Hybrid photocurable composition

Abstract

To provide a urethane (meth)acrylate with improved curing characteristics.SOLUTION: In an aspect, a curable composition comprises: an acid-catalyzed urethane (meth)acrylate oligomer comprising an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anionic polymerization inhibitor. In another aspect, a method of making a cured composition comprises: forming the curable composition; and curing the curable composition by exposing it to light to form the cured composition.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the priority of U.S. Provisional Patent Application No. 63 / 002,664, filed on Mar. 31, 2020. The related application is incorporated herein by reference in its entirety.

Background Art

[0002] The present invention relates to a hybrid photocurable composition.

[0003] Curable compositions based on urethane (meth) acrylate oligomer technology are commonly used in many different applications such as coatings, adhesives, sealants, and inks because they can be easily cured by visible light, ultraviolet light, or electron beam irradiation. Urethane (meth) acrylate oligomers can be produced by preparing a urethane prepolymer having isocyanate end groups and then functionalizing the isocyanate end groups with a reactive acrylate that does not dissociate at elevated temperatures, such as 2 - hydroxyethyl (meth) acrylate. Urethane (meth) acrylate oligomers can then be cured, when their molecular weight is sufficiently low, by reacting with the urethane acrylate oligomer itself or with a polyfunctional acrylate monomer, resulting in more complete curing.

[0004] Although the technology for producing such curable compositions has been constantly improving, there are still significant problems in effective curing in areas blocked by the radiation source. These blocked areas contain uncured materials that pose a reliability risk to the product and can weaken the material or adhesive bond over time.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, it is desirable to develop a urethane (meth) acrylate having improved curing properties.

Means for Solving the Problems

[0007] What is described herein is a hybrid photocurable composition.

[0008] In one aspect, the curable composition includes an acid-catalyzed urethane (meth) acrylate oligomer containing an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anion polymerization inhibitor.

[0009] In another aspect, the curable composition is based on the total mass of the urethane (meth) acrylate oligomer, and is 0.1 to 30% by mass of an acid-catalyzed urethane (meth) acrylate oligomer having at least one structure of formula (1) or formula (2) produced with 0.05 to 6% by mass of an acid catalyst: A-D-(PD) n -A (1) A-(PD) n -P-A (2) (Each A is independently a monohydroxy-functional (meth) acrylate group; each D is independently derived from a di- or trifunctional isocyanate group; each P is independently derived from a polyol having a weight average molecular weight of 50 to 12,000 daltons based on polystyrene standards; n is 10 to 100); 20 to 98% by mass of a cyanoacrylate monomer; 0.005 to 4% by mass or 0.01 to 2% by mass of a metallocene compound; 0.001 to 1% by mass of a free radical polymerization inhibitor; and 0.1% by mass of an acidic anion polymerization inhibitor.

[0010] In one aspect, the cured composition is derived from the curable composition.

[0011] In yet another aspect, a method of manufacturing a cured composition includes the steps of producing a curable composition; and curing the curable composition by exposure to light to produce a cured composition.

[0012] The above and other aspects are demonstrated by the following detailed description and claims.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] Cyanoacrylate compositions are durable fast-curing adhesives based on esters of 2-cyanoacrylic acid. These cyanoacrylate compositions are generally known as strong instant adhesives or instant adhesives and are unique in terms of their curing rate that does not require heat or light and their ability to adhere to many different surfaces. Attempts to combine these cyanoacrylate monomers with urethane (meth)acrylate oligomers to improve the curing of the urethane (meth)acrylate compositions are fraught with problems. Specifically, urethane (meth)acrylate oligomers are generally produced in the presence of a metal-based catalyst or an amine-based catalyst. This residual catalyst in the urethane (meth)acrylate oligomer catalyzes the reaction with the cyanoacrylate monomer and, when mixed with the urethane (meth)acrylate oligomer, results in gel formation. In many cases, the residual catalyst prevents the formation of the desired cured composition by causing almost instantaneous gel formation.

[0014] It has surprisingly been found that a curable composition comprising an acid-catalyzed urethane (meth)acrylate oligomer and a cyanoacrylate monomer can cure to produce a stable composition that can produce a cured composition having improved curing properties. For example, improved curing may be represented by the fact that regions shielded from a radiation source can cure without exposure to radiation. Specifically, the curable composition includes an acid-catalyzed urethane (meth)acrylate oligomer; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anion polymerization inhibitor.

[0015] The acid-catalyzed urethane (meth)acrylate oligomer (hereinafter also referred to as urethane (meth)acrylate oligomer) may have at least one structure of formula (1) or formula (2). A-D-(PD) n -A (1) A-(PD) n -P-A (2) (Each A may independently be a monohydroxy-functional (meth)acrylate group; each D may independently be a di- or trifunctional isocyanate group; each P may independently be a polyol having a weight average molecular weight of 50 to 12,000 Daltons or 100 to 900 Daltons based on polystyrene standards; n may be 1 to 100 or 5 to 75)

[0016] Each D may independently be derived from a diisocyanate. Non-limiting examples of diisocyanates include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, isophorone diisocyanate, tetramethylxylene diisocyanate, trimethylhexamethylene diisocyanate, toluene diisocyanate, or isophorone diisocyanate.

[0017] Each P may independently be derived from an oligomer diol. Non-limiting examples of oligomer diols include 1,4-butanediol, neopentyl glycol, diethylene glycol, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, polyester glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, or polycarbonate glycol.

[0018] The urethane (meth)acrylate oligomer may include at least one of a polyester of hexanedioic acid and diethylene glycol reacted with isophorone diisocyanate and capped with 2-hydroxyethyl (meth)acrylate; a polypropylene glycol reacted with tolylene-2,6-diisocyanate and capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid and diethylene glycol reacted with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2-propanediol reacted with tolylene-2,4-diisocyanate and capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2-propanediol reacted with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid and diethylene glycol reacted with isophorone diisocyanate and capped with 2-hydroxyethyl (meth)acrylate; a polytetramethylene glycol ether reacted with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl (meth)acrylate; or a polypropylene glycol reacted with tetramethylxylene diisocyanate and capped with 2-hydroxyethyl (meth)acrylate. The capping agent means representing the A group of formula (1) and formula (2).

[0019] The curable composition may contain 0.1 to 30% by mass, or 1 to 20% by mass, of the urethane (meth)acrylate oligomer based on the total mass of the curable composition.

[0020] The curable composition may contain a urethane (meth)acrylate oligomer which is an acid-catalyzed urethane (meth)acrylate containing a residual amount of an acid catalyst. In other words, the catalyst used for the production of the urethane (meth)acrylate oligomer may be an acid catalyst. The urethane (meth)acrylate oligomer may not contain a metal-based catalyst or an amine-based catalyst. For example, based on the total mass of the urethane (meth)acrylate oligomer, it contains 0 to 0.001% by mass, or 0% by mass of a metal-based catalyst or an amine-based catalyst.

[0021] The acid catalyst may contain at least one of a non-metallic Lewis acid (for example, boron trifluoride, boron trifluoride etherate) or an organic acid (such as methanesulfonic acid (MSA), para-toluenesulfonic acid (pTSA), sulfuric acid, trifluoromethanesulfonic acid, hypophosphorous acid, phosphoric acid, or diphenyl phosphate). The acid catalyst may contain methanesulfonic acid (MSA). The acid catalyst may be a residual catalyst present in the urethane (meth)acrylate oligomer and thus may be present in the curable composition. The acid catalyst may be present in an amount of 0.05 to 6% by mass, or 0.2 to 3% by mass based on the total mass of the urethane (meth)acrylate oligomer.

[0022] The curable composition may not contain a metal-based catalyst or an amine-based catalyst. Examples of metal-based catalysts include bismuth octoate, bismuth neodecanoate, dibutyltin-di-2-hexonate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, ferrous acetoacetate, lead octoate, tin octoate, tin oleate, zinc neodecanoate, and zinc octoate. Examples of amine-based catalysts include tertiary amines (for example, 1,3,5-tris(3-[dimethylamino]propyl)-hexahydro-s-triazine, 1,4-diazabicyclo[2.2.2]octane, or N,N-dimethylcyclohexylamine).

[0023] The cyanoacrylate monomer may have the formula (3).

Chemical formula

[0024] The metallocene compound can include a compound having the formula (4).

Chemical formula

[0025] The metallocene compound may contain at least one of ferrocene or titanocene. Ferrocene may include vinylferrocene, bis-alkylferrocene (e.g., ferrocenylethane, ferrocenylpropane, or ferrocenylbutane), ferrocene derivatives (e.g., butylferrocene, or diarylphosphino metal complexed ferrocene (e.g., 1,1-bis(diphenylphosphino)ferrocene-palladium dichloride)). Titanocene may include bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium.

[0026] The metallocene compound may be present in an amount of 0.005 to 4% by mass, or 0.01 to 2% by mass, based on the total mass of the curable composition.

[0027] The curable composition may contain a photoinitiator. The photoinitiator can increase the rate of the curing process upon exposure to electromagnetic radiation. The photoinitiator includes commercial photoinitiators such as those from IGM Resin under the trade name "OMNIRAD". For example, the photoinitiator may be OMNIRAD184 (1-hydroxycyclohexyl phenyl ketone), OMNIRAD500 (1-hydroxycyclohexyl phenyl ketone and benzophenone), OMNIRAD651 (2,2-dimethoxy-2-phenylacetophenone), OMNIRAD819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), OMNIRAD1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), OMNIRAD4265 (2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), visible light [blue] photoinitiator, d1-camphorquinone, or OMNIRAD784. It is noted that certain metallocene photoinitiators can function as both metallocene and photoinitiator. The photoinitiator may include at least one of alkyl pyruvate (e.g., methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate), or aryl pyruvate (e.g., phenyl pyruvate, benzyl pyruvate, or substituted aryl pyruvate). The photoinitiator may include OMNIRAD819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide).

[0028] The curable composition may contain a photosensitizer. The photosensitizer enables the photoinitiator to react to radiation beyond, for example, the UV range. The photosensitizer may include at least one of benzophenone, isopropylthioxanthone, 2-chloro-thioxanthone, chloro-4-propoxythioxanthone, 2,4-diethyl-dioxanthone, or 2-ethyl-9,10-dimethoxyanthracene.

[0029] The free radical polymerization inhibitor may include at least one of hydroquinone, catechol, β-naphthol, mono-t-butylhydroquinone, pyrogallol, 4-methoxyphenol (also represented as the methyl ether of hydroquinone), 4-tert-butylphenol, 2,5-di-tert-butylhydroquinone, or 2,6-di-tert-butyl-4-methylphenol. The free radical polymerization inhibitor may be present in an amount of 0.001 to 1% by mass, or 0.01 to 0.5% by mass, based on the total mass of the curable composition.

[0030] The acidic anion polymerization inhibitor may include at least one of a Lewis acid (e.g., boron trifluoride or boron trifluoride etherate), a carboxylic acid, or a sulfonic acid (e.g., p-toluenesulfonic acid). The carboxylic acid may include at least one of acrylic acid, methacrylic acid, acetic acid, ascorbic acid, oxalic acid, phthalic acid, itaconic acid, crotonic acid, 4-methoxyphenylacetic acid, 3,5-dihydroxybenzoic acid, or 3,3-dimethylaminobenzoic acid. The acidic anion polymerization inhibitor may be present in an amount of 0.001 to 0.5% by mass, or 0.001 to 1% by mass, based on the total mass of the curable composition.

[0031] The curable composition may include a polyfunctional (meth)acrylate oligomer. The polyfunctional (meth)acrylate oligomer may include at least one of polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, propoxylated trimethylolpropane triacrylate, or ethoxylated trimethylolpropane triacrylate. The polyfunctional oligomer may be present in an amount of more than 0 to 60% by mass, or 1 to 50% by mass, based on the total mass of the curable composition.

[0032] The curable composition may contain a (meth)acrylate functional monomer. The (meth)acrylate functional monomer may act as a reactive diluent in the curable composition. The (meth)acrylate functional monomer may include at least one of butanediol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, or pentaerythritol tetraacrylate, isobornyl acrylate, isobornyl methacrylate, isodecyl acrylate, ethylhexyl acrylate, or tetrahydrofurfuryl methacrylate. The (meth)acrylate functional monomer may be present in an amount of more than 0 to 30% by mass, or 1 to 25% by mass based on the total mass of the curable composition.

[0033] The curable composition may contain one or more additional additives. For example, the curable composition may include at least one of a filler, a silane coupling agent, a colorant, a flame retardant, a viscosity modifier (which may be the same as or different from the filler), a conductive component, a heat conductive component, an antifoaming agent, a plasticizer, an adhesion promoter, a non-alcohol solvent, or a reactive diluent.

[0034] The filler may include at least one of polymethyl methacrylate or its derivatives, wood flour, corn starch, cotton linter, mica, hydrophobic modified silica, etc. The filler may be added to change at least one of the viscosity of the curable composition or to improve the impact resistance of the cured composition. The silane coupling agent can increase the moisture resistance and the bonding strength to the substrate. The colorant may include at least one of dyes, fluorescent agents, pigments, etc. The dye may include arylmethane dyes (for example, cationic triphenylmethane compounds). The dye may include at least one of Crystal Violet, Victoria Blue, Malachite Green or New Fuchsin. The viscosity modifier may include at least one of a thixotrope, a thickening agent (such as silica gel) or a viscosity reducing agent. The conductive material may include at least one of graphene or carbon nanotubes. The non-alcohol solvent may include at least one of butan-2-one, heptan-2-one, butyl acetate, ethyl acetate, propyl acetate, or acetone. The plasticizer may include at least one of triacetin, dioctyl phthalate, dibutyl phthalate, butyl phthalyl butyl glycolate, tricresyl phosphate, polyester, or chlorinated paraffin.

[0035] The curable composition comprises 0.1 to 30% by mass of a urethane (meth)acrylate oligomer having at least one structure of formula (1) or formula (2) prepared with an acid catalyst in an amount of 0.05 to 6% by mass based on the total mass of the urethane (meth)acrylate oligomer; 20 to 98% by mass of a cyanoacrylate monomer; 0.005 to 4% by mass, or 0.01 to 2% by mass of a metallocene compound; 0.001 to 1% by mass of a free radical polymerization inhibitor; and 0.001 to 0.1% by mass of an acidic anion polymerization inhibitor; and unless otherwise stated, the amounts are based on the total mass of the curable composition.

[0036] The cured composition can be derived from a curable composition. This specification can include a cured composition. The curable composition can be an adhesive for use in a medical device (e.g., a catheter), an electronic device, or a nail coating. The cured composition can be a coating, an adhesive, a sealant, an ink, or an article.

[0037] The cured composition can be tack-free and cured from the curable composition by at least one of light or moisture.

[0038] A method for producing a cured composition from a curable composition can include a step of forming the curable composition and a step of curing the curable composition by exposing it to electromagnetic radiation (also referred to herein as curing radiation) that causes curing of the curable composition. The electromagnetic radiation can include at least one of ultraviolet (UV) or visible light region radiation. The radiation source (also referred to herein as the source) can emit electromagnetic radiation having a wavelength, for example, of 390 - 410 nanometers (nm) or 400 - 405 nm. Curing can result in complete or nearly complete curing of the curable composition even in the shadow region.

[0039] The electromagnetic radiation can be emitted from a radiation source. Examples of the radiation source include a solar source, a fluorescent light source, an ultraviolet (UV) light source, and a visible light source. The radiation source can include a lamp (e.g., a mercury arc lamp or a xenon arc lamp). The radiation source can include at least one of an A-type UV lamp, a D-type UV lamp, an H-type UV lamp, an M-type UV lamp, a V-type UV lamp, or an X-type UV lamp. The radiation source can include a light emitting diode (LED).

[0040] Curing can occur in a curing chamber having any rotation or relative movement with respect to the curing source. Curing can include, for example, a step of selectively controlling an electromagnetic radiation source with the assistance of a reflector or a filter. During curing, the substrate can be positioned at 0.5 - 5.5 centimeters from the radiation source. The curing time can be from 0.1 seconds to 5 minutes or 1 - 60 seconds. The exposure intensity is 0.01 - 600 watts / cm 2 or 0.1 - 450 W / cm 2 or 1 - 300 W / cm2 It may be possible.

[0041] The radiation source can be stored in the lighting device. The lighting device may include an optical condenser that sufficiently transmits light in the ultraviolet and / or visible regions. The condenser may have a light input region and a light output region along its length. Some radiation sources (e.g., light-emitting diodes) can be positioned at the light input ends of their respective series of light guides. The light output end of each light guide can be a condenser along the length of the light input region, and the condensed light radiates along the length of the light output region of the condenser, thereby enabling the condensed light to be directed towards the curable composition. An example of such a lighting device is found in U.S. Patent No. 8,134,132, which can be incorporated herein by reference in its entirety.

[0042] The method may further include a step of depositing the curable composition before curing. For example, the method may include a step of depositing an amount of the curable composition on a substrate and a step of curing the curable composition to form a cured composition. The deposition step may include dispensing the curable composition on the substrate in any desired form, such as droplets, lines, or layers. The deposition step may include coating (e.g., dip coating, curtain coating, spin coating, roller coating, brush coating, or transfer coating), casting, dispensing in the droplet method, dispensing in a continuous method (e.g., forming lines, continuous, dashes, waves, or others), etc. The deposition step can be performed in an environment free of curing radiation. For example, the deposition step can be performed in a dark environment. The temperature during the dispensing step can be changed to adjust the viscosity of the curable composition during dispensing. For example, the temperature during the dispensing step can be 10 to 50°C. Before the deposition step, the curable composition can be stored in a dark environment or in a container that is less susceptible to curing radiation.

[0043] A method of forming a cured composition may include a step of forming a multi-layer deposit. For example, a multi-layer deposit containing a curable composition located between two outer substrates may be compressed together before and / or during curing, for example, by at least one of lamination, calendaring, vacuum bagging, or rotary compression. One or both of the substrates may be a release liner that can be removed later from the cured composition.

[0044] The substrate may include at least one of glass, wood, polymer, or metal. The substrate may include at least one of polymer or glass. The polymer may include at least one of acrylic, epoxy, polyamide, polycarbonate, poly(etherimide), polyimide, polyolefin (e.g., polyethylene or polypropylene), polyurethane, polysulfone, polystyrene, or poly(vinyl acetate). The substrate can be either rigid or flexible. The substrate can be, for example, a woven or non-woven fabric. The substrate may be porous, for example, a foam. The substrate may be non-porous.

[0045] The following examples are provided to illustrate the present invention. The examples are merely illustrative and are not intended to be limited to the apparatus made according to the descriptions of the materials, conditions, or method parameters described therein.

Examples

[0046] In the examples, the following test methods and procedures were used.

[0047] The tack-free time (seconds) is the time when a coating having a thickness of 5 mils (127 micrometers) on stainless steel is exposed to a 405 nanometer (nm) LED light having a light intensity of 100 mW / cm 2 until it becomes tack-free. The tack-free time test is based on ASTM method C679-03, and a 30-gram polyethylene film is placed on the upper end of the cured material. When it is peeled off from the tack-free surface, basically no material should transfer to the polyethylene film.

[0048] The fixation time (seconds) is the time for the adhesive having a thickness of 5 mils (127 micrometers) between the slide glasses to bond to the slide glasses without light exposure. The fixation time is 10 pounds / inch 2 (69 kilopascals) of shear strength. The fixation time test is based on ASTM method D1144.

[0049] The maximum load retention (%) is the load that the material can withstand during a lap-shear test between two slide glasses after being exposed to a temperature of 60 °C and a relative humidity of 90% for one week. The lap-shear test was performed in accordance with ASTM method D3163-01 (2014), where two slide glasses overlapped at 0.125 inches (3.2 centimeters) were bonded with the material of the example and pressed until failure.

[0050] Table 1 shows the components used in the examples.

[0051]

Table 1

[0052] Examples 1-11: Effect of copolymerization with urethane (meth) acrylate oligomer 11 curable compositions were prepared using the amounts shown in Table 1. The cyanoacrylate mixture contained 96.1% by mass of cyanoacrylate, 0.4% by mass of stabilizer, 0.5% by mass of metallocene, 1% by mass of photoinitiator, and 2% by mass of other additives. In Example 1, the only monomer included in the polymerization was the cyanoacrylate monomer. In Examples 2 and 3, cyanoacrylate and various amounts of polyfunctional oligomers were included in the polymerization. In Examples 4-11, cyanoacrylate with or without polyfunctional oligomers and various amounts of urethane (meth) acrylate oligomers were included in the polymerization. The curable compositions were cured by exposure to 385 nanometer LED light at an irradiance of 100 mW / cm 2 for 30 seconds.

[0053] The tack-free time, the setting time, and the maximum load retention value were determined for each composition, and the results are shown in Table 2.

[0054]

Table 2

[0055] Table 2 shows that Examples 1-3 without urethane (meth)acrylate oligomer all unfavorably retained less than 30% of the maximum load after being exposed to high temperature and high humidity conditions. Example 4 incorporating exactly 5% by mass of urethane (meth)acrylate oligomer brought about a remarkable improvement in maximum load retention, and Examples 5-11 showed further improvement when multifunctional oligomers were present. These improvements indicate that the maximum load does not decrease but beneficially increases upon exposure to heat and humidity. Examples 5-11 containing both urethane (meth)acrylate oligomer and multifunctional oligomers have all been shown to retain a maximum load of over 100% with respect to heat and humidity.

[0056] Examples 12-13: Effect of the urethane (meth)acrylate oligomer catalyst Two formulations were prepared with the same components except for the catalyst for producing the urethane (meth)acrylate oligomer. Example 12 was prepared with a urethane (meth)acrylate oligomer produced using a metal catalyst, BisOct (bismuth octanoate). Example 13 was prepared with a urethane (meth)acrylate oligomer produced using a non-metal catalyst, MSA. Table 3 shows the stability of the formulations. The formulation of Example 12 was not stable and a gel formed within 1 hour of stirring, while the formulation of Example 13 was stable for at least 1 week even with a temperature increase such as to 40°C.

[0057]

Table 3

[0058] The following description is a non-limiting aspect of the present invention.

[0059] Aspect 1: A curable composition comprising an acid-catalyzed urethane (meth)acrylate oligomer containing an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anion polymerization inhibitor.

[0060] Aspect 2: The curable composition of Aspect 1, wherein the acid-catalyzed urethane (meth)acrylate oligomer has at least one structure of formula (1) or formula (2): A-D-(PD) n -A (1) A-(PD) n -P-A (2) (Wherein each A is independently a monohydroxy-functional (meth)acrylate group; each D is independently a di- or trifunctional isocyanate group; each P is independently a polyol having a weight average molecular weight of 100 50 to 12,000 daltons based on polystyrene standards, and n is 1 to 100).

[0061] Aspect 3: The acid-catalyzed urethane (meth)acrylate oligomer is a polyester of adipic acid and diethylene glycol that reacts with isophorone diisocyanate and is capped with 2-hydroxyethyl (meth)acrylate; a polypropylene glycol that reacts with tolylene-2,6-diisocyanate and is capped with 2-hydroxyethyl (meth)acrylate; a polyester of adipic acid and diethylene glycol that reacts with 4,4'-methylenebis(cyclohexyl isocyanate) and is capped with 2-hydroxyethyl (meth)acrylate; a polyester of adipic acid, 1,2-ethanediol, and 1,2-propanediol that reacts with tolylene-2,4-diisocyanate and is capped with 2-hydroxyethyl (meth)acrylate; a polyester of adipic acid, 1,2-ethanediol, and 1,2-propanediol that reacts with 4,4'-methylenebis(cyclohexyl isocyanate) and is capped with 2-hydroxyethyl (meth)acrylate; a polyester of adipic acid and diethylene glycol that reacts with isophorone diisocyanate and is capped with 2-hydroxyethyl (meth)acrylate; a polytetramethylene glycol ether that reacts with 4,4'-methylenebis(cyclohexyl isocyanate) and is capped with 2-hydroxyethyl (meth)acrylate; or a curable composition according to Aspect 1 or 2 containing at least one of a polypropylene glycol that reacts with tetramethylxylene diisocyanate and is capped with 2-hydroxyethyl (meth)acrylate.

[0062] Aspect 4: A curable composition according to any one of Aspects 1 to 3, wherein the curable composition contains 0.1 to 30% by mass of the acid-catalyzed urethane (meth)acrylate based on the total mass of the curable composition.

[0063] Aspect 5: A curable composition according to any one of Aspects 1 to 4, wherein the acid catalyst contains at least one of a non-metallic Lewis acid or an organic acid; preferably methanesulfonic acid.

[0064] Aspect 6: A curable composition according to any one of Aspects 1 to 5, wherein the acid catalyst is present in an amount of 0.05% by mass to 6% by mass based on the total mass of the urethane (meth)acrylate oligomer.

[0065] Aspect 7: A curable composition according to any one of Aspects 1 to 6, wherein the cyanoacrylate monomer has the following structure: [Chemical formula] Here, R is an alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl or haloalkyl group having C1 to C 15 of.

[0066] Aspect 8: A curable composition according to any one of Aspects 1 to 7, wherein the cyanoacrylate monomer contains at least one of methyl cyanoacrylate, ethyl 2-cyanoacrylate, propyl cyanoacrylate (for example, isopropyl cyanoacrylate), butyl cyanoacrylate, octyl cyanoacrylate, allyl-2-cyanoacrylate, or β-methoxyethyl-2-cyanoacrylate.

[0067] Aspect 9: A curable composition according to any one of Aspects 1 to 8, wherein the curable composition contains 20 to 98% by mass of the cyanoacrylate monomer based on the total mass of the curable composition.

[0068] Aspect 10: A curable composition according to any one of Aspects 1 to 9, wherein the metallocene compound contains at least one of ferrocene or titanocene.

[0069] Aspect 11: A curable composition according to any one of Aspects 1 to 10, wherein the metallocene compound is present in an amount of 0.005 to 4% by mass, or 0.01 to 2% by mass based on the total mass of the curable composition.

[0070] Aspect 12: A curable composition according to any one of Aspects 1 to 11, wherein the free radical polymerization inhibitor contains at least one of hydroquinone, catechol, β-naphthol, mono-t-butylhydroquinone, pyrogallol, 4-methoxyphenol, 4-tert-butylphenol, 2,5-di-tert-butylhydroquinone, or 2,6-di-tert-butyl-4-methylphenol.

[0071] Aspect 13: A curable composition according to any one of Aspects 1 to 12, wherein the free radical polymerization inhibitor is present in an amount of 0.001 to 1% by mass based on the total mass of the curable composition.

[0072] Aspect 14: A curable composition according to any one of Aspects 1 to 13, wherein the acidic anion polymerization inhibitor contains at least one of a Lewis acid, a carboxylic acid, or a sulfonic acid.

[0073] Aspect 15: A curable composition according to any one of Aspects 1 to 14, wherein the acidic anion polymerization inhibitor is present in an amount of 0.001 to 1% by mass based on the total mass of the curable composition.

[0074] Aspect 16: A curable composition according to any one of Aspects 1 to 15, further comprising a polyfunctional oligomer.

[0075] Aspect 17: A curable composition according to any one of Aspects 1 to 16, further comprising a polyfunctional (meth)acrylate oligomer containing at least one of polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, propoxylated trimethylolpropane triacrylate, or ethoxylated trimethylolpropane triacrylate.

[0076] Aspect 18: A curable composition according to Aspect 16 or 17, wherein the polyfunctional (meth)acrylate oligomer is present in an amount of more than 0 to 60% by mass based on the total mass of the curable composition.

[0077] Aspect 19: A curable composition according to any one of Aspects 1 to 18, further comprising a photoinitiator.

[0078] Aspect 20: A curable composition according to any one of Aspects 1 to 19, further comprising a photoinitiator in an amount of more than 0% to 4% by mass based on the total mass of the curable composition.

[0079] Aspect 21: A curable composition according to any one of Aspects 1 to 20, further comprising a (meth)acrylate monomer.

[0080] Aspect 22: A curable composition according to any one of Aspects 1 to 21, further comprising a (meth)acrylate monomer in an amount of more than 0% to 30% by mass based on the total mass of the curable composition.

[0081] Aspect 23: A curable composition according to any one of Aspects 1 to 22, further comprising a filler, a silane coupling agent, a photosensitizer, a colorant, a flame retardant, a free radical polymerization initiator, a viscosity modifier, a conductive component, a heat conductive component, an antifoaming agent, an adhesion promoter, a reactive diluent, or a plasticizer.

[0082] Aspect 24: An acid-catalyzed urethane (meth)acrylate oligomer having at least one structure of formula (1) or formula (2) prepared with an acid catalyst in an amount of 0.05% to 6% by mass based on the total mass of the urethane (meth)acrylate oligomer, in an amount of 0.1% to 30% by mass A-D-(PD) n -A (1) A-(PD) n -P-A (2) (In the formula, each A is independently a monohydroxy-functional (meth)acrylate group; each D is independently derived from a di- or trifunctional isocyanate group; each P is independently derived from a polyol having a weight average molecular weight of 50 to 12,000 daltons based on polystyrene standards, and n is 1 to 100); A curable composition comprising 20 to 98% by mass of a cyanoacrylate monomer; 0.005 to 4% by mass, or 0.01 to 2% by mass of a metallocene compound; 0.001 to 1% by mass of a free radical polymerization inhibitor; and 0.01 to 0.1% by mass of an acidic anion polymerization inhibitor.

[0083] Aspect 25: A cured composition derived from any one of the curable compositions of Aspects 1 to 24.

[0084] Aspect 26: An article or coating comprising the cured composition of Aspect 25, wherein the article can be a medical device, an electronic device, or a nail.

[0085] Aspect 27: For example, a method for producing a cured composition, comprising the steps of curing any one of the curable compositions of Aspects 1 to 22 by exposing to light to form a cured composition; and optionally, generating a curable composition before the curing step.

[0086] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or components described herein. The compositions, methods, and articles can be formulated, additionally or alternatively, to lack or be substantially free of any materials (or species), steps, or components that are otherwise not necessary for the achievement of the functions or purposes of the compositions, methods, and articles.

[0087] As used herein, "one," "its," and "at least one" do not imply a limitation in quantity, unless the context clearly indicates otherwise, and are intended to cover both the singular and the plural. For example, unless the context clearly indicates otherwise, "one element" has the same meaning as "at least one element." The term "combination" includes blends, mixtures, alloys, reaction products, and the like. Also, "at least one" means that the list includes each element independently, as well as combinations of two or more elements of the list, and combinations of at least one element of the list together with an unnamed element.

[0088] Unless the context clearly indicates otherwise, the term "or" means "and / or". References to "aspect", "another aspect", "some aspects" and the like in the specification mean that a particular element (e.g., feature, structure, step, or property) described in connection with that aspect is included in at least one aspect described herein, and may or may not be present in other aspects. Additionally, it will be understood that the described elements may be combined in a suitable manner in various aspects.

[0089] Unless otherwise specified herein, all test standards are substantially the most recent standards as of the filing date of the present application, or, if priority is claimed, as of the filing date of the earliest priority application in which the test standard appears.

[0090] All endpoints of ranges directed to the same component or property include the endpoints, are independently combinable, and include all intermediate points and ranges. For example, the range "up to 25% by weight, or 5 - 20% by weight" includes the endpoints and all intermediate values of the range "5 - 25% by weight" (such as 10 - 23% by weight, etc.).

[0091] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The weight average molecular weight can be measured using gel permeation chromatography (GPC) or size exclusion chromatography (SEC).

[0092] Compounds are described using nomenclature standards. As used herein, the term "(meth)acrylate" encompasses both acrylate and methacrylate groups.

[0093] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this specification conflicts with or is inconsistent with a term in an incorporated reference, the term of the present invention shall prevail over the conflicting term of the incorporated reference.

[0094] Although specific embodiments have been described, alternative means, modifications, variations, improvements, and substantially equivalent ones not now foreseen or appreciated may occur to the applicant or other persons skilled in the art. As a result, the appended claims as filed and their amended versions are intended to cover all such as alternative means, modifications, variations, improvements, and substantially equivalent ones.

Claims

1. An acid-catalyzed urethane (meth)acrylate oligomer containing an acid catalyst; A cyanoacrylate monomer; A metallocene compound; A free radical polymerization inhibitor; and A curable composition containing an acidic anion polymerization inhibitor, wherein the curable composition The acid-catalyzed urethane (meth)acrylate oligomer has at least one structure of formula (1) or formula (2): A-D-(PD)n-A (1) A-(PD)n-P-A (2) (Wherein each A is independently a monohydroxy-functional (meth)acrylate group; each D is independently a di- or trifunctional isocyanate group; each P is independently a polyol having a weight average molecular weight of 50 to 12,000 daltons based on polystyrene standards; n is 1 to 100); and The curable composition contains 0.1 to 30% by mass of the acid-catalyzed urethane (meth)acrylate oligomer based on the total mass of the curable composition.

2. The acid catalyst contains at least one of a non-metallic Lewis acid or an organic acid; or The curable composition according to claim 1, wherein the acid catalyst is present in an amount of 0.05 to 6% by mass based on the total mass of the urethane (meth)acrylate oligomer.

3. The cyanoacrylate monomer has the following structure: 【Chemical 1】 (wherein R is C 1 ~C 15 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl or haloalkyl group); or, The curable composition according to claim 1 or claim 2, wherein the curable composition contains 20 to 98% by mass of the cyanoacrylate monomer based on the total mass of the curable composition.

4. The metallocene compound contains at least one of ferrocene or titanocene; or The curable composition according to any one of claims 1 to 3, wherein the metallocene compound is present in an amount of 0.005 to 4% by mass or 0.01 to 2% by mass based on the total mass of the curable composition.

5. The free radical polymerization inhibitor contains at least one of hydroquinone, catechol, β-naphthol, mono-t-butylhydroquinone, pyrogallol, 4-methoxyphenol, 4-tert-butylphenol, 2,5-di-tert-butylhydroquinone or 2,6-di-tert-butyl-4-methylphenol; or The curable composition according to any one of claims 1 to 4, wherein the free radical polymerization inhibitor is present in an amount of 0.001 to 1% by mass based on the total mass of the curable composition.

6. The acidic anionic polymerization inhibitor contains at least one of a Lewis acid, a carboxylic acid, or a sulfonic acid; or The curable composition according to any one of claims 1 to 5, wherein the acidic anionic polymerization inhibitor is present in an amount of 0.001 to 1% by mass based on the total mass of the curable composition.

7. A cured composition derived from the curable composition according to any one of claims 1 to 6.

8. An acid-catalyzed urethane (meth)acrylate oligomer containing an acid catalyst; A cyanoacrylate monomer; A metallocene compound; A free radical polymerization inhibitor; and A step of curing a curable composition containing an acidic anionic polymerization inhibitor by exposing it to light to produce a cured composition, The acid-catalyzed urethane (meth)acrylate oligomer has at least one structure of formula (1) or formula (2): A-D-(PD)n-A (1) A-(PD)n-P-A (2) (wherein each A is independently a monohydroxy-functional (meth)acrylate group; each D is independently a di- or trifunctional isocyanate group; each P is independently a polyol having a weight average molecular weight of 50 to 12,000 daltons based on polystyrene standards; and n is from 1 to 100); and A method for producing a cured composition, wherein the curable composition contains 0.1 to 30% by mass of an acid-catalyzed urethane (meth)acrylate oligomer based on the total mass of the curable composition.

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