Urethane prepolymer, polyurethane and sealant using same

Abstract

To provide a polyurethane that has low tackiness, high strength and high transparency.SOLUTION: Provided is a NCO-terminated liquid urethane prepolymer, the urethane prepolymer containing a structural unit represented by formula (1) and having a number average molecular weight of 200 or more and 3,000 or less, in which the degree of unsaturation is 0.020 meq / g or less, and the terminal is a NCO group. In formula (1), Q represents a polymer component containing a halogenated polyether structural unit, m represents an integer of 2 to 8, and R1 represents an active hydrogen-containing compound residue.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a urethane prepolymer, and a polyurethane and a sealant using the same. [Background technology]

[0002] Curable polyurethane compositions used as sealants, paints, coating materials, pressure sensitive adhesives, and adhesives include one-component types that are cured by moisture in the air, two-component types that are cured by mixing a polyol, polyamine, or the like with a curing agent, and 1.5-component types that contain a latent curing agent, etc. As the main component that forms such polyurethane, a curable resin composition containing an NCO-terminated urethane prepolymer obtained by reacting an isocyanate with a polyol, a filler, and an additive is widely used, and examples of the polyol include polyester polyol and polyalkylene oxide polyol.

[0003] Polyurethane obtained by using polyester polyol has a problem that it is inferior in water resistance due to hydrolysis because it contains ester groups.

[0004] Polyalkylene oxides that are industrially produced by addition polymerization of alkylene oxides such as propylene oxide using an alkali metal such as potassium hydroxide as a catalyst contain a large amount of impurities, and therefore have the problem of poor curability and inability to obtain sufficient resin strength.

[0005] Halogen-containing polyether polyols are known as raw materials for polyurethane adhesives that have excellent shear strength, moisture resistance, and water resistance (see, for example, Patent Document 1). Such halogen-containing polyether polyols can be synthesized by ring-opening polymerization of halogen-containing alkylene oxides using an acid catalyst such as a boron trifluoride compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 202573 / 1999 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the polyol used as a raw material for the adhesive composition of Patent Document 1 contains a large amount of impurities and unsaturated components because epichlorohydrin is ring-opened using a Lewis acid catalyst. As a result, the resulting cured product has many defects and a low crosslink density, so there are problems such as the resin not being able to exhibit sufficient strength unless a large amount of filler is included, and the resin surface becoming sticky. [Means for solving the problem]

[0008] The various aspects of the present invention are as follows [1] to [6]. [1] A liquid urethane prepolymer with NCO terminals. The urethane prepolymer is The number average molecular weight of the polymer is 200 or more and 3,000 or less, and the number average molecular weight of the polymer is 200 or more and 3,000 or less. The degree of unsaturation is 0.020 meq / g or less, Liquid urethane prepolymer terminated with NCO groups:

[0009] [ka]

[0010] In formula (1), Q represents a polymer component containing a structural unit represented by formula [I], m represents an integer of 2 to 8; R 1 represents a residue of an active hydrogen-containing compound;

[0011] [ka]

[0012] In formula [I], X represents a halogen atom. [2] A liquid urethane prepolymer described in [1], characterized in that the degree of unsaturation is 0.016 meq / g or less. [3] A liquid urethane prepolymer composition comprising the urethane prepolymer according to any one of [1] and [2], and one or more of a filler, other polyol, a urethane catalyst, a foam stabilizer, an antioxidant, and a plasticizer. [4] A polyurethane obtained by curing the liquid urethane prepolymer according to any one of [1] or [2] or the liquid urethane prepolymer composition according to [3] through a reaction with water in the air or a curing agent (an active hydrogen-containing compound). [5] A composition for sealant comprising the urethane prepolymer according to any one of [1] to [2] or the urethane prepolymer composition according to [3]. [6] A sealant obtained by curing the composition for sealant according to [5] by reaction with water in the air or a curing agent (an active hydrogen-containing compound). Effect of the Invention

[0013] According to one aspect of the present invention, a polyurethane having low tackiness, high strength and high transparency can be provided, and can be suitably used for applications such as a sealing material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Exemplary embodiments for carrying out the present invention are described in detail below. <Urethane prepolymer> The urethane prepolymer according to one embodiment of the present invention comprises: It can be obtained by reacting a halogen-containing polyether polyol with an isocyanate compound. <<Halogen-containing polyether polyol>> The halogen-containing polyether polyol is As shown in equation (2), The average molecular weight is 200 or more and 3,000 or less. :

[0015] [ka]

[0016] In formula (2), Q represents a polymer component containing a structural unit represented by formula [I], m represents an integer of 2 to 8; R 1 represents a residue of an active hydrogen-containing compound;

[0017] [ka]

[0018] In formula [I], X represents a halogen atom.

[0019] In formula [I], the halogen atom represented by X is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred from the viewpoint of ease of handling, and a fluorine atom or a chlorine atom is more preferred.

[0020] In formula (1) and formula (2), R 1 The active hydrogen-containing compound residue represented by the formula (I) is not particularly limited, but examples thereof include a hydroxyl residue, an amine residue, a carboxylic acid residue, and a thiol residue.

[0021] The active hydrogen-containing compound containing such an active hydrogen-containing compound residue is not particularly limited, but examples thereof include hydroxy compounds, amine compounds, carboxylic acid compounds, thiol compounds, and polyether polyols having a hydroxyl group.

[0022] Examples of hydroxy compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, and bisphenol.

[0023] Examples of the amine compound include ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,2-butylenediamine.

[0024] Examples of the carboxylic acid compound include phthalic acid and adipic acid.

[0025] Examples of the thiol compound include ethanedithiol and butanedithiol.

[0026] Examples of polyether polyols having a hydroxyl group include polyether polyols having a molecular weight of 200 or more and 1,000 or less.

[0027] Among these active hydrogen-containing compounds, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonanediol, 2,5-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, ethylenediamine, and polyether polyols having a molecular weight of 200 or more and 1,000 or less are preferred, as they enable efficient production of halogen-containing polyether polyols, and tripropylene glycol, 2,5-hexanediol, 1,9-nonanediol, and polyether polyols having a molecular weight of 200 or more and 1,000 or less are particularly preferred.

[0028] The number average molecular weight of the halogen-containing polyether polyol is from 200 to 3,000, and since this results in excellent handleability and polyurethane production efficiency, the number average molecular weight is preferably from 200 to 2,000, and particularly preferably from 500 to 2,000.

[0029] In order to improve the curability when made into a polyurethane, the degree of unsaturation of the halogen-containing polyether polyol is preferably 0.02 meq / g or less, and particularly preferably 0.01 meq / g or less.

[0030] The ratio (Mw / Mn) of the mass average molecular weight Mw of the halogen-containing polyether polyol to the number average molecular weight Mn is preferably 2.00 or less, particularly preferably 1.50 or less, in order to improve the curability when made into a polyurethane, where Mn is the number average molecular weight determined by gel permeation chromatography measurement using polystyrene as the standard substance, and Mw is the mass average molecular weight.

[0031] The primary terminal hydroxyl group rate in the halogen-containing polyether polyol is not particularly limited, but is preferably less than 10%, more preferably 8% or less, and particularly preferably 5% or less, since this reduces variation in reactivity, allows for a uniform reaction, and tends to result in a uniform molecular weight distribution and composition of the resulting polyurethane. <<Method of manufacturing halogen-containing polyether polyol>> The method for producing the halogen-containing polyether polyol is not particularly limited, and the halogen-containing polyether polyol can be produced by a conventionally known production method.

[0032] Examples of such methods include (A) a method in which a halogen-containing alkylene oxide is added to a bifunctional or higher active hydrogen compound up to a predetermined molecular weight using a Lewis acid catalyst or a composite metal cyanide complex catalyst; and (B) a method in which a halogen-containing alkylene oxide is ring-opened in the presence of a bifunctional or higher active hydrogen-containing compound, an onium salt catalyst such as a phosphazenium salt, an ammonium salt, or a phosphonium salt, and a Lewis acid catalyst.

[0033] Examples of the Lewis acid catalyst include aluminum compounds, zinc compounds, and boron compounds.

[0034] Examples of the aluminum compound include organic aluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-normal-hexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, and monophenyldiisobutylaluminum; aluminoxanes such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum compounds such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

[0035] Examples of the zinc compound include organic zinc compounds such as dimethyl zinc, diethyl zinc, and diphenyl zinc; and inorganic zinc compounds such as zinc chloride and zinc oxide.

[0036] Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane, and trifluoroborane.

[0037] Among these, organoaluminum, aluminoxane and organozinc are preferred, with organoaluminum being particularly preferred, since they provide catalysts for producing halogen-containing polyether polyols with excellent catalytic performance.

[0038] It is preferable to produce a halogen-containing polyether polyol by ring-opening polymerization of the halogen-containing alkylene oxide described in (B), because it is easy to obtain a halogen-containing polyalkylene oxide having a low degree of unsaturation and a narrow molecular weight distribution, which improves the handleability when forming a prepolymer, and the curability of the obtained prepolymer is easy to be excellent.

[0039] The structure of the phosphazenium salt used in the production of the halogen-containing polyether polyol is not particularly limited.

[0040] The phosphazenium salt is, for example, a phosphazenium salt represented by formula (3):

[0041] [ka]

[0042] In formula (3), R 2 and R 3 are each independently Hydrogen atom, A hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 and a ring structure in which R 2 R 3 represents a ring structure in which the rings are bonded together; Z - represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chloride anion, a bromide anion, an iodide anion, or a hydrogen carbonate anion; Y represents a carbon atom or a phosphorus atom; a is 2 when Y is a carbon atom; When Y is a phosphorus atom, the number is 3.

[0043] In formula (3), R 2 , R 3The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecyl group.

[0044] R 2 and R 3 and 2 are bonded to each other to form a ring structure, examples of which include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

[0045] R 2 R 3 The ring structure in which two R 2 Or two R's 3 are each independently a group selected from alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, and one alkylene group and the other alkylene group are bonded to each other to form a ring structure.

[0046] Among these, R 2 and R 3 As the alkylene group, a methyl group, an ethyl group, or an isopropyl group is preferable, since it provides an alkylene oxide polymerization catalyst having particularly excellent catalytic activity and the raw materials are easily available.

[0047] In addition, Z in formula (3) - is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

[0048] The alkoxy anion having 1 to 4 carbon atoms is not particularly limited, but examples thereof include a methoxy anion, an ethoxy anion, an n-propoxy anion, an isopropoxy anion, an n-butoxy anion, an isobutoxy anion, and a t-butoxy anion.

[0049] The alkyl carboxy anion having 2 to 5 carbon atoms is not particularly limited, and examples thereof include an acetoxy anion, an ethyl carboxy anion, an n-propyl carboxy anion, an isopropyl carboxy anion, an n-butyl carboxy anion, an isobutyl carboxy anion, and a t-butyl carboxy anion.

[0050] Among these, Z - As the anion, a hydroxy anion and a hydrogen carbonate anion are particularly preferred since they provide a halogen-containing alkylene oxide polymerization catalyst having excellent catalytic activity.

[0051] The phosphazenium salt represented by the formula (3) is not particularly limited, but specifically includes tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide, Tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydroxide, tetrakis(1,3-diethylimidazolidine-2-imino)phosphonium hydroxide, tetrakis(1,1,3 ,3-tetramethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium Examples of the hydrogen carbonate include tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydrogen carbonate, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydrogen carbonate, and tetrakis(1,3-diethylimidazolidine-2-imino)phosphonium hydrogen carbonate.

[0052] In addition, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene), tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(1,3-dimethylimidazolidin-2-imino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(1,3-dimethylimidazolidin-2-imino)phosphoranylideneamino]phosphonium hydrogen carbonate, and the like can be mentioned.

[0053] Among these, tetrakis(1,1,3,3-tetramethylguanidinophosphonium hydroxide, tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydrogen carbonate, and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide are particularly preferred because they are halogen-containing polyether polyol production catalysts with excellent catalytic performance.

[0054] The structure of the ammonium salt or phosphonium salt is represented by formula (4):

[0055] [ka]

[0056] In formula (4), D represents a nitrogen atom or a phosphorus atom; R 4 , R 5 , R 6 and R 7 are each independently an alkyl group, an aryl group, an alkoxy group, or a dialkylamino group having 1 to 20 carbon atoms; A halogen atom, or Represents a hydrogen atom; E - represents a counter ion consisting of an inorganic or organic group; R 4 ~R 7 Two to four of these may be bonded to form a cyclic structure, and the cyclic structure may contain a heteroatom.

[0057] In formula (4), R 4 , R 5 , R 6 and R 7Examples of the alkyl group and aryl group having 1 to 20 carbon atoms represented by the formula (I) are not particularly limited, and include, for example, a methyl group, an ethyl group, a vinyl group, a normal propyl group, an isopropyl group, a cyclopropyl group, an allyl group, a normal butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, a normal pentyl group, a neopentyl group, a cyclopentyl group, a normal hexyl group, a cyclohexyl group, a phenyl group, a heptyl group, a cycloheptyl group, a benzyl group, a tolyl group, an octyl group, a cyclooctyl group, and a xylyl group.

[0058] In formula (4), R 4 , R 5 , R 6 and R 7 Examples of the alkoxy group having 1 to 20 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a vinyloxy group, a normal propoxy group, an isopropoxy group, a cyclopropoxy group, an allyloxy group, a normal butoxy group, an isobutoxy group, a t-butoxy group, a cyclobutoxy group, a normal pentyloxy group, a neopentyloxy group, a cyclopentyloxy group, a normal hexyloxy group, a cyclohexyloxy group, a phenoxy group, a heptyloxy group, a cycloheptyloxy group, an octyloxy group, a benzyloxy group, a tolyloxy group, a cyclooctyloxy group, and a xylyloxy group.

[0059] In formula (4), R 4 , R 5 , R 6 and R 7 Examples of the dialkylamino group having 1 to 20 carbon atoms represented by the formula (I) include a dimethylamino group, a diethylamino group, a pyrrolidino group, a piperidino group, a di-normal-propylamino group, a diisopropylamino group, and a dicyclopropylamino group.

[0060] The halogen atom is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0061] Since it is a catalyst for producing halogen-containing polyether polyols with excellent catalytic activity, 4 , R5 , R 6 and R 7 are each preferably independently an alkyl group or aryl group having 1 to 10 carbon atoms which may contain a heteroatom, and particularly preferably a methyl group, an ethyl group, a normal butyl group, a normal octyl group, or a phenyl group.

[0062] R 4 ~R 7 Among these, two to four may be bonded to form a cyclic structure, and it is preferable that two or three are bonded to form a cyclic structure. The cyclic structure may contain a heteroatom.

[0063] R 4 ~R 7 Examples of ammonium salt structures in which two or three of the above are bonded to form a cyclic structure include pyridinium salts and imidazolium salts, and imidazolium salts are preferred because they provide a halogen-containing polyether polyol production catalyst with excellent catalytic activity.

[0064] In formula (4), E - The inorganic or organic group represented by the formula (I) is not particularly limited, but specific examples thereof include a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfonic acid group, a boron hydride group, and a hexafluorophosphate group. Since the catalyst for producing halogen-containing polyether polyol has excellent catalytic activity, E - is preferably a bromine atom, a chlorine atom, an iodine atom, or a hexafluorophosphate group.

[0065] The ammonium salt or phosphonium salt represented by formula (4) is not particularly limited, but specifically includes tetramethylammonium bromide, tetraethylammonium bromide, tetra-normal propylammonium bromide, tetra-normal butylammonium bromide, tetra-normal pentylammonium bromide, tetra-normal hexylammonium bromide, tetra-normal heptylammonium bromide, tetra-normal octylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetra-normal propylammonium chloride, tetra-normal butylammonium chloride, tetra-normal pentylammonium chloride, tetra-normal hexylammonium chloride, tetra-normal heptylammonium chloride, tetra-normal octylammonium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-2, Examples of the phosphonium chloride include 3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetra-normal propylphosphonium bromide, tetra-normal butylphosphonium bromide, tetra-normal pentylphosphonium bromide, tetra-normal hexylphosphonium bromide, tetra-normal heptylphosphonium bromide, tetra-normal octylphosphonium bromide, tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetra-normal propylphosphonium chloride, tetra-normal butylphosphonium chloride, tetra-normal pentylphosphonium chloride, tetra-normal hexylphosphonium chloride, tetra-normal heptylphosphonium chloride, tetra-normal octylphosphonium chloride, and bromotris(dimethylamino)phosphonium hexafluorophosphate.

[0066] Among these, tetra-normal-octyl ammonium chloride, tetra-normal-octyl ammonium bromide, tetra-normal-butyl ammonium chloride, tetra-normal-butyl ammonium bromide, tetra-normal-ethyl ammonium chloride, tetra-normal-ethyl ammonium bromide, and tetra-normal-butyl phosphonium bromide are preferably used because they are halogen-containing polyether polyol production catalysts with excellent catalytic activity.

[0067] The polymerization temperature when producing the halogen-containing polyether polyol is not particularly limited, but is preferably in the range of 70 to 150°C, more preferably in the range of 90 to 110°C, because the polyalkylene oxide is unlikely to decompose and the molecular weight distribution is unlikely to broaden, and the catalytic activity is likely to be exhibited.

[0068] In the method for producing a halogen-containing polyether polyol, the polymerization reaction is preferably carried out without a solvent, but can also be carried out in a solvent. Examples of the solvent that can be used include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1,2-dimethoxyethane. <<Isocyanate compounds>> The isocyanate compound is not particularly limited, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, crosslinked cyclic alicyclic isocyanate compounds), and polyisocyanate derivatives thereof.

[0069] Examples of aromatic isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or a mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate, Examples of the isocyanate include 1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate, or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0070] Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate.

[0071] Examples of monocyclic alicyclic isocyanate compounds include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate), or a mixture thereof. Examples of the isocyanate include methyl cyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans cyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI).

[0072] Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornane diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane.

[0073] Examples of the derivatives of these polyisocyanates include polymers of the isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinedione, ureitonimine, isocyanurate modified products, polycarbodiimides, etc.), urethane modified products (e.g., urethane modified products in which a part of the isocyanate groups in the isocyanate compounds or polymers is modified or reacted with a monool or a polyol), biuret modified products (e.g., biuret modified products produced by the reaction of the isocyanate compounds with water), allophanate modified products (e.g., allophanate modified products produced by the reaction of the isocyanate compounds with a monool or polyol component), urea modified products (e.g., urea modified products produced by the reaction of the isocyanate compounds with a diamine), and oxadiazinetriones (e.g., oxadiazinetriones produced by the reaction of the isocyanate compounds with carbon dioxide gas, etc.).

[0074] The above-mentioned isocyanate compounds or derivatives thereof may be used alone or in combination of two or more kinds.

[0075] The amount of the isocyanate compound to be added is not particularly limited as long as it is terminated with NCO, but because free isocyanates that deteriorate the working environment, such as free TDI and HDI, are unlikely to be generated, the amount added is preferably such that the ratio of the total number of NCO groups in the isocyanate compound to the total number of OH groups in the halogen-containing polyether polyol (referred to as the NCO / OH ratio) is in the range of 1.2 to 3.0, and particularly preferably 1.5 to 2.5. <<Liquid urethane prepolymer composition>> The urethane prepolymer composition according to one embodiment of the present invention contains a filler and one or more of other polyols, urethane catalysts, foam stabilizers, antioxidants, and plasticizers. The order of mixing these is not particularly limited and can be appropriately selected.

[0076] Fillers include inorganic and organic fillers.

[0077] Examples of inorganic fillers include silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fibers, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fibers, carbon balun, zinc borate, and various magnetic powders.

[0078] Examples of organic fillers include synthetic organic fine particles such as polystyrene, polyacrylonitrile, polymethyl methacrylate, polypropylene, polyethylene, polyvinyl chloride, and polyurethane; and natural organic fine particles such as wood powder, bamboo powder, sawdust, paper pulp, and wood refined cellulose powder obtained from paper pulp.

[0079] The antioxidant is not particularly limited, and examples thereof include compounds that have the effect of suppressing oxidation of polymer chains, such as thioether-based compounds, phosphorus-based antioxidants, and hindered phenol-based compounds.

[0080] The other polyols are not particularly limited as long as they do not deviate from the purpose, and examples thereof include polyether polyols obtained by ring-opening polymerization of alkylene oxides, polymer polyols obtained by radical polymerization of vinyl monomers in polyether polyols, polyester polyols obtained by polycondensation of polyhydric alcohols and polycarboxylic acids, polyesteramide polyols obtained by polycondensation of polyhydric alcohols, polycarboxylic acids, and amino alcohols, polylactone polyols obtained by ring-opening polymerization of lactones, polycarbonate polyols obtained by polycondensation of polyhydric alcohols and carbonates, acrylic polyols, polybutadiene polyols and hydrogenated products thereof, polyisoprene polyols and hydrogenated products thereof, partially saponified ethylene-vinyl acetate copolymers, natural oil-based polyols such as soybean oil and castor oil, etc.

[0081] As the urethanization catalyst, a known urethanization catalyst can be used, for example, a tertiary amine compound, an organometallic compound, etc.

[0082] The tertiary amine compound is not particularly limited, but examples thereof include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), etc. These may be used alone or in combination of two or more kinds.

[0083] Organometallic compounds include, but are not limited to, tin-based compounds and non-tin-based compounds.

[0084] Examples of tin compounds include, but are not limited to, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurate (also known as DOTDL), and tin 2-ethylhexanoate.

[0085] Examples of non-tin-based compounds include, but are not limited to, titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanium trichloride, and butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium naphthenate.

[0086] Among the above urethane-forming catalysts, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate, etc. are preferred in terms of reactivity and hygiene.

[0087] The above-mentioned catalysts such as tertiary amine compounds and organometallic compounds can be used alone or in combination of two or more kinds.

[0088] The plasticizer is not particularly limited, and examples thereof include phthalates, non-aromatic dibasic acid esters, aliphatic esters, esters of polyalkylene glycol, phosphates, trimellitic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., and preferably phthalates. Specific examples thereof include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and epoxy benzyl stearate.

[0089] The foam stabilizer is not particularly limited, but examples thereof include silicone-based compounds. <Polyurethane> The polyurethane according to one embodiment of the present invention is obtained by curing the above-mentioned liquid urethane prepolymer or urethane prepolymer composition through a reaction with water in the air or a curing agent (an active hydrogen-containing compound).

[0090] When curing the urethane prepolymer composition, it may be cured in one liquid by moisture in the air (one-liquid type), or it may be cured in two liquids by using a curing agent (active hydrogen-containing compound) (two-liquid type).

[0091] Examples of one-component types include one-component moisture-curing types that are cured by reaction with moisture in the air, and one-component latent hardener types (sometimes referred to as 1.5-component types) that are cured by an active hydrogen-containing compound obtained from a latent hardener. Examples of two-component or more types include two-component curing types that are cured by mixing a base agent containing the liquid urethane prepolymer of the present invention with a hardener and other auxiliary materials, and any of these can be suitably used by selecting according to the application and required properties.

[0092] The active hydrogen-containing compound is not particularly limited as long as it contains one or more compounds having one or more active hydrogen groups. For example, water, polypropylene glycol, polyethylene propylene glycol, ethylene glycol (EG), diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol (1,4-BD), 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane and other diols, polypropylene triol, polyethylene propylene triol, glycerin, trimethylolpropane (TMP), triethanolamine. triols such as polypropylene tetraol, polyethylene propylene tetraol, castor oil, sucrose, sorbitol, and other polyols having 4 or more functional groups, modified polyamines such as 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) and modified MOCA modified with aniline, aromatic amines such as toluene diamine, diphenylmethane diamine, diethyltoluene diamine, and other aromatic amines, ethylene diamine, and other aliphatic amines, polyamines such as Jeffamine ED, amino alcohols such as ethanol amine and diethanol amine, and mixtures of two or more of these. Examples of a combination hardener system include a MOCA-polyol combination hardener in which an aromatic amine is mixed with a polyalkylene oxide.

[0093] The reaction temperature and reaction time in producing the polyurethane may be appropriately set depending on the purpose, and a reaction temperature of 20 to 220° C. and a reaction time of 0.1 minute to 24 hours are preferable.

[0094] The coating method for forming polyurethane is not particularly limited, but can be, for example, coating with a spatula, comb, roller, trowel, rake, etc., extrusion or spray with a sealing gun, hand coating, or machine coating to form a coating film, film sheet, thick object, or other desired shape of any thickness. Also, a compound having anti-sagging properties can be blended and applied to vertical surfaces, wall surfaces, curved surfaces, depressions, etc. with a roller, lysine gun, airless gun, etc. to form a coating film or cured product.

[0095] Specific uses of the polyurethane according to one embodiment of the present invention are not particularly limited, but include, for example, waterproof coating materials for balconies, rooftops of buildings, etc., waterproof sheets, waterproof coating materials for vehicles, flooring materials for condominiums, detached houses, and hospitals, elastic paving materials for sports facilities, etc., sealants for civil engineering and construction, vehicle sealants such as direct glazing and body sealers, medical potting agents, and siding joint caulking. <Sealant composition> The sealant composition of the present invention is preferably a one-component type since it forms a uniform composition, hardens and is likely to have excellent resistance to foaming. <Sealing material> A sealant according to one aspect of the present invention contains the above-mentioned polyurethane.

[0096] The application method of sealant is usually to fill a sealing gun, apply directly to the substrate that has been cleaned and / or primed and dried as necessary, and leave to harden. For automotive applications, the sealant is extruded directly onto the required area of ​​a substrate such as a steel plate that has been primed and dried as necessary, and then laminated to glass or other materials and allowed to harden by the moisture in the substrate or air. For architectural applications, the bonding surface is usually cleaned, and a backup material or bond breaker is loaded. Masking tape is applied around the joints, and then a primer is applied to the application area as a pretreatment. After that, the sealant is filled into the desired area such as the joints with a sealing gun, and finished with a spatula before application, followed by cleaning and curing.

[0097] In this case, if the curable resin composition is viscous, it takes time to extrude the composition when filling the joints, etc., and the workability is likely to be poor, so it is preferable that the cartridge extrusion time can be completed within 5 seconds, and more preferably within 4 seconds. If the sealant is too viscous, it may take time to clean the surroundings or the curable resin composition may adhere to the spatula during spatula finishing, making application and molding difficult, so it is preferable that the composition has a viscosity that allows application with a spatula or trowel, which is a normal application method, and has handleability.

[0098] In the case of the two-component type, a method in which a base liquid containing a curable resin composition and a curing agent liquid are mixed and applied directly to a base that has been washed or coated with a primer and dried as necessary, and then allowed to stand and harden, or a method in which the mixture is mixed by mechanical coating and then applied directly to a base that has been washed or coated with a primer and dried as necessary, and then allowed to harden, etc. can be mentioned.

[0099] Applications of the sealant according to one embodiment of the present invention are not particularly limited, but include, for example, sealants for civil engineering and construction, and sealants for vehicles such as direct glazing and body sealers. EXAMPLES

[0100] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The raw materials and evaluation methods used in the following examples and comparative examples are as follows. <Polyol> In the examples and comparative examples, a polyol having a structure shown in formula (5) was used. The properties of the polyol are shown in Table 1.

[0101] [ka]

[0102] [Table 1]

[0103] The raw materials used in Tables 1 to 3 are as follows: <<Halogen-containing polyether polyols (A, (C)>> Tetra-n-butylammonium bromide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum were used in combination to thoroughly dehydrate and remove the solvent, and 17.3 mol equivalents of epichlorohydrin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to polypropylene glycol with a molecular weight of 400 (manufactured by Sanyo Chemical Industries, Ltd., product name: Sannix PP-400) to produce a bifunctional halogen-containing polyether polyol (A) with a molecular weight of 2,000.

[0104] Furthermore, a difunctional halogen-containing polyether polyol (C) having a molecular weight of 1,000 was prepared in the same manner as in the preparation of the halogen-containing polyether polyol (A), except that 6.5 mol equivalents of epichlorohydrin were added instead of 17.3 mol equivalents of epichlorohydrin. <<Halogen-containing polyether polyols (B, (D)>> Tetra-n-butylammonium bromide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum were used in combination to thoroughly dehydrate and remove the solvent, and 20.3 mol equivalents of epichlorohydrin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to 1,6-hexanediol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to produce a difunctional halogen-containing polyether polyol (B) with a molecular weight of 2000.

[0105] Furthermore, in the preparation of the halogen-containing polyether polyol (B), 9.5 mol equivalents of epichlorohydrin were added instead of 20.3 mol equivalents to prepare a difunctional halogen-containing polyether polyol (D) having a molecular weight of 1000. <<Halogen-containing polyether polyol (E)>> Tetra-n-butylammonium bromide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum were used in combination to thoroughly dehydrate and remove the solvent, and 4.3 mol equivalents of epichlorohydrin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to polypropylene glycol with a molecular weight of 600 (manufactured by Sanyo Chemical Industries, Ltd., product name: Sannix PP-600) to prepare a difunctional halogen-containing polyether polyol (E) with a molecular weight of 1,000. <<Halogen-containing polyether polyol (F)>> Using the Lewis acid catalyst BF3-Et2O, epichlorohydrin was added to polypropylene glycol with a molecular weight of 400 (manufactured by Sanyo Chemical Industries, Ltd., product name: Sannix PP-400) to prepare a bifunctional polyether polyol (F) with a molecular weight of 2,000. <Isocyanate compounds> In all of the Examples and Comparative Examples, 4,4'-MDI (manufactured by Aldrich) was used as is without purification. (Analysis of polyol properties) <Unsaturation degree> Measurement was performed according to the method of JIS-K1557-6. <Molecular weight distribution (Mw / Mn)> 10 mg of polyol and 10 ml of THF were added to a sample bottle, allowed to stand overnight to dissolve, and then filtered through a PTFE cartridge filter (0.5 μm) to obtain a sample.

[0106] The detector used was an RI detector RI8020, and the measurement columns used were two TSKgel GMR-HHRL columns in series and an HLC-8020GPC (both manufactured by Tosoh Corporation).

[0107] The measurement conditions were a column temperature of 40° C., a flow rate of 1.0 ml / min, and THF as the solvent. The molecular weight distribution (Mw / Mn) was analyzed using a third-order approximation curve using standard polystyrene from Tosoh Corporation as the calibration curve.

[0108] Production Example (Production of NCO-Terminated Prepolymer Solution) 100 g of halogen-containing polyether polyol A was placed in a four-necked separable flask equipped with a stirring blade, and dehydration was carried out under reduced pressure at 80°C for 2 hours. After cooling to room temperature, 25 g of 4,4'-MDI was placed under nitrogen and the reaction was carried out at 100°C. Prepolymer 1 was synthesized by stirring until the consumption of NCO groups ceased as determined by back titration of the reactor contents with dibutylamine.

[0109] Prepolymers 2 to 8 were produced in the same manner as in the production example of prepolymer 1, except that the specified raw materials shown in Table 2 were used in the specified amounts.

[0110] [Table 2]

[0111] (Method of evaluating polyurethane) <Preparation of polyurethane sheet> The prepolymer obtained in the Synthesis Example of NCO-Terminated Prepolymer was applied to a release-treated PET film (Teijin Film Solutions Purex A31) using an applicator (YOSHIMITSU SEIKI) to a thickness of 150 μm with a tabletop coater (Mitsui Electric Seiki Co., Ltd., TC-1) at a speed of 1.0 m / min, and the coating was left to stand for 7 days in a thermostatic chamber at 23 to 25°C and 50% RH to produce a polyurethane sheet. <Breaking strength> The specimens were punched out into JIS No. 3 dumbbell shapes, and a tensile test was performed at a tensile speed of 200 mm / min using a tensile testing machine (Tensilon TG-1210 manufactured by A&D Corporation) to measure the breaking strength. The measurement was performed in an atmosphere of 23 to 25°C and 50% RH. The test was performed five times, and the average value excluding the maximum and minimum values ​​was calculated to determine the breaking strength. A:10MPa or more B: 5MPa or more and less than 10MPa C: Less than 5MPa <Tackiness> The prepared polyurethane was pressed against a thumb, and the resistance felt when it was peeled off was evaluated. A: Almost no resistance B: Resistance present C: Sticky <Transparency> The haze of the prepared polyurethane sheet was measured using a haze meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.). A: Less than 5% B: 5% or more but less than 10% C: 10% or more Examples 1 to 5. According to the polyurethane evaluation method, polyurethane sheets were produced using prepolymers 1 to 5 and evaluated. All of them had high breaking strength, low tackiness, and high transparency. Comparative Example 1 According to the polyurethane evaluation method, a polyurethane sheet was prepared using prepolymer 7 and evaluated. The transparency was good, but the curing was insufficient, stickiness occurred, and the breaking strength was poor. Comparative Example 2 According to the evaluation method for polyurethane, a polyurethane sheet was prepared using prepolymer 8 and evaluated. The breaking strength of the dumbbell piece was high, but resistance was felt when the thumb was pressed against the sheet surface, and the transparency was low. Comparative Example 3. According to the evaluation method for polyurethane, a polyurethane sheet was prepared using prepolymer 8 and evaluated. The breaking strength of the dumbbell piece was poor, resistance was felt when the thumb was pressed against the sheet surface, and the transparency was low.

[0112] The results of Examples 1 to 6 are shown in Table 3, and the results of Comparative Examples 1 to 3 are shown in Table 4.

[0113] [Table 3]

[0114] [Table 4]

[0115] (Evaluation as a sealing material) <Preparation of sealing material> To 100 parts by weight of the prepolymer obtained in the Synthesis Example of NCO-Terminated Prepolymer, 80 parts by weight of heavy calcium carbonate (Whiten SB, manufactured by Maruo Calcium Co., Ltd.) as a filler, 0.1 parts by weight of Iganox1010 (manufactured by BASF) as an antioxidant, and 0.1 parts by weight of bismuth octylate (Pcat 25, manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst were added, and the mixture was kneaded in a kneader to obtain a paste-like sealant composition.

[0116] The obtained sealant composition was applied to a 25 mm wide SUS304 test piece (manufactured by Partec, one side #320 HL) in a width of 5 mm and a thickness of 2 mm, which was then laminated and left to stand for 24 hours to allow curing to proceed, and test pieces were prepared and evaluated as sealants. <Curability> The test pieces obtained above were allowed to stand for 24 hours, and the feel of the sealant portion when touched with a finger was evaluated. A: Non-sticky B: Sticky C: Sealant sticks to fingers (not hardened) <Adhesiveness> The test pieces obtained above were subjected to a manual peel test, and the fracture surfaces were visually inspected to evaluate the properties. A: Cohesive failure B: Interfacial peeling <Shear peel strength> A shear peel test was performed using a tensile testing machine (A&D Corporation, Tensilon TG-1210) at a tensile speed of 50 mm / min to measure the shear peel strength. A: 5MPa or more B: 2MPa or more, less than 5MPa C: Less than 2MPa Application example 1. Following the sealant evaluation method, a sealant was prepared using prepolymer 3 and evaluated. It was easy to apply and showed good curing properties, adhesion, and shear peel strength. Application comparison example 1. According to the evaluation method for sealants, a sealant was prepared using prepolymer 6 and evaluated. When applied, dripping occurred, making application difficult, the sealant did not cure sufficiently, and the adhesiveness and shear peel strength were poor.

[0117] The results of the above application example are shown in Table 5.

[0118] [Table 5]

Claims

1. It is an NCO-terminated liquid urethane prepolymer, The urethane prepolymer is The number average molecular weight of the polymer is 200 or more and 3,000 or less, and the number average molecular weight of the polymer is 200 or more and 3,000 or less. The degree of unsaturation is 0.020 meq / g or less, The haze of the sheet obtained by coating at a thickness of 150 μm and leaving it for 7 days in a temperature-controlled room at 23 to 25° C. and 50% RH is less than 5%; The terminal is an NCO group, A liquid urethane prepolymer obtained by reacting a composition of a halogen-containing polyether polyol and an isocyanate compound, in which the ratio (NCO / OH ratio) of the total amount of NCO groups in the isocyanate compound to the total amount of OH groups in the halogen-containing polyether polyol is 1.2 or more and 3.0 or less: 【Chemistry 1】 In formula (1), Q represents a polymer component containing a structural unit represented by formula [I], m represents an integer from 2 to 8; R １ represents a residue of an active hydrogen-containing compound; 【Chemistry 2】 In formula [I], X represents a halogen atom.

2. 2. The liquid urethane prepolymer according to claim 1, wherein the degree of unsaturation is 0.016 meq / g or less.

3. A liquid urethane prepolymer composition comprising the liquid urethane prepolymer according to claim 1 and one or more of a filler, other polyols, urethane catalysts, foam stabilizers, antioxidants, and plasticizers.

4. A polyurethane obtained by curing the liquid urethane prepolymer according to any one of claims 1 to 2 or the liquid urethane prepolymer composition according to claim 3 through a reaction with water in the air or a curing agent (an active hydrogen-containing compound).

5. A sealant composition comprising the liquid urethane prepolymer according to claim 1 or the urethane prepolymer composition according to claim 3.

6. A sealant obtained by curing the sealant composition according to claim 5 by reaction with water in the air or a curing agent (an active hydrogen-containing compound).

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