TW202336065A - Thermoplastic polyurethane resin for producing spinning textile fibers - Google Patents

Abstract

A thermoplastic polyurethane resin for producing spinning textile fibers is provided. The thermoplastic polyurethane resin is formed by polymerization of a reaction mixture. The reaction mixture includes an isocyanate component and a polyol component, which includes a first polyether polyol and a second polyether polyol. The first polyether polyol has a weight average molecular weight of 650 to 1,200, and the second polyether polyol has a weight average molecular weight of 1,500 to 2,500. The thermoplastic polyurethane resin meets following physical properties and is suitable for production of multifilament spun fibers below 150 denier: (1) having a rheological viscosity of 400 pa.s to 1,000 pa.s; (2) having a first melting point (Tm1) of 180 to 200 DEG C and a second melting point (Tm2) of 190 to 210 DEG C; and (3) having a cooling crystallization temperature (Tc) of 105 DEG C to 125 DEG C.

Description

Thermoplastic polyurethane resin used in the manufacture of spun fibers

The present invention relates to a thermoplastic polyurethane resin, in particular to a thermoplastic polyurethane resin used for manufacturing spinning fibers.

Thermoplastic polyurethane resin (TPU) is an environmentally friendly polymer. Thermoplastic polyurethane resin can be made into spun fibers through a melt spinning process.

However, in the prior art, during the production of thermoplastic polyurethane resin particles, some infusible small crystals or coarse particles are inevitably formed.

Accordingly, when the existing thermoplastic polyurethane resin is made into spun fibers through melt spinning, it is easy to cause fiber breakage due to small crystals or coarse particles.

In terms of producing fine denier specifications (such as spinning fibers below 150 denier), existing thermoplastic polyurethane resins are prone to problems such as floating yarn and difficulty in winding up during the melt spinning process.

Furthermore, during the melt spinning process of existing thermoplastic polyurethane resins, the melt flow index (MI) varies greatly and the crystallization temperature is too low, which easily results in different thicknesses of the spun fibers, making the weaving process easier. Causes curling and affects the physical properties of the product.

Therefore, the inventor felt that the above-mentioned defects could be improved, so he devoted himself to research and applied scientific principles, and finally proposed an invention that is reasonably designed and effectively improves the above-mentioned defects.

The technical problem to be solved by the present invention is to provide a thermoplastic polyurethane resin for manufacturing spinning fibers in view of the shortcomings of the existing technology.

In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a thermoplastic polyurethane resin for manufacturing spun fibers, which is formed from a reaction mixture through a polymerization reaction, and the reaction mixture includes : an isocyanate component; and a polyol component, which includes: a first polyether polyol and a second polyether polyol, wherein the first polyether polyol has a weight of between 650 and 1,200 g/mol. and the second polyether polyol has a second weight average molecular weight between 1,500 and 2,500 g/mol; wherein, based on the total weight of the reaction mixture, 100 parts by weight, the amount of the polyol component is between 30 parts by weight and 60 parts by weight; wherein the thermoplastic polyurethane resin meets the following physical properties and is suitable for spinning multifilaments with specifications below 150 denier. Fiber: (1) The thermoplastic polyurethane resin is analyzed by a rheometer, and under the analysis conditions of a temperature between 200°C and 220°C and a shear speed between 10 sec ^-1 and 3000 sec ^-1 , it has a 400 Pascal． seconds (pa.s) to 1,000 Pascals. A rheological viscosity between seconds; (2) The thermoplastic polyurethane resin was analyzed with a micro-differential scanning thermal card analyzer, and under the heating condition of a heating rate of 20°C/min, it has a viscosity between 180°C and 200°C. a first melting point (Tm1) and a second melting point (Tm2) between 190°C and 210°C, and the absolute value of a difference between the first melting point and the second melting point is between Between 3°C and 15°C; (3) The thermoplastic polyurethane resin was analyzed with the micro-differential scanning thermal card analyzer and under the cooling condition of a cooling rate of 20°C/min, it has a temperature range between 105°C and 15°C. A cooling crystallization temperature (Tc) of 125 °C.

Preferably, based on the total weight of the reaction mixture being 100 parts by weight, the amount of the first polyether polyol is between 10 and 40 parts by weight, and the amount of the second polyether polyol is between 100 and 40 parts by weight. From 10 parts by weight to 40 parts by weight.

Preferably, the first polyether polyol is selected from the group consisting of: polyoxytetramethylene glycol (PTMG), polyoxypropylene glycol (PPG), and polyethylene glycol (PEG). At least one of the group, and the second polyether polyol is selected from: polyoxytetramethylene glycol, polyoxypropylene glycol, and polyethylene glycol, at least one of the group consisting of one.

Preferably, the isocyanate component is selected from: diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), and isophorone diisocyanate (IPDI). At least one of the material groups; wherein, based on 100 parts by weight of the total weight of the reaction mixture, the amount of the isocyanate component is between 30 and 60 parts by weight.

Preferably, the thermoplastic polyurethane resin is in the form of colloidal particles.

Preferably, the thermoplastic polyurethane resin further has the following physical properties: (4) The thermoplastic polyurethane resin is analyzed with the micro-differential scanning thermal card analyzer, and under the cooling conditions with the cooling rate of 20°C/min, Has a crystallinity between 20% and 40%.

Preferably, the thermoplastic polyurethane resin further has the following physical properties: (5) The thermoplastic polyurethane resin is analyzed by a gel permeation chromatography and has a concentration of between 55,000 g/mol and 70,000 g/mol. a number average molecular weight (Mn) and a weight average molecular weight (Mw) between 90,000 g/mol and 120,000 g/mol; and (6) the thermoplastic polyurethane resin in the gel Permeation chromatography analyzes a ratio between weight average molecular weight (Mw) and number average molecular weight (Mn) (Mw/Mn) which is between 1.55 and 1.75.

Preferably, the thermoplastic polyurethane resin further has the following physical properties: (7) The thermoplastic polyurethane resin is analyzed with a melt flow velocimeter and has a flow rate of between 5 g/10 minutes (190°C) and 8 g/10 minutes (190°C). ℃); and (8) the thermoplastic polyurethane resin is analyzed by the micro-differential scanning thermal card analyzer, under the cooling condition of the cooling rate of 20℃/min, Has a heat of crystallization between 12 and 20 Joules/gram (J/g).

Preferably, the reaction mixture further includes: a chain terminator component, and the chain terminator component is a monohydric alcohol having a boiling point between 210°C and 344°C.

Preferably, the thermoplastic polyurethane resin is further added with an ultraviolet absorber, and the ultraviolet absorber is at least one material selected from the group consisting of benzotriazoles, benzophenones, and triazines. one of them.

One of the beneficial effects of the present invention is that the thermoplastic polyurethane resin provided by the present invention can be designed through the "weight average molecular weight and content range design of the first polyether polyol and the second polyether polyol" and "the physical properties of the thermoplastic polyurethane resin". Design, such as "rheological viscosity, melting point, cooling crystallization temperature" technical solution, so that the thermoplastic polyurethane resin is particularly suitable for the melt spinning process in the form of colloidal particles, and is particularly suitable for use in specifications of 150 Production of multifilament spinning fibers below denier.

Through this, problems such as broken filaments, floating filaments, difficult winding, uneven thickness, etc. in the melt spinning process of the existing technology can be effectively improved. Furthermore, the spun fibers formed by melt spinning of the thermoplastic polyurethane resin have good hydrolysis resistance and elastic recovery rate, and the spun fibers are particularly suitable for use in functional fabrics for sports.

In order to further understand the features and technical content of the present invention, please refer to the following detailed description of the present invention. However, it is only used for reference and explanation and is not used to limit the present invention.

The following is a specific example to illustrate the disclosed embodiments of the present invention. Those skilled in the art can understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of the present invention. The following embodiments will further describe the relevant technical content of the present invention in detail, but the disclosed content is not intended to limit the scope of the present invention.

It should be understood that although terms such as “first”, “second” and “third” may be used herein to describe various elements or signals, these elements or signals should not be limited by these terms. These terms are primarily used to distinguish one component from another component or one signal from another signal. In addition, the term "or" used in this article shall include any one or combination of more of the associated listed items depending on the actual situation.

[Thermoplastic polyurethane resin]

Thermoplastic polyurethane resin can be made into spun fibers through a melt spinning process. However, in the prior art, during the production of thermoplastic polyurethane resin particles, some infusible small crystals or coarse particles are inevitably formed. Accordingly, when the existing thermoplastic polyurethane resin is made into spun fibers through melt spinning, it is easy to cause fiber breakage due to small crystals or coarse particles. In terms of producing fine denier specifications (such as spinning fibers below 150 denier), existing thermoplastic polyurethane resins are prone to problems such as floating yarn and difficulty in winding up during the melt spinning process. Furthermore, during the melt spinning process of existing thermoplastic polyurethane resins, the melt flow index (MI) varies greatly and the crystallization temperature is too low, which easily results in different thicknesses of the spun fibers, making the weaving process easier. Causes curling and affects the physical properties of the product.

In order to solve the technical defects existing in the above-mentioned prior art, embodiments of the present invention provide a thermoplastic polyurethane resin (TPU resin), particularly a thermoplastic polyurethane resin used for manufacturing spinning fibers. The thermoplastic polyurethane resin includes at least two polyether polyols with different molecular weight ranges, and the thermoplastic polyurethane has high crystallinity and high stretching resistance.

When the thermoplastic polyurethane resin of the embodiment of the present invention is formed into spun fibers through a melt spinning process, problems such as broken filaments, floating filaments, and difficulty in winding up in the prior art can be effectively improved. The spun fibers formed by embodiments of the present invention have the advantages of good winding properties and small pressure rise. Furthermore, the melt index and viscosity change rate of the thermoplastic polyurethane resin in the embodiment of the present invention have small variations during the melt spinning process, so the thickness uniformity of the spinning fiber can also be effectively improved, thereby making the product have good physical properties.

More specifically, the thermoplastic polyurethane resin of the embodiment of the present invention is formed from a reaction mixture through a polymerization reaction. Wherein, the reaction mixture includes: an isocyanate component, a polyol component, and a chain terminator component.

Wherein, based on the total weight of the reaction mixture being 100 parts by weight, the amount of the isocyanate component is between 30 and 60 parts by weight (preferably between 40 and 55 parts by weight), and the polyol component is The usage amount is between 30 parts by weight and 60 parts by weight (preferably between 30 parts by weight and 45 parts by weight), and the usage amount of the chain terminator component is between 0.1 parts by weight and 0.5 parts by weight.

It should be noted that in this embodiment, although the reaction mixture is not limited, a chain extender component or other auxiliary additive components can be optionally added, which is not limited by the present invention.

Furthermore, the isocyanate component is selected from: methylene diphenyl di-isocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (4,4'-methylene di-cyclohexyl di -isocyanate, H12MDI), and isophorone di-isocyanate (IPDI), at least one of the material groups composed of. The isocyanate component in the embodiment of the present invention is preferably diphenylmethane diisocyanate (MDI). However, the above-mentioned types of isocyanate materials are only illustrative, and the present invention is not limited thereto.

The polyol component includes a first polyether polyol and a second polyether polyol.

The first polyether polyol has a first weight average molecular weight, and the first weight average molecular weight is between 650 and 1,200 g/mol, and preferably between 800 and 1,200 g/mol. In addition, the second polyether polyol has a second weight average molecular weight, and the second weight average molecular weight is between 1,500 and 2,500 g/mol, and preferably between 1,800 and 2,200 g/mol. .

Furthermore, the absolute value of a difference between the first weight average molecular weight and the second weight average molecular weight is between 300 and 1,850 g/mol, preferably between 600 and 1,400 g/mol, and particularly Preferably it is between 800 and 1,200 g/mo.

In terms of dosage range, based on the total weight of the reaction mixture being 100 parts by weight, the dosage of the polyol component is between 30 and 60 parts by weight, and preferably between 30 and 45 parts by weight. between. That is to say, the total amount of the first polyether polyol and the second polyether polyol is between 30 parts by weight and 60 parts by weight, and preferably between 30 parts by weight and 45 parts by weight. More specifically, the amount of the first polyether polyol is between 10 parts by weight and 40 parts by weight, and preferably between 15 parts by weight and 35 parts by weight. In addition, the amount of the second polyether polyol is between 10 parts by weight and 40 parts by weight, and preferably between 15 parts by weight and 35 parts by weight.

In terms of material type, the first polyether polyol is selected from: polyoxytetramethylene glycol (PTMG), polyoxypropylene glycol (PPG), and polyethylene glycol ( polyethylene glycol (PEG), at least one of the material groups composed of. Furthermore, the second polyether polyol is at least one selected from the group consisting of: polyoxytetramethylene glycol, polyoxypropylene glycol, and polyethylene glycol. Preferably, the first polyether polyol and the second polyether polyol are polyoxytetramethylene glycol (PTMG), but the present invention is not limited thereto.

According to the material selection of the first and second polyether polyols, the spun fibers formed by the thermoplastic polyurethane resin after melt spinning can have good hydrolysis resistance and elastic recovery. rate), and the spun fiber is particularly suitable for use in functional fabrics for sports (for example, functional fabrics for sports are often pulled or moistened by sweat during use), but the present invention is not limited thereto.

The materials of the first polyether polyol and the second polyether polyol may be the same or different, and are not limited by the present invention. The main difference between the first polyether polyol and the second polyether polyol is that the weight average molecular weight (Mw) of the two polyols falls in different numerical ranges. The definition of the numerical range of the weight average molecular weight has been explained above and will not be elaborated here.

Furthermore, the thermoplastic polyurethane resin of the embodiment of the present invention is particularly suitable for the melt spinning process in the form of colloidal particles (such as TPU colloidal particles), and is particularly suitable for use in multifilament yarns with specifications below 150 denier. Production of spun fibers.

It is worth mentioning that the "multifilament spun fiber with a specification of less than 150 denier" referred to in this application refers to a continuous filament consisting of dozens to hundreds of single fibers, and The denier number of each single fiber is less than 150 denier.

In order to make the thermoplastic polyurethane resin in the embodiment of the present invention more suitable for use in the above-mentioned melt spinning process and further improve the problems of broken yarn, floating yarn, and difficulty in winding up, the physical properties of the thermoplastic polyurethane resin in the embodiment of the present invention need to at least meet the following requirements: Conditions (1) to (3):

(1) The thermoplastic polyurethane resin is analyzed by a rheometer, and under the analysis conditions of a temperature ranging from 200°C to 220°C and a shearing speed ranging from 10 sec ^-1 to 3000 sec ^-1 , it has a medium At 400 pascals. seconds (pa.s) to 1,000 Pascals. A rheological viscosity between seconds, and preferably between 600 Pascals. seconds to 800 pascals. between seconds.

It is worth mentioning that the thermoplastic polyurethane resin particles in embodiments of the present invention have lower rheological viscosity and viscosity change rate than generally commercially available TPU particles.

(2) The thermoplastic polyurethane resin was analyzed with a differential scanning calorimeter (DSC). Under the heating condition of a heating rate of 20°C/min, it has a temperature range of 180°C to 200°C ( preferably a first melting point (Tm1) between 185 °C and 198 °C) and a second melting point (Tm2) between 190 °C and 210 °C (preferably between 198 °C and 210 °C), And the absolute value of the difference between the first melting point and the second melting point is between 3°C and 15°C (preferably between 5°C and 10°C).

(3) The thermoplastic polyurethane resin was analyzed with a micro-differential scanning thermal card analyzer, and under the cooling conditions of the cooling rate of 20°C/min, it has a cooling crystallization between 105°C and 125°C. temperature (Tc), and is preferably between 105°C and 120°C.

It is worth mentioning that the thermoplastic polyurethane resin particles in the embodiments of the present invention have a higher cooling crystallization temperature than generally commercially available TPU particles, but the cooling crystallization temperature is lower than the processing temperature of melt spinning (generally pumped). The processing temperature required for wire operations is roughly between 210 °C and 240 °C).

In some embodiments of the present invention, the physical properties of the thermoplastic polyurethane resin can further satisfy the following conditions (4) to (8) to achieve better melt spinning effects.

(4) The thermoplastic polyurethane resin is analyzed with a micro-differential scanning thermal card analyzer and has a crystallinity of between 20% and 40% under the cooling condition of the cooling rate of 20°C/min, and Preferably between 20% and 30%.

It is worth mentioning that the "crystallinity" referred to in this application represents the proportion of the crystalline part in the polymer to the total polymer, expressed by a formula: crystallinity = crystalline part / (crystalline part + amorphous part).

(5) The thermoplastic polyurethane resin was analyzed with a gel permeation chromatography (GPC). Under the analysis conditions of a tube temperature of 35°C and a THF flow rate of 1ml/min, it had a value of between 55,000 g/mol. A number average molecular weight (Mn) between 50,000 g/mol and 70,000 g/mol, and preferably between 58,000 g/mol and 65,000 g/mol. Furthermore, the thermoplastic polyurethane resin was analyzed with a gel permeation chromatography (GPC). Under the analysis conditions of a tube temperature of 35°C and a THF flow rate of 1 ml/min, it had a value of between 90,000 g/mol. A weight average molecular weight (Mw) between 100,000 g/mol and 120,000 g/mol, and preferably between 95,000 g/mol and 105,000 g/mol.

(6) The thermoplastic polyurethane resin is analyzed by the gel permeation chromatography and the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) (Mw/Mn) is between 1.55 and 1.75. , and preferably between 1.60 and 1.70.

(7) The melt flow index (MI) of the thermoplastic polyurethane resin is between 5 g/10 minutes (190°C) and 8 g/10 minutes (190°C), and is preferably between 5 g/10 min (190℃) to 7 g/10 min (190℃).

The "melt index" in this application refers to the weight of the thermoplastic resin passing through the standard die every 10 minutes on a melt flow velocimeter at a temperature of 190°C. The unit is grams/10 minutes (190°C). The melt index marks the fluidity of the resin in the molten state. The greater the melt index and the smaller the molecular weight, the better the fluidity.

The change rate of the melt index of the thermoplastic polyurethane resin in the embodiment of the present invention needs to be controlled within ±15%, which can ensure good processability of the resin and solve the problem that the thickness of the spinning fiber is different and the weaving process easily causes curling.

(8) The thermoplastic polyurethane resin was analyzed with a micro-differential scanning thermal card analyzer, and under the cooling conditions with the cooling rate of 20°C/min, it has a concentration of between 12 and 20 Joules/gram (J/g). A crystallization enthalpy is, and preferably is, between 12 and 18.5 Joules/g.

According to the above configuration, the thermoplastic polyurethane resin provided by the embodiment of the present invention can be designed through "the weight average molecular weight and content range design of the first polyether polyol and the second polyether polyol" and "the physical property design of the thermoplastic polyurethane resin, such as "Rheological viscosity, melting point, cooling crystallization temperature" technical solution, so that the thermoplastic polyurethane resin is particularly suitable for the melt spinning process in the form of colloidal particles, and is particularly suitable for use in specifications below 150 denier. Production of multifilament spinning fibers. Through this, problems such as broken filaments, floating filaments, difficult winding, uneven thickness, etc. in the melt spinning process of the existing technology can be effectively improved.

Furthermore, the spun fibers formed by melt spinning of the thermoplastic polyurethane resin have good hydrolysis resistance and elastic recovery rate, and the spun fibers are particularly suitable for use in functional fabrics for sports.

Further, the chain terminator component is a monohydric alcohol with a boiling point between 210°C and 344°C. For example, the chain terminator component is at least one selected from the group consisting of: arachidyl alcohol, stearyl alcohol, and palmitol. The above-mentioned chain terminator components are particularly suitable for use in melt spinning processes.

The purpose of adding the chain terminator component is to terminate the polymerization reaction after the thermoplastic polyurethane resin reaches a predetermined molecular weight during the polymerization reaction, so that the reaction is complete. Thereby, the molecular weight of the thermoplastic polyurethane resin can be maintained in a stable state, and the molecular weight distribution of the thermoplastic polyurethane resin can become more concentrated. Furthermore, since the molecular weight of the thermoplastic polyurethane resin can be maintained in a stable state and avoid continuing to climb, the thermoplastic polyurethane resin is less likely to have coarse particles or crystal points.

In some embodiments of the present invention, a UV absorber is added to the thermoplastic polyurethane resin, so that the QUV of the thermoplastic polyurethane resin can reach level four or above. The ultraviolet absorber is at least one of the material groups consisting of benzotriazoles, benzophenones, and triazines, but the present invention Not limited to this. The added amount of the ultraviolet absorber in the thermoplastic polyurethane resin is between 0.1 parts by weight and 1.0 parts by weight. The ultraviolet absorber is metered and added at the end of the reaction extrusion machine, which can reduce the cracking of the material and the failure of the ultraviolet absorption function during the extrusion process. Therefore, the ultraviolet absorber does not participate in the polymerization reaction in essence. The ultraviolet absorber is only physically mixed in the thermoplastic polyurethane resin.

[Production method of thermoplastic polyurethane resin]

The above is the relevant description of the material characteristics of the thermoplastic polyurethane resin according to the embodiment of the present invention, and the manufacturing method of the thermoplastic polyurethane resin according to the embodiment of the present invention will be described below.

The manufacturing method of the thermoplastic polyurethane resin includes a mixing stage and a reaction stage.

The mixing stage includes: using a separate meter, according to the measurement described above in the embodiment of the present invention, the above-mentioned isocyanate component and polyol component (including the first polyether polyol and the second polyether polyol) are stably introduced into a Premixing is performed in a mixer to form a reaction mixture.

The reaction stage includes: introducing the reaction mixture containing the isocyanate component and the polyol component into a twin-screw reaction extruder, so that the isocyanate component and the polyol component undergo a polymerization reaction, and introducing a chain terminator component in the post-reaction extrusion stage to The polymerization reaction is terminated and a thermoplastic polyurethane resin is ultimately formed.

The extrusion temperature of the twin-screw reaction extruder is preferably set between 150°C and 250°C, so that the polymerization reaction can fully proceed, but the present invention is not limited thereto. Furthermore, after completing the reaction extrusion step, the thermoplastic polyurethane resin is pelletized in an aqueous environment to form thermoplastic polyurethane resin pellets (TPU pellets).

In some embodiments of the present invention, the manufacturing method of thermoplastic polyurethane resin also monitors the viscosity of the auxiliary line in real time, and feeds back the pouring amount of the raw material based on the monitored viscosity value, thereby improving the pouring accuracy of the raw material and enabling real-time control of NCO/ The OH equivalent ratio falls within a predetermined range, whereby a TPU resin with a stable melt index change rate within a batch can be produced. More specifically, after the reaction mixture comes out of a separate meter, the instant viscosity can be detected by an online viscometer. When the viscosity exceeds the control range, adjust the raw material dosage and correct the viscosity to ensure stable production.

In addition, the NCO/OH equivalent ratio of the reaction mixture in the polymerization reaction is preferably controlled between 0.98 and 1.02, and particularly preferably between 0.995 and 1.005. , but the present invention is not limited thereto.

[Experimental data test]

Hereinafter, the contents of the present invention will be described in detail with reference to Examples 1 to 4 and Comparative Examples 1 to 2. However, the following examples are only provided to help understand the present invention, and the scope of the present invention is not limited to these examples. The experimental conditions and test results of Examples 1 to 4 and Comparative Examples to 2 are as shown in Table 1 below. Among them, Examples 1 to 4 are preferred embodiments of the present invention, and Comparative Examples 1 to 2 are control groups, which are used to prove that Examples 1 to 4 have better technical effects.

Next, the physical properties of the thermoplastic polyurethane resin particles of Examples 1 to 4 and Comparative Examples 1 to 2, such as melting point, cooling crystallization temperature, rheological viscosity, crystallinity, number average molecular weight, weight average molecular weight, Mw/Mn, melt index, The heat of crystallization is also listed in Table 1 below. The relevant test methods have been explained above and will not be described in detail here.

[Table 1 Experimental conditions and test results] Project Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 reaction mixture Isocyanate type MDI MDI MDI MDI MDI MDI Isocyanate weight parts 40.9 40.7 41.2 40.9 41.7 40.2 First polyether polyol molecular weight 1,000 1,000 1,000 1,000 1,000 1,000 First polyether polyol weight part 22.8 15.7 31.8 22.8 47.5 0 Second polyether polyol molecular weight 2,000 2,000 2,000 2,000 2,000 2,000 Second polyether polyol weight part 24.7 31.8 15.7 24.7 0 47.5 Types of chain terminators stearyl alcohol stearyl alcohol stearyl alcohol stearyl alcohol stearyl alcohol stearyl alcohol Chain terminator parts by weight 0.2 0.3 0.3 0.1 0.2 0.2 Physical properties of TPU resin colloidal particles First melting point Tm1(℃) 190 196 186 189 175 200 Second melting point Tm2 (℃) 198 202 192 198 – – Cooling crystallization temperature Tc (℃) 110 114 108 111 104 124 Rheological viscosity (pa.s) 710 680 674 782 590 825 Crystallinity (%) twenty four 26 twenty one 25 18 29 Number average molecular weight (Mn) 62,150 59,455 60,514 63,285 61,887 58,013 Weight average molecular weight (Mw) 102,548 99,281 99,242 102,521 100,256 99,784 Mw/Mn 1.65 1.67 1.64 1.62 1.78 1.72 Melt index (g/10min) 5.4 6.7 6.8 5.7 5.9 6.4 Heat of crystallization (J/g) 16.5 18.1 13.4 12.6 11.1 22.9

[Discussion of test results]

The thermoplastic polyurethane resin particles of Examples 1 to 4 have better physical properties and are particularly suitable for the production of multifilament spun fibers with specifications below 150 denier. The thermoplastic polyurethane resin particles of Examples 1 to 4 will not suffer from problems such as broken yarns, floating yarns, difficulty in winding up, and uneven fiber thickness through the melt spinning process. Comparative Example 1 only uses the first polyether polyol without using the second polyether polyol. The crystallization heat of the TPU resin particles in Comparative Example 1 is relatively low (11.1 J/g), which is not easy to produce spinning fibers. Finalize. Furthermore, Comparative Example 2 only uses the second polyether polyol without using the first polyether polyol. The crystallization heat of the TPU resin colloidal particles in Comparative Example 2 is high (22.9 J/g), which is very important in the production of spinning fibers. It is easy to shape, but it can easily lead to residual stress and warping problems at both ends of the roll.

[Beneficial effects of the embodiment]

One of the beneficial effects of the present invention is that the thermoplastic polyurethane resin provided by the embodiment of the present invention can be designed through the "weight average molecular weight and content range design of the first polyether polyol and the second polyether polyol" and "thermoplastic polyurethane resin". The technical solution is to design physical properties, such as: rheological viscosity, melting point, cooling crystallization temperature, so that the thermoplastic polyurethane resin is particularly suitable for the melt spinning process in the form of colloidal particles, and is particularly suitable for specifications It is the production of multifilament spinning fiber with a density of less than 150 denier. Through this, problems such as broken filaments, floating filaments, difficult winding, uneven thickness, etc. in the melt spinning process of the existing technology can be effectively improved. Furthermore, the spun fibers formed by melt spinning of the thermoplastic polyurethane resin have good hydrolysis resistance and elastic recovery rate, and the spun fibers are particularly suitable for use in functional fabrics for sports.

The contents disclosed above are only preferred and feasible embodiments of the present invention, and do not limit the patentable scope of the present invention. Therefore, all equivalent technical changes made using the contents of the description of the present invention are included in the patentable scope of the present invention. .

Claims (10)

A thermoplastic polyurethane resin for manufacturing spun fibers, which is formed from a reaction mixture through a polymerization reaction, and the reaction mixture includes: an isocyanate component; and a polyol component, which includes: a first polyol Ether polyol and a second polyether polyol, wherein the first polyether polyol has a first weight average molecular weight between 650 and 1,200 g/mol, and the second polyether polyol Having a second weight average molecular weight between 1,500 and 2,500 g/mol; wherein, based on 100 parts by weight of the total weight of the reaction mixture, the amount of the polyol component is between 30 parts by weight and 60 parts by weight Between parts; wherein, the thermoplastic polyurethane resin meets the following physical properties and is suitable for the production of multifilament spinning fibers with specifications below 150 denier: (1) The thermoplastic polyurethane resin is analyzed by a rheometer, and in the temperature range Under the analysis conditions of 200°C to 220°C and shear speed between 10 sec ^-1 and 3000 sec ^-1 , it has a performance of between 400 Pascal. seconds (pa.s) to 1,000 Pascals. A rheological viscosity between seconds; (2) The thermoplastic polyurethane resin was analyzed with a micro-differential scanning thermal card analyzer, and under the heating condition of a heating rate of 20°C/min, it has a viscosity between 180°C and 200°C. a first melting point (Tm1) and a second melting point (Tm2) between 190°C and 210°C, and the absolute value of a difference between the first melting point and the second melting point is between Between 3°C and 15°C; (3) The thermoplastic polyurethane resin was analyzed with the micro-differential scanning thermal card analyzer and under the cooling condition of a cooling rate of 20°C/min, it has a temperature range between 105°C and 15°C. A cooling crystallization temperature (Tc) of 125 °C. The thermoplastic polyurethane resin for manufacturing spun fibers as described in claim 1, wherein the amount of the first polyether polyol is between 10 and 100 parts by weight based on 100 parts by weight of the total weight of the reaction mixture. 40 parts by weight, and the amount of the second polyether polyol is between 10 parts by weight and 40 parts by weight. The thermoplastic polyurethane resin for manufacturing spinning fibers as described in claim 1, wherein the first polyether polyol is selected from: polyoxytetramethylene glycol (PTMG), polyoxypropylene glycol ( PPG), and polyethylene glycol (PEG), at least one of the material groups composed of, and the second polyether polyol is selected from: polyoxytetramethylene glycol, polyoxypropylene glycol At least one of the material groups composed of alcohol and polyethylene glycol. The thermoplastic polyurethane resin for manufacturing spinning fibers as described in claim 1, wherein the isocyanate component is selected from: diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate ( H12MDI), and isophorone diisocyanate (IPDI), at least one of the material group composed of; wherein, based on the total weight of the reaction mixture is 100 parts by weight, the amount of the isocyanate component is between 30 parts by weight to 60 parts by weight. The thermoplastic polyurethane resin used for manufacturing spun fibers as described in claim 1, wherein the thermoplastic polyurethane resin is in the form of colloidal particles. The thermoplastic polyurethane resin for manufacturing spun fibers as described in claim 1, wherein the thermoplastic polyurethane resin further has the following physical properties: (4) The thermoplastic polyurethane resin was analyzed with the micro-differential scanning thermal card analyzer and found to have a crystallinity of between 20% and 40% under the cooling condition of the cooling rate of 20°C/min. The thermoplastic polyurethane resin used for manufacturing spun fibers as described in claim 6, wherein the thermoplastic polyurethane resin further has the following physical properties: (5) The thermoplastic polyurethane resin is analyzed by a gel permeation chromatography, has a number average molecular weight (Mn) between 55,000 g/mol and 70,000 g/mol, and has a number average molecular weight (Mn) between 9 A weight average molecular weight (Mw) between 10,000 g/mol and 120,000 g/mol; and (6) The thermoplastic polyurethane resin is analyzed by the gel permeation chromatography and the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) (Mw/Mn) is between 1.55 and 1.75. . The thermoplastic polyurethane resin used for manufacturing spun fibers as described in claim 7, wherein the thermoplastic polyurethane resin further has the following physical properties: (7) The thermoplastic polyurethane resin is analyzed by a melt flow velocimeter and has a melt index (MI) between 5 g/10 minutes (190°C) and 8 g/10 minutes (190°C); and (8) The thermoplastic polyurethane resin was analyzed with the micro-differential scanning thermal card analyzer, and under the cooling conditions with the cooling rate of 20°C/min, it has a chemical composition of between 12 and 20 Joules/gram (J/g). ) between a crystallization heat. The thermoplastic polyurethane resin for manufacturing spun fibers as described in claim 1, wherein the reaction mixture further includes: a chain terminator component, and the chain terminator component has a boiling point between 210°C and 344°C. monohydric alcohols between °C. The thermoplastic polyurethane resin used for manufacturing spinning fibers as described in claim 1, wherein the thermoplastic polyurethane resin is additionally added with an ultraviolet absorber, and the ultraviolet absorber is selected from: benzotriazole, diphenyl At least one of the material groups composed of ketones and triazines.