Thermoplastic polyurethane resin composition, and molded article using the resin composition

Abstract

To provide: a thermoplastic polyurethane resin composition which is suppressed from formation of a white layer caused by a cyclic compound formed of an aliphatic polyisocyanate and a chain extender, and is suppressed from an optical change of appearance; and a molded article.SOLUTION: A thermoplastic polyurethane resin composition comprises a thermoplastic polyurethane resin (A), a carboxylic acid metal salt (B), and a carboxylic acid bisamide (C). The thermoplastic polyurethane resin (A) is a reaction product of a polyisocyanate component (a1), a chain extender (a2), and a polyol component (a3), where the polyisocyanate component (a1) contains an aliphatic polyisocyanate, the chain extender (a2) contains 1 or more selected from the group consisting of 1,4-butane diol and 1,6-hexane diol, the carboxylic acid metal salt (B) has a part derived from a carboxylic acid represented by C17H35-COOH, and the carboxylic acid bisamide (C) contains a specific carboxylic acid bisamide (c1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a thermoplastic polyurethane resin composition and a molded article using the resin composition.

Background Art

[0002] Thermoplastic polyurethane resin (TPU) is suitable for extrusion-molded products such as film products and injection-molded products. However, when a cyclic oligourethane compound is contained in the thermoplastic polyurethane resin composition, a white layer is formed on the resin surface due to the migration (bloom) of the cyclic compound to the resin surface, resulting in an optical change. It is known that cyclic compounds are likely to be generated by the reaction of a chain extender and 1,6-hexamethylene diisocyanate.

[0003] Patent Document 1 discloses a thermoplastic polyurethane resin molding composition obtained by reacting an aliphatic polyol, a polyisocyanate, and a chain extender at a predetermined blending ratio, and adding a specific lubricant to easily remove a white layer that migrates to the surface of the molded article.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the thermoplastic polyurethane resin molding composition according to Patent Document 1 is premised on migration and contains by-products that can easily remove migration. Therefore, the generation of the white layer is not sufficiently suppressed in the thermoplastic polyurethane resin molding composition according to Patent Document 1.

[0006] Therefore, one aspect of the present disclosure is directed to providing a thermoplastic polyurethane resin composition in which the formation of a white layer caused by a cyclic compound composed of an aliphatic polyisocyanate and a chain extender is suppressed, and an optical change in appearance is suppressed, and a molded article using the resin composition.

Means for Solving the Problems

[0007] According to the thermoplastic polyurethane resin composition according to one aspect of the present disclosure, a thermoplastic polyurethane resin (A), a metal carboxylate (B), a carboxylic acid bisamide (C), and the thermoplastic polyurethane resin (A) is a reaction product of a polyisocyanate component (a1), a chain extender (a2), and a polyol component (a3), the polyisocyanate component (a1) contains an aliphatic polyisocyanate, the chain extender (a2) contains one or more selected from the group consisting of 1,4-butanediol and 1,6-hexanediol, the metal carboxylate (B) has a site (b1) derived from a carboxylic acid represented by C 23 , , 13 , 11 , , NHCO , 21 H 35 -COOH, the carboxylic acid bisamide (C) contains a carboxylic acid bisamide (c1) represented by formula (1) or (2): R 11 -NHCO-R 12 - CONH -R 13 ···Formula (I) R 21 -CONH-R 22 - NHCO -R 23 ···Formula (II) In the formula, R 11 ~R 13 and R<​23 Each of these independently represents a chain-like hydrocarbon group; However, R 11 and R 13 At least one of the following, or R 21 and R 23 At least one of these is a chain-like hydrocarbon group having 9 to 21 carbon atoms.

[0008] According to thermoplastic polyurethane resin compositions of other aspects of this disclosure, Thermoplastic polyurethane resin (A), A metal carboxylate salt (B) and It contains carboxylate bisamide (C) and The thermoplastic polyurethane resin (A) is Polyisocyanate component (a1), Chain extender (a2), The reaction product of the polyol component (a3) ​​is The aforementioned polyisocyanate component (a1) comprises an aliphatic polyisocyanate, The provided thermoplastic polyurethane resin composition comprises one or more chain extenders (a2) selected from the group consisting of 1,4-butanediol and 1,6-hexanediol.

[0009] A molded article comprising the thermoplastic polyurethane resin composition is provided according to yet another aspect of the present disclosure. [Effects of the Invention]

[0010] According to one aspect of this disclosure, it is possible to provide a thermoplastic polyurethane resin composition in which the formation of a white layer caused by a cyclic compound consisting of an aliphatic polyisocyanate and a chain extender is suppressed, thereby suppressing optical changes in appearance, and a molded article using the resin composition. [Modes for carrying out the invention]

[0011] The following describes in detail exemplary embodiments for carrying out each aspect of this disclosure.

[0012] [First embodiment: Thermoplastic polyurethane resin composition] A thermoplastic polyurethane resin composition according to a first aspect of this disclosure is: Thermoplastic polyurethane resin (A), A metal carboxylate salt (B) and It contains carboxylate bisamide (C) and The thermoplastic polyurethane resin (A) is Polyisocyanate component (a1), Chain extender (a2), The reaction product of the polyol component (a3) ​​is The aforementioned polyisocyanate component (a1) comprises an aliphatic polyisocyanate, The chain extender (a2) comprises one or more selected from the group consisting of 1,4-butanediol and 1,6-hexanediol. The aforementioned carboxylate metal salt (B) is C 17 H 35 It has a carboxylic acid-derived moiety (b1) represented by -COOH, The carboxyl bisamide (C) is a thermoplastic polyurethane resin composition comprising a carboxyl bisamide (c1) represented by formula (1) or (2): R 11 -NHCO-R 12 - CONH -R 13 ...Equation (1) R 21 -CONH-R 22 - NHCO -R 23 ...Equation (2) During the ceremony, R 11 ~R 13 , and, R 21 ~R 23 Each of these independently represents a chain-like hydrocarbon group; However, R 11 and R 13 At least one of the following, or R 21 and R 23 At least one of these is a chain-like hydrocarbon group having 9 to 21 carbon atoms.

[0013] The inventors speculate that the thermoplastic polyurethane resin composition according to this embodiment enhances the compatibility of the cyclic compound, which consists of an aliphatic polyisocyanate and a chain extender, with the urethane resin, thereby suppressing the migration of the cyclic compound to the surface and inhibiting the formation of a white layer. Furthermore, by having this resin composition on the surface of an article, the article becomes aesthetically pleasing. Furthermore, even when the thermoplastic polyurethane resin (A) contains one or more reaction products selected from the group consisting of 1,4-butanediol and 1,6-hexanediol, which are particularly prone to forming cyclic compounds, as chain extenders, the formation of a white layer is suppressed. As a result, the thermoplastic polyurethane resin composition exhibits suppressed optical changes in appearance and also enjoys excellent elasticity.

[0014] Thermoplastic polyurethane resin compositions containing 1,4-butanediol or 1,6-hexanediol exhibit excellent elasticity. However, thermoplastic polyurethane resin compositions containing these chain extenders are particularly prone to the formation of cyclic compounds, leading to optical changes in appearance. In contrast, the present inventors hypothesize that the resin composition according to this embodiment, by coexisting a carboxylate metal salt that is difficult to migrate after dispersion in the thermoplastic polyurethane resin with a carboxylate bisamide having a similar chain-like hydrocarbon structure, achieves appropriate surface migration of the carboxylate bisamide, thereby suppressing aggregation of cyclic compounds on the surface and also suppressing excessive surface migration of the carboxylate bisamide, thus having the effect of suppressing aggregation of the carboxylate bisamide on the surface.

[0015] The thermoplastic polyurethane resin composition according to this embodiment will be described in more detail below.

[0016] [[Thermoplastic polyurethane resin (A)]] Thermoplastic polyurethane resin (A) Polyisocyanate component (a1), Chain extender (a2), This is the reaction product of the polyol component (a3) ​​and [another component].

[0017] • Polyisocyanate component (a1) The polyisocyanate component (a1) includes an aliphatic polyisocyanate. Examples of aliphatic polyisocyanates include aliphatic diisocyanates without a ring structure, such as 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 3-methyl-1,5-pentane diisocyanate, and trimethyl-hexamethylene diisocyanate; and diisocyanates with an alicyclic structure, such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and norbornane diisocyanate. Furthermore, these may be isocyanate-terminated compounds obtained by the reaction of these polyisocyanates with active hydrogen-containing compounds, or polyisocyanate modified products obtained by the reaction of these compounds themselves, such as allophanate formation, uretdione formation, isocyanurate formation, or carbodiimide formation. Of these isocyanates, 1,6-hexamethylene diisocyanate is preferred in terms of improving toughness and flexibility.

[0018] • Chain extender (a2) The chain extender (a2) comprises one or more selected from the group consisting of 1,4-butanediol and 1,6-hexanediol. Even when these chain extenders, which are particularly prone to forming cyclic compounds, are included, the formation of the white layer can be suppressed. The chain extender (a2) is particularly preferably 1,4-butanediol because it has superior elasticity. Although 1,4-butanediol is more likely to form a white layer than 1,6-hexanediol, the thermoplastic polyurethane resin composition according to this embodiment can highly suppress the formation of a white layer even when 1,4-butanediol is included as the chain extender (a2).

[0019] • Polyol component (a3) Examples of polyol components (a3) ​​include polyester diols, polyether diols, and polycarbonate diols.

[0020] Specific examples of polyester diols include, for example, one type of dicarboxylic acid or their anhydrides such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, fumaric acid, etc., and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 Examples include those obtained by a condensation polymerization reaction with one or more low molecular weight polyols with a molecular weight of 500 or less, such as -butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol. Also, polyester-amide polyols obtained by substituting some of the low molecular weight polyols with low molecular weight polyamines or low molecular weight amino alcohols such as hexamethylenediamine, isophoronediamine, and monoethanolamine are also examples.

[0021] Specific examples of polyetherdiols include low molecular weight compounds such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diols, bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol. Examples include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, using polyols or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine as initiators; and polyether polyols obtained by ring-opening polymerization of alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and cyclic ether monomers such as tetrahydrofuran.

[0022] Specific examples of polycarbonate diols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, and bisphenol. Examples of polycarbonate diols include those obtained by de-alcoholization reactions, de-phenolization reactions, etc., involving one or more low-molecular-weight polyols such as ethylene oxide or propylene oxide adducts of Nol A, bis(β-hydroxyethyl)benzene, and xylylene glycol, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, diantryl carbonate, diphenanthryl carbonate, and diindanyl carbonate. These can be contained in one or more types. Among these, polycarbonate diols composed of 1,6-hexanediol are preferred because they are easily obtained and exhibit excellent physical properties.

[0023] Furthermore, the number-average molecular weight of the polycarbonate diol is preferably 750 to 3000, more preferably 800 to 2000, and even more preferably 1000 to 2000. When the number-average molecular weight is 750 or higher, the urethane group concentration in the TPU does not become excessively high, further reducing the generation of unmelted material. This further suppresses the occurrence of molding defects during processing due to high viscosity of the molten TPU, making surface defects less likely. Furthermore, it suppresses the decrease in elongation, allowing the inherent properties of thermoplastic resins, such as flexibility and pliability, to be further utilized. On the other hand, if the number-average molecular weight is 3000 or less, the urethane group concentration does not become too low relative to the original, resulting in more desirable physical properties and even better hydrolysis resistance of the molded product of the resin composition.

[0024] The number-average molecular weight of polyols can be measured in accordance with JIS K 7252-3 (Plastics - Method for determining the average molecular weight and molecular weight distribution of polymers by size exclusion chromatography - Part 3: Method at or near room temperature).

[0025] The mixing ratio of the chain extender (a2) and the polyol component (a3) ​​is such that the ratio of the number of moles of active hydrogen groups in the chain extender (a2) to the number of moles of active hydrogen groups in the polyol component (a3) ​​([number of moles of active hydrogen groups in the chain extender (a2)] / [number of moles of active hydrogen groups in the polyol component (a3)] = R' value) is an indicator of the amount of hard segments in the TPU. From the viewpoint of adjusting the amount of physical properties expressed, the R' value is preferably 0.1 to 15, more preferably 0.3 to 12.

[0026] The ratio of the total number of isocyanate groups in the polyisocyanate component to the total number of active hydrogen groups ([total number of isocyanate groups] / [total number of active hydrogen groups] = R value), obtained by summing the number of active hydrogen groups in the chain extender (a2) and the polyol component (a3), is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, from the viewpoint of adjusting the number-average molecular weight and viscosity of TPU to a more favorable range.

[0027] [[Carboxylic acid metal salt (B)]] A metal carboxylate salt (B) is composed of a metal element and a carboxylic acid, and C 17 H 35 It has a carboxylic acid-derived moiety (b1) represented by -COOH. The carboxylic acid metal salt (B) preferably has a melting point of 100°C or higher. The metal element in the carboxylate metal salt (B) is one metal element selected from the group of metals such as lithium, sodium, calcium, magnesium, barium, aluminum, and zinc, and is preferably aluminum. The ligand has 17 carbon atoms in the carbon chain after removing the ester group when forming the metal salt. In other words, it is preferable that the carboxylic acid-derived moiety (b1) of the carboxylic acid metal salt (B) is derived from stearic acid.

[0028] Among these metal carboxylate salts (B), calcium stearate, zinc stearate, and aluminum stearate are preferred, with aluminum stearate being more preferred because it causes less viscosity reduction after addition and is particularly excellent in improving whitening. Furthermore, among aluminum stearates, aluminum stearate-mono and aluminum stearate-di are particularly preferred because they cause less viscosity reduction.

[0029] The amount of metal carboxylate salt (B) added is preferably 0.01 parts by mass or more and 2.0 parts by mass or less per 100 parts by mass of thermoplastic polyurethane resin (A), and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less.

[0030] If the amount of metal carboxylate salt (B) added is less than 0.01 parts by mass, surface migration of the cyclic oligourethane compound cannot be suppressed. Furthermore, if the amount of metal carboxylate salt (B) added exceeds 2.0 parts by mass, the viscosity during thermal melting becomes significantly reduced, making molding difficult. In addition, the metal carboxylate salt (B) aggregates, leading to a poor appearance due to whitening.

[0031] [[Carboxylic acid bisamide (C)]] The carboxylate bisamide (C) preferably includes a carboxylate bisamide (c1) represented by formula (1) or (2): R 11 -NHCO-R 12 - CONH -R 13 ...Equation (1) R 21 -CONH-R22 - NHCO -R 23 ...Equation (2) During the ceremony, R 11 ~R 13 , and, R 21 ~R 23 Each of these independently represents a chain-like hydrocarbon group; However, R 11 and R 13 At least one of the following, or R 21 and R 23 At least one of these is a chain-like hydrocarbon chain group having 9 to 21 carbon atoms.

[0032] Specific examples of carboxylic acid bisamide (c1) include methylenebisstearate, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearate, ethylenebishydroxystearate, ethylenebisbehenamide, hexamethylenebisstearate, hexamethylenebisbehenamide, hexamethylenebishydroxystearate, N,N'-distearyladipamide, methylenebisoleamide, ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacinamide. These may be present individually or in combination of two or more. Among these, ethylenebisoleamide is preferred due to its versatility and superior properties.

[0033] The amount of biscarboxylate bisamide (c1) added is preferably 0.01 parts by mass or more and 1.0 part by mass or less, and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less, per 100 parts by mass of thermoplastic polyurethane resin (A). When the amount of carboxylate bisamide (c1) added is 0.01 parts by mass or more, the blocking of the resulting thermoplastic polyurethane resin composition can be further alleviated. Furthermore, the surface migration of cyclic oligourethane compounds can be further suppressed. When the amount of bisamide carboxylate (C1) added is 1.0 part by mass or less, the lubricity of the thermoplastic polyurethane resin pellets is improved, making molding easier in single-screw extruders and injection molding machines. Furthermore, aggregation of bisamide carboxylate (C1) is further suppressed, and appearance defects due to whitening are more effectively prevented.

[0034] R 11 and R 13 At least one of the following, or R 21 and R 23 At least one of these is a chain-like hydrocarbon group having 9 to 21 carbon atoms, and more preferably a chain-like hydrocarbon group having 15 to 19 carbon atoms. The carboxylic acid-derived site (b1) is C 17 H 35 It is represented as -COOH, and its carbon chain has 17 carbon atoms. On the other hand, the terminal site in carboxylic acid bisamide (c1) is R 11 and R 13 At least one of the following, or R 21 and R 23 At least one of these has 9 to 21 carbon atoms. The closer the ratio of the number of carbon atoms in the terminal portion of the carboxylic acid bisamide (c1) (9 to 21) to the number of carbon atoms in the carboxylic acid-derived portion (b1) (17) approaches 1.0, the easier it is for the carboxylic acid bisamide (c1) to be retained in the thermoplastic polyurethane resin composition due to the effects of affinity and entanglement, which is preferable. R 11 and R 13 However, or, R 21 and R 23 However, it is preferable that all of them are chain-like hydrocarbon groups having 9 to 21 carbon atoms, and more preferably that all of them are chain-like hydrocarbon groups having 15 to 19 carbon atoms.

[0035] [[Method for producing thermoplastic polyurethane resin composition]] The thermoplastic polyurethane resin composition according to this embodiment can be prepared by mixing a thermoplastic polyurethane resin (A), a metal carboxylate salt (B), and a carboxylate bisamide (C) in appropriate proportions using a kneader or Henschel mixer, then supplying the mixture to a twin-screw extruder, melt-kneading it at the temperature used to extrude normal TPU (approximately 150-220°C), and finally forming it into pellets by strand cutting or underwater cutting.

[0036] Alternatively, a thermoplastic polyurethane resin composition can be prepared by blending a metal carboxylate salt (B) and a carboxylate bisamide (C) with a raw material used in the production of a thermoplastic polyurethane resin (A), such as a polyol component (a3) ​​or a polyisocyanate component (a1), mixing them uniformly, and then reacting them.

[0037] In addition to directly adding the amounts described above to the thermoplastic polyurethane resin (A), a method of adding the metal carboxylate salt (B) and bisamide carboxylate (C) can also be used. This method involves preparing a high-concentration masterbatch in advance and then mixing the masterbatch with the thermoplastic polyurethane resin (A) at a reduced concentration.

[0038] The thermoplastic polyurethane resin (A) constituting the thermoplastic polyurethane resin composition according to this embodiment can be obtained by known TPU manufacturing methods, such as the one-shot method, prepolymer method, batch reaction method, continuous reaction method, kneader method, extruder method, etc.

[0039] Furthermore, the thermoplastic polyurethane resin composition according to this embodiment can be obtained individually in the form of flakes, pellets, powders, granules, rods, sheets, blocks, etc., by the manufacturing method described above.

[0040] Furthermore, the powdered or block-shaped solid obtained as described above can be crushed to obtain flakes, which can then be fed into an extruder. After melting and kneading at the temperature used to extrude normal TPU (approximately 150-220°C), pellets can be obtained by strand cutting or underwater cutting.

[0041] In the kneader method, a polyol component (a3), a chain extender (a2), a metal carboxylate salt (B), and a bisamide carboxylate (C) are charged into the kneader, stirred, heated to 100°C, and then the polyisocyanate component (a1) is added. The mixture is reacted for 10 to 120 minutes and then cooled to produce powdered or block-shaped TPU. In these methods, catalysts and additives may be added as needed.

[0042] [[catalyst]] Examples of catalysts used in the production of TPU include amines such as triethylamine, triethylenediamine, N-methylimidazole, N-ethylmorpholine, and 1,8-diazabicyclo-5,4,0-undecene-7 (DBU); organometallic compounds such as potassium acetate, stanus octoate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, titanate esters, and bismuth compounds; organometallic compounds such as iron compounds; organometallic compounds such as zirconium compounds; and phosphorus compounds such as tributylphosphine, phospholene, and phospholene oxide. These compounds can be used individually or in combination of two or more.

[0043] Of these, organometallic compounds, particularly titanate esters, iron, tin, zirconium, and bismuth compounds, are preferred. The total amount of catalyst used is preferably 0% to 5% by mass relative to TPU, and more preferably 0% to 2% by mass.

[0044] [[additives]] In addition to those mentioned above, the thermoplastic polyurethane resin composition may also contain, as needed, various additives commonly used in the manufacture of TPU, such as heat stabilizers, antioxidants, UV absorbers, flame retardants, hydrolysis inhibitors, heat resistance improvers, weather resistance improvers, reaction retarders, lubricants, plasticizers, antistatic agents, conductivity imparters, antibacterial agents, antifungal agents, colorants, inorganic and organic fillers, fibrous reinforcements, and crystal nucleating agents.

[0045] [Second aspect: Molded body] A molded article comprising the thermoplastic polyurethane resin composition is provided according to a second aspect of the present disclosure. The molding method for thermoplastic polyurethane resin compositions can be the same as that used for TPUs. For example, molding methods such as extrusion molding, injection molding, inflation molding, blow molding, vacuum forming, centrifugal molding, rotational molding, calendering, roll forming, and press forming can be used.

[0046] The thermoplastic polyurethane resin composition according to this embodiment can be suitably used as various molded articles. Examples of molded products include interior and exterior building materials, communication cables, industrial cables, automobiles, various vehicle interior and exterior materials, home appliances, decorative items, protective films, etc., and they can be used in a wide range of indoor and outdoor applications. [Examples]

[0047] The present invention will be described in more detail by reference to examples and comparative examples, but the present invention is not limited thereto. Of the following Examples 1 to 8, Examples 1, 2, and 5 are reference examples and test examples that do not fall within the scope of the present invention.

[0048] <Examples 1-8, Comparative Examples 1-9> (Preparation of thermoplastic polyurethane resin (A)) In a reaction vessel equipped with a stirrer and a thermometer, the polyol component (a3) ​​and the chain extender (a2), 1,4-butanediol, were added in the amounts listed in Tables 1 and 2 and mixed uniformly. The resulting mixture was heated to 100°C, and then the isocyanate component (a1) was added in the amounts listed in Tables 1 and 2 to carry out the urethane reaction. When the reaction mixture reached 90°C, it was poured onto a tray and allowed to solidify. The resulting solid was aged in an electric furnace at 80°C for 16 hours, cooled to room temperature, and then crushed to obtain flake-shaped TPU. The resulting flake-like TPU was pelletized into cylindrical shapes using a single-screw extruder.

[0049] (Sample preparation) The base resin pellets obtained above, along with the carboxylate metal salt (B) and carboxylate bisamide (C) in the amounts shown in Tables 1 and 2, were compounded in a twin-screw extruder at 180-220°C to form pellets. The resulting pellets were then extruded using a T-die to produce films with a thickness of 0.15 mm, which were used as samples for the examples and comparative examples.

[0050] [Table 1]

[0051] [Table 2]

[0052] Furthermore, the raw materials used in Tables 1 and 2 are as follows: <Isocyanate component> • HDI: 1,6-Hexamethylene diisocyanate, manufactured by Tosoh Corporation <Chain extender> • 1,4-BG: 1,4-butanediol (number-average molecular weight = 90), manufactured by Mitsubishi Chemical Corporation. <Polycarbonate diol> • PCD(HG)-2000: Polyhexamethylene polycarbonate diol (number average molecular weight = 2000), manufactured by Tosoh Corporation. <Carboxylic acid metal salt (B)> • Calcium stearate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Zinc stearate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Aluminum stearate-mono: Manufactured by Fujifilm & Wako Pure Chemical Industries, Ltd. • Aluminum stearate: Manufactured by Fujifilm & Wako Pure Chemical Industries, Ltd. • Aluminum stearate triphosphate: Manufactured by Fujifilm & Wako Pure Chemical Industries, Ltd. <Carboxylic acid bisamide (C)> • Ethylene bisoleamide: Manufactured by NOF Corporation • Ethylene bis-stearamide: Manufactured by NOF Corporation • Ethylene biscaprate amide: Manufactured by Mitsubishi Chemical Corporation • Ethylene bisbehenamide: Manufactured by Mitsubishi Chemical Corporation <Other> • Low molecular weight polyethylene: Manufactured by Aldrich Corporation • Dioctyl phthalate: Manufactured by Daihachi Chemical Co., Ltd.

[0053] (Characteristic testing) The T-die extruded film produced using the above procedure was evaluated for various properties as shown below. The results are shown in Tables 1 and 2.

[0054] (1) Bloom resistance T-die extruded film (thickness 0.15 mm) was used as a test specimen, and the change in haze was measured after standing for 30 days at room temperature and atmospheric pressure. Samples with a change in haze ("haze % after test" - "haze % before test") of less than 2% were classified as A, and those with a change of 2% or more were classified as D. Haze was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0055] (2) Transparency T-die extruded film (thickness 0.15 mm) was used as a test specimen, and haze was measured. Specimens with haze of less than 5% were classified as A, and those with haze of 5% or more were classified as D.

[0056] (3) Moldability When carboxylate metal salts and carboxylate bisamides were collectively referred to as lubricants, the viscosity retention rate of TPU pellets before and after lubricant addition was measured using a flow tester (CFT-500D, Shimadzu Corporation). A viscosity retention rate of 40% or more ("viscosity retention rate %" = "viscosity of TPU pellets after lubricant addition" / "viscosity of TPU pellets before lubricant addition" × 100) was classified as A, 15% or more but less than 40% as B, and less than 15% as D. Measurement conditions were: measurement temperature: 210°C, measurement load: 98N, preheating time: 240 seconds, TPU pellet pre-drying: 80°C × 30 minutes under reduced pressure.

[0057] Examples that received an A rating in evaluation items (1) and (2) above were considered to have passed.

Claims

1. Thermoplastic polyurethane resin (A), Aluminum stearate-mono or aluminum stearate-di It contains carboxylate bisamide (C) and The thermoplastic polyurethane resin (A) is Polyisocyanate component (a1), Chain extender (a2), The reaction product of the polyol component (a3) ​​is The aforementioned polyisocyanate component (a1) includes an aliphatic polyisocyanate. The chain extender (a2) comprises one or more selected from the group consisting of 1,4-butanediol and 1,6-hexanediol. The polyol component (a3) ​​comprises a polycarbonate diol having a number average molecular weight of 750 or more and 3000 or less. The amount of aluminum stearate-mono or aluminum stearate-di added is 0.01 parts by mass or more and 2.0 parts by mass or less per 100 parts by mass of the thermoplastic polyurethane resin (A). The amount of carboxyl bisamide (C) added is 0.01 parts by mass or more and 1.0 parts by mass or less per 100 parts by mass of the thermoplastic polyurethane resin (A). The carboxyl bisamide (C) is a thermoplastic polyurethane resin composition comprising a carboxyl bisamide (c1) represented by formula (1) or (2): R １１ -NHCO-R １２ -CONH-R １３ ・・・Form (1) R ２１ -CONH-R ２２ -NHCO-R ２３ ・・・Form (2) During the ceremony, R １１ to R １３ , and R ２１ to R ２３ each independently represents a chain hydrocarbon group; However, R １１ and R １３ At least one of the following, or R ２１ and R ２３ At least one of these is a chain-like hydrocarbon group having 9 to 21 carbon atoms.

2. The thermoplastic polyurethane resin composition according to claim 1, wherein the polyisocyanate component (a1) comprises 1,6-hexamethylene diisocyanate.

3. The thermoplastic polyurethane resin composition according to claim 1 or 2, wherein the chain extender (a2) comprises 1,4-butanediol.

4. The thermoplastic polyurethane resin composition according to any one of claims 1 to 3, wherein the carboxylic acid bisamide (C) is ethylenebisoleic acid amide.

5. The thermoplastic polyurethane resin composition according to any one of claims 1 to 3, wherein the carboxylic acid bisamide (C) is ethylene bisstearamide.

6. The thermoplastic polyurethane resin composition according to any one of claims 1 to 3, wherein the carboxylic acid bisamide (C) is ethylene biscapric acid amide.

7. The thermoplastic polyurethane resin composition according to any one of claims 1 to 3, wherein the carboxylic acid bisamide (C) is ethylene bisbehenamide.

8. The amount of aluminum stearate-mono or aluminum stearate-di added is 0.3 parts by mass or more and 2.0 parts by mass or less per 100 parts by mass of the thermoplastic polyurethane resin (A). The thermoplastic polyurethane resin composition according to claim 7, wherein the amount of ethylene bisbehenamide added is 0.01 parts by mass or more and 0.1 parts by mass or less per 100 parts by mass of the thermoplastic polyurethane resin (A).

9. A molded article comprising the thermoplastic polyurethane resin composition according to any one of claims 1 to 8.

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