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

Abstract

To provide urethane oligomers with good surface drying properties by reducing oxygen inhibition.SOLUTION: There is provided a urethane oligomer which comprises: a) at least two backbone residues R issued from a polyisocyanate without the NCO groups, linked between them with a diol residue RB by two urethane bonds and each of the backbone residues R carrying (or linked to) at least two urethane segments each one of which, contains at least one terminal allyl group, preferably from 1 to 5 terminal allyl groups; and b) at least one backbone residue R issued from a polyisocyanate without the NCO groups, the backbone residue R carrying (or linked to) at least two urethane segments each linked to R by one urethane bond.SELECTED DRAWING: None

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 the urethane oligomers, and curable compositions, and their specific uses in ultraviolet (UV) curable surface drying coating applications. [Background technology]

[0002] Compared to traditional solvent-based coatings, the main advantage of UV-curable coatings is that they are environmentally friendly, solvent-free formulations that do not contain volatile organic compounds (VOCs). Urethane acrylate oligomers are often used in coating compositions that utilize acrylate monomers as reactive diluents. When combined with photoinitiators, UV coatings cure by photochemically initiated radical polymerization, which will result in incomplete curing with a sticky surface due to oxygen inhibition from the atmosphere. Oxygen inhibits curing by suppressing the excited triplet state of the photoinitiator, capturing radicals to form peroxy radicals, and terminating polymerization. This oxygen inhibition leads to reduced properties or a sticky surface on the coating. In extreme cases, such as low strength, the curing process may result in an uncured liquid surface.

[0003] Strategies to reduce oxygen inhibition in industrial applications have been explored over the past several decades. Physical methods include removing oxygen with inert gases such as nitrogen, or forming a barrier on the surface using waxes. Chemical methods include increasing free radical concentrations by using formulations with higher concentrations of photoinitiators, by using chemicals that react with peroxyl radicals, or by using UV cationic epoxies to eliminate oxygen inhibition.

[0004] Patent US8268104 reported the use of cationic epoxy to eliminate oxygen inhibition and shrinkage in order to repair cracks on windshields. However, the applicability of this strategy is limited when epoxy cannot provide the required properties and acrylates must be used. In fact, most UV coating systems could not be substituted with cationic epoxy.

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

[0006] One alternative method to eliminate oxygen inhibition is to remove 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 can be economically unfeasible and very expensive.

[0007] Despite the current effectiveness in reducing oxygen-inhibiting effects in UV-curing compositions, there is still a need for new oligomers with rapid curing and air-drying properties. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent No. 8268104 [Overview of the Initiative]

[0009] The subject matter of the present invention relates to a urethane oligomer, and according to a) or b) below, the oligomer is a) At least two skeletal residues R derived from a polyisocyanate that does not have an NCO group, wherein two urethane bonds (-NHCOO-) between the skeletal residues form a diol residue R B A skeletal residue is linked to a (diol without two OH groups), and each of the skeletal residues R has at least two urethane segments (or is linked to at least two urethane segments), and each of the at least two urethane segments contains at least one terminal allyl group, preferably 1 to 5 terminal allyl groups. b) At least one skeletal residue R derived from a polyisocyanate that does not have an NCO group, wherein the skeletal residue R has at least two urethane segments each linked to R by one urethane bond (or is linked to the at least two urethane segments), -At least one urethane segment (arm) comprises at least one terminal allyl group, preferably 1 to 5 terminal allyl groups, and - At least one urethane segment (arm) is a skeletal residue containing at least one terminal (meth)acrylate group, preferably 1 to 5 terminal (meth)acrylate groups. It has.

[0010] Another subject concerns methods for preparing the urethane oligomers.

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

[0012] Another subject matter encompassed in the present invention relates to the use of the urethane oligomer in a curable composition in the presence of air.

[0013] Finally, the present invention encompasses final products selected from the group consisting of coatings, adhesives, sealants, or resin matrices, obtained from the curing of a urethane oligomer or curable composition as defined in accordance with the present invention. [Modes for carrying out 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 embodiments of the present invention, the urethane oligomer comprises at least one backbone which is a polyisocyanate residue (polyisocyanate after all NCO groups have been removed) and two types of urethane arms (also referred to as urethane segments in this text).

[0016] In embodiments of the present invention, the urethane oligomer comprises at least one skeleton and two types of urethane arms (urethane segments) as defined above.

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

[0018] The second type of urethane arm is a urethane arm containing at least one (meth)acrylate group which is the terminal group of the urethane oligomer, or a urethane arm containing a diol residue located between the 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 "skeleton" residue refers to the portion (polyisocyanate residue) formed by removing all NCO groups from a polyisocyanate.

[0020] The first subject matter of the present invention relates to a urethane oligomer, and according to the following option a) or b), the oligomer is a) At least two skeletal residues R derived from a polyisocyanate that does not have an NCO group, wherein two urethane bonds (-NHCOO-) between the skeletal residues form a diol residue R B(A diol without two OH groups) is linked to a skeletal residue R, each of which has at least two urethane segments (or is linked to at least two urethane segments), and each of the at least two urethane segments is a skeletal residue containing at least one terminal allyl group, preferably 1 to 5 terminal allyl groups. b) At least one skeletal residue R derived from a polyisocyanate that does not have an NCO group, wherein the skeletal residue R has at least two urethane segments each linked to R by one urethane bond (or is linked to the 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), - At least one urethane segment (arm) contains at least one terminal (meth)acrylate group (preferably 1 to 5 terminal (meth)acrylate groups), skeletal residue It has.

[0021] More specifically, the urethane oligomer according to the present invention can be represented by the following general formula (Ia) representing option a) defined above, and the following general formula (Ib) representing option b) defined above: (Ia)[(CH2=CHCH2O) m R1-O-CO-NH] n’1 R-NH-CO-OR B -O-CO-NH-R[NH-CO-O-R1(OCH2CH=CH2) m ] n’2 In the formula, independently or dependently for each statement, m>0, preferably m=1~5, n'1>0, n'2>0, where n'=n1'+n2 is 2~10, preferably 2~6, m, n'1 and n'2 are each integers, n'1=n'2=n1+n2-1, n1+n2=n is the functional value (or valence of R) of the polyisocyanate, which varies from 2~6, preferably 2~4, each of n1 and n2 is an integer, and n1 and n2 are either 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, 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, 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 skeleton 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 an allophanate group, a uretdione cyclic group (in the case of a dimer) or an isocyanurate cyclic group (in the case of a trimer), -R1 is, independently or dependently for each description, particularly C2 - C 12 , for example, C2 - C 10 or C2 - C6 or C2 - C3 aliphatic (e.g., saturated) group, or a (m + 1)-valent group selected from (m + 1)-valent oligomer groups or combinations thereof, -R’1 is, particularly C2 - C 12 , for example, C2 - C 10 or C2 - C6 or C2 - C3 aliphatic (e.g., saturated) group, 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 the 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-OR B -O-CO-NH- R1 (as a linker) is especially C2~C 12 For example, C2~C 10 Alternatively, it is a (m+1) valence group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) group or (m+1) valence oligomeric group or a combination thereof. R'1 (as a linker) is especially C2~C 12 For example, C2~C 10 Alternatively, a (m'+1) valence group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) groups or (m'+1) valence oligomeric groups or combinations thereof, R B (As a diol residue) is the part formed by removing two hydroxyl groups from a diol. Here, R2 is either H or CH3. Here, m > 0, m' > 0, and m and m' are integers.

[0023] According to the present invention, the term "linker" R1 is particularly used for C2-C 12 For example, C2~C 10 Alternatively, an (m+1) valence group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) groups or (m+1) valence oligomeric groups or combinations thereof (e.g., a combination of an aliphatic (e.g., saturated) group and an oligomeric group with (m+1) valence), and the term "linker" R'1 is particularly used for C2-C 12 For example, C2~C 10Alternatively, the (m'+1) valence group is selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) groups or (m'+1) valence oligomeric groups or combinations thereof (e.g., combinations of aliphatic (e.g., saturated) groups and (m'+1) valence oligomeric groups), and the oligomeric segment is selected from oligoester segments, oligoether segments, oligourethane segments and combinations thereof. In one embodiment, the oligomeric 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 portion (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 two to six -NCO groups, and more preferably two to four -NCO groups. The polyisocyanate may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a cyclic aliphatic polyisocyanate.

[0026] In one embodiment, the polyisocyanate may have 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, excluding those contained in the NCO group. Isocyanates with fewer carbon atoms are generally too volatile and toxic for practical use, so a smaller number of carbon atoms, C2 to C5, is undesirable.

[0027] Preferred isocyanate compounds include, but are not limited to, 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. Polyisocyanates can be dimers (containing a uretidinedione ring) or trimers (containing an isocyanurate ring). They can also include allophanates, isocyanurates, uretindiones, and biuretes, and more specifically, they are derived from hexamethylene diisocyanate, isophorone diisocyanate, or toluene diisocyanate.

[0028] Other examples of polyisocyanates include:

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

[0030] Aliphatic diisocyanates having cyclic groups include, specifically, 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-methylisocyanate-2-propyl isocyanate, and ω,ω'-n-propyl-biphenyl diisocyanate.

[0031] Benzene diisocyanates, specifically, include isomers such as 1,3-phenylenediisocyanate, 4-chloro-6-methyl-1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, toluene diisocyanate (TDI), 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate and 1-methylbenzene-3,5-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, and 1,3-dimethylbenzene-2,4-diisocyanate. Examples include ethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-ethylbenzene-2,4-diisocyanate, 1-isopropylbenzene-2,4-diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, p-xylylenediisocyanate, m-xylylenediisocyanate, p-tetramethylxylylenediisocyanate, and m-tetramethylxylylenediisocyanate.

[0032] Naphthalene diisocyanates include, specifically, 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 diisocyanates include, specifically, 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 diisocyanates and di- or triphenylethane diisocyanates, specifically 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 Examples include anetes, 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 include, specifically, 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'-diisocyanatocarbamate chloride, and their derivatives.

[0036] Alicyclic diisocyanates and alicyclic (cyclic aliphatic) diisocyanate compounds have a structure comprising an alicyclic hydrocarbon or polycyclic hydrocarbon and two isocyanate groups directly or via alkylene groups. Specific examples include isophorone diisocyanates (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] [ka] In the formula, R 11 R represents an alkylene group selected from a methylene group, an ethylene group, an -O- group, and an -C(CH3)2- group. 12 and R 13 Each of these independently represents a group selected from an alkyl group having 4 or fewer carbon atoms, an alkoxy group having 4 or fewer carbon atoms, and a halogen atom, m 12 and m 13 Each of these independently represents an integer from 0 to 4, and m 12 and / or m13 If it represents 2 or more, multiple R 12 and / or R 13 These may be the same or different from each other, and specific examples include bis(4-isocyanatophenyl)methane, bis(4-isocyanato-2-methylphenyl)methane, bis(4-isocyanato-2,5-dimethylphenyl)methane, bis(4-isocyanato-3-methoxyphenyl)methane, bis(4-isocyanato-5-methoxy-2-methylphenyl)methane, bis(3-chloro-4-isocyanatophenyl)methane, 1,2-bis(4-isocyanatophenyl)ethane, 4,4'-oxybis(isocyanatobenzene), and their derivatives.

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

[0040] [ka] In the formula, R 21 n represents a group selected from a single bond, a methylene group, an ethylene group, or a -C(CH3)2- group, 21 and n 22 Each of these represents an integer from 1 to 5, and n 23 represents an integer between 0 and 2. An example of this is norbornane diisocyanate, which is represented by the following formula.

[0041] [ka]

[0042] A dimer or trimer of the above-mentioned polyisocyanate, for example, an HDI trimer.

[0043] Other polyisocyanates, including the following: Poly(propylene glycol), triylene 2,4-diisocyanate terminus (CAS: 9057-91-4), (2,4,6-trioxotoriadine-1,3,5(2H,4H,6H)-tolyl)tris(methyl-m-phenylene)isocyanate (CAS:26603-40-7), C(CH2O(CH2CH2O) n CH2CH2NCO)4 (average Mn10000~20000), Poly[(phenylisocyanate)-co-formaldehyde] (average Mn: 340-400, CAS: 9016-87-9).

[0044] [ka]

[0045] For more detailed information on polyisocyanates, please refer to SZYCHER'S HANDBOOK OF POLYURETHANES, 2nd edition, by Dr. Michael Szycher, CRC Press. Taylor & Francis Croup. Boca Raton. London, New York (2013).

[0046] According to a specific embodiment of the present invention, linker R1 and / or R'1 is an oligomer segment selected from the group consisting of oligoester segments, oligoether segments, oligourethane segments and combinations thereof, and / or the diol residue R in formula (Ia). B The corresponding diols are alkanediols, especially C2-C2 diols. 10 Alkanediols, cycloalkanediols, especially C5-C5 10 Cycloalkanediols in, more preferably C6-C 10 Cycloalkanediols, aromatic diols, for example, C8-C 12 Preferably, the material is selected from aromatic diols, oligoether diols, oligoester diols, and oligourethane diols.

[0047] <Diol> According to the present invention, the "diol residue" R BThe term is Diol R B This is the part formed by removing two hydroxyl groups from (OH)2. The term "diol" refers to a compound that contains two -OH groups and does not have ethylenically unsaturated compounds. Diols include alkanediols (e.g., C2-C2). 10 Alkanediols), cycloalkanediols (for example, C5~C) 10 Cycloalkanediols, and aromatic diols (e.g., C8-C8) 12 Aromatic diols are included, and cycloalkanediols and aromatic diols are (OH-C 0-2 (alkylene)-cyclic group-(C) 0-2 Diols can be represented as 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 oligocondensation between a diol and a dicarboxylic acid or corresponding anhydride (as specifically described below) in which there is an excess of OH groups relative to the CO2H group, or by a post-reaction of a carboxyl-terminated group with an excess of diol. Oligourethane diols are diols produced by oligocondensation between a diol and a diisocyanate (as specifically described above) in which there is an excess of OH groups relative to the -NCO group, or by a post-reaction of an NCO-terminated group with an excess of diol.

[0048] Specific examples of 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, and 2,2,4-trimethyl-1,3-pentanediol. Examples include 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-diyldimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and hydroquinone, bisphenol A, and dihydroxymethylbenzene.

[0049] <Dicarboxylic acid (oligoester diol residue R B (In this 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 acids are typically halo, C1-C6 alkyl, C6-C 10 It contains aryl and 1 to 4 substituents selected from C1-C4 alkoxys.

[0050] Specific examples of 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-C6 alkyl 10 The terms "can be substituted" refer to aryls and C1-C4 alkoxys, and "halo, C1-C6 alkyl, C6-C 10 This means that the molecule may be substituted with aryl and 1 to 4 substituents selected from C1-C4 alkoxys.

[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 oligomeric segment according to the present invention includes the following: - An oligoester segment consisting of repeating units -OR'-CO- or -OR'-COO-R”-CO-, wherein R' and R” are different, or an oligoester H(OR”-O-OC-R'-CO) based on the diacid HO2C-R'-CO2H and the diol HO-R”-OH. n” Oligoester segments derived by removing H and OH from OH, where n'' is an integer between 2 and 10. -The oligoether segment is a part consisting of repeating units -O-R'- or O-R'-OR''- -The oligourethane segment is a part consisting of the repeating unit -OR'O-OC-HN-R”-NH-CO- Here, R' and R'' are either the same or different, and are selected from an aliphatic (divalent) group containing 2 to 12 carbon atoms, such as a C2-C4 alkylene, a cyclic aliphatic 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, for example, one or more caprolactones.

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

[0056] In one embodiment of the present invention, in an oligomer according to formula Ia, at least two urethane arms each containing at least one terminal allyl group contain 1 to 3, for example, 1, 2, or 3, particularly 3 terminal allyl groups; in formula Ib, 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, for example, 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 (Here, 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), preferably 1 to 5 terminal allyl groups (m=1 to 5), more preferably 1 to 3 terminal allyl groups (m=1 to 3) as terminal groups, 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), preferably 1 to 5 terminal (meth)acrylate groups (m'=1 to 5), more preferably 1 to 3 terminal allyl groups (m'=1 to 3) as terminal groups, and -(3-a) Alkanediol, especially C2-C 10 Alkanediols, cycloalkanediols, especially C5-C5 10 Cycloalkanediol, preferably C6-C 10 Cycloalkanediols, aromatic diols, especially C8-C 12 For example, C8~C 10 (V)R, which is selected from aromatic diols, oligoether diols, oligoester diols, and oligourethane diols and does not have ethylenically unsaturated properties. B (OH)2 This relates to urethane oligomers obtained from the reaction.

[0059] Monoalcohols (II) having at least one allyl group as a terminal group are classified as HO-R1[O-CH2CH=CH2] m (II) can be expressed as, Here, m is a greater-than-zero integer that can range from 1 to 5, more specifically from 1 to 3. R1 is polyol R1(OH) (m+1)It is a residue derived by removing (m+1) OH groups from, and R1 is preferably C2~C 12 For example, C2~C 10 Alternatively, it is a (m+1) valence group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) group, or an (m+1) valence oligomeric group, or a combination thereof.

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

[0061] In one embodiment, the monoalcohol(II) having at least one allyl group has two allyl groups, and the monoalcohol can be selected from the group consisting of diethers of aliphatic triols with allyl alcohols. More specific examples are diallyl diether of trimethylolpropane or diallyl diether of glycerol. The triol can 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 tetrol with allyl (or allyl-type) alcohols. Such examples may be triethers of allyl alcohol with ditrimethylolpropane ether, or triethers of allyl alcohol with diglycerol ether, or triethers of pentaerythritol with allyl alcohol. The tetrol can be alkoxylated with respect to aliphatic C2-C6 diols and oligoester diols as specified above.

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

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

[0065] [ka]

[0066] A monoalcohol (IV) having at least one (meth)acrylate group as a terminal group is HA-[(R3) y -O-COCR2=CH2] m’ It can be expressed as, Here, R2 is either H or CH3. m' is an integer greater than zero, and it can range 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 an oligoester diol residue or an oligolactone residue having one terminal hydroxyl group and one terminal carboxyl group, obtained by removing one H and one OH from each terminal group (including removing OH from the terminal carboxy-C(=O)-OH group of the oligolactone, so that the corresponding terminal group of residue A becomes -C(=O)-). In the case of the oligoether segment A, it corresponds to an oligoether diol residue 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, except when A is an oligolactone segment, in which case 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 functional value 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 a monoacrylate, produced by oligomerization of caprolactone in the presence of hydroxyethyl acrylate.

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

[0070] [ka] Dipentaerythritol pentaacrylate

[0071] [ka] Pentaerythritol triacrylate

[0072] [ka] Caprolactone acrylate

[0073] Suitable commercial products corresponding to the monoalcohols (IV) disclosed above are SR399, SR444D, and SR495, provided by Arkema's Sartomer Division.

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

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

[0076] The urethane oligomer according to the present invention is -(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 (Here, 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), preferably 1 to 5 terminal allyl groups (m=1 to 5), more preferably 1 to 3 terminal allyl groups (m=1 to 3) as terminal groups, and one or both of the following two: -(3-b) At least one monoalcohol having at least one (meth)acrylate group (m'=at least 1), preferably 1 to 5 (meth)acrylate groups (m'=1 to 5), more preferably 1 to 3 (meth)acrylate groups (m'=1 to 3) as a terminal group, and -(3-a) Preferably an alkanediol, especially C2-C 10 Alkanediols, cycloalkanediols, especially C5-C5 10 Cycloalkanediols, aromatic diols, especially C8-C 12 At least one non-ethylenically unsaturated diol selected from aromatic diols, oligoether diols, oligoester diols, and oligourethane diols. This is obtained from the reaction.

[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-OR 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 , In the formula, R2 is either H or CH3. During the ceremony, -n1+n2=n is an integer between 2 and 6, particularly 2, 3, 4, 5, 6, preferably between 2 and 4, particularly 2, 3, 4, and both n1 and n2 are integers greater than 0. -n1'=n1+n2-1=n2', where n1'+n2'=n' is an integer varying from 2 to 10, particularly 2, 4, 6, 8, 10; preferably 2 to 8, particularly 2, 4, 6, 8. - m is an integer from 1 to 5, for example 1, 2, 3, 4, 5, preferably 1 to 3, - m' is an integer from 1 to 5, preferably 1 to 3, and may be the same as or different from m, - R is the residue derived by removing n = n1 + n2 NCO groups from the polyisocyanate R(NCO) (n1+n2) or the 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 The degree of oligomerization n3 can be an integer of 2, 3, 4, 5, 6, preferably 2 or 3, and R is selected from aliphatic, cycloaliphatic or aromatic [[(n1 + n2) / n3]+1]-valent groups, which may be substituted, for example C3 - C o aliphatic, C6 - C 10 cycloaliphatic or C6 - C 10 aromatic groups, and the C3 - C 14 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 10 aromatic groups may be substituted, 14 When derived from the polyisocyanate R(NCO) the group R is selected from optionally substituted aliphatic, cycloaliphatic or aromatic n-valent groups, particularly C6 - C (n1+n2) aliphatic, C6 - C 10 cycloaliphatic or C6 - C 10 aromatic groups, and the C6 - C 14 aliphatic, C6 - C 10 cycloaliphatic or C6 - C 10 aromatic groups may be substituted, 14 When derived from an oligomer (e.g., dimer or trimer) of the polyisocyanate R (NCO) o (NCO) [(n1+n2) / n3]+1 the group R can be an n-valent segment of oligourethane, for example, a residue of a dimer or trimer of a diisocyanate without NCO, - R 1C2~C 12 For example, C2~C 10 Alternatively, a (m+1) valency group selected from C2-C6 or C2-C3 aliphatic (e.g., saturated) groups or (m+1)-valency oligomeric groups or combinations thereof, -A is an oligoester segment of (m+1) value selected from oligoester diols or oligo-lactones having terminal hydroxyl and carboxyl terminal groups by removing one OH and one H per terminal group (H of the OH terminal group and OH of the terminal carboxyl group), oligoether segments and oligourethane segments respectively obtained by removing two terminal groups (i.e., one H and one OH) of oligoether diols or oligourethane diols, and in particular the oligoester segment, oligoether segment and oligourethane segment are as defined above. -R3 is oxyethylene or oxypropylene, and y is 0, 1, or 2, provided that A is an oligolactone segment, then y = 1 or 2. -R2 is -H or CH3, -R B This is a diol residue as defined above.

[0078] The urethane oligomer of the present invention may be defined as a reaction product of one or both of the following: a monoalcohol represented by formula (II), a polyisocyanate represented by formula (III), and 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) HA-[(R3) y -O-COCR2=CH2] m’ (IV) HO-R B -OH(V) During the ceremony, R1, R2, R3, R BR, 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] [ka] TIFF2023103246000010.tif169167 However, the molecular weight Mn of polypropylene glycol in formulas 005 to 007 is 200 to 4000, preferably 500 to 2000. Mn can be calculated from the OH value if the functional value is 2. The "polypropylene glycol" defined in the above formula is a residue of polypropylene glycol obtained by removing two terminal OH groups.

[0081] <Preparation method> The present invention also relates to a method for preparing the urethane oligomer defined above, the method comprising the following steps: 1-i) Polyisocyanates represented by formula (III) R[NCO] n1+n2 (III) The step of reacting with a monoalcohol represented by formula (IV), HA-[(R3) y -O-COCR2=CH2] m’ (IV) 1-ii) A step in which the product of step 1-i) is reacted with a monoalcohol represented by formula (II), HO-R1[O-CH2CH=CH2] m (II) Here, The monoalcohol in formula (II) is a (II) Used in mole quantities, The polyisocyanate in formula (III) is a (III) Used in mole quantities, The monoalcohol in formula (IV) is a (IV) Used in mole quantities, a (II)a (III) and a (IV) The following relationships exist: 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) Polyisocyanates represented by formula (III) R[NCO] n1+n2 (III) The step of reacting with a monoalcohol represented by formula (II), HO-R1[O-CH2CH=CH2] m (II) 2-ii) A step in which the product of step 2-i) is reacted with a diol represented by formula (V), HO-R B -OH(V) Here, The monoalcohol in formula (II) is a (II) Used in mole quantities, The polyisocyanate in formula (III) is a (III) Used in mole quantities, The diol in formula (V) is a (V) Used in mole quantities, a (II) a (III) and a (V) The following relationships exist: 0.8 ≤ (n1 + n2 - 1) × a (III) / a (II) ≤1.25, 0.8 ≤ [(n1 + n2) × a (III) -a (II) ] / (2×a (V) )≦1.25, Compounds of formulas (II), (III), (IV), and (V) are defined as described 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 may be a tin catalyst, for example, tin(II)2-ethylhexanoate.

[0084] In embodiments of the present invention, the antioxidant may be 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT), a mixture of sterically hindered phenols (see, for example, U.S. Patents 3,280,049, 4,007,230, and 3,494,880), or a mixture of sterically hindered phenols with certain diphenylamines (see, for example, U.S. Patents 4,070,304, 4,265,783, 4,275,173, and 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, wherein the composition is curable in the presence of air (also known as air drying). The curable composition is curable by a peroxide initiator system, an 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 may further contain 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 the urethane oligomer of the present invention in curable compositions in the presence of air for good surface properties by reducing oxygen inhibition in coatings, adhesives, sealants, or resin matrices (particularly for encapsulating liquid crystal systems).

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

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

[0092] The following embodiments are provided to illustrate the present invention and its performance, and do not limit the scope of the present invention in any way. [Examples]

[0093] <Example of synthesis> Unless otherwise specified, 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] [ka]

[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 (hexaoate) (0.65 g) were added to a four-necked round-bottom flask and thoroughly mixed at 30°C. Under dry air, SR444D (232.6 g) was added at a constant rate within 120 minutes to carry out the reaction. The reaction was exothermic. The temperature was raised to 60°C within the first 30 minutes and then maintained at 60°C for the remainder of the addition time. After the addition of SR444D was complete, the mixture was kept at 60°C for 20 minutes and sampled for NCO%. After determining the NCO% which was in the theoretical range (6.71%~7.45%), trimethylolpropanediallyl ether (TMPDE) (168.7 g) was added dropwise, and the reaction temperature was raised to 90°C during the addition. After the addition of TMPDE was complete, the mixture was kept at 90°C for 2 hours, and then sampled every hour 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 thoroughly mixed at 30°C. Under dry air, SR495B (174.7 g) was added at a constant rate within 120 minutes to carry out the reaction. The reaction was exothermic. The temperature was raised to 60°C within the first 30 minutes and then maintained at 60°C for the remainder of the addition time. After the addition of SR495B was complete, 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%), trimethylolpropanediallyl ether (TMPDE) (28.5 g) was added dropwise, and the reaction temperature was raised to 90°C during the addition. After the addition of TMPDE was complete, the mixture was kept at 90°C for 2 hours, and then sampled every hour 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 thoroughly mixed at 30°C. Under dry air, trimethylolpropanediallyl ether (TMPDE) (100 g) was added at a constant rate within 90 minutes to carry out the reaction. The reaction was exothermic. The temperature was raised to 55°C within the first 30 minutes and then maintained at 55°C for the remainder of the addition time. After the addition of TMPDE was complete, the mixture was kept at 55°C for 20 minutes and sampled for NCO%. After determining the NCO% which was in 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 complete, 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] <Example Test> Unless otherwise specified, all percentages were used in terms of weight.

[0100] The following known compounds were used in the test examples. All of these compounds were commercially available.

[0101] Irgacure 184 1-Hydroxycyclohexylphenyl ketone CN964 urethane diacrylate oligomer-based aliphatic polyethylene Stel is available commercially from Sartomer. CN9101 Allyl functional group aliphatic oligomer, commercially available from Sartomer. It is being done. 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 WAC / BAC / IPA combination in a weight ratio of 65 / 20 / 15. Specific coating compositions are shown in the table below.

[0103] [Table 1]

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

[0105] UV curing of the printed coating on PET film (Fusion F300s DRS-10 / 12 UV device, H lamp, UV dose 750 mJ / cm²). 2 , UV intensity 1000mw / cm 2 The coating was cured using UV light. The UV curing process was repeated until the surface of the coating layer was completely hardened. The number of curing cycles was recorded, and the total energy consumption was calculated.

[0106] The results showed that the TMPDE-based polyurethane acrylate oligomer exhibited superior surface drying properties and rapid curing compared to the control.

Claims

1. A urethane oligomer according to formula Ia below. (I-a)[(CH) ２ =HHH ２ O) ｍ R １ -O-C-NH] ｎ’１ R-NH---O-R Ｂ -O---NH-R[NH---O-R １ (OCH ２ CH=CH ２ ) ｍ ] ｎ’２ [In the formula, - for each occurrence independently or dependently, m=2 to 5; - n'1>0 and n'2>0, where n'=n1'+n'2 is 2 to 10; the backbone residue R is the moiety formed by removing all NCO groups from a polyisocyanate, the functionality of which (or the valence of R) varies from 2 to 6; -R １ For each statement, independently or dependently, C ２ ~C １２ an (m+1)-valent group selected from an aliphatic group, or an (m+1)-valent oligomeric group, or a combination thereof; -R Ｂ is a moiety formed by removing two hydroxyl groups from a diol selected from the group consisting of alkanediols, cycloalkanediols, aromatic diols, oligoetherdiols, and oligourethanediols.

2. -R １ 2. The urethane oligomer of claim 1, wherein is an oligomeric segment selected from the group consisting of an oligoester segment, an oligoether segment, an oligourethane segment, and combinations thereof.

3. R １ but - an oligoester segment consisting of the repeating unit -OR'-CO- or -OR'-COO-R"-CO-, wherein R' and R" are different, or a diacid HO ２ C-R'-CO ２ Oligoesters H(O-R"-O-OC-R'-CO) based on H and diols HO-R"-OH ｎ” an oligoester segment derived by removing H and OH from OH, wherein n″ is an integer from 2 to 10; - an oligoether segment, which is a moiety consisting of the repeating unit -O-R'- or O-R'-O-R"-, - an oligourethane segment, which is a moiety consisting of the repeating unit -OR'O-OC-HN-R"-NH-CO, wherein 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.

4. The oligoester segment comprises one or more C ４ ~C ６ The urethane oligomer according to claim 2 or 3, which is derived from a lactone.

5. The urethane oligomer according to any one of claims 1 to 4, wherein the urethane oligomer has a number average molecular weight Mn of 500 to 5000 g / mol as measured by GPC in THF using polystyrene standards.

6. (1) at least one polyisocyanate R(NCO) having 2 to 6 isocyanate groups; ｎ a polyisocyanate in which n=n1+n2 and both n′1 and n′2 are integers greater than 0; - (2) at least one monoalcohol having from 2 to 5 allyl groups as terminal groups; -(3-a) at least one diol having no ethylenic unsaturation selected from the group consisting of alkanediols, cycloalkanediols, aromatic diols, oligoetherdiols, and oligourethanediols; The urethane oligomer according to any one of claims 1 to 5, obtained from the reaction of

7. The urethane oligomer of any one of claims 1 to 6, selected from the group consisting of the following formulas: 【Chemical 1】 [However, the molecular weight Mn of the polypropylene glycol in formulas 005, 006 and 007 is 200 to 4000.]

8. A curable composition comprising at least one urethane oligomer according to any one of claims 1 to 7, which is curable in the presence of air.

9. 9. The curable composition of claim 8, which is curable by either a peroxide initiator system, an electron beam, or UV radiation, and in the case of UV radiation, further comprises at least one photoinitiator.

10. 10. The curable composition of claim 8 or 9, further comprising a reactive diluent selected from mono- or polyfunctional (meth)acrylate monomers.

11. The curable composition of any one of claims 8 to 10, which is a UV curable composition selected from the group consisting of a coating, an adhesive, a sealant or a resin matrix composition.

12. 8. Use of the urethane oligomer according to any one of claims 1 to 7 in a coating, adhesive, sealant or curable composition in the presence of air for good surface properties by reducing oxygen inhibition in a resin matrix.

13. The use according to claim 12, wherein the curable composition is a curable urethane acrylate composition or a curable thiol-ene composition, which in the case of the curable thiol-ene composition further comprises a polythiol compound.

14. 12. A cured composition selected from the group consisting of a coating, an adhesive, a sealant, or a resin matrix, resulting from curing the urethane oligomer of any one of claims 1 to 7 or the curable composition of any one of claims 8 to 11.

Images