Thermoplastic polyurethane precursor, thermoplastic polyurethane, method for producing same and use thereof

Abstract

A thermoplastic polyurethane precursor can be used to produce polyurethanes with low initial yellowness, high resistance to yellowing, thermal oxidative aging, and hydrolysis, and reduced fisheyes. The precursor includes a polyisocyanate, a chain extender, a polymer polyol, and a first coagent, the first coagent including (d1) benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester, (d2) phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester, (d3) 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and (d4) at least one of a compound of formula (I) and a compound of formula (II). [Formula 1] JPEG2025527960000019.jpg56161 (wherein R1 is C12 alkenyl.) [chemical 2] JPEG2025527960000020.jpg52161

Description

[Technical Field]

[0001] The present invention provides a thermoplastic polyurethane precursor, particularly a thermoplastic polyurethane precursor containing a specific coagent. The present invention also provides a thermoplastic polyurethane obtained from the thermoplastic polyurethane precursor, a method for producing the same, and uses thereof. [Background technology]

[0002] Thermoplastic polyurethanes belong to the category of thermoplastic elastomers and are characterized by being linear segmented copolymers consisting of hard and soft chain segments. Thermoplastic polyurethanes are derived from the reaction of polyisocyanates with polymer polyols and chain extenders. The hard chain segments are formed by the reaction of polyisocyanates with chain extenders, while the soft chain segments are formed by the reaction of polyisocyanates with polymer polyols. By adjusting the ratio of raw materials, it is possible to obtain thermoplastic polyurethanes with desired mechanical properties, such as abrasion resistance, temperature resistance, flexibility, and elongation. Thermoplastic polyurethanes can typically withstand temperatures as low as -40°C and as high as 120°C. Furthermore, thermoplastic polyurethanes generally exhibit excellent load-bearing capacity, impact resistance, elasticity, toughness, and aging resistance. Thermoplastic polyurethanes are resistant to oils and aliphatic hydrocarbon solvents, as well as oxygen and ozone. As a result, thermoplastic polyurethanes have a wide range of applications in various technical fields, including, but not limited to, coating materials, elastomers, foam materials, adhesives, and sealants.

[0003] Methods for producing thermoplastic polyurethanes include, but are not limited to, the well-known "one-shot" method. In this process, all raw materials (polymer polyol, polyisocyanate, chain extender, etc.) are fed into a twin-screw extruder in a predetermined ratio to produce a highly viscous thermoplastic polyurethane gel. This gel is then aged at 70°C to 100°C and processed into a film product. However, the problem of yellowing of thermoplastic polyurethanes, particularly the problem of fisheyes in the film product, has not yet been resolved by conventional techniques.

[0004] The problem of fisheyes is a common technical problem encountered in the processing of thermoplastic polyurethane films. Particularly in transparent films, fisheyes significantly impair the appearance of the film. Therefore, waste and deteriorated products caused by fisheye defects account for a significant portion of losses in the thermoplastic polyurethane film industry, and this problem has not yet been solved by the prior art.

[0005] Fisheyes in thermoplastic polyurethane films are typically caused by "mechanical impurities" or "excess polymerized materials." "Mechanical impurities" refer to impurities from external sources that are introduced into thermoplastic polyurethane during the fabrication or processing process. This problem can be mitigated through process control and cleaning procedures. "Excess polymerized materials" refer to high-melting-point molecules such as dimers or polymers of polyisocyanates, or ureas, biurets, and similar compounds that result from side reactions. During film processing, the polymer in the fisheye area cannot be uniformly dispersed or mixed with the surrounding polymer due to premature solidification and curing, resulting in granular or arrow-shaped stains on the film surface.

[0006] Furthermore, the high reaction temperature and mixing shear stress during the process of producing thermoplastic polyurethanes using a twin-screw extruder can cause the thermoplastic polyurethanes (especially aromatic thermoplastic polyurethanes) to have a yellowish tinge. The use of hindered phenol-based antioxidants can only prevent molecular degradation, but cannot effectively suppress yellowing. On the other hand, the use of phosphite-based antioxidants can effectively suppress yellowing during the reaction, but they can also cause problems with hydrolysis of the thermoplastic polyurethanes. Adding large amounts of carbodiimide-based hydrolysis inhibitors can suppress hydrolysis, but adding hydrolysis inhibitors not only increases costs but also causes problems such as additive leaching. Summary of the Invention [Problem to be solved by the invention]

[0007] Thus, there is a need for thermoplastic polyurethanes that have low initial yellowness, high resistance to yellowing, high resistance to thermal oxidative aging and hydrolysis, and low fisheyes. [Means for solving the problem]

[0008] The inventors of the present invention have discovered that an unexpected synergistic effect can be obtained by combining a compound having a 3,5-di-tert-4-hydroxybenzoate structure, a specific hindered phenol-based antioxidant, a specific liquid phosphite-based antioxidant, and a specific lactone-based antioxidant in a formulation for producing a thermoplastic polyurethane.

[0009] Therefore, the object of the present invention is to (A) polyisocyanate, (B) a chain extender, (C) a polymer polyol, and (D) First auxiliary agent A thermoplastic polyurethane precursor comprising: The first auxiliary agent is (d1) Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester, (d2) Phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters. (d3) 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and (d4) at least one of a compound of formula (I) and a compound of formula (II) and (c) providing a thermoplastic polyurethane precursor comprising:

[0010] [ka]

[0011] (Wherein, R1 is C12 alkenyl.)

[0012] [ka]

[0013] In some embodiments of the present invention, the polyisocyanate (A) comprises an aromatic polyisocyanate.

[0014] In some embodiments of the present invention, the polymer polyol (C) is selected from the group consisting of polyether polyols, polyester polyols, polysiloxane polyols, and combinations thereof.

[0015] In some embodiments of the present invention, the chain extender (B) is selected from the group consisting of polyols, diamines, aminoalcohols, and combinations thereof.

[0016] In some embodiments of the present invention, the amounts of components (d1) to (d4) are each independently 0.01 wt % to 1.0 wt % of the total weight of the thermoplastic polyurethane precursor.

[0017] In some embodiments of the present invention, the thermoplastic polyurethane precursor further comprises an additive selected from the group consisting of an antifoaming agent, a leveling wetting agent, a thickener, a dispersant, a wax, a powder matting agent, an antibacterial agent, a metal oxide light screening agent, a light stabilizer, a heat stabilizer, an ultraviolet absorber, a blue light absorber, an antioxidant, a peroxide scavenger, a free radical scavenger, a filler, a rubber (including siloxane rubber), a food preservative, a flame retardant, a plasticizer, a dye, a pigment (including titanium white and carbon black), an optical brightener, an anti-degradant, a metal stabilizer, an acid absorber, a hydrolysis inhibitor, and combinations thereof.

[0018] Another object of the present invention is to provide a thermoplastic polyurethane comprising a first coagent, The first auxiliary agent is (d1) Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester, (d2) Phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters. (d3) 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and (d4) at least one of a compound of formula (I) and a compound of formula (II) The present invention provides a thermoplastic polyurethane comprising:

[0019] In some embodiments of the present invention, the thermoplastic polyurethane further comprises an additive selected from the group consisting of an antifoaming agent, a leveling wetting agent, a thickener, a dispersant, a wax, a powder matting agent, an antibacterial agent, a metal oxide light screening agent, a light stabilizer, a heat stabilizer, an ultraviolet absorber, a blue light absorber, an antioxidant, a peroxide scavenger, a free radical scavenger, a filler, a rubber (including siloxane rubber), a food preservative, a flame retardant, a plasticizer, a dye, a pigment (including titanium white and carbon black), an optical brightener, an anti-degradant, a metal stabilizer, an acid absorber, a hydrolysis inhibitor, and combinations thereof.

[0020] It is yet another object of the present invention to provide a method for making a thermoplastic polyurethane, comprising the steps of providing a thermoplastic polyurethane precursor as described above and polymerizing the thermoplastic polyurethane precursor to obtain a thermoplastic polyurethane.

[0021] In some embodiments of the present invention, the method of making the thermoplastic polyurethane further comprises subjecting the thermoplastic polyurethane to pelletizing, extruding, laminating, injection molding, calendaring, casting, blow molding, coating, meltblowing, or faggoting.

[0022] It is a further object of the present invention to provide use of the above thermoplastic polyurethanes to make thermoplastic polyurethane articles having reduced fisheyes, low initial yellowness, and high resistance to yellowing, thermal oxidative aging, and hydrolysis.

[0023] In some embodiments of the present invention, the thermoplastic polyurethane article is selected from the group consisting of transparent housings, packaging articles, household articles, textile articles, medical articles, sporting articles, electronic products, optical products, construction articles, machine parts, automotive articles, military industrial articles, and coatings. DETAILED DESCRIPTION OF THE INVENTION

[0024] To make the above objectives, technical features and advantages of the present invention clearer, the present invention will be described in detail below with reference to several embodiments.

[0025] Specific Embodiments Hereinafter, several embodiments of the present invention will be described in detail. However, the present invention may be embodied in various different embodiments, and the scope of protection of the present invention is not limited to the details described herein.

[0026] Unless otherwise stated, the terms "a," "the," and the like in the specification and claims include both the singular and the plural.

[0027] Unless otherwise specified, the terms "first," "second," and the like used in the specification and claims are used only to distinguish between elements or components being described and have no special meaning. These terms are not used to indicate priority.

[0028] Unless otherwise specified, when the specification and claims recite amounts of components in a solution, mixture, precursor, or thermoplastic polyurethane, the weight of the solvent is not included.

[0029] Thermoplastic polyurethanes are a type of polymer containing characteristic urethane units in the main chain. Generally, urethane groups are formed by reacting an isocyanate functional group (-N=C=O) with a hydroxyl group (-OH). Therefore, the precursors used to make thermoplastic polyurethanes usually contain a polyisocyanate and a polyol. Additionally, chain extenders may be added to further extend the polyurethane chains and increase the molecular weight of the polyurethane.

[0030] The primary advantage of the present application over the prior art is that it provides a thermoplastic polyurethane characterized by low initial yellowness, high resistance to yellowing, high resistance to thermal oxidative aging, and high resistance to hydrolysis, as well as reduced fisheyes. This is achieved by using a compound having a 3,5-di-tert-4-hydroxybenzoate structure, a specific hindered phenol-based antioxidant, a specific liquid phosphite-based antioxidant, and a specific lactone-based antioxidant in combination in the formulation of a thermoplastic polyurethane precursor. Details regarding the thermoplastic polyurethane precursor and its use are described below.

[0031] 1. Thermoplastic polyurethane precursor The thermoplastic polyurethane precursor of the present invention comprises (A) a polyisocyanate, (B) a chain extender, (C) a polymer polyol, and (D) a first coagent.

[0032] 1.1. Polyisocyanate (A) The polyisocyanate (A) may be aliphatic or aromatic, and is preferably an aromatic polyisocyanate.

[0033] Examples of the polyisocyanate (A) include methylene diphenyl diisocyanate (MDI), m-xylylene diisocyanate (XDI), toluene-2,4-diisocyanate (TDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, tolylene-2,6-diisocyanate, 3,3'-diisocyanate, and methyl ... Toxic-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,4-phenylene diisocyanate, isophorone diisocyanate (IPDI), 1,4-cyclohexylene diisocyanate (CHDI), decane-1,10-diyl diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (T ODI), naphthalene-1,5-diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane Examples of suitable polyisocyanates include, but are not limited to, hexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 2,4-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, and 1,2-diphenylethane diisocyanate. These polyisocyanates can be used alone or in combination. In the accompanying examples, methylene diphenyl diisocyanate (MDI) is used as polyisocyanate (A).

[0034] The amount of polyisocyanate (A) can be 0.01% by weight to 50% by weight relative to the total weight of the thermoplastic polyurethane precursor. For example, the amount of polyisocyanate (A) can be 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50% by weight, or within a range between any two of the values ​​recited herein.

[0035] 1.2. Chain extender (B) The chain extender (B) is selected from the group consisting of polyols, diamines, aminoalcohols, and combinations thereof. Examples of polyols include, but are not limited to, diols and triols. Examples of diols include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 1,5-pentylene glycol, 1,6-hexylene glycol, 1,7-heptylene glycol, 1,8-octylene glycol, 1,9-nonylene glycol, 1,10-decylene glycol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, and 1,4-cyclohexanediol. Examples of triols include, but are not limited to, trimethylolpropane, glycerol, and 1,2,6-hexanetriol. Examples of diamines include, but are not limited to, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, N,N'-diisobutyl-1,6-hexanediamine, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-cyclobutanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, p-xylylenediamine, bis(3-aminopropyl)methylamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, diaminotoluene, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl disulfide. Examples of aminoalcohols include, but are not limited to, ethanolamine, propanolamine, and N-phenyldiethanolamine. These chain extenders can be used alone or in combination. In the accompanying examples, 1,4-butylene glycol is used as chain extender (B).

[0036] The amount of chain extender (B) can be 0.01% to 30% by weight based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of chain extender (B) can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30% by weight, or a range between any two of the values ​​described herein.

[0037] 1.3. Polymer polyol (C) The thermoplastic polyurethane precursor of the present invention uses a polymer polyol. The polymer polyol (C) can be selected from the group consisting of polyether polyols, polyester polyols, polysiloxane polyols, and combinations thereof. Examples of polyester polyols include, but are not limited to, lactone polyester diols, polyester amide diols, polyalkyldiene diols (such as polybutadiene diols), polybutylene adipate, and polycarbonate diols. These polymer polyols can be used alone or in combination. In the accompanying examples, polytetrahydrofuran diol is used as the polymer polyol (C).

[0038] The molecular weight of the polymer diol (C) can be 250 to 7000. For example, the molecular weight of the polymer diol (C) can be 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 00, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900 or 7000, or a range between any two of the values ​​described herein.

[0039] The amount of polymer diol (C) can be 0.01% by weight to 50% by weight relative to the total weight of the thermoplastic polyurethane precursor. For example, the amount of polymer diol (C) can be 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50% by weight, or within a range between any two of the values ​​recited herein.

[0040] 1.4. First auxiliary agent (D) The thermoplastic polyurethane precursor of the present invention contains a first auxiliary agent (D) to address problems related to fisheyes, initial yellowness, yellowing resistance, thermal oxidative aging resistance, and hydrolysis resistance in the resulting thermoplastic polyurethane. Specifically, the first auxiliary agent (D) contains the following four components: (d1) a hindered phenol-based antioxidant, (d2) a liquid phosphite-based antioxidant, (d3) a lactone-based antioxidant, and (d4) at least one of a compound of formula (I) and a compound of formula (II), where R1 is a C12 alkenyl.

[0041] [ka]

[0042] [ka]

[0043] 1.4.1. Component (d1) Component (d1) is a hindered phenolic antioxidant, examples of which include, but are not limited to, benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester, triethylene glycol bis[3-(1,1-dimethylethyl)-4-hydroxy-5-methylphenylpropionate], hydrocinnamic acid, 3,5-di-tert-butyl-4-hydroxy-, neopentanetetrayl ester, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,6-di-tert-butyl-p-methylphenol.

[0044] In a preferred embodiment of the present invention, component (d1) is 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester of benzenepropanoic acid. Examples of 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl esters of benzenepropanoic acid include, but are not limited to, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisooctyl ester of benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisooctyl ester of benzenepropanoic acid, and 3,5-bis(1,1-dimethylethyl)-4-hydroxyisononyl ester of benzenepropanoic acid. For example, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester of benzenepropanoic acid can be produced as Deox® BS-1135 (CAS number: 125643-61-0) manufactured by Chitec Technology Company.

[0045] The amount of component (d1) can be 0.01% to 1.0% by weight, based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of component (d1) can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1.0% by weight, or within a range between any two of the values ​​described herein.

[0046] 1.4.2.Component (d2) Component (d2) is a liquid phosphite-based antioxidant. Examples of liquid phosphite-based antioxidants include phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester, tris(dipropylene glycol) phosphite, and poly(dipropylene glycol) phenyl phosphite. In a preferred embodiment of the present invention, component (d2) is phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester, which is a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl-4-(1,1-dimethylpropyl)phenyl phosphite and 2,4-bis(1,1-dimethylpropyl)phenylbis[4-(1,1-dimethylpropyl)phenyl]phosphite. An example of such a mixture is Weston® 705T (CAS No.: 939402-02-5) manufactured by SI Group.

[0047] Component (d2) may further comprise an acid neutralizer to absorb acid or inhibit hydrolysis, an example of which includes, but is not limited to, triisopropanolamine (TIPA).

[0048] The amount of component (d2) can be 0.01% to 1.0% by weight, based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of component (d2) can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1.0% by weight, or within a range between any two of the values ​​described herein.

[0049] Component (d3) Component (d3) is a lactone antioxidant, such as 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, and xylyldibutylbenzofuranone.

[0050] In a preferred embodiment of the present invention, component (d3) is 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate. An example of the component is Revonox® 501 (CAS number: 1261240-30-5) manufactured by Chitec Technology Company.

[0051] The amount of component (d3) can be 0.01% to 1.0% by weight, based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of component (d3) can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1.0% by weight, or within a range between any two of the values ​​described herein.

[0052] Component (d4) Component (d4) comprises a compound of formula (I) or a compound of formula (II), or component (d4) comprises both a compound of formula (I) and a compound of formula (II). Alternatively, component (d4) consists essentially of a compound of formula (I) or a compound of formula (II), or component (d4) consists essentially of both a compound of formula (I) and a compound of formula (II). Alternatively, component (d4) consists of a compound of formula (I) or a compound of formula (II), or component (d4) consists of both a compound of formula (I) and a compound of formula (II). R1 ​​in formula (I) is C12 alkenyl, which can be linear or branched alkenyl, but is preferably linear alkenyl.

[0053] [ka]

[0054] [ka]

[0055] The IUPAC name of the compound of formula (I) is 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-[3-[dodecenyl]-2,5-dioxopyrrolidin-1-yl]propionamide, where dodecenyl corresponds to R1 in formula (I) and can be linear or branched, but is preferably linear. The IUPAC name of the compound of formula (II) is 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-[3-[1,3-dioxo-3a,4,7,7a-tetrahydroisoindol-2-yl]propionamide.

[0056] The compounds of formula (I) and formula (II) are commercially available or can be synthesized by chemical methods. The chemical synthesis method is not particularly limited, but a person skilled in the art would be able to synthesize them using existing chemical mechanisms based on the disclosure of the present specification. For example, the compound of formula (I) can be synthesized by reacting 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propylhydrazine with dodecenylsuccinic anhydride, and the compound of formula (II) can be obtained by reacting 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propylhydrazine with tetrahydrophthalic anhydride.

[0057] The amount of component (d4) can be 0.01% to 1.0% by weight, based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of component (d4) can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1.0% by weight, or within a range between any two of the values ​​described herein.

[0058] 1.5.Additives The thermoplastic polyurethane precursor of the present invention may optionally contain conventional additives that can be used in thermoplastic polyurethanes to adaptively improve the physicochemical properties of the thermoplastic polyurethane or to impart desired functions to the thermoplastic polyurethane. Conventional additives include, but are not limited to, defoamers, leveling wetting agents, thickeners, dispersants, waxes, powder matting agents, antibacterial agents, metal oxide light-blocking agents, light stabilizers, heat stabilizers, ultraviolet absorbers, blue light absorbers, antioxidants, peroxide scavengers, free radical scavengers, fillers, rubbers (including siloxane rubbers), food preservatives, flame retardants, plasticizers, dyes, pigments (including titanium white and carbon black), brighteners, antistatic agents (including graphene and carbon nanotubes), optical brighteners, anti-aging agents, metal stabilizers, acid absorbers, and hydrolysis inhibitors. These additives can be used alone or in combination.

[0059] The amount of additives to be added is not particularly limited as long as the desired function can be achieved. Typically, the amount of additives to be added can be 0.01% to 30% by weight relative to the total weight of the thermoplastic polyurethane precursor. For example, the amount of additives to be added can be 0.01%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30% by weight relative to the total weight of the thermoplastic polyurethane precursor, or within a range between any two of the values ​​described herein.

[0060] 2. Thermoplastic polyurethane The thermoplastic polyurethane can be prepared using the above-mentioned thermoplastic polyurethane precursor. Therefore, the present invention also provides a thermoplastic polyurethane containing a first auxiliary agent. Detailed information about the first auxiliary agent, including the description and amount of the first auxiliary agent, is described in Section "1.4. First auxiliary agent" and will not be repeated here.

[0061] The thermoplastic polyurethane of the present invention may optionally contain conventional additives to adaptively improve the physicochemical properties of the thermoplastic polyurethane or to impart desired functions to the thermoplastic polyurethane. Note that a description of conventional additives applicable to thermoplastic polyurethanes is given in the section "1.5. Additives," and will not be repeated here.

[0062] 3. Thermoplastic Polyurethane Fabrication The present invention also provides a method of making a thermoplastic polyurethane, comprising subjecting a thermoplastic polyurethane precursor to polymerization to obtain a thermoplastic polyurethane.

[0063] In some embodiments of the present invention, the polymerization is carried out in the presence of a catalyst. Examples of catalysts include, but are not limited to, tertiary amine catalysts, organometallic catalysts, and bases. Examples of tertiary amine catalysts include, but are not limited to, triethylamine, dimethylcyclohexylamine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N-methylmorpholine, N,N-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo(2,2,2)octane, N,N-dimethylbenzylamine, and 2-methylimidazole. Examples of organometallic catalysts include, but are not limited to, tin diacetate, tin dioctanoate, stannous octanoate, stannous oleate, tin dilaurate, dibutyltin dilaurate, dibutyltin octoate, dioctyltin diacetate, iron acetylacetonate, titanate, and tetrabutoxytitanium. Examples of bases include, but are not limited to, tetraalkylammonium hydroxide, sodium hydroxide, and sodium phenoxide salts. These catalysts can be used alone or in combination. In the accompanying examples, dibutyltin dilaurate is used as the catalyst.

[0064] The amount of catalyst to be used is not particularly limited as long as it can promote polymerization. Typically, the amount of catalyst to be used can be 0.01 to 2.0% by weight based on the total weight of the thermoplastic polyurethane precursor. For example, the amount of catalyst to be used can be 0.01, 0.1, 0.5, 1, 1.5, or 2% by weight based on the total weight of the thermoplastic polyurethane precursor, or a range between any two of the values ​​described herein.

[0065] 4. Use of thermoplastic polyurethane The thermoplastic polyurethane of the present invention has at least the following advantages: low initial yellowness, high resistance to yellowing, thermal oxidative aging, and hydrolysis, and particularly few fish eyes. Therefore, the present invention also provides use of the above thermoplastic polyurethane for producing a thermoplastic polyurethane article having few fish eyes, low initial yellowness, and high resistance to yellowing, thermal oxidative aging, and hydrolysis. The thermoplastic polyurethane article can be obtained by subjecting the above thermoplastic polyurethane to conventional processing. Conventional processing includes, but is not limited to, pelletizing, extrusion, lamination, injection molding, calendaring, casting, blow molding, coating, meltblowing, faggoting, etc.

[0066] The type of thermoplastic polyurethane article is not particularly limited and can include any article suitable for conventional thermoplastic polyurethane applications. Examples of such articles include, but are not limited to, transparent housings, packaging articles, household articles, textile articles, medical articles, sporting goods, electronic products, optical products, building articles, machine parts, automotive articles, military industry articles, and coatings. An example of a "packaging article" is wrapping film. Examples of "household articles" include food containers, lighting fixture parts, and sheets. Examples of "textile articles" include clothing, bedding, and shoes. Examples of "medical articles" include medical device components. Examples of "electronic products" include display device components. Examples of "optical products" include solar panel components. Examples of "building articles" include road construction components, wind power generation components, fire retardants, waterproofing materials, and the like. Examples of "machinery parts" include agricultural machinery components and transport craft components. An example of an "automotive article" is an airbag. An example of an "arms industry article" is an explosion-proof panel.

[0067] Specific examples of thermoplastic polyurethane articles include, for example, the following embodiments: packaging materials for oxygen-sensitive foods or medicines, air bags, balloons, air cushions, lamp cups, cooking utensils, storage utensils, furniture, curtains, office carpets, toys, parts of sporting goods, balls, shoe parts, sneaker air cushions, hiking shoes, snow shoes, golf shoes, skates, air beds, water bags, wetsuits, snow suits, swimwear, rubber bands, disposable diapers, badges, golf related articles, eyeglass accessories, photochromic lenses, contact lenses, bed sheets, tablecloths, shower curtains, pianos, mobile phone keypads, air-filled plastic toys, computer keyboards, umbrellas, suitcases, wallets, plates, fibers, fabrics, clothing, pants, shapewear, coats, sanitary pants, aprons, upholstery cloth, gloves, medical equipment, dental articles, sterilization containers, filters, hygiene products, diapers, films, medical tubing, medical valves, hoses, hose linings, pipes, pipe linings, protective clothing, wound dressings, surgery scrubs, surgical caps, surgical gloves, hospital bedding, ice packs, bandages, plasma bags, surgical bandages, face masks, hospital bed bladders, infusion bags, urinary catheters, culture flasks, media flasks, instrument sampling windows, liquid storage containers (condoms, storage bags or bottles, infusion bags or bottles, etc.), aluminum-plastic packaging, bubble wrap, bioimplantable devices, pacemaker leads, artificial hearts, heart valves, scaffolding covers, artificial tendons, artificial arteries, artificial veins, implants containing pharmaceutical active agents, drug delivery devices, Vaginal rings, surgical orthodontic articles, implants, bone implants, housings for mobile devices, filters, optical lenses, optical elements, optical articles, films for transparent screens, conductive films, heat transfer films, packaging films, low electrical resistance films, solar panel peripheral materials, lamp cups, roof membranes, roof cushions, eaves, wall materials, floor materials, duct materials, signs, sun visors, greenhouse cover films, backlights, wind turbine parts, electric wire covering materials, sound insulation materials, sound deadening devices, machine parts, adhesives, coatings, foam laminates, encapsulation molding articles, speaker drum paper, fire-resistant clothing,Examples of suitable materials include, but are not limited to, firefighting suits, fire-resistant fabrics, sunshade awnings, waterproof strips, waterproof fabrics, handlebars, hand cranks, carpets, windows, window frame materials, doors, wallpaper, decorative panels, silk screens, metal sheets, films, bearings, joints, valve parts, conveyor belts, timing belts, gears, rubber materials, rollers, stretch films for transportation craft, housings for transportation craft, lighting fixtures for transportation craft, trim parts, thermal insulation layers for transparent panels, sofa seats, thermal insulation panels, tires, steering wheels, crates, casters, pulleys, airbag covers, buffers, radiators, mud flaps, dashboards, car door parts, engine hood parts, choke plates, air deflectors, case covers, outer covers for reflectors, car body panels, side protection molded articles, explosion-proof glass, marine parts, airplane parts, aircraft parts, transparent aircraft parts, radomes, bulletproof panels, explosion-proof glass, microwave absorbing layers, aircraft fuel tanks, coatings for weapon storage, military hydration packs, life jackets, and inflatable boats.

[0068] 5. Working Example 5.1. Test Method The present invention is further described by the following embodiments: In the embodiments, the test device and method are as follows.

[0069] [Melt flow index (MFI) measurement] Five grams of thermoplastic polyurethane was prepared as a sample. The initial MFI of the thermoplastic polyurethane was measured in accordance with ASTM D-1238 using a melt flow indexer (model number: GT-7100-MI, manufactured by GOTECH) at a temperature of 200°C and a pressure of 5 kg, measuring the weight of the material passing through a standard mold (diameter 2.095 mm) within 10 minutes. The unit of MFI is expressed as grams per 10 minutes, or "g / 10 min."

[0070] [Thermal oxidation aging resistance test] Based on the above-mentioned melt flow index (MFI) measurement method, the MFI measurement is carried out three more times on the thermoplastic polyurethane plastic block. In other words, the melting process is carried out three times on the thermoplastic polyurethane plastic block, and the first, second, and third MFIs of the thermoplastic polyurethane are measured.

[0071] [Yellowness test] The initial yellowness index (YI) of the thermoplastic polyurethane test piece is tested in accordance with ASTM 1926-70 using a spectrophotometer (Model: ColorQuest XE, manufactured by Hunter Lab Company).

[0072] [Color difference test] The ΔE of the thermoplastic polyurethane test piece is tested using a UV-Vis spectrophotometer (model number: Varian Cary® 50, manufactured by Agilent Company).

[0073] [Heat yellowing test] The thermoplastic polyurethane test piece is placed in a 120°C oven for aging, and the YI and ΔE values ​​of the thermoplastic polyurethane are measured after 16 hours, 24 hours, and 96 hours, respectively. A lower value indicates better heat yellowing resistance.

[0074] [Hydrolysis resistance test] First, a sample is prepared, and the tensile strength (initial tensile strength) of the prepared thermoplastic polyurethane test piece is measured in accordance with ASTM D-412 using a tensile tester (model number: AI-7000M, manufactured by GOTECH). Next, the thermoplastic polyurethane test piece is exposed to an environment of 95% humidity and 80°C in an oven for 168 hours. After that, the tensile strength (heat-resistant tensile strength) of the thermoplastic polyurethane test piece after 168 hours of exposure in the oven is measured. The unit of tensile strength is kgf / cm. 2 The rate of change in tensile strength (unit: %) is calculated using the following formula and indicates the hydrolysis resistance of the thermoplastic polyurethane. The smaller the rate of change, the better the hydrolysis resistance.

[0075]

number

[0076] [Fisheye test] Thermoplastic polyurethane films were fabricated using the following method. First, a thermoplastic polyurethane resin block was cooled and hardened with liquid nitrogen, then pulverized using a freezer mill (model UPZ100, manufactured by Hosokawa Alpine Company). The milling conditions were -60°C and 22,000 rpm. The thermoplastic polyurethane powder was then fed into a micro twin-screw extruder (model MC15HT, manufactured by Xplore) and melt-extruded. The screw rotation speed was 15 rpm, and the extruder temperature was 175°C to 180°C. Finally, a 15 μm-thick thermoplastic polyurethane film was fabricated using a cooling wheel. The film was then cut into test samples measuring 5 cm in length and 5 cm in width.

[0077] Thermoplastic polyurethane film test samples are observed under a microscope (Model: PEAK 2008-50X STAND MICROSCOPE) at a magnification of 50x or greater to check for the presence of fisheyes (granular or sagittal stains). A score of 1 to 5 is assigned based on the amount of fisheyes. A score of 5 indicates the least amount of fisheyes and represents the highest quality. A score of 1 indicates the most amount of fisheyes and represents the lowest quality.

[0078] 5.2. Preparation of Thermoplastic Polyurethane [Example 1] 100 g of polytetrahydrofuran diol (model number: PTMEG1000, manufactured by Mitsubishi Chemical Corporation, OH value 112.2), 11 g of 1,4-butylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of a hindered phenol-based antioxidant (model number: Deox® BS-1135, manufactured by Chitec Technology Company), 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of a liquid phosphite-based antioxidant (model number: Weston® 705T, manufactured by SI group), and 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of a lactone-based antioxidant (model number: Revonox® 501, manufactured by Chitec Technology 0.1 wt% (based on the total weight of the thermoplastic polyurethane precursor) of BASF (manufactured by BASF Chemical Company), 0.1 wt% (based on the total weight of the thermoplastic polyurethane precursor) of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-[3-[dodecenyl]-2,5-dioxopyrrolidin-1-yl]propionamide, and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF Chemical Company) was preheated to 110°C and added to the reaction pot. The reaction was initiated by stirring for 1 minute, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding the thermoplastic polyurethane plastic block of Example 1.

[0079] [Example 2] 100 g of polytetrahydrofuran diol PTMEG 1000, 11 g of 1,4-butylene glycol, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the hindered phenol-based antioxidant Deox® BS-1135, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the liquid phosphite-based antioxidant Weston® 705T, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the lactone-based antioxidant Revonox® 501, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-[3-[1,3-dioxo-3a,4,7,7a-tetrahydroisoindol-2-yl]]propionamide, and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot, and the mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Example 2.

[0080] [Comparative Example 1] 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.4 wt% (based on the total weight of the thermoplastic polyurethane precursor) of the hindered phenol-based antioxidant Deox® BS-1135, and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 1.

[0081] Comparative Example 2 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.4 wt% (based on the total weight of the thermoplastic polyurethane precursor) of the liquid phosphite ester-based antioxidant Weston® 705T, and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 2.

[0082] Comparative Example 3 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.4 wt% of the lactone antioxidant Revonox® 501 (based on the total weight of the thermoplastic polyurethane precursor), and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 3.

[0083] Comparative Example 4 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.4 wt% of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-[3-[dodecenyl]-2,5-dioxopyrrolidin-1-yl]propionamide (based on the total weight of the thermoplastic polyurethane precursor), and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 4.

[0084] Comparative Example 5 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.2 wt % of the hindered phenol-based antioxidant Deox® BS-1135 (based on the total weight of the thermoplastic polyurethane precursor), 0.2 wt % of the liquid phosphite-based antioxidant Weston® 705T (based on the total weight of the thermoplastic polyurethane precursor), and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 5.

[0085] Comparative Example 6 100 g of polytetrahydrofuran diol PTMEG1000, 11 g of 1,4-butylene glycol, 0.2 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the hindered phenol-based antioxidant Deox® BS-1135, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the liquid phosphite-based antioxidant Weston® 705T, 0.1 wt % (based on the total weight of the thermoplastic polyurethane precursor) of the lactone-based antioxidant Revonox® 501, and 200 ppm of dibutyltin dilaurate were added to a reaction pot and heated to 110°C. Furthermore, 56 g of MDI (manufactured by BASF) was preheated to 110°C and added to the reaction pot. The mixture was stirred for 1 minute to initiate the reaction, yielding a plastic block. The plastic block was then placed in an oven and baked at 70°C for 24 hours for aging, yielding a thermoplastic polyurethane plastic block of Comparative Example 6.

[0086] 5.3.Testing of Thermoplastic Polyurethanes Thermoplastic polyurethane test pieces were prepared using the thermoplastic polyurethane plastic blocks of Examples 1 and 2 and Comparative Examples 1 to 6. First, 55 g of the thermoplastic polyurethane plastic block was placed in a 100°C oven for 2 hours to remove surface moisture and completely dry it. Next, this thermoplastic polyurethane plastic block was placed in a 20 cm x 15 cm x 0.15 cm mold and pressed at a pressure of 20 kg / cm using a hot press (manufactured by Long Chang Mechanical Industrial Company). 2 The hot-pressed thermoplastic polyurethane was then placed in a cold press machine at 50 kg / cm. 2 The mixture was cooled for 5 to 10 minutes under a pressure of 0.15 cm to obtain a thermoplastic polyurethane test piece having a thickness of 0.15 cm.

[0087] The thermoplastic polyurethanes of Examples 1 and 2 and Comparative Examples 1 to 6 were measured for MFI, YI, and ΔE. Furthermore, tests for thermal oxidation aging resistance, thermal yellowing resistance, hydrolysis resistance, and fisheye were conducted according to the above-mentioned test methods. The results are shown in Tables 1 to 5.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] As shown in Tables 1 to 5, thermoplastic polyurethanes prepared from the thermoplastic polyurethane precursors of the present invention simultaneously achieve the advantages of low initial yellowness, high yellowing resistance, thermal oxidative aging resistance, and hydrolysis resistance, as well as few fisheyes. In particular, the results of the fisheye test are very good. In contrast, thermoplastic polyurethanes not derived from the thermoplastic polyurethane precursors of the present invention cannot simultaneously achieve low initial yellowness and high yellowing resistance, thermal oxidative aging resistance, and hydrolysis resistance, and the results of the fisheye test are particularly poor. Specifically, as shown in Comparative Example 1, when the thermoplastic polyurethane precursor contains only a hindered phenol-based antioxidant as the first additive, the resulting thermoplastic polyurethane exhibits poor initial yellowness, thermal yellowing resistance, and thermal oxidative aging resistance, and also exhibits poor results in the fisheye test. As shown in Comparative Example 2, when the thermoplastic polyurethane precursor contains only a liquid phosphite-based antioxidant as the first additive, the resulting thermoplastic polyurethane exhibits poor hydrolysis resistance and poor results in the fisheye test. As shown in Comparative Example 3, when the thermoplastic polyurethane precursor contains only a lactone-based antioxidant as the first auxiliary agent, the resulting thermoplastic polyurethane has poor heat yellowing resistance, heat oxidative aging resistance, and hydrolysis resistance, and also shows poor results in the fisheye test. As shown in Comparative Example 4, when the thermoplastic polyurethane precursor contains only the compound of formula (I) as the first auxiliary agent, the resulting thermoplastic polyurethane has poor heat yellowing resistance and heat oxidative aging resistance, and also shows poor results in the fisheye test. As shown in Comparative Example 5, when the thermoplastic polyurethane precursor contains only a hindered phenol-based antioxidant and a liquid phosphite-based antioxidant as the first auxiliary agents, the resulting thermoplastic polyurethane has poor heat oxidative aging resistance and hydrolysis resistance, and also shows poor results in the fisheye test. As shown in Comparative Example 6, when the thermoplastic polyurethane precursor contains a hindered phenol-based antioxidant, a liquid phosphite-based antioxidant, and a lactone-based antioxidant as the first auxiliary agent but does not contain the compound of formula (I) or (II), the resulting thermoplastic polyurethane has poor resistance to thermal oxidative aging and hydrolysis, and also shows poor results in the fisheye test.

[0094] To more clearly demonstrate the technical effectiveness of the present invention, the Examples and Comparative Examples were compared and evaluated for initial yellowness, yellowing resistance, thermal oxidative aging resistance, hydrolysis resistance, and fisheye performance as follows. Example 1 was used as the evaluation standard. The evaluation criteria were "◎: excellent," "◯: good," "△: fair," and "×: poor." As can be seen from the comparison results shown in Table 6, the thermoplastic polyurethane of the present invention simultaneously achieves excellent performance in all of low initial yellowness, high yellowing resistance, thermal oxidative aging resistance, and hydrolysis resistance, as well as few fisheyes.

[0095] [Table 6]

[0096] The above examples and comparative examples illustrate the principle and effectiveness of the present invention and show its unique features. Those skilled in the art can make various modifications and substitutions based on the disclosure and suggestions of the present invention described without departing from the principle of the present invention.

Claims

1. (A) Polyisocyanate, (B) Chain extender, (C) Polymer polyols, and (D) First adjuvant A thermoplastic polyurethane precursor comprising, The first auxiliary agent is (d1) Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisoheptyl ester, Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisooctyl ester, or Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisononyl ester, (d2) A mixture of 2,4-bis(1,1-dimethylpropyl)phenyl-4-(1,1-dimethylpropyl)phenyl phosphite, 2,4-bis(1,1-dimethylpropyl)phenylbis[4-(1,1-dimethylpropyl)phenyl] phosphite, and tris[4-(1,1-dimethylpropyl)phenyl] phosphite. (d3) 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and (d4) At least one of the compounds of formula (I) and formula (II) A thermoplastic polyurethane precursor containing [the specified ingredient]. 【Chemistry 1】 (In the formula, R1 is dodecenyl.) 【Chemistry 2】

2. The thermoplastic polyurethane precursor according to claim 1, wherein the polyisocyanate (A) comprises an aromatic polyisocyanate.

3. The thermoplastic polyurethane precursor according to claim 1, wherein the polymer polyol (C) is selected from the group consisting of polyether polyols, polyester polyols, polysiloxane polyols, and combinations thereof.

4. The thermoplastic polyurethane precursor according to claim 1, wherein the chain extender (B) is selected from the group consisting of polyols, diamines, amino alcohols, and combinations thereof.

5. The thermoplastic polyurethane precursor according to any one of claims 1 to 4, wherein the amount of each of the components (d1) to (d4) is independently 0.01% by weight to 1.0% by weight of the total weight of the thermoplastic polyurethane precursor.

6. A thermoplastic polyurethane precursor according to any one of claims 1 to 4, further comprising additives selected from the group consisting of defoaming agents, leveling wetting agents, thickeners, dispersants, waxes, powder matting agents, antibacterial agents, metal oxide-based light-shielding agents, light stabilizers, heat stabilizers, ultraviolet absorbers, blue light absorbers, antioxidants, peroxide scavengers, free radical scavengers, fillers, rubber, food preservatives, flame retardants, plasticizers, dyes, pigments, glossing agents, antistatic agents, fluorescent whitening agents, degradation inhibitors, metal stabilizers, acid absorbers, hydrolysis inhibitors, and combinations thereof.

7. A thermoplastic polyurethane containing a first auxiliary agent, The first auxiliary agent is (d1) Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisoheptyl ester, Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisooctyl ester, or Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyisononyl ester, (d2) A mixture of 2,4-bis(1,1-dimethylpropyl)phenyl-4-(1,1-dimethylpropyl)phenyl phosphite, 2,4-bis(1,1-dimethylpropyl)phenylbis[4-(1,1-dimethylpropyl)phenyl] phosphite, and tris[4-(1,1-dimethylpropyl)phenyl] phosphite. (d3) 4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and (d4) At least one of the compounds of formula (I) and formula (II) Thermoplastic polyurethane, including 【Transformation 3】 (In the formula, R1 is dodecenyl.) 【Chemistry 4】

8. The thermoplastic polyurethane according to claim 7, further comprising additives selected from the group consisting of defoaming agents, leveling wetting agents, thickeners, dispersants, waxes, powder matting agents, antibacterial agents, metal oxide-based light-shielding agents, light stabilizers, heat stabilizers, ultraviolet absorbers, blue light absorbers, antioxidants, peroxide scavengers, free radical scavengers, fillers, rubber, food preservatives, flame retardants, plasticizers, dyes, pigments, glossing agents, antistatic agents, fluorescent whitening agents, degradation inhibitors, metal stabilizers, acid absorbers, hydrolysis inhibitors, and combinations thereof.

9. A step of providing a thermoplastic polyurethane precursor according to any one of claims 1 to 4, A method for producing a thermoplastic polyurethane, comprising the step of polymerizing the thermoplastic polyurethane precursor to obtain a thermoplastic polyurethane.

10. The method according to claim 9, further comprising pelletizing, extruding, laminating, injection molding, calendering, casting, blow molding, coating, or melt-blowing the thermoplastic polyurethane.

11. Use of the thermoplastic polyurethane according to claim 7 or claim 8 for producing a thermoplastic polyurethane article.

12. The thermoplastic polyurethane article is selected from the group consisting of transparent housings, packaging articles, household articles, textile articles, medical articles, sports articles, electronic products, optical products, building articles, machine parts, automotive articles, military industry articles and coatings, as per claim 11.

Images