Urethane-forming composition

Abstract

To provide an urethane forming composition contributing to forming polyurethane capable of suppressing cure shrinkage even when using an organic metal catalyst, excellent in curability and moldability, wrinkle-free, smooth and excellent in appearance, and polyurethane using the same.SOLUTION: An urethane forming composition (F) includes a polyol (A), an isocyanate compound (B), a triazole derivative (C) and an urethanization catalyst (D) including a metal component. The content of the triazole derivative (C) in the urethane forming composition (G) is 0.1 mass% or more and 3.0 mass% or less; the content of the urethanization catalyst (D) is 0.5 mass% or less; and the molar ratio of the triazole derivative (C) / the urethanization catalyst (D) including the metal component is 7 times or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to urethane-forming compositions. [Background technology]

[0002] As a method for increasing the reactivity and curing property of the urethanization reaction, various organometallic catalysts are used as catalysts.

[0003] However, when a polyfunctional polyol and a polyfunctional isocyanate are cured using an organometallic catalyst in order to enhance the curability, wrinkles are likely to occur due to shrinkage, and a polyurethane that is smooth and has a good appearance cannot be obtained stably. Furthermore, such catalyst systems are highly active in the urethanization reaction, and urethane-forming compositions using such systems rapidly gel when heated, dried, aged, or the like, resulting in poor moldability.

[0004] Here, Patent Document 1 discloses a method of using a plasticizer as a method of suppressing the cure shrinkage of urethane. However, the method of using a plasticizer requires the use of a large amount of a low molecular weight compound, which increases costs, and since almost the entire amount of the plasticizer remains in the polyurethane, there are problems in that the cure property of the resulting polyurethane deteriorates, the hardness decreases, and the properties as a urethane are impaired.

[0005] In other words, there has been a demand for a urethane-forming composition that can suppress shrinkage during the reaction and curing of a multifunctional polyol and an isocyanate using an organometallic catalyst, has good curability and moldability, and provides a wrinkle-free, smooth, and good appearance without impairing the properties such as hardness of the resulting polyurethane. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6628453 Summary of the Invention [Problem to be solved by the invention]

[0007] One aspect of the present invention is directed to providing a urethane-forming composition that suppresses cure shrinkage even when an organometallic catalyst is used, has good curability and moldability, and contributes to the formation of a polyurethane that has good physical properties such as hardness and is wrinkle-free, smooth, and has a good appearance, and a urethane-forming composition solution containing the urethane-forming composition.

[0008] Yet another aspect of the present invention is directed to providing a polyurethane sheet comprising said polyurethane. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the inventors have surprisingly found that by combining a triazole derivative with a specific urethane-forming catalyst and allowing the triazole derivative to act in an excess ratio of at least a specific molar ratio relative to the specific urethane-forming catalyst, it is possible to solve the problem of poor appearance due to wrinkles while maintaining curability, and have thus completed the present invention.

[0010] The various aspects of the present invention are as follows [1] to

[18] . [1] A urethane-forming composition (G) comprising a polyol (A), an isocyanate compound (B), a triazole derivative (C), and a urethane-forming catalyst (D) containing a metal component, The content of the triazole derivative (C) in the urethane-forming composition (G) is 0.1% by mass or more and 3.0% by mass or less, and The content of the urethane catalyst (D) is 0.5 mass% or less, and A urethane-forming composition (G) characterized in that the molar ratio of the triazole derivative (C) to the urethane-forming catalyst (D) containing a metal component is 7 times or more. [2] The urethane-forming composition (G) according to [1], characterized in that the triazole derivative (C) is a benzotriazole derivative. [3] The urethane-forming composition (G) according to [1] or [2], characterized in that the triazole derivative (C) is a benzotriazole derivative having one or more phenolic hydroxyl groups. [4] The urethane-forming composition (G) contains a keto-enol tautomer compound (E) as an essential component, The urethane-forming composition (G) according to any one of [1] to [3], characterized in that the keto-enol tautomer compound (E) contains at least one of ethyl acetoacetate and acetylacetone as an essential component. [5] The urethane-forming composition (G) according to any one of [1] to [4], characterized in that the urethane-forming composition (G) contains an acid retarder (F) as an essential component. [6] A urethane-forming composition solution (L) comprising the urethane-forming composition (G) according to any one of [1] to [5] and an organic solvent, The urethane-forming composition solution (L) is characterized in that the concentration of the urethane-forming composition (G) in the urethane-forming composition solution (L) is 10% by mass or more and 95% by mass or less. [7] A polyurethane (L) which is a reaction product of the urethane-forming composition (G) according to any one of [1] to [5] and the urethane-forming composition (G) in the urethane-forming composition solution (L) according to [6]. [8] A polyurethane sheet comprising the polyurethane (M) according to [7]. [9] A urethane prepolymer composition (I) comprising a urethane prepolymer (H), a triazole derivative (C), and a urethane-forming catalyst (D) containing a metal component, The urethane prepolymer (H) is a reaction product of at least a polyol (A) and a polyisocyanate (B) and has at least one hydroxyl group in one molecule; The sum of the hydroxyl groups (M OH ) the sum of the NCO groups of the isocyanate (B) relative to NCO ) mole ratio (M NCO / M OH ) is less than 1.0, The content of the triazole derivative (C) in the urethane prepolymer composition (I) is 0.1% by mass or more and 3.0% by mass or less. The content of the urethane catalyst (D) is 0.5 mass% or less, and A urethane prepolymer composition (I), characterized in that the molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component is 7 times or more.

[10] The urethane prepolymer composition (I) according to [9], wherein the triazole derivative (C) is a benzotriazole derivative.

[11] The urethane prepolymer composition (I) according to [9] or

[10] , wherein the triazole derivative (C) is a benzotriazole derivative having one or more phenolic hydroxyl groups.

[12] The urethane prepolymer composition (I) contains a keto-enol tautomer compound (E) as an essential component, The keto-enol tautomer compound (E) contains at least one of ethyl acetoacetate and acetylacetone as an essential component. The urethane prepolymer composition (I) according to any one of [9] to

[11] .

[13] The urethane prepolymer composition (I) according to any one of [9] to

[12] , characterized in that the urethane prepolymer composition (I) contains an acid retarder (F) as an essential component.

[14] A urethane prepolymer composition solution (K) comprising the urethane prepolymer composition (I) according to any one of [9] to

[13] and an organic solvent, wherein the concentration of the urethane prepolymer composition (I) in the urethane prepolymer composition solution (K) is 10% by mass or more and 95% by mass or less.

[15] A urethane-forming composition (G) comprising the urethane prepolymer composition (I) according to any one of [9] to

[13] and an isocyanate compound (J).

[16] A urethane-forming composition solution (L) containing the urethane prepolymer composition solution (K) according to

[14] and an isocyanate compound (J).

[17] A polyurethane (M) which is a reaction product of the urethane-forming composition (G) according to

[15] and the urethane-forming composition (G) in the urethane-forming composition solution (L) according to

[16] .

[18] A polyurethane sheet comprising the polyurethane (M) according to

[17] . Effect of the Invention

[0011] The urethane-forming composition of the present invention has good moldability when applied with a coating machine or the like to obtain a polyurethane, and although it exhibits high curability using an organometallic catalyst, cure shrinkage can be suppressed. It is also capable of forming a polyurethane that has good physical properties such as hardness and is wrinkle-free and smooth in appearance.

[0012] Moreover, polyurethanes obtained by using the urethane-forming composition of the present invention can be suitably used in a wide range of applications, such as sealing materials, paints, pressure sensitive adhesives, and bonding agents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Exemplary embodiments for carrying out the present invention are described in detail below.

[0014] A urethane-forming composition (G) according to one embodiment of the present invention is a urethane-forming composition (G) comprising a polyol (A), an isocyanate compound (B), a triazole derivative (C), and a urethane-forming catalyst (D) containing a metal component, in which the content of the triazole derivative (C) in the urethane-forming composition (G) is 0.1 mass% or more and 3.0 mass% or less, the content of the urethane-forming catalyst (D) is 0.5 mass% or less, and the molar ratio of the triazole derivative (C) / the urethane-forming catalyst (D) containing a metal component is 7 times or more.

[0015] Each component will be described below. <Polyol (A)> The polyol (A) may be a commercially available polyol used in the production of polyurethane. Although not particularly limited, examples thereof include polyether polyols obtained by ring-opening polymerization of alkylene oxide or tetrahydrofuran, polymer polyols obtained by radical polymerization of vinyl monomer in polyether polyol, polyester polyols obtained by polycondensation of polyhydric alcohol and polycarboxylic acid, polyesteramide polyols obtained by polycondensation of polyhydric alcohol, polycarboxylic acid, and amino alcohol, polylactone polyols obtained by ring-opening polymerization of lactones, polycarbonate polyols obtained by polycondensation of polyhydric alcohol and carbonate, acrylic polyols, polybutadiene polyol and its hydrogenated products, polyisoprene polyol and its hydrogenated products, partially saponified ethylene-vinyl acetate copolymer, natural oil polyols such as soybean oil and castor oil, halogen and / or phosphorus polyols, phenol polyols, etc. These polyols may be used alone or in combination of two or more.

[0016] Among them, it is preferable to include at least one of polyester polyols and polyether polyols, since although appearance defects such as wrinkles tend to occur, these can be easily suppressed by adding a triazole derivative, they are highly versatile and easily available, and they tend to exhibit a good balance of physical properties including transparency and hardness. The proportion of polyester polyol and / or polyether polyol is preferably in the range of 10 to 100 parts by weight in 100 parts by weight of polyol.

[0017] Examples of polyester polyols include compounds derived from dibasic acids and polyhydric alcohols. Although not particularly limited, examples of polyester polyols include polyester polyols derived from adipic acid, orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, azelaic acid, sebacic acid, linosyl acid, dimethyl terephthalate, and polyethylene terephthalate. In addition, examples of polyester polyols include lactone-based polyester polyols obtained by ring-opening polymerization of cyclic esters such as ε-caprolactone and methyl valerolactone.

[0018] Examples of polyether polyols include polyether polyol compounds obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide, and tetrahydrofuran to initiators such as ethylene diamine, tolylene diamine, sucrose, amino alcohols, butanol, glycerin, diethylene glycol, and low molecular weight polypropylene glycols having a molecular weight of 1000 or less. When using polyether polyols, although there are no particular limitations, it is preferable that they have at least one of ethylene oxide residues and propylene oxide residues, since this tends to improve moldability and transparency.

[0019] Examples of halogen- and / or phosphorus-based polyols include halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, halogen-based polyols such as brominated pentaerythritol / sucrose-based polyols and tetrabromophthalic acid polyesters, and phosphorus-based polyols obtained by adding alkylene oxide to a phosphoric acid compound.

[0020] Examples of phenol-based polyols include Mannich-based polyols obtained by Mannich-modifying phenol or phenol derivatives such as nonylphenol and alkylphenol with formaldehyde and a secondary amine such as diethanolamine, ammonia, a primary amine, or the like, and then ring-opening addition polymerizing the modified phenol with an alkylene oxide such as ethylene oxide or propylene oxide.

[0021] The polyol is not particularly limited as long as it has at least one hydroxyl group at the polymer end, branched chain end, etc., but the crosslinked structure of the polyurethane obtained by the reaction with the isocyanate compound becomes dense, and although appearance defects such as wrinkles are likely to occur, they can be suppressed by adding a triazole derivative, and the obtained urethane is likely to exhibit a good balance of physical properties including transparency and high hardness, so it is preferable to have 2 to 8 hydroxyl groups in the molecule, more preferably a polyol having 2 to 4 hydroxyl groups in the molecule because it is easy to obtain, has a wide range of design, and is highly versatile, and most preferably a multifunctional polyol having 3 hydroxyl groups. When the average functionality of the polyol is 1.0 or more and less than 2.0, it is preferable to use a multifunctional isocyanate with an isocyanate functionality of 3 or more, and to include a component having two or more active hydrogens that react with isocyanates, such as water or diamine, as necessary, so that the crosslinked structure becomes dense.

[0022] Although not particularly limited, the polyurethane raw material preferably has a hydroxyl value of 1 to 1000 (mgKOH / g), and more preferably has a hydroxyl value of 10 to 800 (mgKOH / g). The hydroxyl value can be calculated according to the method of JIS K1557, for example.

[0023] The molecular weight of the polyol (A) is not particularly limited, but since it tends to have excellent curability and moldability, the number average molecular weight calculated from the hydroxyl value and the number of functional groups is preferably in the range of 100 to 50,000, and more preferably in the range of 500 to 10,000. <Isocyanate compounds (B) and (J)> The isocyanate compounds (B) and (J) are not particularly limited, and examples thereof include commercially available isocyanates used in the production of polyurethanes, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6 -hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers obtained by reacting these with polyols, and mixtures of two or more of these. Furthermore, modified products of these isocyanates (modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group, or an oxazolidone group) and condensates (sometimes called polynuclear products) such as polymethylene polyphenylene polyisocyanate (polymeric MDI) are also included. These isocyanates may be used alone or in combination of two or more.

[0024] The isocyanate compounds (B) and (J) are not particularly limited as long as they have at least one isocyanate group at a polymer end, a branched chain end, or the like. However, it is preferable that the average functionality of the isocyanate groups is 2.0 or more, since the crosslinked structure of the polyurethane obtained by the reaction with the polyol becomes dense, and defects in appearance such as wrinkles tend to occur, but this can be suppressed by adding a triazole derivative, and the obtained urethane tends to exhibit good physical properties such as transparency and high hardness.

[0025] When the average functionality of the isocyanate group is 1.0 or more and less than 2.0, it is preferable to use a multifunctional polyol having a polyol functionality of 3 or more and, if necessary, to contain a multifunctional component that reacts with the polyol, such as polyisothiocyanate, to form a dense crosslinked structure.

[0026] The content of the isocyanate compound (B) is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of polyol, since a small content may result in a decrease in hardness, and a large content may result in poor moldability or may make it difficult to suppress wrinkles even when a triazole derivative is added, and more preferably in the range of 1 to 50 parts by weight per 100 parts by weight of polyol, since this makes it easier to achieve both coating appearance and moldability. When producing a polyurethane foam product, the content is preferably in the range of 10 to 300 parts by weight per 100 parts by weight of polyol.

[0027] A portion of each raw material, such as the polyol (A) and the isocyanate compound (B), used in the present invention may be reacted in advance to form a urethane prepolymer (H). Alternatively, a urethane prepolymer composition (I) containing a catalyst and various additives, or a urethane prepolymer composition solution (K) further containing a solvent, may be formed as necessary.

[0028] When a urethane prepolymer (H) is formed using a composition containing an isocyanate compound (B), a urethane-forming composition (G) can be produced by adding an isocyanate compound (J) as a crosslinking agent after the formation of the prepolymer. <Triazole derivatives (C)> The urethane-forming composition (G) is characterized by containing a triazole derivative (C). By containing the triazole derivative (C) in the urethane-forming composition, it is possible to stably suppress the cure shrinkage that occurs when the multifunctional urethane raw material is cured by reaction using a metal catalyst, and form a urethane with good moldability and a good appearance without wrinkles. Furthermore, the obtained urethane has high hardness and is likely to exhibit good transparency.

[0029] This is thought to be because the triazole derivative (C) acts on the metal catalyst and suppresses the reactivity during the curing reaction during drying, aging, etc., thereby suppressing shrinkage due to the rapid curing of the multifunctional polyol and isocyanate, and also because the reaction proceeds uniformly and the degree of crosslinking after completion of the reaction is high, resulting in the obtained urethane exhibiting high hardness and good transparency.

[0030] If the urethane-forming composition does not contain the triazole derivative (C), it is difficult to form a urethane having a good, wrinkle-free coating appearance stably when a polyol or isocyanate with a high number of functional groups is used and a metal catalyst is used to form the urethane, since the effect of processing conditions is minimal. In addition, transparency is likely to deteriorate, making the composition difficult to use.

[0031] The content of the triazole derivative (C) in the urethane-forming composition (G) is 0.1% by mass or more and 3.0% by mass or less. In particular, the content of the triazole derivative (C) is preferably 0.2% by mass or more and 2.0% by mass or less, and more preferably 0.3% by mass or more and 1.5% by mass or less, because it is easy to form a coating film with higher transparency and good appearance.

[0032] If the content of the triazole derivative (C) in the urethane-forming composition (G) is less than 0.1% by mass, the wrinkle-inhibiting effect is low and it becomes difficult to stably form a urethane with a good coating film appearance. If it exceeds 3% by mass, phase separation is likely to occur during storage, processability deteriorates, and compatibility deteriorates, resulting in poor transparency of the obtained urethane and uneven coating, resulting in poor appearance, and the gel fraction decreases, resulting in deterioration of physical properties such as tack expression and hardness, making it difficult to use.

[0033] The molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component in the urethane-forming composition (G) (triazole derivative (C) / urethanization catalyst (D) containing a metal component) is 7 or more. In particular, the molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component (triazole derivative (C) / urethanization catalyst (D) containing a metal component) is preferably 10 to 500 times, more preferably 15 to 300 times, and most preferably 25 to 200 times, because wrinkles are more stably suppressed regardless of drying and curing conditions, and therefore higher transparency is easily achieved while maintaining good compatibility, and the coating film appearance is also easily improved.

[0034] If the molar ratio of the triazole derivative (C) to the metal catalyst is less than 7 times, the molar ratio of the triazole derivative acting on the metal catalyst becomes relatively small, so that the adjustment effect of the reaction activity of the metal catalyst is small, and it becomes difficult to suppress wrinkles due to cure shrinkage, and it is difficult to form a urethane with a good coating appearance, making it difficult to use.

[0035] The triazole derivative (C) in the urethane-forming composition (G) is not particularly limited as long as it contains a triazole structure containing three nitrogen atoms in a five-membered ring. In a compound that does not contain three nitrogen atoms, such as a triazole derivative, nitrogen is appropriately coordinated to the metal catalyst, and the catalytic activity during heating, drying, and aging is moderated, so that the curing shrinkage suppression effect is small, and it is difficult to stably form a urethane with a good coating film appearance without wrinkles.

[0036] As the triazole derivative (C), for example, a 1,2,4-triazole derivative and a 1,2,3-triazole derivative can be mentioned, and can be suitably used.

[0037] Among them, it is preferable to include one or more benzotriazole derivatives, which are one type of 1,2,3-triazole derivatives, because they have a high effect of suppressing curing shrinkage and are easy to form a urethane with a good coating film appearance. In addition, it is preferable for the benzotriazole derivative to have one or more phenolic hydroxyl groups because it is easy to increase the wrinkle suppression effect, and it is more preferable for the benzotriazole derivative to have a substituent at the ortho position of the phenolic hydroxyl group because it is difficult to react with isocyanate to deactivate and is easy to stably suppress wrinkles. Examples of the substituent that is preferable to have at the ortho position of the phenolic hydroxyl group include quaternary substituents such as t-butyl groups, tertiary substituents such as triazolyl groups, and secondary substituents such as methylene groups. In addition, it is preferable to have an alkyl group or an ester group at the para position of the phenolic hydroxyl group because it is easy to liquefy the triazole derivative, has good compatibility, is unlikely to cause coating unevenness, and is easy to form a urethane with a transparent appearance.

[0038] The triazole derivative (C) is preferably in the range of 100 to 2000 in molecular weight, more preferably in the range of 200 to 1000, and most preferably in the range of 300 to 700, because it is less likely to volatilize or bleed from the urethane during curing, and therefore the wrinkle suppression effect is enhanced, and it is easy to form a urethane with a transparent appearance, because it has good compatibility and the coating unevenness of the obtained urethane is less likely to occur. Although not particularly limited, it is preferable that these triazole derivatives (C) are liquid at room temperature, because they tend to have excellent compatibility and the coating film appearance such as the transparency of the obtained urethane is more likely to be good. If necessary, a small amount of diluent of 10% by mass or less based on the triazole derivative may be contained to make it liquid.

[0039] Although not particularly limited, the 1,2,4-triazole derivative may be a compound represented by the following general formula (1), including tautomers thereof.

[0040] [ka]

[0041] (In formula (1), R1, R2, and R3 are not particularly limited, and the type and presence or absence of a substituent can be selected arbitrarily.) Examples of R1, R2, and R3 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl or alkyl-substituted aryl group, a heteroaryl or alkyl-substituted heteroaryl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxy group, a halogen, a polyoxyalkylene group, and hydrogen.

[0042] Examples of the compound that can be suitably used include 4-amino-1,2,4-triazole, 1,2,4-triazole, and 3-mercapto-1,2,4-triazole.

[0043] Although not particularly limited, the 1,2,3-triazole derivative may be a compound represented by the following general formula (2), which also includes tautomers thereof.

[0044] [ka]

[0045] (In formula (2), R1, R2, and R3 are not particularly limited, and the type and presence or absence of a substituent can be selected arbitrarily.) Examples of R1, R2, and R3 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl or alkyl-substituted aryl group, a heteroaryl or alkyl-substituted heteroaryl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxy group, a halogen, a polyoxyalkylene group, hydrogen, etc. In the formula, R1 and R2 may be independent or may be bonded to form a ring such as an aryl, heteroaryl, cycloalkyl, or cycloalkenyl.

[0046] Benzotriazole derivatives are 1,2,3-triazole derivatives, which are compounds having a benzene ring structure containing the carbon atoms at the 4th and 5th positions of triazole, and include, but are not limited to, compounds represented by the following general formula (3): These tautomers are also included.

[0047] [ka]

[0048] (In formula (3), R1, R2, R3, R4, and R5 are not particularly limited, and the type and presence or absence of a substituent can be selected arbitrarily.) Examples of R1, R2, R3, R4 and R5 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl or alkyl-substituted aryl group, a heteroaryl or alkyl-substituted heteroaryl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxy group, a halogen, a polyoxyalkylene group, hydrogen, etc. Among these, it is preferable that R5 has a phenyl ring structure directly bonded thereto, since this has a high wrinkle-suppressing effect and tends to result in a stable and good coating film appearance.

[0049] The above compound is not particularly limited, but examples thereof include 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (TT-LYK manufactured by Johoku Chemical Industry Co., Ltd.), 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole (TT-LX manufactured by Johoku Chemical Industry Co., Ltd.), carboxybenzotriazole (CBT-1 manufactured by Johoku Chemical Industry Co., Ltd.), 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (BT-LX manufactured by Johoku Chemical Industry Co., Ltd.), 1,2,3-benzotriazole, 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol (Johoku Chemical Industry Co., Ltd.), JAST-500), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (JF-832 manufactured by Johoku Chemical Industry Co., Ltd.), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (JF-83 manufactured by Johoku Chemical Industry Co., Ltd.), 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole (JF-80 manufactured by Johoku Chemical Industry Co., Ltd.), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (JF-79 manufactured by Johoku Chemical Industry Co., Ltd.), and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (JF-77 manufactured by Johoku Chemical Industry Co., Ltd.).

[0050] Benzotriazole derivatives having a phenolic hydroxyl group include compounds having a phenolic hydroxyl group in at least one of R1, R2, R3, R4, and R5 in the above general formula (3). The phenolic hydroxyl group refers to a hydroxyl group directly bonded to a benzene ring, and the aryl group containing the phenolic hydroxyl group may or may not be directly bonded to the benzotriazole, but it is preferable that the aryl group containing the phenolic hydroxyl group is directly bonded to the benzotriazole, since this promotes coordination of the triazole to the metal, adjusts the reactivity, and makes it easier to suppress wrinkles.

[0051] Among them, a compound in which the ortho position of the phenoxy group is directly bonded to the triazole nitrogen is more preferable because isocyanate and phenolic hydroxyl group are less likely to react with each other and the wrinkle suppressing effect is likely to be enhanced, and examples thereof include, but are not limited to, compounds represented by the following general formula (4), including their tautomers.

[0052] [ka]

[0053] (In formula (4), R1, R2, R3, R4, R5, R6, R7, and R8 are not particularly limited, and the type and presence or absence of a substituent can be selected arbitrarily.) Examples of R1, R2, R3, R4, R5, R6, R7, and R8 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl or alkyl-substituted aryl group, a heteroaryl or alkyl-substituted heteroaryl group, an alkoxyalkyl group, an acyloxyalkyl group, a hydroxy group, a halogen, a polyoxyalkylene group, and hydrogen. Among these, R8 in the general formula is more preferably a quaternary substituent such as a t-butyl group, a tertiary substituent such as a triazolyl group, or a secondary substituent such as a methylene group, and it is preferable that R6 has a substituent such as an alkyl group or an ester group in order to facilitate liquefaction.

[0054] Examples of the above-mentioned compound include, but are not limited to, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Tinuvin 571 manufactured by BASF) and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropionic acid (alkyl ester having 7 to 9 carbon atoms) (Tinuvin 99-2 manufactured by BASF), which are most suitable for use in preventing wrinkles. <Urethanization catalyst containing metal components (D)> The urethanization catalyst (D) contains a metal component.

[0055] When using only a urethanization catalyst that does not contain a metal component, such as an amine catalyst, or when using a catalyst-free system that does not contain a urethanization catalyst (D) that contains a metal component, the triazole derivative (C) cannot coordinate to the metal that acts as a catalyst, and the effect of suppressing wrinkles due to cure shrinkage is not obtained, making it difficult to use.In addition, side reactions such as a foaming reaction (urea reaction) between moisture in the air and isocyanate are likely to proceed, and air bubbles may deteriorate the appearance of the coating film, or dangling chains may be formed instead of a uniform crosslinked structure, thereby worsening the curing property and transparency, making it difficult to use.

[0056] The content of the urethanization catalyst (D) containing a metal component in the urethane-forming composition (G) is 0.001% by mass or more and 0.5% by mass or less. Although not particularly limited, the content of the urethanization catalyst (D) containing a metal component is preferably in the range of 0.001% by mass to 0.1% by mass, and more preferably in the range of 0.005% by mass to 0.07% by mass, because this improves the moldability and tends to improve the appearance of the resulting urethane coating film.

[0057] If the content of the urethane-forming catalyst (D) containing a metal component exceeds 0.5 mass %, the curing reaction will be too rapid, resulting in poor moldability, and the catalyst will tend to promote wrinkles, so that the amount of triazole derivative (C) required to suppress wrinkles will be too large, resulting in poor compatibility and poor hardness and transparency of the resulting urethane, making it difficult to use.

[0058] The urethanization catalyst (D) containing a metal component is not particularly limited as long as it is a compound containing a metal component and exhibits urethanization activity, but is preferably an organometallic compound containing one or more metals of Fe, Sn, Zr, Ti, and Al. Among them, it is more preferable to use a Sn catalyst, which is easily available and has low temperature dependency of catalytic activity, and one or more metal chelate catalysts such as an Fe chelate catalyst, a Zr chelate catalyst, a Ti chelate catalyst, and an Al chelate catalyst, which are easy to adjust the reactivity, because wrinkles are easily suppressed when a triazole derivative is added, and it is most preferable to use a Sn catalyst or an Fe chelate catalyst alone.

[0059] The Sn catalyst is not particularly limited, but examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diversatate, and dibutyltin bis(acetylacetonate).

[0060] Although not particularly limited, examples of the Fe chelate catalyst include iron trisacetylacetonate, etc.; examples of the Zr chelate catalyst include zirconium tetraacetylacetonate, zirconium ethylacetoacetate, etc.; examples of the Ti chelate catalyst include titanium acetylacetonate, titanium ethylacetoacetate, etc.; and examples of the Al chelate catalyst include aluminum trisacetylacetonate, etc. <Keto-enol tautomer compounds (E)> The urethane-forming composition (G) of the present invention preferably contains at least one keto-enol tautomer compound, either ethyl acetoacetate or acetylacetone, since the catalytic activity can be adjusted to easily achieve good moldability.

[0061] When the keto-enol tautomer compound (E) is contained, the content thereof is preferably in a molar ratio (keto-enol tautomer compound / metal catalyst) of 10 times or more relative to the urethanization catalyst containing a metal component, since this tends to improve moldability, and more preferably in the range of 50 to 5,000 times, and the content thereof in the urethane-forming composition (G) is preferably in the range of 0.01 to 20% by mass, and more preferably in the range of 0.5 to 10% by mass. <Acid retarder (F)> The urethane-forming composition (G) of the present invention preferably contains an acid retarder (F) because it is easy to suppress rapid gelation during drying, aging, and coating, and it is easy to stably suppress wrinkles and improve moldability, and it is preferable to contain an acid with a pKa of 5.0 or less, but is not particularly limited. Examples of such acids with a pKa of 5.0 or less include phosphorus-based acid retarders such as hydrochloric acid, nitric acid, phosphoric acid, and acidic phosphoric acid esters having 2 to 20 carbon atoms such as ethyl acid phosphate and 2-ethylhexyl acid phosphate, and among them, it is preferable to use a phosphorus-based acid retarder because it is easy to achieve a good balance between reactivity and physical properties. When the acid retarder (F) is used, the content in the urethane-forming composition (G) is preferably in the range of 0.001% by mass to 1% by mass, and more preferably in the range of 0.005% by mass to 0.1% by mass. In addition, when the acid retarder is used, the pH of the urethane-forming composition (G) is preferably in the range of 4 to 9. The pH of the urethane-forming composition (G) refers to the value measured by dispersing the composition at 7% by mass in a mixture of water and IPA at a weight ratio of 5:3 using a pH meter. <Other additives> The urethane-forming composition (G) of the present invention may contain additives such as antioxidants, chain extenders, antistatic agents, plasticizers, leveling agents, and other additives.

[0062] Among them, it is preferable to contain a monofunctional compound in addition to the polyol (A) and the isocyanate compound (B) since the moldability is likely to be good. As such a functional compound, it is preferable to use at least one of monofunctional alcohol, monofunctional isocyanate, and monofunctional amine since the moldability is likely to be good, and more preferably at least one of polyalkylene glycol monoalkyl ether and polyalkylene glycol monofatty acid ester having a molecular weight of 100 to 1000. When a monofunctional compound is used, the content in the urethane-forming composition (G) is preferably in the range of 0.1% by mass to 5% by mass.

[0063] The chain extender is not particularly limited, and examples thereof include glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, and low molecular weight polyalkylene glycols having a molecular weight of 1000 or less; and polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, piperazine, isophoronediamine, and xylylenediamine. Among these, polyvalent amines are preferred because they form urethane urea and are easy to obtain urethane with good physical properties.

[0064] The antistatic agent is not particularly limited, but examples thereof include alkali metal salts and ionic liquids, such as lithium salts such as lithium bis(trifluoromethanesulfonylimide), quaternary ammonium salts, imidazolium salts, phosphonium salts, and pyridinium salts.

[0065] The plasticizer is not particularly limited, but examples thereof include fatty acid esters, alicyclic esters, polyether esters, etc., such as epoxidized fatty acid esters, myristic acid esters, and terminal ester-modified compounds of polyalkylene glycols. <Urethane-forming composition (G)> The urethane-forming composition (G) according to one embodiment of the present invention comprises a polyol (A), an isocyanate compound (B), a triazole derivative (C), and a urethane-forming catalyst (D) containing a metal component, in which the content of the triazole derivative (C) is 0.1% by mass or more and 3.0% by mass or less, the content of the urethane-forming catalyst (D) is 0.5% by mass or less, and the molar ratio of the triazole derivative (C) to the urethane-forming catalyst (D) containing a metal component is 7 times or more. The raw materials such as the polyol (A) and the isocyanate compound (B) may be mixed and reacted in advance to form a urethane prepolymer (H).

[0066] Although not particularly limited, the urethane-forming composition (G) preferably has a viscosity at 25°C when uniformly dispersed in a range of 0.1 to 100 Pa s, more preferably 1 to 30 Pa s, in order to suppress wrinkles in the resulting urethane and to facilitate a transparent and good appearance. Also, it is preferable that the composition is liquid, and that the liquid has low elasticity and high fluidity.

[0067] The preparation of the urethane-forming composition (G) is not particularly limited as long as it is a method capable of uniformly dispersing the raw materials contained in the urethane-forming composition (G), and various stirring methods known in the art can be used, for example, a method of stirring using a stirrer. Examples of the stirrer include a general-purpose stirrer, a planetary stirrer, a disperser disperser, a kneader, a mixer, a lab plastomill, and a planetary mixer. When all the components of the urethane-forming composition (G) are liquid at the stirring temperature, a planetary stirrer, a planetary stirrer, a disperser dissolver, and a planetary stirrer are preferably used. In addition, operations such as heating, pressurization, and standing may be added as necessary for defoaming.

[0068] When the urethane-forming composition (G) contains a urethane prepolymer (H) obtained by previously mixing and reacting some of the raw materials in a certain ratio, various conventionally known stirring methods can also be used for preparing the urethane prepolymer. <Urethane prepolymer composition (I)> A urethane prepolymer composition (I) according to one embodiment of the present invention is a urethane prepolymer composition (I) comprising a urethane prepolymer (H), a triazole derivative (C), and a urethanization catalyst (D) containing a metal component, The urethane prepolymer (H) is a reaction product of at least a polyol (A) and a polyisocyanate (B) and has at least one hydroxyl group in one molecule; The sum of the hydroxyl groups (M OH ) the sum of the NCO groups of the isocyanate (B) relative to NCO ) mole ratio (M NCO / M OH ) is less than 1.0, the content of the triazole derivative (C) in the urethane prepolymer composition (I) is 0.1% by mass or more and 3% by mass or less, the content of the urethanization catalyst (D) is 0.5% by mass or less, and The molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component is 7 times or more.

[0069] When the urethane prepolymer (H) is formed in advance, the weight average molecular weight is preferably 1000 or more because it is easy to suppress rapid curing shrinkage, and the moldability is good, and the polyurethane obtained is less likely to wrinkle and the coating film appearance is good. In particular, the weight average molecular weight is preferably in the range of 5000 to 1,000,000, which is good in fluidity and easy to excel in moldability, and more preferably the weight average molecular weight is in the range of 10,000 to 500,000. In addition, the molecular weight distribution of the urethane prepolymer (H) is preferably 1.05 to less than 6.0, and more preferably 1.5 to less than 4.0, because the elasticity of the liquid is low regardless of the viscosity, and it is easy to excel in fluidity and easy to excel in moldability. The weight average molecular weight and molecular weight distribution of the urethane prepolymer (H) can be measured according to a conventional method using gel permeation chromatography (GPC).

[0070] When the urethane prepolymer (H) is formed in advance, the total number of hydroxyl groups (M OH ) the sum of the NCO groups of the isocyanate (B) relative to NCO ) mole ratio (M NCO / M OH ) is less than 1.0. In particular, it is preferably 0.10 or more and 0.95 or less, and more preferably 0.15 or more and 0.80 or less. NCO / M OH ) represents the molar ratio. NCO / M OHIf the ratio is 1.0 or more, the storage stability of the urethane prepolymer composition is likely to deteriorate, and small amounts of gelled matter and bubbles are likely to form in the urethane-forming composition obtained using the same, which can lead to poor appearance of the coating film, such as bumps and foaming, and thus the appearance of the coating film may deteriorate when the urethane is formed.

[0071] Furthermore, the average functionality of the polyol (A) is preferably, but not limited to, 1.9 or more, and more preferably from 2 to 6. A urethane-forming composition (G) having an average functionality of 1.9 or more calculated from the functionality and the molar ratio is preferred because it has excellent curing (solidification) properties when a polyurethane is obtained by curing accompanying the reaction, and the polyurethane has further good mechanical properties.

[0072] When producing the urethane prepolymer (H), the polyol (A) and the isocyanate compound (B) are preferably dehydrated by vacuum heating or the like before use, but may be used without dehydration if this operation would be complicated. the content of the triazole derivative (C) in the urethane prepolymer composition (I) is 0.1% by mass or more and 3% by mass or less, the content of the urethanization catalyst (D) is 0.5% by mass or less, and The molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component is 7 or more. The preferred content, composition ratio, and liquid viscosity are in the same ranges as those in the urethane-forming composition (G). <Urethane-forming composition solution (L)> The urethane-forming composition (G) can be mixed with an organic solvent to form a urethane-forming composition solution (L) in order to facilitate handling or to obtain the desired viscosity or coatability.

[0073] At this time, the urethane-forming composition solution (L) contains a urethane-forming composition (G) and an organic solvent, and the concentration of the urethane-forming composition (G) in the urethane-forming composition solution (L) is 10% by mass or more and 95% by mass or less.

[0074] Examples of the organic solvent include methyl ethyl ketone, ethyl acetate, butyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide. In terms of solubility and boiling point of the organic solvent, ethyl acetate, toluene, methyl ethyl ketone, or a mixture thereof is particularly preferred. These solvents can be added at any stage.

[0075] The concentration of the urethane-forming composition in the urethane-forming composition solution (L) is 10% by mass or more and 95% by mass or less, and preferably 30% by mass or more and 70% by mass or less. When the concentration is in this range, good coatability can be obtained when the urethane-forming composition solution (L) is applied with a coater or the like, making it easy to handle.

[0076] The viscosity of the urethane-forming composition solution (L) at 25°C is not particularly limited, but The viscosity is preferably in the range of 0.1 to 100 Pa·s, and more preferably in the range of 1 to 30 Pa·s. In addition, it is preferable that the viscosity is liquid, and that the liquid has low elasticity and high fluidity. If the viscosity is within this range, handling can be facilitated, for example, good coatability can be obtained when the urethane-forming composition solution (L) is applied with a coater or the like. <Urethane prepolymer composition solution (K)> The urethane prepolymer composition (I) can be mixed with an organic solvent to form a urethane prepolymer composition solution (K) in order to facilitate handling or to obtain a desired viscosity or coatability.

[0077] In this case, the urethane prepolymer composition solution (K) contains a urethane prepolymer composition (I) and an organic solvent, and the concentration of the urethane-forming composition (G) in the urethane prepolymer composition solution (K) is 10% by mass or more and 95% by mass or less, or the urethane prepolymer composition solution (L) contains a urethane prepolymer composition (I) and an organic solvent, and the concentration of the urethane prepolymer composition (I) in the urethane-forming composition solution (L) is 10% by mass or more and 95% by mass or less.

[0078] Examples of the organic solvent include methyl ethyl ketone, ethyl acetate, butyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide. In terms of solubility and boiling point of the organic solvent, ethyl acetate, toluene, methyl ethyl ketone, or a mixture thereof is particularly preferred. These solvents can be added at any stage.

[0079] The concentration of the urethane-forming composition in the urethane prepolymer composition solution (K) is 10% by mass or more and 95% by mass or less, and preferably 30% by mass or more and 70% by mass or less. When the concentration is in this range, good coatability can be obtained when the urethane prepolymer composition solution (K) is applied with a coater or the like, making it easy to handle.

[0080] The viscosity of the urethane prepolymer composition solution (K) at 25° C. is not particularly limited, but is preferably in the range of 0.1 to 100 Pa s, and more preferably in the range of 1 to 30 Pa s. It is also preferable that the solution is in a liquid state, has low elasticity, and has high fluidity.

[0081] If the viscosity is within this range, the urethane prepolymer composition solution (K) can be easily handled, for example, good coatability can be obtained when the solution is applied with a coater or the like.

[0082] The urethane prepolymer composition solution (K) can be made into a urethane-forming composition solution (L) by being combined with an isocyanate compound (J). <Polyurethane (M)> Polyurethane (M) can be obtained by reacting and curing (solidifying) the urethane-forming composition (G) by various methods. There is no particular limitation on the method for producing the polyurethane (M). For example, the polyurethane-forming composition (G) can be produced by carrying out a urethane-forming reaction or a urea-forming reaction at room temperature or a high temperature of 150° C. or less in the presence of a urethane-forming catalyst, a solvent, an antioxidant, a light stabilizer, a chain extender, a crosslinking agent, and other additives, as necessary.

[0083] In order to achieve good curability, the process may include a step of activating the composition at high temperature and a step of removing the solvent and additives, if necessary. Here, since the urethane-forming composition (G) has remarkably excellent formability when applied using a coating machine or the like, a polyurethane (M) coating film or polyurethane sheet having a thin and uniform thickness can be obtained.

[0084] The thickness of the coating film of polyurethane (M) is not particularly limited, but the thickness of the coating film is preferably from 1 μm to 1000 μm, more preferably from 5 μm to 300 μm, in order to obtain a particularly good appearance of the coating film.

[0085] The applications of polyurethane (M) are not particularly limited, and it can be used in any application where ordinary polyurethane is used, but it is particularly suitable for applications where mechanical properties and tackiness / adhesive properties are required, etc. Specific examples of applications where polyurethane (M) can be used preferably include sealing materials for construction and civil engineering, adhesives such as elastic adhesives for construction, packing tapes and surface protection films, various pressure sensitive adhesives such as those for optical applications, paints, elastomers, waterproof coating materials, flooring materials, plasticizers, soft polyurethane foams, semi-rigid polyurethane foams, and rigid polyurethane foams.

[0086] Among these, polyurethane is particularly preferred for use as a sealant, paint, pressure sensitive adhesive, and bonding agent, since it is required to have high mechanical properties and adhesive properties, and is also required to have good workability and coatability. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to the following examples unless it exceeds the gist of the invention. The raw materials and evaluation methods used in the following examples and comparative examples are as follows. (Raw Material 1) Polyol A used in the Examples and Comparative Examples Polyol A1: Trifunctional polypropylene / polyethylene glycol with a molecular weight of 3400 (ADEKA Polyether GR3308, manufactured by ADEKA Corporation) Polyol A2: Bifunctional polypropylene glycol with a molecular weight of 2000 (Sanyo Chemical Sannix PP2000) Polyol A3: Polyester polyol with molecular weight of 1000 (Nippolan 4009, manufactured by Tosoh Corporation) All of the raw material polyols were dehydrated before use. (Raw Material 2) Isocyanate Compounds (B) and (J) Used in the Examples and Comparative Examples Isocyanate compounds B1 and J1: Isocyanurate modified hexamethylene diisocyanate (Tosoh Coronate HXR) Isocyanate compound B2: Trimethylolpropane adduct modified tolylene diisocyanate (Tosoh Coronate L) (Raw Material 3) Triazole Derivative (C) and Compound (CC) Used in the Examples and Comparative Examples Triazole derivative C1: 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (BASF Tinuvin 571, liquid) Triazole derivative C2: 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropionic acid, alkyl ester with 7 to 9 carbon atoms (BASF Tinuvin 99-2, liquid) Triazole derivative C3: 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (BT-LX, liquid, manufactured by Johoku Chemical Industry Co., Ltd.) Triazole derivative C4: 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol (JAST-500, powder, manufactured by Johoku Chemical Industry Co., Ltd.) Compound CC1: 1,2-dimethylimidazole Compound CC2: N,N'-dimethylpiperazine Compound CC3: Dibutylhydroxytoluene (BHT) (Raw Material 4) Metal-containing urethanization catalyst (D) and non-metallic urethanization catalyst (DC) used in the examples and comparative examples Urethane catalyst D1: Dioctyltin dilaurate Urethane catalyst D2: Iron trisacetylacetonate Urethane catalyst DC1: Triethylenediamine (Raw material 5) Additives Keto-enol tautomeric compound E1: Acetylacetone Acid retarder F1: 2-Ethylhexyl acid phosphate Monofunctional compound 1: Polyethylene glycol monomethyl ether #400 (Preparation of urethane-forming composition (G) and urethane-forming composition solution (L)) In the examples and comparative examples, a predetermined amount of each raw material (e.g., polyol (A), isocyanate compound (B), triazole derivative (C), urethanization catalyst (D), and other raw materials) was placed in a 50 ml sample bottle, and the mixture was stirred and defoamed at room temperature using a planetary centrifugal mixer to obtain a urethane-forming composition. When a prepolymer (H) was used, it was synthesized in advance, and the weight average molecular weight and molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) were measured by gel permeation chromatography before use.

[0088] The centrifugal mixer used was a Thinky Mixer ARE-310 manufactured by Thinky Corporation. The centrifugal mixer was rotated at a rotation speed of 2000 rpm for 5 minutes and rotated at a rotation speed of 2200 rpm for 5 minutes to produce the urethane-forming composition (G) or the urethane-forming composition solution (L). The viscosity was measured immediately after the rotation at a rotation speed of 2000 rpm for 5 minutes and the value measured with a B-type viscometer was recorded as the viscosity. Then, the performance evaluation was started.

[0089] During this process, the properties were evaluated according to the following criteria. (Property evaluation) <Viscosity> Viscosity 0 (good): 0.1 to 30 Pa·s, and the liquid flows 1 cm within 3 seconds when tilted 180° Viscosity △ (possible): Over 30 Pa·s, or the liquid takes more than 3 seconds to flow 1 cm even when tilted 180° (high elasticity) <Weight average molecular weight> Weight average molecular weight 〇 (good): 10,000 to 500,000 Weighted average molecular weight △ (possible): Over 500,000 <Molecular weight distribution> Molecular weight distribution: Good: 1.05 to less than 6.0 Molecular weight distribution △ (possible): 6.0 or more (Performance evaluation) The urethane-forming composition (G) was applied onto a PET film having a thickness of 38 μm using a Baker-type applicator so that the thickness after drying would be 100 μm or less. The film was then placed in an oven set at 130° C. for 3 minutes to volatilize the solvent, and allowed to stand for 1 week in an environment of 23° C. and 50% relative humidity to obtain a coating film.

[0090] In this process, the performance of the urethane-forming composition was evaluated according to the following criteria. <Moldability (coatability, thickness unevenness)> ◎ (Pass formability): When a molded sheet with a uniform thickness is obtained without any uneven coating and the difference in thickness between the edges and center is 3% or less. ○ (Pass moldability): Slight coating unevenness is visible to the naked eye, or there is slight thickness unevenness with the difference in thickness between the edge and center exceeding 3% and not exceeding 5%. × (Failed formability): The liquid flows during application or drying (making uniform forming difficult), or there is clear thickness unevenness of more than 5% at the edges and center. <Curability> ◎ (Curing pass): When the sticky feeling disappears after being removed from the oven and returned to room temperature. ○ (Curing pass): When removed from the oven, a slight tack remains when touched with the fingers, and the sticky feeling disappears almost completely after leaving it for 7 days in an environment of 23°C and a relative humidity of 50%. ×× (failed curing): If, after being removed from the oven, the product still feels sticky even after being left to stand for 7 days in an environment of 23°C and relative humidity of 50% (curing failure). <Appearance of coating film> ◎ (Paint film appearance passes): The obtained urethane has no wrinkles, is visually free of bumps and is smooth. ○ (Paint appearance passed): The obtained urethane has no wrinkles or bubbles, but has slight bumps that make it less smooth or visually transparent. × (coating appearance failed): Air bubbles occurred in the obtained urethane, and the coating appearance was poor. ×× (coating appearance failed): The resulting urethane had wrinkles due to cure shrinkage, resulting in a poor coating appearance. <Coating film properties> ◎ (Paint film physical properties pass): No tack when evaluated by touching with fingers. ○ (Paint film physical properties pass): When evaluated by touch, there is a slight sense of tack. ×× (coating film physical properties fail): If there is tack when evaluated by touch (insufficient hardness).

[0091] Compositions that passed all the evaluation criteria were judged to be urethane-forming compositions that contribute to the formation of polyurethane with excellent coating film appearance and coating film physical properties, and that have good moldability and curability, do not require long periods of time for coating and curing, and have high productivity. <Examples and Comparative Examples> Example 1 contains 100 parts by weight of polyol (A1), 1 part by weight of triazole derivative (C1), 0.02 parts by weight of metal-containing urethanization catalyst (D1), 3.0 parts by weight of keto-enol tautomer compound (E1), and 0.03 parts by weight of acid retarder (F1), and the amount of hydroxyl groups derived from (A1) (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1) NCO / (A1) M OH = 1.05. Table 1 shows the results of Example 1. The urethane-forming composition (G1) had good coatability and curability, and the coating film of the polyurethane (M1) obtained from the composition (G1) had excellent coating appearance and physical properties, being free from appearance defects such as wrinkles and tackiness.

[0092] Comparative Example 1 is a urethane-forming composition (GC1) that does not contain the triazole derivative (C1) as compared with Example 1. Since the composition (GC1) does not contain the triazole derivative (C1), wrinkles are generated when the composition (GC1) is dried, a uniform molded product is not obtained, and the moldability is poor. In addition, the polyurethane (MC1) obtained from the composition (GC1) has no tack when touched with fingers and exhibits hardness, but has a poor appearance due to wrinkles and other factors, making it difficult to use.

[0093] Example 2 contains 100 parts by weight of polyol (A2), 1.5 parts by weight of triazole derivative (C1), 0.015 parts by weight of metal-containing urethanization catalyst (D1), 3.0 parts by weight of keto-enol tautomer compound (E1), and 0.03 parts by weight of acid retarder (F1), and the amount of hydroxyl groups derived from (A1) (M OH ) and the amount of isocyanate groups derived from (B2) (M NCO ) is the molar ratio, and M of (B2) NCO / (A1) M OH = 1.05.

[0094] The urethane-forming composition (G2) had good coatability and curability, and the coating film of the polyurethane (M2) obtained from the composition (G2) had excellent coating appearance and physical properties, being free of appearance defects such as wrinkles and tackiness.

[0095] Comparative Example 2 is a urethane-forming composition (GC2) that does not contain the urethane-forming catalyst (D1) as compared with Example 2. Since the composition (GC2) does not contain the urethane-forming catalyst (D1), the liquid flows when dried, resulting in poor moldability and poor curing properties, and the polyurethane (MC2) obtained from the composition (GC2) was very tacky to the touch, had poor coating film properties, and also had poor coating film appearance, making it difficult to use.

[0096] Example 3 is a urethane-forming composition (G3) in which the amount of triazole derivative (C1) was reduced to 0.4 parts by weight and the amount of urethanization catalyst (D1) was increased to 0.05 parts by weight compared to Example 1. The urethane-forming composition (G3) had good coatability and curability, and the coating film of polyurethane (M3) obtained from the composition (G3) had excellent coating film appearance and coating film physical properties, being free of appearance defects such as wrinkles and tackiness.

[0097] Comparative Example 3 is a urethane-forming composition (GC3) in which the amount of triazole derivative (C1) in Example 3 was further reduced to 0.07 parts by weight, and the molar ratio of triazole derivative (C1) to urethanization catalyst (D1) was reduced to 2.6.

[0098] In the composition (GC3), the ratio of the triazole derivative (C1) to the urethane catalyst (D1) was less than 7:1, so the cure shrinkage during urethane formation could not be suppressed, and wrinkles occurred in the coating film, resulting in poor appearance of the coating film, making it difficult to use.

[0099] Example 4 contains 100 parts by weight of polyol (A3), 2.9 parts by weight of triazole derivative (C2), 0.03 parts by weight of metal-containing urethane catalyst (D1), 5.0 parts by weight of keto-enol tautomer compound (E1), and 0.03 parts by weight of acid retarder (F1), and the amount of hydroxyl groups derived from (A3) (M OH ) and the amount of isocyanate groups derived from (B2) (M NCO) is the molar ratio, and M of (B2) NCO / (A3) M OH = 1.05.

[0100] The urethane-forming composition (G4) had a difference in thickness from Example 2 due to the large amount of liquid triazole, but the moldability and curability were generally good, and the coating film of the polyurethane (M4) obtained from the composition (G4) was free of appearance defects such as wrinkles and was generally free of tack, and had excellent coating appearance and physical properties.

[0101] Comparative Example 4 is a urethane-forming composition (GC4) in which the amount of triazole derivative (C2) was further increased to 4.0 parts by weight relative to Example 4. Since the content of triazole derivative (C1) in the urethane-forming composition in this composition (GC4) exceeds 3.0 mass %, although wrinkles during curing can be suppressed, curing takes time, and the resulting polyurethane (MC4) is also tacky and has poor coating properties, making it a difficult composition to use.

[0102] Example 5 contains 50 parts by weight of polyol (A1), 50 parts by weight of polyol (A2), 0.5 parts by weight of triazole derivative (C2), 0.02 parts by weight of metal-containing urethanization catalyst (D1), and 0.03 parts by weight of acid retarder (F1), and the amount of hydroxyl groups derived from (A1) and (A2) (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1) NCO / M of (A1) and (A2) OH = 1.05.

[0103] Since the urethane-forming composition (G5) does not contain the keto-enol tautomer compound (E1), its moldability is slightly inferior to that of Example 3. However, its moldability and curability are generally good. The coating film of the polyurethane (M5) obtained from the composition (G5) was free from defects in appearance such as wrinkles and was free from tack, and had excellent coating appearance and physical properties.

[0104] Comparative Example 5 is a urethane-forming composition (GC5) which does not contain the triazole derivative (C2) as compared with Example 5, and instead contains a reduced amount of the urethane-forming catalyst (D1) to 0.001 parts by weight in order to adjust the reactivity.

[0105] Since the urethane-forming composition (GC5) does not contain the triazole derivative (C), wrinkles occur during drying even when the amount of the urethane catalyst (D1) is reduced. The polyurethane (MC5) obtained from the composition (GC5) has no tack when touched with a finger and exhibits hardness, but has a poor appearance due to wrinkles and other factors, making it difficult to use.

[0106] Example 6 is a urethane-forming composition (G6) which does not contain the acid retarder (F1) for adjusting the reactivity compared to Example 5, and instead contains an increased amount of triazole derivative (C2) to 1.0 part by weight.

[0107] Since the urethane-forming composition (G6) does not contain the monofunctional compound (1), its moldability is slightly inferior to that of Example 5. However, its moldability and curability are generally good. The coating film of the polyurethane (M6) obtained from the composition (G6) is free of wrinkles and has slight coating unevenness, but has a generally good coating appearance and excellent coating physical properties.

[0108] Examples 1 to 6 and Comparative Examples 1 to 5 shown in Table 1 all had a low viscosity of less than 30 Pa·s and presented no problems with handling.

[0109] [Table 1]

[0110] Example 7 is a urethane-forming composition (G7) in which the urethane-forming catalyst (D1) having Sn as the central metal was changed to a urethane-forming catalyst (D2), which is a metal chelate catalyst, in comparison with Example 1. The urethane-forming composition (G7) had good coatability and curability, and the coating film of the polyurethane (M7) obtained from the composition (G7) had excellent coating film appearance and coating film physical properties, being free of appearance defects such as wrinkles and tackiness.

[0111] Example 8 is a urethane-forming composition (G8) in which the triazole derivative (C1) was changed to (C2) and the amount of the urethane-forming catalyst (D2) was reduced to 0.005 parts by weight compared to Example 7. The urethane-forming composition (G8) had good coatability and curability, and the coating film of the polyurethane (M8) obtained from the composition (G8) had excellent coating film appearance and coating film physical properties, being free of appearance defects such as wrinkles and tackiness.

[0112] Example 9 is a urethane-forming composition (G9) in which the triazole derivative (C1) having a phenolic hydroxyl group in Example 1 is changed to a triazole derivative (C3) having no phenolic hydroxyl group.

[0113] The urethane-forming composition (G9) had good coatability and curability, and since it contained a triazole derivative, the coating of the polyurethane (M9) obtained from said composition (G9) was wrinkle-free and had slight coating unevenness, but the coating appearance was generally good and the coating physical properties were excellent.

[0114] Example 10 is a urethane-forming composition (G10) in which the liquid triazole derivative (C1) in Example 1 is changed to a powder triazole derivative (C4), and the amount of the urethane-forming catalyst (D1) is changed from 0.02 parts by weight to 0.005 parts by weight, thereby increasing the molar ratio of the triazole derivative to the urethane-forming catalyst by 297.5 times.

[0115] The urethane-forming composition (G10) had good coatability and curability, and because it contained a powdered triazole derivative, the coating of the polyurethane (M10) obtained from said composition (G10) was wrinkle-free and slightly less smooth due to a small amount of bumps, but the coating had a generally good appearance, was almost free of tack, and the coating properties were generally excellent.

[0116] Comparative Example 6 is a urethane-forming composition (GC6) in which 1.0 part by weight of the compound (CC1), an imidazole derivative that is a nitrogen-based heterocycle, was used instead of 1.0 part by weight of the triazole derivative (C1) in Example 7. Since the composition (GC6) does not contain the triazole derivative (C) but does contain an imidazole derivative, it generates air bubbles in addition to wrinkles when dried, hardens quickly, and does not give a uniform molded product, resulting in poor moldability. In addition, the polyurethane (MC6) obtained from the composition (GC6) had no tack when touched with fingers and exhibited hardness, but was not smooth due to wrinkles and had a poor appearance, making it difficult to use.

[0117] Comparative Example 7 is a urethane-forming composition (GC7) in which 1.0 part by weight of the triazole derivative (C4) in Example 10 is changed to 1.0 part by weight of the compound (CC2), which is a piperazine derivative that is a nitrogen-based heterocycle. Since the composition (GC7) does not contain the triazole derivative (C) but contains a piperazine derivative, the curability is generally good, but when dried, wrinkles and bubbles are generated, and a molded product cannot be obtained, resulting in poor moldability. In addition, the polyurethane (MC7) obtained from the composition (GC7) had no tack when touched with fingers and exhibited hardness, but was not smooth due to wrinkles and had a poor appearance, making it difficult to use.

[0118] Comparative Example 8 is a urethane-forming composition (GC8) in which 1.0 part by weight of the triazole derivative (C4) in Example 10 was changed to 1.0 part by weight of a compound (CC3) having a phenolic hydroxyl group but not containing a triazole structure.

[0119] Since the composition (GC8) does not contain the triazole derivative (C), wrinkles occur during drying, a uniform molded product cannot be obtained, and the moldability is poor. In addition, the polyurethane (MC8) obtained from the composition (GC8) has no tack when touched with a finger and exhibits hardness, but has a poor appearance due to wrinkles and other factors, making it difficult to use.

[0120] Comparative Example 9 is a urethane-forming composition (GC9) in which, compared to Example 8, 0.005 parts by weight of the urethane-forming catalyst (D2) containing a metal component was changed to 0.07 parts by weight of an amine-based catalyst (DC1) containing no metal component, and the amount of triazole derivative (C2) was increased.

[0121] This composition (GC9) does not contain the urethane catalyst (D2) containing a metal component, but contains an amine catalyst, which causes slight liquid flow and a slight delay in curing, resulting in slightly inferior moldability and curing properties. The polyurethane (MC9) obtained from this composition (GC9) had a poor coating appearance due to the generation of bubbles, was tacky, and had insufficient hardness, making it difficult to use.

[0122] Examples 7 to 10 and Comparative Examples 6 to 9 shown in Table 2 all had a low viscosity of less than 30 Pa·s and presented no problems with handling.

[0123] [Table 2]

[0124] In Example 11, 100 parts by weight of polyol (A1), 0.5 parts by weight of monofunctional compound (1), and isocyanate compound (B1) were mixed in the presence of 0.02 parts by weight of urethanization catalyst (D1) to determine the amount of hydroxyl groups (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1) NCO / (A1) and monofunctional compound (1) M OH =0.35, and the prepolymer (H11) was previously prepared by mixing and reacting.

[0125] The polyurethane prepolymer composition (I11) contains the above prepolymer (H11), 1.0 part by weight of a triazole derivative (C1), 3.0 parts by weight of a keto-enol tautomer compound (E1), and 0.03 part by weight of an acid retarder (F1), and the amount of hydroxyl groups derived from (A1) and the monofunctional compound (1) (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1)NCO / (A1) and monofunctional compound (1) M OH = 0.70, and a urethane-forming composition solution (L11) containing ethyl acetate as an organic solvent. The concentration of (G11) in the solution (L11) is 30%.

[0126] The urethane-forming composition solution (L11) had a low solution viscosity of less than 30 Pa·s, a prepolymer weight average molecular weight of less than 500,000, and a low molecular weight distribution of 1.5 to less than 6.0, providing excellent solution properties for handling.

[0127] The results of Example 11 are shown in Table 3. The urethane-forming composition solution (L11) had good coatability and curability, and the coating of polyurethane (M11) obtained from the composition solution (L11) had excellent coating appearance and physical properties, being free of appearance defects such as wrinkles and tackiness.

[0128] In Example 12, 75 parts by weight of polyol (A1), 25 parts by weight of polyol (A2), 5 parts by weight of monofunctional compound (1), and isocyanate compound (B2) were mixed in advance in the presence of 0.02 parts by weight of urethanization catalyst (D1) to obtain a mixture having a hydroxyl group content (M OH ) and the amount of isocyanate groups derived from (B2) (M NCO ) is the molar ratio, and M of (B2) NCO / (A1) and (A3) and monofunctional compound (1) M OH = 0.35, and the prepolymer (H12) was previously prepared by mixing and reacting.

[0129] The polyurethane prepolymer composition (I12) contains the above prepolymer (H12), 1.0 part by weight of a triazole derivative (C2), 3.0 parts by weight of a keto-enol tautomer compound (E1), and 0.03 parts by weight of an acid retarder (F1), and the amount of hydroxyl groups (M OH ) and the amount of isocyanate groups derived from (B2) (M NCO ) is the molar ratio, and M of (B2) NCO / (A1) and (A3) and monofunctional compound (1) M OH = 0.70, and a urethane-forming composition solution (L12) containing ethyl acetate as an organic solvent. The concentration of (G12) in the solution (L12) is 70%.

[0130] The urethane-forming composition solution (L12) had a low solution viscosity of less than 30 Pa·s, a prepolymer weight average molecular weight of less than 500,000, and a low molecular weight distribution of 1.5 to less than 6.0, providing excellent solution properties for handling.

[0131] The results of Example 12 are shown in Table 3. The urethane-forming composition solution (L12) had good coatability and curability, and the coating of polyurethane (M12) obtained from the composition solution (L12) had excellent coating appearance and physical properties, being free of appearance defects such as wrinkles and tackiness.

[0132] In Example 13, 100 parts by weight of polyol (A1) and isocyanate compound (B1) were mixed in advance in the presence of 0.005 parts by weight of urethanization catalyst (D1) to determine the amount of hydroxyl groups derived from (A1) (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1) NCO / (A1) M OH = 0.52, and the prepolymer (H13) was previously prepared by mixing and reacting.

[0133] The urethane prepolymer composition (I13) contains the above prepolymer (H13) and 1.0 part by weight of a triazole derivative (C3), and the amount of hydroxyl groups derived from (A1) (M OH ) and the amount of isocyanate groups derived from (B1) (M NCO ) is the molar ratio, and M of (B1) NCO / (A1) M OH= 0.53, and a urethane-forming composition solution (L13) containing methyl ethyl ketone as an organic solvent. The concentration of (G13) in the solution (L13) is 60%.

[0134] The urethane-forming composition solution (L13) had a prepolymer weight average molecular weight of over 500,000 and a molecular weight distribution of 6.0 or more, so the fluidity of the solution was somewhat low. Although it was usable, the solution properties made it somewhat difficult to handle.

[0135] The results of Example 13 are shown in Table 3. The urethane-forming composition solution (L13) had generally good coatability and curability, and the coating of the polyurethane (M13) obtained from the composition solution (L13) was wrinkle-free and slightly less smooth, but had a generally good coating appearance and was free of tack, exhibiting excellent coating physical properties.

[0136] Comparative Example 10 is a urethane-forming composition (GC10) in which the triazole derivative (C1) mixed after the formation of the prepolymer is replaced with a compound (CC1) not containing a triazole structure, and a urethane-forming composition solution (LC10) containing ethyl acetate as an organic solvent, in comparison with Example 11. The concentration of (GC10) in the solution (LC10) is 50%.

[0137] Since the composition solution (LC10) does not contain the triazole derivative (C1) but contains an imidazole derivative, wrinkles and air bubbles are generated during drying, making it difficult to obtain a uniform molded product and resulting in poor moldability. In addition, the polyurethane (MC10) obtained from the composition solution (LC10) had no tack when touched with fingers and exhibited hardness, but was not smooth due to wrinkles and had a poor appearance, making it difficult to use.

[0138] Comparative Example 11 is a urethane-forming composition (GC11) in which the triazole derivative (C1) mixed after the formation of the prepolymer is replaced with a compound (CC3) having a phenolic hydroxyl group but not containing a triazole structure, and a urethane-forming composition solution (LC11) containing ethyl acetate as an organic solvent, in which the concentration of (GC11) in the solution (LC11) is 50%.

[0139] Since the composition solution (LC11) does not contain the triazole derivative (C1), wrinkles occur during drying, a uniform molded product cannot be obtained, and the moldability is poor. In addition, the polyurethane (MC11) obtained from the composition solution (LC11) has no tack when touched with a finger and exhibits hardness, but has a poor appearance due to wrinkles and other factors, making it difficult to use.

[0140] In Comparative Example 12, a urethane-forming composition (GC12) not containing a urethane-forming catalyst (D1) having a metal component, and a urethane-forming composition solution (LC12) containing ethyl acetate as an organic solvent, in comparison with Example 11, are used. The concentration of (GC12) in the solution (LC12) is 50%. Since the composition (GC12) does not contain the urethane-forming catalyst (D1), the curing properties are significantly poor, and the polyurethane (MC12) obtained from the composition (GC12) has an opaque coating appearance, is very tacky when touched with a finger, and has poor coating properties, making it difficult to use.

[0141] All of the compositions used in the examples of the present invention had a pH in the range of 4 to 9, and exhibited good liquid properties that were low corrosive and easily exhibited good curing properties.

[0142] [Table 3]

[0143] As shown in the examples above, the urethane-forming composition of this development has excellent formability when applied, dried, and cured using a coating machine, etc., and can suppress deterioration of the coating film appearance due to wrinkles, air bubbles, etc., without impairing curability.

[0144] Furthermore, a polyurethane having little tack and good physical properties such as hardness can be obtained by reaction with an isocyanate compound. By utilizing this characteristic, it has been shown that the polyurethane obtained from the urethane-forming composition can be suitably used for sealing materials, paints, pressure sensitive adhesives, adhesives, etc.

Claims

1. A urethane-forming composition (G) comprising a polyol (A), a polyisocyanate compound (B), a triazole derivative (C), a urethanization catalyst (D) containing a metal component, and one or more keto-enol tautomer compounds (E) of ethyl acetoacetate or acetylacetone, wherein the content of the triazole derivative (C) in the urethane-forming composition (G) is 0.1% by mass or more and 3.0% by mass or less, and The content of the urethanization catalyst (D) is 0.001% by mass or more and 0.5% by mass or less, and The content of the keto-enol tautomeric compound (E) is 0.5% by mass or more and 10% by mass or less, and The molar ratio of the triazole derivative (C) to the urethanization catalyst (D) is 7 times or more; the molar ratio of the keto-enol tautomer compound (E) to the urethanization catalyst (D) is in the range of 50 to 5000 times; The urethane-forming composition (G) comprises an acid retarder (F) in the urethane-forming composition (G).

2. A urethane prepolymer composition (I) comprising a urethane prepolymer (H), a triazole derivative (C), a urethanization catalyst (D) containing a metal component, and one or more keto-enol tautomer compounds (E) of ethyl acetoacetate and acetylacetone, the urethane prepolymer (H) is a reaction product of at least a polyol (A) and a polyisocyanate compound (B) and has at least one hydroxyl group in one molecule; a molar ratio (MNCO / MOH) of the sum of the NCO groups (MNCO) contained in the polyisocyanate compound (B) to the sum of the hydroxyl groups (MOH) contained in the polyol (A) forming the urethane prepolymer (H) is less than 1.0, In the urethane prepolymer composition (I), the content of the triazole derivative (C) is 0.1% by mass or more and 3.0% by mass or less, the content of the urethanization catalyst (D) is more than 0% by mass and 0.5% by mass or less, and the content of the keto-enol tautomer compound (E) is 0.5% by mass or more and 10% by mass or less, and A urethane prepolymer composition (I) characterized in that the molar ratio of triazole derivative (C) to urethanization catalyst (D) containing a metal component is 7 times or more, and the molar ratio of keto-enol tautomer compound (E) to urethanization catalyst (D) is in the range of 50 to 5,000 times.

3. The urethane prepolymer composition (I) according to claim 2, characterized in that the triazole derivative (C) is a benzotriazole derivative.

4. The urethane prepolymer composition (I) according to claim 2 or 3, wherein the benzotriazole derivative has one or more phenolic hydroxyl groups.

5. The urethane prepolymer composition (I) according to any one of claims 2 to 4, wherein the molar ratio of the triazole derivative (C) to the urethanization catalyst (D) containing a metal component is 25 to 200 times.

6. The urethane prepolymer composition (I) according to any one of claims 2 to 5, characterized in that the urethane prepolymer composition (I) contains an acid retarder (F).

7. A urethane prepolymer composition solution (K) comprising the urethane prepolymer composition (I) according to any one of claims 2 to 6 and an organic solvent, The urethane prepolymer composition solution (K) is characterized in that a concentration of the urethane prepolymer composition (I) in the urethane prepolymer composition solution (K) is 10% by mass or more and 95% by mass or less.

8. A urethane-forming composition (G) comprising the urethane prepolymer composition (I) according to any one of claims 2 to 6 and a polyisocyanate compound (J).

9. A urethane-forming composition solution (L) comprising the urethane prepolymer composition solution (K) according to claim 7 and a polyisocyanate compound (J).

10. A polyurethane (M) which is a reaction product of the urethane-forming composition (G) according to claim 8 or the urethane-forming composition (G) in the urethane-forming composition solution (L) according to claim 9.

11. A polyurethane sheet comprising the polyurethane (M) according to claim 10.

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