KR20210147332A - Biodegradable polyester resin composition, biodegradable non-woven fabric and preperation method thereof - Google Patents

Abstract

An embodiment relates to a biodegradable polyester resin composition with improved biodegradability, flexibility, strength and processability by comprising a specific diol component and a dicarboxylic acid component, a biodegradable nonwoven fabric, and a method for preparing the same, wherein the biodegradable polyester resin composition can improve biodegradability, flexibility, strength, and processability as compared with polylactic acid, which is a natural biodegradable polymer widely used in the related art, and thus can be applied to various fields such as a film, a packaging material, and a nonwoven fabric.

Description

Biodegradable polyester resin composition, biodegradable nonwoven fabric, and manufacturing method thereof

Embodiments relate to a biodegradable polyester resin composition, a biodegradable nonwoven fabric, and a method for preparing the same.

Recently, as concerns about environmental problems increase, a solution to the problem of processing various household items, in particular, disposable products is required. Specifically, polymer materials are inexpensive and have excellent properties such as processability, so they are widely used to manufacture various products such as films, fibers, packaging materials, bottles, and containers. It has the disadvantage that it takes hundreds of years for the material to be discharged and completely decomposed in nature.

In order to overcome the limitations of these polymers, research on biodegradable polymers that decompose in a much faster time is being actively conducted. Polylactic acid (PLA) is a natural biodegradable polymer that is derived from plant biomass resources and has been widely used because it can be obtained easily. Therefore, its use is limited.

In particular, the nonwoven fabric is made into a felt shape by arranging fibers in parallel or in an irregular direction without going through a weaving process and bonding them with a synthetic resin adhesive. Recently, disposable tissues, dishcloths, packaging materials, masks, etc. Although it is widely used, in the case of manufacturing a nonwoven fabric with polylactic acid, it has low flexibility and is stiff, so the feeling of use or wearing is not very good.

For example, Korean Patent Application Laid-Open No. 2016-0079770 discloses a nonwoven fabric with improved flexibility by being manufactured through polylactic acid and polypropylene blend spinning, but polylactic acid and polypropylene have poor compatibility with each other, so processability is low, and fish eye The quality of the nonwoven fabric is low because dent defects such as fish eyes may occur.

Korean Patent Publication No. 2016-0079770

Accordingly, embodiments are to provide a biodegradable polyester resin composition capable of improving biodegradability, flexibility, strength and processability, a biodegradable nonwoven fabric, and a manufacturing method thereof.

The biodegradable polyester resin composition according to an embodiment includes a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof, and the dicarboxylic acid component includes the first dicarboxylic acid and the a second dicarboxylic acid different from the first dicarboxylic acid, wherein the first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof, and the second dicarboxylic acid The acid includes at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof.

A biodegradable nonwoven fabric according to another embodiment includes a nonwoven fabric layer formed from a biodegradable polyester resin composition, wherein the biodegradable polyester resin composition includes a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof wherein the dicarboxylic acid component includes a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid, wherein the first dicarboxylic acid is terephthalic acid, dimethyl terephthalic acid, and their and at least one selected from the group consisting of derivatives, and the second dicarboxylic acid includes at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof.

A method for producing a biodegradable nonwoven fabric according to another embodiment includes preparing a prepolymer by esterifying a composition including a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof; preparing a polymer by subjecting the prepolymer to a polycondensation reaction; preparing pellets from the polymer; and spinning the pellets to prepare a nonwoven layer, wherein the dicarboxylic acid component includes a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid, The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof, and the second dicarboxylic acid is at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. includes

Since the biodegradable polyester resin composition according to the embodiment includes a specific diol component and a dicarboxylic acid component, strength, processability, and flexibility can all be improved without inhibiting biodegradability, so it is applied to more diverse fields and has excellent properties can exert

In particular, since the biodegradable nonwoven fabric according to the embodiment includes the nonwoven fabric layer formed from the biodegradable polyester resin composition, the feeling and wearing comfort are good, and the quality is excellent because there are almost no defects such as fish eyes.

Therefore, the biodegradable nonwoven fabric can be easily applied to products in a variety of fields, such as packaging materials, masks, and dishcloths, and in particular, when applied to a mask, it is very comfortable to wear.

1 shows a mask manufactured using a biodegradable nonwoven fabric according to an embodiment.
2 and 3 are cross-sectional views of the mask of FIG. 1 taken along X-X', respectively.
4 schematically shows a method for manufacturing a biodegradable nonwoven fabric according to an embodiment.

Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In addition, it should be understood that all numerical ranges indicating physical property values, dimensions, etc. of the components described in the present specification are modified by the term "about" in all cases unless otherwise specified.

In this specification, terms such as first, second, etc. are used to describe various components, and the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

The size of each component in the drawings may be exaggerated for explanation, and may be different from the size actually applied.

Biodegradable polyester resin composition

The biodegradable polyester resin composition according to an embodiment includes a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof, and the dicarboxylic acid component includes the first dicarboxylic acid and the a second dicarboxylic acid different from the first dicarboxylic acid, wherein the first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof, and the second dicarboxylic acid The acid includes at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof.

The diol component includes 1,4-butanediol or a derivative thereof.

Specifically, the diol component may include 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol% of 1,4-butanediol or a derivative thereof based on the total number of moles of the diol component. When the diol component includes 1,4-butanediol or a derivative thereof, biodegradability, flexibility and strength can be improved. In particular, when the diol component is composed of only 1,4-butanediol, biodegradability, flexibility and strength can be maximized.

The dicarboxylic acid component comprises a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid.

The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof. Specifically, the first dicarboxylic acid may be terephthalic acid or dimethyl terephthalic acid.

In addition, the dicarboxylic acid component is 45 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 70 mol% or more, 45 mol% to 80 mol% based on the total number of moles of the dicarboxylic acid component mole %, 45 mole % to 75 mole % or 50 mole % to 70 mole % of the first dicarboxylic acid.

The second dicarboxylic acid includes at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. Specifically, the second dicarboxylic acid may be adipic acid or succinic acid.

In addition, the dicarboxylic acid component is 45 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 70 mol% or more, 45 mol% to 80 mol% based on the total number of moles of the dicarboxylic acid component mole %, 45 mole % to 75 mole % or 50 mole % to 70 mole % of the second dicarboxylic acid.

The molar ratio of the diol component and the dicarboxylic acid component may be 1 to 2:1. For example, the molar ratio of the diol component and the dicarboxylic acid component may be 1 to 1.8:1, 1.1 to 1.8:1, or 1.3 to 1.6:1. When the molar ratio of the diol component and the dicarboxylic acid component satisfies the above range, biodegradability, strength, and processability can all be improved without discoloration such as yellowing.

In addition, the molar ratio of the first dicarboxylic acid and the second dicarboxylic acid may be 0.5 to 2:1. For example, the molar ratio of the first dicarboxylic acid and the second dicarboxylic acid may be 0.5 to 1.5:1, 0.7 to 1.3:1, or 0.8 to 1.2:1. When the molar ratio of the first dicarboxylic acid and the second dicarboxylic acid satisfies the above range, biodegradability and processability may be improved.

The biodegradable polyester resin composition according to an embodiment may further include nano-cellulose. Specifically, the biodegradable polyester resin composition may include one or more kinds of nano cellulose selected from the group consisting of cellulose nanocrystals, cellulose nanofibers and microfibrillated cellulose, and the cellulose nanocrystals or cellulose nanofibers have strength and thermal properties. It is preferable in terms of characteristics. By further including the nano-cellulose in the biodegradable polyester resin composition, biodegradability, strength and thermal properties may be further improved.

More specifically, the nano cellulose is hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, cellulose acetate, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, pentyl cellulose, hexyl cellulose and It may be at least one selected from the group consisting of cyclohexyl cellulose.

The nano-cellulose may have a diameter of 1 nm to 100 nm. For example, the diameter of the nano-cellulose is 1 nm to 95 nm, 5 nm to 90 nm, 10 nm to 80 nm, 1 nm to 50 nm, 5 nm to 45 nm, 10 nm to 60 nm, 1 nm to 10 nm, 10 nm to 30 nm or 15 nm to 50 nm.

In addition, the length of the nano-cellulose may be 5 nm to 10 μm. For example, the length of the nano-cellulose is 5 nm to 1 μm, 10 nm to 150 nm, 20 nm to 300 nm, 200 nm to 500 nm, 100 nm to 10 μm, 500 nm to 5 μm, 300 nm to 1 μm, may be 1 μm to 10 μm.

When the diameter and length of the nano-cellulose satisfy the above ranges, strength, in particular, tear strength can be further improved.

In addition, the content of the nano-cellulose may be 0.01 wt% to 3 wt% based on the total weight of the composition. For example, the content of the nano-cellulose may be 0.01 wt% to 2.5 wt%, 0.05 wt% to 2 wt%, 0.07 wt% to 1.8 wt%, or 0.07 wt% to 1.2 wt% based on the total weight of the composition have. When the content of nano-cellulose satisfies the above range, biodegradability and strength can be further improved.

The biodegradable polyester resin composition may include a titanium-based catalyst or a germanium-based catalyst. Specifically, the biodegradable polyester resin is titanium isopropoxide, antimony trioxide, dibutyltin oxide, tetrapropyl titanate, tetrabutyl titanate, tetraisopropyl titanate, antimony acetate, calcium acetate and magnesium acetate. One or more titanium-based catalysts selected from the group consisting of, or one or more germanium-based catalysts selected from the group consisting of germanium oxide, germanium methoxide, germanium ethoxide, tetramethyl germanium, tetraethyl germanium and germanium sulfide may be included. .

In addition, the content of the catalyst may be 100 ppm to 1,000 ppm based on the total weight of the composition. For example, the biodegradable polyester resin composition is 100 ppm to 800 ppm, 150 ppm to 700 ppm, 200 ppm to 500 ppm or 250 ppm to 450 ppm of a titanium-based catalyst or a germanium-based catalyst based on the total weight of the composition may include When the content of the catalyst satisfies the above range, processability can be improved without discoloration such as yellowing.

biodegradable non-woven fabric

A biodegradable nonwoven fabric according to another embodiment includes a nonwoven fabric layer formed from a biodegradable polyester resin composition, wherein the biodegradable polyester resin composition includes a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof wherein the dicarboxylic acid component includes a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid, wherein the first dicarboxylic acid is terephthalic acid, dimethyl terephthalic acid, and their and at least one selected from the group consisting of derivatives, and the second dicarboxylic acid includes at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof.

The biodegradable nonwoven fabric may include an antimicrobial coating layer located on at least one surface of the nonwoven fabric layer.

1 shows a mask 1 manufactured using a biodegradable nonwoven fabric according to an embodiment, and FIGS. 2 and 3 are cross-sectional views of the mask of FIG. 1 taken along X-X', respectively. The use of the biodegradable nonwoven fabric is not limited to the mask, and FIG. 1 illustrates a mask to which the biodegradable nonwoven fabric is applied.

Specifically, FIG. 2 illustrates a biodegradable nonwoven fabric 2 having an antimicrobial coating layer 200 formed on one surface of the nonwoven fabric layer 100 , and FIG. 3 is an antimicrobial coating layer 200 formed on both sides of the nonwoven fabric layer 100 . A biodegradable nonwoven fabric (2) is illustrated. More specifically, FIG. 2 shows a cross-sectional view of the mask 1 having an antimicrobial coating layer 200 formed on the inner surface or outer surface, and FIG. 3 is a cross-sectional view of the mask 1 having an antimicrobial coating layer 200 formed on the inner surface and outer surface. have.

As such, the biodegradable nonwoven fabric may further improve antibacterial properties by including a nonwoven fabric layer and an antimicrobial coating layer located on one or both surfaces of the nonwoven fabric layer. Therefore, when the biodegradable nonwoven fabric is used as a food or medical packaging material, it is possible to effectively prevent food deterioration or growth of microorganisms in medical products.

The antimicrobial coating layer may include silver nanoparticles in an amount of 0.5 wt% to 10 wt% based on the total weight of the antimicrobial coating layer. For example, the content of the silver nano may be 0.5 wt% to 8 wt%, 0.5 wt% to 3 wt%, 0.7 wt% to 2.5 wt%, or 0.8 wt% to 1.5 wt% based on the total weight of the antimicrobial coating layer have. When the content of nano-silver satisfies the above range, antibacterial properties can be further improved, and in particular, when the biodegradable nonwoven fabric including the antibacterial coating layer is used as a food packaging material, deterioration of food can be more effectively prevented.

The thickness of the nonwoven layer may be 0.1 mm to 10 mm. For example, the thickness of the nonwoven layer may be 0.1 mm to 5.0 mm, 0.1 mm to 3.0 mm, 0.1 mm to 0.5 mm, 0.5 mm to 3.0 mm, 0.5 mm to 1.0 mm, or 1.0 mm to 2.0 mm.

In addition, the thickness of the antimicrobial coating layer may be 10 nm to 1 ㎛. For example, the thickness of the antimicrobial coating layer may be 10 nm to 700 nm, 20 nm to 500 nm, 20 nm to 100 nm, 50 nm to 500 nm, or 90 nm to 500 nm.

The thickness of the biodegradable nonwoven fabric may be 0.1 mm to 10 mm. For example, the biodegradable nonwoven may have a thickness of 0.1 mm to 5.0 mm, 0.1 mm to 3.0 mm, 0.1 mm to 0.5 mm, 0.5 mm to 3.0 mm, 0.5 mm to 1.0 mm, or 1.0 mm to 2.0 mm.

The average pore size of the nonwoven layer may be 200 μm or less. For example, the average pore size of the sub-foam layer may be 180 μm or less, 160 μm or less, 10 μm to 200 μm, 50 μm to 200 μm, 100 μm to 180 μm, or 130 μm to 160 μm. When the average pore size of the nonwoven layer satisfies the above range, air permeability and flexibility may be further improved.

The tensile strength of the nonwoven fabric layer may be 30 MPa or more. For example, the tensile strength of the nonwoven layer may be 33 MPa or more, 35 MPa or more, 30 MPa to 60 MPa, 33 MPa to 55 MPa, or 33 MPa to 53 MPa.

The tear strength of the nonwoven fabric layer may be 400 N/cm or more. For example, the tear strength of the nonwoven layer is 450 N/cm or more, 500 N/cm or more, 550 N/cm or more, 400 N/cm to 1,500 N/cm, 450 N/cm to 1,300 N/cm, It may be 500 N/cm to 1,200 N/cm or 550 N/cm to 1,100 N/cm.

In addition, the elongation at break of the nonwoven fabric layer may be 400% or more. For example, the elongation at break of the nonwoven fabric layer may be 450% or more, 500% or more, 550% or more, 400% to 900%, 450% to 800%, or 550% to 750%.

Since the tensile strength, tear strength, and elongation at break of the nonwoven fabric layer satisfy the above ranges, it is possible to easily apply to products in various fields and improve lifespan.

The initial modulus of elasticity of the nonwoven layer ^{may be 200 kgf/mm 2} or less. For example, the initial modulus of elasticity of the nonwoven layer is 180 kgf/mm ² or less, 160 kgf/mm ² or less, 60 kgf/mm ² to 200 kgf/mm ² , 80 kgf/mm ² to 180 kgf/mm ² , 85 kgf/mm ² to 160 kgf/mm ² may be. Since the initial modulus of elasticity of the nonwoven fabric layer satisfies the above range, flexibility can be improved, and in particular, when applied to products that contact the skin for a long time, such as a mask, the wearing comfort is excellent.

Method for manufacturing biodegradable non-woven fabric

A method for producing a biodegradable nonwoven fabric according to another embodiment includes preparing a prepolymer by esterifying a composition including a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof; preparing a polymer by subjecting the prepolymer to a polycondensation reaction; preparing pellets from the polymer; and spinning the pellets to prepare a nonwoven layer, wherein the dicarboxylic acid component includes a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid, The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof, and the second dicarboxylic acid is at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. includes

4 schematically shows a method for manufacturing a biodegradable nonwoven fabric according to an embodiment. Hereinafter, a method ( S100 ) of manufacturing a biodegradable nonwoven fabric according to an embodiment will be described with reference to FIG. 4 .

First, a prepolymer is prepared by esterifying a composition including a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof (S110) .

The description of the diol component and the dicarboxylic acid component is the same as described above.

The step S110 may include adding a titanium-based catalyst or a germanium-based catalyst to the composition (S111). Specifically, a titanium-based catalyst or a germanium-based catalyst may be added to the composition before the esterification reaction. The description of the titanium-based catalyst or the germanium-based catalyst is the same as described above.

In addition, the step S110 may include the step of adding cellulose to the composition (S112). Specifically, before the esterification reaction, cellulose may be added to the composition. The description of the cellulose is as described above.

In this case, the cellulose input in step S112 may be cellulose dispersed in the diol component. For example, the diol component may be 1,4-butanediol, and the cellulose input in step S112 may be cellulose dispersed in 1,4-butanediol.

Alternatively, the cellulose input in step S112 may be cellulose re-dispersed in the diol component after being dispersed in water. Specifically, after dispersing the cellulose in water, it may be cellulose that has undergone two dispersion steps by dispersing it again in the diol component.

As such, by dispersing the nano-cellulose in the same diol component as the diol component included in the composition and then adding it to the composition, dispersibility can be improved to maximize strength, particularly tear strength.

In addition, at least one selected from the group consisting of additives such as silica, potassium or magnesium, and stabilizers such as trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid or phosphorous acid is added to the composition of step S110 before the esterification reaction can be put into

The esterification reaction may be performed at 250° C. or less for 0.5 to 5 hours. Specifically, the esterification reaction is carried out at 240 ° C. or less, 235 ° C. or less, 180 ° C. to 250 ° C., 185 ° C. to 240 ° C. or 200 ° C. to 240 ° C. At normal pressure until the by-product water and methanol theoretically reach 90% can be performed in For example, the esterification reaction may be performed for 0.5 hours to 4.5 hours, 0.5 hours to 3.5 hours, or 1 hour to 3 hours, but is not limited thereto.

The number average molecular weight of the prepolymer may be 1,500 to 10,000. For example, the number average molecular weight of the prepolymer may be 1,500 to 8,500, 1,500 to 6,500, or 2,000 to 5,500. When the number average molecular weight of the prepolymer satisfies the above range, it is possible to efficiently increase the molecular weight of the polymer in the polycondensation reaction.

Thereafter, the prepolymer is subjected to a polycondensation reaction to prepare a polymer (S120) .

The polycondensation reaction may be performed at 180° C. to 280° C. and 1.0 Torr or less for 1 hour to 5 hours. For example, the polycondensation reaction may be performed at 190°C to 270°C, 210°C to 260°C, or 230°C to 255°C, and 0.9 Torr or less, 0.7 Torr or less, 0.2 Torr to 1.0 Torr, 0.3 Torr to 0.9 Torr or 0.4 Torr to 0.6 Torr, and may be carried out for 1.5 hours to 4.5 hours, 2 hours to 4 hours, or 2.5 hours to 3.5 hours.

In addition, additives such as silica, potassium or magnesium, a stabilizer such as trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid or phosphorous acid, and antimony trioxide, antimony trioxide or tetrabutyl to the prepolymer before the polycondensation reaction At least one selected from the group consisting of a polymerization catalyst such as titanate may be additionally added.

The number average molecular weight of the polymer may be 40,000 or more. For example, the number average molecular weight of the polymer may be 43,000 or more, 45,000 or more, or 50,000 to 70,000. When the number average molecular weight of the polymer satisfies the above range, strength and processability can be further improved.

Thereafter, a pellet is prepared from the polymer (S130) .

Specifically, the step S130 may include cooling the polymer to 15° C. or less, 10° C. or less, or 6° C. or less, and cutting the cooled polymer.

The cutting step may be performed without limitation as long as it is a pellet cutter used in the art, and the pellets may have various shapes.

Thereafter, the pellets are spun to prepare a non-woven fabric layer (S140) .

The spinning may be a meltblown, spundbond, flashspun, electro-spining or wet-laid method, and melt blown is preferable in terms of pore size. However, the present invention is not limited thereto.

Specifically, the melt blown method is a method of spinning a polymer at a high speed, and it can produce a nonwoven fabric with a small pore size and high filter performance. There is a problem of large and weak strength.

However, the method for producing a biodegradable nonwoven fabric according to the embodiment can produce a nonwoven fabric having excellent strength without degrading biodegradability, flexibility, and processability even when the melt blown method is used.

Specifically, the step S130 is 30 m / min to 100 m / min, 30 m / min to 70 m / min or 70 m at 180 ° C. to 260 ° C., 185 ° C. to 240 ° C. or 190 ° C. to 230 ° C. A nonwoven fabric layer may be prepared by spinning at a spinning speed of /min to 100 m/min.

In addition, the step S140 may further include coating the antimicrobial composition on at least one surface of the nonwoven fabric layer (S141).

Specifically, by coating the antimicrobial composition on at least one surface of the nonwoven fabric layer in step S140 to form an antimicrobial coating layer, a biodegradable nonwoven fabric comprising a nonwoven fabric layer and an antimicrobial coating layer on at least one surface of the nonwoven fabric layer can be obtained. The coating may be performed by gravure coating, slot coating, comma coating, roll coating, spray coating or impregnation coating, but is not limited thereto.

The antimicrobial composition may include silver nanoparticles in an amount of 0.5 wt% to 10 wt% based on the total weight of the antimicrobial composition. For example, the content of the silver nano may be 0.5 wt% to 8 wt%, 0.5 wt% to 3 wt%, 0.7 wt% to 2.5 wt%, or 0.8 wt% to 1.5 wt% based on the total weight of the antimicrobial composition have. When the content of nano-silver satisfies the above range, antibacterial properties can be further improved, and in particular, when the biodegradable nonwoven fabric including the antibacterial coating layer is used as a food packaging material, deterioration of food can be more effectively prevented.

The above will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

<Example>

Preparation of biodegradable non-woven fabric

Example 1

1.4 mol of 1,4-butanediol, 0.5 mol of adipic acid, and 0.5 mol of dimethyl terephthalic acid were mixed, and 300 ppm of tetrabutyl titanate (manufacturer: CAMEO Chemicals), a titanium-based catalyst, was added to the mixture, then 220° C. and atmospheric pressure. A prepolymer having a number average molecular weight of 5,000 was prepared by performing an esterification reaction in

100 ppm of tetrabutyl titanate (manufacturer: CAMEO Chemicals) as a polycondensation catalyst was added to the prepolymer, and the temperature was raised to 240° C., followed by polycondensation reaction at 0.5 torr for 3 hours. A polymer having a number average molecular weight of 50,000 After preparing A, and cooling it to 5°C, it was cut with a pellet cutter to prepare pellets.

The pellets were spun at a spinning speed of 50 m/min at 220° C. using a melt blown method to prepare a nonwoven layer having an average pore size of 150 μm and a thickness of 0.2 mm.

A biodegradable nonwoven fabric having a thickness of 0.2 mm in which an antimicrobial coating layer was formed on one surface of the nonwoven fabric layer was prepared by spin coating an antimicrobial coating composition containing silver nanoparticles in an amount of 1 wt% on one surface of the nonwoven fabric layer.

Example 2

A biodegradable nonwoven fabric was prepared in the same manner as in Example 1, except that 0.1 wt% of nano cellulose (20 nm in diameter, 200 nm in length) dispersed in 1,4-butanediol during the polycondensation reaction was additionally added. did

Example 3

A biodegradable nonwoven fabric was prepared in the same manner as in Example 1, except that 0.5 wt% of nano cellulose (diameter 20 nm, length 200 nm) dispersed in 1,4-butanediol during the polycondensation reaction was additionally added. did

Comparative Example 1

A biodegradable nonwoven fabric was prepared in the same manner as in Example 1, except that a polylactic acid resin (4032D, manufacturer: NatureWorks) was used instead of the polymer A, and an antibacterial coating layer was not formed.

Comparative Example 2

Instead of the polymer A, polylactic acid resin (4032D, manufacturer: NatureWorks) and polypropylene (manufacturer: Hanwha Total) were compounded using twin screws at 190 ° C. Polymer B was used, and an antibacterial coating layer was not formed. Except that, a biodegradable nonwoven fabric was prepared in the same manner as in Example 1.

<Evaluation example>

Evaluation Example 1: Tensile strength, elongation at break and initial modulus of elasticity

After cutting the nonwoven fabric to 100 mm in length and 15 mm in width, according to ASTM D 882, using a universal testing machine (4206-001, manufacturer: UTM) of INSTRON, it was mounted so that the distance between chucks was 50 mm and tension After testing at a speed of 200 mm/min, measurements were made with a program built into the facility.

Evaluation Example 2: Tear strength

The nonwoven fabric was cut according to KPS M 1001-0806, and the maximum load applied until the nonwoven fabric was cut by applying a constant speed of 500 mm/min was measured to calculate the tear strength according to Equation 1 below.

[Equation 1]

Evaluation Example 3: Antibacterial

KS K0890 The antibacterial test method of textile materials was evaluated as pass or fail by the parallel section line method.

Evaluation Example 4: Fish eye

Based on the area of 100 mm ^{2 of the} nonwoven fabric, defects such as foreign substances or deterioration of 100 μm or more were detected with a microscope and the number was measured.

Evaluation Example 5: Biodegradability

The biodegradability was measured by measuring the amount of carbon dioxide generated according to KS M3100-1. Specifically, an inoculum container with only compost manufactured in a compost factory was prepared, and a test container was prepared in which a nonwoven fabric of 5 wt% of the dry weight of the compost was added to the compost. Thereafter, incubated for 180 days at a temperature of 58±2° C., a moisture content of 50%, and an oxygen concentration of 6% or more, the carbon dioxide generated in each container is collected, and the amount of carbon dioxide generated in each container is measured by titrating it with an aqueous phenolphthalein solution. did. The biodegradation degree was calculated according to Equation 2 below with the measured amount of carbon dioxide generated.

[Equation 2]

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile strength (MPa) 35 50 47 37 28 Elongation at break (%) 600 700 800 200 150 Initial modulus of elasticity
(kgf/mm ² ) 100 150 190 350 240 Tear strength (N/cm) 600 1,000 1,100 200 300 Antibacterial (p/f) pass pass Pass fail fail Fish Eye (dog) - - - - 30 Biodegradability (%) 90 90 90 90 40

As shown in Table 1, the biodegradable nonwoven fabrics of Examples 1 to 3 were superior to the biodegradable nonwoven fabrics of Comparative Examples 1 and 2 in biodegradability, tensile strength, tear strength, elongation at break, initial modulus of elasticity, and antibacterial properties. was shown.

Specifically, it can be seen that the biodegradable nonwoven fabrics of Examples 1 to 3 are excellent in biodegradability, tensile strength, tear strength and elongation at break compared to the biodegradable nonwoven fabrics of Comparative Examples 1 and 2, so that they can be easily applied to various fields. have. In addition, the biodegradable nonwoven fabric of Examples 1 to 3 did not have dent defects such as fish eyes, and had a low initial modulus of elasticity and thus excellent flexibility.

1: Mask
2: Biodegradable non-woven fabric
100: non-woven fabric layer
200: antibacterial coating layer

Claims (10)

a diol component and a dicarboxylic acid component including 1,4-butanediol or a derivative thereof;
the dicarboxylic acid component comprises a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid;
The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof,
The second dicarboxylic acid is a biodegradable polyester resin composition comprising at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. The method of claim 1,
The molar ratio of the diol component and the dicarboxylic acid component is 1 to 2 : 1,
The molar ratio of the first dicarboxylic acid and the second dicarboxylic acid is 0.5 to 2: 1, biodegradable polyester resin composition. The method of claim 1,
Containing at least one nano-cellulose selected from the group consisting of cellulose nanocrystals, cellulose nanofibers, and microfibrillated cellulose,
The nano-cellulose has a diameter of 1 nm to 100 nm,
The length of the nano-cellulose is 5 nm to 10 μm,
The content of the nano-cellulose is 0.01% to 3% by weight based on the total weight of the composition, biodegradable polyester resin composition. The method of claim 1,
A biodegradable polyester resin composition further comprising a titanium-based catalyst or a germanium-based catalyst. A nonwoven fabric layer formed from a biodegradable polyester resin composition,
The biodegradable polyester resin composition includes a diol component including 1,4-butanediol or a derivative thereof and a dicarboxylic acid component,
the dicarboxylic acid component comprises a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid;
The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof,
The second dicarboxylic acid is a biodegradable nonwoven fabric comprising at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. 6. The method of claim 5,
The biodegradable nonwoven fabric comprises an antimicrobial coating layer located on at least one surface of the nonwoven fabric layer. 7. The method of claim 6,
The biodegradable nonwoven fabric, wherein the antimicrobial coating layer comprises 0.5 wt% to 10 wt% of silver nanoparticles based on the total weight of the antibacterial coating layer. 6. The method of claim 5,
The nonwoven layer has an average pore size of 200 μm or less, a tensile strength of 30 MPa or more, a tearing strength of 400 N/cm or more, and an initial elastic modulus of 200 kgf/mm ² or less, a biodegradable nonwoven fabric. preparing a prepolymer by subjecting a composition including a diol component including 1,4-butanediol or a derivative thereof and a dicarboxylic acid component to an esterification reaction;
preparing a polymer by subjecting the prepolymer to a polycondensation reaction;
preparing pellets from the polymer; and
Including; producing a nonwoven layer by spinning the pellets,
the dicarboxylic acid component comprises a first dicarboxylic acid and a second dicarboxylic acid different from the first dicarboxylic acid;
The first dicarboxylic acid includes at least one selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof,
The second dicarboxylic acid comprises at least one selected from the group consisting of adipic acid, succinic acid, and derivatives thereof, a method for producing a biodegradable nonwoven fabric. 10. The method of claim 9,
The number average molecular weight of the prepolymer is 1,500 to 10,000,
The number average molecular weight of the polymer is 40,000 or more,
The esterification reaction is carried out at 250° C. or less for 0.5 hours to 5 hours,
The polycondensation reaction is performed at 180 ° C. to 280 ° C. and 1.0 Torr or less for 1 hour to 5 hours, a method for producing a biodegradable nonwoven fabric.

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