylated(5.5) glycerol triacrylate; Ethoxylated(5) trimethylolpropane triacrylate; Trifunctional phosphate ester; Trifunctional acrylate; Pentaerythritol tetraacrylate; Di-trimethylolpropane tetraacrylate; Ethoxylated(4) pentaerythritol tetraacrylate; Pentaerythritol polyoxyethylene tetraacrylate; Dipentaerythritol pentaacrylate; Pentaacrylate, and combinations thereof.

[0093] In some embodiments, the (meth)acrylate monomer is selected from methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, diethylene glycol methyl ether (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, ethoxylated phenyl (meth)acrylate, propoxylated phenyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, ethoxylated nonylphenyl (meth)acrylate, propoxylated nonylphenyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, methoxypolyethylene glycol(350) mono(meth)acrylate, methoxypolyethylene glycol(550) mono(meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, ethoxytriethylene glycol (meth)acrylate, polyethylene glycol(200) di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol(400) di(meth)acrylate, polyethylene glycol(600) di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, and combinations thereof.

[0094] In some embodiments, the (meth)acrylate monomer is ethoxylated (3) bisphenol A diacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, or a combination thereof.

[0095] The weight fraction of the (meth)acrylate monomer in the (meth)acrylate composition will vary depending on the desired properties of the (meth)acrylate composition (e.g., viscosity), or the desired properties of the ultraviolet curable composition or the cured composition formed from the (meth)acrylate composition (e.g., adhesion, hardness, cure rate, or crosslink density).

[0096] In some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition may include 10 wt% to 80 wt% of the (meth)acrylate monomer. For example, in some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition may include 10 wt% to 70 wt%, 20 wt% to 60 wt%, or 30 wt% to 50 wt% of the (meth)acrylate monomer.

[0097] It should be understood that when the (meth)acrylate composition includes more than one discrete type of (meth)acrylate monomer, the weight fraction of the (meth)acrylate monomer in the (meth)acrylate composition is equal to the sum of the individual weight fractions of each discrete type of (meth)acrylate monomer in the (meth)acrylate composition.

[0098] (Meth)acrylate oligomers of the (meth)acrylate composition

[0099] In some embodiments, the (meth)acrylate oligomer of the (meth)acrylate composition may include a methacrylate oligomer and an acrylate oligomer, such as a urethane methacrylate oligomer.

[0100] In some embodiments, the (meth)acrylate oligomer may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and more particularly 2 to 6 acrylate groups.

[0101] In some embodiments, the (meth)acrylate oligomer of the (meth)acrylate composition is monofunctional. In other embodiments, the (meth)acrylate oligomer of the (meth)acrylate composition may be multifunctional, wherein the individual monomer units of the oligomer unit contain two or more active sites that participate in crosslinking upon curing.

[0102] Suitable (meth)acrylate oligomers can include, but are not limited to, (meth)acrylate-functionalized urethane oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (sometimes also referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes also referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (sometimes also referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (sometimes also referred to as "polycarbonate (meth)acrylate oligomers") and (meth)acrylate-functionalized polyester oligomers (sometimes also referred to as "polyester (meth)acrylate oligomers") and combinations thereof.

[0103] In some embodiments, the (meth)acrylate oligomer is selected from urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, polybutadiene (meth)acrylate oligomers, epoxy (meth)acrylate oligomers or combinations thereof.

[0104] In some embodiments, the (meth)acrylate oligomer is an aliphatic urethane methacrylate oligomer.

[0105] In some embodiments, the weight average molecular weight of the (meth)acrylate oligomer can be at least 600 grams per mole (g / mol). In some embodiments, the weight average molecular weight of the oligomer can be from 600 g / mol to 600,000 g / mol.

[0106] The weight fraction of the (meth)acrylate oligomer in the (meth)acrylate composition will depend on the desired properties of the (meth)acrylate composition (e.g., viscosity), or the desired properties of the ultraviolet curable composition containing the (meth)acrylate composition or the cured composition formed by curing the ultraviolet curable composition (e.g., flexibility, strength or modulus).

[0107] In some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition can include from 10 wt% to 80 wt% of the (meth)acrylate oligomer. For example, in some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition can include from 10 wt% to 80 wt%, from 15 wt% to 75 wt% or from 20 wt% to 70 wt% of the (meth)acrylate oligomer.

[0108] It should be understood that when the (meth)acrylate composition comprises more than one discrete type of (meth)acrylate oligomer, the weight fraction of the (meth)acrylate oligomer in the (meth)acrylate composition is equal to the sum of the individual weight fractions of each discrete type of (meth)acrylate oligomer in the (meth)acrylate composition.

[0109] Photoinitiators of the (meth)acrylate composition

[0110] In some embodiments, the photoinitiator of the (meth)acrylate composition can include any photoinitiator known in the art. The photoinitiator can include radical photoinitiators. The photoinitiator can be selected such that it is readily activated by photons having wavelengths associated with actinic radiation (e.g., ultraviolet radiation, visible light) intended to cure the curable composition.

[0111] Suitable photoinitiators can include, but are not limited to, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzyl, benzyl ketals, anthraquinone, phosphine oxides, acylphosphine oxides, α-hydroxy ketones, phenylglyoxylates, α-aminoketones, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoylformates, aromatic oximes, metallocenes, acylsilicon or acylgermanium compounds, camphorquinone, polymeric derivatives thereof, and combinations thereof.

[0112] Examples of suitable photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone, benzyl, benzoin, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, acetophenone, such as 2,2-dialkoxydibenzophenone and 1-hydroxy phenyl ketone, dibenzophenone, 4,4'-bis(diethylamino)dibenzophenone, acetophenone, 2,2-diethoxyacetophenone, diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzoylacetone, α-hydroxy ketones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propanone, oligo-α-hydroxy ketones, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl ester, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, monohydrate sodium salt, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, dibenzophenone / 1-hydroxycyclohexyl phenyl ketone blend, 3,3',4,4'-dibenzophenonetetracarboxylic dianhydride, 4-benzoyl biphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (phenylbutyrophenone), 4,4'-bis(diethylamino)dibenzophenone, 4,4'-bis(dimethylamino)dibenzophenone, camphorquinone, 2-chlorothioxanthone-9-one, dibenzocycloheptenone, 4,4'-dihydroxydibenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)dibenzophenone, 4,4'-dimethylbenzil, 2,5-dimethyldibenzophenone, 3,4-dimethyldibenzophenone, 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-hydroxy dibenzophenone, 4-hydroxy dibenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methyldibenzophenone, 3-methyldibenzophenone, methyl benzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthraquinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthone-9-one and combinations thereof.

[0113] In some embodiments, the photoinitiator is selected from benzophenone, such as SpeedCure® BP (benzophenone), SpeedCure® 7005 (polymerized benzophenone), SpeedCure® 7006 (polymerized benzophenone), SpeedCure® EMK (4,4'-bis(diethylamino)benzophenone), or SpeedCure® BMS (4-benzoyl-4'-methyldiphenyl sulfide); thioxanthone, such as SpeedCure® 7010 (polymerized thioxanthone), SpeedCure® ITX (isopropylthioxanthone), SpeedCure® DETX (2,4-diethylthioxanthone), or SpeedCure® CPTX (1-chloro-4-propoxythioxanthone); α-hydroxyacetophenone; acylphosphine oxide, such as SpeedCure® BPO (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), SpeedCure® TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide), or SpeedCure® TPO-L (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate); phenylglyoxylate, such as SpeedCure® MBF (methyl benzoylformate); or combinations thereof. In some embodiments, the photoinitiator comprises ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate. In some embodiments, the photoinitiator is ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate.

[0114] The weight fraction of the photoinitiator will depend on the nature of the (meth)acrylate composition, such as storage conditions and desired stability, or the desired properties of the ultraviolet-curable composition comprising the (meth)acrylate composition, such as cure rate and cure depth.

[0115] In some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition may comprise from 0.01 wt% to 15 wt% of a photoinitiator. For example, in some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition may comprise from 0.01 wt% to 10 wt%, from 0.1 wt% to 5 wt%, or from 0.5 wt% to 4 wt% of a photoinitiator.

[0116] It should be understood that when the (meth)acrylate composition comprises more than one discrete type of photoinitiator, the weight fraction of the photoinitiator in the (meth)acrylate composition is equal to the sum of the individual weight fractions of each discrete type of photoinitiator in the (meth)acrylate composition.

[0117] Additional components of the (meth)acrylate composition

[0118] In some embodiments, additives may also be included or optionally included in the (meth)acrylate compositions described herein. For example, one or more colorants (e.g., dyes, pigments), adhesion promoters, fillers, rheology modifiers, thixotropic agents, plasticizers, ultraviolet absorbers, ultraviolet stabilizers, and / or dispersants may be included.

[0119] In some embodiments, the (meth)acrylate composition may contain a thiol compound. In other embodiments, the (meth)acrylate composition does not contain a thiol compound. In some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition contains 0 wt% to 5 wt% of a thiol compound. For example, in some embodiments, based on the total weight of the (meth)acrylate composition, the (meth)acrylate composition contains 0 wt% to 4 wt%, 0 wt% to 3 wt%, 0 wt% to 2 wt%, or 0 wt% to 1 wt% of a thiol compound.

[0120] UV-curable composition

[0121] The ultraviolet curable composition may contain a thiol masterbatch composition and a (meth)acrylate composition.

[0122] The thiol masterbatch composition of the ultraviolet curable composition may include any embodiment of the thiol masterbatch composition described in the present disclosure, including individual embodiments or any combination of embodiments.

[0123] The (meth)acrylate composition of the ultraviolet curable composition may include any embodiment of the (meth)acrylate composition described in the present disclosure, including individual embodiments or any combination of embodiments.

[0124] Properties of the UV-curable composition

[0125] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may contain 1 wt% to 40 wt% of a thiol compound, such as 1 wt% to 10 wt%, 1 wt% to 15 wt%, 1 wt% to 20 wt%, 1 wt% to 30 wt%, 5 wt% to 10 wt%, 5 wt% to 15 wt%, 5 wt% to 20 wt%, or 5 wt% to 30 wt%.

[0126] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may contain 10 ppm to 50,000 ppm of a stabilizer, such as 1,000 ppm to 30,000 ppm, 1,000 ppm to 15,000 ppm, 5,000 ppm to 30,000 ppm, or 5,000 ppm to 15,000 ppm.

[0127] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may comprise from 0 wt% to 80 wt% of a diluent, such as from 0 wt% to 60 wt%, from 0 wt% to 50 wt%, from 0 wt% to 40 wt%, from 0 wt% to 30 wt%, from 0 wt% to 20 wt%, from 0 wt% to 15 wt%, from 10 wt% to 80 wt%, from 10 wt% to 70 wt%, from 10 wt% to 60 wt%, from 10 wt% to 50 wt%, from 10 wt% to 40 wt%, from 10 wt% to 30 wt%, from 10 wt% to 20 wt%, from 20 wt% to 80 wt%, from 20 wt% to 70 wt%, from 20 wt% to 60 wt%, from 20 wt% to 50 wt%, from 20 wt% to 40 wt% or from 20 wt% to 30 wt%.

[0128] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may comprise from 10 wt% to 80 wt% of a (meth)acrylate monomer, such as from 10 wt% to 80 wt%, from 10 wt% to 70 wt%, from 10 wt% to 60 wt%, from 10 wt% to 50 wt%, from 10 wt% to 40 wt%, from 10 wt% to 30 wt%, from 10 wt% to 20 wt%, from 20 wt% to 80 wt%, from 20 wt% to 70 wt%, from 20 wt% to 60 wt%, from 20 wt% to 50 wt%, from 20 wt% to 40 wt%, from 20 wt% to 30 wt%, from 30 wt% to 80 wt%, from 30 wt% to 70 wt%, from 30 wt% to 60 wt%, from 30 wt% to 50 wt%, from 30 wt% to 40 wt%, from 40 wt% to 80 wt%, from 40 wt% to 70 wt%, from 40 wt% to 60 wt% or from 40 wt% to 50 wt%.

[0129] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may comprise from 10 wt% to 80 wt% of a (meth)acrylate oligomer, such as from 10 wt% to 80 wt%, from 10 wt% to 70 wt%, from 10 wt% to 60 wt%, from 10 wt% to 50 wt%, from 10 wt% to 40 wt%, from 10 wt% to 30 wt%, from 10 wt% to 20 wt%, from 20 wt% to 80 wt%, from 20 wt% to 70 wt%, from 20 wt% to 60 wt%, from 20 wt% to 50 wt%, from 20 wt% to 40 wt%, from 20 wt% to 30 wt%, from 30 wt% to 80 wt%, from 30 wt% to 70 wt%, from 30 wt% to 60 wt%, from 30 wt% to 50 wt%, from 30 wt% to 40 wt%, from 40 wt% to 80 wt%, from 40 wt% to 70 wt%, from 40 wt% to 60 wt% or from 40 wt% to 50 wt%.

[0130] In some embodiments, based on the total weight of the ultraviolet curable composition, the ultraviolet curable composition may comprise from 1 wt% to 10 wt% of a photoinitiator, such as from 1 wt% to 8 wt%, from 1 wt% to 6 wt%, from 1 wt% to 4 wt%, from 1 wt% to 3 wt%, from 2 wt% to 10 wt%, from 2 wt% to 8 wt%, from 2 wt% to 6 wt%, from 2 wt% to 4 wt%, from 2 wt% to 3 wt%, from 3 wt% to 10 wt%, from 3 wt% to 8 wt%, from 3 wt% to 6 wt% or from 3 wt% to 4 wt%.

[0131] In some embodiments, the ultraviolet curable composition may have improved properties, such as a high concentration of stabilizer, increased stability at higher temperatures, and a longer shelf life.

[0132] The viscosity of the ultraviolet curable composition can be monitored to demonstrate the stability and resistance to premature polymerization of the ultraviolet curable composition.

[0133] The initial viscosity of the ultraviolet curable composition can be measured after preparation. In some embodiments, the initial viscosity of the ultraviolet curable composition can be from 1000 centipoise (cps) to 20000 cps, such as from 2000 cps to 6000 cps.

[0134] The viscosity of the ultraviolet curable composition can be monitored to demonstrate the stability and resistance to premature polymerization of the ultraviolet curable composition.

[0135] The ultraviolet curable composition can be aged, heated, or both aged and heated to demonstrate the stability of the ultraviolet curable composition.

[0136] In some embodiments, when the ultraviolet curable composition is aged at room temperature for at least 28 days, the difference between the final viscosity and the initial viscosity of the ultraviolet curable composition can be 15000 cps or less. For example, in some embodiments, the difference between the final viscosity and the initial viscosity of the ultraviolet curable composition can be 12000 cps or less, 10000 cps or less, 8000 cps or less, 5000 cps or less, 4000 cps or less, 3000 cps or less, 2000 cps or less, 1000 cps or less, 500 cps or less, or even 100 cps or less.

[0137] In some embodiments, when the ultraviolet curable composition is heated at a temperature of at least 60 degrees Celsius (°C) or higher for at least 28 days, the difference between the final viscosity and the initial viscosity of the ultraviolet curable composition can be 15000 cps or less. For example, in some embodiments, the difference between the final viscosity and the initial viscosity of the ultraviolet curable composition can be 12000 cps or less, 10000 cps or less, 8000 cps or less, 5000 cps or less, 4000 cps or less, 3000 cps or less, 2000 cps or less, 1000 cps or less, 500 cps or less, or even 100 cps or less.

[0138] Curing the UV-curable composition

[0139] In some embodiments, the ultraviolet curable composition as described herein can be cured to form a cured composition. In some embodiments, the ultraviolet curable composition is exposed to ultraviolet radiation to cure the ultraviolet curable composition.

[0140] Kit for providing the UV-curable composition

[0141] In some embodiments, a kit for providing an ultraviolet curable composition comprises a first part and a second part separate from the first part.

[0142] In some embodiments, the first part comprises a thiol masterbatch composition, which can comprise any embodiment of the thiol masterbatch composition described herein, either alone or in any combination.

[0143] In some embodiments, the first part may not include a photoinitiator, an oligomer, or neither a photoinitiator nor an oligomer.

[0144] In some embodiments, the second part comprises a (meth)acrylate composition, which can comprise any embodiment of the (meth)acrylate composition described herein, either alone or in any combination.

[0145] In some embodiments, the second part may not include a thiol compound.

[0146] In some embodiments, the kit can comprise the first part and the second part packaged in two separate chambers. For example, the kit can comprise a two-component cartridge.

[0147] In some embodiments, the kit can be a ready-to-use kit, including a thiol masterbatch composition in a first compartment or barrel and a (meth)acrylate composition in a second chamber or barrel in a ratio suitable for direct mixing of the two components (e.g., mixing by a metering pump).

[0148] In some embodiments, the kit additionally includes one or more devices enabling the first and second parts to be mixed. For example, the mixing device may be selected from a metering pump or a static mixer with a diameter suitable for the amount used.

[0149] In some embodiments, the kit may additionally include a separate container for combining the first and second parts of the kit.

[0150] In some embodiments, the kit additionally includes an application device.

[0151] In some embodiments, the kit additionally includes instructions for dispensing, applying, and curing the composition to provide a cured composition. These instructions may be provided in the form of a manual and / or printed on the packaging containing the kit components.

[0152] Without wishing to be bound by any particular theory, it is believed that by separating the thiol compounds in the thiol masterbatch composition from the components of the (meth)acrylate composition, the stability of the thiol masterbatch and the (meth)acrylate composition can be improved, which can reduce premature polymerization.

[0153] Examples

[0154] The various embodiments disclosed herein will be further illustrated by the following examples. These examples are illustrative in nature and should not be construed as limiting the embodiments disclosed herein.

[0155] Materials

[0156] The following materials were used in the examples:

[0157] [Table 1]

[0158]

[0159] Methods

[0160] The following methods were used in this application:

[0161] Method A - Viscosity

[0162] The viscosity was measured at 20 °C using a Brookfield DV-III+ viscometer with an SC-27 spindle. Each sample was measured at a specific RPM required to achieve a 50% torque range. After the temperature and the sample were stabilized (10 minutes), the viscosity was measured in centipoise (cps).

[0163] Thiol masterbatch composition

[0164] Table 2 shows the components used to form the thiol masterbatch compositions of Examples E1 to E10.

[0165] The thiol masterbatch compositions were prepared by adding the components listed in Table 2 to a container and mixing for two minutes at 2000 revolutions per minute (RPM) using a Flactek® high-speed mixer until homogeneous.

[0166] [Table 2]

[0167]

[0168]

[0169] The thiol masterbatch compositions of Examples E1 to E20 include different concentrations of stabilizers, primary thiols or secondary thiols, with or without diluents. Example E2 is a thiol masterbatch composition that includes a primary thiol (PETMP), a diluent (HEMA), 12,500 ppm of one stabilizer (TPP), and 12,500 ppm of a second stabilizer (BHT). Example E11 is a thiol masterbatch composition that includes a secondary thiol (PETMB), a diluent (HEMA), 500 ppm of one stabilizer (TPP), and 500 ppm of a second stabilizer (BHT). Example E17 is a thiol masterbatch composition that includes a secondary thiol (PETMB), 12,500 ppm of one stabilizer (TPP), and 12,500 ppm of a second stabilizer (BHT). Examples E16 - E20 do not include a diluent, but at least 25,000 ppm of stabilizer is dissolved in the thiol masterbatch compositions of Examples E16 - E20.

[0170] Stability of the thiol masterbatch composition

[0171] The viscosities of the thiol masterbatch compositions of Examples E1 to E20 were measured to evaluate the stability of the thiol masterbatch compositions. Specifically, the initial viscosities of Examples E1 to E20 were measured after the preparation of E1 to E20 according to "Method A - Viscosity" described in the present disclosure. Then, Examples E1 to E20 were heated at a temperature of 60 °C for 28 days. After heating at a temperature of 60 °C for 28 days and cooling to 25 °C in the dark for at least 12 hours, the final viscosities of Examples E1 to E20 were measured according to "Method A - Viscosity" described in the present disclosure. Table 3 shows the initial viscosities and final viscosities of Examples E1 to E20.

[0172] [Table 3]

[0173]

[0174] The stability of the thiol masterbatch compositions was evaluated by comparing the initial viscosities of the thiol masterbatch compositions of Examples E1 - E20 and the final viscosities of Examples E1 - E20 after 28 days of heating. As shown in Table 3, the thiol masterbatch compositions of Examples E1 - E20 were stable even at high temperatures. Examples E1 - E10, which included primary thiols and methacrylate monomers, showed a viscosity increase of 1700 cps or less after heating. Examples E11 - E15, which included secondary thiols, methacrylate monomers, and 1500 ppm or less of stabilizer, showed a viscosity increase of less than 3400 cps after heating. Examples E16 - E20, which included secondary thiols, at least 25000 ppm of stabilizer, and no diluent, showed a viscosity increase of 600 cps or less after heating.

[0175] As shown in Tables 2 and 3, the selection of certain thiol compounds, certain stabilizers, the amount of stabilizer, and the selection of diluent in the thiol masterbatch composition can be adjusted to achieve both the desired stability of the thiol masterbatch composition (as indicated by the viscosity before and after heating) and the dissolved stabilizer concentration.

[0176] (Meth)acrylate composition

[0177] Table 4 shows the components of the (meth)acrylate composition used to form the (meth)acrylate composition of Example E21, in weight percentage (wt%) based on the total weight of the (meth)acrylate composition.

[0178] [Table 4]

[0179]

[0180] UV - curable composition

[0181] Table 5 shows the components (amounts based on the weight of the UV - curable composition, in wt%) used to form the UV - curable compositions of Examples E23 - E32.

[0182] The UV - curable compositions E23 - E32 were prepared by adding the thiol masterbatch compositions of Examples E1 to E10 and the (meth)acrylate composition of Example E21 to a container at a weight ratio of the thiol masterbatch composition to the (meth)acrylate composition of 1:4 and mixing until homogeneous at 2000 revolutions per minute (RPM) using a Flactek® high - speed mixer for two minutes.

[0183] [Table 5]

[0184]

[0185] Stability of the UV-curable composition

[0186] The viscosities of the UV-curable compositions of Examples E23 to E32 were measured to evaluate the stability of the UV-curable compositions containing the thiol masterbatch composition. Specifically, according to "Method A - Viscosity" described in the present disclosure, the initial viscosities of Examples E23 to E32 were measured after the preparation of E23 to E32. Then, a portion of Examples E23 to E32 was held at room temperature (25 °C) for 28 days. A separate portion of Examples E23 to E32 was heated at a temperature of 60 °C for 28 days. According to "Method A - Viscosity" described in the present disclosure, after 28 days at 25 °C and 60 °C, the final viscosities of Examples E23 to E32 were measured for both portions, where all viscosity measurements were carried out at 25 °C. Table 6 shows the initial viscosities of Examples E23 to E32, the final viscosities after 28 days at room temperature, and the final viscosities after 28 days at 60 °C.

[0187] [Table 6]

[0188]

[0189] The stability of the UV-curable compositions was evaluated by comparing the initial viscosities of the UV-curable compositions of Examples E23 - E32 and the final viscosities after heating for 28 days in both cases at room temperature and at a temperature of 60 °C. As shown in Table 6, the UV-curable compositions of Examples E23 - E32 were stable after 28 days at room temperature. Examples E7 and E29 - E32 were still stable even after 28 days at high temperature.

[0190] As shown in Tables 5 and 6, the selection of certain stabilizers and the amount of stabilizers in the thiol masterbatch composition can be adjusted to achieve the desired stability of the UV-curable composition containing the thiol masterbatch composition, as shown by the viscosities before and after heating and before and after aging. As described herein, a thiol masterbatch composition forming both a thiol compound and a stabilizer at a higher concentration can be added to a (meth)acrylate composition to provide a UV-curable composition having improved stability even at higher temperatures.

[0191] Clause

[0192] A further aspect of the present invention is provided by the subject matter of the following clauses:

[0193] Clause 1. A mercaptan masterbatch composition for preparing a UV-curable composition, the mercaptan masterbatch composition comprising: at least 70% by weight of a mercaptan compound, based on the total weight of the mercaptan masterbatch composition; and at least one stabilizer, wherein the mercaptan compound is selected from primary mercaptans, secondary mercaptans, or a combination thereof; and wherein: at least 50% by weight of the mercaptan compound is a primary mercaptan, based on the total weight of the mercaptan compound, and the mercaptan masterbatch composition comprises at least 22,000 parts per million (ppm) of the stabilizer, based on the total weight of the mercaptan masterbatch composition; or less than 50% by weight of the mercaptan compound is a primary mercaptan, based on the total weight of the mercaptan compound, and the mercaptan masterbatch composition comprises at least 10,000 parts per million (ppm) of the stabilizer, based on the total weight of the mercaptan masterbatch composition.

[0194] Clause 2. The mercaptan masterbatch composition of Clause 1, wherein the mercaptan compound is selected from pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), or a combination thereof.

[0195] Clause 3. The mercaptan masterbatch composition of Clause 1 or 2, wherein the at least one stabilizer is selected from radical scavenger compounds, hydroperoxide decomposer compounds, or hydrogen donor compounds.

[0196] Clause 4. The mercaptan masterbatch composition of any one of Clauses 1 to 3, wherein the at least one stabilizer is selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, phosphites, or a combination thereof.

[0197] Clause 5. The mercaptan masterbatch composition of any one of Clauses 1 to 4, wherein at least 50% by weight of the stabilizer is dissolved in the mercaptan masterbatch composition, based on the total weight of the stabilizer.

[0198] Clause 6. The mercaptan masterbatch composition of any one of Clauses 1 to 5, further comprising a diluent selected from non-reactive diluents, reactive diluents, or a combination thereof.

[0199] Clause 7. The mercaptan masterbatch composition of Clause 6, wherein the diluent comprises at least 50% by weight of (meth)acrylate monomers, based on the total weight of the diluent.

[0200] Clause 8. The mercaptan masterbatch composition of Clause 6 or 7, wherein the diluent is a (meth)acrylate monomer.

[0201] Clause 9. The mercaptan masterbatch composition of any one of Clauses 1 to 8, wherein when the mercaptan masterbatch composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the final viscosity of the mercaptan masterbatch composition after heating and the initial viscosity of the mercaptan masterbatch composition before heating is less than 10,000 centipoise (cps).

[0202] Clause 10. A mercaptan masterbatch composition according to any one of Clauses 1 to 9, wherein the mercaptan compound is a primary mercaptan.

[0203] Clause 11. A mercaptan masterbatch composition according to any one of Clauses 1 to 10, wherein the mercaptan compound is a secondary mercaptan.

[0204] Clause 12. A mercaptan masterbatch composition according to any one of Clauses 1 to 11, wherein the mercaptan masterbatch composition contains at least 50,000 ppm of a stabilizer based on the total weight of the mercaptan masterbatch composition.

[0205] Clause 13. A mercaptan masterbatch composition according to any one of Clauses 1 to 12, wherein when the mercaptan masterbatch composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the final viscosity of the mercaptan masterbatch composition after heating and the initial viscosity of the mercaptan masterbatch composition before heating is less than 5,000 centipoise (cps).

[0206] Clause 14. A mercaptan masterbatch composition according to any one of Clauses 1 to 13, wherein when the mercaptan masterbatch composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the final viscosity of the mercaptan masterbatch composition after heating and the initial viscosity of the mercaptan masterbatch composition before heating is less than 2,000 centipoise (cps).

[0207] Clause 15. A kit for providing an ultraviolet curable composition, comprising: a first part comprising a mercaptan masterbatch composition, wherein the mercaptan masterbatch composition contains at least 70 wt% of a mercaptan compound and at least one stabilizer based on the total weight of the mercaptan masterbatch composition; and a second part, separate from the first part, and comprising a (meth)acrylate composition, the (meth)acrylate composition comprising a (meth)acrylate monomer, a (meth)acrylate oligomer, and a photoinitiator.

[0208] Clause 16. The kit of Clause 15, wherein the mercaptan compound is selected from primary mercaptans, secondary mercaptans, or combinations thereof; and wherein: at least 50 wt% of the mercaptan compound is a primary mercaptan based on the total weight of the mercaptan compound, and the mercaptan masterbatch composition contains at least 22,000 parts per million by weight (ppm) of a stabilizer based on the total weight of the mercaptan masterbatch composition; or less than 50 wt% of the mercaptan compound is a primary mercaptan based on the total weight of the mercaptan compound, and the mercaptan masterbatch composition contains at least 10,000 parts per million by weight (ppm) of a stabilizer based on the total weight of the mercaptan masterbatch composition.

[0209] Clause 17. The kit of Clause 15 or 16, wherein the mercaptan compound is selected from pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), or combinations thereof.

[0210] Clause 18. A kit according to any one of Clauses 15 to 17, wherein at least one stabilizer is selected from free radical scavenger compounds, hydroperoxide decomposer compounds, or hydrogen donor compounds.

[0211] Clause 19. A kit according to any one of Clauses 15 to 18, wherein at least one stabilizer is selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, phosphites, or combinations thereof.

[0212] Clause 20. A kit according to any one of Clauses 15 to 19, wherein at least 50% by weight of the stabilizer, based on the total weight of the stabilizer, is dissolved in the thiol masterbatch composition.

[0213] Clause 21. A kit according to any one of Clauses 15 to 20, wherein the kit further comprises a separate container for combining the first part and the second part.

[0214] Clause 22. A kit according to any one of Clauses 15 to 21, wherein the kit further comprises an application device.

[0215] Clause 23. A kit according to any one of Clauses 15 to 22, wherein the second part does not contain a thiol compound.

[0216] Clause 24. A kit according to any one of Clauses 15 to 23, wherein the kit further comprises a two-component cartridge.

[0217] Clause 25. A method for preparing an ultraviolet curable composition, the method comprising: combining a thiol masterbatch composition with a (meth)acrylate composition to obtain an ultraviolet curable composition; wherein, based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition comprises at least 70% by weight of a thiol compound and at least one stabilizer; and the (meth)acrylate composition comprises a (meth)acrylate monomer, a (meth)acrylate oligomer, and a photoinitiator.

[0218] Clause 26. The method of Clause 25, wherein the weight ratio of the thiol masterbatch composition to the (meth)acrylate composition is from 1:1 to 1:20.

[0219] Clause 27. The method of Clause 25 or 26, wherein the thiol compound is selected from primary thiols, secondary thiols, or combinations thereof; and wherein: at least 50% by weight of the thiol compound, based on the total weight of the thiol compound, is a primary thiol, and the thiol masterbatch composition comprises at least 22000 parts per million (ppm) of the stabilizer, based on the total weight of the thiol masterbatch composition; or less than 50% by weight of the thiol compound, based on the total weight of the thiol compound, is a primary thiol, and the thiol masterbatch composition comprises at least 10000 parts per million (ppm) of the stabilizer, based on the total weight of the thiol masterbatch composition.

[0220] Clause 28. The method according to any one of Clauses 25 to 27, wherein the thiol compound is selected from pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), or a combination thereof.

[0221] Clause 29. The method according to any one of Clauses 25 to 28, wherein at least one stabilizer is selected from a radical scavenger compound, a hydroperoxide decomposer compound, or a hydrogen donor compound.

[0222] Clause 30. The method according to any one of Clauses 25 to 29, wherein at least one stabilizer is selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4-methoxyphenol, propyl gallate, oxalic acid, phosphite esters, or a combination thereof.

[0223] Clause 31. A UV-curable composition prepared by the method according to any one of Clauses 25 to 30.

[0224] Clause 32. The UV-curable composition according to Clause 31, wherein when the UV-curable composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the viscosity of the UV-curable composition after heating and the initial viscosity of the UV-curable composition is 15,000 centipoise (cps) or less.

[0225] Clause 33. The UV-curable composition according to Clause 31, wherein when the UV-curable composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the viscosity of the UV-curable composition after heating and the initial viscosity of the UV-curable composition is 10,000 centipoise (cps) or less.

[0226] Clause 34. The UV-curable composition according to Clause 31, wherein when the UV-curable composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the viscosity of the UV-curable composition after heating and the initial viscosity of the UV-curable composition is 5,000 centipoise (cps) or less.

[0227] Clause 35. A cured composition obtained by exposing the UV-curable composition according to any one of Clauses 31 to 34 to ultraviolet radiation to cure the UV-curable composition.

[0228] It will be apparent to those of ordinary skill in the art that various modifications and variations can be made without departing from the scope disclosed herein. Since modifications, combinations, sub-combinations, and variations of the disclosed embodiments that incorporate the spirit and substance disclosed herein may occur to those of ordinary skill in the art, the scope disclosed herein should be construed to include all such modifications, combinations, sub-combinations, and variations within the scope of the appended claims and their equivalents.

[0229] To define the present technology, the transitional phrase "consisting of" may be introduced in a claim as a closed introductory term to limit the scope of the claim to the recited components or steps and any naturally occurring impurities. To define the present technology, the transitional phrase "consisting essentially of" may be introduced in a claim to limit the scope of one or more claims to the recited elements, components, materials, or method steps, and any unrecited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter.

[0230] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. The verb "comprising" and its conjugations are to be construed as referring to elements, components, or steps in a non-exclusive manner. The recited elements, components, or steps may be present, used, or combined with other elements, components, or steps not expressly recited.

[0231] It should be understood that any two quantitative values that confer a given property can form a range of that property, and the present disclosure contemplates all combinations of ranges formed by all quantitative values of a given property. The subject matter disclosed herein has been described in detail by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily mean that the component or feature is essential to a particular embodiment or any other embodiment.

Claims

1. A thiol masterbatch composition for preparing a UV - curable composition, the thiol masterbatch composition comprising: Based on the total weight of the thiol masterbatch composition, at least 70% by weight of a thiol compound; and At least one stabilizer, wherein the thiol compound is selected from primary thiols, secondary thiols or a combination thereof; and wherein: Based on the total weight of the thiol compound, at least 50% by weight of the thiol compound is a primary thiol, and based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition contains at least 22,000 parts per million (ppm) of the stabilizer; or Based on the total weight of the thiol compound, less than 50% by weight of the thiol compound is a primary thiol, and based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition contains at least 10,000 parts per million (ppm) of the stabilizer.

2. The thiol masterbatch composition according to claim 1, wherein the thiol compound is selected from pentaerythritol tetra(3 - mercaptopropionate), pentaerythritol tetra(3 - mercaptobutyrate) or a combination thereof.

3. The thiol masterbatch composition according to claim 1 or 2, wherein the at least one stabilizer is selected from radical scavenger compounds, hydroperoxide decomposer compounds or hydrogen donor compounds.

4. The thiol masterbatch composition according to any one of claims 1 to 3, wherein the at least one stabilizer is selected from triphenylantimony, triphenyl phosphite, butylated hydroxytoluene, 4 - methoxyphenol, propyl gallate, oxalic acid, phosphite esters or a combination thereof.

5. The thiol masterbatch composition according to any one of claims 1 to 4, based on the total weight of the stabilizer, at least 50% by weight of the stabilizer is dissolved in the thiol masterbatch composition.

6. The thiol masterbatch composition according to any one of claims 1 to 5, further comprising a diluent selected from non - reactive diluents, reactive diluents or a combination thereof.

7. The thiol masterbatch composition according to claim 6, wherein based on the total weight of the diluent, the diluent contains at least 50% by weight of (meth)acrylate monomers.

8. The thiol masterbatch composition according to claim 6 or 7, wherein the diluent is a (meth)acrylate monomer.

9. The thiol masterbatch composition according to any one of claims 1 to 8, wherein when the thiol masterbatch composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the final viscosity of the thiol masterbatch composition after heating and the initial viscosity of the thiol masterbatch composition before heating is less than 10,000 centipoise (cps).

10. A kit for providing a UV - curable composition, comprising: A first part comprising a thiol masterbatch composition, wherein based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition contains at least 70% by weight of a thiol compound and at least one stabilizer; and A second part separate from the first part and comprising a (meth)acrylate composition, the (meth)acrylate composition comprising (meth)acrylate monomers, (meth)acrylate oligomers and a photoinitiator.

11. A method for preparing a UV - curable composition, the method comprising: Combining the thiol masterbatch composition with a (meth)acrylate composition to obtain a UV - curable composition; wherein: Based on the total weight of the thiol masterbatch composition, the thiol masterbatch composition comprises at least 70% by weight of a thiol compound and at least one stabilizer; and (Meth)acrylate composition comprises (meth)acrylate monomer, (meth)acrylate oligomer and a photoinitiator.

12. The method of claim 11, wherein the weight ratio of the thiol masterbatch composition to the (meth)acrylate composition is from 1:1 to 1:

20.

13. A UV-curable composition prepared by the method of claim 11 or 12.

14. The UV-curable composition of claim 13, wherein when the UV-curable composition is heated at a temperature of at least 60 degrees Celsius (°C) for at least 28 days, the difference between the viscosity of the UV-curable composition after heating and the initial viscosity of the UV-curable composition is 15,000 centipoise (cps) or less.

15. A cured composition obtained by exposing the UV-curable composition of claim 13 to ultraviolet radiation to cure the UV-curable composition.

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