Thermoplastic polyurethane elastomer composition, molded article, and method for producing the thermoplastic polyurethane elastomer composition

Abstract

To provide a thermoplastic polyurethane elastomer composition that maintains mechanical properties while having fewer fish eyes. [Solution] A thermoplastic polyurethane elastomer composition containing a reaction product of a polyol (B) comprising at least one selected from the group consisting of polyisocyanate (A), polycarbonate polyol and polyester polyol, and a chain extender (C), and a compound (D) having a group represented by the following general formula (I). TIFF2026142025000010.tif31149 [In formula (I), R 1 and R 2 Each of these independently represents a substituted or unsubstituted hydrocarbon group, and R 1 and R 2 The elements may be joined to each other to form a ring, and * indicates a bonding hand.

Description

[Technical Field]

[0001] This disclosure relates to thermoplastic polyurethane elastomer compositions, molded articles, and methods for producing thermoplastic polyurethane elastomer compositions. [Background technology]

[0002] Thermoplastic polyurethane elastomers (hereinafter also referred to as "TPU") are generally obtained by reacting polyols, polyisocyanates, and chain extenders such as short-chain diols. They consist of a hard segment made of polyisocyanate and chain extenders, and a soft segment mainly composed of polyols. TPU has a wide range of hardness control, high mechanical strength, and abrasion resistance, and is used in a wide range of fields, including industrial hoses, tubes, belts, automobiles, home appliances, toy parts, general merchandise, and sporting goods. In particular, sheets, films, and fibers made of TPU are being developed for applications that take advantage of not only their toughness but also their elasticity. These include stretchable films used for disposable diapers, sanitary napkins, sealing, dustproofing, and cushioning materials, as well as clothing such as swimwear, sportswear, socks, and underwear. In such applications, good appearance and design are sometimes required.

[0003] During the manufacturing of TPU, a partial gel-like substance called a "fish eye" may occur. This fish eye can appear as granular protrusions or other defects on the surface of molded products made of TPU, causing cosmetic defects.

[0004] Several methods have been investigated to reduce the fisheye effect of TPU. For example, Patent Document 1 discloses a method for producing thermoplastic polyurethane characterized by rapidly mixing all raw materials at a specific shear rate or higher before melt polymerization, and then supplying the mixture to an extruder and continuously polymerizing it while kneading it for a predetermined residence time and temperature range. Patent Document 2 also discloses a method for producing thermoplastic polyurethane resin characterized by adding a specific compatibilizer to improve the compatibility between hard segments and soft segments. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-214062 [Patent Document 2] Japanese Patent Application Publication No. 6-166738 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, suppressing the occurrence of fish eyes through mechanical methods such as stirring is prone to manufacturing inconsistencies. Furthermore, the addition of certain third components may lead to a decrease in the mechanical properties of TPU.

[0007] Therefore, one aspect of this disclosure aims to provide a thermoplastic polyurethane elastomer composition that maintains mechanical properties while exhibiting fewer fish eyes. [Means for solving the problem]

[0008] Some aspects of this disclosure provide the following [1] to

[11] .

[0009] [1] A reaction product of a polyol (B) comprising at least one selected from the group consisting of polyisocyanate (A), polycarbonate polyol, and polyester polyol, and a chain extender (C), A thermoplastic polyurethane elastomer composition comprising a compound (D) having a group represented by the following general formula (I).

Chemical Formula

[0010] [2] R 1 and R 2 are each independently an alkyl group, the thermoplastic polyurethane elastomer composition according to [1].

[0011] [3] R 1 and R 2 are each independently a methyl group or an ethyl group, the thermoplastic polyurethane elastomer composition according to [1] or [2].

[0012] [4] The compound (D) comprises at least one selected from the group consisting of tetraalkylthiuram monosulfide and tetraalkylthiuram disulfide, the thermoplastic polyurethane elastomer composition according to [1] or [2].

[0013] [5] The compound (D) comprises at least one selected from the group consisting of tetramethylthiuram monosulfide, tetramethylthiuram disulfide and tetraethylthiuram disulfide, the thermoplastic polyurethane elastomer composition according to any one of [1] to [4].

[0014] [6] The thermoplastic polyurethane elastomer composition according to any one of [1] to [5], wherein the content of the compound (D) is 3 to 100 mass ppm based on the total mass of the polyisocyanate (A), the polyol (B) and the chain extender (C).

[0015] [7] The thermoplastic polyurethane elastomer composition according to any one of [1] to [6], wherein the polyisocyanate (A) comprises hexamethylene diisocyanate.

[0016] [8] The thermoplastic polyurethane elastomer composition according to any one of [1] to [7], wherein the polyol (B) is a polycarbonate polyol comprising, as a monomer unit, at least one diol selected from the group consisting of 1,4-butanediol, 1,6-hexanediol and 3-methyl-1,5-pentanediol.

[0017] [9] The thermoplastic polyurethane elastomer composition according to any one of [1] to [8], wherein the chain extender (C) comprises an aliphatic diol having 2 to 10 carbon atoms.

[0018]

[10] A molded article comprising the thermoplastic polyurethane elastomer composition according to any one of [1] to [9].[

[0019]

[11] A method for producing a thermoplastic polyurethane elastomer composition, comprising a step of reacting a polyisocyanate (A), a polyol (B) comprising at least one selected from the group consisting of polycarbonate polyols and polyester polyols, and a chain extender (C) in the presence of a compound (D) having a group represented by the following general formula (I).

Chemical Formula

[0020] According to one aspect of this disclosure, it is possible to provide a thermoplastic polyurethane elastomer composition that maintains mechanical properties while having fewer fish eyes. [Modes for carrying out the invention]

[0021] Several embodiments of this disclosure are described below. However, this disclosure is not limited to the embodiments described below.

[0022] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Unless otherwise specified, the units of the numbers before and after "~" are the same. In numerical ranges described in stages within this specification, the upper or lower limit of one stage may be replaced with the upper or lower limit of another stage. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Also, individually stated upper and lower limits can be combined in any way. The materials exemplified below may be used individually or in combination of two or more, unless otherwise specified. The content of each component in a composition, if multiple substances corresponding to each component exist in the composition, means the total amount of those multiple substances present in the composition, unless otherwise specified.

[0023] <Thermoplastic polyurethane elastomer composition> One embodiment of the present disclosure relates to a thermoplastic polyurethane elastomer composition containing a reaction product of a polyol (B) comprising at least one selected from the group consisting of polyisocyanate (A), polycarbonate polyol and polyester polyol, and a chain extender (C), and a compound (D) having a group represented by the following general formula (I). [ka]

[0024] In formula (I), R 1 and R 2 Each of these independently represents a substituted or unsubstituted hydrocarbon group, and R 1 and R 2 The elements may be joined to each other to form a ring, and * indicates a bonding hand.

[0025] The above thermoplastic polyurethane elastomer composition exhibits minimal fisheye while maintaining mechanical properties. The reason for this effect is unclear, but it is presumed to be as follows.

[0026] In the manufacturing processes of polycarbonate polyols and polyester polyols, metal compounds such as titanium compounds are generally used as transesterification catalysts. Therefore, polyols containing polycarbonate polyols or polyester polyols may contain trace amounts of transesterification catalyst. It is presumed that during the manufacturing of thermoplastic polyurethane elastomers, this transesterification catalyst promotes the uneven formation of hard segments and, as a side reaction, allophanation of urethane bonds, resulting in the formation of fish eyes, which are partially gel-like structures. On the other hand, in the thermoplastic polyurethane elastomer composition described above, the addition of compound (D) suppresses the activity of the transesterification catalyst, thereby suppressing the uneven formation of hard segments and side reactions, and reducing fish eyes.

[0027] The above thermoplastic polyurethane elastomer composition may include, for example, a thermoplastic polyurethane elastomer containing structural units derived from polyisocyanate (A), structural units derived from polyol (B), and structural units derived from a chain extender (C), and compound (D). In the thermoplastic polyurethane elastomer composition, compound (D) may be included as a component independent of the above thermoplastic polyurethane elastomer.

[0028] Examples of thermoplastic polyurethane elastomer compositions include flakes, pellets, powders, granules, rods, sheets, and blocks.

[0029] The following describes the components of the thermoplastic polyurethane elastomer composition.

[0030] [Polyisocyanate (A)] Polyisocyanate (A) is a compound having two or more isocyanate groups (-N=C=O), preferably a compound having two isocyanate groups (diisocyanate). Examples of polyisocyanate (A) include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and their polyisocyanate derivatives. Examples of derivatives include isocyanurate, allophanate, biuret, dimer, trimer, carbodiimide, uretonimine, and adduct compounds obtained by the reaction of a bifunctional or more polyol with the isocyanate. The derivative may be prepolymerized using a polyol or the like as a modifying agent. Polyisocyanate (A) may be one type of polyisocyanate used alone, or two or more types of polyisocyanates may be used in combination.

[0031] Aromatic polyisocyanates include, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or mixtures thereof) (MDI), diphenylpropane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylpropane diisocyanate, or mixtures thereof), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylidine Examples include diisocyanates (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,4-, 1,5- or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), 2-nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. These may be used individually or in combination of two or more.

[0032] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, pentamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 3-methylpentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, decamethylene diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. These may be used individually or in combination of two or more.

[0033] Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate, or mixtures thereof) (hydrogenated diphenylmethane diisocyanate (hydrogenated MDI)), methylcyclohexane diisocyanate (methyl-2,4-cyclohex Examples include diisocyanate or methyl-2,6-cyclohexane diisocyanate, or mixtures thereof; bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane, or mixtures thereof) (hydrogenated XDI); dimer acid diisocyanate; transcyclohexane 1,4-diisocyanate; hydrogenated tolylene diisocyanate (hydrogenated TDI); hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI); norbornene diisocyanate; norbornane diisocyanate methyl; diisocyanate methylbicycloheptane, etc. These may be used individually or in combination of two or more.

[0034] From the viewpoint of easily exhibiting good mechanical properties, polyisocyanate (A) preferably contains at least one selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, and more preferably contains hexamethylene diisocyanate.

[0035] From the viewpoint of suppressing discoloration (e.g., yellowing) over time, polyisocyanate (A) preferably contains at least one selected from the group consisting of hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate, and more preferably contains hexamethylene diisocyanate for the production of a completely yellow-free thermoplastic polyurethane elastomer.

[0036] The content of polyisocyanate (A) may be, for example, 10-30% by mass, 11-27% by mass, or 11.5-26% by mass, based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C).

[0037] [Polyol (B)] Polyol (B) includes at least one selected from the group consisting of polycarbonate polyols and polyester polyols. Polyol (B) may be one polyol used alone, or two or more polyols may be used in combination.

[0038] Polycarbonate polyols are compounds having multiple hydroxyl groups (-OH) and multiple carbonate groups (-OCOO-). For example, polycarbonate polyols are reaction products of a polyol component and a carbonate component, and contain the polyol component and the carbonate component as monomer units.

[0039] The polyol component preferably contains a diol, and more preferably an aliphatic diol. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,16-hex Examples include linear aliphatic diols such as sadecanediol, 1,18-octadecanediol, and 1,20-eicosanediol, and branched aliphatic diols such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 2-methyl-1,8-octanediol, and 1,12-octadecanediol. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred, and it is more preferable that they be at least one selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol. These may be used individually or in combination of two or more.

[0040] The carbonate component can be any compound capable of condensing with the polyol component to produce a polycarbonate polyol. Examples of carbonate components include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; and diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, diantlyl carbonate, diphenanthryl carbonate, diindanyl carbonate, and bistetrahydronaphthyl carbonate. These may be used individually or in combination of two or more.

[0041] The hydroxyl value of polycarbonate polyols may be, for example, 32 to 160 mg KOH / g, or 38 to 140 mg KOH / g or 50 to 120 mg KOH / g. In this specification, the hydroxyl value refers to the number of milligrams (mg) of potassium hydroxide equivalent to hydroxyl groups in 1 g of sample, and is measured in accordance with JIS K1557-1.

[0042] The number-average molecular weight of the polycarbonate polyol may be, for example, 700 to 3500, or 800 to 3000 or 900 to 2200. In this specification, the number-average molecular weight refers to the number-average molecular weight measured by gel permeation chromatography (for example, the converted molecular weight using a polycarbonate diol composed of 1,6-hexanediol as a calibration curve), but it can also be calculated from the hydroxyl value and the number of hydroxyl groups (theoretical value).

[0043] The viscosity of the polycarbonate polyol at 70°C may be, for example, 500 to 5000 mPa·s, or it may be 1000 to 4000 mPa·s or 1500 to 3500 mPa·s.

[0044] Polycarbonate polyols can be obtained, for example, by reacting a polyol component with a carbonate component under the conditions of transesterification catalyst. The proportions of each component may be adjusted as appropriate, for example, from the viewpoint of hydroxyl value.

[0045] The polycarbonate polyol may contain the above-mentioned transesterification catalyst. In this case, the polycarbonate polyol can be called a transesterification catalyst-containing polycarbonate polyol. As the transesterification catalyst, metal compounds such as titanium compounds and alkali metal compounds can be used, with titanium compounds being particularly preferred. Specific examples of titanium compounds include tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, tetra(octadecyl) titanate, polyhydroxytitanium stearate, polyisopropoxytitanium stearate, titanium acetylacetonate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium octylene glycolate.

[0046] The content of the transesterification catalyst in the transesterification catalyst-containing polycarbonate polyol may be, for example, 0.1 to 1000 ppm by mass, 1 to 500 ppm by mass, or 2 to 250 ppm by mass, based on the total mass of the transesterification catalyst-containing polycarbonate polyol.

[0047] The content of polycarbonate polyol in polyol (B) may be, for example, 30-100% by mass, 50-100% by mass, or 70-100% by mass, based on the total mass of polyol (B).

[0048] Polyester polyols are compounds having multiple hydroxyl groups (-OH) and multiple ester bonds (-COO-). Examples of polyester polyols include condensed polyester polyols and lactone-based polyester polyols. Condensed polyester polyols are, for example, condensation polymers of a low molecular weight polyol component with a molecular weight of 60 to 400 and a polybasic acid component, and contain the low molecular weight polyol component and the polybasic acid component as monomer units. Lactone-based polyester polyols are, for example, ring-opening addition polymers of cyclic ester compounds such as lactones, using a low molecular weight polyol as an initiator, and contain the cyclic ester compound component as a monomer unit.

[0049] Examples of low molecular weight polyol components include ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,1 6-Hexadecanediol, 1,17-Heptadecanediol, 1,18-Octadecanediol, 1,19-Nonadecanediol, 1,20-Eicosanediol, 1,21-Henicosanediol, 1,22-Docosanediol, Diethylene glycol, Triethylene glycol, Dipropylene glycol, 1,3- or 1,4-Cyclohexanedimethanol and mixtures thereof, 1,4-Cyclohexanediol, 1,2-Heptadecanediol, 1,2-Octadecanediol, 1,2-Nonadecanediol, 1,2 -Eicosanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-n-propyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 2-n-butyl-1,3-propanediol, 2-isobutyl-1,3-propanediol, 2-tert-butyl-1,3-propanediol, neopentyl glycol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol Diol, 2-ethyl-2-n-propyl-1,3-propanediol, 2-ethyl-3-ethyl-1,4-butanediol, 2-methyl-3-ethyl-1,4-butanediol, 2,3-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,3,4-triethyl-1,5-pentanediol, dimethylolpropionic acid, dimethylolbutanoic acid, diol dimer acid, alkylene oxide adduct of bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A, 1,Examples include 4-dihydroxy-2-butene, p-xylylene glycol, bis(2-hydroxyethyl) terephthalate, bis(2-hydroxyethyl) isophthalate, 1,4-bis(2-hydroxyethoxy)benzene, 1,3-bis(2-hydroxyethoxy)benzene, resorcinol, hydroquinone, 2,2'-bis(4-hydroxycyclohexyl)propane, 2,6-dimethyl-1-octen-3,8-diol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, dihydric alcohols such as bisphenol F and bisphenol A, trihydric alcohols such as glycerin and trimethylolpropane, polyhydric alcohols having four or more hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, and D-mannitol. These may be used individually or in combination of two or more types.

[0050] The polybasic acid component preferably contains a dicarboxylic acid, and more preferably contains a dicarboxylic acid with a molecular weight of 90 to 400. Examples of dicarboxylic acids with a molecular weight of 90 to 400 include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, methylhexandioic acid, citraconic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, dimer acid, hetic acid, and acid anhydrides and ester-forming derivatives derived from these carboxylic acids. These may be used individually or in combination of two or more types.

[0051] Examples of cyclic ester compound components include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, and ε-palmitractone. These may be used individually or in combination of two or more.

[0052] The hydroxyl value of the polyester polyol may be, for example, 32 to 160 mg KOH / g, or it may be 38 to 140 mg KOH / g or 50 to 120 mg KOH / g.

[0053] The number-average molecular weight of the polyester polyol may be, for example, 700 to 3500, or it may be 800 to 3000 or 900 to 2200.

[0054] The viscosity of the polyester polyol at 70°C may be, for example, 50 to 1000 mPa·s, or it may be 100 to 700 mPa·s or 300 to 800 mPa·s.

[0055] Polyester polyols can be obtained, for example, by reacting a low molecular weight polyol component with a polybasic acid component under transesterification catalyst. The proportion of each component may be adjusted as appropriate, for example, from the viewpoint of hydroxyl value.

[0056] The polyester polyol may contain the above-mentioned transesterification catalyst. In this case, the polyester polyol can be called a transesterification catalyst-containing polyester polyol. The transesterification catalyst is the same as that listed above for use in the reaction between the polyol component and the carbonate component.

[0057] The content of the transesterification catalyst in the transesterification catalyst-containing polyester polyol may be, for example, 0.1 to 1000 ppm by mass, 1 to 500 ppm by mass, or 2 to 250 ppm by mass, based on the total mass of the transesterification catalyst-containing polyester polyol.

[0058] The polyester polyol content in polyol (B) may be, for example, 30-100% by mass, 50-100% by mass, or 70-100% by mass, based on the total mass of polyol (B).

[0059] Polyol (B) may consist only of polyols selected from the group consisting of polycarbonate polyols and polyester polyols, and may also contain other polyols (except for compounds corresponding to the chain extender (C) described later). Examples of other polyols include polyether polyols and polyolefin polyols.

[0060] Examples of polyether polyols include polyethylene glycol, polypropylene ether polyol, and polytetramethylene ether polyol. These may be used individually or in combination of two or more.

[0061] Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and its hydrogenated derivatives, and hydroxyl-containing chlorinated polyolefins. These may be used individually or in combination of two or more.

[0062] The content of the other polyols in polyol (B) may be, for example, 0 to 50% by mass, 0 to 30% by mass, or 0 to 10% by mass, based on the total mass of polyol (B).

[0063] The average hydroxyl value of polyol (B) may be, for example, 32 to 160 mgKOH / g, or 38 to 140 mgKOH / g or 50 to 120 mgKOH / g. The average hydroxyl value of polyol (B) is the weighted average value of the hydroxyl values ​​weighted by the mass of each polyol contained in polyol (B). It is calculated by multiplying the hydroxyl value of each polyol by its respective mass, summing the values, and dividing by the total mass of polyol (B) (the sum of the masses of each polyol).

[0064] The content of polyol (B) may be, for example, 55-88.5% by mass, 60-87% by mass, or 63-86% by mass, based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C).

[0065] [Chain extender (C)] As the chain extender (C), compounds generally known as chain extenders for thermoplastic polyurethane elastomers can be used. Examples include compounds having functional groups that can react with isocyanate groups such as hydroxyl groups (-OH), primary amino groups (-NH2), or secondary amino groups (-NH-), or water (H2O). It is preferable to use a compound having a hydroxyl group as the chain extender (C), and more preferably a diol. As the chain extender (C), one type of chain extender may be used alone, or two or more types of chain extenders may be used in combination.

[0066] Examples of diols include linear alkanediols such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-n-propyl-1,3-propanediol, and 2-isopropyl -1,3-propanediol, 2-n-butyl-1,3-propanediol, 2-isobutyl-1,3-propanediol, 2-tert-butyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-propyl-1,3-propanediol, 2-ethyl-3-ethyl-1,4-butanediol, 2-methyl-3-ethyl-1,4-butanediol, 2,3-diethyl-1,5-pentanediol, 2,4-diethyl Branched alkanediols such as -1,5-pentanediol and 2,3,4-triethyl-1,5-pentanediol; diethylene glycol, triethylene glycol, dipropylene glycol, 1,3- or 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, dimethylolpropionic acid, dimethylolbutanoic acid, dimergol, alkylene oxide adducts of bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, p-xylylene glycol, bis Examples include (2-hydroxyethyl) terephthalate, bis(2-hydroxyethyl) isophthalate, 1,4-bis(2-hydroxyethoxy)benzene, 1,3-bis(2-hydroxyethoxy)benzene, resorcinol, hydroquinone, 2,2'-bis(4-hydroxycyclohexyl)propane, 2,6-dimethyl-1-octen-3,8-diol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, bisphenol F, bisphenol A, etc.Among these, as diols, aliphatic diols having 2 to 10 carbon atoms are preferred from the viewpoint of improving mechanical strength, aliphatic diols having 2 to 6 carbon atoms are more preferred, and 1,4-butanediol or 1,6-hexanediol are even more preferred. These may be used individually or in combination of two or more.

[0067] The content of the chain extender (C) may be, for example, 1.5 to 15% by mass, 2.0 to 12% by mass, or 2.5 to 11% by mass, based on the total mass of the polyisocyanate (A), polyol (B), and chain extender (C).

[0068] [Compound (D)] Compound (D) is a compound having a group represented by the general formula (I) above. Compound (D) may be used alone or in combination of two or more compounds.

[0069] The bond represented by * in general formula (I) may be bonded to a carbon atom, a sulfur atom, or a metal atom by a covalent bond or a coordinate bond. Examples of metal atoms include zinc, potassium, sodium, selenium, tellurium, cobalt, copper, lead, bismuth, nickel, manganese, and iron.

[0070] The number of groups represented by general formula (I) in compound (D) is, for example, 1 to 4, preferably 1 or 2. If compound (D) has 2 or more groups represented by general formula (I), multiple R 1 They may be the same or different from each other, and there may be multiple R 2 They may be the same or different from each other, and one of the bases R 1 or R 2 R of the other base 1 or R 2 They may be bound together with each other.

[0071] In general formula (I), R 1 and R 2This represents a substituted or unsubstituted hydrocarbon group. Some of the carbon atoms in the hydrocarbon group (excluding carbon atoms directly bonded to the nitrogen atom in general formula (I)) may be substituted with at least one heteroatom selected from the group consisting of, for example, oxygen atoms (-O-), nitrogen-containing groups (-NH-, etc.), and sulfur atoms (-S). The number of carbon atoms in the hydrocarbon group may be, for example, 1 to 12. The hydrocarbon group may be an aliphatic hydrocarbon group (e.g., alkyl or cycloalkyl group), an aromatic hydrocarbon group (e.g., aryl group), or an organic group consisting of a combination thereof (e.g., aralkyl group).

[0072] Alkyl groups may be linear or branched. The number of carbon atoms in an alkyl group may be, for example, 1 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group. The number of carbon atoms in a cycloalkyl group may be, for example, 5 to 8. Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. The number of carbon atoms in an aryl group may be, for example, 6 to 10. Examples of aryl groups include phenyl group and naphthyl group. The number of carbon atoms in an aralkyl group may be, for example, 7 to 10. Examples of aralkyl groups include benzyl group.

[0073] R 1 and R 2 These atoms may be bonded to each other to form a ring (heterocycle) with the nitrogen atom. 1 and R 2 The ring formed by the bonding of these elements may be, for example, a 4- to 6-membered ring. 1 and R 2 The ring formed by the bonding of these elements may be, for example, a pyrrolidine ring or a piperazine ring.

[0074] In formula (I), R 1 and R 2From the viewpoint of further reducing fish eyes, each of these is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.

[0075] From the viewpoint of reducing the amount of fish-eye, compound (D) is preferably a compound represented by the following general formula (II). [ka]

[0076] In formula (II), R 1 and R 2 R in equation (I) 1 and R 2 This is equivalent to the above. x represents an integer from 1 to 6.

[0077] In equation (II), x is preferably an integer between 1 and 4, and more preferably 1 or 2, from the viewpoint of further reducing the fisheye effect.

[0078] Compound (D) may contain at least one selected from the group consisting of tetraalkylthiuram monosulfide and tetraalkylthiuram disulfide.

[0079] Tetraalkylthiuram monosulfide is a tetraalkylthiuram monosulfide in which the alkyl group has 1 to 6 carbon atoms. 1-6 It may be an alkylthiuram monosulfide, and from the viewpoint of reducing fisheye, the alkyl group has 1 to 2 carbon atoms, such as tetraC 1-2 It may be an alkylthiuram monosulfide.

[0080] Tetraalkylthiuram disulfide is a tetraalkylthiuram disulfide in which the alkyl group has 1 to 6 carbon atoms. 1-6 It may be an alkylthiuram disulfide, and from the viewpoint of reducing fisheye, the alkyl group has 1 to 2 carbon atoms, such as tetraC 1-2 It may be an alkylthiuram disulfide.

[0081] Examples of compound (D) include tetraalkyl thiuram monosulfides such as tetramethyl thiuram monosulfide, tetraethyl thiuram monosulfide, tetrapropyl thiuram monosulfide, tetrabutyl thiuram monosulfide, tetrapentyl thiuram monosulfide, tetrahexyl thiuram monosulfide, tetraheptyl thiuram monosulfide, and tetraoctyl thiuram monosulfide; and tetracyclopentyl thiuram monosulfide, tetracyclohexyl thiuram monosulfide, and tetracycloheptyl thiuram monosulfide. Tetracycloalkyl thiuram monosulfides such as tetracyclooctyl thiuram monosulfide; tetraaryl thiuram monosulfides such as tetraphenyl thiuram monosulfide and tetranaphthyl thiuram monosulfide; tetraaralkyl thiuram monosulfides such as tetrabenzyl thiuram monosulfide; dipentamethylenethiuram monosulfide; tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrapropyl thiuram disulfide, tetrabutyl thiuram disulfide, tetrapentyl thiuram disulfide Tetraalkyl thiuram disulfides such as tetrahexyl thiuram disulfide, tetraheptyl thiuram disulfide, tetraoctyl thiuram disulfide, tetrakis(2-ethylhexyl) thiuram disulfide; tetracycloalkyl thiuram disulfides such as tetracyclopentyl thiuram disulfide, tetracyclohexyl thiuram disulfide, tetracycloheptyl thiuram disulfide, tetracyclooctyl thiuram disulfide; tetraphenyl thiuram disulfide, tetranaphthyl thiuram disulfide, etc. Tetraaryl thiuram disulfide; tetraaralkyl thiuram disulfide such as tetrabenzyl thiuram disulfide; dipentamethylenethiuram disulfide; tetraalkyl thiuram trisulfide such as tetramethyl thiuram trisulfide and tetraethyl thiuram trisulfide; tetraalkyl thiuram tetrasulfide such as tetramethyl thiuram tetrasulfide and tetraethyl thiuram tetrasulfide; tetraalkyl thiuram hexasulfide such as tetramethyl thiuram hexasulfide and tetraethyl thiuram hexasulfide;Examples include N,N'-dimethyl-N,N'-diphenylthiuram disulfide. These may be used individually or in combination of two or more.

[0082] Compound (D) may contain at least one selected from the group consisting of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and tetraethylthiuram disulfide, from the viewpoint of reducing fish eyes.

[0083] The content of compound (D) may be 0.5 ppm or more, 1 ppm or more, or 2 ppm or more based on the total mass of polyol (B), and may be 3 ppm or more, 5 ppm or more, 10 ppm or more, or 15 ppm or more from the viewpoint of reducing fisheye. The content of compound (D) may be 1000 ppm or less, 500 ppm or less, or 300 ppm or less based on the total mass of polyol (B), and may be 100 ppm or less, 70 ppm or less, 50 ppm or less, or 30 ppm or less from the viewpoint of reducing fisheye. The content of compound (D) may be 0.5 to 1000 ppm by mass, 1 to 500 ppm by mass, or 2 to 300 ppm by mass, based on the total mass of polyol (B), and from the viewpoint of reducing fisheye, it may be 3 to 100 ppm by mass, 5 to 70 ppm by mass, 10 to 50 ppm by mass, or 15 to 30 ppm by mass.

[0084] The content of compound (D) may be 0.5 ppm or more, 1 ppm or more, or 2 ppm or more by mass, based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C), and may be 3 ppm or more, 5 ppm or more, 7 ppm or more, or 10 ppm or more by mass, from the viewpoint of reducing fish eyes. The content of compound (D) may be 500 ppm or less by mass, 300 ppm or less, or 200 ppm or less by mass, based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C), and may be 100 ppm or less by mass, 60 ppm or less, 40 ppm or less, or 30 ppm or less by mass, from the viewpoint of reducing fish eyes. The content of compound (D) may be 0.5 to 500 ppm by mass, 1 to 300 ppm by mass, or 2 to 200 ppm by mass, based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C). From the viewpoint of reducing fisheye, it may also be 3 to 100 ppm by mass, 5 to 60 ppm by mass, 7 to 40 ppm by mass, or 10 to 30 ppm by mass.

[0085] [Other ingredients] The thermoplastic polyurethane elastomer composition may further contain other components besides those described above. Other components may include known additives that are usable for the formation of thermoplastic polyurethane elastomers and molded articles containing thermoplastic polyurethane elastomers. Examples of such additives include lubricants, solvents, hydrolysis inhibitors, antioxidants, UV absorbers, UV stabilizers, fillers, plasticizers, foaming agents, flame retardants, anti-blocking agents, antifungal agents, processing aids, and reinforcing fibers. The thermoplastic polyurethane elastomer composition may contain one of these additives, or two or more. The mixing order when using these additives is not particularly limited.

[0086] In the thermoplastic polyurethane elastomer composition described above, the other components may be included in the reaction product of a polyol (B) containing at least one selected from the group consisting of polyisocyanate (A), polycarbonate polyol, and polyester polyol, and a chain extender (C), or they may be included as components independent of the reaction product.

[0087] The content of the other components mentioned above may be, for example, 0.05 to 10% by mass, 0.1 to 5% by mass, or 0.2 to 2% by mass, based on the total mass of the thermoplastic polyurethane elastomer composition.

[0088] The ratio of the total number of moles of isocyanate groups in an isocyanate group-containing compound to the total number of moles of active hydrogen groups in an active hydrogen group-containing compound (total number of moles of isocyanate groups / total number of moles of active hydrogen groups), which is included as a component of the thermoplastic polyurethane elastomer composition, is preferably 0.7 to 1.3, and more preferably 0.8 to 1.2, from the viewpoint of easily forming a thermoplastic polyurethane elastomer composition with an appropriate molecular weight and melt viscosity. In this specification, "active hydrogen group" means a functional group having a hydrogen atom that reacts with an isocyanate group.

[0089] The thermoplastic polyurethane elastomer composition of this embodiment may be formed from a composition (hereinafter also referred to as the "thermoplastic polyurethane elastomer forming composition") containing a polyisocyanate (A), a polyol (B) containing at least one selected from the group consisting of polycarbonate polyols and polyester polyols, a chain extender (C), and a compound (D). The thermoplastic polyurethane elastomer forming composition may be a one-component composition in which all constituent components are contained in one liquid, or it may be a multi-component composition in which the constituent components exist separately in multiple liquids. For example, the thermoplastic polyurethane elastomer forming composition may contain a first liquid containing polyol (B) and a second liquid containing polyisocyanate (A). In this case, the other constituent components (chain extender (C), compound (D), and other components) may be contained in either the first liquid or the second liquid, but it is preferable that the chain extender (C) and compound (D) are contained in the first liquid.

[0090] According to the thermoplastic polyurethane elastomer forming composition, by mixing and reacting the above-mentioned components, a thermoplastic polyurethane elastomer composition with fewer fish eyes can be obtained while maintaining mechanical properties.

[0091] <Method for producing thermoplastic polyurethane elastomer composition> Another embodiment of the present disclosure relates to a method for producing a thermoplastic polyurethane elastomer composition, comprising the step of reacting a polyisocyanate (A), a polyol (B) comprising at least one selected from the group consisting of polycarbonate polyols and polyester polyols, and a chain extender (C) in the presence of a compound (D) (hereinafter also referred to as the "reaction step"). The polyisocyanate (A), polyol (B), chain extender (C), and compound (D) are as described above.

[0092] According to the above manufacturing method, a thermoplastic polyurethane elastomer composition with fewer fish eyes can be obtained while maintaining mechanical properties. In other words, according to the above manufacturing method, the thermoplastic polyurethane elastomer composition of the above embodiment can also be obtained.

[0093] The above reaction step may be a step of reacting a mixture containing a polyisocyanate (A), a polyol (B), a chain extender (C), and a compound (D). The mixture may be the one-component thermoplastic polyurethane elastomer forming composition described above. The components of the mixture may be those exemplified as components of the above thermoplastic polyurethane elastomer composition, and the amount used (mixing amount) may be within the range exemplified as the content of components in the above thermoplastic polyurethane elastomer composition.

[0094] In the above manufacturing method, a pre-prepared mixture may be used, or the mixture may be prepared by mixing the components of the mixture. The mixing order of the components is not particularly limited, but from the viewpoint of deactivating the transesterification catalyst contained in the polyol (B), it is preferable to prepare a first solution containing the polyol (B), a chain extender (C), and a compound (D), and a second solution containing polyisocyanate (A), and then mix them to prepare the mixture. The first and second solutions may be mixed after their temperatures have been adjusted to a predetermined temperature (for example, 70 to 120°C).

[0095] In the reaction step, the polyisocyanate (A), polyol (B), and chain extender (C) may be reacted by heating the mixture. The heating temperature is preferably 80 to 250°C, and more preferably 120 to 250°C. The heating time may be, for example, 30 seconds to 60 minutes.

[0096] As for the specific form of the reaction process, known methods can be appropriately adopted. Examples include the one-shot method, prepolymer method, batch reaction method, continuous reaction method, kneader method, extruder method, etc.

[0097] A specific example of the extruder method involves supplying the above-mentioned raw materials (mixture) to an extruder set to a cylinder temperature of 80 to 250°C, kneading and conveying the raw materials within the extruder while polymerization is carried out, and extruding the thermoplastic polyurethane elastomer composition from a strand die. The resulting strand-like thermoplastic polyurethane elastomer composition may then be subjected to strand cutting to form pellets.

[0098] After the above reaction process, a thermoplastic polyurethane elastomer composition is obtained, for example, in the form of a powder or blocks. The thermoplastic polyurethane elastomer composition may then be pulverized to form flakes, and the flake-shaped thermoplastic polyurethane elastomer composition may be supplied to an extruder and melt-kneaded, and then formed into pellets by strand cutting or underwater cutting. The melt-kneading may be carried out at the temperature used to extrude a typical thermoplastic polyurethane elastomer composition (approximately 150-220°C).

[0099] The thermoplastic polyurethane elastomer composition obtained by the above manufacturing method may be subjected to a drying treatment. The drying temperature may be, for example, 70 to 120°C. The drying time may be, for example, 1 to 20 hours.

[0100] <Molded body> Another embodiment of the present disclosure relates to a molded article comprising a thermoplastic polyurethane elastomer composition. The thermoplastic polyurethane elastomer composition constituting the molded article may be the thermoplastic polyurethane elastomer composition of the above embodiment, or it may be a thermoplastic polyurethane elastomer composition obtained by the manufacturing method of the above embodiment.

[0101] The molded article may consist solely of a thermoplastic polyurethane elastomer composition, or it may contain other components besides the thermoplastic polyurethane elastomer composition. Examples of other components include the additives exemplified above as other components that may be included in the thermoplastic polyurethane elastomer composition. The other components may be mixed with the thermoplastic polyurethane elastomer composition during the manufacturing of the molded article, or they may be pre-mixed during the manufacturing of the thermoplastic polyurethane elastomer composition.

[0102] The molding method for the molded article can be any known method for molding thermoplastic polyurethane elastomers, and is not particularly limited. Examples of molding methods include injection molding, extrusion molding, compression molding, blow molding, calendering, and roll forming. The molding temperature may be, for example, 150 to 220°C.

[0103] The molded body may be a molded body of various shapes, such as a resin plate, film, sheet, fiber, or irregularly shaped product.

[0104] The fields of application of the molded articles of this disclosure are not particularly limited and can be used in many fields such as electrical and electronic components, precision instruments, home appliances and AV equipment, office automation equipment, automobiles, agriculture, forestry and fisheries, food, textiles, clothing, leather, and medical equipment. Specifically, the molded articles can be used in a variety of applications as shown below. Automotive parts: Tire inner liners, ball joints, dust covers, pedal stoppers, door lock strikers, bushings, spring covers, bearings, vibration damping components, interior and exterior parts, tire chains, side molds, timing belts, headrests, and seat covers. Machinery and industrial parts: various gears, seals, rollers, packings, vibration damping components, pickers, bushings, bearings, caps, connectors, rubber screens, printing drums, O-rings, casters. Shoes: Soles and studs for baseball, golf, and soccer shoes, air cushions, women's shoe top lifts, ski boots, safety shoes. Hoses and tubes: High-pressure hoses, medical tubes, oil and pneumatic tubes, air tubes, fuel tubes, paint hoses, fire hoses. Electrical wires and cables: Power and communication cables, computer and automotive wiring, various types of coiled cords. Other products: conveyor belts, air mattresses, diaphragms, keyboard sheets, waterproof sheets, synthetic leather, life jackets, wetsuits, rollers, grips, watch bands, ear tags, various ropes, round belts, V-belts, anti-slip materials, road sign components (traffic guidance markers), escalator handrails, flexible containers, binders, hot melt adhesives, synthetic leather, coatings for ropes, wires, gloves, etc., food and medical packaging materials, artificial organs, artificial skin, disposable diapers, wound bandages, wallpaper. [Examples]

[0105] The contents of this disclosure will be described in more detail below using examples and comparative examples, but this disclosure is not limited to the following examples.

[0106] <Preparation of thermoplastic polyurethane elastomer compositions> [Raw materials] The raw materials used in this embodiment are shown below.

[0107] Polyisocyanate (A) • HDI: 1,6-Hexamethylene diisocyanate, manufactured by Tosoh Corporation

[0108] Polyol (B) N-964: 3-methyl-1,5-pentanediol / 1,6-hexanediol copolymer polycarbonate diol, number average molecular weight: 2000, melting point: -50℃, viscosity at 70℃: 2400 mPa·s, manufactured by Tosoh Corporation, product name N-980N: 1,6-Hexanediol-based polycarbonate diol, number average molecular weight: 2000, melting point: 53℃, viscosity at 70℃: 3000 mPa·s, manufactured by Tosoh Corporation, product name

[0109] Chain extender (C) • 1,4-BG: 1,4-butanediol, manufactured by BASF.

[0110] Compound (D) • TMTM: Tetramethylthiuram monosulfide, manufactured by Tokyo Chemical Industry Co., Ltd. • TMTD: Tetramethylthiuram disulfide, manufactured by Tokyo Chemical Industry Co., Ltd. • TETD: Tetraethyl thiuram disulfide, manufactured by Tokyo Chemical Industry Co., Ltd. • TBTD: Tetrabutylthiuram disulfide, manufactured by Tokyo Chemical Industry Co., Ltd.

[0111] [Example 1] Polyisocyanate (A), polyol (B), chain extender (C), and compound (D) were supplied to a twin-screw extruder with the cylinder temperature set to 180°C, in the types and proportions shown in Table 1, at a total feed rate of 15 kg / hr. Polymerization was carried out while the raw materials (reaction solution) were kneaded and conveyed within the twin-screw extruder, and strand pellets (TPU pellets) containing the thermoplastic polyurethane elastomer composition were extruded from the strand die. The obtained TPU pellets were dried at 80°C for 16 hours to obtain the TPU pellets of Example 1. The ratio of the total number of isocyanate groups in polyisocyanate (A) to the total number of moles of active hydrogen groups in polyol (B) and chain extender (C) (total number of isocyanate groups / total number of moles of active hydrogen groups) was set to 1.00. Furthermore, the blending ratio of compound (D) shown in Table 1 refers to the blending ratio (unit: mass ppm) based on the total mass of polyisocyanate (A), polyol (B), and chain extender (C).

[0112] [Examples 2-26] TPU pellets for Examples 2 to 26 were obtained in the same manner as in Example 1, except that the types of polyol (B), compound (D), and / or the mixing ratios of components (A) to (D) were changed as shown in Tables 1 to 3.

[0113] [Comparative Example 1] TPU pellets for Comparative Example 1 were obtained in the same manner as in Example 1, except that compound (D) was not included.

[0114] [Comparative Example 2] TPU pellets for Comparative Example 2 were obtained in the same manner as for Comparative Example 1, except that the polyol (B) was changed to include N-964 and N-980N in the blending ratios shown in Table 1.

[0115] <Rating> [Preparation of molded products for evaluation] Evaluation molded bodies were prepared using the TPU pellets of the examples and comparative examples. Specifically, the TPU pellets of each example were extruded using a Laboplastmill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) T-die at 180-220°C to produce film-like molded bodies with a thickness of 150 μm.

[0116] [Fish Eye] The resulting molded body was then subjected to a 90cm test using Micro Ace (manufactured by Ayaha Engineering Co., Ltd., model OMI-FE). 2 The number of fisheyes was measured within a rectangular area measuring (6cm x 15cm).

[0117] [Mechanical properties] The mechanical properties (A hardness, 100% modulus (M100), breaking strength, and elongation at break) of the obtained molded articles were measured according to the measurement method described in JIS K 7311 (Test method for polyurethane thermoplastic elastomers).

[0118] [Table 1]

[0119] [Table 2]

[0120] [Table 3]

Claims

1. A reaction product of a polyol (B) comprising at least one selected from the group consisting of polyisocyanate (A), polycarbonate polyol, and polyester polyol, and a chain extender (C), A thermoplastic polyurethane elastomer composition containing a compound (D) having a group represented by the following general formula (I). 【Chemistry 1】 [In formula (I), R １ and R ２ Each of these independently represents a substituted or unsubstituted hydrocarbon group, and R １ and R ２ These elements may be joined to form a ring, and * indicates a bonding hand.

2. R １ and R ２ The thermoplastic polyurethane elastomer composition according to claim 1, wherein each of them is independently an alkyl group.

3. R １ and R ２ The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein each of them is independently a methyl group or an ethyl group.

4. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the compound (D) comprises at least one selected from the group consisting of tetraalkylthiuram monosulfide and tetraalkylthiuram disulfide.

5. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the compound (D) comprises at least one selected from the group consisting of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and tetraethylthiuram disulfide.

6. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the content of compound (D) is 3 to 100 ppm by mass, based on the total mass of the polyisocyanate (A), the polyol (B), and the chain extender (C).

7. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the polyisocyanate (A) comprises hexamethylene diisocyanate.

8. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the polyol (B) is a polycarbonate polyol containing at least one diol selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol as a monomer unit.

9. The thermoplastic polyurethane elastomer composition according to claim 1 or 2, wherein the chain extender (C) comprises an aliphatic diol having 2 to 10 carbon atoms.

10. A molded article comprising the thermoplastic polyurethane elastomer composition according to claim 1 or 2.

11. A method for producing a thermoplastic polyurethane elastomer composition, comprising the step of reacting a polyisocyanate (A), a polyol (B) containing at least one selected from the group consisting of polycarbonate polyols and polyester polyols, and a chain extender (C) in the presence of a compound (D) having a group represented by the following general formula (I). 【Chemistry 2】 [In formula (I), R １ and R ２ each independently represent a substituted or unsubstituted hydrocarbon group, R １ and R ２ may be bonded to each other to form a ring, and * represents a bond.]]

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