Polyglycerin-based urethane (meth)acrylate

Abstract

The present invention relates to urethane (meth)acrylates obtained from the reaction of at least one polyglycerol polyol, at least one polyisocyanate, and at least one hydroxy-functional (meth)acrylate. The present invention further relates to a method for obtaining the urethane (meth)acrylates, a curable composition comprising the urethane (meth)acrylates, and a cured product obtained from the curing of the urethane (meth)acrylates.

Description

[Technical Field]

[0001] The present invention relates to urethane (meth)acrylates obtained from the reaction of at least one polyglycerol polyol; at least one polyisocyanate; and at least one hydroxy-functional (meth)acrylate.

[0002] The present invention further relates to a method for obtaining the urethane (meth)acrylate, a curable composition containing the urethane (meth)acrylate, and a cured product obtained by curing the urethane (meth)acrylate. [Background technology]

[0003] (Meth)acrylate-functionalized urethane oligomers have been found to be useful components of compositions that can be cured (polymerized) using UV radiation or other methods to form cured compositions that function as coatings, adhesives, sealants, additive-manufactured resins, molding resins, etc. However, the hydrophobic nature of these materials makes them difficult to formulate with other ingredients (e.g., tackifiers, acrylate monomers, photoinitiators, etc.), limiting their applications.

[0004] Therefore, the demand for hydrophilic or water-soluble materials continues to grow in various applications, such as coatings, medical applications, automotive, and 3D printing. More specifically, currently available energy-cured materials lack the balanced properties of water solubility and toughness. In addition, most materials are monomers or emulsion-type polymers, making them difficult to use in various energy-cured systems.

[0005] Furthermore, due to their high viscosity, urethane (meth)acrylate oligomers or polymers with good hydrophilicity, as well as good mechanical properties and high reactivity, are not available on the market.

[0006] JP 2018178071 A relates to an active energy ray-curable resin composition that can provide a cured product exhibiting high surface hardness and low curling properties. The radiation-curable resin composition contains a (meth)acrylate of a polyglycerin alkylene oxide adduct and a (meth)acrylate having three or more (meth)acryloyl groups.

[0007] JP 2016-186034 A relates to an active energy ray-curable coating resin composition that is hydrophilic, has good antifogging properties, and provides a cured film surface with sufficient surface hardness. Such an active energy ray-curable coating resin composition contains a polyglycerol ethylene oxide-modified (meth)acrylate product and a phosphate ester compound having an ethylene oxide group.

[0008] EP 2013302 relates to a radiation-curable aqueous composition comprising an ethylenically unsaturated polyurethane prepolymer obtained from the reaction of a polyisocyanate, a high molecular weight polyol, at least one hydrophilic compound containing at least one reactive group capable of reacting with an isocyanate group and capable of dispersing the polyurethane prepolymer in an aqueous medium either directly or after reacting with a neutralizing agent to form a salt, an ethylenically unsaturated compound containing at least two reactive groups capable of reacting with an isocyanate group, and an ethylenically unsaturated compound containing essentially one reactive group capable of reacting with an isocyanate group.

[0009] U.S. Patent Application Publication No. 2004 / 259970 relates to aqueous, UV-curable polyurethane emulsions and their use in producing soft-touch coatings prepared by reacting certain hydroxy-functional components with diisocyanates and / or polyisocyanates, forming a dispersion of the resulting product in water, and reacting the dispersion with an amine-functional material.

[0010] JP 2021-046483 A discloses urethane (meth)acrylates containing an excess amount of units derived from polyglycerin polyol for use in anti-fogging applications.

[0011] Therefore, there is a need for curable urethane (meth)acrylate polymer compositions that exhibit high hydrophilicity and good mechanical properties or elongation. Summary of the Invention

[0012] The first object of the present invention is to at least one polyglycerol polyol, at least one polyisocyanate, and at least one hydroxy-functional (meth)acrylate The present invention provides a urethane (meth)acrylate obtained by the reaction of

[0013] According to some embodiments, the urethane (meth)acrylate has a number average molecular weight of 1,000 to 50,000 g / mol, preferably 1,500 to 10,000 g / mol, and more preferably 2,000 to 5,000 g / mol.

[0014] According to some embodiments, the urethane (meth)acrylate has hydroxy residues.

[0015] According to some embodiments, the urethane (meth)acrylate does not have a hydroxy group.

[0016] According to some embodiments, the polyglycerin polyol is free of oxyethylene and / or oxypropylene groups, and preferably free of oxyalkylene groups.

[0017] According to some embodiments, the polyglycerol polyol has a number average molecular weight of at least 100 g / mol, preferably from 100 to 10,000 g / mol, more preferably from 200 to 500 g / mol.

[0018] According to some embodiments, the polyglycerol polyol has the following general formula (I): TIFF2024539932000001.tif26170 [wherein a is a number from 2 to 20, preferably from 2 to 10].

[0019] According to some embodiments, the polyisocyanate is preferably a diisocyanate selected from aliphatic, cycloaliphatic, or aromatic diisocyanates, preferably a cycloaliphatic diisocyanate, more preferably the polyisocyanate is isophorone diisocyanate.

[0020] According to some embodiments, the hydroxy-functional (meth)acrylate is selected from hydroxyalkyl (meth)acrylates and polyethylene glycol mono(meth)acrylates, preferably 2-hydroxyethyl (meth)acrylate or polyethylene glycol mono(meth)acrylate containing 2 to 20, preferably 5 to 10, ethylene glycol units.

[0021] According to some embodiments, the urethane (meth)acrylate has the following general formula (III): JPEG2024539932000002.jpg36170[In the formula, R is a unit derived from a hydroxy-functional (meth)acrylate, preferably R has the following general formula (IV): TIFF2024539932000003.tif29170 (where, R1 is selected from a hydrogen atom and a methyl group, and - b is a number from 1 to 30, preferably from 1 to 10 and - X is a unit derived from a polyisocyanate, said unit optionally being substituted with a urethane acrylate group if the polyisocyanate has an NCO functionality greater than 2; A is a unit derived from a polyglycerol polyol, preferably A has the following general formula (V): TIFF2024539932000004.tif28170 (where, - each Z is independently selected from a hydrogen atom or a group -C(=O)-NH-X-NH-C(=O)-OR; and - c is a number from 1 to 19, preferably from 1 to 9 and - n is a number between 1 and 30.

[0022] When X is a unit derived from a polyisocyanate having an NCO functionality greater than 2, X may be substituted with a urethane(meth)acrylate group comprising at least one urethane bond and at least one (meth)acrylate group, for example, X may be substituted with a urethane(meth)acrylate group of formula —NH—C(═O)—OR, where R is as defined above.

[0023] According to some embodiments, the urethane (meth)acrylate has an OH value of 50 mg KOH / g to 400 mg KOH / g, preferably 100 mg KOH / g to 200 mg KOH / g.

[0024] According to some embodiments, the urethane (meth)acrylate has an OH value of 0 mg KOH / g to 199 mg KOH / g, in particular 0.1 mg KOH / g to 190 mg KOH / g, more particularly 0.5 mg KOH / g to 180 mg KOH / g, and even more particularly 0.8 to 170 mg KOH / g.

[0025] According to some embodiments, the ratio R of polyisocyanate to hydroxy-functional (meth)acrylate is 1 is 0.2 to 0.9, preferably 0.5 to 0.8, and / or the ratio R of polyglycerin polyol to polyisocyanate is 2 is 0.1 to 0.8, preferably 0.2 to 0.5.

[0026] The present invention relates to a method for producing a method comprising the steps of: - reacting a polyisocyanate with a hydroxy-functional (meth)acrylate to form a isocyanate-functional adduct; and - Reacting an isocyanate-functional adduct with a polyglycerin polyol to obtain a urethane (meth)acrylate The present invention also relates to a method for obtaining a urethane (meth)acrylate, comprising:

[0027] The present invention also relates to a urethane (meth)acrylate obtainable by the above method.

[0028] The present invention provides - urethane (meth)acrylates as mentioned above, an ethylenically unsaturated compound selected from ethylenically unsaturated monomers or ethylenically unsaturated oligomers, preferably selected from monofunctional or polyfunctional (meth)acrylic monomers or oligomers, more preferably selected from acryloylmorpholine and polyethylene glycol di(meth)acrylate; The present invention also relates to a curable composition comprising:

[0029] According to some embodiments, the ethylenically unsaturated compound is present in an amount of at least 5 wt. %, preferably 5 to 99 wt. %, more preferably 10 to 50 wt. %, and even more preferably 15 to 35 wt. %, based on the total weight of the curable composition.

[0030] The present invention also relates to the cured product obtained from the curing of the above-described urethane (meth)acrylate or the curable composition described above.

[0031] The present invention makes it possible to meet the above needs. In particular, the present invention provides curable urethane (meth)acrylate polymer compositions that exhibit high hydrophilicity and good mechanical properties.

[0032] This is achieved by the urethane (meth)acrylate of the present invention. More specifically, the presence of polyglycerin polyol makes it possible to obtain a product with high hydrophilicity, high reactivity, and good mechanical properties. In addition, the viscosity of the urethane (meth)acrylate of the present invention can be controlled by optimizing the equivalent ratio of polyisocyanate to polyglycerin polyol. DETAILED DESCRIPTION OF THE INVENTION

[0033] The invention will now be explained in more detail by the following description, without limiting it.

[0034] Urethane (meth)acrylate The present invention provides at least one polyglycerol polyol, at least one polyisocyanate, and at least one hydroxy-functional (meth)acrylate The present invention relates to a urethane (meth)acrylate obtained by the reaction of

[0035] The term "urethane (meth)acrylate" refers to a compound containing at least one urethane linkage and at least one (meth)acrylate functional group. Such compounds are sometimes called urethane (meth)acrylate oligomers. A "urethane linkage" refers to an -NH-C(=O)-O- or -OC(=O)-NH- linkage. The term "(meth)acrylate functional group" refers to either an acrylate functional group (-OC(=O)-CH=CH2) or a methacrylate functional group (-OC(=O)-C(CH3)=CH2).

[0036] The urethane (meth)acrylate according to the present invention is a reaction product of the above compounds. The urethane (meth)acrylate according to the present invention can be a mixture of urethane (meth)acrylates.

[0037] The urethane (meth)acrylates according to the invention are based on polyglycerol polyols, i.e., comprise one or more units derived from polyglycerol polyols. The urethane (meth)acrylates according to the invention can be based on mixtures of polyglycerol polyols.

[0038] "Polyglycerol polyol" or "polyglycerol" refers to the polymerization product of glycerol, in other words, a molecule containing repeating units derived from glycerol.

[0039] According to some embodiments, the hydroxy groups of the polyglycerol polyol are not substituted (free hydroxy groups). By "hydroxy groups" is meant -OH groups. In particular, the polyglycerol polyol may be free of oxyethylene and / or oxypropylene groups, and preferably free of oxyalkylene groups. In other words, the polyglycerol glycol is preferably not ethoxylated and / or propoxylated, and more preferably not alkoxylated.

[0040] According to a preferred embodiment, the polyglycerol polyol has the following general formula (I): TIFF2024539932000005.tif25170 [wherein a is a number from 2 to 20, preferably from 2 to 10] can have:

[0041] The weight content of the polyglycerin polyol unit in the urethane (meth)acrylate can be 1 to 50% by weight, preferably 2 to 40% by weight, and more preferably 4 to 30% by weight, based on the total weight of the urethane (meth)acrylate.

[0042] In one embodiment, the weight content of the polyglycerin polyol units in the urethane (meth)acrylate can be 4 to 25 wt %, 4 to 20 wt %, 4 to 15 wt %, or 4 to 10 wt %, based on the total weight of the urethane (meth)acrylate.

[0043] In another embodiment, the weight content of the polyglycerin polyol units in the urethane (meth)acrylate can be 5 to 25 wt %, 10 to 25 wt %, 15 to 25 wt %, or 20 to 25 wt %, based on the total weight of the urethane (meth)acrylate.

[0044] The weight content of polyglycerin polyol units (% PG) in the urethane (meth)acrylate can be determined by the following formula: TIFF2024539932000006.tif12170[In the formula, m ポリグリセリン is the weight of polyglycerin polyol used to prepare the urethane (meth)acrylate (in grams), m ポリイソシアネート is the weight (in grams) of polyisocyanate used to prepare the urethane (meth)acrylate, m アクリレート is the weight (in grams) of hydroxy-functional (meth)acrylate used to prepare the urethane (meth)acrylate].

[0045] According to some embodiments, the polyglycerol polyols may have a number average molecular weight of at least 100 g / mol, preferably 100 to 10,000 g / mol, and more preferably 200 to 500 g / mol. For example, the polyglycerol polyols may have a number average molecular weight of 100 to 200 g / mol; or 200 to 400 g / mol; or 400 to 600 g / mol; or 600 to 800 g / mol; or 800 to 1,000 g / mol; or 1,000 to 1,500 g / mol; or 1,500 to 2,000 g / mol; or 2,000 to 2,500 g / mol; or 2,500 to 3,000 g / mol; or 3,000 to 3,500 g / mol; or 3,500 to 4,000 g / mol; or 4,000 to 4,500 g / mol; or 4,500 to 5,000 g / mol. or 6,000 to 6,500 g / mol; or 6,500 to 7,000 g / mol; or 7,000 to 7,500 g / mol; or 7,500 to 8,000 g / mol; or 8,000 to 8,500 g / mol; or 8,500 to 9,000 g / mol; or 9,000 to 9,500 g / mol; or 9,500 to 10,000 g / mol; or greater than 10,000 g / mol.

[0046] The number average molecular weight can be determined by the following formula: Mw = (56100 × F) / OHV [In the formula, F is the hydroxyl functionality of the polyglycerol polyol; OHV is the hydroxyl value of the polyglycerol polyol (in mg KOH / g)].

[0047] The urethane (meth)acrylates according to the invention are based on polyisocyanates, i.e., comprise one or more units derived from polyisocyanates. The urethane (meth)acrylates according to the invention can be based on mixtures of polyisocyanates.

[0048] "Polyisocyanate" means a compound having at least two -N=C=O groups. Accordingly, "diisocyanate" means a compound having two -N=C=O groups.

[0049] With regard to the polyisocyanate, this compound can be selected from aliphatic, cycloaliphatic, and aromatic polyisocyanates, and combinations thereof, more preferably aliphatic and cycloaliphatic polyisocyanates, and combinations thereof, and even more preferably the polyisocyanate can be a cycloaliphatic polyisocyanate.

[0050] According to a preferred embodiment, the polyisocyanate is a diisocyanate compound or a mixture of diisocyanate compounds.

[0051] According to one particular embodiment of the present invention, the diisocyanate can be represented by the following general formula (II): (II) OCN-X-NCO wherein X is a divalent organic moiety, such as a divalent hydrocarbon moiety. The divalent hydrocarbon moiety may be, for example, aliphatic (such as a straight-chain, branched-chain, or cyclic aliphatic moiety), aromatic, or araliphatic. The divalent organic moiety may contain, in addition to carbon and hydrogen atoms, one or more heteroatoms, such as N, O, or halogens.

[0052] Cycloaliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate or IPDI) can be utilized. Other suitable polyisocyanates can include, but are not limited to, toluene diisocyanate (TDI), diphenylmethane diisocyanate, dicyclohexyl diisocyanate, tetramethylxylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, hexamethylene diisocyanate (HDI), norborane diisocyanate (NBDI), trimethylene hexamethylene diisocyanate, naphthylene diisocyanate, and the like (including their isocyanate-functional biurets, allophonates, and isocyanurates). Mixtures of different polyisocyanates can also be used.

[0053] The weight content of the polyisocyanate unit in the urethane (meth)acrylate can be 10 to 70% by weight, preferably 15 to 65% by weight, and more preferably 20 to 60% by weight, based on the total weight of the urethane (meth)acrylate.

[0054] In one embodiment, the weight content of the polyisocyanate units in the urethane (meth)acrylate may be 20 to 55% by weight, 20 to 50% by weight, 20 to 45% by weight, 20 to 40% by weight, or 20 to 35% by weight, based on the total weight of the urethane (meth)acrylate.

[0055] In another embodiment, the weight content of the polyisocyanate units in the urethane (meth)acrylate may be 25 to 60%, 30 to 60% by weight, 35 to 60% by weight, 40 to 60% by weight, or 45 to 60% by weight, based on the total weight of the urethane (meth)acrylate.

[0056] The weight content of polyisocyanate units (%PI) in the urethane (meth)acrylate can be determined by the following formula: TIFF2024539932000007.tif12170[In the formula, m ポリグリセリン is the weight of polyglycerin polyol used to prepare the urethane (meth)acrylate (in grams), m ポリイソシアネート is the weight (in grams) of polyisocyanate used to prepare the urethane (meth)acrylate, m アクリレート is the weight (in grams) of hydroxy-functional (meth)acrylate used to prepare the urethane (meth)acrylate].

[0057] The urethane (meth)acrylates according to the invention are based on hydroxy-functional (meth)acrylates, i.e., comprise one or more units derived from hydroxy-functional (meth)acrylates. The urethane (meth)acrylates according to the invention can be based on a mixture of hydroxy-functional (meth)acrylates.

[0058] By "hydroxy-functional (meth)acrylate" is meant a compound containing at least one hydroxy group and at least one (meth)acrylate group (corresponding to the structure -OC(=O)-CH=CH2 or -OC(=O)-C(CH3)=CH2).

[0059] According to a preferred embodiment, the hydroxy-functional (meth)acrylate has a (meth)acrylate functionality (acrylate and / or methacrylate functionality) ranging from 1 to 5 (i.e., contains 1 to 5 (meth)acrylate functional groups per molecule).

[0060] According to some embodiments, the hydroxy-functional (meth)acrylate may preferably have one hydroxyl functionality.

[0061] Alternatively, the hydroxy-functional (meth)acrylate may have a hydroxyl functionality of 2 or more (ie, contain 2 or more hydroxyl groups per molecule).

[0062] The hydroxy-functional (meth)acrylates can be selected from hydroxyalkyl (meth)acrylates and alkoxylated hydroxyalkyl (meth)acrylates.

[0063] Suitable hydroxyalkyl (meth)acrylates include esters of acrylic and methacrylic acid, where the acid is esterified to provide the hydroxyalkyl group. The alkyl group may be, for example, a branched or linear C2-C6 group, such as ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, or decyl. 10The hydroxyl group may be an alkyl group. The hydroxyl group may be present at the terminal position of the alkyl group or along the chain of the alkyl group, and the hydroxyl group is preferably primary or secondary. The alkyl group may be optionally substituted with an aromatic group, a halogen, or the like. Multiple hydroxyl groups may be present on the alkyl group (e.g., glycerin mono(meth)acrylate, etc.). As mentioned above, the hydroxyalkyl(meth)acrylate may contain one, two, or more (meth)acrylate groups per molecule. Examples of hydroxyalkyl(meth)acrylates useful in the present invention include 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, and 3-chloro-2-hydroxypropyl(meth)acrylate. , glycerin mono- and di(meth)acrylate, 2-hydroxy-1-acryloxy-3-(meth)acryloxypropane, trimethylolpropane mono- and di(meth)acrylate, di(trimethylolpropane) mono-, di-, and tri(meth)acrylate, trimethylolethane mono- and di(meth)acrylate, pentaerythritol mono-, di-, and tri(meth)acrylate, dipentaerythritol mono-, di-, tri-, tetra-, and penta(meth)acrylate, and the like, and combinations thereof.

[0064] Suitable alkoxylated hydroxyalkyl (meth)acrylates include, but are not limited to, diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, ethylene / propylene mixed polyol monoesterified with a (meth)acrylate group, di(tetramethylene)glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, and the like, as well as combinations thereof. A preferred alkoxylated hydroxyalkyl (meth)acrylate is polyethylene glycol mono(meth)acrylate containing 2 to 20, preferably 5 to 10, ethylene glycol units.

[0065] Suitable hydroxyl-functional epoxy(meth)acrylates include, but are not limited to, monomeric and oligomeric compounds obtained by the reaction of an epoxy compound (e.g., an epoxy resin such as bisphenol A resin) with (meth)acrylic acid, where both hydroxyl and (meth)acrylate functionality are introduced by ring-opening of the epoxy group with the (meth)acrylic acid. Examples of suitable commercially available hydroxyl-functional epoxy(meth)acrylates include the CN132 and CN116 products sold by Sartomer (a division of Arkema), which are aliphatic epoxy acrylates having both methacrylate and secondary hydroxyl functionality by ring-opening of the epoxy group.

[0066] Suitable hydroxyl-functional polyester (meth)acrylates include, but are not limited to, mono(meth)acrylate esters of polyester polyols, where the polyester polyol is the condensation polymerization reaction product of a diacid and a diol.

[0067] Mixtures or combinations of different hydroxyl-functional (meth)acrylates can be utilized to form the urethane (meth)acrylates according to the present invention.

[0068] The weight content of the hydroxy-functional (meth)acrylate units in the urethane (meth)acrylate can be 20 to 80% by weight, preferably 25 to 75% by weight, more preferably 30 to 75% by weight, based on the total weight of the urethane (meth)acrylate.

[0069] In one embodiment, the weight content of the hydroxy-functional (meth)acrylate units in the urethane (meth)acrylate can be 30 to 55 wt %, 30 to 50 wt %, 30 to 45 wt %, 30 to 40 wt %, or 30 to 35 wt %, based on the total weight of the urethane (meth)acrylate.

[0070] In another embodiment, the weight content of the hydroxy-functional (meth)acrylate units in the urethane (meth)acrylate can be 35 to 75 wt %, 40 to 75 wt %, 45 to 75 wt %, 50 to 75 wt %, or 55 to 75 wt %, based on the total weight of the urethane (meth)acrylate.

[0071] The weight content of hydroxy-functional (meth)acrylate units (% HF) in a urethane (meth)acrylate can be determined by the following formula: TIFF2024539932000008.tif12170[In the formula, m ポリグリセリン is the weight of polyglycerin polyol used to prepare the urethane (meth)acrylate (in grams), m ポリイソシアネート is the weight (in grams) of polyisocyanate used to prepare the urethane (meth)acrylate, m アクリレート is the weight (in grams) of hydroxy-functional (meth)acrylate used to prepare the urethane (meth)acrylate].

[0072] As mentioned above, the urethane (meth)acrylate according to the present invention is a reaction product of the above compounds.

[0073] The urethane (meth)acrylate may have a backbone composed of units derived from a polyglycerol polyol and units derived from a polyisocyanate. Such units may alternate. Thus, the hydroxyl groups of the polyglycerol polyol can react with the isocyanate groups of the polyisocyanate to form urethane bonds. Thus, the isocyanate-derived units can be positioned between and bonded to the polyglycerol polyol units. Furthermore, the terminus of such a product may include units derived from a hydroxy-functional (meth)acrylate. In other words, such terminus may be formed after the isocyanate groups of the polyisocyanate and the hydroxyl groups of the hydroxy-functional (meth)acrylate react to form a urethane bond.

[0074] According to a preferred embodiment, the urethane (meth)acrylate consists essentially of, or consists of, units derived from a polyisocyanate, units derived from a polyglycerol polyol, and units derived from a hydroxy-functional (meth)acrylate.

[0075] The urethane (meth)acrylates according to the present invention may have a number average molecular weight of 1,000 to 50,000 g / mol, preferably 1,500 to 10,000 g / mol, more preferably 2,000 to 5,000 g / mol. For example, such number average molecular weight can be 1,000 to 5,000 g / mol; or 5,000 to 10,000 g / mol; or 10,000 to 15,000 g / mol; or 15,000 to 20,000 g / mol; or 20,000 to 25,000 g / mol; or 25,000 to 30,000 g / mol; or 30,000 to 35,000 g / mol; or 35,000 to 40,000 g / mol; or 40,000 to 45,000 g / mol; or 45,000 to 50,000 g / mol. Number average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene standards.

[0076] According to some embodiments, the urethane (meth)acrylate according to the present invention may have a linear structure. This is the case, for example, when the urethane (meth)acrylate contains hydroxyl residues. In other words, the secondary hydroxyl groups present in the polyglycerol glycol have not reacted with the polyisocyanate.

[0077] According to another embodiment, the urethane (meth)acrylate according to the present invention may have a branched structure. In this case, the secondary hydroxyl group of the polyglycerin polyol is reacted with the polyisocyanate. Therefore, in this case, the urethane (meth)acrylate may not have a hydroxyl group.

[0078] If the secondary hydroxyl groups present in the polyglycerol glycol are not reacted with the polyisocyanate, the water resistance and water solubility of the urethane (meth)acrylate will be higher. The reaction between the secondary hydroxyl groups present in the polyglycerol glycol and the polyisocyanate can be controlled by the reaction temperature (for example, at a low temperature, the reaction between the secondary hydroxyl groups and the polyisocyanate can be avoided) and the addition rate of the polyglycerol polyol during the reaction.

[0079] The urethane (meth)acrylate reaction product may have an OH value of from 50 mg KOH / g to 400 mg KOH / g, preferably from 100 mg KOH / g to 200 mg KOH / g.

[0080] The urethane (meth)acrylate may have an OH value of 0 mg KOH / g to 199 mg KOH / g, particularly 0.1 mg KOH / g to 190 mg KOH / g, more particularly 0.5 mg KOH / g to 180 mg KOH / g, and even more particularly 0.8 mg KOH / g to 170 mg KOH / g. For example, the urethane (meth)acrylate may have an OH value of 0 mg KOH / g to 50 mg KOH / g, particularly 0.1 mg KOH / g to 10 mg KOH / g. Alternatively, the urethane (meth)acrylate may have an OH value of 50 mg KOH / g to 199 mg KOH / g, particularly 70 mg KOH / g to 170 mg KOH / g.

[0081] The OH value of the urethane (meth)acrylate can be determined by titration. This procedure involves quantitatively reacting the hydroxyl group of the urethane (meth)acrylate with excess p-toluenesulfonyl isocyanate (TSI) to form an acidic carbamate. At the end of the reaction, water is added to convert the unreacted isocyanate to sulfonamide. The carbamate is titrated with t-butylammonium hydroxide by potentiometric titration in an essentially non-aqueous medium. The titration method can be as described in ASTM standard E1899-16.

[0082] Preferably, the urethane (meth)acrylate reaction product has the following general formula (III): JPEG2024539932000009.jpg36170

[0083] In this formula, X is a unit derived from a polyisocyanate, and X is as defined above.

[0084] R is a unit derived from a hydroxy-functional (meth)acrylate (such compounds are described above). Preferably, R may have the following general formula (IV): TIFF2024539932000010.tif29170

[0085] In this formula, R1 is selected from a hydrogen atom and a methyl group, and b is a number from 1 to 30, preferably from 1 to 10.

[0086] Furthermore, A may be a unit derived from a polyglycerol polyol (such compounds are also described above). Preferably, A may have the following general formula (V): TIFF2024539932000011.tif28170

[0087] In this formula, each Z is independently selected from a hydrogen atom or a group -C(=O)-NH-X-NH-C(=O)-OR.

[0088] c is a number from 1 to 19, preferably from 1 to 9.

[0089] Finally, in formula (III), n is a number from 1 to 30.

[0090] Method for obtaining urethane (meth)acrylate The present invention further relates to a method for obtaining urethane (meth)acrylates. According to a preferred embodiment, the implementation of such a method results in obtaining the above-mentioned urethane (meth)acrylates.

[0091] Such methods include a first step of reacting a polyisocyanate with a hydroxy-functional (meth)acrylate to form a isocyanate-functional adduct.

[0092] The polyisocyanate and hydroxy-functional (meth)acrylate can be as described above.

[0093] "Isocyanate-functional adduct" means the product of the polyaddition reaction of a polyisocyanate with a hydroxy-functional (meth)acrylate.

[0094] Such a process can be carried out, for example, in a reactor.

[0095] Ratio of polyisocyanate to hydroxy-functional (meth)acrylate, R 1 can be 0.2 to 0.9, preferably 0.5 to 0.8.

[0096] The above ratio R 1 can be calculated by the following formula: TIFF2024539932000012.tif12170[In the formula, n アクリレート is the number of moles of OH groups in the hydroxy-functional (meth)acrylate used to prepare the urethane (meth)acrylate, n ポリイソシアネート is the number of moles of NCO groups in the polyisocyanate used to prepare the urethane (meth)acrylate].

[0097] n アクリレート and n ポリイソシアネート The number of moles of can be calculated by the following formula: TIFF2024539932000013.tif12170[In the formula, m アクリレート is the weight (in grams) of the hydroxy-functional (meth)acrylate used to prepare the urethane (meth)acrylate; Mw アクリレート is the molecular weight of the hydroxy-functional (meth)acrylate in g / mole; f アクリレート The number of OH groups in the hydroxy-functional (meth)acrylate. TIFF2024539932000014.tif12170[In the formula, m ポリイソシアネート is the weight (in grams) of polyisocyanate used to prepare the urethane (meth)acrylate, Mw ポリイソシアネート is the molecular weight of the polyisocyanate in g / mole, f ポリイソシアネート is the number of NCO groups in the polyisocyanate].

[0098] According to some embodiments, the formation of the isocyanate-functional adduct can be carried out without the use of a catalyst.

[0099] According to other embodiments, the formation of the isocyanate-functional adduct can be carried out in the presence of a catalyst known as a urethane catalyst. As used herein, "urethane catalyst" refers to a substance capable of catalyzing the reaction between a hydroxyl group and an isocyanate group to form a urethane bond. Thus, a urethane catalyst can accelerate the rate at which such a reaction occurs at a given temperature and / or can achieve a target degree of completion of such a reaction at a lower temperature than the temperature at which the target degree of completion would be achieved in the absence of the urethane catalyst.

[0100] Any of the tin-based urethane catalysts known in the art can be utilized (e.g., dibutyltin dilaurate), however, according to certain embodiments, a non-tin urethane catalyst, or a combination of non-tin urethane catalysts, is used.

[0101] Suitable non-tin urethane catalysts include, for example, one or more non-tin urethane catalysts selected from the group consisting of bismuth carboxylate complexes (such as bismuth octanoate); zirconium acetylacetonate complexes; hafnium acetylacetonate complexes; titanium acetylacetonate complexes; zirconium β-diketiminate complexes; hafnium β-diketiminate complexes; titanium β-diketiminate complexes; zirconium amidinate complexes; hafnium amidinate complexes; titanium amidinate complexes; zinc carboxylate complexes; tertiary amines; imidazoles; N-heterocyclic carbenes; tetraalkylammonium (pseudo)halides; phosphines; and combinations thereof.

[0102] Typically, the urethane catalyst may be utilized in an amount of 0.0001 to 0.1 weight percent, based on the total weight of the urethane (meth)acrylate.

[0103] Such a step can be carried out at a temperature of 30 to 60°C, preferably 50 to 55°C.

[0104] The process according to the present invention further comprises a second step of reacting the isocyanate-functional adduct with a polyglycerin polyol to obtain a urethane (meth)acrylate. The polyglycerin polyol and the urethane (meth)acrylate may be as defined above.

[0105] The second step can be carried out, for example, by adding the polyglycerol polyol to the reactor containing the isocyanate-functional adduct. According to some preferred embodiments, this addition is carried out dropwise. Alternatively, this addition can be carried out batchwise (e.g., the polyglycerol polyol can be added to the reactor in one or more portions).

[0106] The rate of addition of polyglycerol polyol into the reactor can be faster for urethane (meth)acrylates having hydroxyl residues than for urethane (meth)acrylates lacking hydroxyl groups, thereby avoiding side reactions (especially reactions between the secondary hydroxyl groups of the polyglycerol polyol and the polyisocyanate).

[0107] For example, the addition rate of polyglycerin polyol can be 10 to 15 g / min in a 1,000 mL reactor for a urethane (meth)acrylate having an OH group, whereas the addition rate of polyglycerin polyol can be 2 to 3 g / min in a 1,000 mL reactor for a urethane (meth)acrylate without an OH group.

[0108] Ratio of polyglycerin polyol to polyisocyanate R 2 can be 0.1 to 0.8, preferably 0.2 to 0.5.

[0109] The above ratio R 2 can be calculated by the following formula: TIFF2024539932000015.tif12170[In the formula, n ポリグリセリン is the number of moles of OH groups in the polyglycerol polyol, n ポリイソシアネート is the number of moles of NCO groups in the polyisocyanate].

[0110] n ポリグリセリン and n ポリイソシアネート The number of moles of can be calculated by the following formula: TIFF2024539932000016.tif12170[In the formula, m ポリグリセリン is the weight of polyglycerin polyol used to prepare the urethane (meth)acrylate (in grams), Mw ポリグリセリン is the molecular weight of the polyglycerol polyol in g / mole, f ポリグリセリン is the number of OH groups in the polyglycerol polyol]. TIFF2024539932000017.tif12170[In the formula, m ポリイソシアネート is the weight (in grams) of polyisocyanate used to prepare the urethane (meth)acrylate, Mw ポリイソシアネート is the molecular weight of the polyisocyanate in g / mole, f ポリイソシアネート is the number of NCO groups in the polyisocyanate].

[0111] When the urethane (meth)acrylate has a hydroxyl residue, such a step can be carried out at a temperature of 55 to 70°C, preferably 60 to 65°C.

[0112] When the urethane (meth)acrylate does not have a hydroxy group, such a step can be carried out at a temperature of 75 to 85°C.

[0113] Additionally, to prevent undesired side reactions, an antioxidant (stabilizer), such as butylated hydroxytoluene, may be present during the reaction of the components used to prepare the oligomer, and / or the reaction mixture may be sparged with air while such reactions are occurring. Furthermore, the stoichiometry between the different components used to prepare the oligomer may be adjusted according to conventional practices to achieve a particular desired degree of polyurethane chain extension and / or end-group functionalization.

[0114] curable composition The present invention further relates to curable compositions. By "curable composition" is meant a composition that can be cured to provide a polymerized, hardened material.

[0115] The curable composition includes a urethane (meth)acrylate and an ethylenically unsaturated compound.

[0116] The urethane (meth)acrylate can be as described above.

[0117] The urethane (meth)acrylate may be present in the curable composition in a content of 95% by weight or less, preferably 1 to 95% by weight, more preferably 50 to 90% by weight, and even more preferably 65 to 85% by weight, relative to the total weight of the curable composition.

[0118] Ethylenically unsaturated compounds typically contain one or more ethylenically unsaturated functional groups per molecule, preferably one or more (meth)acrylic functional groups per molecule. As used herein, the term "(meth)acrylic functional group" refers to either an acryloyl functional group (-C(=O)-CH=CH2) or a methacryloyl functional group (-C(=O)-C(CH3)=CH2). The (meth)acrylic functional group can be contained in an acrylate, methacrylate, acrylamide, or methacrylamide functional group. A compound having a (meth)acrylic functional group is called a (meth)acrylic-functionalized compound.

[0119] Alternatively, the ethylenically unsaturated compound may contain other types of suitable ethylenically unsaturated functional groups, including, for example, vinyl functional groups and allyl functional groups.

[0120] The additional reactive component may be monomeric or oligomeric in nature, as described in more detail below.

[0121] According to some embodiments, the ethylenically unsaturated compound may comprise a (meth)acrylic-functionalized compound selected from a (meth)acrylic-functionalized monomer and a (meth)acrylic-functionalized oligomer.

[0122] Any of the (meth)acrylate-functionalized oligomers known in the art can be used in the curable compositions of the present invention. According to some embodiments, such oligomers contain two or more (meth)acrylate functional groups per molecule. The number average molecular weight of such oligomers can vary widely, for example, from about 500 to about 50,000.

[0123] Suitable (meth)acrylate-functionalized oligomers include, for example, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polyurethane (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, polydiene (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and combinations thereof. Such oligomers can be selected and used in combination with one or more (meth)acrylate-functionalized monomers to enhance properties such as flexibility, strength, and / or modulus of cured resin foams prepared using the multi-component systems of the present invention.

[0124] Exemplary polyester (meth)acrylate oligomers include the reaction product of acrylic acid or methacrylic acid, or a mixture thereof, with a hydroxyl-terminated polyester polyol. The reaction process can be carried out so that all or essentially all of the hydroxy groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyol can be produced by the polycondensation reaction of a polyhydroxyl-functional component (particularly a diol) with a polycarboxylic acid-functional compound (particularly a dicarboxylic acid and anhydride). The polyhydroxyl-functional component and the polycarboxylic acid-functional component can each have a linear, branched, alicyclic, or aromatic structure and can be used individually or in mixtures.

[0125] Examples of suitable epoxy (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid, or mixtures thereof, with glycidyl ethers or esters.

[0126] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic acid or methacrylic acid or a mixture thereof with a polyetherol, such as a polyether polyol (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxy groups. Polyetherols can be prepared by the ring-opening polymerization of cyclic ethers, such as tetrahydrofuran or alkylene oxides, with a starter molecule. Suitable starter molecules include water, polyhydroxyl-functional materials, polyester polyols, and amines.

[0127] Polyurethane (meth)acrylate oligomers (sometimes referred to as "urethane (meth)acrylate oligomers") that can be used in the multi-component systems of the present invention include urethanes based on aliphatic and / or aromatic polyester polyols and polyether polyols, and aliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates capped with (meth)acrylate end groups. Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane diacrylate and tetraacrylate oligomers, aliphatic polyether-based urethane di- and tetra-acrylate oligomers, and aliphatic polyester / polyether-based urethane di- and tetra-acrylate oligomers.

[0128] In various embodiments, polyurethane (meth)acrylate oligomers can be prepared by reacting aliphatic and / or aromatic diisocyanates with OH-terminated polyester polyols (including aromatic, aliphatic, and mixed aliphatic / aromatic polyester polyols), polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g., polydimethylsiloxane polyols), or polydiene polyols (e.g., polybutadiene polyols), or combinations thereof, to form isocyanate-functionalized oligomers, which can then be reacted with hydroxy-functionalized (meth)acrylates, such as hydroxyethyl acrylate or hydroxyethyl methacrylate, to provide terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers can contain two, three, four, or more (meth)acrylate functional groups per molecule.

[0129] Suitable acrylic (meth)acrylate oligomers (also referred to in the art as "acrylic oligomers") include oligomers that can be described as materials having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups, which can be terminal to the oligomer or pendant to the acrylic backbone. The acrylic backbone can be a homopolymer, random copolymer, or block copolymer composed of repeating units of acrylic monomers. The acrylic monomers can be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates bearing hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, such as oligomerizing monomers at least some of which are functionalized with hydroxy, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to provide a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0130] Exemplary (meth)acrylate functionalized monomers and oligomers 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 (wherein 600 refers to the approximate number average molecular weight of the polyethylene glycol portion); Polyethylene glycol (200) diacrylate; 1,12-dodecanediol dimethacrylate; Tetraethylene glycol diacrylate; Triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, Tripropylene glycol diacrylate, Polybutadiene diacrylate; Methylpentanediol diacrylate; Polyethylene glycol (400) diacrylate; Ethoxylated 2 bisphenol A dimethacrylate; Ethoxylated 3 bisphenol A dimethacrylate; Ethoxylated 3 bisphenol A diacrylate; Cyclohexanedimethanol dimethacrylate; Cyclohexanedimethanol diacrylate; Ethoxylated 10 Bisphenol A dimethacrylate (where the number after "ethoxylated" is the average number of oxyalkylene moieties per molecule); dipropylene glycol diacrylate; ethoxylated 4 bisphenol A dimethacrylate; ethoxylated 6 bisphenol A dimethacrylate; ethoxylated 8 bisphenol A dimethacrylate; alkoxylated hexanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; dodecane diacrylate; ethoxylated 4 bisphenol A diacrylate; ethoxylated 10Bisphenol A diacrylate;Polyethylene glycol (400) dimethacrylate;Polypropylene glycol (400) dimethacrylate;Metal diacrylates;Modified metal diacrylates;Metal dimethacrylates;Polyethylene glycol (1000) dimethacrylate;Methacrylated polybutadiene;Propoxylated 2-neopentyl glycol diacrylate;Ethoxylated 30 Bisphenol A dimethacrylate; ethoxylated 30 Bisphenol A diacrylate;Alkoxylated neopentyl glycol diacrylate;Polyethylene glycol dimethacrylate;1,3-butylene glycol diacrylate;Ethoxylated 2 bisphenol A dimethacrylate;Dipropylene glycol diacrylate;Ethoxylated 4 bisphenol A diacrylate;Polyethylene glycol (600) diacrylate;Polyethylene glycol (1000) dimethacrylate;Tricyclodecane dimethanol diacrylate;Propoxylated 2 neopentyl glycol diacrylate;Alcohol-alkoxylated aliphatic diacrylates, alcohols Trimethylolpropane trimethacrylate;Trimethylolpropane triacrylate;Tris(2-hydroxyethyl) isocyanurate triacrylate;Ethoxylated 20 Trimethylolpropane triacrylate;Pentaerythritol triacrylate;Ethoxylated 3 trimethylolpropane triacrylate;Propoxylated 3 trimethylolpropane triacrylate;Ethoxylated 6 trimethylolpropane triacrylate;Propoxylated 6 trimethylolpropane triacrylate;Ethoxylated 9 trimethylolpropane triacrylate;Alkoxylated trifunctional acrylate esters;Trifunctional methacrylate esters;Trifunctional acrylate esters;Propoxylated 3 glyceryl triacrylate;Propoxylated 5.5 Glyceryl triacrylate; ethoxylated 15Examples of the polymerizable monomer include trimethylolpropane triacrylate, trifunctional phosphate esters, trifunctional acrylic esters, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, ethoxylated 4-pentaerythritol tetraacrylate, pentaerythritol polyoxyethylene tetraacrylate, dipentaerythritol pentaacrylate, pentaacrylate esters, epoxy acrylate oligomers, epoxy methacrylate oligomers, urethane acrylate oligomers, urethane methacrylate oligomers, polyester acrylate oligomers, polyester methacrylate oligomers, stearyl methacrylate oligomers, acrylic acrylate oligomers, perfluorinated acrylate oligomers, perfluorinated methacrylate oligomers, aminoacrylate oligomers, amine-modified polyether acrylate oligomers, and amino methacrylate oligomers.

[0131] According to some embodiments, the ethylenically unsaturated compound may comprise a (meth)acrylate-functionalized compound containing a single acrylate or methacrylate functional group per molecule (referred to herein as a "mono(meth)acrylate-functionalized compound"). Any such compound known in the art may be used.

[0132] Examples of suitable mono(meth)acrylate functionalized compounds include mono-(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or cycloaliphatic and may be a mono-, di-, or polyalcohol, but where only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono-(meth)acrylate esters of oligomeric and polymeric glycols, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol. mono-(meth)acrylate esters of monoalkyl ethers of glycols, oligomeric glycols, polymeric glycols; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) fatty alcohols (wherein the fatty alcohol may be linear, branched, or alicyclic and may be a mono-alcohol, di-alcohol, or polyalcohol, provided that only one hydroxyl group of the alkoxylated fatty alcohol is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylate; and the like.

[0133] The following compounds are specific examples of mono(meth)acrylate-functionalized compounds suitable for use in 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 ( METHACRYLATES;TRIDECYL(METH)ACRYLATE;TETRADECYL(METH)ACRYLATE;HEXADECYL(METH)ACRYLATE;2-HYDROXYETHYL(METH)ACRYLATE;2- AND 3-HYDROXYPROPYL(METH)ACRYLATE;2-METHOXYETHYL(METH)ACRYLATE;2-ETHOXYETHYL(METH)ACRYLATE;2- AND 3-ETHOXYPROPYL(METH)ACRYLATE;TETRAHYDROFURFURYL(METH)ACRYLATE;ALKOXYLATED TETRAHYDROFURFURYL(METH)ACRYLATE;ISOMETHYL(METH)ACRYLATE Bornyl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; lauryl (meth)acrylate; isobornyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (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; and combinations thereof.

[0134] The ethylenically unsaturated compound may comprise a (meth)acrylamide monomer. Examples of suitable (meth)acrylamide monomers include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, isopropyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-cyclopentyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N,N-dibutyl (meth)acrylamide, N-butyl (meth)acrylamide, diacetone (meth)acrylamide, N-(N,N-dimethylamino)ethyl (meth)acrylamide, N,-(N,N-dimethylamino)propyl (meth)acrylamide, N,N-diethyl(meth)acrylamide; N,N-dimethyl(meth)acrylamide; N-octyl(meth)acrylamide; N-decyl(meth)acrylamide; N-dodecyl(meth)acrylamide; N-octadecyl(meth)acrylamide; N-isopropyl(meth)acrylamide; N-tert-butyl(meth)acrylamide; N-isobutyl(meth)acrylamide, N,N,3,3-tetramethylacrylamide; N-methylol(meth)acrylamide; N-[2-hydroxyethyl](meth)acrylamide; N-phenyl(meth)acrylamide; acryloylmorpholine; and combinations thereof.

[0135] According to a preferred embodiment, the ethylenically unsaturated compound may be selected from mono- or polyfunctional (meth)acrylic monomers or oligomers, more preferably from acryloylmorpholine and polyethylene glycol di(meth)acrylate.

[0136] The ethylenically unsaturated compound may be present in the curable composition in an amount of at least 5% by weight, preferably 5 to 99% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 35% by weight, based on the total weight of the curable composition.

[0137] The curable composition according to the present invention may further comprise one or more additives. Such additives include, but are not limited to, stabilizers, photoinitiators, antioxidants / light stabilizers, light screeners / absorbers, polymerization inhibitors, antifoaming agents, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, chain transfer agents, thixotropic agents, matting agents, impact modifiers, waxes, or various other additives, including any of the additives conventionally used in coating, sealant, adhesive, molding, 3D printing, or ink technology. Such additives may be present in an amount of up to 15 wt. %, preferably up to 10 wt. %, based on the total weight of the curable composition.

[0138] With regard to stabilizers, these components can provide sufficient storage stability and shelf life. To prevent undesired reactions of the components of the curable composition (especially those components of the curable composition having (meth)acrylate functionality), it is advantageous to have one or more such stabilizers present at each stage of the process used to prepare the curable composition. As used herein, the term "stabilizer" refers to a compound or substance that retards or prevents the reaction or curing of (meth)acrylate functional groups present in the composition in the absence of actinic radiation. However, it is advantageous to select the amount and type of stabilizer so that the composition remains curable upon exposure to actinic radiation (i.e., the stabilizer does not interfere with radiation curing of the composition). Typically, stabilizers useful for purposes of the present invention are classified as free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions).

[0139] Any stabilizer known in the art related to (meth)acrylate-functionalized compounds can be used in the present invention.Quinones are a particularly preferred type of stabilizer that can be used in the context of the present invention.As used herein, the term "quinone" includes both quinone and hydroquinone, as well as their ethers, such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone.Hydroquinone monomethyl ether is one example of a suitable stabilizer that can be used.

[0140] The concentration of stabilizer in the curable composition will vary depending on the particular stabilizer or combination of stabilizers selected for use, as well as the degree of stabilization desired and the susceptibility of the components in the curable composition to degradation in the absence of the stabilizer. Typically, however, curable compositions are formulated to contain 50 to 5,000 ppm of stabilizer. According to certain embodiments, the reaction mixture at each stage of the process used to prepare the curable composition contains at least some stabilizer, e.g., at least 50 ppm of stabilizer.

[0141] According to some embodiments, the curable compositions described herein can include at least one photoinitiator. A photoinitiator can be considered any type of substance that, upon exposure to radiation (e.g., actinic radiation), forms a species that initiates reaction and curing of polymerized organic materials present in the curable composition. Suitable photoinitiators include both free-radical and cationic photoinitiators, and combinations thereof.

[0142] A free radical polymerization initiator is a substance that forms free radicals when irradiated. In particular, the use of free radical photoinitiators is preferred. Non-limiting examples of free radical photoinitiators suitable for use in the curable compositions of the present invention include benzoin, benzoin ethers, acetophenone, benzil, benzil ketals, anthraquinone, phosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, and triazine compounds.

[0143] The amount of photoinitiator can vary depending on the photoinitiator(s) selected, the amount and type of polymerizable species present in the curable composition, the radiation source and radiation conditions used, and other factors. Typically, however, the amount of photoinitiator can be from 0.05% to 5% by weight, preferably from 0.1% to 2% by weight, based on the total weight of the curable composition.

[0144] Additionally, the curable compositions of the present invention may contain one or more light-blocking agents (sometimes referred to in the art as absorbers), particularly when the curable compositions are used as resins in three-dimensional printing methods involving photocuring of the curable compositions. The light-blocking agent(s) may be any such material known in three-dimensional printing technology, including, for example, non-reactive pigments and dyes. The light-blocking agent may be, for example, a visible light blocker or a UV light blocker. Examples of suitable light-blocking agents include, but are not limited to, titanium dioxide, carbon black, and organic UV absorbers such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, Sudan I, bromothymol blue, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) (sold under the brand name "Benetex OB Plus"), and benzotriazole UV absorbers.

[0145] The amount of light-blocking agent can be varied as needed or for a particular application. Generally, when the curable composition includes a light-blocking agent, it is present in a concentration of 0.001 to 10% by weight, based on the total weight of the curable composition.

[0146] Advantageously, the curable compositions of the present invention can be formulated to be solvent-free, i.e., free of non-reactive volatile materials (materials having a boiling point of 150° C. or less at atmospheric pressure). For example, the curable compositions of the present invention may contain little or no non-reactive solvent, such as less than 10%, or less than 5%, or less than 1%, or even 0% non-reactive solvent, based on the total weight of the curable composition.

[0147] Use of the curable composition As mentioned above, curable compositions according to the present invention may include one or more photoinitiators and may be photocurable.

[0148] Alternatively, the curable composition according to the present invention may be initiator-free and curable (at least partially) by electron beam energy.

[0149] Alternatively, the curable composition according to the present invention may include at least one free radical initiator that decomposes upon heating or in the presence of an accelerator and is chemically curable (i.e., the curable composition does not need to be exposed to radiation). The at least one free radical initiator that decomposes upon heating or in the presence of an accelerator may include, for example, a peroxide or an azo compound. Suitable peroxides for this purpose include any compound, particularly any organic compound, containing at least one peroxy (—OO—) moiety, such as dialkyl, diaryl, and aryl / alkyl peroxides, hydroperoxides, percarbonates, peresters, peracids, acyl peroxides, etc. The at least one accelerator may include, for example, at least one tertiary amine and / or one or more other reducing agents based on metal-containing salts (e.g., carboxylates of transition metals such as iron, cobalt, manganese, vanadium, etc., and combinations thereof). The accelerator(s) can be selected to accelerate the decomposition of the free radical initiator to generate active free radical species at room or ambient temperature, such that curing of the curable composition is achieved without heating or baking the curable composition. In other embodiments, no accelerator is present, and the curable composition is heated to a temperature effective to cause decomposition of the free radical initiator to generate free radical species that initiate curing of the polymerizable compound(s) present in the curable composition.

[0150] The urethane (meth)acrylate may have a viscosity of 100 to 100,000 mPa·s at 60° C., preferably 200 to 20,000 mPa·s at 60° C. The viscosity is measured with a rotational Brookfield viscometer using either ASTM standard D1084 or ASTM standard D2556.

[0151] The curable compositions described herein can be compositions that undergo curing by free radical polymerization, cationic polymerization, or other types of polymerization. One or more initiators, such as free radical initiators (e.g., photoinitiators, peroxide initiators), may be present in the curable composition.

[0152] In certain embodiments, the curable composition is photocured (ie, cured by exposure to actinic radiation such as light, especially visible or UV light).

[0153] End uses of the curable compositions include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (such as 3D printing resins), molding resins, sealants, composites, antistatic layers, electronic applications, reusable materials, smart materials that can sense and respond to stimuli, and biomedical materials.

[0154] Cured compositions prepared from the curable compositions described herein can be used, for example, in three-dimensional articles (where the three-dimensional article can consist essentially of or consist of the cured composition), coated articles (including encapsulated articles in which a substrate is coated with one or more layers of the cured composition such that the substrate is completely encased in the cured composition), laminated or bonded articles (in which a first component of an article is laminated or bonded to a second component by the cured composition), composite articles, or printed articles (in which the cured composition is used to print a graphic or the like onto a substrate such as paper, plastic, or an M-containing substrate).

[0155] Before curing, the curable composition can be applied to the substrate surface by any known conventional method, such as spraying, knife coating, roller coating, casting, drum coating, dipping, etc., and combinations thereof. Indirect application using a transfer process can also be used. The substrate can be any commercially relevant substrate, such as a high-surface energy substrate or a low-surface energy substrate, such as a metal substrate or a plastic substrate, respectively. Substrates include metal, paper, cardboard, glass, thermoplastics such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS), and blends thereof, composites, wood, leather, and combinations thereof. When used as an adhesive, the curable composition can be placed between two substrates and then cured, and the cured composition bonds the substrates to form a bonded article. The curable composition according to the present invention can also be formed or cured in a bulk manner (e.g., the curable composition can be poured into a suitable mold and then cured).

[0156] Curing can be accelerated or facilitated by providing energy to the curable composition, such as by heating the curable composition and / or exposing the curable composition to a radiation source, such as visible or UV light, infrared light, and / or electron beam radiation. Thus, the cured composition can be considered the reaction product of the curable composition formed by curing. The curable composition can be partially cured by exposure to actinic radiation, and further curing can be achieved by heating the partially cured article. For example, an article (e.g., a 3D printed article) formed from the curable composition can be heated at a temperature of 40°C to 120°C for 5 minutes to 12 hours.

[0157] Multiple layers of a curable composition according to the present invention can be applied to a substrate surface; the multiple layers can be cured simultaneously (e.g., by a single radiation exposure), or each layer can be cured sequentially before an additional layer of the curable composition is applied.

[0158] The curable compositions described herein can be used as resins in three-dimensional printing applications. Three-dimensional (3D) printing (also known as additive manufacturing) is a process of building materials to produce 3D digital models. 3D printed objects are produced by utilizing computer-aided design (CAD) data of an object and sequentially building two-dimensional (2D) layers or slices corresponding to cross sections of the 3D object. Stereolithography (SL) is a type of additive manufacturing method in which a liquid resin is cured by selectively exposing it to radiation to form each 2D layer. The radiation can be in the form of electromagnetic waves or an electron beam. The most commonly applied energy sources are ultraviolet, visible light, or infrared light. Thus, the curable compositions described herein can be used as 3D printing resin formulations intended for use in producing three-dimensional articles using 3D printing techniques. Such three-dimensional articles can be freestanding / self-supporting and can consist essentially of, or consist of, the cured compositions according to the present invention. The three-dimensional article may also be a composite material comprising at least one component consisting essentially of, or consisting of, the cured composition described above, and at least one additional component consisting of one or more materials other than the cured composition (e.g., a metal component or a thermoplastic component). The curable compositions of the present invention are particularly useful in digital light printing (DLP), but other types of three-dimensional (3D) printing methods (e.g., SLA, inkjet) can also be performed using the curable compositions of the present invention. The curable compositions of the present invention can be used in three-dimensional printing operations together with another material that serves as a scaffold or support for the article formed from the curable composition of the present invention.

[0159] The curable compositions of the present invention are therefore useful in implementing various types of three-dimensional manufacturing or printing techniques, including methods in which a three-dimensional object is built up stepwise or layer by layer. In such methods, layer formation can be achieved by solidifying (curing) the curable composition under the action of exposure to radiation, such as visible light, UV, or other actinic radiation. For example, new layers can be formed on the top or bottom surface of a growing object. The curable compositions of the present invention can also be advantageously used in methods for producing three-dimensional objects by continuous additive manufacturing. For example, objects can be generated from a liquid interface. Suitable methods of this type are sometimes referred to in the art as "continuous liquid interface (or interphase) production (or printing)" ("CLIP") methods. Such methods are described, for example, in International Publication Nos. WO 2014 / 126830; WO 2014 / 126834; WO 2014 / 126837; and Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects," Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015), the disclosures of which are incorporated herein by reference in their entirety for all purposes.

[0160] When stereolithography is performed on an oxygen-permeable build window, the CLIP procedure can be used to fabricate products using the curable composition of the present invention by creating an oxygen-containing "dead zone," a thin, uncured layer of the curable composition, between the window and the surface of the cured article being fabricated. Such processes use curable compositions whose cure (polymerization) is inhibited by the presence of molecular oxygen; such inhibition is typically observed, for example, in curable compositions that are curable by a free-radical mechanism. The desired dead zone thickness can be maintained by selecting various control parameters, such as the photon flux and the optical and cure properties of the curable composition. The CLIP process proceeds by projecting a continuous sequence of actinic radiation (e.g., UV) images (which may be generated by a digital light processing image unit, for example) through an oxygen-permeable, actinic radiation (e.g., UV)-transparent window below a bath of the curable composition maintained in liquid form. The liquid interface below the advancing (growing) object is maintained by the dead zone created above the window. The curing article is continuously withdrawn from the bath of curable composition above the dead zone, which can be replenished by supplying additional amounts of curable composition to the bath to make up for the amount of curable composition that is incorporated into the growing article as it hardens. [Example]

[0161] The following examples illustrate the invention without limiting it.

[0162] Materials and Methods The following compounds were used in the examples: TIFF2024539932000018.tif194170

[0163] The following methods were used to measure various properties of the examples:

[0164] water resistance: Water resistance can be evaluated by the degree of hydrophilicity, with a higher value indicating higher hydrophilicity. To measure water resistance, 0.5 g of urethane (meth)acrylate was mixed with 10 mL of tetrahydrofuran in a 100 mL beaker at 25°C, dispersed, and then added to the mixture using a burette. Ion-exchanged water was gradually added, and the amount (mL) of ion-exchanged water required to make the mixture cloudy was measured. This amount (mL) of ion-exchanged water was defined as the water resistance capacity.

[0165] Water soluble: Water solubility was measured by mixing the urethane (meth)acrylate with water and then determining the level at which incompatibility was indicated by either turbidity or phase separation. 10.0 g of the urethane (meth)acrylate was mixed and dispersed in 90 mL of water at 25° C. The mixed solution was kept at 25° C. for 1 hour, and the water solubility was defined as follows: 1: Non-soluble 2: Partially dissolved, phase separation or cloudiness occurs after 1 hour 3: Completely dissolved, but phase separation or cloudiness occurs after 1 hour 4: Completely dissolved, no phase separation or cloudiness occurs after 1 hour.

[0166] Tensile testing (tensile stress, tensile modulus, and elongation) The elongation at break (machine direction), tensile stress, and modulus of elasticity of cured specimens (dumbbell No. 5) with thicknesses of 30 to 100 μm were measured in accordance with JIS K 7127:1999 and JIS K 7161:1994. The distance between the grips was 8 cm. The initial specimen length used to calculate the elongation at break was the length of the narrow part of the specimen (2.5 cm). The strain rate was 3 cm / min. The tensile stress value was recorded just before the specimen broke.

[0167] Pendulum stiffness Pendulum hardness was measured on 10 micron thick hardened samples with a pendulum hardness tester according to ISO 1522:2006 by the SP0505 Koenig method. number average molecular weight The number average molecular weight was determined by gel permeation chromatography (GPC) using polystyrene standards under the following GPC measurement conditions: Model: Alliance, Waters Corporation high performance liquid chromatograph system - Column: SHODEX GPC KF-G / -401HQ / -402.5HQ / -403HQ (4.6 x 250 mm) - Eluent: THF - Flow rate: 0.45mL / min - Temperature: 40℃ - Sample injection volume and concentration: 5 μL, 10 mg / mL - Detection: RI (differential refractometer) - Data collection and processing system: Waters Empower3

[0168] viscosity Viscosity was measured at 60°C using a rotational Brookfield viscometer. As is known in the art, various ASTM methods (such as ASTM D1084 and ASTM D2556) can be used to measure viscosity using a rotational Brookfield viscometer, all of which are very similar, with the spindle size selected to provide between 50% and 70% torque. The particular ASTM method was selected based on factors such as how viscous the liquid sample was and whether the liquid was a Newtonian or non-Newtonian fluid.

[0169] Examples 1-11 are in accordance with the present invention, while Examples 12-15 are comparative examples. In Comparative Examples 12-14, the polyglycerin polyol was replaced with a different polyol outside the scope of the present invention. Comparative Example 15 is obtained by using a (meth)acrylate having NCO functionality instead of the polyisocyanate and the hydroxy-functional (meth)acrylate.

[0170] Example 1 (according to the present invention) 43.3 g of IPDI, 0.1 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 30.20 g of HEA was added dropwise while blowing dry air into the mixture, and the mixture was reacted at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 20.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 6.3 g of R-PG was then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of the R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 75-85 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 22,500 mPa·s at 60 °C. The final resin consisted of 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate had an Mn of 2,550 g / mol. The OH value of the urethane acrylate is 0.9 mg KOH / g.

[0171] Example 2 (according to the present invention) 38.75 g of IPDI, 0.1 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 24.30 g of HEA was added dropwise while blowing dry air through the mixture, and the mixture was reacted at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 6.75 g of R-PG was then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of the R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 75-85 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 15,800 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 2,720 g / mol. The OH value of the urethane acrylate is 1.0 mg KOH / g.

[0172] Example 3 (according to the present invention) 37.80 g of IPDI, 0.2 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 24.30 g of HEA was added dropwise while blowing dry air into the mixture, and the mixture was reacted at 50–60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 8.15 g of PGL-06 was then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of PGL-06 to react with the isocyanate-functional adduct. The mixture was reacted at 75–85 °C for 2–4 hours. The final resin was a clear, colorless material with a viscosity of 17,250 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 3,170 g / mol. The OH value of the urethane acrylate is 1.0 mg KOH / g.

[0173] Example 4 (according to the present invention) 25.9 grams of IPDI, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1 L reactor. 49.3 grams of EA-051 were added dropwise while blowing dry air through the mixture, and the mixture was allowed to react for 2 hours at 50-60°C to form an isocyanate-functional adduct. 20.0 grams of ACMO were added to the mixture, which was then heated to 75°C. 4.5 grams of R-PG were then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of the R-PG to react with the isocyanate-functional adduct. The mixture was allowed to react for 2-4 hours at 75-85°C. The final resin was a clear, colorless material with a viscosity of 1,630 mPa·s at 60°C. The final resin contained 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate had an Mn of 3,250 g / mol. The OH value of the urethane acrylate is 1.0 mg KOH / g.

[0174] Example 5 (according to the present invention) 19.8 grams of IPDI, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1000 mL reactor. 56.45 grams of AE-400 were added dropwise while blowing dry air into the mixture, and the mixture was allowed to react at 50-60°C for 2 hours to form an isocyanate-functional adduct. 20.0 grams of ACMO were added to the mixture, which was then heated to 75°C. 3.45 grams of R-PG were then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of the R-PG to react with the isocyanate-functional adduct. The mixture was allowed to react at 75-85°C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 1,850 mPa·s at 60°C. The final resin contained 80% by weight of urethane acrylate and 20% by weight of ACMO. The urethane acrylate has an Mn of 4,400 g / mol. The OH value of the urethane acrylate is 0.8 mg KOH / g.

[0175] Example 6 (according to the present invention) 34.0 g of IPDI, 0.2 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 21.40 g of HEA was added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, and the reactor temperature was maintained at 60 °C. Next, 14.30 g of R-PG was added very quickly to the mixture, allowing the primary hydroxyl functionality of the R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 60-65 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 2,670 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 1,860 g / mol. The OH value of the urethane acrylate is 140 mg KOH / g.

[0176] Example 7 (according to the present invention) 24.0 grams of IPDI, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1 L reactor. 45.50 grams of EA-051 were added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 20.0 grams of ACMO were added to the mixture, and the reactor temperature was maintained at 60 °C. Next, 10.20 grams of R-PG were added very quickly to the mixture, allowing the primary hydroxyl functionality of the R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 60-65 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 900 mPa·s at 60 °C. The final resin contained 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate had an Mn of 2,200 g / mol. The OH value of the urethane acrylate is 108 mg KOH / g.

[0177] Example 8 (according to the present invention) 23.02 grams of IPDI, 0.08 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1 L reactor. 48.80 grams of EA-051 were added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60°C for 2 hours to form an isocyanate-functional adduct. 20.0 grams of SR252NS was added to the mixture, and the reactor temperature was maintained at 60°C. Next, 8.0 grams of R-PG was added very quickly to the mixture, allowing the primary hydroxyl functionality of the R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 60-65°C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 700 mPa·s at 60°C. The final resin contained 80% by weight of urethane acrylate and 20% by weight of SR252NS. The urethane acrylate has an Mn of 1,970 g / mol. The OH value of the urethane acrylate is 88 mg KOH / g.

[0178] Example 9 (according to the present invention) 20.85 grams of IPDI, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1 mL reactor. 43.95 grams of EA-051 was added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 20.0 grams of ACMO was added to the mixture, and the reactor temperature was maintained at 60 °C. Next, 14.90 grams of PGL-06 was added very quickly to the mixture, allowing the primary hydroxyl functionality of R-PG to react with the isocyanate-functional adduct. The mixture was allowed to react at 60-65 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 650 mPa·s at 60 °C. The final resin contained 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate has an Mn of 2,090 g / mol. The OH value of the urethane acrylate is 147 mg KOH / g.

[0179] Example 10 (according to the present invention) 18.65 grams of IPDI, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1 L reactor. 53.15 grams of AE-400 were added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 20.0 grams of ACMO were added to the mixture, and the reactor temperature was maintained at 60 °C. Next, 7.9 grams of R-PG were added very quickly to the mixture, allowing the primary hydroxyl functionality of the R-PG to react with the isocyanate-functional adduct. The mixture was allowed to react at 60-65 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 1,120 mPa·s at 60 °C. The final resin contained 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate had an Mn of 3,120 g / mol. The OH value of the urethane acrylate is 75 mg KOH / g.

[0180] Example 11 (according to the present invention) 30.0 g of IPDI, 0.2 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 23.60 g of HEA was added dropwise while blowing dry air through the mixture, and the reaction was carried out at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, and the reactor temperature was maintained at 60 °C. Next, 16.10 g of PGL-06 was added very quickly to the mixture, allowing the primary hydroxyl functionality of R-PG to react with the isocyanate-functional adduct. The mixture was reacted at 60-65 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 920 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 1,750 g / mol. The OH value of the urethane acrylate is 155 mg KOH / g.

[0181] Example 12 (Comparative Example) 40.1 g of IPDI, 0.1 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 25.20 g of HEA was added dropwise while blowing dry air into the mixture, and the mixture was reacted at 50–60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 4.75 g of glycerol was then added dropwise to the mixture, allowing the primary and secondary hydroxyl functional groups of the glycerol to react with the isocyanate-functional adduct. The mixture was reacted at 75–85 °C for 2–4 hours. The final resin was a clear, colorless material with a viscosity of 10,650 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had a Mn of 2,200 g / mol.

[0182] Example 13 (Comparative Example) 38.3 g of IPDI, 0.1 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 24.05 g of HEA was added dropwise while blowing dry air into the mixture, and the mixture was allowed to react at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 7.45 g of DEG was then added dropwise to the mixture. The mixture was allowed to react at 75-85 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 870 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 1,750 g / mol.

[0183] Example 14 (Comparative Example) 24.05 g of IPDI, 0.1 g of butylated hydroxytoluene, and 0.1 g of dibutyltin dilaurate were placed in a 1 L reactor. 15.1 g of HEA was added dropwise while blowing dry air through the mixture, and the mixture was allowed to react at 50-60 °C for 2 hours to form an isocyanate-functional adduct. 30.0 g of ACMO was added to the mixture, which was then heated to 75 °C. 30.65 g of PTMG was then added dropwise to the mixture. The mixture was allowed to react at 75-85 °C for 2-4 hours. The final resin was a clear, colorless material with a viscosity of 480 mPa·s at 60 °C. The final resin consisted of 70 wt% urethane acrylate and 30 wt% ACMO. The urethane acrylate had an Mn of 2,150 g / mol.

[0184] Example 15 (Comparative Example) 20.3 grams of R-PG, 0.2 grams of butylated hydroxytoluene, and 0.1 grams of dibutyltin dilaurate were placed in a 1000 mL reactor. 59.40 grams of AOI-VM were added dropwise while blowing dry air into the mixture, and the mixture was allowed to react at 55-60°C for 2 hours. 20.0 grams of ACMO was added to the mixture, and the mixture was allowed to react at 60°C for 2 hours. The final resin was a clear, colorless material with a viscosity of 560 mPa·s at 60°C. The final resin contained 80 wt% urethane acrylate and 20 wt% ACMO. The urethane acrylate had an Mn of 1,240 g / mol.

[0185] Example 16 (Comparative Example) A urethane (meth)acrylate was synthesized by reproducing Synthesis Example 1 of JP 2021-046483 A. The final resin was a cloudy white substance with a viscosity of 180,000 mPa·s at 60°C. The urethane (meth)acrylate had an OH value of more than 200 mg KOH / g and a weight content of polyglycerin polyol units of more than 50 wt.% based on the total weight of the urethane (meth)acrylate.

[0186] Example 17 The above formulation was cured using the following process:

[0187] Each formulation (resin) was mixed with 5% by weight Irgacure 184, based on the weight of the polymerizable compound. The blend was coated onto a 100 μm PET film using a #10 to #50 application wire rod. The coated substrate was exposed to 400 to 1,000 mJ / cm. 2 The coating was cured in a UV curing device equipped with a 1000 W Hg lamp at a speed of 15 m / min. TIFF2024539932000019.tif149170

[0188] From the above data, it can be concluded that the formulations according to the invention (Examples 1 to 11) make it possible to obtain cured products exhibiting high hydrophilicity compared to the comparative formulations (Examples 12 to 16). Urethane (meth)acrylates based on polyethylene glycol mono(meth)acrylate as the hydroxy-functional (meth)acrylate have the highest hydrophilicity and good elongation. Urethane (meth)acrylates obtained using hydroxyl alkyl (meth)acrylates as the hydroxy-functional (meth)acrylate have excellent mechanical properties.

[0189] The urethane (meth)acrylate of Comparative Example 16 disclosed in Jordan Patent Application Publication No. 2021-046483 has an extremely high viscosity, is very turbid, has poor hydrophilicity, has poor resistance to alcohol, alkali, and acid, and exhibits poor mechanical properties compared to the urethane (meth)acrylate of the present invention.

Claims

1. A urethane (meth)acrylate, wherein the product is - at least one polyglycerol polyol, - at least one polyisocyanate, and - at least one hydroxy-functional (meth)acrylate The urethane (meth)acrylate obtained from the reaction of.

2. The urethane (meth)acrylate according to claim 1, having a number average molecular weight of 1,000 to 50,000 g / mol, preferably 1,500 to 10,000 g / mol, more preferably 2,000 to 5,000 g / mol.

3. The urethane (meth)acrylate according to claim 1, having a hydroxy residue.

4. The urethane (meth)acrylate according to claim 1, having no hydroxy group.

5. The urethane (meth)acrylate according to claim 1, wherein the polyglycerol polyol does not contain an oxyethylene group and / or an oxypropylene group, preferably does not contain an oxyalkylene group.

6. The urethane (meth)acrylate according to claim 1, wherein the polyglycerol polyol has a number average molecular weight of at least 100 g / mol, preferably 100 to 10,000 g / mol, more preferably 200 to 500 g / mol.

7. The polyglycerol polyol has the following general formula (I): [In the formula, a is a number from 2 to 20, preferably 2 to 10] The urethane (meth)acrylate according to claim 1, having.

8. The urethane (meth)acrylate according to claim 1, wherein the weight content of the polyglycerol polyol unit in the urethane (meth)acrylate is 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 5 to 30% by weight based on the total weight of the urethane (meth)acrylate.

9. The polyisocyanate is a diisocyanate, and the diisocyanate is preferably selected from aliphatic, alicyclic, or aromatic diisocyanates, preferably an alicyclic diisocyanate, and more preferably the polyisocyanate is isophorone diisocyanate. The urethane (meth)acrylate according to claim 1.

10. The weight content of the polyisocyanate unit in the urethane (meth)acrylate is 10 to 70% by weight, preferably 15 to 65% by weight, more preferably 20 to 60% by weight based on the total weight of the urethane (meth)acrylate, the urethane (meth)acrylate according to claim 1.

11. The hydroxy-functional (meth)acrylate is selected from hydroxyalkyl (meth)acrylate and polyethylene glycol mono (meth)acrylate, preferably 2-hydroxyethyl (meth)acrylate, or polyethylene glycol mono (meth)acrylate containing 2 to 20, preferably 5 to 10 ethylene glycol units, the urethane (meth)acrylate according to claim 1.

12. The weight content of the hydroxy-functional (meth)acrylate unit in the urethane (meth)acrylate is 20 to 80% by weight, preferably 25 to 75% by weight, more preferably 30 to 75% by weight based on the total weight of the urethane (meth)acrylate, the urethane (meth)acrylate according to claim 1.

13. The following general formula (III): [Wherein, - R is a unit derived from a hydroxy-functional (meth)acrylate, preferably, R is the following general formula (IV): (Wherein, -R １ is selected from a hydrogen atom and a methyl group; and - b is a number from 1 to 30, preferably from 1 to 10) having, - X is a unit derived from a polyisocyanate, and when the polyisocyanate has an NCO functionality greater than 2, the unit may be substituted with a urethane (meth)acrylate group; - A is a unit derived from a polyglycerin polyol, preferably, A is the following general formula (V): (Wherein, - Each Z is independently selected from a hydrogen atom or the group -C(=O)-NH-X-NH-C(=O)-OR; and - c is a number from 1 to 19, preferably from 1 to 9) having, - n is a number from 1 to 30] having, the urethane (meth)acrylate according to claim 1.

14. The urethane (meth)acrylate according to claim 1 having an OH value of 50 mg KOH / g to 400 mg KOH / g, preferably 100 mg KOH / g to 200 mg KOH / g.

15. The urethane (meth)acrylate according to claim 1, having an OH value of 0 mg KOH / g to 199 mg KOH / g, particularly 0.1 mg KOH / g to 190 mg KOH / g, more specifically 0.5 mg KOH / g to 180 mg KOH / g, and even more specifically 0.8 to 170 mg KOH / g.

16. Ratio R of polyisocyanate to hydroxy-functional (meth)acrylate １ is 0.2 to 0.9, preferably 0.5 to 0.8; and / or ratio R of polyglycerin polyol to polyisocyanate ２ is 0.1 to 0.8, preferably 0.2 to 0.5, the urethane (meth)acrylate according to claim 1.

17. The following consecutive steps: - Reacting a polyisocyanate with a hydroxy-functional (meth)acrylate to form an isocyanate-functional adduct, and - Reacting the isocyanate-functional adduct with a polyglycerin polyol to obtain a urethane (meth)acrylate A method for obtaining a urethane (meth)acrylate, comprising.

18. A curable composition, comprising: - The urethane (meth)acrylate according to claim 1 or obtained according to the method of claim 17, and - An ethylenically unsaturated compound selected from an ethylenically unsaturated monomer or an ethylenically unsaturated oligomer, preferably selected from a monofunctional or polyfunctional (meth)acrylic monomer or oligomer, more preferably selected from acryloylmorpholine and polyethylene glycol di(meth)acrylate A curable composition, comprising.

19. The curable composition according to claim 18, wherein the ethylenically unsaturated compound is present in an amount of at least 5% by weight, preferably 5 to 99% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 35% by weight, based on the total weight of the curable composition.

20. A cured product obtained by curing the urethane (meth)acrylate according to claim 1.

21. A cured product obtained by curing the curable composition according to claim 18.

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