Allyl-functional urethane oligomers and related compositions for coatings and adhesives

Abstract

The present invention provides a method for producing a diol copolymer according to the following a) or b): a) a diol copolymer having at least two backbone residues R derived from a polyisocyanate having no NCO groups, the backbone residues being connected by two urethane bonds (—NHCOO—) between the backbone residues; B (a) a diol having no two OH groups, each of said backbone residues R having at least two urethane segments (or linked to said at least two urethane segments), each one of said at least two urethane segments containing at least one terminal allyl group, preferably 1 to 5 terminal allyl groups; b) at least one backbone residue R derived from a polyisocyanate having no NCO groups, said backbone residue R having at least two urethane segments (or linked to said at least two urethane segments), each linked to R by one urethane bond; At least one urethane segment (arm) contains at least one terminal allyl group (preferably 1 to 5 terminal allyl groups), and The present invention relates to a urethane oligomer in which at least one urethane segment (arm) has a backbone residue containing at least one terminal (meth)acrylate group (preferably 1 to 5 terminal (meth)acrylate groups). The present invention also relates to a curable composition containing the urethane oligomer, a method for preparing the urethane oligomer, and the use of the urethane oligomer or the curable composition in the presence of air for improved surface properties by reducing oxygen inhibition in coatings, adhesives, sealants, or resin matrices.

Description

Technical Field

[0001] The present invention relates to allyls having good surface drying properties by reducing oxygen inhibition, more particularly to urethane oligomers having allyl and (meth)acrylate groups, methods for producing such urethane oligomers, and curable compositions, particularly their specific use in ultraviolet (UV) curable surface drying coating applications.

Background Art

[0002] Compared with traditional solvent-based coatings, the main advantage of UV curable coatings is their solvent-free formulations that are environmentally friendly and contain no volatile organic compounds (VOCs). Urethane acrylate oligomers are often used in coating compositions using acrylate monomers as reactive diluents. When formulated with a photoinitiator, the UV coating cures by photochemically initiated radical polymerization, which would result in incomplete curing with a tacky surface due to oxygen inhibition from the atmosphere. Oxygen suppresses the excited triplet state of the photoinitiator, captures radicals to form peroxy radicals and terminates the polymerization, thereby inhibiting curing. This oxygen inhibition effect results in a degradation of properties or a tacky surface on the coating. In extreme cases such as low intensity, the curing process will result in an uncured liquid surface.

[0003] Strategies for reducing oxygen inhibition in industrial processes have been investigated over the past few decades. Physical methods include removing oxygen with an inert gas such as nitrogen or forming a barrier on the surface using wax. Chemical methods include increasing the free radical concentration by formulating with a higher content of photoinitiator, or using a chemical that reacts with peroxy radicals, or using a UV cationic epoxy to eliminate oxygen inhibition.

[0004] U.S. Patent No. 8,268,104 reported using cationic epoxy to eliminate oxygen inhibition and shrinkage to repair cracks on the windshield. However, when epoxy cannot provide the necessary properties and acrylates have to be used, the application of this strategy is limited. In fact, most of the UV coating systems could not be substituted with cationic epoxy.

[0005] In the industry, about 3 - 5% (w / w) photoinitiator is added to generate sufficient free radicals under UV irradiation for polymerization. Oxygen inhibition could be reduced by formulating with more than 10% (w / w) photoinitiator to increase the radical concentration. Due to the high cost of photoinitiators, the final product will be more expensive with a higher photoinitiator content. Another aspect is that the final formulation may be impaired and the properties after curing may be affected. Also, since photoinitiators are low molecular weight, their derivatives can migrate even after curing. In many industries such as food packaging, the migration of organic compounds is restricted.

[0006] One alternative method to eliminate the oxygen inhibition effect is to exclude oxygen with an inert gas such as nitrogen while curing the composition. In many cases, this method means that a specially designed and manufactured system is required, which may not be economically feasible and can be very costly.

[0007] Despite the current effects of reducing the oxygen inhibition effect in UV - curable compositions, there is still a need for new oligomers with fast curing and air - drying properties.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

[0009] The subject of the present invention relates to urethane oligomers, according to a) or b) below, said oligomers being a) at least two backbone residues R derived from a polyisocyanate having no NCO groups, with a diol residue R B (diol having no two OH groups) linked between the backbone residues by two urethane bonds (-NHCOO-), each of said backbone residues R having at least two urethane segments (or linked to said at least two urethane segments), each one of said at least two urethane segments containing at least one terminal allyl group, preferably 1 to 5 terminal allyl groups, a backbone residue b) at least one backbone residue R derived from a polyisocyanate having no NCO groups, said backbone residue R having at least two urethane segments each linked to R by one urethane bond (or linked to said at least two urethane segments), - at least one urethane segment (arm) containing at least one terminal allyl group, preferably 1 to 5 terminal allyl groups, and - at least one urethane segment (arm) containing at least one terminal (meth)acrylate group, preferably 1 to 5 terminal (meth)acrylate groups, a backbone residue having.

[0010] Another subject relates to a method for preparing said urethane oligomers.

[0011] Another subject relates to a curable composition containing at least one of said urethane oligomers according to the invention.

[0012] Another subject included in the present invention relates to the use of said urethane oligomers in a curable composition in the presence of air.

[0013] Finally, the present invention includes end products selected from the group consisting of coatings, adhesives, sealants or resin matrices obtained from the curing of urethane oligomers or curable compositions defined according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0014] According to the present invention, the term "urethane oligomer" means a compound containing at least two -NH-CO-O (urethane) moieties.

[0015] In an embodiment of the present invention, the urethane oligomer comprises at least one backbone which is a polyisocyanate residue (the polyisocyanate after all NCO groups have been removed), and two types of urethane arms (also referred to as urethane segments in the present text).

[0016] In an embodiment of the present invention, the urethane oligomer consists of at least one backbone as defined above and two types of urethane arms (urethane segments).

[0017] The first type of urethane arm is a urethane arm containing at least one allyl group which is a terminal group of the urethane oligomer.

[0018] The second type of urethane arm is either a urethane arm containing at least one (meth)acrylate group which is a terminal group of the urethane oligomer, or a urethane arm containing a diol residue located between two main chains and linked to each of the two main chains via a urethane -NHCOO- linking group.

[0019] According to the present invention, the term "backbone" residue means the moiety (polyisocyanate residue) formed by removing all NCO groups from a polyisocyanate.

[0020] The first subject of the present invention relates to a urethane oligomer, and according to the following options a) or b), the oligomer is a) at least two backbone residues R derived from a polyisocyanate having no NCO groups, with a diol residue R between the backbone residues by two urethane bonds (-NHCOO-) B(A diol having no two OH groups) and each of the skeletal residues R has at least two urethane segments (or is linked to said at least two urethane segments), and each of said at least two urethane segments contains at least one terminal allyl group, preferably 1 to 5 terminal allyl groups, a skeletal residue, b) At least one skeletal residue R derived from a polyisocyanate having no NCO groups, wherein each of said skeletal residues R has at least two urethane segments each linked to R by one urethane bond (or is linked to said at least two urethane segments), - At least one urethane segment (arm) contains at least one terminal allyl group (preferably 1 to 5 terminal allyl groups), and - At least one urethane segment (arm) contains at least one terminal (meth)acrylate group (preferably 1 to 5 terminal (meth)acrylate groups), a skeletal residue having.

[0021] More specifically, the urethane oligomer according to the present invention can be represented by the following general formula (I-a) representing option a) defined above, and the following general formula (I-b) representing option b) defined above: (I-a) [(CH2=CHCH2O) m R1-O-CO-NH] n’1 R-NH-CO-O-R B -O-CO-NH-R [NH-CO-O-R1 (OCH2CH=CH2) m n’2 In the formula, for each description, independently or dependently, m>0, preferably m = 1 to 5, n'1>0, n'2>0, where n'=n1'+n2 is 2 to 10, preferably 2 to 6, and each of m, n'1 and n'2 is an integer, n'1=n'2=n1+n2-1, and n1+n2=n is the functionality of the polyisocyanate (or the valence of R), which varies from 2 to 6, preferably 2 to 4, and each of n1 and n2 is an integer, and n1 and n2 are the same or different, or ​(I-b)[(CH2=CHCH2O) m R1-O-CO-NH] n1 R[NH-CO-O-R’1(O-CO-C(R2)=CH2) m’ n2 、 wherein R2 is H or CH3, wherein, -n = n1 + n2 ≧ 2 and up to 6, preferably 2 to 4, and n represents the functionality of the polyisocyanate or the valence of the residue R derived from the polyisocyanate, -n1 > 0, n2 > 0, m > 0, m’ > 0, preferably m = 1 to 5, m’ = 1 to 5, n > 0, and each of m, m’, n, n1 and n2 is an integer, and n1 and n2 may be the same or different, -m’ is an integer of 1 to 5 which is the same as or different from m, wherein, -the skeletal residue R is a part formed by removing all NCO groups from the polyisocyanate, and the polyisocyanate may be a monomer (without repeating units) or an oligomer (with repeating units), and may contain allophanate groups, uretdione cyclic groups (in the case of dimers) or isocyanurate cyclic groups (in the case of trimers), -R1 is, independently or dependently for each description, especially C2-C 12 , for example, C2-C 10 or C2-C6 or C2-C3 aliphatic (e.g., saturated) groups, or a (m + 1)-valent group selected from (m + 1)-valent oligomer groups or combinations thereof, -R’1 is, especially C2-C 12 , for example, C2-C 10 or C2-C6 or C2-C3 aliphatic (e.g., saturated) groups, or a (m’ + 1)-valent group selected from (m’ + 1)-valent oligomer groups or combinations thereof, and in the formula, R1 and R’1 may be the same or different, -m is an integer of 1 to 5, for example 1, 2, 3, 4, 5, preferably 1 to 3, the diol residue R B is a part formed by removing two hydroxyl groups from the diol.​

[0022] According to the present invention, the term "urethane segment or arm" means a chain group containing a urethane -NH-CO-O subgroup (bond), and includes the following groups: (a’)-NH-CO-O-R1(OCH2CH=CH2) m (b’)-NH-CO-O-R’1(O-CO-C(R2)=CH2) m’ (c’)-NH-CO-O-R B -O-CO-NH- R1 (as a linker) is a (m + 1)-valent group particularly selected from C2 - C 12 , for example, C2 - C 10 or C2 - C6 or C2 - C3 aliphatic (e.g., saturated) groups or (m + 1)-valent oligomeric groups or combinations thereof, R’1 (as a linker) is a (m’ + 1)-valent group particularly selected from C2 - C 12 , for example, C2 - C 10 or C2 - C6 or C2 - C3 aliphatic (e.g., saturated) groups or (m’ + 1)-valent oligomeric groups or combinations thereof, R B (as a diol residue) is a moiety formed by removing two hydroxyl groups from a diol, wherein R2 is H or CH3, wherein m > 0, m’ > 0, and each of m and m’ is an integer.

[0023] According to the present invention, the term "linker" R1 is a (m + 1)-valent group particularly selected from C2 - C 12 , for example, C2 - C 10 or C2 - C6 or C2 - C3 aliphatic (e.g., saturated) groups or (m + 1)-valent oligomeric groups or combinations thereof (e.g., (m + 1)-valent combinations of aliphatic (e.g., saturated) groups and oligomeric groups), and the term "linker" R’1 is a (m + 1)-valent group particularly selected from C2 - C 12 , for example, C2 - C 10or an (m'+1)-valent group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) groups or (m'+1)-valent oligomer groups or combinations thereof (e.g., (m'+1)-valent combinations of aliphatic (e.g., saturated) groups and oligomer groups), wherein the oligomer segment is selected from oligoester segments, oligoether segments, oligourethane segments, and combinations thereof. In one embodiment, the oligomer segment contains 2 to 50, preferably 2 to 30, for example 2 to 4 repeating units. According to the present invention, R1 and R'1 may be the same or different.

[0024] According to the present invention, the term "skeleton" residue R refers to the moiety (polyisocyanate residue) formed by removing all NCO groups from a polyisocyanate.

[0025] <Polyisocyanate> In the present invention, the term "polyisocyanate" refers to a compound containing at least two -NCO groups, preferably 2 to 6 -NCO groups, more preferably 2 to 4 -NCO groups. The polyisocyanate can be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a cycloaliphatic polyisocyanate.

[0026] In one embodiment, the polyisocyanate can have 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, excluding those contained in the NCO groups. Isocyanates with fewer carbons are generally too volatile and toxic for practical use, so fewer carbon atoms, C2-C5, are not preferred.

[0027] As the isocyanate compound, preferably, isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane 4,4'-diisocyanate (MDI), hexamethylene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), xylene diisocyanate, octadecyl isocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, and polymethylene polyphenyl isocyanate are mentioned, but not limited thereto. The polyisocyanate can be a dimer (including a uretdione ring) or a trimer (including an isocyanurate ring). Further, they can contain allophanate, isocyanurate, uretdione, biuret, and more specifically, they are derived from hexamethylene diisocyanate, isophorone diisocyanate or toluene diisocyanate.

[0028] Examples of the polyisocyanate also include the following:

[0029] Aliphatic diisocyanates, specific examples thereof include hexamethylene diisocyanate and its dimer (uretdione ring) and trimer (isocyanurate) derivatives, heptane diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octane diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonane diisocyanate (e.g., 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane), decane diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, undecane diisocyanate, dodecane diisocyanate, and thiodihexyl diisocyanate.

[0030] Aliphatic diisocyanates having a cyclic group, specific examples thereof include ω,ω’-1,3-dimethylbenzene diisocyanate, ω,ω’-1,2-dimethylbenzene diisocyanate, ω,ω’-1,2-dimethylcyclohexane diisocyanate, ω,ω’-1,4-dimethylcyclohexane diisocyanate, ω,ω’-1,4-diethylbenzene diisocyanate, ω,ω’-1,4-dimethylnaphthalene diisocyanate, ω,ω’-1,5-dimethylnaphthalene diisocyanate, 3,5-dimethylcyclohexane-1-methyl isocyanate-2-propyl isocyanate and ω,ω’-n-propyl-biphenyl diisocyanate.

[0031] Benzene diisocyanates, specific examples thereof include 1,3-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate (TDI), isomers such as 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate and 1-methylbenzene-3,5-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-ethylbenzene-2,4-diisocyanate, 1-isopropylbenzene-2,4-diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, p-tetramethylxylylene diisocyanate and m-tetramethylxylylene diisocyanate.

[0032] Naphthalene diisocyanate, and specific examples thereof include 1,4 - diisocyanatonaphthalene, 1,5 - diisocyanatonaphthalene, 1,6 - diisocyanatonaphthalene, 1,7 - diisocyanatonaphthalene, 2,3 - diisocyanatonaphthalene, 2,4 - diisocyanatonaphthalene, 2,5 - diisocyanatonaphthalene, 2,6 - diisocyanatonaphthalene, 2,7 - diisocyanatonaphthalene, and 2,2’ - diisocyanato - 1,1’ - binaphthyl.

[0033] Biphenyl diisocyanate, and specific examples thereof include biphenyl - 2,4’ - diisocyanate, biphenyl - 4,4’ - diisocyanate, 3,3’ - dimethylbiphenyl - 4,4’ - diisocyanate, 3,3’ - dimethoxybiphenyl - 4,4’ - diisocyanate, 3,3’ - dichlorobiphenyl - 4,4’ - diisocyanate, and 2 - nitrobiphenyl - 4,4’ - diisocyanate.

[0034] Di - or triphenylmethane diisocyanate and di - or triphenylethane diisocyanate, and specific examples thereof include diphenylmethane - 4,4’ - diisocyanate, 2,2’ - dimethyldiphenylmethane - 4,4’ - diisocyanate, diphenyldimethylmethane - 4,4’ - diisocyanate, 2,5,2’,5’ - tetramethyldiphenylmethane - 4,4’ - diisocyanate, 3,3’ - dimethoxydiphenylmethane - 4,4’ - diisocyanate, 4,4’ - dimethoxyphenylmethane - 3,3’ - diisocyanate, 4,4’ - diethoxyphenylmethane - 3,3’ - diisocyanate, 2,2’ - dimethyl - 5,5’ - dimethoxydiphenylmethane - 4,4’ - diisocyanate, 3,3 - dichlorodiphenyldimethylmethane - 4,4’ - diisocyanate, benzophenone - 3,3’ - diisocyanate, α,β - diphenylethane - 2,4 - diisocyanate, 3 - nitrotriphenylmethane - 4,4’ - diisocyanate, 4 - nitrotriphenylmethane - 4,4’ - diisocyanate, and their derivatives.

[0035] Triisocyanates, specific examples of which include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-1,3,7-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4',4''-triisocyanate, diphenyl-4,4'-diisocyanatocarbamic acid chloride, and derivatives thereof.

[0036] Alicyclic diisocyanates. The alicyclic (cycloaliphatic) diisocyanate compound has a structure containing an alicyclic hydrocarbon or a polycyclic hydrocarbon and two isocyanate groups bonded directly or via an alkylene group thereto. Specific examples thereof include isophorone diisocyanate (i.e., 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane), 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2-(2-isocyanatoethyl)-1-(isocyanatomethyl)-3,5-dimethylcyclohexane, and bis(4-isocyanatocyclohexylmethane).

[0037] Diisocyanates represented by the following general formula

[0038]

Chemical formula

[0039] Polycyclic alicyclic diisocyanates represented by the following general formula:

[0040]

Chemical formula

[0041]

Chemical formula

[0042] Dimers or trimers of the above polyisocyanate, such as HDI trimer.

[0043] Other polyisocyanates including the following Poly(propylene glycol), tolylene 2,4-diisocyanate-terminated (CAS: 9057-91-4), (2,4,6-Trioxotriazine-1,3,5(2H,4H,6H)-trilyl)tris(methyl-m-phenylene) isocyanate (CAS: 26603-40-7), C(CH2O(CH2CH2O) n CH2CH2NCO)4 (average Mn 10,000 - 20,000), Poly[(phenyl isocyanate)-co-formaldehyde] (average Mn: 340 - 400, CAS: 9016-87-9).

[0044]

Chem.

[0045] For detailed information on polyisocyanates, reference can be made to SZYCHER’s HANDBOOK OF POLYURETHANES, 2nd Edition, Dr. Michael Szycher, CRC Press. Taylor & Francis Croup. Boca Raton. London New York (2013).

[0046] According to a specific embodiment of the present invention, the linker R1 and / or R'1 is an oligomeric segment selected from the group consisting of oligoester segments, oligoether segments, oligourethane segments, and combinations thereof, and / or the diol residue R in formula (I-a) B The corresponding diol for 10 is preferably selected from alkane diols, especially C2 - C 10 alkane diols, cycloalkane diols, especially C5 - C 10 cycloalkane diols in, more preferably C6 - C 12 cycloalkane diols, aromatic diols, such as C8 - C

[0047] <Diol> According to the present invention, the "diol residue" R BThe term "diol R" B is a moiety formed by removing two hydroxyl groups from diol R(OH)2. The term "diol" refers to a compound containing two -OH groups and having no ethylenic unsaturation. Diols include alkanediols (e.g., C2 - C 10 alkanediols), cycloalkanediols (e.g., C5 - C 10 cycloalkanediols), and aromatic diols (e.g., C8 - C 12 aromatic diols), and cycloalkanediols and aromatic diols can be represented by (OH - C 0-2 alkylene)-cyclic group-(C 0-2 alkylene - OH). Diols further include oligoether diols, oligoester diols, and oligourethane diols. Oligoether diols are diols formed by oligomerization of alkylene oxides such as ethylene oxide, propylene oxide, or butylene oxide (also called tetrahydrofuran or THF). Oligoester diols are diols formed by oligo - condensation between a diol and a dicarboxylic acid or the corresponding anhydride (such as those specifically described below) where the OH groups are in excess relative to the CO2H groups, or by post - reaction of carboxy - terminated groups with excess diol. Oligourethane diols are diols produced by oligo - condensation between a diol and a diisocyanate (such as those specifically described above) where the OH groups are in excess relative to the -NCO groups, or by post - reaction of NCO - terminated groups with excess diol.

[0048] Specific diols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2-butyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane, dihydroxycyclopentane, 1,4-cyclohexanediol, cyclohexane-1,1-diyl dimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and hydroquinone, bisphenol A, dihydroxymethylbenzene.

[0049] <Dicarboxylic acid (oligoester diol residue R B in the case)> In the present invention, the dicarboxylic acid can be a substituted or unsubstituted linear or branched non-aromatic dicarboxylic acid selected from aliphatic dicarboxylic acids containing 2 to 12 carbon atoms and alicyclic dicarboxylic acids containing 5 to 10 carbon atoms, or a substituted or unsubstituted aromatic dicarboxylic acid containing 6 to 10 carbon atoms. The substituted aromatic or non-aromatic dicarboxylic acid typically contains 1 to 4 substituents selected from halo, C1-C6 alkyl, C6-C 10 aryl, and C1-C4 alkoxy.

[0050] Specific dicarboxylic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,3 - cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, diglycolic acid, 2,5 - norbornane - dicarboxylic acid, phthalic acid, terephthalic acid, 1,4 - naphthalenedicarboxylic acid, 2,5 - naphthalenedicarboxylic acid, 2,6 - naphthalenedicarboxylic acid, 2,7 - naphthalenedicarboxylic acid, diphenic acid, 4,4’ - oxydibenzoic acid, 4,4’ - sulfonyldibenzoic acid, isophthalic acid, and combinations thereof.

[0051] <Substituent> Here, the term "substituent" refers to halo, C1 - C6 alkyl, C6 - C 10 aryl, and C1 - C4 alkoxy, and terms such as "can be substituted" mean "may be substituted by 1 - 4 substituents selected from halo, C1 - C6 alkyl, C6 - C 10 aryl, and C1 - C4 alkoxy".

[0052] <Oligomer segment> The total number of repeating units is preferably less than 100, for example less than 50, less than 25, for example 10, 9, 8, 7, 6, 5, 4, and 3.

[0053] The oligomer segment according to the present invention includes the following: - An oligoester segment which is a part consisting of repeating units -OR’ - CO - or -OR’ - COO - R” - CO -, where R’ and R” are different, or an oligoester H(O - R” - O - OC - R’ - CO) n” OH derived by removing H and OH from OH, and n” is an integer from 2 to 10. - An oligoether segment which is a part consisting of repeating units -O - R’ - or O - R’ - O - R”. - An oligourethane segment which is a part consisting of repeating units -OR’O - OC - HN - R” - NH - CO -. Here, R’ and R” are the same or different and are selected from an aliphatic (divalent) group containing 2 to 12 carbon atoms, such as C2-C4 alkylene, a cycloaliphatic group containing 5 to 10 carbon atoms, or an aromatic group containing 8 to 10 carbon atoms. R’ and R” may be substituted.

[0054] In one embodiment, the oligoester segment is derived from one or more C4-C6 lactones, such as one or more caprolactones.

[0055] In one embodiment of the present invention, the urethane segment (arm) containing at least one terminal allyl group contains 1 to 5 allyl groups, such as 1, 2, 3, 4, 5 allyl groups, which are the terminal groups of the urethane oligomer, and the urethane segment (arm) containing at least one terminal (meth)acrylate group contains 1 to 5 (meth)acrylate groups, such as 1, 2, 3, 4, 5 (meth)acrylate groups, which are the terminal groups of the urethane oligomer.

[0056] In one embodiment of the present invention, in the oligomer according to formula I-a, at least two urethane arms each containing at least one terminal allyl group contain 1 to 3 terminal allyl groups, such as 1, 2, 3 terminal allyl groups, particularly 3 terminal allyl groups; in formula I-b, at least one urethane segment containing at least one terminal allyl group contains 1 to 3 terminal allyl groups; and at least one urethane segment containing at least one terminal (meth)acrylate group contains 1 to 3 terminal (meth)acrylate groups.

[0057] According to a specific embodiment, the urethane oligomer has a number average molecular weight Mn of 250 to 5000 g / mol, such as 500 to 5000 g / mol, preferably 750 to 3000 g / mol, or preferably 650 to 3000 g / mol, as measured by GPC in THF using a polystyrene standard.

[0058] The present invention also -(1) At least one polyisocyanate (III) R(NCO) having at least two isocyanate groups (at least 2 n), preferably 2 to 6 isocyanate groups (n = 2 to 6), more preferably 2 to 4 isocyanate groups (more preferably n = 2 to 4), n (where n = n1 + n2, and both n1 and n2 are integers greater than 0), -(2) At least one monoalcohol (II) having at least one allyl group (m = at least 1) as a terminal group, preferably 1 to 5 terminal allyl groups (m = 1 to 5), more preferably 1 to 3 terminal allyl groups (m = 1 to 3), and one or both of the following two, -(3-b) At least one monoalcohol (IV) having at least one (meth)acrylate group (m' = at least 1) as a terminal group, preferably 1 to 5 terminal (meth)acrylate groups (m' = 1 to 5), more preferably 1 to 3 terminal allyl groups (m' = 1 to 3), and -(3-a) An alkanediol, especially C2 - C 10 alkanediol, cycloalkanediol, especially C5 - C 10 cycloalkanediol, preferably C6 - C 10 cycloalkanediol, aromatic diol, especially C8 - C 12 , for example C8 - C 10 aromatic diol, and at least one diol (V) R B (OH)2 without ethylenic unsaturation selected from oligoether diols, oligoester diols, and oligourethane diols. It relates to a urethane oligomer obtained from the reaction of

[0059] The monoalcohol (II) having at least one allyl group as a terminal group can be represented by HO - R1[O - CH2CH = CH2] m (II), where m is an integer greater than 0 that can vary from 1 to 5, more specifically from 1 to 3, R1 is a polyol R1(OH) (m+1)a residue derived by removing (m + 1) OH groups therefrom, and R1 is preferably C2 - C 12 , for example C2 - C 10 or C2 - C6, or a C2 - C3 aliphatic (e.g., saturated) group, or a polyvalent oligomeric group or a combination thereof, a polyvalent group selected from the group consisting of.

[0060] In certain embodiments, said monoalcohol (II) having at least one allyl group has only one allyl group and can be selected from the group consisting of allyl alcohol and at least one ether of allyl alcohol with a diol, wherein in said diol, one OH is etherified and the other remains free. Such diols may be aliphatic diols (e.g., C2 - C6 aliphatic diols) or oligoether diols or oligoester diols, and in both cases, the number of repeating ether units or repeating ester units is 2 - 4. Said aliphatic C2 - C6 diols and said oligoester diols may be alkoxylated with at least one alkoxy unit, preferably 1 - 6 alkoxy units. Said alkoxy may be ethoxy or propoxy or a mixture of both, preferably ethoxy.

[0061] In one embodiment, said monoalcohol (II) having at least one allyl group has two allyl groups, and said monoalcohol can be selected from the group consisting of diethers of aliphatic triols with allyl alcohol. More specific examples are diallyl diethers of trimethylolpropane or diallyl diethers of glycerol. Said triols may be alkoxylated as defined above for aliphatic C2 - C6 diols and oligoester diols.

[0062] In another embodiment, the monoalcohol (II) having at least one allyl group has three allyl groups, and the monoalcohol can be selected from the group consisting of triethers of aliphatic tetrols with allyl (or allyl-type) alcohols. Such examples can be triethers of allyl alcohol with ditrimethylolpropane ether, or triethers of allyl alcohol with diglycerol ether, or triethers of allyl alcohol with pentaerythritol. The tetrol can be alkoxylated as defined above for aliphatic C2-C6 diols and oligoester diols.

[0063] In another embodiment, the monoalcohol (II) having at least one allyl group has a higher allyl functionality (4 and 5), and the monoalcohol (II) can be selected from polyethers of pentitols (such as xylitol) and polyethers of hexitols (such as dipentaerythritol ether) with allyl alcohol.

[0064] In another specific embodiment of the present invention, the monoalcohol (IV) having at least one (meth)acrylate group is selected from the following: Trimethylolpropane diallyl ether

[0065]

Chemical formula

[0066] The monoalcohol (IV) having at least one (meth)acrylate group as a terminal group can be represented by H-A-[(R3) y -O-COCR2=CH2] m’ wherein, R2 is H or CH3, and m' is an integer greater than zero, which can vary from 1 to 5, more specifically from 1 to 3. A is an (m'+1)-valent oligomeric segment, and the oligomeric segment is selected from an oligoester segment, an oligoether segment, and an oligourethane segment. In the case of the oligoester segment A, it corresponds to the residue of an oligoester diol obtained by removing one H and one OH per terminal group (including removing OH from the terminal carboxy -C(=O)-OH group of an oligolactone, and the corresponding terminal group of the residue A becomes -C(=O)-), or the residue of an oligolactone having one terminal hydroxyl group and one terminal carboxy group. In the case of the oligoether segment A, it corresponds to the residue of an oligoether diol from which one terminal OH and one terminal H have been removed. Finally, in the case of the oligourethane segment A, it corresponds to an oligourethane diol from which one terminal OH and one terminal H have been removed. -R3 is oxyethylene or oxypropylene, and y is 0, 1, or 2, provided that when A is an oligolactone segment, y = 1 or 2.

[0067] In another specific embodiment, the monoalcohol (IV) having at least one (meth)acrylate group has 1 to 5 (meth)acrylate groups, and the monoalcohol (IV) is a partial ester of an oligomeric polyol having an OH functionality of 2 to 6 and (meth)acrylic acid, and the oligomeric segment is selected from oligoethers, oligoesters, and oligourethanes.

[0068] In one embodiment, the monoalcohol (IV) having at least one (meth)acrylate group is a polycaprolactone monoacrylate or monomethacrylate, preferably monoacrylate, resulting from the oligomerization of caprolactone in the presence of hydroxyethyl acrylate.

[0069] In a specific and preferred embodiment, the monoalcohol (IV) having at least one (meth)acrylate group is selected from the following:

[0070] [Chemistry] Dipentaerythritol pentaacrylate

[0071] [Chemistry] Pentaerythritol triacrylate

[0072] [Chemistry] Caprolactone acrylate

[0073] Suitable commercially available products corresponding to the monoalcohol (IV) disclosed above are SR399, SR444D and SR495 provided by the Sartomer Division of Arkema.

[0074] In one embodiment, when both allyl and (meth)acrylate end groups are present, for example according to formula (I-b) disclosed above, the ratio (allyl) / (meth)acrylate can vary from 0.1 to 10, particularly from 0.2 to 5.

[0075] In one embodiment, the urethane oligomer contains at least two allyl groups, preferably 2 to 6 allyl groups.

[0076] The urethane oligomer according to the present invention -(1) at least one polyisocyanate R(NCO) having at least two isocyanate groups (at least 2 n), preferably 2 to 6 isocyanate groups (n = 2 to 6), more preferably 2 to 4 isocyanate groups (more preferably n = 2 to 4) n (where n = n1 + n2 and both n1 and n2 are integers greater than 0), -(2) at least one monoalcohol having at least one allyl group (m = at least 1) as an end group, preferably 1 to 5 terminal allyl groups (m = 1 to 5), more preferably 1 to 3 terminal allyl groups (m = 1 to 3) and one or both of the following two: - at least one monoalcohol having at least one (meth)acrylate group (m' = at least 1) as a (3-b) terminal group, preferably 1 to 5 (meth)acrylate groups (m' = 1 to 5), more preferably 1 to 3 (meth)acrylate groups (m' = 1 to 3), and -(3-a) preferably an alkanediol, especially C2 - C 10 alkanediol, cycloalkanediol, especially C5 - C 10 cycloalkanediol, aromatic diol, especially C8 - C 12 at least one diol having no ethylenic unsaturation selected from aromatic diol, oligoether diol, oligoester diol, and oligourethane diol obtained from the reaction with.

[0077] In one embodiment of the present invention, the urethane oligomer is represented by the following general formula (I-1) or (I-2): (I-1) [(CH2=CHCH2O) m R1-O-CO-NH] n1’ R-NH-CO-O-R B -O-CO-NH-R[NH-CO-O-R1(OCH2CH=CH2) m n2’ (I-2) [(CH2=CHCH2O) m R1-O-CO-NH] n1 R[NH-CO-A-((R3) y -OCOCR2=CH2) m’ n2 , wherein R2 is H or CH3, wherein, - n1 + n2 = n is an integer from 2 to 6, especially 2, 3, 4, 5, 6, preferably 2 to 4, especially 2, 3, 4, and both n1 and n2 are integers greater than 0, - n1' = n1 + n2 - 1 = n2', and n1' + n2' = n' is an integer varying from 2 to 10, especially 2, 4, 6, 8, 10; preferably 2 to 8, especially 2, 4, 6, 8,​​ - m is an integer from 1 to 5, for example 1, 2, 3, 4, 5, preferably from 1 to 3, - m' is an integer from 1 to 5, preferably from 1 to 3, and may be the same as or different from m, - R is a residue derived by removing n = n1 + n2 NCO groups from the polyisocyanate R(NCO) (n1+n2) or a residue derived by removing all NCO groups from an oligomer (e.g., dimer or trimer) of the polyisocyanate R o (NCO) [(n1+n2) / n3]+1 wherein n3 is the degree of oligomerization and can be an integer of 2, 3, 4, 5, 6, preferably 2 or 3, n3 is the degree of oligomerization and can be an integer of 2, 3, 4, 5, 6, preferably 2 or 3, R o is selected from aliphatic, cycloaliphatic or aromatic [[(n1 + n2) / n3]+1]-valent groups, which may be substituted, for example C3 - C 10 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 14 aromatic groups, and the C3 - C 10 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 14 aromatic groups may be substituted, when derived from the polyisocyanate R(NCO) (n1+n2) the group R is selected from optionally substituted aliphatic, cycloaliphatic or aromatic n-valent groups, especially C6 - C 10 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 14 aromatic groups, and the C6 - C 10 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 14 aromatic groups may be substituted, when derived from an oligomer (e.g., dimer or trimer) of the polyisocyanate R o (NCO) [(n1+n2) / n3]+1 the group R can be an n-valent segment of an oligourethane, for example, a residue of a dimer or trimer of a diisocyanate without NCO, - R 1is C2 - C 12 , for example C2 - C 10 or C2 - C6, or a (m + 1)-valent group selected from C2 - C3 aliphatic (e.g., saturated) groups or (m + 1)-valent oligomer groups or combinations thereof, -A is an oligomeric segment selected from an oligoester diol or an oligoester segment resulting from removing one OH and one H per terminal group (the H of the OH terminal group and the OH of the terminal carboxy group), an oligoether segment resulting from removing two terminal groups (i.e., one H and one OH) of an oligoether diol, and an oligourethane segment resulting from removing two terminal groups (i.e., one H and one OH) of an oligourethane diol, respectively, and in particular, the oligoester segment, the oligoether segment, and the oligourethane segment are as defined above, -R3 is oxyethylene or oxypropylene, and y is 0, 1, or 2, provided that when A is an oligolactone segment, y = 1 or 2, -R2 is -H or CH3, -R B is a diol residue as defined above.

[0078] The urethane oligomer of the present invention can be defined as a reaction product of a monoalcohol represented by formula (II), a polyisocyanate represented by formula (III), and one or both of a monoalcohol represented by formula (IV) and a diol represented by formula (V): HO - R1[O - CH2CH = CH2] m (II) R[NCO] n1+n2 (III) H - A - [(R3) y -O - COCR2 = CH2] m’ (IV) HO - R B -OH(V) wherein, R1, R2, R3, R B, R, A, m, m’, n1 + n2, and y are as defined above.

[0079] In one embodiment of the present invention, the oligomer of the present invention can be selected from the group consisting of the following formulas 001 to 007.

[0080] [Chemical Formula] TIFF0007710295000010.tif169167However, the molecular weight Mn of the polypropylene glycol in Formulas 005 to 007 is 200 to 4000, preferably 500 to 2000. Mn can be calculated from the OH value assuming a functionality of 2. The "polypropylene glycol" defined in the above formulas is the residue of polypropylene glycol after removing two terminal OH groups.

[0081] [Preparation Method] The present invention also relates to a method for preparing a urethane oligomer as defined above by the present invention, the method comprising the following steps: 1-i) Reacting a polyisocyanate represented by formula (III) R[NCO] n1+n2 (III) with a monoalcohol represented by formula (IV). H-A-[(R3) y -O-COCR2=CH2] m’ (IV) 1-ii) Reacting the product of step 1-i) with a monoalcohol represented by formula (II). HO-R1[O-CH2CH=CH2] m (II) Here, the monoalcohol of formula (II) is used in an amount of a (II) moles, the polyisocyanate of formula (III) is used in an amount of a (III) moles, the monoalcohol of formula (IV) is used in an amount of a (IV) moles, a (II), a (III) and a (IV) have the following relationship: 0.8 ≦ (n1 + n2) × a (III) / a (IV) ≦ 1.25, 0.8 ≦ (n1 + n2) × a (III) / (a (II) + a (IV) ) ≦ 1.25, or 2-i) A step of reacting the polyisocyanate represented by formula (III) R[NCO] n1+n2 (III) with the monoalcohol represented by formula (II), HO-R1[O-CH2CH=CH2] m (II) 2-ii) A step of reacting the product of step 2-i) with the diol represented by formula (V), HO-R B -OH (V) Here, the monoalcohol of formula (II) is used in an amount of a (II) moles, the polyisocyanate of formula (III) is used in an amount of a (III) moles, the diol of formula (V) is used in an amount of a (V) moles, a (II) , a (III) and a (V) have the following relationship: 0.8 ≦ (n1 + n2 - 1) × a (III) / a (II) ≦ 1.25, 0.8 ≦ [(n1 + n2) × a (III) - a (II) / (2 × a (V) ) ≦ 1.25, The compounds of formulas (II), (III), (IV) and (V) are defined as above.

[0082] The above reaction is carried out in the presence of a catalyst and / or an antioxidant.

[0083] In one embodiment of the present invention, the catalyst can be a tin catalyst, such as tin(II) 2-ethylhexanoate.

[0084] In embodiments of the present invention, the antioxidant can be 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT), a mixture of sterically hindered phenols (see, e.g., U.S. Patent No. 3,280,049, U.S. Patent No. 4,007,230, and U.S. Patent No. 3,494,880), or a mixture of sterically hindered phenols with certain diphenylamines (see, e.g., U.S. Patent No. 4,070,304, U.S. Patent No. 4,265,783, U.S. Patent No. 4,275,173, and U.S. Patent No. 4,021,385). For detailed information on reaction conditions, see SZYCHER’S HANDBOOK OF POLYURETHANES, 2nd Edition, Dr. Michael Szycher, CRC Press. Taylor & Francis Crup. Boca Raton. London New York (2013).

[0085] Another subject of the present invention relates to a curable composition comprising at least one urethane oligomer as defined above by the present invention, wherein the composition is curable in the presence of air (also known as air drying). This curable composition is curable by any of a peroxide initiator system, electron beam, or UV irradiation, and in the case of UV irradiation, the composition further comprises at least one photoinitiator.

[0086] In a preferred embodiment, the curable composition is curable by UV irradiation.

[0087] The curable composition can further comprise a reactive diluent selected from monofunctional or polyfunctional (meth)acrylate monomers.

[0088] More specifically, the curable composition is a UV curable composition selected from the group consisting of coatings, adhesives, sealants, or resin matrix compositions.

[0089] Another subject of the present invention relates to the use of said urethane oligomer of the present invention in a curable composition in the presence of air for good surface properties by reducing oxygen inhibition in coatings, adhesives, sealants or resin matrices (especially for confining liquid crystal systems).

[0090] More specifically, said use is in a curable urethane acrylate composition or in a curable thiol-ene composition, and in the case of a curable thiol-ene composition, said composition further comprises a polythiol (having at least two thiol - SH groups).

[0091] Finally, the present invention also encompasses end products selected from the group consisting of coatings, adhesives, sealants or resin matrices resulting from the curing of at least one urethane oligomer or resulting from the curing of a curable composition as defined above according to the present invention.

[0092] The following examples are presented to illustrate the present invention and its performance and are not intended to limit the scope of the present invention in any way.

Examples

[0093] <Synthesis Example> Unless otherwise indicated, all starting materials in the synthesis examples are commercially available, room temperature refers to a temperature of 15 - 30 °C, and all percentages are based on weight percentages.

[0094] In the synthesis example, the starting compounds SR444D and SR495B used have the following structures and are commercially available from Sartomer.

[0095]

Chemical formula

[0096] <Preparation Example 1> Hexamethylene diisocyanate (HDI) trimer (246.8 g), 2,6-di-tert-butyl-4-methylphenol (1.3 g), and tin(II) 2-ethylhexanoate (0.65 g) were added to a four-necked round-bottom flask and mixed well at 30 °C. SR444D (232.6 g) was added at a constant rate within 120 minutes under dry air to carry out the reaction. The reaction was an exothermic process. The temperature was raised to 60 °C within the first 30 minutes and then maintained at 60 °C during the remaining addition time. After the addition of SR444D was completed, the mixture was kept at 60 °C for 20 minutes and sampled for NCO%. After determining the NCO% within the theoretical range (6.71% - 7.45%), trimethylolpropane diallyl ether (TMPDE) (168.7 g) was added dropwise, and the reaction temperature rose to 90 °C during the addition. After the addition of TMPDE was completed, the mixture was kept at 90 °C for 2 hours, and then sampled hourly for NCO% until the NCO% was less than 0.06%.

[0097] <Preparation Example 2> Hexamethylene diisocyanate trimer (HDI) (92.7 g), 2,6-di-tert-butyl-4-methylphenol (0.6 g), and tin(II) 2-ethylhexanoate (0.3 g) were added to a four-necked round-bottom flask and mixed well at 30 °C. SR495B (174.7 g) was added at a constant rate within 120 minutes under dry air to carry out the reaction. The reaction was an exothermic process. The temperature was raised to 60 °C within the first 30 minutes and then maintained at 60 °C during the remaining addition time. After the addition of SR495B was completed, the mixture was kept at 60 °C for 20 minutes and sampled for NCO%. After determining the NCO% within the theoretical range (2.26% - 2.51%), trimethylolpropane diallyl ether (TMPDE) (28.5 g) was added dropwise, and the reaction temperature rose to 90 °C during the addition. After the addition of TMPDE was completed, the mixture was kept at 90 °C for 2 hours, and then sampled hourly for NCO% until the NCO% was less than 0.06%.

[0098] <Preparation Example 3> Isophorone diisocyanate (IPDI) (113.74 g), 2,6-di-tert-butyl-4-methylphenol (0.95 g) and tin(II) 2-ethylhexanoate (0.45 g) were added to a four-necked round-bottom flask and mixed well at 30 °C. Trimethylolpropane diallyl ether (TMPDE) (100 g) was added at a constant rate within 90 minutes under dry air, and the reaction was carried out. The reaction was an exothermic process. The temperature was raised to 55 °C within the first 30 minutes and then maintained at 55 °C for the remaining addition time. After the addition of TMPDE was completed, the mixture was kept at 55 °C for 20 minutes and sampled for NCO%. After determining the NCO% within the theoretical range (9.6% - 10.5%), polypropylene glycol (Mn: 1000, 254 g) was added dropwise, and the reaction temperature rose to 85 °C during the addition. After the addition of polypropylene glycol was completed, the mixture was kept at 85 °C for 2 hours, and then sampled every hour for NCO% until the NCO% was less than 0.06%.

[0099] <Test Example> Unless otherwise specified, all percentages were used by weight.

[0100] In the test example, the following known compounds were used. All of these compounds were commercially available.

[0101] Irgacure 184 1-Hydroxycyclohexyl phenyl ketone CN964 Aliphatic polyester based on urethane diacrylate oligomer Ster, commercially available from Sartomer. CN9101 Allyl-type functional group aliphatic oligomer, commercially available from Sartomer are. EAC Ethyl acetate BAC Butyl acetate IPA Isopropyl alcohol

[0102] Several coating compositions were prepared. The prepared coating compositions contained oligomers, photoinitiators, and mixed solvents. The photoinitiator was Irgacure 184, and the mixed solvent was a combination of WAC / BAC / IPA with a weight ratio of 65 / 20 / 15. The specific coating compositions are shown in the following table.

[0103]

Table 1

[0104] The prepared coating compositions were dispersed at 400 RPM (revolutions per minute) for 5 minutes and filtered. The coating compositions were printed onto a PET film using a wire bar, the OSG No. 8 bar, in a wire bar printing machine, and after evaporation at a temperature of 60 °C for 5 minutes, the wet layer was controlled to a constant thickness (about 5 μm) so that the resulting dried layer had a thickness of about 2 - 3 μm. The obtained thickness was measured with a thickness gauge and shown in the above table.

[0105] The PET film printed with the coating was subjected to UV curing (using a Fusion F300s DRS - 10 / 12 UV device, H lamp, UV dose of 750 mj / cm 2 , UV intensity of 1000 mw / cm 2 ). The UV curing was repeated until the surface of the coating layer was completely cured. The number of repetitions of curing was recorded and the total energy consumption was calculated.

[0106] The results showed that the TMPDE - based polyurethane acrylate oligomer had excellent surface drying characteristics and rapid curing compared to the control.

Claims

1. A urethane oligomer according to the following formula (I-b). (I-b)[(CH ２ =CHCH ２ O) ｍ R １ -O-CO-NH] ｎ１ R[NH-CO-O-R' １ (O-CO-C(R ２ )=CH ２ ) ｍ’ ｎ２ 、​ [In the formula, R ２ is H or CH ３ and -n = n1 + n2 ≧ 2 and up to 6, -n1 > 0, n2 > 0, and each of n, n1, and n2 is an integer, and n1 and n2 are the same or different, -m is an integer from 1 to 5, -m' is an integer from 1 to 5 that is the same as or different from m, In the formula, -the skeletal residue R is a portion formed by removing all NCO groups from a polyisocyanate, -R １ is, for each description independently or dependently, C ２ to C １２ a polyvalent group selected from aliphatic groups or from polyvalent oligomeric groups of (m + 1) valency or combinations thereof, -R' １ is an optionally C ２ -C １２ aliphatic group-bonded (m'+1)-valent oligoester segment, where R １ and R' １ may be the same or different.] **Claim 2**: The oligoester segment is a portion consisting of repeating units -OR'-CO- or -OR'-COO-R"-CO-, where R' and R" are different, or the diacid HO ２ C-R'-CO ２ H and the oligoester H(O-R"-O-OC-R'-CO) based on the diol HO-R"-OH ｎ” OH is derived by removing H and OH therefrom, n" is an integer from 2 to 10, and R' and R" are the same or different and are selected from an aliphatic group containing 2 to 12 carbon atoms, a cycloaliphatic group containing 5 to 10 carbon atoms, or an aromatic group containing 8 to 10 carbon atoms. The urethane oligomer according to claim 1.

3. The oligoester segment is one or more C ４ to C ６ derived from lactone, the urethane oligomer according to claim 1.

4. R １ is - Repeating unit - an oligoester segment consisting of -OR'-CO- or -OR'-COO-R"-CO-, wherein the oligoester segment has different R' and R", or a diacid HO ２ C-R'-CO ２ An oligoester H(O-R"-O-OC-R'-CO)OH derived by removing H and OH from H and diol HO-R"-OH, and the oligoester segment wherein n" is an integer from 2 to 10 ｎ” is derived by removing H and OH, and n" is an integer from 2 to 10 -an oligoether segment consisting of repeating units -O-R'- or O-R'-O-R", -an oligourethane segment consisting of repeating units -OR'O-O-C-HN-R"-NH-CO, In the formula, R' and R" may be the same or different and are selected from an aliphatic (divalent) group containing 2 to 12 carbon atoms, a cycloaliphatic group containing 5 to 10 carbon atoms, or an aromatic group containing 8 to 10 carbon atoms. The urethane oligomer according to any one of Claims 1 to 3.

5. R １ is an oligoester segment derived from one or more C ４ to C ６ lactones, the urethane oligomer according to claim 3 or 4.

6. The urethane oligomer according to any one of Claims 1 to 5, having a number average molecular weight Mn of 500 to 5000 g / mol as measured by GPC in THF using a polystyrene standard.

7. The urethane oligomer is - (1) at least one polyisocyanate R(NCO) having at least two isocyanate groups (at least 2 n) ｎ wherein n = n1 + n2, and both n1 and n2 are integers greater than 0 -(2) at least one monoalcohol having at least one allyl group (m = at least 1) as a terminal group, and -(3-b) at least one monoalcohol having an oligoester segment and at least one (meth)acrylate group (m' = at least 1) as a terminal group The urethane oligomer according to any one of Claims 1 to 6, obtained from the reaction of.

8. The ratio of (allyl) / (meth)acrylate is 0.1 to 10, or 0.2 to 5. The urethane oligomer according to any one of Claims 1 to 7.

9. The urethane oligomer according to any one of Claims 1 to 8, containing at least two allyl groups.

10. The urethane oligomer according to Claim 1, selected from the group consisting of one of the following formulas. 【Chemical 1】

11. A curable composition containing at least one urethane oligomer according to any one of Claims 1 to 10 and curable in the presence of air.

12. The curable composition according to claim 11, which is curable by any of a peroxide initiator system, electron beam or UV irradiation, and further contains at least one photoinitiator in the case of the UV irradiation.

13. The curable composition according to claim 11 or 12, further comprising a reactive diluent selected from monofunctional or polyfunctional (meth)acrylate monomers.

14. The curable composition according to any one of claims 11 to 13, which is a UV curable composition selected from the group consisting of a coating, an adhesive, a sealant or a resin matrix composition.

15. Use of the urethane oligomer according to any one of claims 1 to 10, for use in a curable composition in the presence of air to reduce oxygen inhibition in a coating, an adhesive, a sealant or a resin matrix.

16. The use according to claim 15, wherein the curable composition is a curable urethane acrylate composition or a curable thiol-ene composition, and the curable thiol-ene composition further contains a polythiol compound.

17. A cured composition selected from the group consisting of a coating, an adhesive, a sealant or a resin matrix, which results from the curing of the urethane oligomer according to any one of claims 1 to 10 or the curable composition according to any one of claims 11 to 14.

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