TW201309741A - Thermoplastic elastomer shoe material composition - Google Patents

Abstract

A thermoplastic elastomer shoe material composition is suitable to make the wear resistant part of a sole and comprises an elastomer part and a plastic part for carrying out copolymerization. The plastic part comprises polyamide, polyethylene terephthalate, compatibilizer and modifier. Accordingly, the elastomer part can enable the thermoplastic elastomer shoe material composition to have an elasticity effect of absorbing impact force, the polyamide in the plastic part can enable the thermoplastic elastomer shoe material composition to have an effect of wear resistance, and the polyethylene terephthalat in the plastic part can enable the thermoplastic elastomer shoe material composition to generate the effect of high strength.

Description

Thermoplastic elastomer shoe composition

The present invention relates to a shoe material, and more particularly to a thermoplastic elastomer shoe material composition.

Referring to FIG. 1, a general sole 1 includes a sole body 11 including a rear end 111 of the shoe, a cushioning device 12 disposed at the rear end 111 of the shoe, and a wear layer 13 disposed on a bottom surface of the sole body 11.

When the user wears a shoe having the sole 1, the cushioning device 12 can reduce the impact force that the user receives when running or jumping, thereby further reducing the damage to the user's body organs. On the other hand, since the sole 1 of the shoe contacts the ground of different roughness, the wear of the sole 1 is caused, in particular, the rear end 111 of the sole 1 of the sole 1 , in order to extend the service life of the shoe, the wear layer is required 13 reaches the time to delay the wear of the sole 1 .

The wear layer 13 is generally made of natural rubber or synthetic rubber. The rubber has good wear resistance and flexibility, but the elasticity and strength are not good. Therefore, the buffer device 12 is required to make the wear layer 12 The sole 1 has a cushioning effect. Although the sulfurization treatment can be used to produce a slight cross-linking structure between the rubber molecules, the vulcanized rubber has a viscoelastic property and can return to the original shape after being stressed, but there is still insufficient strength. The problem, therefore, there is still a large demand for the development of different shoe materials for this industry sector.

Accordingly, it is an object of the present invention to provide a thermoplastic elastomer shoe composition having elasticity, abrasion resistance and high strength.

Thus, the thermoplastic elastomer shoe composition of the present invention is suitable for forming a wear portion of a sole comprising an elastomer component and a plastic component.

The plastic component is copolymerized with the elastomer component, which comprises polyamine, polyethylene terephthalate, a compatibilizer and a modifier, polyamine, polyterephthalic acid. The content of the ethylene diester and the compatibilizer is 30 wt% to 85 wt%, 5 wt% to 15 wt%, and 5 wt% to 60 wt%, respectively, based on the total weight of the plastic component.

The effect of the present invention is that the thermoplastic elastomer shoe material composition can have an elastic effect of absorbing impact force by the elastomer component, and the plastic component of the polyamide component can make the thermoplastic elastomer shoe material composition The wear-resistant effect, together with the polyethylene component of the plastic component, enables the thermoplastic elastomer shoe composition to exert a high strength effect.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.

Referring to FIG. 2, the thermoplastic elastomer shoe composition of the present invention is suitable for forming two wear parts 21 of a sole 2, and the wear parts 21 are respectively formed on the front end 222 of the sole 221 of the sole body 22 and the rear of the shoe. End 223.

The thermoplastic elastomer shoe composition comprises an elastomer component and a plastic component, the plastic component being copolymerized with the elastomer component, the plastic component comprising polyamine (Nylon), polyterephthalic acid Ethylene glycol (PET), and a compatibilizing agent, by copolymerizing the elastomer component with the plastic component, the thermoplastic elastomer shoe composition can be thermoplasticized and elastomer-free without vulcanization. characteristic.

Since polyamine and polyethylene terephthalate in the plastic component are highly polar polymers, non-polar and crystalline polyolefin elastomers such as ethylene-propylene rubber (ethylene propylene copolymer) Rubber, EPR), ethylene propylene diene terpolymer (EPDM), etc. have poor compatibility, so the use of maleic anhydride and polyamines of the plastic component can be used. The mechanism of the ethylene phthalate reaction allows the plastic component to bond to the polyolefin elastomer.

Preferably, the elastomer component has a maleic anhydride grafted elastomer, which enables the elastomer component to have both physical properties of the elastomer and an amino group (NH) or The alcohol-based (OH) phase-bonded active acid anhydride group further enables the thermoplastic elastomer shoe material composition to have an elastic effect of absorbing impact force. Preferably, the maleic anhydride graft elastomer is selected from the group consisting of Maleic anhydride grafted thermoplastic elastomer, maleic anhydride grafted thermoplastic rubber or maleic anhydride grafted rubber, more preferably, the Malay The anhydride grafted elastomer is selected from the group consisting of maleic anhydride grafted vinyl acetate (EVA-g-MAH) and maleic anhydride grafted styrene-butadiene-styrene embedded copolymer. (maleic anhydride grafted styrene butadiene styrene block copolymer, SBS-g-MAH), maleic anhydride grafted ethylene-propylene rubber (maleic anhydride grafted ethylene propylene copolymer rub Ber, EPR-g-MAH) or maleic anhydride grafted ethylene propylene diene terpolymer (EPDM-g-MAH).

It should be noted that the ratio of the elastomer component to the plastic component can be appropriately adjusted, but the physical properties of the thermoplastic elastomer shoe composition are also changed, and adding too little of the elastomer component causes the The elasticity of the thermoplastic elastomer shoe composition is poor or non-elastic, and adding too much of the elastomer component reduces the abrasion resistance and strength of the thermoplastic elastomer shoe composition, so that the thermoplastic elastomer shoe The composition of the material has the elastic effect required for the shoe material. Preferably, the elastomer component is from 1 to 80% by weight based on the total weight of the plastic component.

Polyamide has better tensile strength and toughness, which can make the thermoplastic elastomer shoe composition have wear-resisting effect, but the flexural strength and dimensional stability of polyamide are poor, so by poly-p-phenylene The addition of ethylene diformate enhances the performance of the thermoplastic elastomer shoe composition in terms of flexural strength and dimensional stability. Furthermore, since polyamine and ethylene terephthalate are two distinct materials, the compatibilizer is added to improve the compatibility of polyamine with polyethylene terephthalate and balance The rate of crystallization between the two, and the polyamine in the plastic component is stably compatible with ethylene terephthalate, resulting in good dimensional stability, on the other hand, by the compatibilizer The addition of the plastic component from a highly crystalline plastic to a rubber-like rubber has softness and good touch characteristics. Preferably, the compatibilizer comprises a polymer containing a monoepoxy functional group, preferably The polymer is selected from the group consisting of a bromide type epoxy resin or an alicyclic type epoxy resin.

It should be noted that polyamine, polyethylene terephthalate, and the ratio of the compatibilizing agent can be appropriately adjusted, but the physical properties of the thermoplastic elastomer shoe composition obtained are also changed. Adding too little polyamine reduces the wear resistance of the thermoplastic elastomer shoe composition, and adding too little polyethylene terephthalate reduces the strength of the thermoplastic elastomer shoe composition, while adding too little The compatibilizing agent lowers the softness of the thermoplastic elastomer shoe composition, so that the thermoplastic elastomer shoe composition has the abrasion resistance and strength effect required for the shoe material, preferably, the plastic component The content of polyamine, polyethylene terephthalate, and the compatibilizer is 30 wt% to 85 wt%, 5 wt% to 15 wt%, and 5 wt% to 60 wt%, respectively, based on the total weight of the plastic component.

Since the polyamide material has a tough material relative to the polyethylene terephthalate brittle material, in order to enhance the impact strength of the thermoplastic elastomer shoe composition and the effect at low temperature, the plastic component is added. a modifier for improving the mixed interface of the polyamide and the polyethylene terephthalate. Preferably, the modifier is contained in an amount of 30 to 70% by weight based on the total weight of the plastic component. The modifier may be an ethylene octene trepolymer (POE).

It is worth mentioning that the good workability of the thermoplastic elastomer shoe material composition can be performed by hot pressing, injection or profile extrusion molding, and the wear parts 21 are formed on the sole body 22 . The shoe front end 222 of the bottom surface 221 and the shoe rear end 223, or directly forming the thermoplastic elastomer shoe material composition by hot pressing, injection or profile extrusion molding, thereby producing a convenient manufacturing effect, and further Recycling and recycling, resulting in the effect of resource reuse.

Hereinafter, the production method of the preferred embodiment and the physical properties thereof will be further described by the following specific examples.

Source of chemicals:

Nylon6: The molecular weight range is from 16,000 to 19,000, which is the waste cloth and waste yarn of Li Peng Company.

PET: The molecular weight is 200000. It is the waste cloth of Li Peng Company and the waste yarn is crushed by the crusher.

Compatibilizer: Silane Coupling Agent A-187 (KH-560), chemical name γ-(2,3-epoxypropoxy)propyltrimethoxysilane , purchased from Chengdu Chenbang Chemical, the structural formula is as in general formula (I).

Elastomer component: EVA-g-MAH, molecular weight range 3000-4000, available from Dupont Dow Chemical Company.

Modifier: POE, molecular weight 5000, purchased from Dopont Dow Chemical Company.

testing method:

Tensile yield strength test: The raw materials are put into a twin-screw extruder for blending, and then extruded to make a sample for testing. The sample is made of ASTM D638 type I, and the test method is in accordance with ASTM D638. .

Elongation at break test: The test method and specifications are the same as the tensile strength test. The test method is carried out in accordance with ASTM D638.

Flexural strength test: The test method and specifications are the same as the tensile strength test. The test method is in accordance with ASTM D790.

Flexural modulus test: The test method and specifications are the same as the tensile strength test. The test method is carried out in accordance with ASTM D790, and the flexural modulus is taken as 0.3%.

Impact strength: The test method is the same as the tensile strength test. The test specimen is in accordance with ASTM D256 and the test method is carried out in accordance with ASTM D256.

Hardness test: The test method is the same as the tensile strength test. The test specimen is in accordance with ASTM D2240. The test method is carried out in accordance with ASTM D2240 (share D).

Heat deflection temperature test: The sample preparation method is the same as the tensile strength test. The test method is carried out in accordance with ASTM D648. The load is applied to the center of the sample, and the temperature is raised at 2 ° C / min. The temperature is 0.25 mm.

Wearing test: the sample is clamped on the film lifted by air pressure and rubbed against the sandpaper pressed downward from the top. The movement of the sandpaper is to move back and forth, and the sample is rotated in situ, and the test sample is tested. The wear resistance of broken yarns or holes is generated in accordance with ASTM D3886.

Linear expansion coefficient test: The sample preparation method is the same as the tensile strength test. The test method is carried out in accordance with ASTM D696. The sample is a cylinder with a diameter of 5 mm and records between -30 ° C and 30 ° C per liter. The sample was changed by an average length per 1 cm at a temperature of 1 °C.

<Specific Example 1> Nylon 6: PET: Compatibilizer = 30: 10: 60

Referring to Figure 3, 30 wt% of Nylon 6, 10 wt% of PET, and 60 wt% of the compatibilizer, and 40 wt% of EVA-g-MAH and 30 wt% of POE, respectively, based on the total weight of the above three are taken. Blending through a feed inlet 31 of a twin screw extruder 3 (Intermeshing Co-Rotating type, ψ=30 mm, L/D=43.2, available from Kobe steel) through which the above-mentioned raw materials are passed through the twin screw extruder A molten compression kneading zone 32 of the mixture 3 is heated and fully compressed to form a flowing rubber compound, and the rubber compound is pushed from a discharge section 33 of the twin screw extruder 3 into a mold 34 to obtain a thermoplastic elastomer shoe material. Preferably, the rotation speed of the twin-screw extruder 3 is 20 rpm to 100 rpm, and the operating temperatures of the six heating sections 321, 322, 323, 324, 325, and 326 of the melt compression mixing zone 32 are 230 respectively. °C~250°C, 240°C~260°C, 250°C~270°C, 255°C~275°C, 250°C~270°C, and 240°C~260°C, the mold 34 operating temperature is 90°C~100°C.

In this embodiment, the rotation speed of the twin-screw extruder 3 is 60 rpm, and the operating temperatures of the six heating sections 321, 322, 323, 324, 325, and 326 of the melt compression mixing section 32 are 240 ° C and 250 ° C, respectively. The mold 34 was operated at a temperature of 80 ° C at 260 ° C, 265 ° C, 260 ° C, and 250 ° C.

The thermoplastic elastomer shoe material composition sample obtained above is subjected to the aforementioned tensile stress reduction test, tensile elongation test, flexural strength test, flexural modulus test, impact strength test, heat distortion temperature test, And linear expansion coefficient test, respectively, can obtain tensile strength of 53MPa, tensile elongation of 89%, flexural strength of 1374MPa, flexural modulus test of 3668MPa, impact strength of 89J / m, hardness of 75, heat The deformation temperature was 85 ° C, the abrasion resistance was 20 cc, and the coefficient of linear expansion was 22 × 10 ^-5 cm / cm / ° C, and the above material ratio and test data were collected in Table-1.

<Specific Example 2> Nylon 6: PET: Compatibilizer = 60: 10: 30

It was produced and tested in the same manner as in <Specific Example 1>, and the main difference was that 60% by weight of Nylon 6, 10% by weight of PET, and 30% by weight of the compatibilizing agent were taken, and the total weight of the above three were respectively calculated. The blending ratio of 60 wt% EVA-g-MAH and 50 wt% POE was obtained, and the tensile strength at break was 60 MPa, the elongation at break was 85%, the flexural strength was 1299 MPa, and the flexural modulus was obtained. The test was 3138 MPa, the impact strength was 92 J/m, the hardness was 80, the heat distortion temperature was 86 ° C, the wear resistance was 22 cc, and the coefficient of linear expansion was 15×10 ^-5 cm/cm/°C, and the above materials were also matched. And the test data is summarized in Table-1.

<Specific Example 3> Nylon 6: PET: Compatibilizer = 85: 10: 5

Made and tested in the same manner as in <Specific Example 1>, the main difference is: taking 85 wt% of Nylon 6, 10 wt% of PET, and 5 wt% of the compatibilizer, and respectively based on the total weight of the above three The blending ratio of 80 wt% EVA-g-MAH and 70 wt% POE was obtained, and the tensile strength at 51 MPa, the elongation at break was 60%, the flexural strength was 1297 MPa, and the flexural modulus was obtained. The test was 3884 MPa, the impact strength was 85 J/m, the hardness was 100, the heat distortion temperature was 101 ° C, the abrasion resistance was 32 cc, and the coefficient of linear expansion was 5×10 ^-5 cm/cm/°C, and the above materials were also matched. And the test data is summarized in Table-1.

From the above results, the thermoplastic elastomer shoe material sample obtained by mixing Nylon 6, PET, the compatibilizer, EVA-g-MAH, and POE can be illustrated in addition to the strength. The improvement and the good performance in the heat distortion temperature and the coefficient of linear expansion show that the thermoplastic elastomer shoe composition of the present invention does have the elasticity, abrasion resistance and high strength effect required for the shoe material.

In summary, the thermoplastic elastomer shoe composition of the present invention can achieve the following effects and advantages, so that the object of the present invention can be achieved:

1. The use of the elastomer component of the present invention enables the thermoplastic elastomer shoe composition to have an elastic effect of absorbing impact force.

2. The polyacetamide of the present invention by the present invention enables the thermoplastic elastomer shoe composition to have an abrasion resistance effect.

3. The polyethylene terephthalate of the present invention utilizing the plastic component enables the thermoplastic elastomer shoe composition to exert a high strength effect.

4. The present invention further enhances the impact strength of the thermoplastic elastomer shoe composition and the effect at low temperatures by the modifier.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

1. . . Sole

11. . . Sole body

111. . . Shoe rear end

12. . . Buffer device

13. . . Wear layer

2. . . Sole

twenty one. . . Wear part

twenty two. . . Sole body

221. . . Bottom

222. . . Shoe front end

223. . . Shoe rear end

3. . . Twin screw extruder

31. . . Grain inlet

32. . . Melt compression mixing zone

321. . . Heating section

322. . . Heating section

323. . . Heating section

324. . . Heating section

325. . . Heating section

326. . . Heating section

33. . . Export section

34. . . Mold

Figure 1 is a perspective view of a general sole;

Figure 2 is a perspective view of a preferred embodiment of the thermoplastic elastomer shoe composition of the present invention;

Figure 3 is a schematic illustration of a twin screw extruder.

2. . . Sole

twenty one. . . Wear part

twenty two. . . Sole body

221. . . Bottom

222. . . Shoe front end

223. . . Shoe rear end

Claims (8)

A thermoplastic elastomer shoe material composition suitable for forming a wear portion of a sole, the thermoplastic elastomer shoe composition comprising: an elastomer component; and a plastic component, the plastic component and the elastomer The component is copolymerized, and the plastic component comprises polyamine, polyethylene terephthalate, a compatibilizer and a modifier, polyamine, polyethylene terephthalate, and the compatibility The content of the agent is 30 wt% to 85 wt%, 5 wt% to 15 wt%, and 5 wt% to 60 wt%, respectively, based on the total weight of the plastic component. The thermoplastic elastomer shoe material composition according to claim 1, wherein the elastomer component is contained in an amount of from 1% by weight to 80% by weight based on the total mass of the plastic component. The thermoplastic elastomer shoe material composition according to claim 1, wherein the elastomer component has a maleic anhydride graft elastomer. The thermoplastic elastomer shoe composition according to claim 1, wherein the maleic anhydride graft elastomer is selected from the group consisting of maleic anhydride grafted thermoplastic elastomer, maleic anhydride grafted thermoplastic rubber or Malay. Anhydride grafted rubber. The thermoplastic elastomer shoe composition according to claim 1, wherein the maleic anhydride graft elastomer is selected from the group consisting of maleic anhydride grafted ethylene-polyvinyl acetate, maleic anhydride grafted styrene. - Butadiene-styrene embedded copolymer, maleic anhydride grafted ethylene-propylene rubber or maleic anhydride grafted ethylene propylene diene monomer. The thermoplastic elastomer shoe composition according to claim 1, wherein the compatibilizing agent has a polymer containing a monoepoxy functional group. The thermoplastic elastomer shoe material composition according to claim 6, wherein the polymer is selected from the group consisting of an epoxy oxirane resin or an alicyclic epoxy resin. The thermoplastic elastomer shoe material composition according to claim 1, wherein the modifier is contained in an amount of 30% by weight to 70% by weight based on the total weight of the plastic component.