TW202219173A - Bio-resin composition, bio-resin composite and bio-foam material - Google Patents

Abstract

Provided are a bio-resin composition, a bio-resin composite and a bio-foam material. The bio-resin composition includes a base, a toughener and an antistatic agent. The weight ratio of the base to the toughener is between 90:10 and 60:40. Based on the total weight of the base and the toughener, the content of the antistatic agent is between 1% and 10%.

Description

Bio-resin composition, bio-resin composite and bio-foamed material

The present disclosure relates to a resin composition, resin composite, and foamed material, and more particularly, to a bio-resin composition, bio-resin composite, and biomass Foam material (bio-foam material).

For materials with antistatic properties in general, it is obtained by blending a resin compound containing an antistatic agent, and the antistatic agent contained therein forms a conductive path in the resin, so that the compound has antistatic properties. electrostatic properties.

However, for resin composites containing antistatic agents, after foaming, the antistatic agents dispersed in the resin tend to be more dispersed due to the increase in the volume of the resin, so that the conductive paths in the original composite are destroyed, Thus, the antistatic effect of the foamed material is reduced. In order to solve the aforementioned problems, it is necessary to increase the content of the antistatic agent to improve the electrical conductivity, which not only increases the cost of the foamed material, but also leads to a decrease in the foaming ratio.

The present disclosure provides a green resin composition comprising a matrix, a toughening agent and an antistatic agent.

The present disclosure provides a green resin composite in which an antistatic agent is present at the interface between the matrix and the toughening agent and/or in the toughening agent.

The present disclosure provides a biomass foaming material, which is formed by performing a foaming reaction of the above-mentioned biomass resin composite.

The green resin composite of the present disclosure includes a matrix, a toughening agent, and an antistatic agent. The toughening agent is dispersed in the matrix. The antistatic agent is present at the interface between the matrix and the toughening agent and/or in the toughening agent. The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40. The content of the antistatic agent is between 1% and 10% based on the total weight of the matrix and the toughening agent.

The biomass foamed material of the present disclosure includes a biomass resin composite and is a foaming reaction product of the biomass resin composite. The green resin composite includes a matrix, a toughening agent and an antistatic agent. The toughening agent is dispersed in the matrix. The antistatic agent is present at the interface between the matrix and the toughening agent and/or in the toughening agent. The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40. The content of the antistatic agent is between 1% and 10% based on the total weight of the matrix and the toughening agent.

The green resin composition of the present disclosure includes a matrix, a toughening agent, and an antistatic agent. The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40. The content of the antistatic agent is between 1% and 10% based on the total weight of the matrix and the toughening agent.

In order to make the above-mentioned features and advantages of the present disclosure more obvious and easy to understand, the following embodiments are given and described in detail with reference to the accompanying drawings as follows.

The following examples are described in detail with the accompanying drawings, but the provided examples are not intended to limit the scope of the present disclosure.

The terms "including", "including", "having", etc. mentioned in this article are all open-ended terms, that is, "including but not limited to".

Also, herein, a range represented by "one value to another value" is a general representation that avoids listing all the values in the range in the specification. Thus, the recitation of a particular numerical range includes any number within that numerical range as well as any smaller numerical range bounded by any number within that numerical range.

The green resin composition of the embodiment of the present disclosure includes a matrix, a toughening agent and an antistatic agent. In addition, in the bioresin composite formed with the bioresin composition, the toughening agent is dispersed in the matrix, and the antistatic agent is present at the interface between the matrix and the toughening agent and/or is present in the toughening agent in toughener. As such, the antistatic agent can be distributed as a continuous phase at the interface between the matrix and the toughening agent and/or in the toughening agent. Further, since the antistatic agent can be distributed in the form of a continuous phase at the interface between the matrix and the toughening agent and/or in the toughening agent, when the green resin composite of the embodiment of the present disclosure is foamed During the reaction, the conductive path formed by the antistatic agent in the formed biomass foam material is not easily damaged. Therefore, the biomass foaming material of the embodiment of the present disclosure can have good electrical conductivity and antistatic properties. The biomass resin composition, the biomass resin composite, and the biomass foaming material according to the embodiments of the present disclosure will be described below.

The green resin composition of the embodiment of the present disclosure includes a matrix, a toughening agent and an antistatic agent. In the embodiment of the present disclosure, the matrix is, for example, polylactic acid (PLA), and its melt flow index (MI) is, for example, between 2 g/10 min@190 °C and 10 g/10 min@190 between °C. In addition, the toughening agent is, for example, polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT) ) or a combination thereof with a melt flow index between 15 g/10 min@190 °C and 120 g/10 min@190 °C. In one embodiment, the melt flow index of the toughening agent is, for example, between 15 g/10 min@190 °C and 100 g/10 min@190 °C. In another embodiment, the melt flow index of the toughening agent is, for example, between 15 g/10 min @ 190 °C and 80 g/10 min @ 190 °C. In yet another embodiment, the melt flow index of the toughening agent is, for example, between 15 g/10 min @ 190 °C and 50 g/10 min @ 190 °C. That is to say, in the embodiments of the present disclosure, the flow characteristics of the toughening agent are higher than that of the matrix.

In addition, in the green resin composition of the embodiment of the present disclosure, the weight ratio of the matrix to the toughening agent is between 90:10 and 60:40. When the weight ratio of the matrix to the toughening agent is outside the above-mentioned range, the rigidity of the material decreases and a foamed material with a high expansion ratio cannot be obtained.

In the disclosed embodiment, the antistatic agent includes carbon black, carbon nanotube, graphene, or a combination thereof. The antistatic agent has good electrical conductivity, so that the bioresin composite formed from the bioresin composition of the embodiment of the present disclosure and the biofoamed material formed from the bioresin composite have good antistatic properties It is used in the packaging of electronic precision instruments, high-end panels, glass substrates, and semiconductor products with antistatic requirements to protect and maintain the functions of electronic products. In an embodiment of the present disclosure, the content of the antistatic agent is, for example, between 1% and 10% based on the total weight of the matrix and the toughening agent. When the content of the antistatic agent is less than 1%, after the biomass resin composite formed from the biomass resin composition undergoes a foaming reaction to form a biomass foam material, the biomass foam material is replaced by the antistatic agent. The resulting conductive paths are disrupted by the increase in volume during foaming. When the content of the antistatic agent is higher than 10%, it will lead to inability to smoothly knead, extrude and granulate, the mechanical properties will be significantly reduced, and it will be difficult to obtain a foamed material with a high expansion ratio. In one embodiment, the content of the antistatic agent is, for example, between 1% and 5% based on the total weight of the matrix and the toughening agent.

In addition, in the embodiments of the present disclosure, the flow characteristics of the toughener are higher than the flow characteristics of the matrix. Therefore, in the bio-resin composites formed from the bio-resin compositions of the embodiments of the present disclosure, the antistatic agent is mainly present at the interface between the matrix and the toughening agent and/or in the toughening agent to continuously The conductive paths are formed by distributing in a phase manner, and after the biomass foam material is formed, the conductive paths can still be kept intact to provide good antistatic properties. In the disclosed embodiment, the surface impedance of the green resin composite is, for example, between 10 ⁵ Ω/sq. to 10 ⁷ Ω/sq.

In one embodiment, a twin-screw extruder can be used to perform melt blending, reactive extrusion and strand granulation of the green resin composition of the embodiment of the present disclosure to form a green resin composite.

The biomass resin composite of the embodiment of the present disclosure is subjected to a foaming reaction (eg, a supercritical batch foaming reaction) to form the biomass foamed material of the embodiment of the present disclosure, which can be foamed to a thickness of 10 times to 30 times. volume of. In the disclosed embodiment, the pore size of the cells of the biomass foam material is, for example, between 1 μm and 100 μm, and the density thereof is, for example, between 0.02 g/cm ³ and 0.2 g/cm ³ . In one embodiment, the density of the biomass foam material is, for example, between 0.02 g/cm ³ to 0.15 g/cm ³ . In addition, the surface impedance of the formed biomass foam material is, for example, between 10 ⁴ Ω/sq and 10 ⁷ Ω/sq. That is, after performing the foaming reaction, the biomass foamed material may have the same or even lower surface impedance compared to the biomass resin composite, and thus may have good antistatic properties.

The following will describe the bio-resin composite of the present disclosure and the bio-foamed material formed by the foaming reaction of the bio-resin composite by way of experimental examples and comparative examples.

Experimental example 1

90 wt.% polylactic acid (melt flow index of 4.3) was used as the matrix, and 10 wt.% of polycaprolactone (melt flow index of 45) was added as a toughening agent and 5 phr of carbon nanotubes as antistatic agent to prepare biomass resin composition.

Then, using a twin-screw extruder (set the temperature to be ramped from 120 °C to 190 °C, set the rotation speed to 60 rpm to 300 rpm, and set the aspect ratio to 28 to 60), the above biomass The resin composition was melt-blended, reactively extruded and pelletized to form a green resin composite (surface impedance was 10 ⁵ Ω/sq, density was 1.256 g/cm ³ ).

After that, the above-mentioned green resin composite is dried at a temperature of 50°C to 80°C for 8 hours to 12 hours. Next, the green resin is compounded at a temperature of 90°C to 140°C and a gas pressure of 1500 psi to 3500 psi using a supercritical batch foam molding machine and a gas with a carbon dioxide content of 70% to 100%. The material undergoes a foaming reaction to form a biomass foam material (surface impedance is 105 Ω/sq, density is 0.053 g/cm ³ ).

Surface impedance testing of green resin composites and their foams was performed according to ASTM D257.

Experimental example 2

Except using 80 wt.% polylactic acid (melt flow index of 4.3), 20 wt.% of polycaprolactone (melt flow index of 45), and 1 phr of carbon nanotubes, the same procedure as in Experimental Example 1 was carried out. method to form bioresin composites (surface impedance of 10 ⁷ Ω/sq, density of 1.228 g/cm ³ ) and biofoamed materials (surface impedance of 10 ⁵ Ω/sq, density of 0.066 g/cm ^{3 )} ).

FIG. 1 is a transmission electron microscope image of the biomass foam material of Experimental Example 2. FIG. It can be seen from Figure 1 that the antistatic agent is present at the interface between the matrix and the toughening agent as well as in the toughening agent and is distributed as a continuous phase.

Experimental example 3

Except using 80 wt.% polylactic acid (melt flow index: 4.3), 20 wt.% polycaprolactone (melt flow index: 45), and 3 phr carbon nanotubes, the same procedure as in Experimental Example 1 was used. method to form bioresin composites (surface impedance 10 ⁵ Ω/sq, density 1.236 g/cm ³ ) and biofoamed materials (surface impedance 10 ⁵ Ω/sq, density 0.057 g/cm ^{3 )} ). In addition, the pore size of the cells of the biomass foam material is between 40 μm and 60 μm.

FIG. 2 is a transmission electron microscope image of the biomass foam material of Experimental Example 3. FIG. As can be seen from Figure 2, the antistatic agent is present at the interface between the matrix and the toughening agent as well as in the toughening agent and is distributed as a continuous phase.

Experimental example 4

Except using 80 wt.% polylactic acid (melt flow index of 4.3), 20 wt.% of polycaprolactone (melt flow index of 45), and 5 phr of carbon nanotubes, the same procedure as in Experimental Example 1 was carried out. method to form bioresin composites (surface impedance 10 ⁵ Ω/sq, density 1.251 g/cm ³ ) and biofoamed materials (surface impedance 10 ⁵ Ω/sq, density 0.069 g/cm ^{3 )} ).

Experimental example 5

Except using 70 wt.% polylactic acid (melt flow index of 4.3), 30 wt.% of polycaprolactone (melt flow index of 45), and 5 phr of carbon nanotubes, the same procedure as in Experimental Example 1 was carried out. method to form bioresin composites (surface impedance of 10 ⁵ Ω/sq to 10 ⁶ Ω/sq, density of 1.230 g/cm ³ ) and biofoamed materials (surface impedance of 10 ⁵ Ω/sq to 10 ⁶ Ω/sq with a density of 0.079 g/cm ³ ).

Experimental example 6

Except using 60 wt.% polylactic acid (melt flow index of 4.3), 40 wt.% of polycaprolactone (melt flow index of 45), and 5 phr of carbon nanotubes, the same procedures as in Experimental Example 1 were used. method to form bio-resin composites (surface impedance of 10 ⁵ Ω/sq to 10 ⁶ Ω/sq, density of 1.221 g/cm ³ ) and biofoamed materials (surface impedance of 10 ⁴ Ω/sq to 10 ⁵ Ω/sq with a density of 0.125 g/cm ³ ).

Experimental example 7

Except using 90 wt.% polylactic acid (melt flow index of 4.3), 10 wt.% of polybutylene succinate (melt flow index of 30), and 5 phr of carbon nanotubes, to compare with In the same manner as in Experimental Example 1, a bioresin composite (surface impedance of 10 ⁶ Ω/sq and density of 1.269 g/cm ³ ) and a bio-foamed material (surface impedance of 10 ⁵ Ω/sq and density of 0.085) were formed. g/cm ³ ).

Experimental example 8

Except using 80 wt.% polylactic acid (melt flow index of 4.3), 20 wt.% of polybutylene adipate terephthalate (melt flow index of 18), and 3 phr of carbon nanotubes In addition, in the same manner as in Experimental Example 1, a biomass resin composite (surface impedance of 10 ⁶ Ω/sq to 10 ⁷ Ω/sq, density of 1.257 g/cm ³ ) and a biomass foam material (surface impedance of 10 6 Ω/sq to 10 7 Ω/sq) were formed. 10 ⁶ Ω/sq to 10 ⁷ Ω/sq with a density of 0.064 g/cm ³ ).

Comparative example 1

A green resin composite ( Surface impedance is 10 ⁷ Ω/sq to 10 ⁸ Ω/sq, density is 1.169 g/cm ³ ) and biofoamed material (surface impedance is 10 ¹² Ω/sq, density is 0.027 g/cm ³ ).

Comparative example 2

A green resin composite ( Surface impedance 10 ⁶ Ω/sq to 10 ⁷ Ω/sq, density 1.179 g/cm ³ ) and biofoamed material (surface impedance 10 ⁷ Ω/sq to 10 ⁹ Ω/sq, density 0.023 g/ cm ³ ).

It can be seen from Experimental Example 1 to Experimental Example 8, Comparative Example 1 and Comparative Example 2 that when the green resin composite contains a toughening agent, the antistatic agent can exist at the interface between the matrix and the toughening agent and/or or present in the toughening agent and distributed in a continuous phase, so that after the foaming reaction is performed to form the biofoamed material, the formed biofoamed material can have the same or even lower surface impedance, and thus Can have good antistatic properties.

Although the present disclosure has been disclosed above with examples, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in the technical field may make some changes and modifications without departing from the spirit and scope of the present disclosure. The scope of protection of the present disclosure shall be determined by the scope of the appended patent application.

none.

FIG. 1 is a transmission electron microscope (TEM) image of the biomass foam material of Experimental Example 2. FIG. FIG. 2 is a transmission electron microscope image of the biomass foam material of Experimental Example 3. FIG.

Claims (20)

A biomass resin composite comprising: substrate; a toughening agent, dispersed in the matrix; and an antistatic agent present at the interface between the matrix and the toughening agent and/or present in the toughening agent, The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40, and based on the total weight of the matrix and the toughening agent, the content of the antistatic agent is between 90:10 and 60:40. Between 1% and 10%. The biomass resin composite of claim 1, wherein the matrix comprises polylactic acid. The biomass resin composite of claim 1, wherein the toughening agent comprises polycaprolactone, polybutylene succinate, polybutylene adipate terephthalate, or a combination thereof. The biomass resin composite of claim 1, wherein the antistatic agent comprises carbon black, carbon nanotubes, graphene, or a combination thereof. The green resin composite of claim 1, wherein the matrix has a melt flow index between 2 g/10 min@190 °C and 10 g/10 min@190 °C, and the toughened The melt flow index of the agent is between 15 g/10 min@190 °C and 120 g/10 min@190 °C. The green resin composite according to claim 1, wherein the content of the antistatic agent is between 1% and 5% based on the total weight of the matrix and the toughening agent. A biomass foaming material, comprising a biomass resin composite and a foamed product of the biomass resin composite, wherein the biomass resin composite comprises: substrate; a toughening agent, dispersed in the matrix; and an antistatic agent present at the interface between the matrix and the toughening agent and/or present in the toughening agent, The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40, and based on the total weight of the matrix and the toughening agent, the content of the antistatic agent is between 90:10 and 60:40. Between 1% and 10%. The biomass foam material of claim 7, wherein the matrix comprises polylactic acid. The biomass foam material of claim 7, wherein the toughening agent comprises polycaprolactone, polybutylene succinate, polybutylene adipate terephthalate, or a combination thereof. The biomass foam material according to claim 7, wherein the antistatic agent comprises carbon black, carbon nanotubes, graphene or a combination thereof. The biomass foam material of claim 7, wherein the matrix has a melt flow index between 2 g/10 min@190 °C and 10 g/10 min@190 °C, and the toughened The melt flow index of the agent is between 15 g/10 min@190 °C and 120 g/10 min@190 °C. The biomass foam material according to claim 7, wherein the content of the antistatic agent is between 1% and 5% based on the total weight of the matrix and the toughening agent. The biomass foam material of claim 7, wherein the surface impedance of the biomass foam material is between 10 ⁴ Ω/sq to 10 ⁷ Ω/sq. The biomass foam material of claim 7, wherein the density of the biomass foam material is between 0.02 g/cm ³ to 0.2 g/cm ³ . A biomass resin composition, comprising: substrate; toughening agents; and antistatic agent, The weight ratio of the matrix to the toughening agent is between 90:10 and 60:40, and based on the total weight of the matrix and the toughening agent, the content of the antistatic agent is between 90:10 and 60:40. Between 1% and 10%. The biomass resin composition of claim 15, wherein the matrix comprises polylactic acid. The biomass resin composition of claim 15, wherein the toughening agent comprises polycaprolactone, polybutylene succinate, polybutylene adipate terephthalate, or a combination thereof. The biomass resin composition of claim 15, wherein the antistatic agent comprises carbon black, carbon nanotubes, graphene, or a combination thereof. The green resin composition of claim 15, wherein the matrix has a melt flow index between 2 g/10 min@190 °C and 10 g/10 min@190 °C, and the toughened The melt flow index of the agent is between 15 g/10 min@190 °C and 120 g/10 min@190 °C. The biomass resin composition according to claim 15, wherein the content of the antistatic agent is between 1% and 5% based on the total weight of the matrix and the toughening agent.

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