TWI823802B - Antibacterial and antifungal polyester laminated structure - Google Patents

Abstract

An antibacterial and antifungal polyester laminated structure includes a supporting base layer and an antibacterial and antifungal layer. The supporting base layer is formed of a polyester material, and the supporting base layer enables the entire polyester laminated structure to have an impact-strength of not less than 20 kg-cm/cm. The antibacterial and antifungal layer is formed of an antibacterial and antifungal polyester material, and the antibacterial and antifungal polyester material includes antibacterial and antifungal additives. The antibacterial and antifungal additives include glass beads, which are dispersed in the antibacterial and antifungal layer. Among them, an outer surface of each glass bead is distributed with nano silver particles, and the antibacterial and antifungal additives enable the antibacterial and antifungal layer to have abilities of antibacterial and antifungal.

Description

Antibacterial and mildew resistant polyester laminated construction

The invention relates to a laminated structure, in particular to an antibacterial and mildew-proof polyester laminated structure.

Based on market demand, products such as suitcases, food trays, and frozen trays are beginning to require antibacterial and mildew-proof capabilities. In order to make the material surface antibacterial and mildewproof, most of the existing technologies use coating or spraying methods to achieve this. Although the use of these methods can make the material surface have antibacterial and antifungal capabilities, the antibacterial and antifungal effects on the surface of these materials cannot be maintained for too long. Furthermore, the types of antibacterial and mildew-resistant bacteria corresponding to the surface of these materials are limited.

In addition, existing technology also uses membrane materials with antibacterial and anti-mildew capabilities to be attached to sheets such as ABS, PC, PP, etc. However, using the attachment method will make the material cost too high, and the entire material is not composed of a single material. Therefore, It will cause the problem that the materials are not easy to recycle.

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 an antibacterial and mildew-proof polyester laminated structure 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 an antibacterial and mildewproof polyester laminated structure, which includes: a main structural support layer with two side surfaces located on opposite sides; wherein , the main structural support layer is formed of an impact-resistant polyester material, and the main structural support layer enables the entire polyester laminated structure to have an impact-resistant strength of not less than 20 kg-cm/cm; and Two antibacterial and antifungal functional layers are respectively formed on the two side surfaces of the main structural support layer; wherein each of the antibacterial and antifungal functional layers is formed of an antibacterial and antifungal polyester material, And the antibacterial and antifungal polyester material contains an antibacterial and antifungal additive. The antibacterial and antifungal additive includes a plurality of glass beads. The plurality of glass beads are dispersed in the antibacterial and antifungal functional layer, each of which A plurality of silver nanoparticles are distributed on the outer surface of the glass beads, and the antibacterial and antifungal additive makes the antibacterial and antifungal functional layer have antibacterial and antifungal capabilities.

Preferably, the main structural support layer and the two antibacterial and antifungal functional layers are formed into an antibacterial and antifungal polyester sheet material with a sandwich structure by co-extrusion; wherein, the The thickness of the main structural support layer is greater than the thickness of each of the antibacterial and anti-mildew functional layers, the thickness of the main structural support layer is between 80 microns and 4,000 microns, and all of the anti-bacterial and anti-mildew functional layers are The thickness is between 10 microns and 200 microns.

Preferably, in the main structure support layer, the impact-resistant polyester material includes: a polyester resin base material; a toughening agent dispersed in the polyester resin base material; wherein the toughening agent The toughening agent is polyolefin elastomer (POE); and a compatibilizer is dispersed in the polyester resin base material, and the compatibilizer is configured to assist in improving the toughening agent and the polyester resin. Compatibility between substrates; wherein the compatibilizer is configured to assist the toughening agent to be dispersed into the polyester resin substrate with a particle size between 0.5 microns and 1.5 microns to Such that the impact-resistant polyester material has the impact-resistant strength of not less than 20 kg-cm/cm.

Preferably, in the main structure support layer, the compatibilizer is polyolefin elastomer grafted glycidyl methacrylate (POE-g-GMA) and polyolefin elastomer grafted maleic anhydride (POE-g-GMA). g-MAH) at least one of them.

Preferably, based on the total weight of the impact-resistant polyester material being 100 wt.%, the content range of the polyester resin base material is between 70 wt.% and 95 wt.%, and the toughening agent The content range is between 5 wt.% and 15 wt.%, and the content range of the compatibilizer is between 2 wt.% and 15 wt.%; wherein, the toughening agent The content range is not less than the content range of the compatibilizer, and the weight ratio range of the toughening agent to the compatibilizer is between 1:1 and 4:1.

Preferably, the molecular structure of the toughening agent is all polyolefin elastomer (POE), and the compatibilizer is polyolefin elastomer grafted glycidyl methacrylate (POE-g-GMA); wherein, The molecular structure of the compatibilizer has a main chain and side chains melt-grafted with the main chain. The main chain is polyolefin elastomer (POE), and the side chain is glycidyl methacrylate ( GMA); wherein, the glycidyl methacrylate can produce a ring cleavage during a mixing process, and the epoxy group in the glycidyl methacrylate can react after the ring-opening reaction. Chemically reacts with the ester group in the molecular structure of the polyester resin base material. This reaction is the key to improving material compatibility.

Preferably, in each of the antibacterial and antifungal functional layers, the antibacterial and antifungal polyester material includes: a polyester resin base material; and a plurality of functional polyester masterbatches, and a plurality of the functional polyester masterbatches. The ester masterbatch is dispersed in the polyester resin base material by melt extrusion molding; wherein each functional polyester masterbatch includes: a polyester resin matrix and the antibacterial and antifungal additive, and A plurality of the glass beads of the antibacterial and antifungal additive are dispersed in the polyester resin matrix.

Preferably, based on the total weight of the antibacterial and mildewproof polyester material being 100 wt.%, the content of the polyester resin base material ranges from 80 wt.% to 98 wt.%, and a plurality of the functions The content range of the functional polyester masterbatch is between 2 wt.% and 20 wt.%; wherein, in each of the functional polyester masterbatch, the polyester resin matrix and the antibacterial and antifungal additive are The weight ratio range is between 70~99:1~30.

Preferably, the antibacterial and antifungal polyester laminated structure can be formed into an extended polyester material through an extension molding process; wherein, in each of the antibacterial and antifungal functional layers, among the plurality of glass beads At least part of the glass beads are distributed on the surface layer of the antibacterial and antifungal functional layer, thereby exposing at least part of the plurality of silver nanoparticles to the external environment, and making the antibacterial The anti-mildew functional layer has the anti-bacterial and anti-mildew capability.

Preferably, the polyester resin matrix is polyethylene terephthalate, and in each of the functional polyester masterbatch, the polyester resin matrix is polyethylene terephthalate; Wherein, the polyester resin substrate has a first refractive index, the polyester resin matrix has a second refractive index, and the glass beads have a third refractive index; wherein the first refractive index is Between 1.55 and 1.60, the second refractive index is between 95% and 105% of the first refractive index, and the third refractive index is between 95% of the first refractive index. % to 105%.

Preferably, in each of the glass beads, the matrix material of the glass beads is soluble glass powder, the particle size of the glass beads is no more than 10 microns, and the density of the glass beads is between 2 g/ cm ³ to 3 g/cm ³ , and the heat-resistant temperature of the glass beads is not less than 500 ^o C.

Preferably, the antibacterial and antifungal additive has antibacterial ability against the following bacterial species, including: Escherichia coli, Staphylococcus aureus, Pneumoniae, Salmonella, Pseudomonas aeruginosa, and drug-resistant Staphylococcus aureus; wherein, The antibacterial and anti-mold additive has anti-mold ability against the following types of mold, including: Kojima nigra, Penicillium tetris, Chaetomium globosum, Scopus viridis, and Aureobasidium pullulans.

Preferably, the matrix material of the main structural support layer is polyethylene terephthalate, and the matrix material of each of the antibacterial and antifungal functional layers is polyethylene terephthalate.

In order to solve the above technical problems, another technical solution adopted by the present invention is to provide an antibacterial and mildewproof polyester laminated structure, which includes: a main structural support layer with two side surfaces located on opposite sides; wherein , the main structural support layer is formed of an impact-resistant polyester material, and the main structural support layer enables the entire polyester laminated structure to have an impact-resistant strength of not less than 20 kg-cm/cm; and An antibacterial and anti-mildew functional layer is formed on one of the side surfaces of the main structural support layer; wherein the anti-bacterial and anti-mildew functional layer is formed of an anti-bacterial and anti-mildew polyester material, and the anti-bacterial and anti-mildew functional layer The anti-mildew polyester material contains an anti-bacterial and anti-mildew additive. The anti-bacterial and anti-mildew additive contains a plurality of glass beads. The plurality of glass beads are dispersed in the anti-bacterial and anti-mildew functional layer. Each of the glass beads has A plurality of silver nanoparticles are distributed on the outer surface, and the antibacterial and antifungal additive makes the antibacterial and antifungal functional layer have antibacterial and antifungal capabilities.

One of the beneficial effects of the present invention is that the antibacterial and antifungal polyester laminated structure provided by the present invention can be achieved by "the surface layer of the polyester laminated structure is an antibacterial and antifungal functional layer with antibacterial and antifungal capabilities, and the polyester The inner layer of the laminated structure is a supportive main structural support layer" and "the main structural support layer is formed of impact-resistant polyester material, and the main structural support layer can make the overall polyester laminated structure "Having an impact resistance strength of not less than 20 kg-cm/cm" and "Each of the antibacterial and anti-mildew functional layers is formed of an anti-bacterial and anti-mildew polyester material, and the anti-bacterial and anti-mildew polyester material can make polyester The technical solution is that the surface layer of the laminated structure E has an antibacterial and anti-mildew effect, so that the anti-bacterial and anti-mildew polyester laminated structure can be applied to products with anti-bacterial and anti-mildew requirements and impact resistance requirements, such as luggage, food Serving dishes, and frozen serving dishes...etc.

In order to further understand the features and technical content of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and illustration and are 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. In addition, the drawings of the present invention are only simple schematic illustrations and are not depictions based on actual dimensions, as is stated in advance. 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.

[First Embodiment]

Referring to FIGS. 1 to 3 , a first embodiment of the present invention provides an antibacterial and antifungal polyester laminated structure E (antibacterial and antifungal polyester laminated structure). The antibacterial and antifungal polyester laminate structure E may be, for example, a sandwich structure (A-B-A) formed by co-extrusion.

One object of the present invention is that the two surface layers of the sandwich structure are antibacterial and antifungal functional layers A with antibacterial and antifungal capabilities, and the middle layer of the sandwich structure is a supportive main structure support layer B. Furthermore, the antibacterial and mildewproof polyester laminated structure E can be used directly, or can be formed into an extended molding process through a vacuum forming process or a blister molding process. polyester sheet material.

One object of the present invention is that the matrix material of each layer of the antibacterial and mildewproof polyester laminated structure E is polyester material (such as PET). That is to say, the matrix materials of all layers of the antibacterial and antifungal polyester laminated structure E are made of the same material. Accordingly, the antibacterial and mildewproof polyester laminated structure E can be recycled and discarded relatively easily. Furthermore, the antibacterial and antifungal polyester laminated structure E has the characteristics of antibacterial and antifungal ability and high impact strength. Therefore, the antibacterial and anti-mold polyester laminated structure E can be applied to products with anti-bacterial and anti-mold requirements and impact resistance requirements, such as suitcases, food trays, frozen trays, etc.

Please continue to refer to Figures 1 to 3. More specifically, the antibacterial and antifungal polyester laminated structure E includes a main structural support layer B and two antibacterial and antifungal functional layers A. The main structure support layer B has two side surfaces (not numbered in the figure) located on opposite sides, and the two antibacterial and antifungal functional layers A are respectively formed on the two side surfaces of the main structure support layer B.

The main structure support layer B is formed of an impact resistant polyester material 100, and the main structure support layer B can make the entire polyester laminated structure E have a weight of not less than 20 kg-cm /cm impact strength. Furthermore, each of the antibacterial and antifungal functional layers A is formed of an antibacterial and antifungal polyester material 200, and the antibacterial and antifungal polyester material 200 can make the polyester laminate structure Both surfaces of E have antibacterial and mildew-proof effects.

In terms of thickness range, the thickness of the main structure support layer B is greater than the thickness of each of the antibacterial and anti-mildew functional layers A. The thickness of the main structure support layer B is between 80 microns and 4,000 microns, and each The thickness of each of the antibacterial and antifungal functional layers A is between 10 microns and 200 microns. To put it another way, the thickness of the main structural support layer B is between 2 times and 400 times the thickness of each of the antibacterial and antifungal functional layers A, but the present invention is not limited thereto. The material characteristics of the impact-resistant polyester material 100 of the main structural support layer B and the material characteristics of the antibacterial and antifungal polyester material 200 of the antibacterial and antifungal functional layer A will be described in sequence below.

[Impact-resistant polyester material]

Please refer to Figure 2. The impact-resistant polyester material 100 of the main structural support layer B includes a polyester resin base material 101, a toughening agent 102 (or impact-resistant modifier), and a compatibilizer. (Figure not labeled).

One of the purposes of the present invention is to improve the compatibility between the toughening agent 102 and the polyester resin base material 101 and to improve the dispersion of the toughening agent 102 in the polyester resin base material 101 . Thereby, the impact-resistant polyester material 100 according to the embodiment of the present invention can have relatively high impact strength. For example, the impact strength of general polyester materials is not greater than 5kg-cm/cm. In contrast, the impact resistance strength of the impact-resistant polyester material 100 according to the embodiment of the present invention can be greatly improved to no less than 20 kg-cm/cm, and preferably between 28 kg-cm/cm and 50 kg-cm/cm. between.

In this embodiment, the polyester resin base material 101 is the matrix material of the impact-resistant polyester material 100 . The polyester resin base material 101 is a high molecular polymer obtained by condensation polymerization of dibasic acid and dihydric alcohol or its derivatives. That is to say, the polyester resin base material 101 is polyester material. Preferably, the polyester material is polyethylene terephthalate (PET), but the invention is not limited thereto.

In terms of content range, based on the total weight of the impact-resistant polyester material 100, the content range of the polyester resin base material 101 is preferably between 70 wt.% and 95 wt.%, and particularly preferably between 70 wt.% and 95 wt.%. Between 70 wt.% and 90 wt.%. It should be noted that the term "substrate" or "matrix material" used herein refers to a material that accounts for at least half of the composition.

Please continue to refer to Figure 2. In order to make the impact-resistant polyester material 100 have high impact-resistant strength, the impact-resistant polyester material 100 is added with the toughening agent 102 (or impact-resistant modifier). ), and the toughening agent 102 is dispersed in the polyester resin base material 101. In terms of material type, the toughening agent is polyolefin elastomer (POE), or polyolefin thermoplastic elastomer (polyolefin thermoplastic elastomer). The toughening agent 102 dispersed in the polyester resin base material 101 can be used to improve the impact strength of the polyester material 100 .

In terms of content range, based on the total weight of the impact-resistant polyester material 100, the content range of the toughening agent 102 is preferably between 5 wt.% and 15 wt.%, and particularly preferably between 7 wt.% and 7 wt.%. Between wt.% and 10 wt.%.

According to the above configuration, the impact-resistant polyester material 100 can have high impact-resistant strength through the addition of the toughening agent 102 . If the content of the toughening agent 102 is lower than the lower limit of the above content range, the impact-resistant polyester material 100 will not have sufficient impact-resistant strength and cannot be applied to products with high impact-resistant requirements. On the contrary, if the content of the toughening agent 102 is higher than the upper limit of the above content range, the toughening agent 102 will not be uniformly dispersed in the polyester resin base material 101, and aggregation or precipitation will occur, thereby causing It may affect the forming effect of the final product and may also affect the impact strength.

From another perspective, one of the objectives of the present invention is to improve the impact strength of polyester materials so that the polyester materials have high impact strength, high rigidity, and low material cost at the same time. In order to achieve the above object, the impact-resistant polyester material 100 according to the embodiment of the present invention uses polyolefin elastomer (POE) as a toughening agent (or impact-resistant modifier).

Compared with acrylic elastomer or polyester elastomer, polyolefin elastomer has better intrinsic toughness and lower material price. Therefore, polyolefin elastomer is used to improve the impact strength of polyester materials. advantages. However, polyolefin elastomers do not have good compatibility with polyester materials. If the polyolefin elastomer is simply mixed with the polyester material using the additive modification method, the polyolefin elastomer will easily agglomerate, and the impact strength of the polyester material will not be significantly improved.

Accordingly, the key technology of the present invention is to adjust the dispersion particle size of the polyolefin elastomer in the polyester material through compatibility modification, viscosity matching, and mixing and dispersion technology between the polyolefin elastomer and the polyester material. Up to between 0.5 micron and 1.5 micron, and preferably between 0.5 micron and 1.2 micron. Under this dispersed particle size, the impact-resistant polyester material 100 of the embodiment of the present invention can achieve high impact resistance.

More specifically, the compatibilizer (not shown) is dispersed in the polyester resin base material 101 . The compatibilizer is configured to assist in improving the compatibility between the toughening agent 102 and the polyester resin substrate 101 .

In terms of material type, the compatibilizer is a polyolefin elastomer compatibilizer. Specifically, the compatibilizer is polyolefin elastomer grafted with glycidyl methacrylate (POE-g-GMA) and polyolefin elastomer grafted maleic anhydride (polyolefin elastomer grafted). with maleic anhydride, POE-g-MAH) at least one of them. Preferably, the compatibilizer is polyolefin elastomer grafted glycidyl methacrylate (POE-g-GMA).

Further, the compatibilizer is configured to assist the toughening agent 102 to be dispersed into the polyester resin base material 101 with a particle size between 0.5 microns and 1.5 microns, so that the impact resistance The polyester material 100 has an impact resistance strength of not less than 20 kg-cm/cm. That is to say, the compatibilizer can effectively improve the compatibility and dispersion of the toughening agent 102 in the polyester resin base material 101, so that the toughening agent 102 can be produced with a smaller particle size. The size is dispersed into the polyester resin base material 101 and is less likely to agglomerate.

In a preferred embodiment of the present invention, the toughening agent 102 is dispersed into the polyester resin base material 101 with a particle size between 0.5 microns and 1.2 microns, and the impact-resistant polyester The material 100 has said impact strength ranging from 28 kg-cm/cm to 50 kg-cm/cm, and particularly preferably from 30 kg-cm/cm to 45 kg-cm/cm.

In terms of content range, based on the total weight of the impact-resistant polyester material 100, the content range of the compatibilizer is preferably between 2 wt.% and 15 wt.%, and particularly preferably between 2 wt. .% to 5 wt.%.

According to the above configuration, the compatibilizer can well assist the toughening agent 102 to be dispersed into the polyester resin base material 101 with a smaller particle size. If the content of the compatibilizer is lower than the lower limit of the above content range, the compatibilizer cannot well assist the toughening agent 102 to be dispersed into the polyester resin base material 101 with a smaller particle size. , so the auxiliary effect provided by the compatibilizer is not good. On the contrary, if the content of the compatibilizer is higher than the upper limit of the above content range, the compatibilizer may affect the forming effect of the polyester material.

Furthermore, the content range of the toughening agent 102 has a matching relationship with the content range of the compatibilizer. Specifically, the content range of the toughening agent 102 is not less than the content range of the compatibilizer. Furthermore, a weight ratio range between the toughening agent 102 and the compatibilizer is preferably between 1:1 and 4:1, and particularly preferably between 1:1 and 2:1.

In one embodiment of the present invention, the molecular structure of the toughening agent 102 is entirely polyolefin elastomer (POE). The molecular structure of the compatibilizer has a main chain and a side chain, and the main chain is polyolefin elastomer (POE). Thereby, the compatibilizer can have excellent compatibility with the toughening agent 102 through its main chain (because the molecular structure is the same).

In one embodiment of the present invention, the compatibilizer is further limited to polyolefin elastomer grafted glycidyl methacrylate (POE-g-GMA). The molecular structure of the compatibilizer has a main chain and side chains melt-grafted with the main chain. The main chain is polyolefin elastomer (POE), and the side chain is glycidyl methacrylate ( GMA).

The glycidyl methacrylate can produce a ring cleavage during a mixing process, and the epoxy group (epoxy) in the glycidyl methacrylate can react with the ring cleavage after the ring-opening reaction. The ester group in the molecular structure of the polyester resin base material undergoes a chemical reaction, so that the toughening agent 102 is more uniformly dispersed in the polyester resin base material 101 .

In one embodiment of the present invention, in order to improve the dispersion of the toughening agent 102 (POE) in the polyester resin base material 101, the impact-resistant polyester material 100 can be extruded and granulated, for example. It is formed into a polyester masterbatch so that the toughening agent 102 is dispersed in the polyester material for the first time. The polyester masterbatch is then molded into a molded product such as an injection part or an extrusion part through injection molding or extrusion molding, so that the toughening agent 102 is dispersed in the polyester material for a second time.

In one embodiment of the present invention, in order to improve the dispersion and compatibility of the toughening agent 102 (POE) in the polyester resin base material 101, the melt index and toughening of the polyester resin base material 101 are The melt index of agent 102 has a matching relationship.

Specifically, the polyester resin base material 101 (PET) has a first melt index, and the toughening agent 102 (POE) has a second melt index. Wherein, the first melt index of the polyester resin base material 101 is between 55 g/10min and 65 g/10min, and the second melt index of the toughening agent 102 is between 55 g/10min and 65 g/10min. The first melt index of the polyester resin base material 101 is between 75% and 125%, and preferably between 80% and 120%. For example, the first melt index of the polyester resin base material 101 is about 60 g/10min, and the second melt index of the toughening agent 102 (POE) is about 50 g/10min.

It should be noted that the "melt flow index" (English: melt flow index, MI) referred to in this article can also be called melt flow rate (MFR). The melt index refers to the weight of the polymer melt passing through the standard die (2.095 mm) every ten minutes under a certain temperature and a certain load.

In one embodiment of the present invention, the polyester resin base material 101 is a continuous phase, and the toughening agent 102 is a dispersed phase dispersed in the continuous phase. Wherein, the dispersed phase and the continuous phase interact with each other so that the material surface of the impact-resistant polyester material forms an island structure.

It is worth mentioning that the above-mentioned "island structure" refers to the poor compatibility between the two polymers (polyester resin base material 101 and toughening agent 102). Two polymers are blended with each other to form a heterogeneous system. The dispersed phase is dispersed in the continuous phase, just like small islands dispersed in the ocean. The properties of the polymer can be improved by utilizing the two-phase interaction mechanism of the sea-island structure.

[Antibacterial and mildew-proof polyester material]

Please refer to FIG. 3 . In each of the antibacterial and antifungal functional layers A, the antibacterial and antifungal polyester material 200 has good antibacterial and antifungal capabilities. The antibacterial and antifungal polyester material 200 can still maintain a certain antibacterial and antifungal effect after being used for a period of time, and the antibacterial and antifungal ability of the antibacterial and antifungal polyester material 200 can correspond to more types of bacteria and mold types. .

In order to achieve the above purpose, the antibacterial and mildewproof polyester material 200 of this embodiment includes a polyester resin base material 201 (polyester resin base material) and a plurality of functional polyester masterbatches 202 (functional polyester master-batches). The functional polyester masterbatch 202 is dispersed in the polyester resin base material 201 through melt extrusion molding. Among them, the antibacterial and antifungal polyester material 200 of this embodiment can have antibacterial and antifungal capabilities through the introduction of the functional polyester masterbatch 202 .

More specifically, each functional polyester masterbatch 202 includes: a polyester resin matrix material 2021 and an antibacterial and antifungal additive 2022. Wherein, the antibacterial and anti-mildew additive 2022 includes a plurality of glass beads 2022a (glass beads). The plurality of glass beads 2022a are dispersed in the polyester resin matrix 2021, and the outer surface of each glass bead 2022a is distributed There are multiple nanosilver particles 2022b (nano silver particles). Thereby, the antibacterial and antifungal polyester material 200 of this embodiment can have the abilities of antibacterial and antifungal through the introduction of the functional polyester masterbatch 202 .

In more detail, since the plurality of silver nanoparticles 2022b are distributed on the outer surface of the glass bead 2022a, and the plurality of silver nanoparticles 2022b are dispersed on the outer surface of the glass bead 2022a, the plurality of silver nanoparticles 2022b are dispersed on the outer surface of the glass bead 2022a. The silver nanoparticles 2022b will not agglomerate with each other, and a plurality of the silver nanoparticles 2022b can be dispersed in nanoscale sizes on the outer surface of the glass beads 2022a, thereby providing the antibacterial and antifungal capabilities.

It is worth mentioning that the glass beads 2022a and the plurality of silver nanoparticles 2022b distributed on the outer surface thereof are dispersed in the polyester resin base material 201 through the functional polyester masterbatch 202, so that the antibacterial and antibacterial properties are The moldy polyester material 200 contains a plurality of silver nanoparticles 2022b dispersed in nanoscale sizes, so that the antibacterial and moldproof polyester material 200 has antibacterial and moldproofing capabilities.

In terms of content range, based on the total weight of the antibacterial and mildewproof polyester material being 100 wt.%, the content range of the polyester resin base material 201 is preferably between 80 wt.% and 98 wt.%. And particularly preferably, it is between 90 wt.% and 98 wt.%. Furthermore, the content range of the plurality of functional polyester masterbatches 202 is preferably between 2 wt.% and 20 wt.%, and particularly preferably between 2 wt.% and 10 wt.%. .

Furthermore, in each of the functional polyester masterbatch 202, the weight proportion range of the polyester resin matrix 2021 and the antibacterial and antifungal additive 2022 (including glass beads 2022a and nanosilver particles 2022b) is preferably It is between 70~99:1~30, and particularly preferably between 85~95:5~15. Overall, the content range of the plurality of silver nanoparticles 2022b in the antibacterial and antifungal polyester material 200 is preferably between 0.1 wt.% and 5.0 wt.%, and particularly preferably between 0.2 wt. % to 2.0 wt.%.

According to the above configuration, the antibacterial and antifungal additives 2022 in the functional polyester masterbatch 202 can provide sufficient antibacterial and antifungal effects in the polyester material. If the content range of the antibacterial and antifungal additive 2022 is lower than the lower limit of the above content range, the concentration of the silver nanoparticles 22 may be insufficient, thereby failing to provide sufficient antibacterial and antifungal effects. On the contrary, if the content range of the antibacterial and antifungal additive 2022 is higher than the upper limit of the above content range, the concentration of the glass beads 2022a may be too high to be evenly dispersed in the polyester resin base material 201 , and excessive glass beads 2022a may affect the molding effect of the polyester material.

In one embodiment of the present invention, in each of the glass beads 2022a, a plurality of silver nanoparticles 2022b are distributed on the outer surface of the glass beads 2022a through physical adsorption. However, this The invention is not limited thereto.

It is worth mentioning that since the silver nanoparticles 2022b use glass beads 2022a as carriers and are dispersed on the outer surface of the glass beads 2022a in nanoscale sizes, the silver nanoparticles 2022b are not easily The phenomenon of agglomeration occurs. Furthermore, when the functional polyester masterbatch 202 is dispersed in the polyester resin base material 201 by melt extrusion molding, the glass beads 2022a may break. However, most of the silver nanoparticles 2022b will still be dispersed in nanoscale sizes and adsorbed on the outer surface of the glass beads 2022a without agglomeration, thereby providing sufficient antibacterial and anti-mildew capabilities.

In one embodiment of the present invention, in the antibacterial and mildewproof polyester material 200, at least part of the glass beads 2022a among the plurality of glass beads 2022a are distributed on the surface layer of the polyester material 100, so that a plurality of the glass beads 2022a are distributed on the surface of the polyester material 100. At least part of the silver nanoparticles 2022b is exposed to the external environment, so that the polyester material 100 has antibacterial and antifungal capabilities.

In one embodiment of the present invention, the antibacterial and antifungal polyester material 200 can be extended to form an extended polyester material. It is worth mentioning that after the antibacterial and mildewproof polyester material 200 is extended, the glass beads 2022a distributed on the surface of the polyester material 100 can protrude further from the surface of the polyester material 100 (as shown in Figure 3 ), thereby, the number of silver nanoparticles 2022b exposed to the external environment can be increased, thereby making the antibacterial and antifungal ability of the polyester material 200 more significant.

In terms of material selection, the polyester resin base material 201 is the matrix material of the antibacterial and mildewproof polyester material 200, and the polyester resin base material 201 is made of dibasic acid and diol or their derivatives through condensation polymerization. obtained by reaction. Furthermore, the polyester resin matrix 2021 in the functional polyester masterbatch 202 is also obtained by condensation polymerization of dibasic acid and diol or its derivatives.

It is worth mentioning that, as shown in Figure 3, the material of the polyester resin base material 201 and the polyester resin matrix 2021 are approximately the same. Therefore, there is a gap between the polyester resin base material 201 and the polyester resin matrix 2021. Good compatibility without obvious boundaries.

In one embodiment of the present invention, in order to maintain high transparency and low haze of the antibacterial and mildewproof polyester material 200, the refractive index of different materials has a matching relationship.

For example, the polyester resin substrate 201 has a first refractive index, the polyester resin matrix 2021 has a second refractive index, and the glass beads 2022a have a third refractive index. Wherein, the first refractive index is preferably between 1.55 and 1.60, and particularly preferably between 1.57 and 1.59. Furthermore, the second refractive index is preferably between 95% and 105% of the first refractive index, and the third refractive index is preferably between 95% and 105 of the first refractive index. between %.

According to the above matching relationship of the refractive index of different materials, the antibacterial and mildewproof polyester material 200 can have high transparency and low haze.

For example, the antibacterial and antifungal polyester material 200 preferably has a visible light transmittance of not less than 80%, and particularly preferably not less than 90%. The antibacterial and antifungal polyester material 200 preferably has a haze of no more than 5%, and particularly preferably no more than 3%.

In one embodiment of the present invention, the polyester resin matrix 2021 in each functional polyester masterbatch 202 is polyethylene terephthalate (PET) with low crystallinity, and the polyester The crystallinity of the resin substrate is between 5% and 15%.

It is worth mentioning that in the existing technology, antibacterial and anti-mildew treatment on the material surface is carried out by coating or spraying methods, which can make the material have excellent transparency. However, such products suffer from poor durability and limited antibacterial types. Furthermore, the current masterbatch carriers for the internal addition method are mostly polypropylene (PP) and polybutylene terephthalate (PBT), which have poor compatibility with polyester materials (PET), thus making the product Poor transparency and extensibility.

Compared with the existing technology, the antibacterial and antifungal polyester material 200 in the embodiment of the present invention uses polyethylene terephthalate (PET) with low crystallinity as the masterbatch carrier. The functional polyester masterbatch 202 can disperse the glass beads 2022a adsorbed with the silver nanoparticles 2022b through a twin-screw extruder, and introduce PET polyester materials (such as : polyester resin base material 201), so that the antibacterial and antifungal polyester material 200 maintains excellent antibacterial and antifungal capabilities, visible light transmittance, and extensibility at the same time.

In an embodiment of the present invention, the specifications of the glass beads 2022a have a preferred range. For example, the matrix material of the glass beads 2022a is soluble glass powder, and the particle size of the glass beads is no more than 10 microns (preferably between 3 microns and 10 microns). The density of the glass beads is between 2 g/cm ³ and 3 g/cm ³ (preferably between 2.3 g/cm ³ and 2.8 g/cm ³ ), and the heat-resistant temperature of the glass beads is not less than 500 ^° C.

According to the above configuration, the glass beads 2022a can absorb a sufficient amount of silver nanoparticles 2022b and be dispersed into the polyester resin matrix 2021. The glass beads 2022a can withstand the high temperature and high pressure of the twin-screw extrusion process, and can still absorb a sufficient amount of silver nanoparticles 2022b, so that the antibacterial and antifungal polyester material 200 has antibacterial and antifungal capabilities.

In terms of antibacterial and antifungal ability, the antibacterial and antifungal additive has antibacterial ability against the following bacteria, including: Escherichia coli, Staphylococcus aureus, Pneumoniae, Salmonella ( Salmonella), Pseudomonas aeruginosa, and Methicillin-resistant staphylococcus aureus.

Furthermore, the antibacterial and anti-mold additives have anti-mold ability against the following molds, including: Aspergillus niger, Penicillium tetrapine, Chaetomium globosum, and green slime. Gliocladium virens, and Aureobasidium pullulans.

In terms of antibacterial testing, the antibacterial and mildew-proof polyester material 200 was tested against six types of bacteria, including Escherichia coli, Staphylococcus aureus, Pneumoniae, Salmonella, Pseudomonas aeruginosa, and drug-resistant Staphylococcus aureus, and all passed SGS determination (antibacterial The activity value R is greater than 2), which shows excellent antibacterial effect. In terms of anti-mold testing, the antibacterial and anti-mold polyester material 200 has passed SGS judgment (grade 0, no mold growth), which shows excellent anti-mold effect.

It is worth mentioning that in an unillustrated embodiment of the present invention, the antibacterial and antifungal additive is directly dispersed in the polyester resin base material. That is to say, the antibacterial and antifungal additive is not dispersed in the polyester resin base material through functional polyester masterbatch, but the antibacterial and antifungal additive is directly dispersed in the polyester resin base material. More specifically, the antibacterial and antifungal polyester material of this embodiment includes a polyester resin base material and an antibacterial and antifungal additive. The antibacterial and antifungal additive includes a plurality of glass beads dispersed in the polyester resin base material, and a plurality of silver nanoparticles are distributed on the outer surface of each glass bead. The polyester material has antibacterial and mildew-proof capabilities.

[Second Embodiment]

Please refer to Figure 4. The second embodiment of the present invention also provides an antibacterial and mildewproof polyester laminated structure E’. The antibacterial and mildewproof polyester laminated structure E’ of this embodiment is substantially the same as the above-mentioned first embodiment. The difference is that the antibacterial and mildewproof polyester laminated structure E' of this embodiment is a double-layered laminated structure rather than a sandwich structure.

Specifically, the antibacterial and antifungal polyester laminated structure E' of this embodiment includes a main structural support layer B and an antibacterial and antifungal functional layer A. The main structural support layer B has two side surfaces located on opposite sides. The antibacterial and antifungal functional layer A is formed on one of the side surfaces of the main structural support layer B.

The main structure support layer B is formed of an impact-resistant polyester material, and the main structure support layer B enables the entire polyester laminated structure E to have an impact-resistant strength of not less than 20 kg-cm/cm.

The antibacterial and anti-mildew functional layer A is formed of an anti-bacterial and anti-mildew polyester material, and the anti-bacterial and anti-mildew polyester material contains an anti-bacterial and anti-mildew additive. The anti-bacterial and anti-mildew additive contains a plurality of glass beads. Each of the glass beads is dispersed in the antibacterial and anti-mildew functional layer. A plurality of silver nanoparticles are distributed on the outer surface of each glass bead, and the anti-bacterial and anti-mildew additive makes the anti-bacterial and anti-mildew functional layer A has antibacterial and antifungal capabilities.

[Beneficial effects of the embodiment]

One of the beneficial effects of the present invention is that the antibacterial and antifungal polyester laminated structure provided by the present invention can be achieved by "the surface layer of the polyester laminated structure is an antibacterial and antifungal functional layer with antibacterial and antifungal capabilities, and the polyester The inner layer of the laminated structure is a supportive main structural support layer" and "the main structural support layer is formed of impact-resistant polyester material, and the main structural support layer can make the overall polyester laminated structure "Having an impact resistance strength of not less than 20kg-cm/cm" and "Each of the antibacterial and anti-mildew functional layers is formed of an anti-bacterial and anti-mildew polyester material, and the anti-bacterial and anti-mildew polyester material can make the polyester laminate The technical solution is that the surface layer of the layer structure E has an antibacterial and anti-mildew effect, so that the anti-bacterial and anti-mildew polyester laminated structure can be applied to products with anti-bacterial and anti-mildew requirements and impact resistance requirements, such as suitcases and food containers. plates, and frozen serving platters...etc.

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

E, E’: Antibacterial and mildew-proof polyester laminated structure A: Antibacterial and anti-mildew functional layer B: Main structural support layer 100: Impact-resistant polyester material 101:Polyester resin base material 102: Toughening agent 200: Antibacterial and mildew-proof polyester material 201:Polyester resin base material 202: Functional polyester masterbatch 2021:Polyester resin matrix 2022: Antibacterial and anti-mildew additives 2022a: Glass Beads 2022b: Silver nanoparticles

Figure 1 is a schematic diagram of an antibacterial and antifungal polyester laminate structure according to the first embodiment of the present invention.

FIG. 2 is a partial enlarged schematic diagram of area II in FIG. 1 .

FIG. 3 is a partially enlarged schematic diagram of area III in FIG. 1 .

Figure 4 is a schematic diagram of the antibacterial and mildewproof polyester laminate structure according to the second embodiment of the present invention.

200: Antibacterial and mildew-proof polyester material

201:Polyester resin base material

202: Functional polyester masterbatch

2021:Polyester resin matrix

2022: Antibacterial and anti-mildew additives

2022a: Glass Beads

2022b: Silver nanoparticles

Claims (10)

An antibacterial and mildewproof polyester laminated structure, which includes: A main structural support layer having two side surfaces located on opposite sides; wherein the main structural support layer is formed of an impact-resistant polyester material; wherein in the main structural support layer, the resistant The impact polyester material includes a polyester resin base material, a toughening agent and a compatibilizer; wherein the toughening agent is dispersed in the polyester resin base material and is polyolefin elastomer (POE), and The compatibilizer is dispersed in the polyester resin base material and is configured to assist in improving the compatibility between the toughening agent and the polyester resin base material; wherein, based on the impact-resistant polyester material The total weight is 100 wt.%, the content range of the polyester resin base material is between 70 wt.% and 95 wt.%, and the content range of the toughening agent is between 5 wt.% and 15 wt.%, and the compatibilizer content range is between 2 wt.% and 15 wt.%; and An antibacterial and anti-mildew functional layer is formed on one of the side surfaces of the main structural support layer; wherein the anti-bacterial and anti-mildew functional layer is formed of an anti-bacterial and anti-mildew polyester material, and the anti-bacterial and anti-mildew functional layer The anti-mildew polyester material contains an anti-bacterial and anti-mildew additive. The anti-bacterial and anti-mildew additive contains a plurality of glass beads. The plurality of glass beads are dispersed in the anti-bacterial and anti-mildew functional layer. Each of the glass beads has A plurality of silver nanoparticles are distributed on the outer surface, and the antibacterial and anti-mildew additive makes the anti-bacterial and anti-mildew functional layer have anti-bacterial and anti-mildew capabilities; wherein, in the anti-bacterial and anti-mildew functional layer, the anti-bacterial and anti-mildew polymer The ester material includes a polyester resin base material and a plurality of functional polyester masterbatches, and a plurality of the functional polyester masterbatch are dispersed in the polyester resin base material by melt extrusion molding; wherein , each of the functional polyester masterbatch includes: a polyester resin matrix and the antibacterial and antifungal additive, and a plurality of the glass beads of the antibacterial and antifungal additive are dispersed in the polyester resin matrix ; Wherein, based on the total weight of the antibacterial and mildewproof polyester material being 100 wt.%, the content range of the polyester resin base material is between 80 wt.% and 98 wt.%, and multiple of the functions The content range of the functional polyester masterbatch is between 2 wt.% and 20 wt.%; wherein, in each of the functional polyester masterbatch, the polyester resin matrix and the antibacterial and antifungal additive are The weight ratio range is between 70~99:1~30. The antibacterial and mildewproof polyester laminated structure as claimed in claim 1, wherein the main structural support layer and the antibacterial and mildewproof functional layer are formed into an antibacterial and mildewproof polyester by co-extrusion. Ester sheet material; wherein, the thickness of the main structure support layer is greater than the thickness of the antibacterial and antifungal functional layer, the thickness of the main structure support layer is between 80 microns and 4,000 microns, and the antibacterial and antibacterial functional layer The thickness of the mold functional layer is between 10 microns and 200 microns. The antibacterial and mildewproof polyester laminated structure as claimed in claim 1, wherein the compatibilizer is configured so that the toughening agent can be dispersed in the particle size between 0.5 microns and 1.5 microns. In polyester resin base material. The antibacterial and mildewproof polyester laminated structure according to claim 3, wherein in the main structure support layer, the compatibilizer is polyolefin elastomer grafted glycidyl methacrylate (POE-g- GMA) and polyolefin elastomer grafted maleic anhydride (POE-g-MAH). The antibacterial and mildewproof polyester laminated structure according to claim 3, wherein the content range of the toughening agent is not less than the content range of the compatibilizer, and the toughening agent is consistent with the content range of the compatibilizer. The weight ratio of compatibilizer ranges from 1:1 to 4:1. The antibacterial and mildewproof polyester laminated structure as claimed in claim 3, wherein the molecular structure of the toughening agent is all polyolefin elastomer (POE), and the compatibilizer is polyolefin elastomer grafted glycidyl acrylate (POE-g-GMA); wherein, the molecular structure of the compatibilizer has a main chain and a side chain melt-grafted with the main chain, and the main chain is a polyolefin elastomer (POE ), and the side chain is glycidyl methacrylate (GMA); wherein the glycidyl methacrylate can produce a ring cleavage during a mixing process, and the methacrylic acid shrinks The epoxy group in the glyceryl ester can chemically react with the ester group in the molecular structure of the polyester resin base material after the ring-opening reaction. The antibacterial and mildew-proof polyester laminated structure as claimed in claim 1, wherein the antibacterial and mildew-proof polyester laminated structure can be formed into an extended polyester material through an stretch molding process; wherein, in the antibacterial and mildew-proof polyester laminated structure In the anti-mildew functional layer, at least part of the glass beads among the plurality of glass beads are distributed on the surface layer of the anti-bacterial and anti-mildew functional layer, so that at least part of the nano-silver particles among the plurality of nano-silver particles The rice silver particles are exposed to the external environment and enable the antibacterial and antifungal functional layer to have the antibacterial and antifungal ability. The antibacterial and mildewproof polyester laminated structure according to claim 1, wherein the polyester resin base material is polyethylene terephthalate, and in each of the functional polyester masterbatch, The polyester resin matrix is polyethylene terephthalate; wherein the polyester resin matrix has a first refractive index, the polyester resin matrix has a second refractive index, and the glass beads have a third refractive index; wherein the first refractive index is between 1.55 and 1.60, the second refractive index is between 95% and 105% of the first refractive index, and the The third refractive index is between 95% and 105% of the first refractive index. The antibacterial and mildewproof polyester laminated structure as claimed in claim 1, wherein in each of the glass beads, the matrix material of the glass beads is soluble glass powder, and the particle size of the glass beads is no larger than 10 microns, the density of the glass beads is between 2 g/cm ³ and 3 g/cm ³ , and the heat-resistant temperature of the glass beads is not less than 500 ^° C. The antibacterial and antifungal polyester laminated structure according to claim 1, wherein the antibacterial and antifungal additive has antibacterial ability against the following bacterial species, including: Escherichia coli, Staphylococcus aureus, Pneumoniae, Salmonella, Pseudomonas aeruginosa, and drug-resistant Staphylococcus aureus; wherein, the antibacterial and antifungal additive can have antifungal ability against the following types of mold, including: Kojima koji, Penicillium tetris, Chaetomium globus, and Green slime. Mildew, and Aureobasidium pullulans.

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