Polyurethane chain extender, composition for forming polyurethane resin, polyurethane resin, polyurethane resin composition, molded article, and article

Abstract

A polyurethane chain extender containing an amine compound (X) represented by the following formula (1) and having a trans isomer ratio of 50 mol% or more in the amine compound (X); a composition for forming a polyurethane resin containing the aforementioned polyurethane chain extender, a polyurethane resin formed using the composition for forming a polyurethane resin; a polyurethane resin obtained by reacting a polyisocyanate compound (A), a polyol compound (B), and the aforementioned polyurethane chain extender; a polyurethane resin composition containing the aforementioned polyurethane resin; a molded article obtained by molding the aforementioned polyurethane resin composition; and an article containing the aforementioned polyurethane resin composition or the aforementioned molded article. (In the following formula (1), R 1 ~R 12 each independently represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, p and q are each independently an integer of 0 or more and 4 or less, and at least one of p and q is 1 or more.)

Description

Technical Field

[0001] The present invention relates to a polyurethane chain extender, a composition for forming a polyurethane resin, a polyurethane resin, a polyurethane resin composition, a molded article, and an article. Background Art

[0002] Polyurethane resins are excellent in, for example, mechanical strength, flexibility, abrasion resistance, oil resistance, etc., and are widely used in various industrial fields.

[0003] Polyurethane resins can be obtained, for example, by the reaction of polyisocyanates, polyols, and chain extenders. By changing the types and compounding ratios of polyisocyanates, polyols, and chain extenders, various physical properties of the obtained polyurethane resins can be adjusted.

[0004] As technologies related to such polyurethane resins, for example, the technologies described in Patent Documents 1 and 2 can be cited.

[0005] Patent Document 1 describes a thermoplastic polyurethane resin obtained by compounding a dispersion liquid of a chain extender containing a chain extender, a non-aqueous dispersion medium, and a dispersion stabilizer into an isocyanate group-terminated prepolymer in a non-aqueous dispersion medium and performing a chain extension reaction.

[0006] Patent Document 2 describes a polyurethane dispersion liquid containing a polyisocyanate and a molecule having an active hydrogen moiety, and an optional mixture of a chain extender and / or a surfactant, and the polyisocyanate contains a bis(isocyanatomethyl)cyclohexane compound.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-91519

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2011-46968 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] According to the research by the present inventors, it is known that the polyurethane resins described in Patent Documents 1 and 2 still have room for improvement from the viewpoints of mechanical properties such as tensile strength, tensile elastic modulus, and hardness.

[0013] The present invention has been completed in view of the above circumstances, and provides a polyurethane chain extender, a composition for forming a polyurethane resin, a polyurethane resin with improved mechanical properties, a polyurethane resin composition, a molded article, and an article that can improve the mechanical properties of the obtained polyurethane resin.

[0014] Solution for solving problems

[0015] The inventors found that by using a specific amine compound in a polyurethane chain extender, the mechanical properties of the resulting polyurethane resin can be improved, thus completing the present invention.

[0016] That is, according to the present invention, there are provided the following polyurethane chain extender, composition for forming a polyurethane resin, polyurethane resin, polyurethane resin composition, molded article, and article.

[0017] [1] A polyurethane chain extender comprising an amine compound (X) represented by the following formula (1),

[0018] The ratio of the trans form in the amine compound (X) is 50 mol% or more.

[0019]

[0020] (In the above formula (1), R 1 ~R 12 each independently represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, p and q are each independently an integer of 0 or more and 4 or less, and at least one of p and q is 1 or more.)

[0021] [2] The polyurethane chain extender according to the above [1], wherein the amine compound (X) contains at least one selected from 1,4-bis(aminomethyl)cyclohexane and its derivatives.

[0022] [3] The polyurethane chain extender according to the above [1] or [2], wherein the ratio of the trans form in the amine compound (X) is 100 mol% or less.

[0023] [4] A composition for forming a polyurethane resin, comprising: a polyisocyanate compound (A), a polyol compound (B), and the polyurethane chain extender (C) according to any one of the above [1] to [3].

[0024] [5] A composition for forming a polyurethane resin, comprising: an isocyanate group-terminated prepolymer formed by reacting a polyisocyanate compound (A) and a polyol compound (B), and the polyurethane chain extender (C) according to any one of the above [1] to [3].

[0025] [6] A polyurethane resin formed from the composition for forming a polyurethane resin according to the above [4] or [5].

[0026] [7] A polyurethane resin obtained by reacting a polyisocyanate compound (A), a polyol compound (B), and the polyurethane chain extender (C) according to any one of the above [1] to [3].

[0027] [8] The polyurethane resin according to the foregoing [6] or [7], wherein the ratio of the number of active hydrogens in the polyurethane chain extender (C) to the total number of active hydrogens in the polyol compound (B) and the polyurethane chain extender (C) is 0.01 or more and 0.5 or less.

[0028] [9] The polyurethane resin according to any one of the foregoing [6] to [8], wherein the ratio of the number of isocyanate groups in the polyisocyanate compound (A) to the total number of active hydrogens in the polyol compound (B) and the polyurethane chain extender (C) is 0.5 or more and 1.5 or less.

[0029]

[10] The polyurethane resin according to any one of the foregoing [6] to [9], wherein the tensile strength of the polyurethane resin measured under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm in accordance with JIS K6251:2017 is 1.0 MPa or more.

[0030]

[11] The polyurethane resin according to any one of the foregoing [6] to

[10] , wherein the tensile elastic modulus of the polyurethane resin measured under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm in accordance with JIS K6251:2017 is 2.5 MPa or more.

[0031]

[12] The polyurethane resin according to any one of the foregoing [6] to

[11] , wherein the Shore A hardness of the polyurethane resin measured in accordance with JIS K6253:2012 is 50 or more.

[0032]

[13] The polyurethane resin according to any one of the foregoing [6] to

[12] is a polyurethane-urea resin.

[0033]

[14] A polyurethane resin composition comprising the polyurethane resin according to any one of the foregoing [6] to

[13] .

[0034]

[15] A molded article formed by molding the polyurethane resin composition according to the foregoing

[14] .

[0035]

[16] An article comprising the polyurethane resin composition according to the foregoing

[14] or the molded article according to the foregoing

[15] .

[0036] Effects of the Invention

[0037] According to the present invention, there can be provided a polyurethane chain extender, a composition for forming a polyurethane resin, a polyurethane resin with improved mechanical properties, a polyurethane resin composition, a molded article, and an article, which can improve the mechanical properties of the obtained polyurethane resin. Detailed Description of Embodiments

[0038] The mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an illustration for explaining the present invention and does not limit the content of the present invention. The present invention can be appropriately modified and implemented within the scope of its gist. In the present embodiment, the provisions defined as preferred can be arbitrarily adopted, and it can be said that the combination of the preferred ones is more preferred. In the present embodiment, the description of "XX to YY" means "XX or more and YY or less".

[0039] [Polyurethane Chain Extender]

[0040] The polyurethane chain extender of the present invention contains an amine compound (X) represented by the following formula (1), and the ratio of the trans isomer in the amine compound (X) is 50 mol% or more.

[0041]

[0042] In the above formula (1), R 1 ~R 12 each independently represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms, and p and q are each independently an integer of 0 or more and 4 or less, and at least one of p and q is 1 or more.

[0043] The polyurethane chain extender of the present invention can improve the mechanical properties of the obtained polyurethane resin by being used as a chain extender in the production of polyurethane resins. Here, in this specification, examples of the mechanical properties include tensile strength, tensile elastic modulus, hardness, etc.

[0044] (Amine Compound (X))

[0045] The amine compound (X) is a compound represented by the above formula (1).

[0046] In the above formula (1), R 1 ~R 12 each independently represents a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms.

[0047] From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom, and still more preferably R 1and R 2 Both are hydrogen atoms.

[0048] From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, R 3 ~R 12 are each independently preferably a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group, further preferably a hydrogen atom, and still further preferably R 3 ~R 12 are all hydrogen atoms.

[0049] p and q are each independently an integer of 0 or more and 4 or less. From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, it is preferably 1 or more, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1. Even further preferably, both p and q are 1. Here, at least one of p and q is an integer of 1 or more and 4 or less.

[0050] As the amine compound (X), from the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, it preferably contains at least one selected from 1,4-bis(aminomethyl)cyclohexane and its derivatives, and more preferably 1,4-bis(aminomethyl)cyclohexane.

[0051] Here, as derivatives of 1,4-bis(aminomethyl)cyclohexane, for example, compounds in which at least 1 of the hydrogen atoms of R 1 ~R 12 in the above formula (1) are substituted with a hydrocarbon group having 1 or more and 4 or less carbon atoms can be mentioned. As the aforementioned hydrocarbon group in the derivatives of 1,4-bis(aminomethyl)cyclohexane, from the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, it is preferably an alkyl group having 1 or more and 3 or less carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0052] These amine compounds (X) can be used alone or in combination of two or more. The amine compound (X) can be produced by a known method.

[0053] The ratio of the trans isomer in the amine compound (X) is 50 mol% or more, preferably 55 mol% or more, more preferably 58 mol% or more, still more preferably 60 mol% or more, and preferably 100 mol% or less, more preferably less than 100 mol%, still more preferably 99 mol% or less, from the viewpoint of further improving the mechanical properties of the resulting polyurethane resin. It should be noted that, from the viewpoint of practical manufacturability, the ratio of the trans isomer in the amine compound (X) is further preferably 97 mol% or less, further preferably 95 mol% or less, further preferably 93 mol% or less, further preferably 90 mol% or less, further preferably 88 mol% or less.

[0054] Here, the amine compound (X) contains both the cis and trans isomers of the amine compound represented by the aforementioned formula (1), and the total of the cis and trans isomers in the amine compound (X) is 100 mol%. In addition, the cis isomer of the amine compound (X) refers to the amine compound in which the two amino-containing groups in the cyclohexane ring in the aforementioned formula (1) are in the cis position, and the trans isomer of the amine compound (X) refers to the amine compound in which the two amino-containing groups in the cyclohexane ring in the aforementioned formula (1) are in the trans position.

[0055] The ratio of the trans isomer in the amine compound (X) can be measured by the method described in the examples.

[0056] From the viewpoint of further improving the mechanical properties of the resulting polyurethane resin, the content of the amine compound (X) in the polyurethane chain extender of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less, from the same viewpoint.

[0057] (Other components)

[0058] The polyurethane chain extender of the present invention may appropriately contain a chain extender other than the amine compound (X) within the range not impairing the object of the present invention. As the chain extender other than the amine compound (X), for example, chain extenders generally used as chain extenders for polyurethane resins can be cited. As such chain extenders, for example, conventionally known polyols and amine compounds other than the amine compound (X) can be cited.

[0059] [Composition for forming polyurethane resin]

[0060] The composition for forming a polyurethane-based resin of the present invention is a composition for forming a polyurethane-based resin, and it contains: a polyisocyanate compound (A), a polyol compound (B), and the polyurethane chain extender of the present invention described above (hereinafter also referred to as "polyurethane chain extender (C)").

[0061] In addition, the composition for forming a polyurethane-based resin of the present invention may also be a composition containing an isocyanate group-terminated prepolymer formed by reacting a polyisocyanate compound (A) and a polyol compound (B) and a polyurethane chain extender (C).

[0062] Since the composition for forming a polyurethane-based resin of the present invention contains the polyurethane chain extender (C) of the present invention described above, the mechanical properties of the obtained polyurethane-based resin can be improved.

[0063] (Polyisocyanate compound (A))

[0064] As the polyisocyanate compound (A), as long as it has two or more isocyanate groups, there is no particular limitation, and conventionally known polyisocyanate compounds can be used.

[0065] Examples of the diisocyanate compound having two isocyanate groups include: chain aliphatic diisocyanate compounds such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylidene diisocyanate, lysine diisocyanate, lysine diisocyanate methyl ester, 1,5-octylene diisocyanate; alicyclic structure-containing diisocyanate compounds such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), norbornane diisocyanate, hydrogenated toluene diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), dimer acid diisocyanate; aromatic ring-containing diisocyanate compounds such as 2,4-toluene diisocyanate or 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, p-phenylene diisocyanate or m-phenylene diisocyanate (XDI), tolidine diisocyanate, p-phenylene diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate, dianisidine diisocyanate, tetramethyl-m-phenylene diisocyanate, etc.

[0066] Examples of the polyisocyanate compound having three or more isocyanate groups include: triphenylmethane triisocyanate, triisocyanate phenyl thiophosphate, polymethylene polyphenylene polyisocyanate (polymeric MDI), isocyanurate-modified body, biuret-modified body, etc. which are trimers of HDI or TDI.

[0067] The polyisocyanate compound (A) can be used alone or in combination of two or more kinds.

[0068] Among them, as the polyisocyanate compound (A), a diisocyanate having two isocyanate groups is preferred, and a diisocyanate compound containing an alicyclic structure is more preferred, and isophorone diisocyanate is further preferred.

[0069] (Polyol compound (B))

[0070] There is no particular limitation on the polyol compound (B), and conventionally known polyol compounds can be used.

[0071] Examples of the polyol compound (B) include polyester polyols, polyether polyols, polycarbonate polyols, and polylactone polyols.

[0072] The polyester polyol is not particularly limited as long as it is a condensate of a polycarboxylic acid or its reactive derivative and a polyol. For example, a substance obtained by polycondensing a dicarboxylic acid and a diol can be cited.

[0073] Examples of the dicarboxylic acid include chain aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, and maleic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; and their reactive derivatives; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more kinds.

[0074] Examples of the diols include chain aliphatic diols such as dimethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, butylethylpropylene glycol, 1,2-butanediol, butanediol, 1,4-butanediol, dimethylbutanediol, 1,5-pentanediol, 2,4-diethylpentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and poly(ethylene-alt-butylene) glycol; alicyclic diols such as 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2-bis(4-hydroxycyclohexyl)propane; and diols containing an aromatic ring such as isophthalyl alcohol, terephthalyl alcohol, bisphenol A, bisphenol F, and bisphenol S.

[0075] These diols can be used alone or in combination of two or more kinds.

[0076] As the polyester polyol, examples thereof include condensation polyester polyols such as ethylene glycol adipate, butylene glycol adipate, hexamethylene adipate, ethylene / butylene adipate, etc.

[0077] As the polyether polyol, examples thereof include aliphatic polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, etc.

[0078] As the polycarbonate polyol, examples thereof include polyols obtained by the dealcoholization reaction of low molecular weight polyols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, nonylene glycol, 1,4-cyclohexanedimethanol, etc. with carbonate compounds such as diethyl carbonate, dipropyl carbonate, diphenyl carbonate, etc.

[0079] As the polylactone polyol, examples thereof include lactone polyester diols such as polylactone diol, polycaprolactone diol, polymethylvalerolactone diol, etc. obtained by ring-opening polymerization of the above low molecular weight polyols as initiators.

[0080] In addition, as the polyol compound (B), a polyol used in an aqueous polyurethane resin can be used. The polyol used in the aqueous polyurethane resin is not particularly limited, and examples thereof include polyols having an anionic group, and preferably include carboxyl group-containing polyols such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, etc.

[0081] The polyol compound (B) can be used alone or in combination of two or more.

[0082] Among these, as the polyol compound (B), at least one selected from the group consisting of polyester polyols and polyether polyols is preferably used, more preferably a polyether polyol, further preferably at least one selected from the group consisting of polytetramethylene glycol, polyethylene glycol, and polypropylene glycol, and further preferably polytetramethylene glycol.

[0083] From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, in the composition for forming a polyurethane resin of the present invention, the ratio of the number of active hydrogens in the polyurethane chain extender (C) to the total number of active hydrogens in the polyol compound (B) and the polyurethane chain extender (C) is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.04 or more, and from the same viewpoint, preferably 0.5 or less, more preferably 0.4 or less, further preferably 0.3 or less, further preferably 0.2 or less, and further preferably 0.15 or less.

[0084] From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, in the polyurethane resin-forming composition of the present invention, the ratio of the number of isocyanate groups in the polyisocyanate compound (A) to the total number of active hydrogen groups in the polyol compound (B) and the active hydrogen groups in the polyurethane chain extender (C) is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, further preferably 0.8 or more, further preferably 0.9 or more, and from the same viewpoint, it is preferably 1.5 or less, more preferably 1.4 or less, further preferably 1.3 or less, further preferably 1.2 or less, further preferably 1.1 or less.

[0085] The polyurethane resin-forming composition of the present invention may contain one or more solvents as needed. As the solvent, known solvents can be used, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, water, etc.

[0086] When the polyurethane resin-forming composition of the present invention contains a solvent, the solid content concentration of the polyurethane resin-forming composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 65% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less.

[0087] When the polyurethane resin-forming composition of the present invention contains water as a solvent, the polyurethane resin-forming composition can be an emulsion.

[0088] From the viewpoint of further improving the mechanical properties of the obtained polyurethane resin, when the total solid components contained in the polyurethane resin-forming composition of the present invention are set to 100% by mass, the total content of the polyisocyanate compound (A), the polyol compound (B), and the polyurethane chain extender (C) in the polyurethane resin-forming composition of the present invention, or the total content of the isocyanate group-terminated prepolymer formed by reacting the polyisocyanate compound (A) and the polyol compound (B) and the polyurethane chain extender (C) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, further preferably 99% by mass or more, and from the same viewpoint, it is preferably 100% by mass or less.

[0089] [Polyurethane resin]

[0090] The polyurethane resin of the present invention is formed from the aforementioned polyurethane resin-forming composition of the present invention.

[0091] In addition, the polyurethane resin of the present invention can be obtained by reacting a polyisocyanate compound (A), a polyol compound (B), and the polyurethane chain extender (C) of the present invention described above.

[0092] Since the polyurethane resin of the present invention contains the polyurethane chain extender (C) of the present invention described above, its mechanical properties can be improved.

[0093] Here, since the amine compound (X) is used as the polyurethane chain extender (C) in the polyurethane resin of the present invention, a urea bond is present in the structure. Therefore, the polyurethane resin of the present invention contains a polyurethane-urea resin, and is preferably a polyurethane-urea resin.

[0094] The polyurethane resin of the present invention can be produced by heating the composition for forming the polyurethane resin of the present invention described above.

[0095] In addition, the polyurethane resin of the present invention can be produced, for example, by the so-called prepolymer method in which an isocyanate group-terminated prepolymer obtained by pre-reacting a polyisocyanate compound (A) and a polyol compound (B) is reacted with a polyurethane chain extender (C); or the so-called one-shot method in which a polyol compound (B) and a urethane chain extender (C) are premixed, and then this mixture is reacted with a polyisocyanate compound (A).

[0096] From the viewpoint of further improving the mechanical properties of the polyurethane resin, the tensile strength of the polyurethane resin of the present invention is preferably 1.0 MPa or more, more preferably 1.1 MPa or more, further preferably 1.2 MPa or more, further preferably 1.3 MPa or more, and further preferably 1.4 MPa or more. From the viewpoint of further improving the mechanical properties of the polyurethane resin, the higher the above-mentioned tensile strength, the more preferable it is, and thus the upper limit is not particularly limited. For example, it is 10 MPa or less, can be 5.0 MPa or less, and can be 2.0 MPa or less.

[0097] The above-mentioned tensile strength can be measured according to JIS K 6251:2017 under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm. Specifically, it can be measured by the method described in the examples below.

[0098] From the viewpoint of further improving the mechanical properties of the polyurethane resin, the tensile elastic modulus of the polyurethane resin of the present invention is preferably 2.5 MPa or more, more preferably 2.6 MPa or more, further preferably 2.7 MPa or more, further preferably 2.8 MPa or more, further preferably 2.9 MPa or more. From the viewpoint of further improving the mechanical properties of the polyurethane resin, the higher the above-mentioned tensile elastic modulus, the more preferable it is. Therefore, the upper limit is not particularly limited. For example, it is 10 MPa or less, may be 5.0 MPa or less, and may be 3.5 MPa or less.

[0099] The above-mentioned tensile elastic modulus can be measured in accordance with JIS K 6251:2017 under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm. Specifically, it can be measured by the method described in the examples below.

[0100] From the viewpoint of further improving the mechanical properties of the polyurethane resin, the Shore A hardness of the polyurethane resin of the present invention is preferably 50 or more, more preferably 53 or more, further preferably 55 or more, further preferably 56 or more, further preferably 58 or more, further preferably 59 or more. From the viewpoint of further improving the mechanical properties of the polyurethane resin, the higher the above-mentioned Shore A hardness, the more preferable it is. Therefore, the upper limit is not particularly limited. For example, it is 80 or less, may be 70 or less, and may be 65 or less.

[0101] The above-mentioned Shore A hardness can be measured in accordance with JIS K 6253:2012. Specifically, it can be measured by the method described in the examples below.

[0102] [Polyurethane resin composition]

[0103] The polyurethane resin composition of the present invention contains the above-mentioned polyurethane resin of the present invention. The polyurethane resin composition of the present invention contains the above-mentioned polyurethane resin of the present invention, and thus can improve the mechanical properties.

[0104] From the viewpoint of further improving the mechanical properties, when all the resin components contained in the polyurethane resin composition of the present invention are set to 100% by mass, the content of the polyurethane resin of the present invention in the polyurethane resin composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, and even more preferably 99% by mass or more. From the same viewpoint, it is preferably 100% by mass or less.

[0105] The polyurethane resin composition of the present invention may contain one or more solvents as needed. As the solvent, known solvents can be used, and examples thereof include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, water, and the like.

[0106] When the polyurethane resin composition of the present invention contains a solvent, the solid content concentration of the polyurethane resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, still further preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, still further preferably 60% by mass or less.

[0107] When the polyurethane resin composition of the present invention contains water as a solvent, the polyurethane resin composition can be an emulsion.

[0108] The polyurethane resin composition of the present invention is not particularly limited, and can be widely used, for example, in foams, elastomers, coatings, fibers, fiber processing agents, adhesives, binders, sealants, inks, floor materials, sealants, caulking materials, medical materials, leather materials, tire materials, coating agents, active energy ray curable resin compositions, and the like.

[0109] The polyurethane resin composition of the present invention can further contain, for example, silane coupling agents, fillers, thixotropy imparting agents, tackifiers, waxes, plasticizers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, fiber-based reinforcing materials, pigments, fluorescent brighteners, foaming agents, thermoplastic resins other than the above polyurethane resins, thermosetting resins, dyes, conductivity imparting agents, antistatic agents, moisture permeability improving agents, water repellents, oil repellents, hollow foams, compounds containing crystal water, flame retardants, water absorbents, moisture absorbents, deodorants, antibacterial agents, mildew proofing agents, anti-blocking agents, anti-hydrolysis agents, organic water-soluble compounds, inorganic water-soluble compounds, release agents, and other known additives according to the use and needs.

[0110] As the production method of the polyurethane resin composition of the present invention, there is no particular limitation, and examples thereof include the following methods: after mixing the polyurethane resin composition of the present invention and the above additives as needed by a kneader, a Henschel mixer, etc., supplying the obtained mixture to an extrusion molding machine, and performing melt kneading at the normal temperature (for example, 150 to 250 °C) at which normal thermoplastic polyurethane resins are extruded, and then forming into a pellet shape by strand cutting or underwater cutting for preparation; a method of dispersing, dissolving or emulsifying the polyurethane resin composition of the present invention in a solvent for preparation, and the like.

[0111] [Molded article and article]

[0112] The molded article of the present invention is formed by molding the aforementioned polyurethane resin composition of the present invention. In addition, the article of the present invention contains the aforementioned polyurethane resin composition of the present invention or the molded article of the present invention. That is, the aforementioned polyurethane resin composition of the present invention can be suitably used in the production of various molded articles and articles.

[0113] Since the molded article and article of the present invention contain the aforementioned polyurethane resin composition of the present invention, the mechanical properties can be improved.

[0114] The article of the present invention can be entirely composed of the polyurethane resin composition or molded article of the present invention, or can be composed of a part of the polyurethane resin composition or molded article of the present invention. As a mode of being composed of a part of the polyurethane resin composition or molded article of the present invention, for example, there can be cited: a structure having a layer of the polyurethane resin composition or molded article of the present invention on the surface or inside; a structure having a layer impregnated with the polyurethane resin composition of the present invention on the surface or inside, etc.

[0115] As a molding method of the polyurethane resin composition of the present invention, general molding methods for thermoplastic polyurethane resins can be applied. For example, there can be cited molding methods such as extrusion molding, injection molding, blow molding, blow extrusion molding, vacuum molding, centrifugal molding, rotational molding, calendering, roll processing, stamping, etc. By these molding methods, molded articles of various shapes such as resin plates, films, sheets, and shaped articles can be manufactured from the polyurethane resin composition of the present invention.

[0116] As molded articles and articles, for example, there can be cited: belts, tubes, hoses, wire coating materials, cable coating materials, fire hoses, gears, casters, gaskets, mechanical industrial parts such as wind turbines for wind power generation; vehicle parts such as tires, tire parts, bumpers, side moldings, tail light seals, snow chains, ball joint seals, constant velocity joint boots, bellows, spring cover materials, ABS cables, ABS cable plugs, instrument panel skins, shift knobs, console boxes, door seal covers, seat materials, knobs, etc.; various films and sheets such as various thin sheets, various laminates, air cushions, artificial leather, synthetic leather, protective films; daily necessities such as shoe soles, watch bands, camera grips, animal ear tags, smartphone cases, tablet cases, keyboard covers, ornaments; medical use products such as heart valves, bypass devices, artificial ventricles, dialysis tubes, films, connectors, catheters, medical tubes, insulators for pacemakers; building materials such as interior and exterior finishing materials; sports goods such as snowboards, rackets; painted articles; printed matter, etc.

[0117] [Examples]

[0118] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the scope of the examples.

[0119] (Determination of the ratio of the trans isomer in the amine compound)

[0120] The ratio of the trans isomer was determined using a GC apparatus, Agilent 7890B GC (manufactured by Agilent Technologies, inc.). Specifically, the ratio of the trans isomer was calculated from the ratio of the detection intensities (area values) by FID.

[0121] In each of the examples and comparative examples, the following substances were used as the polyurethane chain extender, polyisocyanate compound, and polyol compound.

[0122] (Polyurethane chain extender)

[0123] 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane (ratio of trans isomer: 25 mol%, manufactured by Mitsubishi Gas Chemical Company, Inc.)

[0124] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 43 mol%, manufactured by Mitsubishi Gas Chemical Company, Inc.)

[0125] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 85 mol%, manufactured by Mitsubishi Gas Chemical Company, Inc.)

[0126] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 100 mol%, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0127] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 99 mol%, prepared according to Production Example 1 below.)

[0128] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 70 mol%, prepared according to Production Example 2 below.)

[0129] 1,4-BAC: 1,4-bis(aminomethyl)cyclohexane (ratio of trans isomer: 60 mol%, prepared according to Production Example 3 below.)

[0130] IPDA: isophorone diamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0131] (Production Example 1: 1,4-BAC (ratio of trans isomer: 99 mol%))

[0132] It was prepared by mixing 1,4-BAC (2 parts by mass) with a trans isomer ratio of 43 mol% and 1,4-BAC (98 parts by mass) with a trans isomer ratio of 100 mol%.

[0133] (Production Example 2: 1,4-BAC (Ratio of trans form: 70 mol%))

[0134] It was prepared by mixing 1,4-BAC (35 parts by mass) with a trans form ratio of 43 mol% and 1,4-BAC (65 parts by mass) with a trans form ratio of 85 mol%.

[0135] (Production Example 3: 1,4-BAC (Ratio of trans form: 60 mol%))

[0136] It was prepared by mixing 1,4-BAC (58 parts by mass) with a trans form ratio of 43 mol% and 1,4-BAC (42 parts by mass) with a trans form ratio of 85 mol%.

[0137] (Polyisocyanate compound)

[0138] IPDI: Isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0139] (Polyol compound)

[0140] PTMG: Polytetramethylene glycol (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0141] (Other compounds)

[0142] MEK: Methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.)

[0143] Example 1

[0144] (1) Synthesis of isocyanate group-terminated prepolymer 1

[0145] 101 g of PTMG (OH group equivalent: 500 g / eq.) was added to a 500 mL four-neck separable flask equipped with a stirring blade and a thermocouple, and dehydration treatment was carried out at 100 °C / under a reduced pressure of 100 - 200 hPa for 1 hour. Then, after air-cooling to 70 °C, a condenser was installed, 79 g of MEK and 0.045 g of dibutyltin dilaurate were added, and it was heated to 70 °C under a nitrogen atmosphere. After reaching 70 °C, a dropping funnel was installed, and 25 g of IPDI was added dropwise over 60 minutes. Then, it was stirred at 70 °C for 3 hours. After that, 210 g of MEK was added to make the solid content concentration 30% by mass, and it was taken out in the form of a solution of an isocyanate group-terminated prepolymer (prepolymer 1).

[0146] (2) Synthesis of polyurethane urea resin based on chain extension reaction

[0147] Under a nitrogen atmosphere, 150 g of the solution of the aforementioned prepolymer 1 was added to a 500 mL four-neck separable flask equipped with a stirring blade, a nitrogen inlet tube, a thermocouple, a condenser tube, and a dropping funnel, and heated to 60 °C. After reaching 60 °C, 0.51 g of 1,4-BAC (ratio of trans isomer: 85 mol%) as a polyurethane chain extender was added dropwise over 1 minute, and then stirred at 60 °C for 30 minutes. The resulting solution was poured into a stainless-steel mold coated with a release agent and cured for 1 week under the conditions of 23 °C / 50% RH, and then cured in an oven at an internal temperature of 60 °C for 1 hour to obtain a test plate of polyurethane-urea resin with a thickness of 1.5 mm.

[0148] The following various evaluations were carried out on the obtained test plates of polyurethane-urea resin. The results obtained are shown in the table.

[0149] (Tensile strength and tensile modulus of elasticity)

[0150] A tensile test of the test plate was carried out, and the tensile strength (MPa) and the tensile modulus of elasticity (MPa) were measured respectively. Specifically, according to the method described in JIS K 6251:2017, a sample with a width of 10 mm was cut out from the test plate, and using a tensile testing machine (manufactured by Toyo Seiki Seisaku-sho, Ltd., Strograph EII-L05), it was measured under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm. It should be noted that the tensile modulus of elasticity was calculated by the following formula.

[0151] E = (σ2 - σ1) / (ε2 - ε1)

[0152] E: Tensile modulus of elasticity (MPa)

[0153] σ1: Tensile stress measured at a strain ε1 = 0.05

[0154] σ2: Tensile stress measured at a strain ε2 = 0.1

[0155] (Hardness (Shore A))

[0156] The hardness (Shore A) of the test plate was measured. Specifically, according to the method described in JIS K 6253:2012, a hardness tester (manufactured by TECLOCK Corporation, Durometer A type GS-719N) was pressed against the test plate, and the value was read.

[0157] Examples 4 to 6, Comparative Examples 1 to 2

[0158] 1,4-BAC (ratio of trans isomer: 85 mol%) as a polyurethane chain extender was changed to the polyurethane chain extenders shown in the table, and otherwise, the same procedure as in Example 1 was carried out to obtain test plates of polyurethane-urea resin respectively.

[0159] For the test plates of the obtained polyurethane-urea resin, the above various evaluations were carried out. The results obtained are shown in the table.

[0160] Comparative Example 3

[0161] 0.51 g of 1,4-BAC (ratio of trans isomer: 85 mol%) as a polyurethane chain extender was changed to 0.61 g of IPDA shown in the table, and otherwise, the procedure was the same as in Example 1 to obtain test plates of polyurethane-urea resin, respectively.

[0162] For the test plates of the obtained polyurethane-urea resin, the above various evaluations were carried out. The results obtained are shown in the table.

[0163] Example 2

[0164] (1) Synthesis of isocyanate group-terminated prepolymer 2

[0165] 90 g of PTMG (OH group equivalent: 500 g / eq.) was added to a 500 mL four-neck separable flask equipped with a stirring blade and a thermocouple, and dehydration treatment was carried out at 100 °C / under a reduced pressure of 100 - 200 hPa for 1 hour. After that, it was air-cooled to 70 °C, a condenser was installed, 77 g of MEK and 0.045 g of dibutyltin dilaurate were added, and it was heated to 70 °C under a nitrogen atmosphere. After reaching 70 °C, a dropping funnel was installed, and 25 g of IPDI was added dropwise over 30 minutes. Then, it was stirred at 70 °C for 3 hours. After that, 199 g of MEK was added to make the solid content concentration 30 mass%, and it was taken out in the form of a solution of isocyanate group-terminated prepolymer (prepolymer 2).

[0166] (2) Synthesis of polyurethane-urea resin by chain extension reaction

[0167] Under a nitrogen atmosphere, 156 g of the solution of the aforementioned prepolymer 2 was added to a 500 mL four-neck separable flask equipped with a stirring blade, a nitrogen inlet tube, a thermocouple, a condenser and a dropping funnel, and it was heated to 60 °C. After reaching 60 °C, 1.28 g of 1,4-BAC (ratio of trans isomer: 85 mol%) as a polyurethane chain extender was added dropwise over 1 minute, and then it was stirred at 60 °C for 30 minutes. The obtained solution was poured into a stainless steel mold coated with a release agent and cured under the conditions of 23 °C / 50% RH for 1 week, and then cured in an oven at an internal temperature of 60 °C for 1 hour to obtain a test plate of polyurethane-urea with a thickness of 1.5 mm.

[0168] For the test plates of the obtained polyurethane-urea resin, the above various evaluations were carried out. The results obtained are shown in the table.

[0169] Comparative Example 4

[0170] In a 500 mL four-neck separable flask equipped with stirring blades and a thermocouple, 112.5 g of PTMG (OH group equivalent: 500 g / eq.) was added, and dehydration treatment was carried out for 1 hour under the conditions of 100 °C and a reduced pressure of 100 - 200 hPa. After that, it was air-cooled to 70 °C, a condenser was installed, 77 g of MEK and 0.045 g of dibutyltin dilaurate were added, and it was heated to 70 °C under a nitrogen atmosphere. After reaching 70 °C, a dropping funnel was installed, and 25 g of IPDI was added dropwise over 30 minutes. Then, it was stirred at 70 °C for 3 hours. After that, 200 g of MEK was added to make the solid component concentration 30 mass%, and it was taken out in the form of a polyurethane resin solution. The obtained solution was poured into a stainless-steel mold coated with a mold release agent and cured for 1 week under the conditions of 23 °C / 50% RH, and then cured in an oven at a box temperature of 60 °C for 1 hour to obtain a test plate of polyurethane resin with a thickness of 1.5 mm.

[0171] Comparative Examples 5 and 6

[0172] The 1,4-BAC (ratio of trans form: 85 mol%) used as a polyurethane chain extender was changed to the polyurethane chain extenders shown in the table, and the rest was carried out in the same manner as in Example 2 to obtain test plates of polyurethane urea resin respectively.

[0173] For the obtained test plates of polyurethane urea resin, the above various evaluations were carried out. The obtained results are shown in the table.

[0174] Comparative Example 7

[0175] 1.28 g of 1,4-BAC (ratio of trans form: 85 mol%) used as a polyurethane chain extender was changed to 1.53 g of IPDA shown in the table, and the rest was carried out in the same manner as in Example 2 to obtain test plates of polyurethane urea resin respectively.

[0176] For the obtained test plates of polyurethane urea resin, the above various evaluations were carried out. The obtained results are shown in the table.

[0177] Example 3

[0178] (1) Synthesis of Isocyanate-Terminated Prepolymer 3

[0179] In a 500 mL four-neck separable flask equipped with a stirring blade and a thermocouple, 107 g of PTMG (OH group equivalent: 500 g / eq.) was added, and dehydration treatment was carried out for 1 hour under the conditions of 100 °C and a reduced pressure of 100 - 200 hPa. After that, it was air-cooled to 70 °C, a condenser was installed, 88 g of MEK and 0.045 g of dibutyltin dilaurate were added, and it was heated to 70 °C under a nitrogen atmosphere. After reaching 70 °C, a dropping funnel was installed, and 25 g of IPDI was added dropwise over 30 minutes. Then, it was stirred at 70 °C for 3 hours. After that, 222 g of MEK was added to make the solid component concentration 30 mass%, and it was taken out in the form of a solution of an isocyanate group-terminated prepolymer (prepolymer 3).

[0180] (2) Synthesis of polyurethaneurea resin by chain extension reaction

[0181] Under a nitrogen atmosphere, 80 g of the solution of the aforementioned prepolymer 3 was added to a 500 mL four-neck separable flask equipped with a stirring blade, a nitrogen inlet tube, a thermocouple, a condenser, and a dropping funnel, and it was heated to 60 °C. After reaching 60 °C, 0.14 g of 1,4-BAC (ratio of trans form: 85 mol%) as a polyurethane chain extender was added dropwise over 1 minute. Then, it was stirred at 60 °C for 30 minutes. The obtained solution was poured into a stainless-steel mold coated with a release agent and cured for 1 week under the conditions of 23 °C / 50% RH, and then cured in an oven at an internal temperature of 60 °C for 1 hour to obtain a test plate of polyurethaneurea with a thickness of 1.5 mm.

[0182] For the test plates of the obtained polyurethaneurea resin, the above various evaluations were carried out. The obtained results are shown in the table.

[0183] Comparative Examples 8 and 9

[0184] The 1,4-BAC (ratio of trans form: 85 mol%) as a polyurethane chain extender was changed to the polyurethane chain extenders shown in the table, and the rest was carried out in the same manner as in Example 3 to obtain test plates of polyurethaneurea resin respectively.

[0185] For the test plates of the obtained polyurethaneurea resin, the above various evaluations were carried out. The obtained results are shown in the table.

[0186] Comparative Example 10

[0187] 0.14 g of 1,4-BAC (ratio of trans form: 85 mol%) as a polyurethane chain extender was changed to 0.17 g of IPDA shown in the table, and the rest was carried out in the same manner as in Example 3 to obtain test plates of polyurethaneurea resin respectively.

[0188] For the test plates of the obtained polyurethane-urea resin, the above various evaluations were carried out. The results obtained are shown in the table.

[0189] [Table 1]

[0190] Table 1

[0191]

[0192] [Table 2]

[0193] Table 2

[0194]

[0195] [Table 3]

[0196] Table 3

[0197]

[0198] [Table 4]

[0199] Table 4

[0200] Example 1 Example 4 Example 5 Example 6 Comparative Example 2 Polyisocyanate (eq.) IPDI 1 1 1 1 1 Polyol (eq.) PTMG 0.9 0.9 0.9 0.9 0.9 Chain extender (eq.) 1,4-BAC 0.1 0.1 0.1 0.1 0.1 Ratio of chain extender trans isomer (mol%) 85 99 70 60 43 Tensile strength MPa 1.49 1.72 1.45 1.86 1.25 Tensile elastic modulus MPa 3.09 2.93 2.90 3.05 2.83 Hardness (Shore A) Type A 60 62 61 62 58

[0201] In Tables 1 to 4, when comparing the examples with the same ratios of polyisocyanate compounds, polyol compounds, and polyurethane chain extenders with the comparative examples, it was found that the mechanical properties of the polyurethane-urea resin in the examples were improved.

Claims

1. A composition for forming a polyurethane-based resin, comprising: a polyisocyanate compound (A), a polyol compound (B), and a polyurethane chain extender (C). The polyisocyanate compound (A) contains a cycloaliphatic structure-containing diisocyanate compound. The polyol compound (B) contains a polyether-based polyol. The polyurethane chain extender (C) consists of 1,4-bis(aminomethyl)cyclohexane, and the ratio of the trans form in the 1,4-bis(aminomethyl)cyclohexane is 60 mol% or more and 99 mol% or less. The number of active hydrogen atoms in the polyurethane chain extender (C) is 0.01 or more and 0.5 or less relative to the total number of active hydrogen atoms in the polyol compound (B) and the polyurethane chain extender (C). The number of isocyanate groups in the polyisocyanate compound (A) is 0.5 or more and 1.5 or less relative to the total number of active hydrogen atoms in the polyol compound (B) and the polyurethane chain extender (C).

2. A composition for forming a polyurethane-based resin, comprising: an isocyanate group-terminated prepolymer formed by reacting a polyisocyanate compound (A) and a polyol compound (B), and a polyurethane chain extender (C). The polyisocyanate compound (A) contains a cycloaliphatic structure-containing diisocyanate compound. The polyol compound (B) contains a polyether-based polyol. The polyurethane chain extender (C) consists of 1,4-bis(aminomethyl)cyclohexane, and the ratio of the trans form in the 1,4-bis(aminomethyl)cyclohexane is 60 mol% or more and 99 mol% or less. The number of active hydrogen atoms in the polyurethane chain extender (C) is 0.01 or more and 0.5 or less relative to the total number of active hydrogen atoms in the polyol compound (B) and the polyurethane chain extender (C). The number of isocyanate groups in the polyisocyanate compound (A) is 0.5 or more and 1.5 or less relative to the total number of active hydrogen atoms in the polyol compound (B) and the polyurethane chain extender (C).

3. A polyurethane-based resin formed from the composition for forming a polyurethane-based resin according to claim 1 or 2.

4. A polyurethane-based resin formed by reacting a polyisocyanate compound (A), a polyol compound (B), and a polyurethane chain extender (C). The polyisocyanate compound (A) contains a cycloaliphatic structure-containing diisocyanate compound. The polyol compound (B) contains a polyether-based polyol. The polyurethane chain extender (C) consists of 1,4-bis(aminomethyl)cyclohexane, and the ratio of the trans form in the 1,4-bis(aminomethyl)cyclohexane is 60 mol% or more and 99 mol% or less. The number of active hydrogen atoms in the polyurethane chain extender (C) is 0.01 or more and 0.5 or less relative to the total number of active hydrogen atoms in the polyol compound (B) and the polyurethane chain extender (C). The ratio of the number of isocyanate groups in the polyisocyanate compound (A) to the total number of active hydrogen groups in the polyol compound (B) and the active hydrogen groups in the polyurethane chain extender (C) is 0.5 or more and 1.5 or less.

5. The polyurethane resin according to claim 3 or 4, wherein The tensile strength of the polyurethane resin measured according to JIS K 6251:2017 under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm is 1.0 MPa or more.

6. The polyurethane resin according to claim 3 or 4, wherein The tensile elastic modulus of the polyurethane resin measured according to JIS K 6251:2017 under the conditions of a tensile speed of 200 mm / min and a distance between clamps of 50 mm is 2.5 MPa or more.

7. The polyurethane resin according to claim 3 or 4, wherein The Shore A hardness of the polyurethane resin measured according to JIS K 6253:2012 is 50 or more.

8. The polyurethane resin according to claim 3 or 4, which is a polyurethane-urea resin.

9. A polyurethane resin composition comprising the polyurethane resin according to any one of claims 3 to 8.

10. A molded article formed by molding the polyurethane resin composition according to claim 9.

11. An article comprising the polyurethane resin composition according to claim 9 or the molded article according to claim 10.

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