TWI704180B - Cured composition, cured product and composite material - Google Patents

Abstract

A curing composition includes an epoxy resin component and a hardener, wherein the epoxy resin component includes a thermoplastic polymer, a bisphenol epoxy resin, a polyurethane-modified epoxy resin, and an isocyanate-modified epoxy resin. The total amount of the epoxy resin component is 100wt%, the amount of the bisphenol epoxy resin ranges from 30wt% to 50wt%, the amount of the polyurethane modified epoxy resin ranges from 10wt% to 20wt%, and the isocyanate modified The amount of high-quality epoxy resin ranges from 30wt% to less than 60wt%. The present invention also provides a cured product and composite material with excellent strength and elongation.

Description

Cured composition, cured product and composite material

The present invention relates to a curing material, in particular to a curing composition containing an epoxy resin component, wherein the epoxy resin component includes a thermoplastic polymer, a bisphenol epoxy resin, a polyurethane modified epoxy resin and Isocyanate modifies epoxy resin.

Epoxy resin is often widely used in electronic materials or optical materials because of its excellent heat resistance, chemical resistance and formability. Among epoxy resins, bisphenol epoxy resins are often used due to their good bonding properties, and are usually combined with thermoplastic polymers and hardeners to be configured into cured compositions for subsequent applications.

Although the bisphenol epoxy resin has good bonding characteristics, the cured product formed by the bisphenol epoxy resin still does not meet the requirements in terms of strength (such as tensile strength or bending strength) and elongation, and even improves When it is strong, it tends to cause the loss of elongation. In addition, when applied to products with high functionality (such as elasticity, strength, or strength feedback), such as sports goods, there is a problem of deformation or breakage after long-term use.

Therefore, the first object of the present invention is to provide a cured composition that can provide excellent strength and elongation.

Therefore, the cured composition of the present invention includes an epoxy resin component and a hardener, wherein the epoxy resin component includes a thermoplastic polymer, a bisphenol epoxy resin, a polyurethane modified epoxy resin, and an isocyanate modified epoxy resin, And based on the total amount of the epoxy resin component being 100wt%, the amount of the bisphenol epoxy resin ranges from 30wt% to 50wt%, and the amount of the polyurethane modified epoxy resin ranges from 10wt% to 20wt%, and The amount of the isocyanate-modified epoxy resin ranges from 30 wt% to less than 60 wt%.

The second objective of the present invention is to provide a cured product with excellent strength and elongation.

The cured product of the present invention is formed by the curing reaction of the above-mentioned cured composition.

The third objective of the present invention is to provide a composite material with excellent strength and elongation.

The composite material of the present invention includes a cured product, wherein the cured product is formed from the above-mentioned cured composition through a curing reaction.

The effect of the present invention is that through the combination of the epoxy resin component and the amount thereof, the cured composition can make the cured product and the composite material have excellent strength and elongation.

The cured composition of the present invention includes an epoxy resin component and a hardener, wherein the epoxy resin component includes a thermoplastic polymer, a bisphenol epoxy resin, a polyurethane modified epoxy resin, and an isocyanate modified epoxy resin, and The total amount of the epoxy resin component is 100wt%, the amount of the bisphenol epoxy resin ranges from 30wt% to 50wt%, the amount of the polyurethane modified epoxy resin ranges from 10wt% to 20wt%, and the isocyanate The amount of modified epoxy resin ranges from 30wt% to less than 60wt%.

[Epoxy resin component]

＜Bisphenol epoxy resin＞

The bisphenol epoxy resin is, for example, bisphenol A diglycidyl ether with an epoxide equialent weight (EEW) of 180 to 600.

＜Polyurethane modified epoxy resin＞

The polyurethane-modified epoxy resin is, for example, a polyurethane-modified epoxy resin having an epoxy equivalent of 200 to 300. The polyurethane-modified epoxy resin is, for example, polyurethane-modified bisphenol epoxy resin. The polyurethane-modified bisphenol epoxy resin, for example, the polyurethane-modified bisphenol A epoxy resin.

＜Isocyanate modified epoxy resin＞

The isocyanate-modified epoxy resin is, for example, an isocyanate epoxy having an epoxy equivalent of 300 to 400. The isocyanate-modified epoxy resin is, for example, isocyanate-modified bisphenol epoxy resin. The isocyanate-modified bisphenol epoxy resin, for example, the isocyanate-modified bisphenol A epoxy resin.

＜Thermoplastic polymer＞

The purpose of the thermoplastic polymer is to make the cured composition have anti-sagging properties and to improve the toughness of the cured product. In order to be able to improve the compatibility with other components in the epoxy resin component, the thermoplastic polymer such as polyester, phenoxy resin, polyethersulfone, or polyether ( polyether) and so on.

[hardener]

The hardening agent is, for example, dicyandiamide (DICY).

＜Cured products and composite materials＞

The cured product of the present invention is formed by the curing reaction of the above-mentioned cured composition. The composite material of the present invention contains the above-mentioned cured product. In some embodiments of the present invention, the tensile strength of the cured product is above 80 MPa, the bending strength is above 150 MPa, the tensile elongation is above 6%, and the bending elongation is above 10%. Under such characteristics, The applied sports goods (such as sports shoes) can have excellent elasticity, bending resistance, and not easy to be brittle.

In addition to the cured product, the composite material may further include other raw materials. This raw material is used as a fiber material for reinforcement, for example. The fiber material can be used alone or in combination of multiple types, and the fiber material is for example carbon fiber material, glass fiber material, mineral fiber material, or polyphenylene terephthalate fiber material. The polyphenylene terephthalate fiber material is, for example, Kevlar ^® fiber from DuPont. In terms of structure, the fiber material is, for example, continuous filament or staple fiber (also known as staple fiber), and in use, it can be mixed with fiber materials of different structure types. The composite material can be applied to sports goods (such as sports shoes).

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

Example 1

Modified bisphenol A epoxy resin with 10 grams of polyurethane (brand: Nanya; model: NPER-133M; epoxy equivalent 220±25), and 30 grams of bisphenol A diglycidyl ether (brand: Nanya; Model: NPEL-134; epoxy equivalent of 250±20), 50 grams of isocyanate modified bisphenol A epoxy resin (brand: Nanya; Model: NPEX-152M; epoxy equivalent of 310±10) and 10 grams The phenoxy resin (brand: Nippon Steel; model: YP-50; molecular weight is 50,000) is mixed to form an epoxy resin component. 100 grams of epoxy resin component and 10 grams of dicyandiamide are mixed to form a cured composition.

Examples 2 to 3 and Comparative Examples 1 to 14

Examples 2 to 3 and Comparative Examples 1 to 14 were carried out in the same steps as in Example 1, with the main difference being: changing the amount of each component in the epoxy resin component.

Evaluation item

Tensile strength measurement: the cured compositions of Examples 1 to 3 and Comparative Examples 1 to 14 were vacuum defoamed, and then placed in a mold, and then a thermocompression molding machine was used at a temperature of 200°C. A 30-minute hot press molding process is performed to obtain a cured molded sheet, wherein a curing reaction is accompanied by the hot press molding process. After cutting the cured sheet to an appropriate size, use a universal testing machine to measure it in accordance with the ASTM D638 standard method.

Bending strength measurement: The cured compositions of Examples 1 to 3 and Comparative Examples 1 to 14 were vacuum defoamed, and then placed in a mold, and then a thermocompression molding machine was used for 30 Minutes of the hot press molding process to obtain a cured molded sheet, wherein the curing reaction is accompanied by the hot press molding process. After cutting the cured sheet to an appropriate size, use a universal testing machine to measure it according to the ASTM D790 standard method.

Tensile elongation measurement: the cured compositions of Examples 1 to 3 and Comparative Examples 1 to 14 were vacuum defoamed, and then placed in a mold, and then a thermocompression molding machine was used at a temperature of 200°C A thermo-compression molding process is performed for 30 minutes to obtain a cured molded sheet, wherein a curing reaction is accompanied by the thermo-compression molding process. After cutting the cured sheet to an appropriate size, use a universal testing machine to measure it in accordance with the ASTM D638 standard method.

Measurement of bending elongation: The cured compositions of Examples 1 to 3 and Comparative Examples 1 to 14 were vacuum defoamed, and then placed in a mold, and then a thermocompression molding machine was used at a temperature of 200°C. A 30-minute hot press molding process is performed to obtain a cured molded sheet, wherein a curing reaction is accompanied by the hot press molding process. After cutting the cured sheet to an appropriate size, use a universal testing machine to measure it according to the ASTM D790 standard method.

Table 1 Curing composition Example Comparative example 1 2 3 1 2 3 4 5 6 Epoxy resin composition g (wt%) Polyurethane modified bisphenol A epoxy resin (EEW is 220±25) 10 (10) 20 (20) 10 (10) 50 (50) 0 (0) 50 (50) 5 (5) 30 (30) 10 (10) Bisphenol A diglycidyl ether (EEW is 250±20) 30 (30) 30 (30) 50 (50) 40 (40) 40 (40) 0 (0) 50 (50) 50 (50) 55 (55) Isocyanate modified bisphenol A epoxy resin (EEW is 310±10) 50 (60) 40 (40) 30 (30) 0 (0) 50 (50) 40 (40) 35 (35) 10 (10) 25 (25) Phenoxy resin 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) Hardener (g) Dicyandiamide 10 10 10 10 10 10 10 10 10 Evaluation item Tensile strength (MPa) 82.3 80.4 87.2 74.4 71.4 65.7 79.8 78.9 83.3 Flexural strength (MPa) 153.2 150.2 156.3 138.2 139.1 126.7 143.8 148.2 150.4 Tensile elongation (%) 6.6 6.7 6.5 5.2 4.9 7.1 5.8 6.1 3.2 Bending elongation (%) 10.34 11.12 10.78 8.01 8.01 11.9 9.4 9.8 5.8

Table 2 Curing composition Comparative example 7 8 9 10 11 12 13 14 Epoxy resin composition g (wt%) Polyurethane modified bisphenol A epoxy resin (EEW is 220±25) 10 (10) 10 (10) 70 (70) 10 (10) 5 (5) 90 (90) 0 (0) 0 (0) Bisphenol A diglycidyl ether (EEW is 250±20) 25 (25) 70 (70) 10 (10) 10 (10) 10 (10) 0 (0) 0 (0) 90 (90) Isocyanate modified bisphenol A epoxy resin (EEW is 310±10) 55 (55) 10 (10) 10 (10) 70 (70) 75 (75) 0 (0) 90 (90) 0 (0) Phenoxy resin 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) 10 (10) Hardener (g) Dicyandiamide 10 10 10 10 10 10 10 10 Evaluation item Tensile strength (MPa) 73.3 81.3 71.2 72.1 78.4 72.1 69.4 86.9 Flexural strength (MPa) 133.3 153.4 132.1 132.2 142.1 138.2 129.1 152.9 Tensile elongation (%) 5.6 3.4 5.3 5.8 5.2 6.8 6.9 3.4 Bending elongation (%) 9.01 5.6 9.01 8.92 8.01 10.98 11.01 6.8

According to the experimental data of Examples 1 to 3 in Table 1, bisphenol epoxy resin, polyurethane-modified epoxy resin and the isocyanate-modified epoxy resin are added to the curing composition, and the amounts of these components are all in this Within the range stated in the invention, the cured product formed by the curing inhibitors has a tensile strength of 80 MPa or more, a bending strength of 150 MPa or more, a tensile elongation of 6% or more, and a bending elongation of 10% The above characteristics.

In contrast to the cured compositions of Comparative Examples 1 to 14, from the experimental data of Comparative Examples 1 to 3 in Table 1, it can be seen that only bisphenol epoxy resin, polyurethane modified epoxy resin and the isocyanate modified ring were added to the cured composition. It can be seen from the experimental data of Comparative Examples 12 to 14 in Table 2 that only bisphenol epoxy resin, polyurethane-modified epoxy resin and the isocyanate-modified epoxy resin are added to the cured composition. First, these cured products cannot have both strength and elongation, and even strength and elongation are not good. Furthermore, from the experimental data of Comparative Examples 4 to 6 in Table 1 and Comparative Examples 7 to 11 in Table 2, it can be seen that even if bisphenol epoxy resin, polyurethane-modified epoxy resin and the isocyanate-modified epoxy resin are added to the cured composition For epoxy resin, when at least one of these components is not within the scope of the present invention, the cured products cannot have both strength and elongation, and even the strength and elongation are not good.

In summary, the present invention, through the combination of the epoxy resin component and its amount, the cured composition can make the cured product and the composite material have excellent strength and elongation, so the objective of the invention can indeed be achieved.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope of the patent for the present invention.

no.

Claims (10)

A curing composition comprising: Epoxy resin components, including thermoplastic polymers, bisphenol epoxy resins, polyurethane modified epoxy resins and isocyanate modified epoxy resins, and the total amount of the epoxy resin components is 100wt%, the bisphenol The amount of epoxy resin ranges from 30wt% to 50wt%, the amount of the polyurethane-modified epoxy resin ranges from 10wt% to 20wt%, and the amount of the isocyanate-modified epoxy resin ranges from 30wt% to less than 60wt%; and hardener. The cured composition according to claim 1, wherein the bisphenol epoxy resin is bisphenol A diglycidyl ether having an epoxy equivalent of 180 to 600. The cured composition according to claim 1, wherein the polyurethane-modified epoxy resin is a polyurethane-modified epoxy resin having an epoxy equivalent of 200 to 300. The cured composition according to claim 1, wherein the isocyanate-modified epoxy resin is an isocyanate-modified epoxy resin having an epoxy equivalent of 300 to 400. The cured composition according to claim 1, wherein the hardener is dicyandiamide. A cured product is formed from the cured composition of any one of claims 1 to 5 through a curing reaction. A composite material comprising a cured product, wherein the cured product is formed from the cured composition of any one of claims 1 to 5 through a curing reaction. The composite material according to claim 7, further comprising fiber materials. The composite material according to claim 8, wherein the fiber material is selected from carbon fiber material, glass fiber material, mineral fiber material, polyphenylene terephthalate fiber material, or any combination of the foregoing. The composite material according to claim 8, wherein the fiber material is selected from continuous fibers, short fibers, or a combination of the foregoing.