KR102571095B1 - Biodegradable material, biodegradable fiber member, biodegradable fabric member and manufacturing methods thereof - Google Patents

Abstract

A biodegradable material, a biodegradable fibrous member, a biodegradable fabric member, and a method for producing the same are disclosed. The disclosed biodegradable material may include a biodegradable resin having a triblock copolymer in which poly hydroxy alkanoate (PHA), poly lactic acid (PLA), and poly caprolactone (PCL) are combined. The disclosed method for manufacturing a biodegradable fibrous member includes forming a biodegradable resin having a triblock copolymer in which PHA, PLA, and PCL are combined, and biodegradable by mixing a functional metal-containing additive having static electricity retention properties with the biodegradable resin. It may include forming a biodegradable composite resin and forming a biodegradable fibrous member from the biodegradable composite resin. The method of manufacturing the biodegradable fibrous member may further include applying an antiviral agent on the biodegradable fibrous member. The method of manufacturing the biodegradable fibrous member may further include charging at least a portion of the functional metal-containing additive with electrostatic charge.

Description

Biodegradable material, biodegradable fiber member, biodegradable fabric member and manufacturing method thereof {Biodegradable material, biodegradable fiber member, biodegradable fabric member and manufacturing methods thereof}

The present invention relates to the manufacture and utilization of biodegradable materials/members, and more particularly to biodegradable materials, biodegradable fibrous members, biodegradable fabric members, and methods for producing them.

Recently, interest in the use of eco-friendly materials is rapidly increasing due to changes in environmental regulation policies around the world. Accordingly, efforts and research to reduce the proportion of non-degradable plastics, which are considered the main culprits of environmental pollution, to produce products that are easy to recycle, or to develop materials that can be biodegraded in landfill are greatly increasing. In this regard, interest in biodegradable polymers (or referred to as biodegradable plastics) having a chemical structure that can be easily degraded by microorganisms is increasing.

In addition, with rapid urbanization and industrialization around the world, the problem of air pollution caused by particulate matter, for example, fine dust or ultrafine dust, is a significant threat to human health, and filter materials applied to masks or air filters Significant research effort is being invested in its development. In addition, in a situation where economic and social damage is increasing due to a global pandemic caused by the spread of infectious diseases (coronavirus infection, etc.), interest in personal quarantine products is increasing. Global use of masks is rapidly increasing, and tens of billions of masks, usually made of polypropylene (PP), are thrown away every month worldwide, raising concerns that this may lead to catastrophic environmental pollution.

A technical problem to be achieved by the present invention is to provide a biodegradable material that can be usefully and easily applied to a mask or an air filter while having excellent biodegradable properties.

In addition, the technical problem to be achieved by the present invention is to provide a biodegradable fabric member such as a biodegradable fiber member having semi-permanent static electricity retention characteristics and excellent antiviral function and a biodegradable nonwoven fabric member using the same.

In addition, a technical problem to be achieved by the present invention is to provide a method for manufacturing the biodegradable material, a method for manufacturing the biodegradable fibrous member, and a method for manufacturing the biodegradable fabric member.

The problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be understood by those skilled in the art from the description below.

According to one embodiment of the present invention, a biodegradable material comprising a biodegradable resin having a triblock copolymer in which poly hydroxy alkanoate (PHA), poly lactic acid (PLA), and poly caprolactone (PCL) are combined is provided.

In the triblock copolymer, the PLA may be disposed between the PHA and the PCL, a first end of the PLA may be connected to an end of the PHA, and a second end of the PLA may be connected to an end of the PCL. can

The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) may include at least one of

It is mixed with the biodegradable resin and may further include a functional metal-containing additive having static electricity retention properties.

The functional metal-containing additive may include at least one of magnesium stearate (MgSt), Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ .

The content of the functional metal-containing additive relative to the biodegradable resin may be about 0.1 to about 5 wt%.

According to another embodiment of the present invention, a biodegradable polymer material comprising a triblock copolymer in which poly hydroxy alkanoate (PHA), poly lactic acid (PLA), and poly caprolactone (PCL) are combined. A fibrous member is provided.

In the triblock copolymer, the PLA may be disposed between the PHA and the PCL, a first end of the PLA may be connected to an end of the PHA, and a second end of the PLA may be connected to an end of the PCL. can

The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) may include at least one of

The biodegradable fiber member is mixed with the biodegradable polymer material and may further include a functional metal-containing additive having static electricity retention properties.

The functional metal-containing additive may include at least one of magnesium stearate (MgSt), Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ .

The content of the functional metal-containing additive relative to the biodegradable polymeric material may be about 0.1 to 5 wt%.

At least a portion of the functional metal-containing additive may be charged with an electrostatic charge.

An antiviral agent applied on the biodegradable fibrous member may be further included.

The antiviral agent may include polyoxometalate (POM).

An applied amount of the antiviral agent to the biodegradable fibrous member may be about 0.05 to 5 g/m ² .

According to another embodiment of the present invention, a biodegradable fabric member comprising the aforementioned biodegradable fibrous member is provided.

The biodegradable fabric member may be a biodegradable nonwoven fabric member.

The biodegradable nonwoven fabric member may be a meltblown nonwoven fabric member.

The biodegradable fabric member may constitute at least a part of a mask filter, an air purifier filter, a patient sheet, or a protective clothing.

According to another embodiment of the present invention, a PHA-PLA diblock copolymer according to the first polymerization reaction is obtained by mixing a source material of poly hydroxy alkanoate (PHA), a source material of poly lactic acid (PLA), and a first catalyst. forming coalescence; And a biodegradable resin having a PHA-PLA-PCL triblock copolymer according to the second polymerization reaction by mixing the PHA-PLA diblock copolymer, a poly caprolactone (PCL) source material, and a second catalyst. There is provided a method for producing a biodegradable material comprising the step of forming.

In the triblock copolymer, the PLA may be disposed between the PHA and the PCL, a first end of the PLA may be connected to an end of the PHA, and a second end of the PLA may be connected to an end of the PCL. can

The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) may include at least one of

The method may further include mixing a functional metal-containing additive having static electricity retention properties with the biodegradable resin.

The functional metal-containing additive may include at least one of magnesium stearate (MgSt), Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ .

The content of the functional metal-containing additive relative to the biodegradable resin may be about 0.1 to about 5 wt%.

According to another embodiment of the present invention, forming a biodegradable resin having a triblock (triblock) copolymer in which PHA (poly hydroxy alkanoate), PLA (poly lactic acid) and PCL (poly caprolactone) are combined; forming a biodegradable composite resin by mixing the biodegradable resin with a functional metal-containing additive having static electricity retention properties; and forming a biodegradable fibrous member from the biodegradable composite resin.

In the triblock copolymer, the PLA may be disposed between the PHA and the PCL, a first end of the PLA may be connected to an end of the PHA, and a second end of the PLA may be connected to an end of the PCL. can

The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) may include at least one of

The functional metal-containing additive may include at least one of magnesium stearate (MgSt), Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ .

The content of the functional metal-containing additive relative to the biodegradable resin may be about 0.1 to about 5 wt%.

The method may further include applying an antiviral agent on the biodegradable fibrous member.

The antiviral agent may include polyoxometalate (POM).

An applied amount of the antiviral agent to the biodegradable fibrous member may be about 0.05 to 5 g/m ² .

The method may further include charging at least a portion of the functional metal-containing additive with an electrostatic charge.

According to another embodiment of the present invention, there is provided a method for manufacturing a biodegradable fabric member comprising the step of manufacturing a biodegradable fabric member using the above-described method for manufacturing a biodegradable fibrous member.

The biodegradable fabric member may be a biodegradable nonwoven fabric member.

The biodegradable nonwoven fabric member may be a meltblown nonwoven fabric member.

According to the embodiments of the present invention, it is possible to implement a biodegradable material that can be usefully/easily applied to a mask or an air filter while having excellent biodegradation characteristics. In addition, according to embodiments of the present invention, a biodegradable fibrous member having semi-permanent static electricity retention characteristics and excellent antiviral function and a biodegradable fabric member (ex, biodegradable nonwoven fabric member) to which the same is applied can be implemented.

The biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to an embodiment of the present invention is a plant-derived resin having biodegradability, and can reduce environmental pollution caused by petroleum-based solid waste, and greenhouse gas, which is the main culprit of air pollution. can contribute to reduction.

In addition, the biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to an embodiment of the present invention can sustain static electricity that enhances the fine dust blocking function for about 1 year or more, and the ultra-fine PM 2.5 (particulate matter 2.5 ㎛) It can show about 99% blocking effect against dust.

In addition, the biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to an embodiment of the present invention has antiviral performance essential for pandemic situations such as COVID-19 (coronavirus disease 2019), and has about 95% or more. It can exhibit antibacterial/antiviral effects.

The biodegradable fabric member (ex, biodegradable nonwoven fabric member) manufactured according to the embodiment of the present invention is a nonwoven fabric for most filters such as air purifier filters as collective quarantine products in addition to personal quarantine products (masks, protective clothing / protective clothing, patient sheets, etc.) is expected to be able to replace

1 is a view for explaining a method for manufacturing a biodegradable material according to an embodiment of the present invention.
Figure 2a is a view for explaining PHA (poly hydroxy alkanoate) that can be applied to a biodegradable material according to an embodiment of the present invention.
Figure 2b is a view for explaining the type of PHA (poly hydroxy alkanoate) that can be applied to the biodegradable material according to an embodiment of the present invention.
Figure 3 is a view for explaining PLA (poly lactic acid) that can be applied to a biodegradable material according to an embodiment of the present invention.
Figure 4 is a view for explaining PCL (poly caprolactone) that can be applied to a biodegradable material according to an embodiment of the present invention.
Figure 5 is a flow chart for explaining a method for manufacturing a biodegradable fibrous member and a biodegradable fabric member using the biodegradable fibrous member according to an embodiment of the present invention.
6 is a view for explaining a meltblown process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.
7 is a view for explaining an antiviral agent application process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.
8 is a view for explaining an electrostatic charging process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.
9 is a view showing a biodegradable fabric member (biodegradable meltblown nonwoven fabric member) manufactured according to an embodiment of the present invention and results of evaluating its characteristics.
10 is a view showing a biodegradable fabric member (biodegradable meltblown nonwoven fabric member) manufactured according to an embodiment of the present invention and the results of evaluating its characteristics.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Embodiments of the present invention to be described below are provided to more clearly explain the present invention to those skilled in the art, and the scope of the present invention is not limited by the following examples, Embodiments may be modified in many different forms.

Terms used in this specification are used to describe specific embodiments and are not intended to limit the present invention. Terms in the singular form used herein may include plural forms unless the context clearly indicates otherwise. Also, as used herein, the terms "comprise" and/or "comprising" specify the presence of the stated shape, step, number, operation, member, element, and/or group thereof. and does not exclude the presence or addition of one or more other shapes, steps, numbers, operations, elements, elements and/or groups thereof. In addition, the term “connection” used in this specification means not only direct connection of certain members, but also a concept including indirect connection by intervening other members between the members.

In addition, when a member is said to be located “on” another member in the present specification, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members. As used herein, the term “and/or” includes any one and all combinations of one or more of the listed items. In addition, terms of degree such as "about" and "substantially" used in the present specification are used in a range of values or degrees or meanings close thereto, taking into account inherent manufacturing and material tolerances, and are used to help the understanding of the present application. Exact or absolute figures provided for this purpose are used to prevent undue exploitation by infringers of the stated disclosure.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The size or thickness of areas or parts shown in the accompanying drawings may be slightly exaggerated for clarity of the specification and convenience of description. Like reference numbers indicate like elements throughout the detailed description.

1 is a view for explaining a method for manufacturing a biodegradable material according to an embodiment of the present invention.

Referring to FIG. 1, a PHA-PLA diblock copolymer according to a first polymerization reaction is formed by mixing a source material of poly hydroxy alkanoate (PHA), a source material of poly lactic acid (PLA), and a first catalyst can do. Here, a case of using PHB (poly hydroxy butyrate) as a type of PHA is shown. In this case, as the PHB source material, for example, Me-PHB-OH may be used. Here, Me means methyl. The source material of the PLA may include, for example, D,L-lactide. As the first catalyst, for example, stannous octoate [Sn(Oct) ₂ ] may be used. Here, the stannous octoate may be tin (II) 2-ethylhexanoate (concentration: 92.5 to 100%). A polymerization reaction (first polymerization reaction) may be induced by mixing D,L-lactide and Sn(Oct) ₂ catalyst with the PHB source material, and under a nitrogen atmosphere. At this time, the reaction temperature may be, for example, about 75 ± 15 °C. A PHB-PLA diblock copolymer may be formed by the first polymerization reaction. The PHB-PLA diblock copolymer may correspond to the PHA-PLA diblock copolymer.

Next, the PHA-PLA diblock copolymer (ie, the PHB-PLA diblock copolymer in this embodiment), the PCL (poly caprolactone) source material, and the second catalyst are mixed to obtain PHA according to the second polymerization reaction. - A biodegradable resin containing a PLA-PCL triblock copolymer can be formed. That is, the second polymerization reaction may be induced by mixing the PHB-PLA diblock copolymer with the PCL source material and the second catalyst. Here, the source material of the PCL may include, for example, ε-caprolactone. As the second catalyst, for example, stannous octoate [Sn(Oct) ₂ ] may be used. Here, the stannous octoate may be tin(II) 2-ethylhexanoate (concentration: 92.5 to 100%). The second polymerization reaction may be a kind of ring-opening polymerization reaction. PHB-PLA-PCL triblock copolymer may be formed by the second polymerization reaction. The PHB-PLA-PCL triblock copolymer may correspond to the PHA-PLA-PCL triblock copolymer.

In the triblock copolymer, the PLA may be disposed between the PHA (PHB in this embodiment) and the PCL. In this case, the first end of the PLA may be connected to the end of the PHA, and the second end of the PLA may be connected to the end of the PCL. Copolymers can be formed in the sequence PHA-PLA-PCL, and these three bonding units can be linked repeatedly.

In FIG. 1, a case in which PHB is applied as the PHA is illustrated and described as an example, but the type of the PHA may be variously changed. For example, the PHAs include poly 3-hydroxy butyrate (P3HB), poly 3-hydroxy butyrate valerate (P3HBV), poly hydroxy valerate (PHV), poly 4-hydroxy butyrate (P4HB), poly hydroxy hexanoate (PHHX) and PHD (poly hydroxy dodecanoate). Here, it can be said that the P3HB is a type of the PHB. When P3HB, P3HBV, PHV, P4HB, PHHX, PHD, etc. are applied as the PHA, it may be advantageous to prepare a PHA-PLA-PCL triblock copolymer having excellent biodegradability.

In the PHA-PLA-PCL triblock copolymer, the PHA-PLA portion may be a 'hard segment domain' and the PCL portion may be a 'soft segment matrix'. The PHA-PLA hard segment domain may serve as a physical cross-linking agent for the PCL soft segment matrix.

Each of PHA, PLA, and PCL included in the PHA-PLA-PCL triblock copolymer may be a biodegradable polymer. In particular, PHAs can be constructed only by biosynthesis without any chemical synthesis. The PHA-PLA-PCL triblock copolymer may have excellent biodegradation properties because the copolymer is formed by ring-opening polymerization and polymerization is formed in a specific order.

The biodegradable material according to an embodiment of the present invention may be an environmentally degradable (biodegradable) material (eg, fiber-type material) including a sheath-core structure. In a preferred configuration, multiple blends of PHA (PHB, PHBV, etc.) may be placed in the core with PLA, PCL polymer in the coating. These blends can also be placed in the sheath of sheath-core bicomponent fibers, provided they are sufficiently vitrified during the fiber forming process or crystallized in the spin line to avoid processing problems of fiber stickiness or shrinkage.

An active PHB-O-AlEt2 macroinitiator species can be prepared from the reaction between a mono-hydroxyl-terminated PHB macromonomer and AlEt3. The macroinitiator can be used to obtain PHB-PCL and PHB-PLA diblock copolymers by carrying out ring-opening polymerization of ε-caprolactone (CL) or lactide monomers. Similarly, crystals of poly hydroxy octanoate (PHO) elastomeric soft segment copolymers of PCL can also be combined to prepare semi-crystalline PHO-PCL diblock copolymers controlled by two different block lengths. Following continuous ring-opening polymerization (ROP) of lactide, PHB-PLA-PCL triblock copolymers can be prepared using PHB as a macroinitiator and caprolactone (CL). An A-B-C type triblock copolymer (i.e., a PHB-PLA-PCL copolymer) can be composed of a PHB-PLA hard segment and a PCL soft segment induced microphase separation in a polymer film.

In the ABC-type triblock copolymer, group A may include one or more short chain length (scl) PHA of C ₃ to C ₅ and medium chain length (mcl) PHA of C ₆ to C ₁₄ . The PHA may be P3HB, P3HBV, PHV, P4HB, PHHX, PHD, etc., and one or two or more of them may be copolymerized. In an embodiment of the present invention, when P3HB or P3HBV is used as the PHA, the scl PHA in the copolymer may be about 5 to 10%, or the mcl PHA may be about 90 to 95%.

In the A-B-C type triblock copolymer, group B may use L-PLA, enantiomer D-PLA, or D,L-PLA. In an embodiment of the present invention, D,L-PLA may be used. Meanwhile, in the A-B-C type triblock copolymer, the C group may be PCL.

Figure 2a is a view for explaining PHA (poly hydroxy alkanoate) that can be applied to a biodegradable material according to an embodiment of the present invention.

Referring to Figure 2a, (A) shows the general molecular formula of PHA, (B) some synthetic short-chain-length PHA monomers (SCL-HA) and middle-chain-length PHA monomers (MCL -HA).

PHA, which can be applied to the biodegradable material according to an embodiment of the present invention, is a thermoplastic natural polyester polymer that accumulates in microbial cells, and can be composted as a biodegradable material, without generating toxic waste, and finally carbon dioxide, water, organic matter. can be broken down into waste. Certain bacteria can accumulate PHA intracellularly to store carbon sources and energy when nutrients (nitrogen source, phosphorus, etc.) are supplied disproportionately. PHAs can be classified as bioplastics derived from renewable resources that are biodegradable and biocompatible. However, it is still limitedly used due to problems of production cost and processing instability.

Unlike other eco-friendly plastic materials, such as polybutylene succinate (PBS), PLA, and poly trimethylene terephthalate (PTT), PHA can be synthesized with more than 150 types of monomers, so it has the advantage of being able to control its structure and physical properties.

Among the PHA-based polymers, the most representative known material is polyhydroxy butyrate (PHB) polymerized with the C4 monomer 3-hydroxybutyrate (3HB), and various other PHAs are 3-hydroxyvalerate (3HV) and 3-hydroxybutyrate (3HV). It consists of long carbon chain 3-hydroxy fatty acids such as -hydroxyhexanoate (3HHX). PHB and PHV are classified as short carbon chain length PHAs, medium carbon chain length PHAs contain C6-C16 3-hydroxy fatty acids. PHB has similar physical properties to polypropylene and can be synthesized relatively efficiently by microorganisms, so many studies on commercial production have been conducted. However, it has a strong and brittle property due to its high crystallinity, and its melting point is relatively high, and decomposition begins near the melting point, limiting its processability. In order to compensate for these problems, many studies have been conducted on the synthesis of various types of PHA copolymers through blending of various materials and copolymerization of monomers. The physical properties of the PHA polymer vary depending on the ratio of C5 or higher monomers, which can be applied to the production of various products.

In an embodiment of the present invention, poly-3-hydroxy butyrate (P3HB) and poly(3-hydroxy butyrate-co-4-hydroxy butyrate) (P3HB4HB) may be used. P3HB4HB and poly(3-hydroxy butyrate-co-3-hydroxy valerate) (PHBV) can use acetate as a major carbon source. Overexpression of phosphotransacetylase can produce PHBV.

Acetate kinase and AMP-forming acetate assimilation and acetyl-CoA synthase production for P3HB may be possible. In addition, succinate semialdehyde dehydrogenase, 4-hydroxybutyrate dehydrogenase and CoA transferase can be overexpressed to establish a P3HB4HB accumulation pathway. The introduction of the propionyl-CoA transferase propionate permease helps to achieve PHBV synthesis of the 3-hydroxy valerate precursor from propionate. P3HB, P3HB4HB and PHBV could be carbon source biomaterials for various high-value productions effectively opening new approaches.

Bacterial strain and culture medium Escherichia coli JM109 can be used as host, plasmid construction and can produce P3HB and PHBV, succinate semialdehyde dehydrogenase mutant JM109SG can be used as host for P3HB4HB. For production, recombinant and plasmid amplification, E. coli strains can be grown in Luria-Bertani at 37°C and 200 rpm (LB), containing 5 g/L yeast extract, 10 g/L in LB medium. Bactotryptone and 10 g/L NaCl may be added. 100 μg/mL ampicillin or 50 μg/mL kanamycin may be required to maintain plasmid stability. In this manufacturing process, E. coli is designed to synthesize P3HB. The production of P3HB4HB and PHBV biopolymers using acetate as the main carbon can be improved by overexpression of phosphotransacetylase.

Acetate kinase can produce 1.27 g/L of P3HB and 1.71 g/L of P(3HB-co-5.79 mol% 4HB) in E. coli in shake flask culture. When each minimal medium was supplemented with 10 g/L yeast extract and 5 g/L acetate, and 1 g/L citrate was added as an auxiliary carbon, the production titer of P3HB4HB could be increased to 2.15 g/L.

Overexpression of propionyl-CoA transferase can lead to the production of propionate permease. At 5 g/L, 1.09 g/L P (3HB-co-10.37 mol % 3HV) titer of acetate and 1.5 g/L propionate can be supplied simultaneously. Acetate can be used as a major carbon source by efficient production engineering of P3HB, P3HB4HB and PHBV.

Figure 2b is a view for explaining the type of PHA (poly hydroxy alkanoate) that can be applied to the biodegradable material according to an embodiment of the present invention.

Referring to Figure 2b, the PHA that can be applied to the biodegradable material according to an embodiment of the present invention is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB ( poly 4-hydroxy butyrate), poly hydroxy hexanoate (PHHX), and poly hydroxy dodecanoate (PHD).

Figure 3 is a view for explaining PLA (poly lactic acid) that can be applied to a biodegradable material according to an embodiment of the present invention.

Referring to FIG. 3, the process of forming PLA from lactic acid through cyclic lactide monomer is shown as an example.

PLA, which can be applied to the biodegradable material according to an embodiment of the present invention, may be a biodegradable/compostable polymer for the manufacture of plastics and fibers. Although PLA is obtained from natural and renewable materials, it is also a thermoplastic, polyolefin (polyethylene and polypropylene) and polyester (polyethylene terephthalate and polybutylene terephthalate). terephthalate and polybutylene terephthalate)] can be melt extruded to produce plastic items, fibers and fabrics with good mechanical strength and flexibility comparable to oil-based compounds. PLA is made from lactic acid, which can be a fermentation byproduct obtained from corn, cassava or sugar beet.

Unlike other synthetic fiber materials derived from plants (eg cellulosic compounds), PLA may be more suitable for melt spinning into fibers. Compared to the solvent spinning process required for synthetic cellulose fibers, PLA fibers made by employing melt spinning allow for lower economic and environmental costs, and the resulting PLA can have a wider range of properties. . PLA molecules can easily form a helical structure resulting in easier crystallization. In addition, the lactic dimer has three types of isomers: an L form that rotates polarized light in a clockwise direction, a D form that rotates polarized light in a counterclockwise direction, and an optically inactive racemic form. have During polymerization, the relative proportions of these forms can be controlled, allowing relatively wide property control for important polymer properties.

The melting temperature can be controlled between about 120° C. and 175° C. to control the content and arrangement of the three isomers, in which case the polymer may be completely amorphous below the lower melting temperature.

PLA may not be directly biodegradable in the molded state. Instead, it first needs to be hydrolyzed before becoming biodegradable. To achieve significant levels of hydrolysis of PLA, humidity of about 98% or greater and temperatures of about 60° C. or greater may both be required simultaneously. Once these conditions are satisfied, degradation can occur rapidly.

PLA breaks down into small molecules through a number of different mechanisms, and the final degradation products are CO ₂ and H ₂ O. While the degradation process remains unaffected by UV light, it can be influenced by temperature, humidity, pH value, enzyme and microbial activity.

Figure 4 is a view for explaining PCL (poly caprolactone) that can be applied to a biodegradable material according to an embodiment of the present invention.

Referring to Figure 4, it shows a molecular structure including PCL that can be applied to the biodegradable material according to this embodiment by way of example.

PCL, which can be applied to biodegradable materials according to an embodiment of the present invention, is generally a diol, that is, a semi-crystalline compound synthesized by ring-opening polymerization of dihydric alcohol and caprolactone monomer in which tin (II) or tin salt acts as an initiator. It may be an aliphatic polyester. PCL has the characteristics of biodegradability, biocompatibility and non-toxicity. Among the family of biodegradable polymers, PLA and PCL can be useful for packaging applications due to their easy solubility, good biodegradability and excellent mechanical properties. PCL exhibits excellent chemical and solvent resistance, excellent toughness, and has a low glass transition temperature (-60 ° C). The high mobility and low intermolecular interactions of chain segments in PCL can lead to very low melting and glass transition temperatures. PCL is more thermally stable than PLA and can be completely degraded through enzymatic activity. PCL can have good chain flexibility. PCL is soluble in almost all aromatic, polar and chlorinated hydrocarbons and may be insoluble in aliphatic hydrocarbons, alcohols and glycols. PCL can exhibit similar mechanical properties to other existing non-biodegradable synthetic polymers. High molecular weight PCL can have mechanical properties and oxygen permeability comparable to polyethylene (PE). PCL is a biodegradable polyester and when blended with PLA, an entirely new material with biodegradable properties can be created.

According to one embodiment of the present invention, a functional metal-containing additive having static electricity retention is mixed with a biodegradable resin including a PHA-PLA-PCL triblock copolymer prepared by the method described with reference to FIG. Biodegradable composite resins can be prepared. For example, the functional metal-containing additive may be melt-mixed with the biodegradable resin including the triblock copolymer using a twin screw extruder, and then pelletized. A mixture of the biodegradable resin and the functional metal-containing additive may be referred to as a 'biodegradable composite resin'. The biodegradable composite resin may be referred to as 'electric masterbatch'.

In the production of the electric masterbatch, it is necessary to control or optimize the operating conditions of the twin screw extruder. Since the melting point of the biodegradable PHA-PLA-PCL triblock copolymer resin may be in the range of 130 ° C to 160 ° C, the temperature conditions of the extruder are less than 40 ° C in the feed section, about 130 ° C in the mixing section, and about 130 ° C in the melting section. About 160 ℃, the die can be adjusted to about 165 ℃, and the screw speed can be about 200 ~ 300 rpm. However, these process conditions are exemplary and may vary depending on the case. In addition, cooling of the melt-mixed resin can be performed by air cooling. Since hydrolysis of the biodegradable PHA-PLA-PCL triblock copolymer can be accelerated by moisture, when moisture is used, the physical properties of the resin may be lowered, so it may be preferable to cool by air cooling as described above. there is.

The functional metal-containing additive may include, for example, at least one of magnesium stearate (MgSt), Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ . The content of the functional metal-containing additive relative to the biodegradable resin may be about 0.1 to about 5 wt%. The functional metal-containing additive may have a plurality of particle forms and may be uniformly (substantially uniformly) mixed with the biodegradable resin. Fibers may be formed through a subsequent process using a biodegradable composite resin in which the functional metal-containing additive and the biodegradable resin are mixed. Accordingly, the functional metal-containing additive may be uniformly (substantially uniformly) dispersed in the fiber. In addition, the functional metal-containing additive may be treated to retain electrostatic charge through a subsequent process. According to an embodiment of the present invention, the electrostatic charge contained in the functional metal-containing additive is hardly dissipated in a general atmospheric environment and can be maintained semi-permanently for about one year or more. Therefore, fine dust filtering performance by electrostatic charge can be greatly improved, and such performance can be maintained semi-permanently.

According to one embodiment of the present invention, when MgSt is used as the functional metal-containing additive, an excellent electrostatic effect can be obtained. In addition, when a nucleating agent (nucleating agent) is added to the biodegradable resin, the nucleating agent may serve to improve the crystal structure and further improve electret performance. As the nucleating agent, for example, LAK301 of Takemoto Oil & Fat Co., Ltd may be used, and the amount of the nucleating agent added may be, for example, about 0.5 to 3 wt%, preferably. , which may be on the order of about 0.8 to 2 wt%. MgSt particles can act as charge enhancers. The nonwoven fabric member made of the PHB-PLA-PCL/MgSt sample by the electrostatic capture mechanism can exhibit higher particulate filtration efficiency. The MgSt content may be on the order of about 0.1 to 5 wt %. If the MgSt content is less than about 0.1 wt%, the electrostatic force may not be sufficient, and if the MgSt content is more than about 5 wt%, the filtration efficiency may decrease. Preferably, the MgSt content may be about 0.2 to 3 wt%. The biodegradable nonwoven fabric member made of the biodegradable composite resin manufactured by the method according to the embodiment of the present invention may exhibit a filtration efficiency of about 99% for PM 2.5 ultrafine dust.

When the functional metal-containing additive includes an oxide such as Al ₂ O ₃ , Fe ₂ O ₃ , or TiO _{2 ,} metal ions of the functional metal-containing additive may hydrogen bond with the biodegradable resin. The hydrogen bond may be made possible by oxygen included in the oxide. Accordingly, when the functional metal-containing additive includes an oxide such as Al ₂ O ₃ , Fe ₂ O ₃ , or TiO ₂ , excellent static electricity retention characteristics may be exhibited.

Figure 5 is a flow chart for explaining a method for manufacturing a biodegradable fibrous member and a biodegradable fabric member using the biodegradable fibrous member according to an embodiment of the present invention.

Referring to FIG. 5, the method for manufacturing a biodegradable fabric member applying a biodegradable fibrous member according to an embodiment of the present invention forms a biodegradable resin having a triblock copolymer in which PHA, PLA and PCL are combined. (S10), mixing the biodegradable resin with a functional metal-containing additive having static electricity retention properties to form a biodegradable composite resin (S20), and forming a biodegradable fibrous member from the biodegradable composite resin and the biodegradable composite resin. It may include a step (S30) of producing a biodegradable fabric member to which the active fiber member is applied. In addition, in the method of manufacturing a biodegradable fabric member applying a biodegradable fibrous member according to an embodiment of the present invention, after step S30, applying an antiviral agent on the biodegradable fabric member to which the biodegradable fibrous member is applied (S40) and charging at least a portion of the functional metal-containing additive included in the biodegradable fabric member with electrostatic charge (S50).

Step S10 may be performed according to the manufacturing method of the biodegradable material described with reference to FIGS. 1 to 4 . Through step S10, a biodegradable resin including the PHA-PLA-PCL triblock copolymer may be formed.

Step S20 may be performed according to the method of forming a biodegradable composite resin (ie, electric masterbatch) by mixing the functional metal-containing additives described above. The biodegradable composite resin may be manufactured in a kind of pellet form. The biodegradable composite resin may be a biodegradable polymer material.

In step S30, a biodegradable fibrous member may be formed from the biodegradable composite resin and a biodegradable fabric member applying the biodegradable fibrous member may be manufactured. The biodegradable fabric member may be a biodegradable nonwoven fabric member. In addition, the biodegradable nonwoven fabric member may be a biodegradable meltblown nonwoven fabric member manufactured by a meltblown method. That is, in step S30, a biodegradable nonwoven fabric can be prepared from the biodegradable composite resin by a meltblown method.

6 is a view for explaining a meltblown process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.

Referring to FIG. 6, the equipment for the meltblown process includes a resin feeder 1, an extruder 2 receiving resin from the resin feeder 1, and a pump member connected to the extruder 2 ( 3), a melt blown die 4 connected to the pump member 3 may be included. The resin (ie, the biodegradable composite resin according to the embodiment of the present invention) may be moved from the resin feeder 1 to the melt blown die 4 via the extruder 2 and the pump member 3. In the melt blown die 4, the resin (polymer) is melted by heating, and can be spun (released) in the form of fibers through a nozzle at the bottom of the die 4 by hot air blowing. . The meltblown fibers may be disposed on the collector 5 to form a web, and may be wound by a predetermined winder 6 (ie, a winding unit). Through this process, a biodegradable meltblown nonwoven fabric can be manufactured. However, the melt blown equipment and process described with reference to FIG. 6 are exemplary, and may be variously changed.

The first step in producing fibers is a compounding or mixing step in which raw materials (i.e., biodegradable composite resins) are typically heated under shear. Shearing in the presence of heat can result in uniform melting with proper compositional selection. The melt may be placed in an extruder where fibers are formed. The fibrous assemblies may be bonded together using heat, pressure, chemical binders, mechanical entanglement, or a combination thereof to form a nonwoven web.

A preferred mixing device may be a multiple mixing zone twin screw extruder. Twin screw batch mixers or single screw extrusion systems can also be used. The particular equipment used may not be critical as long as sufficient mixing and heating occurs. Alternatively, the polymer melt may be injected into the main extruder using a side extruder of the main extruder.

As an alternative method of compounding the materials, the polymer (i.e., biodegradable composite resin) can be added to the extrusion system where it is mixed at a gradually increasing temperature. For example, in a twin screw extruder with 6 heating zones, the first 3 zones can be heated to 40°C, 120°C and 150°C, and the last 3 zones can be heated above the melting point of the polymer.

In the extrusion of the biodegradable resin, the melt flow rate (MFR) according to the melting temperature is also important, but the maintenance of the optimum temperature may be particularly important. Due to the nature of the extruder, even if it is set at a constant temperature, the temperature rises due to the rotation of the screw and friction with the resin, so a cooling system may be important to maintain the temperature. The rotational speed of the screw may be about 100 to 600 rpm, preferably about 150 to 500 rpm, and more preferably about 200 to 350 rpm. In addition, it may be desirable to use an extruder that employs a cooling system that expands the cooling area in the barrel by about 50% or more than the cooling line of a typical extruder.

In an embodiment of the present invention, a melt spinning process may be used. In melt spinning, there may be no mass loss in the extrudate. The principle of melt spinning is to blow resin melted in an extruder with hot air to spin through a nozzle. Fiber rotation may occur at a hot air temperature of about 100 to 270°C, preferably 120 to 240°C, more preferably 170 to 220°C. In addition, the speed of hot air may be about 100 to 400 mm/sec. Processing conditions may be determined by chemical properties, molecular weight and concentration of each component.

Also, fiber spinning speeds of about 100 m/min or higher may be required. Preferably, the fiber spinning speed may be about 500 to about 10000 m/min, preferably about 2000 to about 7000 m/min, more preferably about 2500 to about 5000 m/min. At this time, the average diameter of the spun fibers may be, for example, about 2 to 10 μm.

In addition, the distance between the nozzle and the collector may be important for forming a web of spun fibers. If the distance between the nozzle and the collector is too far, physical properties such as tensile strength of the nonwoven fabric may deteriorate. In an embodiment of the present invention, the distance between the nozzle and the collector may be about 10 to 40 cm. Continuous fibers can be produced through a meltblowing process or a spunbond method, and in some cases, non-continuous (staple) fibers can also be produced. Combination techniques can also be created by combining different fiber manufacturing methods. However, the method of manufacturing the fiber and the fabric member using the same described herein may be variously changed, depending on the case.

Referring back to FIG. 5, in step S40, an antiviral agent may be applied on the biodegradable fabric member to which the biodegradable fiber member is applied. The antiviral agent may include, for example, polyoxometalate (POM). The application amount of the antiviral agent to the biodegradable fibrous member (ie, the amount of spread) is about 0.05 to 5 g/m ² , preferably about 0.5 to 5 g/m ² , more preferably about 1 It may be on the order of -3 g/m ² .

The antiviral agent may include polyoxometalate (POM). The POM may include a metal that is coordinated. The metal may be a transition metal such as Cu, Mo, or W, and the transition metal may serve to generate ions. These ions can attack the envelope of the virus to destroy the virus and prevent the virus from multiplying. Therefore, the antiviral and antibacterial performance of the biodegradable fabric member can be greatly improved by the application of the antiviral agent.

Polyoxometalate (POM) can exhibit biological activities in vitro as well as in vivo, including anticancer, antiviral, antibacterial, antigenic, and antidiabetic activities. Antibacterial activity study of POM showed enhancement of several beta-lactam antibiotics in antibacterial activity against methicillin-resistant Staphylococcus aureus under the synergistic action of polyoxometallate, substituted type POM K7 [PTi2W10O40] 6H2O, K7 [BVW11O40] 7H2O can do. [SiFeW11O40]6/5 and [SiCoW11O40]6 and lacunary-type POMs [XW11O39] n- (X = Si, P) and [XW9O34] n-, and resistance mechanisms can be applied. Beta-lactams with polyoxometalates (K6 [P2W1818O62]ㆍ14H2O, K4 [SiMo12O40]ㆍ _3H2O and K7 [PTi2W10O40]ㆍ6H2O) enhanced antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin The reaction mechanism with resistant S. aureus (VRSA) to the antibiotic oxacillin may also be applied. The synergistic antibacterial action of Ag nanoparticles and POM based on physical damage to bacterial cells can be applied.

An asymmetric unit of the compound according to an embodiment applicable to POM may be composed of one Kegin anion [H4W12O40]6-, two Cu2+ ions, and four pen molecules. [H4W12O40]6- Four edge-sharing W3O13 units joined together via anionic edge-sharing linkages may be included. Both Cu2+ ions can be 5 coordinated. The Cu1 ion is represented by a square prism shape, and the shape of Cu2 ion can be described as a triangular pair pyramid. Donor atoms binding to Cu ions come from two phen molecules with a chelate coordination mode and a Kegin anion, and can form a complex fragment {Cu (phen) 2} 2+.

Compounds used in antibacterial experiments can be divided into four types. Such compounds include, for example, phenanthroline and inorganic-organic hybrid compounds, monosubstituted Keggin-type compounds in which Ti atoms occupy one of the 12 sites, complex compounds of mono-lacunaria lindquist anions and lanthanides, or mono-lacunaria Keggin anions and lanthanides. A complex of ids may be included.

A method for preparing polyoxometalate (POM) may be as follows.

Routes to create new POM clusters are often very simple synthetic operations requiring few numbers, or just one step (so-called 'one pot' synthesis), e.g. This can be done as the pH decreases. This is standard for aqueous synthesis of POM clusters, which can be performed in the presence of simple metal cations. It can also be an organic cation and the solvent system can be extended to solvent mixtures, for example water/CH3CN. The most important synthetic variable clusters in the synthesis are (1) concentration/type of metal oxide anion, (2) pH, (3) ionic strength, (4) heteroatom type/concentration, (5) presence of additional ligands, (6) ) reducing agent and (7) reaction and processing temperatures (eg microwave, hydrothermal and reflux). The cation templation effect of protonated organic amine cations, or the application of mixed solvent strategies, can lead to new separations.

In an embodiment of the present invention, POM can be prepared by the following synthesis method.

The synthesis of [Cu ₂ (phen) ₄ (H ₄ W ₁₂ O ₄₀ )] is (NH ₄ ) ₆ (H ₂ W ₁₂ O ₄₀ )·3H ₂ O (0.1 mmol, 0.30 g) of CuCl ₂ 2H ₂ O (2.0 mmol, 0.34 g), phenanthroline (0.5 mmol, 0.099 g), succinic acid (0.5 mmol, 0.06 g) and 12 mL of water. Hydrochloric acid is added to adjust the pH of the starting mixture to about 2.0 and the mixture can be stirred under air for about 1 hour. The final solution is transferred to a 25 mL Teflon-lined autoclave and allowed to crystallize at about 160° C. for about 96 hours. Thereafter, the autoclave can be cooled to room temperature at a rate of 10 °C·h ⁻¹ . It can be prepared by filtering the resulting green-striped crystals, washing with distilled water, and drying in the air.

The prepared antiviral agent POM is coated on a meltblown nonwoven fabric by the following method and can be applied to various products such as masks, air purifier filters, patient sheets, and protective clothing (protective clothing).

When antibacterial and antiviral processing is performed on substrates such as textile fabrics, nonwoven fabrics, and paper, electrodeposition processing using a biodegradable binder may be performed. Compared to melt processing, electrodeposition processing increases the surface exposure of antibacterial and antiviral agents to the substrate surface, and there is a tendency that antibacterial and antiviral effects can be expressed even when a small amount of the processing agent is applied. Although it is often somewhat inferior in terms of durability, it can be said that it is sufficient when compared to the durability of the substrate itself. An antibacterial, antiviral agent, biodegradable binder, and a solvent such as water are mixed in the electrodeposition processing solution, and a dispersing agent, a viscosity modifier, an antifoaming agent, or a preservative may be added as needed. The mixing ratio may be an appropriate amount of 30 to 100 parts by weight of the biodegradable binder solid content based on 100 of the antibacterial and antiviral agent. If the binder solids are too small, the antibacterial and antiviral agents may easily fall off, and if the binder is too large, the antibacterial and antiviral agents may be buried in the binder, making it difficult to express the effect.

The solvent may be formulated in an appropriate amount in consideration of the absorbency of the substrate and the viscosity that is easy to process. As a non-limiting example, an emulsion such as polyvinyl alcohol (PVAc) or a PLA-PEG composite resin may be used as a binder, and water may be used as a solvent. Adjustment of the working fluid, that is, the dispersion method, may use an agitating mixer. The method of processing the electrodeposition processing fluid on fibers, fabrics, etc. is a dipping process in which the entire fiber or fabric is immersed in the processing fluid and then weaving an appropriate amount, knife coating and gravure coating processing in which the processing fluid is applied to one side of the fiber fabric, An electrodeposition processing method such as spray processing using a spray and spraying may be used. In one embodiment of the present invention, electrodeposition processing may be performed using a spray processing method. The amount of POM, which is an antiviral agent, may be preferably about 0.5 to 5 g/m 2 , more preferably about 1 to 3 g/m 2 .

7 is a view for explaining an antiviral agent application process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.

Referring to FIG. 7, the equipment (ie, the coating device) for the antiviral agent application process includes a coating member supply unit 20 for supplying the coated member 10, and a coating agent 30 to be coated on the coated member 10. A dipping tub 40 in which is contained, a heat treatment chamber (ie, an oven) 50 for heat-treating and curing the coating agent coated on the member 10 to be coated (ie, an oven) 50, and a cured coating agent (ie, the coating layer) A winding unit 60 for winding the formed coated member 10 may be included. Here, the coated member 10 may be a biodegradable fabric member (ex, a biodegradable nonwoven fabric member) manufactured according to an embodiment of the present invention. The coating agent 30 may include the aforementioned antiviral agent. A two-step or more coating process may be performed. However, the equipment for the antiviral agent application process described with reference to FIG. 7 is only exemplary and may be variously changed.

Referring back to FIG. 5, in step S50, at least a portion of the functional metal-containing additive included in the biodegradable fabric member may be charged with electrostatic charge. Accordingly, a process of imparting static electricity to the functional metal-containing additive included in the biodegradable fabric member may be performed. The process of imparting static electricity may be referred to as a kind of 'corona treatment process'.

8 is a view for explaining an electrostatic charging process that can be applied in the manufacture of a biodegradable fabric member to which a biodegradable fibrous member according to an embodiment of the present invention is applied.

Referring to FIG. 8 , the electrostatic charging process (corona treatment process) may be performed as a high voltage process. Equipment for electrostatic charging may include a charging system and a surface potential measurement system. Equipment for the electrostatic charge may include a power supply, a point-shaped electrode, and a ground electrode. Due to the high potential under high voltage power, a corona discharge may occur on the electrode and ions may be deposited on the electret material. In an embodiment of the present invention, a biodegradable fabric member (eg, a biodegradable meltblown nonwoven fabric member) may be charged (charged) with a voltage of about 50 to 150 kV. The charging (charging) time may be about 10 to 60 seconds, and the charging (charging) distance between the electrodes may be about 50 to 200 mm. The electrostatic ability of the fabric member (eg, nonwoven fabric member) manufactured by the above method may last for about 1 year or more in an atmospheric environment.

The functional metal-containing additive included in the biodegradable fabric member (eg, biodegradable meltblown nonwoven fabric member) may be treated to retain electrostatic charge through the electrostatic charge process described above. As described above, the electrostatic charge contained in the functional metal-containing additive is hardly dissipated in a general atmospheric environment and can be maintained semi-permanently for about one year or more. Therefore, fine dust filtering performance by electrostatic charge can be greatly improved, and such performance can be maintained semi-permanently.

The biodegradable fabric member manufactured according to the embodiment of the present invention may have excellent static electricity retention characteristics and excellent antiviral performance, as well as excellent biodegradation characteristics. Such a biodegradable fabric member can be applied to configure at least a part of a mask filter (body/filter part of a mask for blocking fine particles or a mask for blocking droplets), an air purifier filter, a sheet for a patient, and protective clothing (protective clothing).

According to embodiments of the present invention, a biodegradable fibrous member having semi-permanent static electricity retention characteristics and excellent antiviral function and a biodegradable fabric member (ex, biodegradable nonwoven fabric member) to which the same is applied can be implemented. The biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to the embodiment is a plant-derived resin having biodegradability, which can reduce environmental pollution caused by petroleum-based solid waste, and contribute to reducing greenhouse gases, which are the main culprit of air pollution. can In addition, the biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to an embodiment of the present invention can sustain static electricity that enhances the fine dust blocking function for about 1 year or more, and about 99% of the ultrafine dust of PM 2.5 may have a blocking effect. In addition, the biodegradable fabric member (ex, biodegradable nonwoven fabric member) according to an embodiment of the present invention has antiviral performance essential to pandemic situations such as COVID-19, and has an antibacterial/antiviral effect of about 95% or more. can represent The biodegradable fabric member (ex, biodegradable nonwoven fabric member) manufactured according to the embodiment of the present invention is a nonwoven fabric for most filters such as air purifier filters as collective quarantine products in addition to personal quarantine products (masks, protective clothing / protective clothing, patient sheets, etc.) is expected to be able to replace

9 is a view showing a biodegradable fabric member (biodegradable meltblown nonwoven fabric member) manufactured according to an embodiment of the present invention and results of evaluating its characteristics. That is, FIG. 9 is melt spinning (ie, meltblown) with a biodegradable composite resin (ie, electric masterbatch) in which a functional metal-containing additive is mixed with a biodegradable PHA-PLA-PCL triblock copolymer to prepare a nonwoven fabric, As a subsequent process, a meltblown filter prepared by coating POM, an antiviral agent, and performing corona charging, and a characteristic evaluation result thereof are shown.

Referring to FIG. 9, drawings (a) to (f) show changes in the shape of the nonwoven fabric according to the distance (DCD) between the nozzle and the collector in the melt blown process. (a) the drawing is when the distance (DCD) is 10 cm, (b) the drawing is when the distance (DCD) is 15 cm, (c) the drawing is when the distance (DCD) is 20 cm, , (d) the drawing is when the distance (DCD) is 25 cm, (e) the drawing is when the distance (DCD) is 30 cm, (f) the drawing is when the distance (DCD) is 35 cm am. Figure 9 (g) shows the results of measuring the average diameter of fibers in each case, (h) shows the results of measuring the average pore size and porosity of the nonwoven fabric in each case, (i) shows the results of measuring the pore size distribution of the nonwoven fabric in each case. (h) In the figure, it can be seen that as the distance (DCD) increases, the porosity of the nonwoven fabric tends to increase.

10 is a view showing a biodegradable fabric member (biodegradable meltblown nonwoven fabric member) manufactured according to an embodiment of the present invention and the results of evaluating its characteristics. That is, FIG. 10 is a biodegradable composite resin (ie, electric masterbatch) in which MgSt is mixed with a biodegradable PHA-PLA-PCL triblock copolymer and MgSt as a functional metal-containing additive is melt-spun (ie, meltblown) to prepare a nonwoven fabric, , shows a meltblown filter prepared by coating POM, an antiviral agent, as a follow-up process, and the evaluation results for its properties. However, FIG. 10 includes the case where the content of MgSt is 0 wt%.

Referring to Figure 10, (a) to (f) shows the change in the shape of the nonwoven fabric according to the change in the content of MgSt. (a) the drawing shows the case where the MgSt content is 0 wt%, (b) the drawing shows the case the MgSt content is 0.1 wt%, (c) the drawing shows the case the MgSt content is 0.3 wt%, (d ) is a case in which the MgSt content is 0.5 wt%, (e) is a case in which the MgSt content is 0.7 wt%, and (f) is a case in which the MgSt content is 1 wt%. Figure 10 (g) shows the results of measuring the average diameter of fibers in each case, (h) shows the results of measuring the average pore size and porosity of the nonwoven fabric in each case, (i) shows the results of evaluating the filtration efficiency and pressure drop characteristics of the nonwoven fabric in each case. (i) The drawing shows the results of evaluating the filtration efficiency and pressure drop characteristics of each nonwoven fabric in a state where the electrostatic charging process (corona charging process) is not performed on each nonwoven fabric. In a state where the electrostatic charging process is not performed, relatively low filtration efficiency may be exhibited regardless of the content of MgSt. However, when an electrostatic charging process is performed, the biodegradable nonwoven fabric can exhibit very good filtration efficiency depending on the content of MgSt.

Table 1 below shows the filter according to the content (MgSt/nucleating agent content) of MgSt and nucleating agent (nucleating agent) contained in the biodegradable nonwoven fabric filter (biodegradable meltblown nonwoven fabric filter) prepared according to an embodiment of the present invention. The results of evaluating the characteristics (particle collection efficiency, face inhalation resistance, and leakage rate) are summarized. At this time, the weight per unit area of the biodegradable nonwoven fabric filter was 30 g/m ² . A 2% NaCl solution was used as the dust, and the average particle diameter of the dust was 0.4 μm.

Referring to Table 1, it can be confirmed that a very high dust collection efficiency of about 98 to 99.4% can be obtained by mixing a functional metal-containing additive such as MgSt and imparting electrostatic properties.

Table 2 below summarizes the results of evaluating the filter characteristics (particle collection efficiency) according to humidity for the biodegradable nonwoven fabric filter (biodegradable meltblown nonwoven fabric filter) manufactured according to an embodiment of the present invention. Here, the humidity represents relative humidity (RH) (%). The weight per unit area of the biodegradable nonwoven fabric filter was 30 g/m ² . A 2% NaCl solution was used as the dust, and the average particle diameter of the dust was 0.4 μm.

Referring to Table 2, it can be confirmed that even when the humidity is increased from 70% to 100%, a very high fractionation and collection efficiency of about 97 to 99.4% can be maintained.

Table 3 below summarizes the results of evaluating the filter characteristics (particle collection efficiency) according to the temperature for the biodegradable nonwoven fabric filter (biodegradable meltblown nonwoven fabric filter) manufactured according to the embodiment of the present invention. The weight per unit area of the biodegradable nonwoven fabric filter was 30 g/m ² . A 2% NaCl solution was used as the dust, and the average particle diameter of the dust was 0.4 μm.

Referring to Table 3, it can be confirmed that even if the temperature is increased to 30 ° C. or more and 60 ° C., a very high fractionation and collection efficiency of about 98 to 99.3% can be maintained.

Table 4 below summarizes the results of evaluating the antiviral performance of the filter according to the application amount (content) of POM included in the biodegradable nonwoven fabric filter (biodegradable meltblown nonwoven fabric filter) manufactured according to an embodiment of the present invention. will be. At this time, the weight per unit area of the biodegradable nonwoven fabric filter was 30 g/m ² . The antiviral performance was evaluated according to ISO 18184 measurement standards.

Referring to Table 4, it can be confirmed that a high antiviral effect of about 80 to 96% can be obtained by applying an antiviral agent such as POM.

In this specification, preferred embodiments of the present invention have been disclosed, and although specific terms have been used, they are only used in a general sense to easily explain the technical details of the present invention and help understanding of the present invention, and do not limit the scope of the present invention. It is not meant to be limiting. It is obvious to those skilled in the art that other modifications based on the technical idea of the present invention can be implemented in addition to the embodiments disclosed herein. Those of ordinary skill in the art, the biodegradable material, biodegradable fibrous member, biodegradable fabric member and their manufacturing method according to the embodiment described with reference to FIGS. 1 to 10, the technical idea of the present invention It will be appreciated that various substitutions, changes, and modifications may be made within the range that does not deviate from this. In addition, it will be appreciated that the biodegradable nanofibers according to the embodiments can be applied to various fields other than the filter member. Therefore, the scope of the invention should not be determined by the described embodiments, but by the technical idea described in the claims.

* Description of symbols for main parts of drawings *
1: resin feeder 2: extruder
3: pump member 4: melt blown die
5: Collector 6: Winder
10: coated member 20: coated member supply unit
30: coating agent 40: dipping container
50: heat treatment chamber 60: winding unit
S10 to S50: Steps

Claims (38)

delete delete delete delete delete delete As a biodegradable fiber member,
It includes a biodegradable polymer material having a triblock copolymer in which poly hydroxy alkanoate (PHA), poly lactic acid (PLA), and poly caprolactone (PCL) are combined,
Further comprising a functional metal-containing additive mixed with the biodegradable polymer material and having static electricity retention properties, wherein the functional metal-containing additive includes an oxide, wherein the oxide is selected from among Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ . It includes at least one, and the metal ion of the functional metal-containing additive is hydrogen-bonded with the biodegradable polymer material by oxygen contained in the oxide,
Further comprising an antiviral agent applied on the biodegradable fibrous member, wherein the antiviral agent includes polyoxometalate (POM), and the amount of the antiviral agent applied to the biodegradable fibrous member is 1 to 5 g/m ² , Absence of biodegradable fibers. According to claim 7,
In the triblock copolymer, the PLA is disposed between the PHA and the PCL, a first end of the PLA is connected to an end of the PHA, and a second end of the PLA is a biodegradable fiber connected to an end of the PCL. absence. According to claim 7,
The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) Biodegradable fibrous member comprising at least one of. delete delete According to claim 7,
The content of the functional metal-containing additive to the biodegradable polymer material is 0.1 to 5 wt% of the biodegradable fibrous member. According to claim 7,
At least a portion of the functional metal-containing additive is a biodegradable fibrous member charged with an electrostatic charge. delete delete delete A biodegradable fabric member comprising the biodegradable fibrous member according to any one of claims 7 to 9, 12 and 13. 18. The method of claim 17,
The biodegradable fabric member is a biodegradable non-woven fabric member biodegradable fabric member. According to claim 18,
The biodegradable nonwoven fabric member is a biodegradable fabric member that is a meltblown nonwoven fabric member. 18. The method of claim 17,
The biodegradable fabric member is a biodegradable fabric member constituting at least a part of a mask filter, an air purifier filter, a sheet for a patient, or a protective clothing. delete delete delete delete delete delete As a method for producing a biodegradable fibrous member,
Forming a biodegradable resin having a triblock copolymer in which poly hydroxy alkanoate (PHA), poly lactic acid (PLA), and poly caprolactone (PCL) are combined;
forming a biodegradable composite resin by mixing the biodegradable resin with a functional metal-containing additive having static electricity retention properties; and
Forming a biodegradable fibrous member from the biodegradable composite resin,
The functional metal-containing additive includes an oxide, the oxide includes at least one of Al ₂ O ₃ , Fe ₂ O ₃ and TiO ₂ , and the metal ion of the functional metal-containing additive is absorbed by oxygen contained in the oxide. By hydrogen bonding with the biodegradable resin,
Further comprising applying an antiviral agent on the biodegradable fibrous member, wherein the antiviral agent includes polyoxometalate (POM), and an applied amount of the antiviral agent to the biodegradable fibrous member is 1 to 5 g/m ² A method for producing a phosphorus, biodegradable fibrous member. 28. The method of claim 27,
In the triblock copolymer, the PLA is disposed between the PHA and the PCL, a first end of the PLA is connected to an end of the PHA, and a second end of the PLA is a biodegradable fiber connected to an end of the PCL. How to make a member. 28. The method of claim 27,
The PHA is P3HB (poly 3-hydroxy butyrate), P3HBV (poly 3-hydroxy butyrate valerate), PHV (poly hydroxy valerate), P4HB (poly 4-hydroxy butyrate), PHHX (poly hydroxy hexanoate) and PHD (poly hydroxy dodecanoate) ) Method for producing a biodegradable fibrous member comprising at least one of. delete 28. The method of claim 27,
The method for producing a biodegradable fibrous member in which the content of the functional metal-containing additive relative to the biodegradable resin is 0.1 to 5 wt%. delete delete delete 28. The method of claim 27,
Method for producing a biodegradable fibrous member further comprising the step of charging at least a portion of the functional metal-containing additive with an electrostatic charge. A method for manufacturing a biodegradable fabric member comprising the step of manufacturing a biodegradable fabric member using the method for manufacturing a biodegradable fibrous member according to any one of claims 27 to 29, 31 and 35. 37. The method of claim 36,
The biodegradable fabric member is a method for producing a biodegradable nonwoven fabric member of the biodegradable fabric member. 38. The method of claim 37,
The biodegradable nonwoven fabric member is a method for producing a biodegradable fabric member that is a meltblown nonwoven fabric member.